CN103642190B - Polyethylene glycol modified cyclodextrin, as well as preparation and application thereof - Google Patents
Polyethylene glycol modified cyclodextrin, as well as preparation and application thereof Download PDFInfo
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- CN103642190B CN103642190B CN201310676803.4A CN201310676803A CN103642190B CN 103642190 B CN103642190 B CN 103642190B CN 201310676803 A CN201310676803 A CN 201310676803A CN 103642190 B CN103642190 B CN 103642190B
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- cyclodextrin
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Abstract
The invention relates to polyethylene glycol modified cyclodextrin, as well as a preparation and an application thereof. The polyethylene glycol modified cyclodextrin comprises polyethylene glycol and cyclodextrin in the molar ratio of (1: 1)-(1: 10); and the preparation comprises the following steps: dissolving the cyclodextrin in water at the temperature of 30-100 DEG C, then adding the polyethylene glycol (PEG), stirring for 1-48h, reducing the temperature to room temperature, standing, filtering to obtain a precipitate, and drying to obtain the polyethylene glycol modified cyclodextrin. The application is as follows: adding the polyethylene glycol modified cyclodextrin into waterborne polyurethane, uniformly stirring, performing vacuum defoaming, then forming a film on a glass sheet, drying, washing with water, and then drying to obtain a film sample. The polyethylene glycol modified cyclodextrin provided by the invention has higher water solubility than the original cyclodextrin; and the average particle size is smaller, the operation is simple, convenient and easy, and equipment is simple.
Description
Technical field
The invention belongs to the preparation field of modified cyclodextrin, particularly to a kind of preparation side of poly ethyldiol modified cyclodextrin
Method.
Background technology
Cyclodextrin (cyclodextrin, abbreviation cd), is that starch ferments in the presence of cyclodextrin glycosyltransferase
The one group of cyclic oligosaccharide producing., organic molecule inorganic with many can form Host-guest inclusion complex, and can change by inclusion compound
Chemical and physical features, have the characteristic of protection, stable, solubilized guest molecule and selective oriented molecule, thus in food, ring
The aspects such as border, medicine, chemical detection suffer from important application.(Wang Yongjian, Zhang Zhengpiao, He Ping Lin. the height of cyclodextrin
Molecular effect [j]. chemical progress, 2000,12(3): 318-324；Chen Qingrui, Yang Meng, Liu Li, Jiang Guoqing, Zhang Dan, Liu Fengqi.
Beta-schardinger dextrin and the crystallization behavior [j] of OPEO mixed system, SCI, 2010,31(9):
1890-1895；Liao Caizhi, application progress [j] of beta-schardinger dextrin, chemical science and technology, 2010,18(5): 69-72)
Because cyclodextrin water solubility is poor, thus limit its application further in industrial circle.Water soluble Beta-cyclodextrin
Widely use, have effect unique.Water soluble Beta-cyclodextrin can greatly increase solubility in water for the insoluble medicine, improves insoluble medicine
Stability and bioavilability.At present chemical method and enzyme engineering are mainly passed through for the raising water miscible method of cyclodextrin
Method.If HP-β-CD is the etherification derivative being obtained by beta-schardinger dextrin chemical modification.(Yuan Chao, Jin Zhengyu. hydroxypropyl-
The structure [j] of beta-schardinger dextrin, food and biotechnology journal, 2007,26(4): 34-36)；Zhang Yuanchao, Huang Lixin, Xu Zhengkang.
The modification of cyclodextrin and application progress [j]. modern food science and technology, 2008,24 (9): 947-951)
Due to chemical method and enzyme engineering method to cyclodextrin water-soluble modified aspect, technological process is complicated, relatively costly, and thing
Reason method of modifying is simple, and cost is relatively low, easily implements, therefore using Physical, cyclodextrin can be modified, obtain Novel ring
Dextrin system.Alpha-cyclodextrin is penetrated the modified peg strand of cinnamic acid and is formed using ultrasonic method and comprises to be combined by Li Yuan etc.
