CN104387737A - Reinforced modified poly(propylene carbonate) composition and preparation method thereof - Google Patents
Reinforced modified poly(propylene carbonate) composition and preparation method thereof Download PDFInfo
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- CN104387737A CN104387737A CN201410647191.0A CN201410647191A CN104387737A CN 104387737 A CN104387737 A CN 104387737A CN 201410647191 A CN201410647191 A CN 201410647191A CN 104387737 A CN104387737 A CN 104387737A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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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 reinforced modified poly(propylene carbonate) composition and a preparation method thereof, belonging to the field of modification of high polymer materials. The reinforced modified poly(propylene carbonate) composition comprises poly(propylene carbonate), ethylene-vinyl acetate copolymer and poly(1,2-propanediol adipate), wherein the weight ratio of the poly(propylene carbonate) to the ethylene-vinyl acetate copolymer to the poly(1,2-propanediol adipate) is (20-80):(20-80):(2-10). The reinforced modified poly(propylene carbonate) composition has higher tensile strength than the poly(propylene carbonate); the tensile strength can be up to 34.5 MPa; and the material has high tensile break extension percentage, flexibility and toughness and increases the anti-stick capability, thus ensuring that the poly(propylene carbonate) material has wider application space.
Description
Technical field
The present invention relates to polymer modification field, particularly a kind of enhancing modified polypropylene carbonic ester compound and preparation method thereof.
Background technology
Polypropylene carbonate (Poly (propylene carbonate)), also known as poly (propylene carbonate), be abbreviated as PPC, it is the multipolymer of carbonic acid gas and propylene oxide, is raw material with carbonic acid gas, is a kind of environment protection biological degradable material, it synthesizes (Inoue by the aboveground auspicious equality people of Japanese Scientists the earliest, S., Koinuma, H., Tsuruta, T., J.Polym.Sci., Polym.Lett.Ed., 1969,7,287-292.), and first achieve industrialization in China.Polypropylene carbonate material, owing to having stabilizing carbon dioxide and biodegradable characteristic, thus has a wide range of applications at wrapping material, fiber and non-woven fabric and medicine and hygiene fields.
Though polypropylene carbonate has above-mentioned advantage, but compared with general-purpose plastics, polypropylene carbonate has non-crystallizable, second-order transition temperature is lower features such as (about 30 DEG C), cause cold flow bonding easily occurs during the material at high temperature formed by this multipolymer, crisp and hard during low temperature, its mechanical property such as intensity, toughness is poor, thus limits its application in packaging, food, medicine and other fields.
In order to promote the mechanical property of polypropylene carbonate, particularly promote the toughness of polypropylene carbonate, mostly prior art is the method adopting polycomponent blending and modifying, such as: application number be 200710055513.2 Chinese patent literature disclose the blend of a kind of carbon dioxide-epoxy propane copolymer and poly butylene succinate (PBS), this kind of method uses PBS to carry out toughening modifying to PPC, improves mechanical property and the thermostability of PPC.And for example: starch blending PPC and glycerine plastified, thermoplastic starch is utilized to improve mechanical property and the thermostability (Carbohyd.Polym., 2008,71:229-234) of PPC.Also have in prior art and the hydroxyapatite (HA) after silane coupling agent KH570 process is prepared PPC/HA matrix material, in order to promote PPC toughness (Chinese Plastics, 2006,20 (2): 61-64) with PPC is blended.
Jiao etc. (Jiao J, Wang S J, Meng Y Z, et al.Polym.Eng.Sci., 2007,47 (2): 174-180.) have prepared the PPC/EVOH matrix material of excellent performance by melt-blending process.Result of study shows, compound system is two phase structure, has good consistency between PPC and EVOH.(the plastics industry such as Fu Luxiang, 2006,34 (11): 14-16.) utilized mechanical blending legal system for complete biodegradable plastics PLA/PPC alloy, the people that adds of PPC makes system tensile strength fall little, elongation at break is elevated to 23.8%, improves nearly 20 times than pure PLA.People (the eXPRESS Polym.Lett. such as Sichuan University Fu Qiang, 2011,5 (11): 937-949.) have studied the melt blending modifying function of maleic anhydride to PLA/PPC blend, maleic anhydride can significantly improve the mechanical property of PLA/PPC blend.The people such as Fu Qiang (eXPRESS Polym.Lett., 2012,6 (11): 860-870.) be investigated polyvinyl acetate (PVA) (PVAc) to the compatibilization of PPC/PLA blend, PVAc can significantly improve the mechanical property such as tensile strength and tension fracture elongation rate of PPC/PLA blend.
