CN101045814A - Carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method - Google Patents
Carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method Download PDFInfo
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- CN101045814A CN101045814A CN 200710055513 CN200710055513A CN101045814A CN 101045814 A CN101045814 A CN 101045814A CN 200710055513 CN200710055513 CN 200710055513 CN 200710055513 A CN200710055513 A CN 200710055513A CN 101045814 A CN101045814 A CN 101045814A
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- carbon dioxide
- epoxy propane
- propane copolymer
- polybutylene succinate
- polyblend
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Abstract
This invention relates to mixture of carbon dioxide/ propylene oxide copolymer and poly- succinic acid butanediol ester and preparation method. It is composed by carbon dioxide/ propylene oxide copolymer, poly- succinic acid butanediol ester and antioxidant four ( beta - ( 3, 5 - di- tertiary butyl - 4 - hydroxy) propanoic acid) pentaerythritol ester ( ky - 7910). These materials blend in Banbury mixer, temperature control at 120 to 160 deg, and time for 10 minutes. The product has biodegradability, useful for preparing film, plates, sheet, effervesce and plastic piece and so on.
Description
Technical field
The invention belongs to polymer processing field, relate to carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method thereof.
Background technology
Carbon dioxide-epoxy propane copolymer (PPC) and poly butylene succinate (PBS) all are macromolecular materials of fully biodegradable.One of main raw material of synthetic PPC, carbonic acid gas is the CO that many industrial production field is produced
2Waste gas is discharged into and has not only caused environmental pollution in the atmospheric layer, and is the waste of carbon resource.Can be by the synthetic of PPC with CO
2The resource immobilization, this has not only opened up new carbon resource, alleviates the shortage of petrochemical materials, and can protect human ecotope.On the other hand, the complete biodegradable characteristic of PPC, the nonbiodegradable common plastics of the replacement of using also has important meaning for solving " white pollution ", and therefore, this technology has the double environmental protection function.Carbon dioxide-epoxy propane copolymer is a class water white transparency solid, and is nontoxic, tasteless, has excellent barrier property, printing performance and heat sealability, is particularly suitable for making disposable medicine and packaging material for food.From Japanese scientist aboveground auspicious flat [Inoue S, Koinuma H., Tsuruta T. in 1969, J.Polym.Sci.Polym.Lett.Ed., 1969,7,287] disclose after this technology, cause various countries scientist's attention in the world, thereby carry out a large amount of research and development work.Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences has successively applied for Chinese invention patent [preparation method of high-molecular aliphatic polycarbonate, the preparation method of publication number: 1257885A and rare earth combination catalyst, publication number: 1257753].But PPC is a class amorphous polymer, and second-order transition temperature is about 37 ℃.Carbonic acid gas and epoxy propane copolymer that the alternating copolymerization rate reaches more than 98% just become the rubber-like material for 37 ℃ above second-order transition temperature, its tensile strength, yang type modulus and modulus in flexure descend significantly, the dimensional stability extreme difference of material product, thus the performance that plastic material should possess lost.Limited the practical application of PPC so to a great extent.
In order to improve the performance of PPC, Robeson etc. are the same polyvinyl acetate (PVA) of PPC (PVAC) blend, thereby the strength ratio PPC of blend are doubled [L M Robenson, J AKuphal, 1990US, 4,912,149].PPC and paracril are at dicumyl peroxide (DCP) and triallyl isocyanurate (TAIC) vulcanization system, or DCP adds under the compound initiation of maleic anhydride vulcanization system blend formation interpenetrating polymer networks (IPN) elastomerics.This elastomerics has kept the good oil-proofness of styrene-butadiene rubber(SBR), has improved mechanical mechanics property again greatly, heatproof air aging performance also very excellent [Yang Xianghong, topaz favour, Zhao Shulu etc., ZL91,105,618,1,1991].These blending modification methods to PPC can make the performance of PPC improve to a certain extent, and still, they but make material lose the characteristic of fully biodegradable, thereby the obvious environment benefit of material is reduced.In addition, Chinese patent (1226438C) discloses PPC and poly-3-hydroxyalkanoate copolymer blended, although the mechanical property of material makes moderate progress after the blend, and has biological degradability completely.But poly-3-hydroxy alkanoic acid ester copolymer is to be made by microbial fermentation, and its cost is higher, has limited the popularization that changes a technology so to a great extent.