Thing, improves the hydrophily of cyclodextrin, as new nano-medicament carrier, for drug controlled release.(Li Yuan, Ji Li, king
Just etc., alpha-cyclodextrin/polyethylene glycol self-assembled supermolecular nano-medicament carrier [j] Chinese science, 2010,40(3): 247-
254).
Water soluble Beta-cyclodextrin is mainly used in medicine, field of food at present, and its modified aqueous resin aspect does not especially relate to
And the application in field of waterborne polyurethane.With the enhancing of people's environmental consciousness and environmental regulation, eco-friendly aqueous poly-
The research of urethane, exploitation are increasingly subject to pay attention to, and its application constantly expands to the fields such as coating, binder by leather finishing agent,
Represent the developing direction of coating, binder.Wherein China's only building coating annual requirement at 2,500,000 tons about, wherein
1,200,000 tons can be reached by what aqueous polyurethane coating substituted, only this will have 10,000,000,000 yuan of demand spaces.Domestic at present aqueous poly-
Ten thousand tons about of the gross annual output value of urethane about 30-50, growth rate is 20%.(Zhu Zegang, aqueous polyurethane coating quickly grows market
Have very promising prospects [j] rubber and plastic utilization of resources, 2011, (1): 19-25).
Content of the invention
The technical problem to be solved is to provide a kind of poly ethyldiol modified cyclodextrin and its preparation and application, should
Invent the poly ethyldiol modified cyclodextrin of the preparation water solubility higher than former cyclodextrin；Average grain diameter is less, easy and simple to handle, easy
OK, equipment is simple.
A kind of poly ethyldiol modified cyclodextrin of the present invention, described poly ethyldiol modified cyclodextrin includes polyethylene glycol and ring
The mol ratio of dextrin, wherein polyethylene glycol and cyclodextrin is 1:1-1:10.
The mol ratio of described polyethylene glycol and cyclodextrin is 1:2-1:4.
Described cyclodextrin is one of alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin, preferably beta-schardinger dextrin.
The molecular weight of described polyethylene glycol peg is 200-10000.
The molecular weight of described polyethylene glycol peg is 1000-4000.
A kind of preparation method of the poly ethyldiol modified cyclodextrin of the present invention, comprising:
Under the conditions of 30-100 DEG C, cyclodextrin is soluble in water, it is subsequently adding polyethylene glycol peg, stir 1-48h, be down to
Room temperature, standing, filters to obtain sediment, dries, obtain final product poly ethyldiol modified cyclodextrin, its cyclodextrin is with polyethylene glycol peg's
Mol ratio is 1:1-1:10, and water is 1:2-1:50 with the mass ratio of cyclodextrin..
Described temperature is 50-80 DEG C.
Described mixing time is 1-5h.
The particle diameter of described poly ethyldiol modified cyclodextrin is 300-1000nm.
The application of a kind of poly ethyldiol modified cyclodextrin of the present invention, poly ethyldiol modified cyclodextrin is added to aqueous
In polyurethane, stir, after vacuum defoamation, masking, drying on the glass sheet, through water washing post-drying, obtains film sample,
The mass ratio of wherein poly ethyldiol modified cyclodextrin and aqueous polyurethane is 4-10:50-150.
The present invention is directed to the water-soluble low deficiency of cyclodextrin, under certain condition, two kinds of materials is passed through physical blending, from
And it is prepared for water-soluble higher cyclodextrin product.The present invention is that a kind of physical blending method preparation is produced compared with highly-water-soluble cyclodextrin
The method of thing, the average grain diameter of this method products therefrom is little, and average grain diameter is in 300-1000nm.
Beneficial effect
(1) the inclusion product of the present invention, has and has higher water solubility than former cyclodextrin；
(2) the inclusion product of the present invention, has the average grain diameter less than former cyclodextrin；
(3) this method is simple and easy to do, and equipment is simple；
(4) this product is added in aqueous polyurethane, can increase substantially the combination property of aqueous polyurethane.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Take beta-schardinger dextrin 4.5g, be dissolved in 50ml water (coolant-temperature gage is 65 DEG C).Add 8g peg(molecular weight 1000 afterwards) arrive
In the beta-schardinger dextrin aqueous solution.Stirring 1h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 30 DEG C.Through grain
Degree analyzer test, the average grain diameter of product is 360.2nm.
