CN103289015A - Method for preparing quaternary phosphonium salt type cationic starch - Google Patents
Method for preparing quaternary phosphonium salt type cationic starch Download PDFInfo
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- CN103289015A CN103289015A CN2012100438784A CN201210043878A CN103289015A CN 103289015 A CN103289015 A CN 103289015A CN 2012100438784 A CN2012100438784 A CN 2012100438784A CN 201210043878 A CN201210043878 A CN 201210043878A CN 103289015 A CN103289015 A CN 103289015A
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Abstract
The invention relates to a method for preparing quaternary phosphonium salt type cationic starch. The method is characterized in that starch, quaternary phosphonium salt monomers and acrylamide serve as raw materials, grafting copolymerization is carried out under the action of a free radical polymerization initiator or ionizing radiation, and cationic functional groups of a quaternary phosphonium salt are connected to starch macromolecules through C-C bonds instead of ether bonds, so as to prepare the quaternary phosphonium salt type cationic starch. According to the method for preparing quaternary phosphonium salt type cationic starch, the process is simple, and the industrial production is facilitated; and compared with a quaternary ammonium salt, the quaternary phosphonium salt has the advantages that the thermal stability is good, the bacterium resistance is about 100 times higher than that of the quaternary ammonium salt, and the capability of being bonded with counter ions or radicals is strong. Thus, compared with the existing quaternary ammonium salt type cationic starch, the quaternary phosphonium salt type cationic starch prepared by the method has the advantages of good thermal stability and strong adsorption capacity.
Description
Technical field
The present invention relates to polymer modification, a kind of quaternary phosphine salt type preparation of cationic starch method specifically namely is grafted with the side group that has the quaternary phosphine cation group and/or the starch product of side chain at the starch chain skeleton.The cationic starch that adopts this technology to produce can be applied to industry and fields such as papermaking, weaving, chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry.
Background technology
Starch belongs to natural high moleculer eompound, is the polysaccharide polymer that is formed by a plurality of glucose molecule condensations, can be synthetic by photosynthesis by plant.Starch is the nutrient of storing in the plant materials, is stored in seed and the stem tuber, and the starch content in all kinds of plants is all higher.Naturally occurring starch is called ative starch, and the starch of process physics, chemistry or biological method modification is called modified starch.Big series products in the numerous modified starch kinds of cationic starch.
Cationic starch at present domestic and international patent and the open source literature all is to be connected with side group and/or the side chain that has quaternary ammonium cation at the starch main chain basically, does not then appear in the newspapers about be connected with the starch that has the cationic side group of quaternary phosphine and/or side chain at the starch main chain.
The similar of quaternary alkylphosphonium salt is in quaternary ammonium salt, but You Yu Phosphonium atomic radius is bigger than carbon atom, and polarized action is strong.Its thermostability is better than quaternary ammonium salt, and anti-microbial activity is also far above quaternary ammonium salt.
Summary of the invention
Purpose of the present invention just is being based on above-mentioned prior art situation and the quaternary phosphine salt type preparation of cationic starch method that provides, and can realize by two kinds of approach: a kind of is chemical graft process, and a kind of is radiation graft process.Be under radical polymerization initiator or effects of ionizing radiation, to carry out graft copolymerization, by the C-C key quaternary alkylphosphonium salt Cationic functional groups be connected on the starch polymer, rather than by ehter bond the quaternary alkylphosphonium salt Cationic functional groups be connected on the starch polymer.
The objective of the invention is to be achieved through the following technical solutions: quaternary phosphine salt type preparation of cationic starch method of the present invention, be to be raw material with starch, quaternary alkylphosphonium salt monomer, acrylamide, by chemical initiation grafting mode or radiation initiation grafting mode, prepare the quaternary phosphine salt type cationic starch.
Preparation method's concrete steps by the chemical initiation grafting mode are as follows:
(1) take by weighing starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01～0.5/0.01～1/0.1～20; Take by weighing the radical polymerization initiator of Zhan quaternary alkylphosphonium salt monomer, acrylamide gross weight 0.1～3%;
(2) water is starch pasting, be cooled to normal temperature after, add quaternary alkylphosphonium salt monomer, acrylamide, stir, fill the nitrogen deoxygenation; Temperature control adds radical polymerization initiator at 25～90 ℃ then, reacts 0.5～10 hour;
(3) cooling obtains quaternary phosphine salt type cationic starch aqua; Further dry, obtain quaternary phosphine salt type cationic starch pulvis.
