CN105061733A - Synthesis method of cellulose grafted polycaprolactone - Google Patents
Synthesis method of cellulose grafted polycaprolactone Download PDFInfo
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- CN105061733A CN105061733A CN201510456907.3A CN201510456907A CN105061733A CN 105061733 A CN105061733 A CN 105061733A CN 201510456907 A CN201510456907 A CN 201510456907A CN 105061733 A CN105061733 A CN 105061733A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a synthesis method of cellulose grafted caprolactone. According to the synthesis method, an ionic liquid BMIMC1 is taken as the solvent, n-butyl titanate is taken as the catalyst, caprolactone is taken as the grafting modifier, cellulose is taken as the raw material, and homogenous grafting reactions are carried out to synthesize cellulose grafted caprolactone. The invention also discloses a synthesis method of cellulose grafted polycaprolactone. According to the synthesis method, n-butyl titanate is taken as the catalyst, caprolactone is taken as the monomer, an ionic liquid BMIMC1 is taken as the reactions solvent, and ring-opening polymerization is performed under a homogenous condition to prepare grafted copolymer of cellulose and caprolactone (Cellulose-g-PCL). Then infrared spectrum (FT-IR) is used to characterize the grafted copolymer and the results show that the monomer (caprolactone) has been successfully grafted to the cellulose.
Description
Technical field
The invention belongs to cellulose modified technical field, be specifically related to a kind of synthetic method of cellulose graft polycaprolactone.
Background technology
Mierocrystalline cellulose, due to the good characteristic such as its environmental protection, nontoxic, easy degraded, renewable and easy derivatize, receives pay close attention to widely in oil, coal resources consumption is rapid and environmental pollution is serious today.Research and development take natural cellulose as the new fine chemical product of raw material is one of important topic of 21 century Sustainable development chemical engineering research field.Carrying out derivatize modification to Mierocrystalline cellulose is various monomer or macromolecular compound in grafting on cellulosic skeleton, given the performance of the more excellences of Mierocrystalline cellulose by the various target substance of grafting, make the Application Areas of cellulose materials expand all respects of production, life to.Effectively utilizing cellulose resource, having great importance for solving the resource problem faced now.
Caprolactone source is wide, and product can biological degradation, and achieving the circulation at occurring in nature, is desirable Green Polymer Material.Caprolactone molecule segment is introduced in cellulosic molecule, will the cellulose materials with biodegradability be obtained.But the complex structure of Mierocrystalline cellulose own, indissoluble, difficulty are melted, and make it apply and are restricted.Therefore, find environmental friendliness and be conducive to the major issue that the solvent of reaction controlling and catalyzer have become numerous research field.
Ionic liquid is as a kind of green solvent having potential using value, non-volatile with it, stable in properties, the advantages such as strong polarity, is used for replacing conventional organic solvent in a lot of field.In field of polymer technology, become a large focus of scientific worker's research as the polyreaction of solvent using ionic liquid, in the problems such as the environmental pollution existed in solution conventional polymerization process, the immobilized and recycling of catalyzer, embody huge potentiality.Caprolactone is grafted in cellulose skeleton, the new functional macromolecule material with Mierocrystalline cellulose and caprolactone common property can be obtained, the introducing of caprolactone short chain can destroy the regularity of cellulosic molecule and molecule is interior and intermolecular hydrogen bond, reaches reduction second-order transition temperature, internally plasticized object.In addition, this material also has renewable, the feature such as degradable, environmental friendliness, meets the requirement of Green Sustainable.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of synthetic method of cellulose graft polycaprolactone, natural polymer Mierocrystalline cellulose, caprolactone and green solvent ionic liquid are combined, by tetrabutyl titanate Ti-(O-
n-Bu)
4catalysis, synthetic cellulose polycaprolactone co-polymer, the investigation and application for Mierocrystalline cellulose new function material opens a new road.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
The synthetic method of cellulose graft caprolactone: adopt ionic liquid BMIMC1 to be a solvent, being catalyzer with tetrabutyl titanate, is graft modification agent with caprolactone, is raw material, carries out homogeneous phase graft reaction with Mierocrystalline cellulose, synthetic cellulose grafting caprolactone.