Summary of the invention
The present invention will solve technical problem of the prior art, a kind of enhancing modified polypropylene carbonic ester compound and preparation method thereof is provided, not only tensile strength is higher for this enhancing modified polypropylene carbonic ester compound, and has higher tension fracture elongation rate and kindliness; Meanwhile, material anti-seizure performance improves.
The invention provides a kind of enhancing modified polypropylene carbonic ester compound, comprising: polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester; The weight ratio of described polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10.
Preferably, the number-average molecular weight of described polypropylene carbonate is 30000 ~ 200000g/mol.
Preferably, the number-average molecular weight of described poly-1,2-PD adipic acid ester is 1000 ~ 10000g/mol.
The present invention also provides a kind of preparation method of enhancing modified polypropylene carbonic ester compound, step and condition as follows:
Carry out banburying by after polypropylene carbonate, ethylene-vinyl acetate copolymer, poly-1,2-PD adipic acid ester mixing at 120 DEG C ~ 160 DEG C, be enhanced modification polypropylene carbonic ester compound; The blending ratio of described polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10 by weight.
Preferably, the blending ratio of ethylene-vinyl acetate copolymer and polypropylene carbonate is 40 ~ 60:40 ~ 60 by weight.
Method the present invention for banburying preferably adopts the blended banburying of Banbury mixer, and banburying temperature is set to 120 DEG C ~ 160 DEG C, and be preferably set to 140 DEG C ~ 160 DEG C, rotating speed is preferably set to 50rpm ~ 120rpm, and the banburying time is preferably 5 minutes ~ 10 minutes.
The invention has the beneficial effects as follows:
The invention provides a kind of enhancing modified polypropylene carbonic ester compound and preparation method thereof, said composition comprises polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester.In composition, ethylene-vinyl acetate copolymer is the multipolymer of a kind of ethene and vinyl acetate, and copolymer molecule chain is containing vinyl, and Chain Flexibility is good; Ethylene-vinyl acetate copolymer owing to introducing Vinyl Acetate Monomer in molecular chain, thus reduces high-crystallinity, improves snappiness, shock resistance.In general, the performance of ethylene-vinyl acetate copolymer depends primarily on the content of vinyl acetate on molecular chain.Adjustable thus meet different application needs because forming component ratio, the content of vinyl acetate is higher, its transparency, and pliability and toughness can improves relatively.It is used to add the tensile strength that can improve polypropylene carbonate in raw material as properties-correcting agent.Simultaneously, ethylene-vinyl acetate copolymer also has certain consistency with polypropylene carbonate, thus the material after itself and polypropylene carbonate is blended can keep the second-order transition temperature that purer polypropylene carbonate is higher, overcomes a difficult problem for the easy bonds itself of polypropylene carbonate normal temperature storage and cold flow.Therefore, use ethylene-vinyl acetate copolymer as the reinforced modifier of polypropylene carbonate.
Poly-1,2-monobehenate is a kind of aliphatic polyester, on aliphatic poly ester molecule, side chain is few, Chain Flexibility is good, uses it to add the snappiness that can improve polypropylene carbonate in raw material as properties-correcting agent, and, poly-1,2-monobehenate and polypropylene carbonate have good consistency, and the present invention is by adjusting the processing fluidity of the content regulation and control polypropylene carbonate of poly-1,2-PD adipic acid ester.
Relative to existing polypropylene carbonic ester compound, the tensile strength of polypropylene carbonic ester compound provided by the invention can reach 34.5MPa, and tension fracture elongation rate reaches 86%, extends the application space of polypropylene carbonate material.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of enhancing modified polypropylene carbonic ester compound, comprising: polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester; Wherein, the weight ratio of polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10.
The weight ratio of above-mentioned ethylene-vinyl acetate copolymer and polypropylene carbonate is 20 ~ 80:20 ~ 80, is preferably 40 ~ 60:40 ~ 60.In the present invention, preferred number average molecular weight is the polypropylene carbonate of 30000 ~ 200000g/mol, too high then its viscosity of polypropylene carbonate number-average molecular weight is excessive, increase the difficulty blended with ethylene-vinyl acetate copolymer, molecular weight is too low, and its mechanical property such as tensile strength, elongation at break reduces greatly.