According to how many differences of solvent for use amount, described chemical graft method can also be further divided into multiple implementation methods such as wet method, dry method, semidrying.Described wet method preparation process is that the water dissolved monomer obtains the monomer phase, and water obtains the starch phase with starch pasting, then two-phase is mixed the back and reacts with the chemical initiator initiation grafting; The starch that perhaps grafted monomer directly is dissolved in gelatinization mutually in, mix the back with the reaction of chemical initiator initiation grafting.Described dry preparation process is to add monomer in less water or organic solvent, mixes with starch then, with the reaction of chemical initiator initiation grafting.It is the situation of aqua that wet method preparation process is fit to the finished product, and the suitable the finished product of dry preparation process are the situation of pulvis.Semidrying is the processing method between wet method and dry method.In the chemical graft method provided by the present invention, according to the difference of institute's water consumption, also can be divided into wet method, dry method, semidrying.
Preparation method's concrete steps by radiation initiation grafting mode are as follows:
(1) take by weighing starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01～0.5/0.01～1/0.1～20;
(2) water is starch pasting, be cooled to normal temperature after, add quaternary alkylphosphonium salt monomer, acrylamide, stir, fill the nitrogen deoxygenation; Place radiation field irradiation then, absorption dose 0.5～100KGy, preferred 0.5～50KGy.Described radiation field comprises gamma-radiation radiation field, electron beam irradiation field;
(3) in radiation chamber, take out, obtain quaternary phosphine salt type cationic starch aqua; Further dry, obtain quaternary phosphine salt type cationic starch pulvis.
According to how many differences of solvent for use amount, described method for radio-grafting also can be further divided into multiple implementation methods such as wet method, dry method, semidrying.Gamma-radiation or electron beam act on the water molecules in the water solution system, and water molecules is stimulated or ionization, produce a large amount of active free radicals.These free radicals act on starch polymer, can make and produce active site on the starch polymer, and monomer carries out chainpropagation at the active site place, form grafted chain; These free radicals are directly trigger monomer polymerization also, forms free macromolecular chain.Simultaneously, gamma-radiation or electron beam direct act on the starch in the water solution system, make the starch polymer direct ionization, form active site, and monomer carries out chainpropagation at the active site place, form grafted chain.
The quaternary alkylphosphonium salt monomer has general formula described in above-mentioned chemical graft and the method for radio-grafting:
And/or
Wherein, n=1～20; R
1, R
2, R
3, R
4, R
5, R
6Be H, C independently of one another
1-C
40Alkyl, aryl or heteroaryl; X represents halogen, comprises Cl or Br.A kind of in the preferred allyl group trimethylammonium of described quaternary alkylphosphonium salt monomer phosphonium halide, allyl group tributyl phosphonium halide, allyl group triphenyl phosphonium halide, vinyl benzyl trimethylammonium phosphonium halide, vinyl benzyl tributyl phosphonium halide, the vinyl benzyl triphenyl phosphonium halide, or multiple.
The main effect of acrylamide is to improve the grafting efficiency of quaternary alkylphosphonium salt monomer on starch in described chemical graft and method for radio-grafting, therefore should select for use be easy on starch polymer grafting and also easily Yu the monomer of quaternary alkylphosphonium salt monomer copolymerization, can certainly.
Be persulphate, ceric ammonium nitrate, persulphate-sulphite at radical polymerization initiator described in the chemical graft method.
Preparation quaternary phosphine salt type cationic starch among the present invention, technology is simple, is easy to suitability for industrialized production.Quaternary alkylphosphonium salt is compared with quaternary ammonium salt, and is thermally-stabilised good, and it is high about 100 times that anti-microbial property is wanted, strong with the binding ability of gegenion or group.Therefore, compare the Heat stability is good of the prepared De quaternary phosphine of the present invention type cationic starch, high adsorption capacity with existing quaternary ammonium cation starch.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
20 gram corn ative starchs (water ratio 12.7%) are dissolved in 120 ml distilled waters, and 85 ℃ of gelatinization 30min are chilled to room temperature, obtain the starch phase.Under the mechanical stirring, 12 gram acrylamides, 8 gram vinyl benzyl triphenyl phosphonium chlorides and 0.25 gram ammonium persulphate are dissolved in 80 ml distilled waters, obtain the monomer phase.With 10 ml distilled waters dissolving, 0.10 gram sodium bisulfite.With monomer be added to starch mutually in, fill the nitrogen deoxygenation, stir, be warming up to 40 ℃, drip sodium sulfite solution, drip off in half an hour, reacted 4 hours.Room temperature is cooled off, and obtains the aqua of quaternary phosphine salt type cationic starch.Product with acetone precipitation obtains places loft drier to dry precipitation then, puts into the cooling of moisture eliminator room temperature, pulverizes, and crosses 100 mesh sieves, and packing namely obtains pulvis.
