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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- starch
- polyamino
- organic compound
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Abstract
The invention discloses a polyamino starch and a preparation method thereof. The polyamino starch is prepared by carrying out crosslinking reaction on starch, a crosslinking agent and an organic compound containing two primary amino terminal groups. The polyamino starch is prepared by a dry process. The preparation method is characterized by comprising the following steps: adding the organic compound containing two primary amino terminal groups and the crosslinking agent into alkalified starch, uniformly mixing in a stirrer, and reacting the solid mixture at certain temperature to prepare the polyamino starch. By introducing the amino group, the polyamino starch has some new properties; and by regulating the proportion of the polyamine, crosslinking agent and starch, the nitrogen content, adsorptivity, stability and the like of the polyamino starch can be regulated. The preparation method has the characteristics of simple technique, environment friendliness, mild reaction conditions and the like; and the produced polyamino starch has the characteristics of low cost, adjustable adsorptivity, adjustable stability and the like, and is applicable to the fields of purification separation, wastewater treatment, fillers and the like.
Description
Technical field
The invention belongs to the preparing technical field of starch conversion product, particularly relate to and prepare polyamines base starch by dry process reaction.
Background technology
Starch is ubiquitous store polysaccharides in plant, is a kind of source not only cheap but also natural polymer widely.Treated starch have nontoxic, raw material sources are wide, price is low, be easy to the advantages such as biological degradation, paid attention in recent years and development and application.Domestic and international production modified starch method mainly contains wet method, dry method etc.; Current China modified starch production overwhelming majority adopts wet processing.Wet method also claims slurry processes, by starch dispersion in water or other liquid medium, is made into finite concentration suspension, reacts under certain temperature condition with chemical reagent, generates modified starch.Its advantage be reaction evenly, constant product quality, production control be easy; Shortcoming is that product not easily reclaims, production water loss large, sewage needs process, and thus cost is higher.Abroad, dry process becomes production modified starch main method gradually.Dry production modified starch is generally under starch contains a small amount of water (usual about 20%) situation, is sprayed onto by reaction reagent on starch, after sufficiently mixing, reacts under certain condition and obtain drying products; There is the advantages such as technique is simple, reaction efficiency is high, environmental pollution is little, production cost is low.
Polyamines base starch is a kind of important derivatives of treated starch.Polyamines base starch refers to introduces multiple amido in starch polymer.Due to the introducing of amido, make treated starch have special activity, polyamines base starch can be used for the field such as additive, purifies and separates, wastewater treatment of matrix material.Because selectable polyamines and linking agent have broad variety, so polyamines base starch varieties is various; Dissimilar polyamines base starch can be applied in different fields according to adsorptivity, stability etc.
About the report preparing polyamines base starch is not a lot, nearly all method is all wet method.Zulkovsky starch, epoxy chloropropane and diethylenetriamine are passed through single step reaction legal system for many amino-starch resin [Qu Rongjun by Qu Rongjun etc. in alkaline aqueous solution, Sun Yanzhi, Wang Chunhua, the synthesis and property of novel globular amino-starch resin, investigation of materials journal, 2009,15,473-478]; Phase waves etc. have prepared cross-linked amino-starch by three-step approach in aqueous; first in alkaline medium, starch and epichlorohydrin reaction are prepared cross-linking starch; be that the chloro-Hydroxy-propenyl of 3-introduced by initiator on cross-linking starch again with perchloric acid; finally above-mentioned intermediate product is obtained by reacting corresponding cross-linked amino-starch [phase wave to diethylenetriamine, triethylene tetramine, TEPA tetraethylene pentamine respectively in alkaline aqueous solution; Li Yijiu; Ni Yaming; amino starch flocculant synthesis technique; chemical industry environmental protection; 2003; 23,300-303; Phase wave, Li Yijiu, Ni Yaming, the preparation of cross-linked amino-starch and chelating ability research thereof, Treatment of Industrial Water, 2003,23,26-28; Phase wave, Li Yijiu, Ni Yaming, the preparation of cross-linked amino-starch and the absorption property to cupric ion, Shanghai environmental science, 2003,22,828-831].Polyamines base starch prepared by phase wave etc. only reacts an amido on polyamines.Above-mentioned two kinds of methods are wet-layer preparation polyamines base starch, and technics comparing is complicated.By linking agent, polyamines directly and the starch reaction method of preparing polyamines base starch after this further do not developed.Polyamines base starch is the important starch derivative of a class, but up to now also not about with polyamines, linking agent and the starch report by a step dry process polyamines base starch.
