CN1687234A - Composite material of complete degradable polymer and preparation method thereof - Google Patents
Composite material of complete degradable polymer and preparation method thereof Download PDFInfo
- Publication number
- CN1687234A CN1687234A CN 200510034174 CN200510034174A CN1687234A CN 1687234 A CN1687234 A CN 1687234A CN 200510034174 CN200510034174 CN 200510034174 CN 200510034174 A CN200510034174 A CN 200510034174A CN 1687234 A CN1687234 A CN 1687234A
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- CN
- China
- Prior art keywords
- polyvinyl alcohol
- matrix material
- ethylene carbonate
- polymer composites
- polymethyl ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920006237 degradable polymer Polymers 0.000 title description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 35
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims description 25
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 4
- 229920006238 degradable plastic Polymers 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 poly(lactic acid) Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a polymethyl ethylene carbonic ester/polyvinyl alcohol composite material which can be completely degraded and its preparation method. Said composite material adopts degradable plastics polymethyl ethylene carbonic ester as base body, and uses polyvinyl alcohol with various polymerization degrees and alcoholysis degrees as filling material, and adopts solution blending process to prepare the invented composite material, in which the polyvinyl alcohol content can be 10-40%.
Description
Technical field
The present invention relates to a kind of lined polymethyl ethylene carbonate/polyvinyl alcohol composite material that can degrade fully and preparation method thereof.
Background technology
Carbonic acid gas is the main gas that causes Greenhouse effect that generally acknowledge in the whole world, therefore how to utilize carbonic acid gas attracting various countries scientist's concern.The present relatively technology of utilizing carbonic acid gas of success is exactly to adopt special technology to make carbonic acid gas and some organic compound aggregate into the degradable polymer plastics, thereby solves Greenhouse effect and " white pollution " problem that makes various countries scientist headache at one stroke.Polymer blending is a kind of simple effective method that improves polymer physics or chemical property, can make matrix material satisfy unappeasable some requirement of single polymers by the interaction between the polymkeric substance.Simultaneously, sneaking into cheap polymkeric substance and can also reduce the matrix material cost, is to achieve many things at one stroke.Polyvinyl alcohol also is a kind of polymkeric substance that can degrade fully, and it has a lot of good physicochemical property, such as, have than high glass transition temperature, higher mechanical property and anti-oil soluble.But polyvinyl alcohol is a kind of water-soluble polymers, and this has just limited its application greatly.Therefore, polyvinyl alcohol sneaked into not only can solve the water-soluble problem of polyvinyl alcohol in the water-fast matrix, can also improve the mechanics and the thermal characteristics of matrix material greatly.
Researched and developed at present degraded macromolecular material is few fully, as poly(lactic acid), polycaprolactone, poly butyric ester etc., but cost an arm and a leg, be 3～5 times of common plastics.Lined polymethyl ethylene carbonate [Y.Z.Meng, L.C.Du, S.C.Tjong that this laboratory utilizes efficient catalyst to be formed by carbonic acid gas and propylene oxide production, Q.Zhu.J.Polym.Sci.Part A, Polym.Chem., 40 (21), 3579-3591 (2002); S.J.Wang, L.C.Du, X.S.Zhao, Y.Z.Meng, S.C.Tjong.J.Appl. Polym.Sci., 85,2327-2334 (2002); Q.Zhu, Y.Z.Meng, S.C.Tjong, Y.M.Zhang, W.Wan, Polymer Inter, 52,799-804 (2003); Q.Zhu, Y.Z.Meng, S.C.Tjong, X.S.Zhao, Y.L.Chen, Polym.Inter.], be a kind of degradable high polymer material with applications well prospect, its cost and common plastics are approaching.Low-molecular-weight lined polymethyl ethylene carbonate as barrier material [WO 9 925 751,1999; WO 9 925751,1999], whipping agent [JP 08 031 700,1996], tamanori [WO 9 606 877,1996; US 5 744 907,1998] research appears in the newspapers.Matrix materials such as high-molecular weight lined polymethyl ethylene carbonate/natural fiber or mineral filler also appear in the newspapers [CN 1422899A, 2003; CN 1422898A, 2003].But the second-order transition temperature of lined polymethyl ethylene carbonate is lower, and mechanical property is relatively poor, and its range of application is restricted.
The chemical structure of lined polymethyl ethylene carbonate is as follows:
Summary of the invention
The purpose of this invention is to provide a kind of polymer composites and preparation method thereof, this matrix material still can be realized complete biodegradable when improving substrate performance.