Get pulvis as crude product, wrap with the filter paper of extracting, place in the Soxhlet extractor, with volume ratio be acetone/glacial acetic acid mixed solvent of 1:1 as extractant, after the extracting 18h, 50 ℃ of vacuum-dryings obtain pure product to constant weight (about 12h).
Get about pure product 1g and (be accurate to 0.001), accurately weighing is designated as m.Be dissolved into then in the 50ml deionized water and (can suitably heat), adopt Mohr's method (also can adopt Fo Erhadefa or method to raise the administration of justice) to measure chloride ion content.Be calculated as follows cationic degree:
CD=M×0.05×(V-V
0)/1000m
The molecular weight of M---quaternary alkylphosphonium salt in the formula
0.05---the concentration of silver nitrate solution, mol/L
The V---sample consumes the volume of silver nitrate solution, ml
V
0---blank test consumes the volume of silver nitrate solution, ml
The quality of m---sample, g
Replicate(determination) three times, last calculating mean value.CD=0.11mmol/g。
Embodiment 2:
12 gram acrylamides, 8 gram allyl group tributyl phosphonium bromides and 0.1 gram ceric ammonium nitrate are dissolved in 50 ml distilled waters, obtain the monomer phase.Under agitation monomer is added in the 30 gram potato ative starchs (water ratio 11.4%), nitrogen filled protection is warming up to 55 ℃, reacts 3 hours.Be transferred in the loft drier and dry, put into the cooling of moisture eliminator room temperature then, pulverize, cross 100 mesh sieves, pack, namely obtain the pulvis of quaternary phosphine salt type cationic starch.
Get an amount of pulvis, extracting, pure system.Analyze CD=0.08mmol/g by embodiment 1 described method.
Embodiment 3:
6 gram corn ative starchs (water ratio 12.7%) are dissolved in 60 ml distilled waters, and 85 ℃ of gelatinization 30min are chilled to room temperature.Under the mechanical stirring, add 8 gram acrylamides and 2 gram allyl group tributyl phosphonium bromides.Stir.Be transferred in the polyethylene bag, the inflated with nitrogen excluding air, airtight sealing places the indoor irradiation of gamma-ray irradiation, and absorption dose is 3kGy.Then, shift out radiation chamber.With the product that acetone precipitation obtains, place loft drier to dry then, put into the cooling of moisture eliminator room temperature, pulverize, cross 100 mesh sieves, pack, namely obtain the pulvis of quaternary phosphine salt type cationic starch.
Get an amount of pulvis, extracting, pure system.Analyze CD=0.17mmol/g by embodiment 1 described method.
Embodiment 4:
In 20 ml distilled waters, add 4 gram acrylamides and 4 gram vinyl benzyl tributyl phosphonium chlorides (77% pair of vinyl benzyl, 18% adjacent vinyl benzyl), stirring and dissolving.Then, under agitation the aqueous solution is joined in the 10 gram Zulkovsky starches, mix.Be transferred in the polyethylene bag, the inflated with nitrogen excluding air, airtight sealing places electron beam irradiation field irradiation, and absorption dose is 5kGy.Then, shift out radiation chamber.
Get an amount of pulvis, extracting, pure system.Analyze CD=0.15mmol/g by embodiment 1 described method.
Claims (7)
1. quaternary phosphine salt type preparation of cationic starch method is characterized in that: be to be raw material with starch, quaternary alkylphosphonium salt monomer, acrylamide, by chemical initiation grafting mode or radiation initiation grafting mode, prepare the quaternary phosphine salt type cationic starch.
2. quaternary phosphine salt type preparation of cationic starch method according to claim 1, it is characterized in that: the preparation method's concrete steps by the chemical initiation grafting mode are as follows:
(1) take by weighing starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01～0.5/0.01～1/0.1～20; Take by weighing the radical polymerization initiator of Zhan quaternary alkylphosphonium salt monomer, acrylamide gross weight 0.1～3%;
(2) water is starch pasting, be cooled to normal temperature after, add quaternary alkylphosphonium salt monomer, acrylamide, stir, fill the nitrogen deoxygenation; Temperature control adds radical polymerization initiator at 25～90 ℃ then, reacts 0.5～10 hour;
(3) cooling obtains quaternary phosphine salt type cationic starch aqua; Further dry, obtain quaternary phosphine salt type cationic starch pulvis.