Summary of the invention
The object of the present invention is to provide polyamine species base starch and preparation method thereof.Polyamines base starch in the present invention is prepared from by dry process reaction by starch, linking agent and the organic compound containing two terminal primary amine bases; The preparation method of the polyamines base starch involved by this invention possesses the features such as technique is simple, environmental friendliness, reaction conditions are gentle, the polyamines base starch produced has that cost is low, adsorptivity and the feature such as stability is adjustable, can be applicable to the fields such as purifies and separates, wastewater treatment, weighting agent.
This invents the technical scheme that proposes: by containing the organic compound of two terminal primary amine bases, linking agent directly and starch reaction prepare polyamines base starch, linking agent one end and starch hydroxyl reaction, the other end and amido react; Polyamines base starch in the present invention has following chemical molecular general structure:
(St-R)
nNH
mR'NH
m(R-St)
n
In formula: St is starch molecule; R is 1 ~ 3 kind in ethylene glycol diglycidylether, formaldehyde, glutaraldehyde, epoxy chloropropane, Trisodium trimetaphosphate; NH
2r'NH
2for 1 ~ 4 kind in urea, trimeric cyanamide, thiocarbamide, quadrol, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines; 1≤n≤2,0≤m≤1, m+n=2.
Polyamines base starch is prepared in point alkalization, crosslinked two steps: (1) alkalinization selects basic catalyst to be KOH, NaOH, Na
2cO
3, K
2cO
3, CH
3cOOK, CH
31 ~ 3 kind in COONa.Be 1 ~ 100% by concentration, more excellent be 30 ~ 70% alkali lye under agitation join in starch, be then uniformly mixed 1 ~ 30min with homogenizer, then mixture be placed in environment alkalization 0.1 ~ 5h that temperature is 20 ~ 60 DEG C, obtain the starch that alkalizes.Alkali mole dosage is starch by 0.01 ~ 3 times of glucose unit mole number calculated amount.Alkalization temperature is preferably 40 ~ 50 DEG C, and alkalization time is preferably 0.5 ~ 3h.
(2) crosslinking reaction be by alkalization starch, tentatively mix containing the organic compound of two terminal primary amine bases and linking agent after be uniformly mixed 1 ~ 30min with homogenizer, then mixture is placed in environment crosslinking reaction 1 ~ 10h that temperature is 20 ~ 80 DEG C.React complete by kind of the solvent repetitive scrubbing of 1 ~ 3 in product with methylalcohol, ethanol, water, acetone, then filtration, drying, pulverizing obtain polyamines base starch.Mole dosage containing the organic compound of two terminal primary amine bases is starch by 0.01 ~ 3 times of glucose unit mole number calculated amount, and linking agent mole dosage is 2 ~ 8 times of the mole dosage of organic compound containing two terminal primary amine bases.Crosslinking temperature is preferably 40 ~ 70 DEG C, and cross-linking reaction time is preferably 3 ~ 8h.
Prepare polyamines base starch linking agent used be ethylene glycol diglycidylether, formaldehyde, glutaraldehyde, epoxy chloropropane, 1 ~ 3 kind of Trisodium trimetaphosphate; Organic compound containing two terminal primary amine bases used comprises 1 ~ 4 kind in urea, thiocarbamide, quadrol, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
In the present invention, alkalinization step mainly improves the reaction efficiency of starch and linking agent, when directly starch, alkaline catalysts, linking agent also being reacted after mixing with the organic compound containing two terminal primary amine bases.When the organic compound containing two terminal primary amine bases selecting reactive behavior high is as quadrol, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines etc., when adopting wet-layer preparation polyamines base starch, react very violent, be difficult to control even cannot react, adopt the semidrying solid phase reaction method in the present invention can make reaction temperature and carry out, and also have that by product is few, productive rate advantages of higher.
The invention has the beneficial effects as follows and directly use organic compound, linking agent and the starch containing two terminal primary amine bases to prepare polyamines base starch by dry process reaction, replace traditional route preparing polyamines base starch by Wet Method Reaction.This polyamines base starch has some new character due to the introducing of amido; The nitrogen content, adsorptivity, stability etc. of polyamines base starch can be adjusted by the ratio adjusting polyamines, linking agent and starch.The preparation method of the polyamines base starch involved by this invention possesses the features such as technique is simple, environmental friendliness, reaction conditions are gentle, the polyamines base starch produced has that cost is low, adsorptivity and the feature such as stability is adjustable, can be applicable to the fields such as purifies and separates, wastewater treatment, weighting agent.