The synthetic method of described cellulose graft caprolactone, comprises the following steps:
1) Mierocrystalline cellulose is added BMIMC1,80 DEG C of constant temperature oil bath heating, at N
2the lower continuously stirring of protection, guarantees that Mierocrystalline cellulose is dissolved in ion BMIMC1 completely;
2) in the Mierocrystalline cellulose/BMIMC1 solution prepared to step 1), add monomer caprolactone and tetrabutyl titanate, temperature control 90 ~ 140 DEG C, continue stirring reaction 14 ~ 32h;
3) reaction system is cooled to room temperature, pours in deionized water to precipitate and cross and filter BMIMC1 and polycaprolactone (PCL), then remove unreacted monomer caprolactone with dehydrated alcohol eccysis; Finally crude product is poured into room temperature in methylene dichloride to whisk, filters, and repeatedly to wash with methylene dichloride, remove caprolactone homopolymer PCL further, namely obtain after drying product cellulose graft polycaprolactone (Mierocrystalline cellulose-
g-PCL); Wherein, monomer caprolactone and Mierocrystalline cellulose mass ratio are 10 ~ 30:1; Tetrabutyl titanate consumption is 6.2 ~ 18.7% of Mierocrystalline cellulose quality.
The synthetic method of described cellulose graft caprolactone, monomer caprolactone and Mierocrystalline cellulose mass ratio are 15:1.
Step 2) in, stirring reaction 24h.
Step 2) in, temperature of reaction is 120 DEG C.
The synthetic method of described cellulose graft caprolactone, tetrabutyl titanate consumption is 12.2% of Mierocrystalline cellulose quality.
Described Mierocrystalline cellulose is pourous wood bleached kraft pulp, softwood bleached kraft pulp.
The cellulose graft polycaprolactone that the synthetic method of described cellulose graft polycaprolactone obtains.
Beneficial effect: compared with prior art, the synthetic method of cellulose graft polycaprolactone of the present invention, take tetrabutyl titanate as catalyzer, take caprolactone as monomer, under the homogeneous phase condition being reaction solvent with ionic liquid BMIMC1, the graft copolymer (Cellulose-g-PCL) of Mierocrystalline cellulose and caprolactone is prepared in ring-opening polymerization.Utilize infrared spectra (FT-IR) to characterize graft copolymer, demonstrate monomer caprolactone and be successfully grafted on Mierocrystalline cellulose, after grafting PCL, cellulosic crystalline texture is destroyed.Be 120 DEG C in temperature of reaction, the reaction times is 24h, and catalyst levels is 12.2%, and when Mierocrystalline cellulose and caprolactone monomer mass ratio are 1:15, obtaining percentage of grafting is 86.7% graft copolymer.
Accompanying drawing explanation
Fig. 1 caprolactone monomer consumption is on the impact of cellulose graft rate;
Fig. 2 reaction times is on the impact of cellulose graft rate;
Fig. 3 temperature of reaction is on the impact of cellulose graft rate;
Fig. 4 catalyst levels is on the impact of cellulose graft rate;
The FT-IR figure of Fig. 5 Mierocrystalline cellulose and graft copolymer thereof.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
The raw material that following examples use and reagent as follows:
Ionic liquid, 1-butyl-3-Methylimidazole villaumite (BMIMCl) (>99%, fusing point: 73 DEG C); Catalyzer, tetrabutyl titanate (CP) (>98.0%); Caprolactone (ε-caprolactone) (>99%); Cellulosic material, vacuum drying softwood bleached kraft pulp.
Embodiment 1
Cellulose-
gthe synthetic method of-PCL, step is as follows:
1) dissolving of softwood bleached kraft pulp in ionic liquid: add in 29gBMIMC1 by 0.5 ~ 1.0g softwood bleached kraft pulp, 80 DEG C of constant temperature oil bath heating, at N
2the lower continuously stirring 2h of protection, ensures that Mierocrystalline cellulose is dissolved in ionic liquid completely.
2) graft copolymerization of softwood bleached kraft pulp in ionic liquid: in the Mierocrystalline cellulose prepared/BMIMC1 solution, add monomer caprolactone and catalyzer tetrabutyl titanate, continue to be stirred to setting-up time with dropping funnel, terminates reaction.
3) aftertreatment of graft copolymer: above-mentioned solution is cooled to room temperature, pours in deionized water and precipitates and filter deionizing liquid and polycaprolactone (PCL), then uses dehydrated alcohol (on a small quantity repeatedly) eccysis to remove monomer caprolactone.Finally crude product is poured into room temperature in methylene dichloride and whisk 48h, filter, and repeatedly wash with methylene dichloride, further the homopolymer PCL of removing caprolactone, namely solid vacuum-drying 24h at 50 DEG C obtains cellulose graft copolymer.