3. quaternary phosphine salt type preparation of cationic starch method according to claim 1, it is characterized in that: the preparation method's concrete steps by radiation initiation grafting mode are as follows:
(1) take by weighing starch, quaternary alkylphosphonium salt monomer, acrylamide, water, mass percent is 1/0.01～0.5/0.01～1/0.1～20;
(2) water is starch pasting, be cooled to normal temperature after, add quaternary alkylphosphonium salt monomer, acrylamide, stir, fill the nitrogen deoxygenation; Place radiation field irradiation then, absorption dose 0.5～100KGy, preferred 0.5～50Kgy; Described radiation field comprises gamma-radiation radiation field or electron beam irradiation field;
(3) in radiation chamber, take out, obtain quaternary phosphine salt type cationic starch aqua; Further dry, obtain quaternary phosphine salt type cationic starch pulvis.
4. according to claim 1,2 or 3 described quaternary phosphine salt type preparation of cationic starch methods, it is characterized in that: described starch is a kind of in W-Gum, tapioca (flour), yam starch, green starch, sweet potato starch, sweet potato starch, wheat kind of starch, water caltrop starch, the Rhizoma Nelumbinis starch, or multiple.
5. according to claim 1,2 or 3 described quaternary phosphine salt type preparation of cationic starch methods, it is characterized in that: described quaternary alkylphosphonium salt monomer has general formula:
And/or
Wherein, n=1～20; R
1, R
2, R
3, R
4, R
5, R
6Be H, C independently of one another
1-C
40Alkyl, aryl or heteroaryl; X represents Cl or Br.
6. quaternary phosphine salt type preparation of cationic starch method according to claim 5, it is characterized in that: a kind of in the preferred allyl group trimethylammonium of described quaternary alkylphosphonium salt monomer phosphonium halide, allyl group tributyl phosphonium halide, allyl group triphenyl phosphonium halide, vinyl benzyl trimethylammonium phosphonium halide, vinyl benzyl tributyl phosphonium halide, the vinyl benzyl triphenyl phosphonium halide, or multiple.
7. quaternary phosphine salt type preparation of cationic starch method according to claim 2, it is characterized in that: described radical polymerization initiator is persulphate, ceric ammonium nitrate, persulphate-sulphite.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107674153A (en) * | 2017-10-12 | 2018-02-09 | 威尔（福建）生物有限公司 | A kind of auxiliary agent for improving greyness of paper and preparation method thereof |
| CN110194806A (en) * | 2019-05-21 | 2019-09-03 | 广西高源淀粉有限公司 | A kind of preparation method of cationic starch |
| CN111440278A (en) * | 2020-05-12 | 2020-07-24 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN111549529A (en) * | 2020-05-12 | 2020-08-18 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN113799514A (en) * | 2021-09-24 | 2021-12-17 | 广州松源实业有限公司 | Environment-friendly paper file box with mould-proof and insect-proof functions |
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| CN101033230A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院上海药物研究所 | Cmptothecine derivative and application thereof |
| CN101665554A (en) * | 2009-09-25 | 2010-03-10 | 上海大学 | Preparation method of cationic starch graft copolymer flocculant |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033230A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院上海药物研究所 | Cmptothecine derivative and application thereof |
| CN101665554A (en) * | 2009-09-25 | 2010-03-10 | 上海大学 | Preparation method of cationic starch graft copolymer flocculant |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674153A (en) * | 2017-10-12 | 2018-02-09 | 威尔（福建）生物有限公司 | A kind of auxiliary agent for improving greyness of paper and preparation method thereof |
| CN110194806A (en) * | 2019-05-21 | 2019-09-03 | 广西高源淀粉有限公司 | A kind of preparation method of cationic starch |
| CN110194806B (en) * | 2019-05-21 | 2021-09-17 | 广西高源淀粉有限公司 | Preparation method of cationic starch |
| CN111440278A (en) * | 2020-05-12 | 2020-07-24 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN111549529A (en) * | 2020-05-12 | 2020-08-18 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111549529B (en) * | 2020-05-12 | 2022-08-23 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111440278B (en) * | 2020-05-12 | 2022-09-27 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN113799514A (en) * | 2021-09-24 | 2021-12-17 | 广州松源实业有限公司 | Environment-friendly paper file box with mould-proof and insect-proof functions |
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