CN101367993B - Method for improving thermostability of propylene carbonate with cyclodextrin - Google Patents
Method for improving thermostability of propylene carbonate with cyclodextrin Download PDFInfo
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- CN101367993B CN101367993B CN2008102009293A CN200810200929A CN101367993B CN 101367993 B CN101367993 B CN 101367993B CN 2008102009293 A CN2008102009293 A CN 2008102009293A CN 200810200929 A CN200810200929 A CN 200810200929A CN 101367993 B CN101367993 B CN 101367993B
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- cyclodextrin
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Abstract
The invention provides a method for improving the thermal stability of poly propylene carbonate with cyclodextrin in the technical field of supramolecular chemistry. The method comprises the following steps: a. the poly propylene carbonate and the cyclodextrin are mechanically stirred; the mass ratio of the poly propylene carbonate to the cyclodextrin is 10:1 to 1:1; b. the product of step a is washed by deionized water and receives suction filtration, to remove the cyclodextrin which is not compounded; c. the solid product of step b is put under vacuum condition to be baked. The method has simple technological process and quite low cost; the transition temperature of the formed cyclodextrin and poly propylene carbonate compound is 5 DEG C to 10 DEG C higher than that of pure poly propylene carbonate. The product can be applied in fields, such as biodegradation packaging materials, medicine releasing carrier, solid electrolyte, inorganic filler surface conditioning agent and the like.
Description
Technical field
The present invention relates to a kind of method of chemical technology field, specifically, what relate to is a kind of method of utilizing cyclodextrin to improve thermostability of propylene carbonate.
Background technology
Poly (propylene carbonate) is a kind of novel high polymer material that utilizes carbonic acid gas and propylene oxide to be polymerized.The scale operation of such material has realized the utilization again of greenhouse gases carbonic acid gas, has reduced the consumption to the energy and material hydrocarbon, has reduced production cost.Poly (propylene carbonate) is a kind of brand-new bio-degradable plastics, and is environmentally friendly, pollution-free.In addition, because poly (propylene carbonate) has good low temperature kindliness, gas barrier property and the transparency etc., make the carrier, film packing material, solid electrolyte, inorganic filler surface treatment agent of its useful as drug slow-releasing system etc.But because the relatively poor thermostability of poly (propylene carbonate) self has a strong impact on its practical application in each field.
Find through literature search prior art, the physical blending modification is the main method that improves thermostability of propylene carbonate, promptly add other component in the matrix poly (propylene carbonate), under heated condition, carry out mechanical blending, form two-phase or multiphase co-mixing system.As X.C.Ge etc. at " Journal of Applied PolymerScience " (applied polymer science, 2006 the 99th volumes, the 782nd page to the 787th page, the preparation and the sign of " Fabricationand Characterization of Biodegradable Poly (propylene Carbonate)/WoodFlour Composites " biodegradable poly (propylene carbonate)/wood powder co-mixing system) in reported wood powder and poly (propylene carbonate) at 150 ℃ of following melt blendings, obtain the two-phase co-mixing system, because there is interaction of hydrogen bond in the two, make wood powder can be dispersed in preferably in the matrix poly (propylene carbonate), thereby improved the thermostability of poly (propylene carbonate) as weighting material.But, adopt co-mixing system that above method obtains under certain condition, as be heated, the influence of pH etc., the interaction of hydrogen bond of weighting material and matrix may be destroyed, causes occurring being separated, thereby have influence on the performance of this product.In addition, thermal destruction takes place in poly (propylene carbonate) easily when high-temperature blending.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of production technique cyclodextrin that utilizes simple, with low cost to improve the method for thermostability of propylene carbonate, cyclodextrin and poly (propylene carbonate) are stirred the mixture that includes that forms host-guest interaction by the solid phase mechanical blending at a lower temperature, be that the cavity that the molecular chain of poly (propylene carbonate) penetrates cyclodextrin forms stable supramolecular system, thereby improve thermostability of propylene carbonate.This product can be applicable to fields such as biological degradation packaging material, drug release carrier, solid electrolyte, inorganic filler surface treatment agent.
The present invention is achieved through technology, and raw materials used is cyclodextrin and poly (propylene carbonate), comprises the steps:
Step a: with poly (propylene carbonate) and cyclodextrin mechanical stirring.
