CN103965602B - The preparation method of modification poly (propylene carbonate) - Google Patents
The preparation method of modification poly (propylene carbonate) Download PDFInfo
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- CN103965602B CN103965602B CN201310029498.XA CN201310029498A CN103965602B CN 103965602 B CN103965602 B CN 103965602B CN 201310029498 A CN201310029498 A CN 201310029498A CN 103965602 B CN103965602 B CN 103965602B
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Abstract
The present invention relates to a kind of preparation method of modification poly (propylene carbonate), particularly by the method for sorbitan fatty acid ester modification poly (propylene carbonate).Sorbitan fatty acid ester and poly (propylene carbonate) are made into uniform Preblend by the present invention, then Preblend are carried out melt blending at temperature is 80 ~ 180 DEG C, thus obtain modification poly (propylene carbonate).Preparation method of the present invention can obtain the modification poly (propylene carbonate) with higher glass transition temperature and better thermostability.Preparation method's simple process of the present invention, easy handling, modified effect is remarkable, has higher using value, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of modification poly (propylene carbonate), particularly by the method for sorbitan fatty acid ester modification poly (propylene carbonate).
Technical background
Poly (propylene carbonate) is the aliphatic polycarbonate become with epoxypropane copolymerization by carbonic acid gas, complete biodegradable can be realized in physical environment or under the condition of mandatory compost, in addition, poly (propylene carbonate) is a class water white transparency solid, nontoxic, tasteless, there is the features such as snappiness is high, gas permeation rate is low, good biocompatibility, the toughner of hard brittle material can be used as, as food and pharmaceutical packing preservative film, as slow releasing carrier of medication etc.China faces serious white pollution and energy scarcity problem at present, the Biodegradable materials such as PPC are used as Phthalates etc. substitutes common polyolefin material in some field, not only solve current plastics to be difficult to degrade and the white pollution problems that causes, decrease CO
2discharge, and save the petroleum resources of worsening shortages to a certain extent.At present, developed the catalyst system of the synthesis poly (propylene carbonate) of multiple high efficiency low cost both at home and abroad, scale operation poly (propylene carbonate) enters industrialization; But because poly (propylene carbonate) molecular weight is comparatively submissive, Intermolecular Forces is weak, it is in amorphous state at normal temperatures, and be a kind of amorphism superpolymer, processing characteristics is not ideal enough; Also easily there is the solution slide fastener degraded caused by molecular chain-end hydroxyl in it, thermostability is poor when being heated.Above shortcoming greatly limit promoting the use of of poly (propylene carbonate).
In recent years, people attempt adopting blending and modifying means to improve the performance of poly (propylene carbonate).Meng Yuezhong, (Essential work of fracture analysis for starch filled poly (propylenecarbonate) composites.Wang.XL such as Peng Shuwen, Li.RKY, Cao.YX and Meng.YZ.Materialsand Design, 2007, 28, 1934 and Special interaction between poly (propylenecarbonate) and corn starch.Peng.SW, Wang.XY and Dong.LS.Polym.Compos., 2005, 26, 37.) by Banbury mixer by starch and poly (propylene carbonate) is direct has blendedly prepared poly (propylene carbonate)/starch blend, research finds, the second-order transition temperature of blend is (when the addition of starch is 30%, improve 6 DEG C), thermostability is obtained for raising to a certain degree, (CompletelyBiodegradable Composites of Poly (propylene carbonate) the and short such as Li Xiaohong, LignocelluloseFiber Hildegardia populifolia.Li.XH, Meng.YZ, Wang.SJ, Rajulu.AV andTjong.SC.J Poly Sci Part B:Polym Phys, 2004, 42, 666) with lignocellulose fiber, study on the modification is carried out to poly (propylene carbonate), adding of lignocellulose fiber, make the second-order transition temperature of blend (time in blend containing 40wt% lignocellulose equally, improve 6.5 DEG C) and thermostability (in blend containing 40wt% lignocellulose time, improve 40 DEG C) be improved, although the performance that can to a certain extent improve poly (propylene carbonate) blended with other superpolymer, does not make a breakthrough, and blend prepared by this method is also easier to macroface separation occurs, thus makes goods lose use value.