Embodiment: the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1: get dry W-Gum 100g, the NaOH separately getting 0.01 ~ 3 times of starch mole number (calculating by glucose unit mole number) is made into the alkali lye of 1 ~ 100%, alkali lye is under agitation joined in starch, then 1 ~ 30min is uniformly mixed with homogenizer, again mixture is placed in environment alkalization 0.1 ~ 5h that temperature is 20 ~ 60 DEG C, obtains the starch that alkalizes.
By 0.01 ~ 3 times of starch mole number (by glucose unit mole number calculate) quadrol, 2 ~ 8 times of quadrol mole numbers epoxy chloropropane mix after under agitation join alkalization starch in, after preliminary mixing, be uniformly mixed 1 ~ 30min with homogenizer, then mixture be placed in environment crosslinking reaction 1 ~ 10h that temperature is 20 ~ 80 DEG C.React complete by the aqueous ethanolic solution repetitive scrubbing of product volume ratio 5:5, then filtration, drying, pulverizing obtain polyamines base starch.
Embodiment 2-5: method, with embodiment 1, namely utilizes the epoxy chloropropane in ethylene glycol diglycidylether, formaldehyde, glutaraldehyde, Trisodium trimetaphosphate alternate embodiment 1, obtains corresponding polyamines base starch respectively.
Embodiment 6-14: with urea, thiocarbamide, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 1 respectively, and other conditions, with embodiment 1, obtain corresponding polyamines base starch.
Embodiment 15-23: with urea, thiocarbamide, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 2 respectively, and other conditions, with embodiment 2, obtain corresponding polyamines base starch.
Embodiment 24-32: with urea, thiocarbamide, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 3 respectively, and other conditions, with embodiment 3, obtain corresponding polyamines base starch.
Embodiment 33-41: with urea, thiocarbamide, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 4 respectively, and other conditions, with embodiment 4, obtain corresponding polyamines base starch.
Embodiment 42-50: with urea, thiocarbamide, 1,3-propylene diamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 5 respectively, and other conditions, with embodiment 5, obtain corresponding polyamines base starch.
Epoxy chloropropane in embodiment 51-60: two kinds in spent glycol diglycidylether, epoxy chloropropane, formaldehyde, glutaraldehyde, Trisodium trimetaphosphate, three kinds alternate embodiments 1, with urea, thiocarbamide, quadrol, 1,3-propylene diamine, 1, two kinds, three kinds, four kinds in 6-hexanediamine, phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines replace the quadrol in embodiment 5 respectively, other conditions, with embodiment 1, obtain corresponding polyamines base starch.
Claims (4)
1. a polyamine species base starch, it is characterized in that being formed by starch, linking agent and the organic compound reaction containing two terminal primary amine bases, linking agent one end and starch hydroxyl reaction, the other end and amido react; Polyamines base starch in the present invention has following chemical molecular general structure: (St-R)
nnH
mr'NH
m(R-St)
n
In formula: St is starch molecule; R is 1 ~ 3 kind in ethylene glycol diglycidylether, formaldehyde, glutaraldehyde, epoxy chloropropane, Trisodium trimetaphosphate; NH
2r'NH
2for 1 ~ 4 kind in urea, trimeric cyanamide, thiocarbamide, quadrol, 1,3-propylene diamine, 1,6-hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines; 1≤n≤2,0≤m≤1, m+n=2.
2. a preparation method for polyamines base starch described in claim 1, it is characterized in that with starch, basic catalyst, linking agent and containing the organic compound of two terminal primary amine bases for raw material, polyamines base starch is prepared in point alkalization, crosslinked two steps:
(1) alkali that alkalinization is selected is KOH, NaOH, Na
2cO
3, K
2cO
3, CH
3cOOK, CH
31 ~ 3 kind in COONa; By mass concentration be 1 ~ 100% alkali lye join in starch under whipped state, above-mentioned pure alkali consumption is 0.01 ~ 3 times of starch mole number (calculating by glucose unit mole number), then be uniformly mixed 1 ~ 30min with homogenizer, then mixture be placed in environment alkalization 0.1 ~ 5h that temperature is 20 ~ 60 DEG C;
(2) crosslinking reaction is uniformly mixed 1 ~ 30min with homogenizer after the organic compound containing two terminal primary amine bases of alkalization starch, 0.01 ~ 3 times of starch mole number (calculating by glucose unit mole number) and 2 ~ 8 times of linking agents containing the organic compound mole number of two terminal primary amine bases tentatively being mixed, then mixture is placed in environment crosslinking reaction 1 ~ 10h that temperature is 20 ~ 80 DEG C; React complete by kind of the solvent repetitive scrubbing of 1 ~ 3 in product with methylalcohol, ethanol, water, acetone, then filtration, drying, pulverizing obtain polyamines base starch.
