CN104327475A - Poly(propylene carbonate)/cellulose blend and preparation method thereof - Google Patents
Poly(propylene carbonate)/cellulose blend and preparation method thereof Download PDFInfo
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- CN104327475A CN104327475A CN201310308781.6A CN201310308781A CN104327475A CN 104327475 A CN104327475 A CN 104327475A CN 201310308781 A CN201310308781 A CN 201310308781A CN 104327475 A CN104327475 A CN 104327475A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a poly(propylene carbonate)/cellulose blend and a preparation method thereof. The poly(propylene carbonate)/cellulose blend is prepared by preparing a premix of cellulose with the content of 1 wt%-60 wt% and poly(propylene carbonate) with the content of 40 wt%-99 wt% and performing melt blending on the premix at a temperature of 80-180 DEG C. Cellulose can be used as an electron acceptor because the cellulose molecule chain contains a large amount of hydroxyl, while poly(propylene carbonate) contains carbonyl and can be used as an electron donor, hydrogen-bond effect is formed between cellulose and poly(propylene carbonate), and thus the prepared poly(propylene carbonate)/cellulose blend has relatively good compatibility, and also poly(propylene carbonate) is substantially improved in thermal stability, glass-transition temperature, mechanical properties and other performances. The poly(propylene carbonate)/cellulose blend has relatively high glass-transition temperature, thermal stability and mechanical properties.
Description
Technical field
The present invention relates to polymer modification field, particularly a kind of poly (propylene carbonate)/cellulose blending thing and preparation method thereof.
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.But because poly (propylene carbonate) molecular chain 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 the hydroxyl of molecule chain end in it, thermostability is poor when being heated.Above shortcoming greatly limit promoting the use of of poly (propylene carbonate).
In order to promote the using value of poly (propylene carbonate), can more areas be applied to, need to carry out modification to it.At present, people mainly adopt blending and modifying to improve the performance of poly (propylene carbonate).Meng Yue medium (J Appl.Polym.Sci., 2006,99,782 – 787) prepare poly (propylene carbonate)/wood chip blend, adding of wood chip makes the second-order transition temperature of poly (propylene carbonate) improve 10 DEG C, and tensile strength improves about 16%, and thermostability also increases; (the J Poly Sci Part B:Polym Phys such as Li Xiaohong, 2004,42,666) with lignocellulose fiber, study on the modification is carried out to poly (propylene carbonate), adding of lignocellulose fiber, the second-order transition temperature of blend (time in blend containing 40wt% lignocellulose, improving 6.5 DEG C) and thermostability (time in blend containing 40wt% lignocellulose fiber, improving 40 DEG C) is made to be improved equally; (Materials and Design, 2007,28,1934 such as Meng Yuezhong, Peng Shuwen; 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 (when the addition of starch is 30%, improving 6 DEG C) of blend, thermostability are obtained for raising to a certain degree.Although the performance of poly (propylene carbonate) can be improved to a certain extent by the method for blending and modifying, do not make a breakthrough, still limit the application of poly (propylene carbonate).
Summary of the invention
An object of the present invention is to provide a kind of poly (propylene carbonate)/cellulose blending thing, significantly to improve the second-order transition temperature of poly (propylene carbonate), and mechanical property and thermostability.
Two of object of the present invention is to provide the preparation method of a kind of poly (propylene carbonate)/cellulose blending thing.
Poly (propylene carbonate) of the present invention/cellulose blending thing is prepared after melt blending by following raw material, and before melt blending, each component raw material and content are:
Poly (propylene carbonate) 40wt% ~ 99wt%(is preferably 40wt% ~ 95wt%)
Mierocrystalline cellulose 1wt% ~ 60wt%(is preferably 5wt% ~ 60wt%)
Described poly (propylene carbonate) can be the poly (propylene carbonate) of various molecular weight and molecular weight distribution.
Described Mierocrystalline cellulose is selected from one or more in cotton, fiber crops, wood pulp vegetable fibre.