Up to now, about use sorbitan fatty acid ester, obtain the modification poly (propylene carbonate) material with higher glass transition temperature and better thermostability by the method for simple physical modification, there is no report.
Summary of the invention
The object of this invention is to provide a kind of preparation method of modification poly (propylene carbonate).
Sorbitan fatty acid ester and poly (propylene carbonate) are made into uniform Preblend by the preparation method of modification poly (propylene carbonate) of the present invention, then Preblend are carried out melt blending at temperature is 80 ~ 180 DEG C, thus obtain modification poly (propylene carbonate).
Sorbitan fatty acid ester in described Preblend is 1 ~ 100:100 with the massfraction ratio of poly (propylene carbonate); Preferred mass mark ratio is 1 ~ 50:100.
Described melt blending can carry out in mill, Banbury mixer or twin screw extruder.
Described sorbitan fatty acid ester is selected from the one in anhydrous sorbitol laurate, sorbitan monopalmitate, sorbitan monostearate, anhydrous sorbitol tristearate, sorbitan monooleate and Witconol AL 69-66.
Described poly (propylene carbonate) can be the poly (propylene carbonate) of various molecular weight and molecular weight distribution.
Preparation method of the present invention can prepare the modification poly (propylene carbonate) with higher glass transition temperature and thermostability.Preparation method's simple process of the present invention, easy handling, modified effect is remarkable, has higher using value, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
The second-order transition temperature of the poly (propylene carbonate) in embodiment and modification poly (propylene carbonate) is obtained (TA-Q800) by Dynamic Mechanical Analyzer test, and Range of measuring temp is-20 DEG C-90 DEG C, and test speed is 3 DEG C/min.
The thermal degradation temperature of the poly (propylene carbonate) in embodiment and modification poly (propylene carbonate) is obtained by the test of Perkin – Elmer Pyris1TGA thermal analyzer, and Range of measuring temp is 50 DEG C-500 DEG C, and test speed is 20 DEG C/min.
Embodiment 1
5g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 90 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 35 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 257 DEG C.
Embodiment 2
10g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 39 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 245 DEG C.
Embodiment 3
25g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 90 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 45 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 248 DEG C.
Embodiment 4
1g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 100 DEG C ~ 180 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 32 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 248 DEG C.
Embodiment 5
50g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 42 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 240 DEG C.
Embodiment 6
100g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 90 DEG C ~ 180 DEG C in temperature, obtain modification poly (propylene carbonate).
Utilize TA-Q800 to measure poly (propylene carbonate) and product modification poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of modification poly (propylene carbonate) is 32 DEG C; Analyzed by Perkin – Elmer Pyris 1 TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of modification poly (propylene carbonate) is 237 DEG C.
Embodiment 7
10g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 110 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 8
1g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 120 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 9
50g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 130 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 10
10g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 110 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 11
1g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 120 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 12
50g sorbitan monostearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 130 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 13
10g anhydrous sorbitol laurate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 90 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Embodiment 14
10g anhydrous sorbitol laurate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 100 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 15
10g anhydrous sorbitol laurate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 120 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 16
10g sorbitan monopalmitate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 100 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Embodiment 17
10g sorbitan monopalmitate and 100g are gathered carbonic acid trimethylene ester and be made into uniform Preblend, then Preblend is placed in mill and at 110 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification and gathers carbonic acid trimethylene ester.
Embodiment 18
10g sorbitan monopalmitate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 130 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 19
10g anhydrous sorbitol tristearate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 90 DEG C ~ 180 DEG C in temperature, obtain modification poly (propylene carbonate).