3. the preparation method of polyamines base starch according to claim 2, it is characterized in that: the organic compound containing two terminal primary amine bases used, for urea, trimeric cyanamide, thiocarbamide, quadrol, 1,1 ~ 4 kind in 3-propylene diamine, 1,6-hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
4. the preparation method of polyamines base starch according to claim 2, is characterized in that: linking agent used is 1 ~ 3 kind in ethylene glycol diglycidylether, formaldehyde, glutaraldehyde, epoxy chloropropane, Trisodium trimetaphosphate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105013447A (en) * | 2015-07-01 | 2015-11-04 | 南通大学 | Preparation method of modified cellulose heavy metal adsorbent |
| WO2016119557A1 (en) * | 2015-01-30 | 2016-08-04 | 成都新柯力化工科技有限公司 | Thermoplastic starch that can be heated repeatedly, and preparation method for same |
| CN106117426A (en) * | 2016-06-20 | 2016-11-16 | 上海东升新材料有限公司 | A kind of preparation method of modified corn starch chelating agen and products thereof |
| CN108822864A (en) * | 2018-06-11 | 2018-11-16 | 代彦霞 | One heavy metal species soil-repairing agent and preparation method thereof |
| CN111056664A (en) * | 2019-09-15 | 2020-04-24 | 南京霄祥工程技术有限公司 | Zero-emission treatment process and device for oil-containing emulsion wastewater |
| CN113121002A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
| CN113582770A (en) * | 2021-08-12 | 2021-11-02 | 吉林隆源农业服务有限公司 | Slow-release long-acting compound fertilizer for corn planting and preparation method thereof |
| CN113828016A (en) * | 2021-11-25 | 2021-12-24 | 欣格瑞（山东）环境科技有限公司 | Demulsifier for resin polymerization liquid and preparation method thereof |
| CN114133303A (en) * | 2021-11-29 | 2022-03-04 | 山东省鲁洲食品集团有限公司 | Preparation method for producing efficient water-soluble fertilizer from resin regeneration wastewater |
| CN115354426A (en) * | 2022-09-06 | 2022-11-18 | 朱财雄 | Preparation method of antibacterial graphene fabric |
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Cited By (14)
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| WO2016119557A1 (en) * | 2015-01-30 | 2016-08-04 | 成都新柯力化工科技有限公司 | Thermoplastic starch that can be heated repeatedly, and preparation method for same |
| CN105013447A (en) * | 2015-07-01 | 2015-11-04 | 南通大学 | Preparation method of modified cellulose heavy metal adsorbent |
| CN106117426A (en) * | 2016-06-20 | 2016-11-16 | 上海东升新材料有限公司 | A kind of preparation method of modified corn starch chelating agen and products thereof |
| CN108822864A (en) * | 2018-06-11 | 2018-11-16 | 代彦霞 | One heavy metal species soil-repairing agent and preparation method thereof |
| CN111056664A (en) * | 2019-09-15 | 2020-04-24 | 南京霄祥工程技术有限公司 | Zero-emission treatment process and device for oil-containing emulsion wastewater |
| CN111056664B (en) * | 2019-09-15 | 2021-12-10 | 济南灵秀环保科技有限公司 | Zero-emission treatment process and device for oil-containing emulsion wastewater |
| CN113121002B (en) * | 2019-12-31 | 2022-07-12 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
| CN113121002A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Flocculating agent and preparation method and application thereof |
| CN113582770A (en) * | 2021-08-12 | 2021-11-02 | 吉林隆源农业服务有限公司 | Slow-release long-acting compound fertilizer for corn planting and preparation method thereof |
| CN113828016B (en) * | 2021-11-25 | 2022-03-15 | 欣格瑞（山东）环境科技有限公司 | Demulsifier for resin polymerization liquid and preparation method thereof |
| CN113828016A (en) * | 2021-11-25 | 2021-12-24 | 欣格瑞（山东）环境科技有限公司 | Demulsifier for resin polymerization liquid and preparation method thereof |
| CN114133303A (en) * | 2021-11-29 | 2022-03-04 | 山东省鲁洲食品集团有限公司 | Preparation method for producing efficient water-soluble fertilizer from resin regeneration wastewater |
| CN114133303B (en) * | 2021-11-29 | 2022-12-06 | 山东省鲁洲食品集团有限公司 | Preparation method for producing efficient water-soluble fertilizer from resin regeneration wastewater |
| CN115354426A (en) * | 2022-09-06 | 2022-11-18 | 朱财雄 | Preparation method of antibacterial graphene fabric |
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