The present invention also provides a kind of preparation method of above-mentioned enhancing modified polypropylene carbonic ester compound, step and condition as follows:
Carry out banburying at 120 DEG C ~ 160 DEG C after polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester being mixed, be enhanced modification polypropylene carbonic ester compound; The blending ratio of polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10 by weight.
Method the present invention for banburying preferably adopts the blended banburying of Banbury mixer, and banburying temperature is set to 120 DEG C ~ 160 DEG C, and be preferably set to 140 DEG C ~ 160 DEG C, rotating speed is preferably set to 50rpm ~ 120rpm, and the banburying time is preferably 5 minutes ~ 10 minutes.
In order to understand the present invention further, below in conjunction with embodiment, enhancing modified polypropylene carbonic ester compound provided by the invention and preparation method thereof is described.Polypropylene carbonate in following examples provides by Taizhou Bang Feng plastics company limited; Ethylene-vinyl acetate copolymer provides by Mitsui chemical company, trade mark P2505; Poly-1,2-PD adipic acid ester is by unit of the present invention oneself synthesis, and the poly-1,2-PD adipic acid ester used in following examples is prepared all by the following method:
With 1,2-PD and hexanodioic acid prepared by polycondensation under catalyst action, obtains the poly-1,2-PD adipic acid ester of different number-average molecular weight by controlling temperature of reaction, reaction times and pressure.
In following examples, tensile property is undertaken testing by the standard of ASTM D638-2008, and Banbury mixer is that Germany produces HaakeRheomix 600 torque rheometer.
Embodiment 1:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 48g of 150000g/mol
Ethylene-vinyl acetate copolymer 12g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 3g of 1500g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 140 DEG C, rotating speed is 50rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Embodiment 2:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 36g of 150000g/mol
Ethylene-vinyl acetate copolymer 24g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 3g of 2000g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 140 DEG C, rotating speed is 100rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Embodiment 3:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 24g of 150000g/mol
Ethylene-vinyl acetate copolymer 36g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 3g of 1500g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 140 DEG C, rotating speed is 100rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Embodiment 4:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 12g of 200000g/mol
Ethylene-vinyl acetate copolymer 48g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 3g of 3000g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 140 DEG C, rotating speed is 120rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Embodiment 5:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 36g of 30000g/mol
Ethylene-vinyl acetate copolymer 24g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 6g of 1500g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 140 DEG C, rotating speed is 50rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Embodiment 6:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 36g of 100000g/mol
Ethylene-vinyl acetate copolymer 24g
Number-average molecular weight is the poly-1,2-PD adipic acid ester 1.2g of 10000g/mol
2, above-mentioned polypropylene carbonate, ethylene-vinyl acetate copolymer are added in Banbury mixer, setting Banbury mixer temperature is 120 DEG C, rotating speed is 50rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 7 minutes, be enhanced modification polypropylene carbonic ester compound, and measure the tensile strength of enhancing modified polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Comparative example 1:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 60g of 150000g/mol
Number-average molecular weight is the poly-1,2-PD adipic acid ester 3g of 1000g/mol
2, above-mentioned polypropylene carbonate is added in Banbury mixer, setting Banbury mixer temperature is 160 DEG C, rotating speed is 60rpm, poly-1,2-PD adipic acid ester, after 3 minutes, adds in Banbury mixer by banburying, continue banburying 5 minutes, obtain polypropylene carbonic ester compound, measure the tensile strength of polypropylene carbonic ester compound, elongation at break and Young's modulus, test result lists in table 1.
Comparative example 2:
1, following component is taken by weight:
Number-average molecular weight is the polypropylene carbonate 60g of 150000g/mol
2, add in Banbury mixer by above-mentioned polypropylene carbonate, setting Banbury mixer temperature is 160 DEG C, and rotating speed is 60rpm, banburying 5 minutes, banburying product is hot-forming at 160 DEG C, obtains polypropylene carbonate sample, measure its tensile strength, elongation at break and Young's modulus, test result lists in table 1.