Percentage of grafting GR(%) massfraction of monomer of matrix grafting of representation unit quality.Calculation formula is as follows:
In formula, W
0for cellulosic quality, g; W
1for the quality of graft copolymer, g.
When temperature of reaction be 120 DEG C, the reaction times is 24h, catalyst levels is 12% time, caprolactone monomer consumption affects result as shown in Figure 1 to graft copolymerization.Along with the continuous increase of caprolactone and Mierocrystalline cellulose mass ratio, grafting takes the lead in increasing and then reduces, and after monomer and cellulosic mass ratio are more than 15, percentage of grafting declines on the contrary, and as can be seen here, monomer and cellulosic mass ratio should control to be advisable about 15.
When temperature of reaction be 120 DEG C, Mierocrystalline cellulose and caprolactone monomer mass ratio be 1:15, catalyst levels is 12.2% time, the graft reaction time affects result as shown in Figure 2 to percentage of grafting.Along with the continuous prolongation in reaction times, grafting takes the lead in increasing rear reduction.With the prolongation in reaction times, graft reaction carries out more complete.When being when reacted 24h, percentage of grafting reaches maximum value.But along with the further prolongation in reaction times, percentage of grafting declines on the contrary to some extent.Therefore, the most suitable reaction times is 24h.
When reacted for 24h, Mierocrystalline cellulose and caprolactone monomer mass ratio be 1:15, catalyst levels be 12.2% time, graft reaction temperature affects result as shown in Figure 3 to percentage of grafting.Along with the rising of temperature of reaction, percentage of grafting presents the variation tendency first increasing and reduce afterwards.When temperature of reaction is 120 DEG C, percentage of grafting reaches maximum value.Visible most suitable temperature of reaction is 120 DEG C.
When temperature of reaction be 120 DEG C, the reaction times is 24h, Mierocrystalline cellulose and caprolactone monomer monomer weight ratio are 1:15 time, catalyst levels affects result as shown in Figure 4 to graft reaction.With the continuous increase of catalyst levels, percentage of grafting increases thereupon; When catalyzer and Mierocrystalline cellulose mass ratio are greater than 12.2%, percentage of grafting declines on the contrary.The optimum value of visible catalyst levels is 12.2%.
FTIR spectrum (FT-IR): Mierocrystalline cellulose and the percentage of grafting obtained at 110 DEG C, 100 DEG C, 90 DEG C are respectively the FT-IR of the Mierocrystalline cellulose polycaprolactone co-polymer of 76.1%, 62.4%, 52.5% as shown in Figure 5.3100-3600cm
-1between be the charateristic avsorption band of hydroxyl and hydrogen bond thereof on cellulose chain glucose unit.Along with the increase of percentage of grafting, hydroxyl group absorption peak weakens, and this is because caprolactone is grafted in the part of hydroxyl on cellulose molecular chain glucose unit, reduces hydroxy radical content, and destroys the hydrogen bond in Mierocrystalline cellulose between hydroxyl.1735cm
-1be the charateristic avsorption band of carbonylic stretching vibration in ester bond, on the FT-IR collection of illustrative plates obviously can seeing graft copolymer, the intensity of ester bond carbonyl absorption peak strengthens gradually along with the increase of percentage of grafting.Compared with raw cellulose, graft copolymer is at 1303cm
-1, 1248cm
-1, 1070cm
-1for the charateristic avsorption band of C-O-C, illustrate that Mierocrystalline cellulose and caprolactone there occurs graft polymerization reaction, generate Mierocrystalline cellulose polycaprolactone co-polymer.
Claims (8)
1. a synthetic method for cellulose graft caprolactone, is characterized in that: adopting ionic liquid BMIMC1 to be solvent, take tetrabutyl titanate as catalyzer, take caprolactone as graft modification agent, take Mierocrystalline cellulose as raw material, carry out homogeneous phase graft reaction, synthetic cellulose grafting caprolactone.