Embodiment 20
10g anhydrous sorbitol tristearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 110 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 21
10g anhydrous sorbitol tristearate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 120 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 22
10g sorbitan monooleate and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 100 DEG C ~ 170 DEG C in temperature, obtain modification poly (propylene carbonate).
Embodiment 23
10g sorbitan monooleate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 100 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 24
10g sorbitan monooleate and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 110 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 25
10g Witconol AL 69-66 and 100g poly (propylene carbonate) are made into uniform Preblend, then Preblend are joined in twin screw extruder, be carry out melt blending extruding pelletization between 100 DEG C ~ 160 DEG C in temperature, obtain modification poly (propylene carbonate).
Embodiment 26
10g Witconol AL 69-66 and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend is placed in mill and at 110 DEG C, carries out melting and open blended 10 minutes of refining, product cools in atmosphere, obtains modification poly (propylene carbonate).
Embodiment 27
10g Witconol AL 69-66 and 100g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 120 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains modification poly (propylene carbonate).
Claims (5)
1. the preparation method of a modification poly (propylene carbonate), it is characterized in that: sorbitan fatty acid ester and poly (propylene carbonate) are made into uniform Preblend, then Preblend is carried out melt blending at temperature is 80 ~ 180 DEG C, obtain modification poly (propylene carbonate).
2. preparation method according to claim 1, is characterized in that: the sorbitan fatty acid ester in described Preblend is 1 ~ 100:100 with the massfraction ratio of poly (propylene carbonate).
3. preparation method according to claim 2, is characterized in that: the sorbitan fatty acid ester in described Preblend is 1 ~ 50:100 with the massfraction ratio of poly (propylene carbonate).
4. preparation method according to claim 1, is characterized in that: described melt blending carries out in mill, Banbury mixer or twin screw extruder.
5. the preparation method according to claim 1,2 or 3, is characterized in that: described sorbitan fatty acid ester is selected from the one in anhydrous sorbitol laurate, sorbitan monopalmitate, sorbitan monostearate, anhydrous sorbitol tristearate, sorbitan monooleate and Witconol AL 69-66.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486829A (en) * | 2008-11-28 | 2009-07-22 | 内蒙古蒙西高新技术集团有限公司 | Method for improving poly(propylene carbonate) glass transition temperature by nano calcium carbonate filling modification |
| WO2010060038A1 (en) * | 2008-11-23 | 2010-05-27 | Novomer, Inc. | Polycarbonates as adhesives in electronics manufacturing |
| CN101831165A (en) * | 2010-05-10 | 2010-09-15 | 海南大学 | Fully-degradable polypropylene carbonate/alkali lignin compound sheet material and preparation method thereof |
| CN101962470A (en) * | 2009-07-22 | 2011-02-02 | 中国海洋石油总公司 | Biodegradable polypropylene carbonate composite material and preparation method thereof |
| CN102482404A (en) * | 2009-09-03 | 2012-05-30 | Co2斯塔奇私人有限公司 | Polymer/thermoplastic starch compositions |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010060038A1 (en) * | 2008-11-23 | 2010-05-27 | Novomer, Inc. | Polycarbonates as adhesives in electronics manufacturing |
| CN101486829A (en) * | 2008-11-28 | 2009-07-22 | 内蒙古蒙西高新技术集团有限公司 | Method for improving poly(propylene carbonate) glass transition temperature by nano calcium carbonate filling modification |
| CN101962470A (en) * | 2009-07-22 | 2011-02-02 | 中国海洋石油总公司 | Biodegradable polypropylene carbonate composite material and preparation method thereof |
| CN102482404A (en) * | 2009-09-03 | 2012-05-30 | Co2斯塔奇私人有限公司 | Polymer/thermoplastic starch compositions |
| CN101831165A (en) * | 2010-05-10 | 2010-09-15 | 海南大学 | Fully-degradable polypropylene carbonate/alkali lignin compound sheet material and preparation method thereof |
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