4g product is added in 50g aqueous polyurethane, stirs at 25 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through Mechanics Performance Testing, the Young's modulus of film is
30mpa, elongation at break is 510%, and fracture strength is 42mpa.
Embodiment 2
Take beta-schardinger dextrin 3.75g, be dissolved in 50ml water (coolant-temperature gage is 70 DEG C).Add 8.4g peg(molecular weight 2000 afterwards)
To in the beta-schardinger dextrin aqueous solution.Stirring 1h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 35 DEG C.Warp
Particle Size Analyzer is tested, and the average grain diameter of product is 460.7nm.
5g product is added in 60g aqueous polyurethane, stirs at 30 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
32mpa, elongation at break is 520%, and fracture strength is 45mpa.
Embodiment 3
Take beta-schardinger dextrin 5g, be dissolved in 60ml water (coolant-temperature gage is 60 DEG C).Add 12.6g peg(molecular weight 2000 afterwards) arrive
In the beta-schardinger dextrin aqueous solution.Stirring 2h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 35 DEG C.Through grain
Degree analyzer test, the average grain diameter of product is 500.3nm.
8g product is added in 65g aqueous polyurethane, stirs at 45 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
35mpa, elongation at break is 550%, and fracture strength is 50mpa.
Embodiment 4
Take alpha-cyclodextrin 10g, be dissolved in 100ml water (coolant-temperature gage is 60 DEG C).Add 70g peg(molecular weight 4000 afterwards) arrive
In the alpha-cyclodextrin aqueous solution.Stirring 10h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 40 DEG C.Warp
Particle Size Analyzer is tested, and the average grain diameter of product is 600nm.
10g product is added in 80g aqueous polyurethane, stirs at 50 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
37mpa, elongation at break is 450%, and fracture strength is 55mpa.
Embodiment 5
Take gamma-cyclodextrin 15g, be dissolved in 100ml water (coolant-temperature gage is 80 DEG C).Add 80g peg(molecular weight 4000 afterwards)
To in the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 50 DEG C.
Through Particle Size Analyzer test, the average grain diameter of product is 500nm.
6g product is added in 70g aqueous polyurethane, stirs at 55 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
40mpa, elongation at break is 470%, and fracture strength is 57mpa.
Embodiment 6
Take gamma-cyclodextrin 15g, be dissolved in 100ml water (coolant-temperature gage is 70 DEG C).Add 60g peg(molecular weight 6000 afterwards)
To in the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 40 DEG C.
Through Particle Size Analyzer test, the average grain diameter of product is 600.3nm.
10g product is added in 80g aqueous polyurethane, stirs at 60 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
42mpa, elongation at break is 480%, and fracture strength is 55mpa.
Embodiment 7
Take gamma-cyclodextrin 20g, be dissolved in 100ml water (coolant-temperature gage is 70 DEG C).Add 60g peg(molecular weight 6000 afterwards)
To in the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 70 DEG C.
Through Particle Size Analyzer test, the average grain diameter of product is 600.3nm.
10g product is added in 90g aqueous polyurethane, stirs at 65 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
37mpa, elongation at break is 510%, and fracture strength is 50mpa.
Embodiment 8
Take alpha-cyclodextrin 20g, be dissolved in 100ml water (coolant-temperature gage is 70 DEG C).Add 60g peg(molecular weight 6000 afterwards) arrive
In the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 70 DEG C.Warp
Particle Size Analyzer is tested, and the average grain diameter of product is 600nm.
10g product is added in 100g aqueous polyurethane, stirs at 60 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
35mpa, elongation at break is 490%, and fracture strength is 53mpa.
Embodiment 9
Take alpha-cyclodextrin 30g, be dissolved in 100ml water (coolant-temperature gage is 70 DEG C).Add 60g peg(molecular weight 6000 afterwards) arrive
In the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 70 DEG C.Warp
Particle Size Analyzer is tested, and the average grain diameter of product is 600nm.