2. the synthetic method of cellulose graft caprolactone according to claim 1, is characterized in that, comprise the following steps:
1) Mierocrystalline cellulose is added BMIMC1,80 DEG C of constant temperature oil bath heating, at N
2the lower continuously stirring of protection, guarantees that Mierocrystalline cellulose is dissolved in ion BMIMC1 completely;
2) in the Mierocrystalline cellulose/BMIMC1 solution prepared to step 1), add monomer caprolactone and tetrabutyl titanate, temperature control 90 ~ 140 DEG C, continue stirring reaction 14 ~ 32h;
3) reaction system is cooled to room temperature, pours in deionized water to precipitate and cross and filter BMIMC1 and polycaprolactone (PCL), then remove unreacted monomer caprolactone with dehydrated alcohol eccysis; Finally crude product is poured into room temperature in methylene dichloride to whisk, filters, and repeatedly to wash with methylene dichloride, remove caprolactone homopolymer PCL further, namely obtain after drying product cellulose graft polycaprolactone (Mierocrystalline cellulose-
g-PCL); Wherein, monomer caprolactone and Mierocrystalline cellulose mass ratio are 10 ~ 30:1; Tetrabutyl titanate consumption is 6.2 ~ 18.7% of Mierocrystalline cellulose quality.
3. the synthetic method of cellulose graft caprolactone according to claim 1 and 2, is characterized in that: monomer caprolactone and Mierocrystalline cellulose mass ratio are 15:1.
4. the synthetic method of cellulose graft caprolactone according to claim 1 and 2, is characterized in that: step 2) in, stirring reaction 24h.
5. the synthetic method of cellulose graft caprolactone according to claim 1 and 2, is characterized in that: step 2) in, temperature of reaction is 120 DEG C.
6. the synthetic method of cellulose graft caprolactone according to claim 1 and 2, is characterized in that: tetrabutyl titanate consumption is 12.2% of Mierocrystalline cellulose quality.
7. the synthetic method of cellulose graft caprolactone according to claim 1 and 2, is characterized in that: described Mierocrystalline cellulose is pourous wood bleached kraft pulp, softwood bleached kraft pulp.
8. the cellulose graft polycaprolactone that the synthetic method of the cellulose graft polycaprolactone described in claim 1 or 2 obtains.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106399416A (en) * | 2016-10-26 | 2017-02-15 | 江南大学 | Synthesis method of maillard product modified polycaprolactone in ionic liquid |
| CN107522789A (en) * | 2017-09-05 | 2017-12-29 | 广西师范学院 | The preparation method of banana cellulose nanofibers g-polycaprolactone composite |
| CN107550893A (en) * | 2017-09-05 | 2018-01-09 | 广西师范学院 | Carry the preparation method of paracetamol nano-fiber composite material |
| CN107619469A (en) * | 2017-09-30 | 2018-01-23 | 铜陵家宴生态农业发展有限公司 | A kind of preparation method of banana tegument extract g-polycaprolactone cross-linked material |
| CN111995691A (en) * | 2020-08-21 | 2020-11-27 | 南京林业大学 | Cellulose ether derivative, preparation method and application |
| CN114933688A (en) * | 2022-07-11 | 2022-08-23 | 南京林业大学 | Preparation method of magnetic degradable cellulose-based shape memory polyester material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106399416A (en) * | 2016-10-26 | 2017-02-15 | 江南大学 | Synthesis method of maillard product modified polycaprolactone in ionic liquid |
| CN106399416B (en) * | 2016-10-26 | 2019-10-25 | 江南大学 | A kind of synthetic method of Mei Lade product modification polycaprolactone in ionic liquid |
| CN107522789A (en) * | 2017-09-05 | 2017-12-29 | 广西师范学院 | The preparation method of banana cellulose nanofibers g-polycaprolactone composite |
| CN107550893A (en) * | 2017-09-05 | 2018-01-09 | 广西师范学院 | Carry the preparation method of paracetamol nano-fiber composite material |
| CN107550893B (en) * | 2017-09-05 | 2020-07-17 | 南宁师范大学 | Preparation method of acetaminophen-loaded nanofiber composite material |
| CN107619469A (en) * | 2017-09-30 | 2018-01-23 | 铜陵家宴生态农业发展有限公司 | A kind of preparation method of banana tegument extract g-polycaprolactone cross-linked material |
| CN111995691A (en) * | 2020-08-21 | 2020-11-27 | 南京林业大学 | Cellulose ether derivative, preparation method and application |
| CN114933688A (en) * | 2022-07-11 | 2022-08-23 | 南京林业大学 | Preparation method of magnetic degradable cellulose-based shape memory polyester material |
| CN114933688B (en) * | 2022-07-11 | 2023-08-08 | 南京林业大学 | Preparation method of magnetic degradable cellulose-based shape memory polyester material |
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Application publication date: 20151118 |