Summary of the invention
In order to solve above-mentioned technical problem, the object of the invention provides a kind of carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method thereof.The carbon dioxide-epoxy propane copolymer of selecting (PPC) is a class with catalyzer and the method synthetic high molecular weight material narrated in the Chinese invention patent [publication number 1257753 and 1257885A], its number-average molecular weight Mn is 40000-140000g/mol, and this PPC significantly improves its processing heat stability by closed-end technology and thermostabilization technology, and its heat decomposition temperature (in the air atmosphere) is 200-220 ℃.Its number-average molecular weight of the poly butylene succinate 30000-200000g/mol that selects.
Carbon dioxide-epoxy propane copolymer that the present invention is prepared and polybutylene succinate polyblend, its composition material and weight proportion are: poly butylene succinate (PBS) 30-70 part, carbon dioxide-epoxy propane copolymer (PPC) 70-30 part, oxidation inhibitor is 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910);
Described carbon dioxide-epoxy propane copolymer number-average molecular weight is 40000-140000g/mol; Its heat decomposition temperature in air atmosphere is 200-220 ℃;
The number-average molecular weight of described poly butylene succinate is 30000-200000g/mol.
The carbon dioxide-epoxy propane copolymer that the present invention is prepared and the preparation method's of polybutylene succinate polyblend step and condition are:
Take by weighing material according to its composition material and weight proportion, in Banbury mixer, carry out the blend of composition material, the banburying temperature of Banbury mixer is 120-160 ℃, and the banburying time is 10 minutes, obtains carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend.
With carbon dioxide-epoxy propane copolymer and the polybutylene succinate polyblend that obtains, hot-forming under the pressure of 10MPa at 140 ℃, the sheet material that 1.0mm is thick is made the dumbbell shape batten again, and its thin neck is of a size of long 20mm, wide/4mm.It is as follows to form different measured mechanical property scopes according to sample: tensile strength is 31.9-40MPa, tensile modulus 750-1350MPa, and elongation at break 11.5-21.6%, notched Izod impact strength is 43.6-66.1J/m, energy absorption is 280-400mJ.Because PBS is to the enhancement of PPC and the good characteristic of PPC self, thereby make blend have excellent mechanical property, printing performance, barrier property, processing characteristics, the overall equilbrium of multiple performance such as biological degradation.Obtain to such an extent that copolymer particle can be used for extrusion board, sheet material, plastic uptake, preparation film, production technique such as injection moulding and foaming.
The present invention adopts the poly butylene succinate (PBS) of fully biodegradable polymkeric substance, and it can eventual degradation become materials such as carbonic acid gas and water, environmental sound under the effect of bacterium or enzyme.And because synthetic raw materials usedly be easy to get relatively, synthesis technique is also easy with respect to microbe fermentation method etc., so remarkable advantages is arranged on cost.Moreover, the fusing point of poly butylene succinate is higher, and is functional, is hopeful to replace general polyethylene or polypropylene and enters the general-purpose plastics field, alleviates the conventional plastic pollution on the environment.
Embodiment
Embodiment 1:
Getting molecular weight is PPC70 part of 40000g/mol, and molecular weight is PBS30 part of 30000g/mol, 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910).Above-mentioned substance, banburying 10 minutes in Banbury mixer under 120 ℃, 140 ℃, under the pressure of 10MPa hot-forming after, the mechanical property that records material is as follows: tensile strength is 31.9MPa, tensile modulus 750MPa, elongation at break 11.5%, notched Izod impact strength is 43.6J/m, and energy absorption is 280mJ.
Embodiment 2:
Getting molecular weight is PPC30 part of 140000g/mol, and molecular weight is PBS70 part of 80000g/mol, 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910).Above-mentioned substance, banburying 10 minutes in Banbury mixer under 160 ℃, 140 ℃, under the pressure of 10MPa hot-forming after,, the mechanical property that records material is as follows: tensile strength is 40MPa, tensile modulus 1350MPa, elongation at break 21.6%, notched Izod impact strength are 66.1J/m, and energy absorption is 400mJ.
Embodiment 3:
Getting molecular weight is PPC40 part of 50000g/mol, and molecular weight is PBS60 part of 200000g/mol, 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910).Above-mentioned substance, banburying 10 minutes in Banbury mixer under 140 ℃, 140 ℃, under the pressure of 10MPa hot-forming after,, the mechanical property that records material is as follows: tensile strength is 38.9MPa, tensile modulus 1230MPa, elongation at break 19.5%, notched Izod impact strength are 60.2J/m, and energy absorption is 380mJ.