Step b:, remove not compound cyclodextrin with the product of step a deionized water wash suction filtration.
Step c: the solid product of step b placed under the vacuum condition cure.
Among the step a, the mass ratio of described poly (propylene carbonate) and cyclodextrin is 10:1-1:1.
Among the step a, poly (propylene carbonate) is particulate solid or the powder of granularity smaller or equal to 500 μ m.
Among the step a, described cyclodextrin is meant a kind of in α cyclodextrin, beta-cyclodextrin and the γ cyclodextrin.
Among the step a, described mechanical stirring, its temperature are 40 ℃-140 ℃.
Among the step a, described mechanical stirring, its time is 48 hours.
Among the step b, described washing suction filtration, its number of times are at least 2 times.
Among the step c, cure under the described vacuum condition, its temperature is 40 ℃-80 ℃.
Among the step c, cure under the described vacuum condition, its time is 24 hours.
Cyclodextrin molecular has hydrophobic cavity, can be penetrated by linear poly (propylene carbonate) molecule to form accurate poly-wheel alkyl structure, and the rigidity of system increases to some extent.After the poly (propylene carbonate) molecule penetrated the hydrophobic cavity of cyclodextrin, the protection that the carbonic acid ester bond of the easily generation fracture of being heated on the chain is subjected to cavity became stable.In addition, when the content of cyclodextrin increases,, carry out regular accumulation between the cyclodextrin, formed the crystalline composites that includes of cyclodextrin and poly (propylene carbonate) owing to there is the hydrogen bond cooperative interaction.These factors all impel the thermostability of poly (propylene carbonate) to increase.
The preparation-obtained product of the present invention is through WAXD, solid
13C-NMR, DSC, TGA and FTIR characterize, and have proved the feasibility of present method.
Technology of the present invention is simple, cost is lower, the cyclodextrin that forms and the mixture second-order transition temperature that includes of poly (propylene carbonate) have improved 5-10 ℃ than pure poly (propylene carbonate), and this product can be used for fields such as biological degradation packaging material, drug release carrier, solid electrolyte, inorganic filler surface treatment agent.
Description of drawings
Fig. 1 is beta-cyclodextrin and poly (propylene carbonate) blending and stirring product WAXD figure.
Fig. 2. be beta-cyclodextrin and poly (propylene carbonate) blending and stirring product D SC figure.
Fig. 3 is beta-cyclodextrin and poly (propylene carbonate) blending and stirring product TGA figure.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 0.2 gram beta-cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 40 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is the compound beta-cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 0.4 gram beta-cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 140 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeated washing 3 times is removed not compound beta-cyclodextrin.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Embodiment 3
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 2 gram beta-cyclodextrins, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 80 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeated washing 3 times is removed not compound beta-cyclodextrin.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Embodiment 4
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 1 gram beta-cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 80 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is the compound beta-cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 0.5 gram beta-cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 80 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is the compound beta-cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Embodiment 6
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and the α cyclodextrin of 0.5 gram, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 90 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is compound α cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 60 ℃ of vacuum drying ovens after.
Embodiment 7
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 0.5 gram γ cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 90 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is compound γ cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 80 ℃ of vacuum drying ovens after.
Embodiment 8
Step a: (number-average molecular weight is about 1.3 * 10 to weighing 2 gram poly (propylene carbonate)s
5G/mol) and 0.2 gram beta-cyclodextrin, join in the single necked round bottom flask, insert stirring rod and stir plug, stirring rod is fixed on the mechanical stirrer.Flask is immersed in 90 ℃ of constant temperature oil baths, opens mechanical stirrer and stirred 48 hours.
Step b: the product of gained among the step a is poured in the beaker that 500 ml deionized water are housed, and magnetic agitation is suction filtration after 30 minutes, and same procedure repeats 3 times, and flush away is the compound beta-cyclodextrin not.
Step c: take out gained solid product among the step b cured 24 hours in 40 ℃ of vacuum drying ovens after.