Polymer composites of the present invention is composited by lined polymethyl ethylene carbonate and polyvinyl alcohol, and the weight percentage of polyvinyl alcohol is 10-40% in the matrix material.
According to the polymer composites of the invention described above, the molecular weight of lined polymethyl ethylene carbonate wherein is generally 50000～150000.Usually the polymerization degree of the polyvinyl alcohol in the matrix material is 500～1700, and alcoholysis degree is 88%～99%.Polyvinyl alcohol in the matrix material can be to be selected from various different polymerization degrees and the alcoholysis degree polyvinyl alcohol one or more; For example can be that the industrial trade mark is one or more the mixture in 0588,0599,1588,1599,1788 and 1799 etc. the polyvinyl alcohol.
According to the present invention, the weight content of polyvinyl alcohol is preferably 20-40% in the polymer composites, can make the mechanics of matrix material and thermal property and water resistance reach optimization.Can certainly add more polyvinyl alcohol, to obtain better mechanical property, polyvinyl alcohol but more can make the water resistance variation of matrix material, and the application scenario is restricted.
Polymer composites of the present invention can prepare by the following method: be that solvent is with lined polymethyl ethylene carbonate and polyvinyl alcohol dissolving with the dimethyl sulfoxide (DMSO), the solution total concn is 40-80 ℃ in 5%～10% by weight/volume (w/t) in temperature and stirred 12～24 hours down, then through solution coat, remove to desolvate and promptly obtain required polymer composites.
Among the present invention, the factor that composite property is had the greatest impact is the add-on of filler polyvinyl alcohol, and other factor is little to the material property influence.
The aliphatic polycarbonate lined polymethyl ethylene carbonate is a kind of environment-friendly material, it is the complete alternating copolymer of carbonic acid gas and propylene oxide, carbonic acid gas structure weight percentage in its backbone structure is 43%, the preparation process of lined polymethyl ethylene carbonate is exactly one and consumes greenhouse gases, alleviates the process of topsoil.The ester bond structure of the main chain of lined polymethyl ethylene carbonate is given its degradable characteristic again.Sneak into polyvinyl alcohol and not only can improve the mechanics and the thermal property of polymkeric substance greatly, because of the polyvinyl alcohol price is lower than lined polymethyl ethylene carbonate, can also reduce the cost of material again.
The present invention is a matrix with the degradable plastics lined polymethyl ethylene carbonate, the polyvinyl alcohol of the various polymerization degree and alcoholysis degree is a packing material, by with lined polymethyl ethylene carbonate with polyvinyl alcohol is dissolved in dimethyl sulfoxide (DMSO) or other can dissolve in the solvent of these two kinds of polymkeric substance, make the lined polymethyl ethylene carbonate/polyvinyl alcohol composite material of Wholly-degradable again through the solution coat technology.This matrix material has second-order transition temperature, physical strength and the modulus that is higher than matrix (lined polymethyl ethylene carbonate), and because lined polymethyl ethylene carbonate and polyvinyl alcohol all are the materials that can degrade fully, so this matrix material can complete biodegradable, be a kind of environmental protection matrix material of novel Sustainable development.For the industrial applications of lined polymethyl ethylene carbonate has been opened up new approach.
Embodiment
Below the invention will be further described by specific embodiment:
Embodiment 1-5
The composition and performance of matrix material is as shown in table 1.With lined polymethyl ethylene carbonate and the trade mark is that 1588 polyvinyl alcohol is dissolved in the dimethyl sulfoxide (DMSO) under 60 ℃, and total concn is 5～10% (w/v).Mechanical stirring 12～16 hours is poured over solution on the sheet glass that is covered with the PET film, dries by the fire in 60 ℃ of a conventional ovens and the 120 ℃ of vacuum drying ovens to desolventize.The vertical bar that the gained composite material film is cut into 75 * 5mm carries out mechanical property and thermal performance test.