The preparation method of poly (propylene carbonate) of the present invention/cellulose blending thing is: Mierocrystalline cellulose and poly (propylene carbonate) are made into uniform Preblend, wherein in Preblend, the content of poly (propylene carbonate) is that 40wt% ~ 99wt%(is preferably 40wt% ~ 95wt%), cellulosic content is that 1wt% ~ 60wt%(is preferably 5wt% ~ 60wt%); Then Preblend is carried out melt blending at temperature is 80 ~ 180 DEG C, thus prepare poly (propylene carbonate)/cellulosic blend.
Described melt blending can be carry out between 80 ~ 180 DEG C in temperature.
Described melt blending can carry out in mill, Banbury mixer or twin screw extruder.
Although have bibliographical information use lignocellulose fiber to carry out modification to poly (propylene carbonate), but because this lignocellulose fiber forms (being a kind of polymer composite in fact) by Mierocrystalline cellulose, xylogen and hemicellulose etc., and and poor compatibility between poly (propylene carbonate), be not therefore clearly to the raising of the thermostability, second-order transition temperature, mechanical property etc. of poly (propylene carbonate).And Mierocrystalline cellulose is that a kind of single material is (as from cotton, fiber crops, obtain through series of process in wood pulp vegetable fibre), due to cellulose molecular chain containing a large amount of hydroxyls, can as electron acceptor(EA), and containing carbonyl in poly (propylene carbonate), can as electron donor(ED), make to form hydrogen bond action between Mierocrystalline cellulose and poly (propylene carbonate), Mierocrystalline cellulose is used to carry out modification to poly (propylene carbonate) thus in the present invention, thus make the poly (propylene carbonate)/cellulose blending thing prepared have better consistency, and the thermostability of poly (propylene carbonate) can be made, second-order transition temperature and mechanical property etc. are largely increased.
Preparation method of the present invention can prepare the poly (propylene carbonate)/cellulose blending thing with higher glass transition temperature, thermostability and mechanical property.Preparation method of the present invention is easy, easy handling, and 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)/cellulose blending thing in poly (propylene carbonate) and embodiment is tested by Dynamic Mechanical Analyzer to obtain (TA-Q800), 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)/cellulose blending thing in poly (propylene carbonate) and embodiment is tested by Perkin – Elmer Pyris1TGA thermal analyzer to obtain, and Range of measuring temp is 50 DEG C ~ 500 DEG C, and test speed is 20 DEG C/min.
The tensile strength of the poly (propylene carbonate)/cellulose blending thing in poly (propylene carbonate) and embodiment is tested by tensilon (INSTRON3365) to obtain, and test speed is 5mm/min.
Embodiment 1
5g wood pulp cellulose and 95g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/wood pulp cellulose blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/wood pulp cellulose blend and poly (propylene carbonate), the second-order transition temperature of known poly (propylene carbonate) is 32 DEG C, and the second-order transition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 35 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate) is 205 DEG C, and the initial decomposition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 220 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate) is 19MPa, and the tensile strength of poly (propylene carbonate)/wood pulp cellulose blend is 24MPa.
Embodiment 2
60g wood pulp cellulose and 40g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/wood pulp cellulose blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/wood pulp cellulose blend, the second-order transition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 48 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 260 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate)/wood pulp cellulose blend is 34MPa.
Embodiment 3
10g wood pulp cellulose and 90g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/wood pulp cellulose blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/wood pulp cellulose blend, the second-order transition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 39 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 225 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate)/wood pulp cellulose blend is 30MPa.
Embodiment 4
20g wood pulp cellulose and 80g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/wood pulp cellulose blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/wood pulp cellulose blend, the second-order transition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 42 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate)/wood pulp cellulose blend is 227 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate)/wood pulp cellulose blend is 32MPa.
Embodiment 5
10g gossypin and 90g 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 poly (propylene carbonate)/gossypin blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/gossypin blend, the second-order transition temperature of poly (propylene carbonate)/gossypin blend is 39 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate)/gossypin blend is 226 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate)/gossypin blend is 29MPa.
Embodiment 6
10g cotton fibriia element (weight ratio of gossypin and flaxen fiber element is 1:1) and 90g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/cotton fibriia element blend.