20g product is added in 100g aqueous polyurethane, stirs at 50 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
28mpa, elongation at break is 400%, and fracture strength is 55mpa.
Embodiment 10
Take alpha-cyclodextrin 20g, be dissolved in 100ml water (coolant-temperature gage is 70 DEG C).Add 60g peg(molecular weight 6000 afterwards) arrive
In the gamma-cyclodextrin aqueous solution.Stirring 20h, standing.By sediment vacuumizing filtration, after be dried under vacuum to constant weight at 90 DEG C.Warp
Particle Size Analyzer is tested, and the average grain diameter of product is 700nm.
10g product is added in 150g aqueous polyurethane, stirs at 30 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
30mpa, elongation at break is 350%, and fracture strength is 60mpa.
Comparative example
Take beta-schardinger dextrin 10g, be dissolved in 100ml water (coolant-temperature gage is 65 DEG C), stir 10h, standing.Sediment is vacuumized
Filter, under 80oc, be dried under vacuum to constant weight.Through Particle Size Analyzer test, the average grain diameter of product is 1436nm.
5g product is added in 100g aqueous polyurethane, stirs at 65 DEG C, make on the glass sheet after vacuum defoamation
Film, dries in 60 DEG C of baking ovens, through water washing post-drying, obtains film sample.Through mechanical test, the Young's modulus of film is
25mpa, elongation at break is 500%, and fracture strength is 34mpa.
Claims (1)
1. a kind of application of poly ethyldiol modified cyclodextrin it is characterised in that: poly ethyldiol modified cyclodextrin is added to aqueous
In polyurethane, stir, after vacuum defoamation, masking, drying on the glass sheet, through water washing post-drying, obtains film sample,
The mass ratio of wherein poly ethyldiol modified cyclodextrin and aqueous polyurethane is 4-10:50-150；Poly ethyldiol modified cyclodextrin is former
The mol ratio that material includes polyethylene glycol peg and cyclodextrin, wherein polyethylene glycol and cyclodextrin is 1:1-1:10；
Wherein poly ethyldiol modified cyclodextrin is prepared by following methods: under the conditions of 30-100 DEG C, cyclodextrin is soluble in water, so
Add polyethylene glycol peg afterwards, stir 1-48h, be down to room temperature, standing, filters to obtain sediment, dries, obtain final product poly ethyldiol modified
Cyclodextrin.
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| CN104437414B (en) * | 2014-12-25 | 2017-05-17 | 江南大学 | Montmorillonite-reinforced polyethylene glycol/ cyclodextrin gel and preparation method thereof |
| CN104726956B (en) * | 2015-03-13 | 2017-06-06 | 东华大学 | A kind of preparation method of cyclodextrin complexes modification polyurethane elastomer fiber |
| CN106245379B (en) * | 2016-08-16 | 2018-08-31 | 嘉兴华晟助剂工业有限公司 | Environment-friendly type level dyeing healant composition and its application |
| CN106480753B (en) * | 2016-08-31 | 2019-04-12 | 浙江德誉进出口有限公司 | A kind of silk blend polyester fabric digit printing ink and preparation method thereof |
| CN106468024B (en) * | 2016-08-31 | 2019-04-12 | 浙江德誉进出口有限公司 | A kind of silk digit printing ink and preparation method thereof |
| CN106565861A (en) * | 2016-11-15 | 2017-04-19 | 常熟市凯力达蜂窝包装材料有限公司 | Modified cyclodextrin preparation method |
| CN107955437A (en) * | 2017-12-05 | 2018-04-24 | 安徽建邦建材有限公司 | A kind of preparation method of high tenacity water-borne acrylic coatings |
| CN110202157B (en) * | 2019-06-21 | 2022-05-31 | 王韬 | Titanium alloy composite material and method for preparing titanium alloy fishing rod special-shaped guide ring based on powder injection molding technology |
| CN115894944B (en) * | 2023-01-06 | 2023-05-12 | 四川科宏达集团有限责任公司 | Modified functional surfactant derivative, preparation method and application |
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