Embodiment 4:
Getting molecular weight is PPC50 part of 40000g/mol, and molecular weight is PBS50 part of 100000g/mol, 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910).Above-mentioned substance, banburying 10 minutes in Banbury mixer under 150 ℃, 140 ℃, under the pressure of 10MPa hot-forming after,, the mechanical property that records material is as follows: tensile strength is 35.2MPa, tensile modulus 1010MPa, elongation at break 15.5%, notched Izod impact strength are 50.6J/m, and energy absorption is 352mJ.
Embodiment 5:
Getting molecular weight is PPC60 part of 40000g/mol, and molecular weight is PBS40 part of 100000g/mol, 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910).Above-mentioned substance, banburying 10 minutes in Banbury mixer under 130 ℃, 140 ℃, under the pressure of 10MPa hot-forming after,, the mechanical property that records material is as follows: tensile strength is 32.3MPa, tensile modulus 840MPa, elongation at break 12.8%, notched Izod impact strength are 48.5J/m, and energy absorption is 300mJ.
Claims (5)
1. carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend, it is characterized in that, its composition material and weight proportion are: poly butylene succinate (PBS) 30-70 part, carbon dioxide-epoxy propane copolymer (PPC) 70-30 part, oxidation inhibitor is 1 part of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol ester (ky-7910);
2, described carbon dioxide-epoxy propane copolymer as claimed in claim 1 and polybutylene succinate polyblend is characterized in that, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 40000-140000g/mol.
3, described carbon dioxide-epoxy propane copolymer as claimed in claim 2 and polybutylene succinate polyblend is characterized in that, described carbon dioxide-epoxy propane copolymer heat decomposition temperature in air atmosphere is 200-220 ℃;
4, described carbon dioxide-epoxy propane copolymer as claimed in claim 1 and polybutylene succinate polyblend is characterized in that, the number-average molecular weight of described poly butylene succinate is 30000-200000g/mol.
5, the preparation method of carbon dioxide-epoxy propane copolymer as claimed in claim 1 and polybutylene succinate polyblend is characterized in that, step and condition are:
Take by weighing material according to its composition material and weight proportion, in Banbury mixer, carry out the blend of composition material, the banburying temperature of Banbury mixer is 120-160 ℃, and the banburying time is 10 minutes, obtains carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend.
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| CN 200710055513 CN101045814A (en) | 2007-04-12 | 2007-04-12 | Carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method |
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| CN 200710055513 CN101045814A (en) | 2007-04-12 | 2007-04-12 | Carbon dioxide-epoxy propane copolymer and polybutylene succinate polyblend and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102341455A (en) * | 2009-03-03 | 2012-02-01 | 巴斯夫欧洲公司 | Method for producing polymer mixtures |
| CN103205100A (en) * | 2013-03-22 | 2013-07-17 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
| CN104302701A (en) * | 2012-05-04 | 2015-01-21 | Sk新技术株式会社 | Polyalkylene carbonate resin composition having an interpenetrating crosslinked structure |
| CN112143204A (en) * | 2020-10-21 | 2020-12-29 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN113388241A (en) * | 2020-03-13 | 2021-09-14 | 北京化工大学 | Rubber-plastic blended composite material of polyester elastomer toughened and modified carbon dioxide-based plastic and preparation method thereof |
| CN117603570A (en) * | 2024-01-24 | 2024-02-27 | 山东联欣环保科技有限公司 | Dimensionally stable polycarbonate compositions |
-
2007
- 2007-04-12 CN CN 200710055513 patent/CN101045814A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102341455A (en) * | 2009-03-03 | 2012-02-01 | 巴斯夫欧洲公司 | Method for producing polymer mixtures |
| CN104302701A (en) * | 2012-05-04 | 2015-01-21 | Sk新技术株式会社 | Polyalkylene carbonate resin composition having an interpenetrating crosslinked structure |
| CN103205100A (en) * | 2013-03-22 | 2013-07-17 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
| CN103205100B (en) * | 2013-03-22 | 2015-07-22 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
| CN113388241A (en) * | 2020-03-13 | 2021-09-14 | 北京化工大学 | Rubber-plastic blended composite material of polyester elastomer toughened and modified carbon dioxide-based plastic and preparation method thereof |
| CN113388241B (en) * | 2020-03-13 | 2023-05-09 | 北京化工大学 | Rubber-plastic blending composite material of polyester elastomer toughened and modified carbon dioxide-based plastic and preparation method thereof |
| CN112143204A (en) * | 2020-10-21 | 2020-12-29 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN112143204B (en) * | 2020-10-21 | 2021-07-23 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN117603570A (en) * | 2024-01-24 | 2024-02-27 | 山东联欣环保科技有限公司 | Dimensionally stable polycarbonate compositions |
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