Utilize TA-Q800 to measure poly (propylene carbonate)/cotton fibriia element blend, the second-order transition temperature of poly (propylene carbonate)/cotton fibriia element blend is 39 DEG C; Analyzed by Perkin – Elmer Pyris1TGA and learn, the initial decomposition temperature of poly (propylene carbonate)/cotton fibriia element blend is 224 DEG C; Tested known by tensilometer, the tensile strength of poly (propylene carbonate)/cotton fibriia element blend is 30MPa.
Embodiment 7
1g wood pulp cellulose and 99g poly (propylene carbonate) are made into uniform Preblend, then Preblend is joined in twin screw extruder, be carry out melt blending extruding pelletization between 80 DEG C ~ 180 DEG C in temperature, obtain poly (propylene carbonate)/wood pulp cellulose blend.
Embodiment 8
10g wood pulp cellulose and 90g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in mill and at 80 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/wood pulp cellulose blend.
Embodiment 9
20g wood pulp cellulose and 80g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in mill and at 140 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/wood pulp cellulose blend.
Embodiment 10
50g wood pulp cellulose and 50g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in mill and at 180 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/wood pulp cellulose blend.
Embodiment 11
10g flaxen fiber element and 90g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 80 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/flaxen fiber element blend.
Embodiment 12
20g flaxen fiber element and 80g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 140 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/flaxen fiber element blend.
Embodiment 13
50g flaxen fiber element and 50g poly (propylene carbonate) are made into uniform Preblend, and then Preblend be placed in Banbury mixer and at 180 DEG C, carry out melt blending 10 minutes, product cools in atmosphere, obtains poly (propylene carbonate)/flaxen fiber element blend.
Claims (6)
1. poly (propylene carbonate)/cellulose blending thing, it is characterized in that, described blend is prepared after melt blending by following raw material, before melt blending, each component raw material and content are:
Poly (propylene carbonate) 40wt% ~ 99wt%
Mierocrystalline cellulose 1wt% ~ 60wt%
Described Mierocrystalline cellulose is selected from one or more in cotton, fiber crops, wood pulp vegetable fibre.
2. poly (propylene carbonate) according to claim 1/cellulose blending thing, is characterized in that: the content of described poly (propylene carbonate) is 40wt% ~ 95wt%.
3. poly (propylene carbonate) according to claim 1/cellulose blending thing, is characterized in that: described cellulosic content is 5wt% ~ 60wt%.
4. the preparation method of the poly (propylene carbonate) described in a claims 1 to 3 any one/cellulose blending thing, it is characterized in that: Mierocrystalline cellulose and poly (propylene carbonate) are made into uniform Preblend, wherein in Preblend, the content of poly (propylene carbonate) is 40wt% ~ 99wt%, and cellulosic content is 1wt% ~ 60wt%; Then Preblend is carried out melt blending at temperature is 80 ~ 180 DEG C, prepare poly (propylene carbonate)/cellulose blending thing;
Described Mierocrystalline cellulose is selected from one or more in cotton, fiber crops, wood pulp vegetable fibre.
5. preparation method according to claim 4, is characterized in that: described melt blending is carry out between 80 ~ 180 DEG C in temperature.
6. the preparation method according to claim 4 or 5, is characterized in that: described melt blending carries out in mill, Banbury mixer or twin screw extruder.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061971A (en) * | 2015-06-16 | 2015-11-18 | 华南理工大学 | Method for preparing completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate) |
| CN110133112A (en) * | 2019-05-30 | 2019-08-16 | 伊犁师范大学 | A kind of mechanoscopy measurement method of polyblend phase separation |
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2013
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| CN101914294A (en) * | 2010-08-26 | 2010-12-15 | 成都新柯力化工科技有限公司 | Paper-imitating biodegradable resin and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061971A (en) * | 2015-06-16 | 2015-11-18 | 华南理工大学 | Method for preparing completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate) |
| CN110133112A (en) * | 2019-05-30 | 2019-08-16 | 伊犁师范大学 | A kind of mechanoscopy measurement method of polyblend phase separation |
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