Embodiment the results are shown in accompanying drawing:
The beta-cyclodextrin of the corresponding embodiment 3-5 preparation of collection of illustrative plates a-c and the WAXD collection of illustrative plates of poly (propylene carbonate) mechanical blending product among Fig. 1, this collection of illustrative plates locates to occur sharp-pointed diffraction peak at 18 °, proof has obtained the crystalline composites that includes of beta-cyclodextrin and poly (propylene carbonate) really, collection of illustrative plates d is the WAXD collection of illustrative plates of poly (propylene carbonate), this collection of illustrative plates a diffuse peaks occurs at 20 °, illustrate that this polymkeric substance is an amorphous, collection of illustrative plates e is the WAXD collection of illustrative plates of beta-cyclodextrin.
The DSC figure of the beta-cyclodextrin of the respectively corresponding embodiment 3-5 preparation of collection of illustrative plates a-c and poly (propylene carbonate) mechanical blending product among Fig. 2, collection of illustrative plates d are the DSC figure of poly (propylene carbonate).
The TGA figure of the beta-cyclodextrin of the respectively corresponding embodiment 3-5 preparation of collection of illustrative plates a-c and poly (propylene carbonate) mechanical blending product among Fig. 3, collection of illustrative plates d are the TGA figure of poly (propylene carbonate).DSC and TGA experimental result show, cyclodextrin and poly (propylene carbonate) include compound after, improved the thermostability of poly (propylene carbonate) significantly.
Claims (7)
1. a method of utilizing cyclodextrin to improve thermostability of propylene carbonate is characterized in that comprising the steps:
Step a: with poly (propylene carbonate) and cyclodextrin mechanical stirring, the mass ratio of described poly (propylene carbonate) and cyclodextrin is 10: 1-1: 1;
Described mechanical stirring, its temperature are 40 ℃-140 ℃;
Step b:, remove not compound cyclodextrin with the product of step a deionized water wash suction filtration;
Step c: the solid product of step b placed under the vacuum condition cure.
2. the method for utilizing cyclodextrin to improve thermostability of propylene carbonate according to claim 1 is characterized in that among the step a, poly (propylene carbonate) is particulate solid or the powder of granularity smaller or equal to 500 μ m.
3. the method for utilizing cyclodextrin to improve thermostability of propylene carbonate according to claim 1 is characterized in that, among the step a, described cyclodextrin is meant a kind of in α cyclodextrin, beta-cyclodextrin and the γ cyclodextrin.
4. the method for utilizing cyclodextrin to improve thermostability of propylene carbonate according to claim 1 is characterized in that, among the step a, and described mechanical stirring, its time is 48 hours.
5. the method for utilizing cyclodextrin to improve thermostability of propylene carbonate according to claim 1 is characterized in that among the step b, described washing suction filtration, its number of times are at least 2 times.
6. the method for utilizing cyclodextrin to improve thermostability of propylene carbonate according to claim 1 is characterized in that among the step c, cure under the described vacuum condition, its temperature is 40 ℃-80 ℃.
7. according to claim 1 or the 6 described methods of utilizing cyclodextrin to improve thermostability of propylene carbonate, it is characterized in that among the step c, cure under the described vacuum condition, its time is 24 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10008508A1 (en) * | 2000-02-24 | 2001-08-30 | Bayer Ag | New polycarbonate with cyclodextrin units, used e.g. as a chromatographic stationary phase, catalyst, drug delivery system, extractant or moulding material, especially for removing organic compounds from water |
| CN1944494A (en) * | 2006-09-14 | 2007-04-11 | 上海交通大学 | Process for separating and purifying different end group polymer using cyclic dextrin |
| CN101139405A (en) * | 2007-10-18 | 2008-03-12 | 上海交通大学 | Method for preparing hyper branched polyrotaxane based on cyclodextrin |
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2008
- 2008-10-09 CN CN2008102009293A patent/CN101367993B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10008508A1 (en) * | 2000-02-24 | 2001-08-30 | Bayer Ag | New polycarbonate with cyclodextrin units, used e.g. as a chromatographic stationary phase, catalyst, drug delivery system, extractant or moulding material, especially for removing organic compounds from water |
| CN1944494A (en) * | 2006-09-14 | 2007-04-11 | 上海交通大学 | Process for separating and purifying different end group polymer using cyclic dextrin |
| CN101139405A (en) * | 2007-10-18 | 2008-03-12 | 上海交通大学 | Method for preparing hyper branched polyrotaxane based on cyclodextrin |
Non-Patent Citations (1)
| Title |
|---|
| 刘琼等.环糊精高分子.《高分子通报》.2002,(第5期),第41-48页. * |
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