Table 1 tensile strength, elongation at break and Young's modulus test result
| Test event | Tensile strength (MPa) | Elongation at break (%) | Young's modulus (MPa) |
| Embodiment 1 | 28.5 | 160 | 975 |
| Embodiment 2 | 21.9 | 310 | 928 |
| Embodiment 3 | 24.2 | 180 | 865 |
| Embodiment 4 | 34.5 | 86 | 1250 |
| Embodiment 5 | 19.3 | 570 | 391 |
| Embodiment 6 | 23.1 | 120 | 1180 |
| Comparative example 1 | 31.0 | 210 | 1090 |
| Comparative example 2 | 27.8 | 4.6 | 920 |
From the above results, employing the invention provides enhancing modified polypropylene carbonic ester compound tensile strength and can reach 34.5MPa, and material has higher tension fracture elongation rate simultaneously, makes polypropylene carbonate material have more wide application space.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. an enhancing modified polypropylene carbonic ester compound, is characterized in that, comprising: polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester; The weight ratio of described polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10.
2. enhancing modified polypropylene carbonic ester compound according to claim 1, is characterized in that, the number-average molecular weight of described polypropylene carbonate is 30000 ~ 200000g/mol.
3. enhancing modified polypropylene carbonic ester compound according to claim 1, is characterized in that, the number-average molecular weight of described poly-1,2-PD adipic acid ester is 1000 ~ 10000g/mol.
4. the preparation method of the enhancing modified polypropylene carbonic ester compound according to claim 1-3 any one, is characterized in that, step and condition as follows:
Carry out banburying by after polypropylene carbonate, ethylene-vinyl acetate copolymer, poly-1,2-PD adipic acid ester mixing at 120 DEG C ~ 160 DEG C, be enhanced modification polypropylene carbonic ester compound;
The blending ratio of described polypropylene carbonate, ethylene-vinyl acetate copolymer and poly-1,2-PD adipic acid ester is 20 ~ 80:20 ~ 80:2 ~ 10 by weight.
5. the preparation method of enhancing modified polypropylene carbonic ester compound according to claim 4, is characterized in that, the blending ratio of ethylene-vinyl acetate copolymer and polypropylene carbonate is 40 ~ 60:40 ~ 60 by weight.
6. the preparation method of enhancing modified polypropylene carbonic ester compound according to claim 4, it is characterized in that, described banburying adopts the blended banburying of Banbury mixer, and banburying temperature is 120 DEG C ~ 160 DEG C, rotating speed is 50rpm ~ 120rpm, and the banburying time is 5 minutes ~ 10 minutes.
7. the preparation method of enhancing modified polypropylene carbonic ester compound according to claim 6, is characterized in that, banburying temperature is 140 DEG C ~ 160 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113795548A (en) * | 2020-01-29 | 2021-12-14 | 株式会社Lg化学 | Polyalkylene carbonate resin and molded article produced therefrom |
| CN114702638A (en) * | 2022-03-02 | 2022-07-05 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
| US12139604B2 (en) | 2020-01-29 | 2024-11-12 | Lg Chem, Ltd. | Polyalkylene carbonate-based resin, and molded article produced therefrom |
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| CN102177193A (en) * | 2008-11-05 | 2011-09-07 | 独立行政法人产业技术综合研究所 | Aliphatic polycarbonate complex derived from carbon dioxide, and process for producing same |
| CN102964801A (en) * | 2012-12-21 | 2013-03-13 | 中国科学院长春应用化学研究所 | Modified poly (propylene carbonate) and preparation method thereof |
| CN103087494A (en) * | 2013-01-25 | 2013-05-08 | 深圳市通产丽星股份有限公司 | Polymethyl ethylene carbonate modification method, modified material and application thereof |
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| CN102177193A (en) * | 2008-11-05 | 2011-09-07 | 独立行政法人产业技术综合研究所 | Aliphatic polycarbonate complex derived from carbon dioxide, and process for producing same |
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| CN113795548A (en) * | 2020-01-29 | 2021-12-14 | 株式会社Lg化学 | Polyalkylene carbonate resin and molded article produced therefrom |
| US12139604B2 (en) | 2020-01-29 | 2024-11-12 | Lg Chem, Ltd. | Polyalkylene carbonate-based resin, and molded article produced therefrom |
| CN114702638A (en) * | 2022-03-02 | 2022-07-05 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
| CN114702638B (en) * | 2022-03-02 | 2024-02-13 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
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Application publication date: 20150304 |