The composition and the performance of table 1 polyvinyl alcohol 1588 and lined polymethyl ethylene carbonate matrix material
| Embodiment | Polyvinyl alcohol 1588 consumptions, weight % | Second-order transition temperature/℃ | Tensile strength, MPa | Young's modulus, MPa |
| Matrix | ????0 | ????28.7 | ????25.8 | ????962 |
| ????1 | ????10 | ????31.6 | ????32.8 | ????1841 |
| ????2 | ????20 | ????71.0 | ????33.1 | ????1860 |
| ????3 | ????30 | ????73.9 | ????31.2 | ????2207 |
| ????4 | ????40 | ????81.1 | ????26.7 | ????2308 |
Claims (6)
1. a polymer composites is characterized in that this matrix material is composited by lined polymethyl ethylene carbonate and polyvinyl alcohol, and the weight percentage of polyvinyl alcohol is 10-40% in the matrix material.
2. according to the described polymer composites of claim 1, the molecular weight that it is characterized in that the lined polymethyl ethylene carbonate in the matrix material is 50000～150000.
3. according to the described polymer composites of claim 1, the weight percentage that it is characterized in that polyvinyl alcohol in the matrix material is 20-40%.
4. according to the described polymer composites of claim 1,2 or 3, the polymerization degree that it is characterized in that polyvinyl alcohol in the matrix material is 500～1700, and alcoholysis degree is 88%～99%.
5. according to right 4 described polymer composites, it is characterized in that polyvinyl alcohol in the matrix material is to be selected from various different polymerization degrees and the alcoholysis degree polyvinyl alcohol one or more.
6. the preparation method of the described polymer composites of one of claim 1-5, with the dimethyl sulfoxide (DMSO) is that solvent is with lined polymethyl ethylene carbonate and polyvinyl alcohol dissolving, the solution total concn is in 5%～10% by weight/volume, is 40-80 ℃ in temperature and stirred 12～24 hours down, then through solution coat, remove to desolvate and promptly obtain required polymer composites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100341740A CN100386383C (en) | 2005-04-20 | 2005-04-20 | Composite material of complete degradable polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100341740A CN100386383C (en) | 2005-04-20 | 2005-04-20 | Composite material of complete degradable polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687234A true CN1687234A (en) | 2005-10-26 |
| CN100386383C CN100386383C (en) | 2008-05-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100341740A Expired - Fee Related CN100386383C (en) | 2005-04-20 | 2005-04-20 | Composite material of complete degradable polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100386383C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702718A (en) * | 2012-07-09 | 2012-10-03 | 贵州省复合改性聚合物材料工程技术研究中心 | Modified polypropylene carbonate material (PPC) material and preparation method thereof |
| CN104448640A (en) * | 2014-11-13 | 2015-03-25 | 苏州经贸职业技术学院 | Preparation method of green graphene-poly(propylene carbonate) composite material |
| CN106832850A (en) * | 2016-12-22 | 2017-06-13 | 苏州缔绿电子科技有限公司 | A kind of ester group composite and preparation method thereof |
| CN107641307A (en) * | 2017-09-27 | 2018-01-30 | 华南理工大学 | A kind of lined polymethyl ethylene carbonate/polyvinyl alcohol degradable composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3861188B2 (en) * | 1997-05-14 | 2006-12-20 | 株式会社ジェイエスピー | Polycarbonate resin extruded foam |
| JP2001247738A (en) * | 2000-03-06 | 2001-09-11 | Unitika Chem Co Ltd | Polyvinyl alcohol-based resin composition and paper coating agent consisting essentially of the same |
| CN1259371C (en) * | 2002-12-12 | 2006-06-14 | 中山大学 | Degradable polymer/natural mineal filler composite material and preparation method thereof |
| CN1528811A (en) * | 2003-09-29 | 2004-09-15 | 中山大学 | Full-degradable-polymethyl ethylene carbonate/starch composite material and preparing method thereof |
-
2005
- 2005-04-20 CN CNB2005100341740A patent/CN100386383C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702718A (en) * | 2012-07-09 | 2012-10-03 | 贵州省复合改性聚合物材料工程技术研究中心 | Modified polypropylene carbonate material (PPC) material and preparation method thereof |
| CN104448640A (en) * | 2014-11-13 | 2015-03-25 | 苏州经贸职业技术学院 | Preparation method of green graphene-poly(propylene carbonate) composite material |
| CN106832850A (en) * | 2016-12-22 | 2017-06-13 | 苏州缔绿电子科技有限公司 | A kind of ester group composite and preparation method thereof |
| CN107641307A (en) * | 2017-09-27 | 2018-01-30 | 华南理工大学 | A kind of lined polymethyl ethylene carbonate/polyvinyl alcohol degradable composite material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100386383C (en) | 2008-05-07 |
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Granted publication date: 20080507 Termination date: 20120420 |