CN102936307B - The preparation method of a kind of epoxy-functional chainextender, epoxy-functional chainextender and application thereof - Google Patents
The preparation method of a kind of epoxy-functional chainextender, epoxy-functional chainextender and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of epoxy-functional chainextender for bio-based and biological degradation based polyalcohol, epoxy-functional chainextender preparation method and application thereof, this chainextender is made up of (by mass fraction) following composition of raw materials: styrene monomer: 50 ~ 75; Glycerol acrylate class monomer: 25 ~ 50; Initiator: 2 ~ 12.The preparation method of epoxy-functional chainextender comprises the above-mentioned reaction monomers of selection and initiator, and add reactor according to the order of setting, at suitable temperature and stirring velocity, carry out copolymerization, reactor product becomes product after desolvation, granulation.This epoxy-functional chainextender can be applicable to poly(lactic acid) (PLA), polypropylene carbonate (PPC) has the bio-based of fatty group polyester construction and the growth of biodegradable plastic molecular chain and crosslinked.The feature of epoxy-functional chainextender of the present invention is that molecular weight distribution is narrower, second-order transition temperature is high, its manufacturing process simple, and react under whole raw materials being blended in the temperature of solvent refluxing, the reaction times shortens.
Description
Technical field
The present invention relates to a kind of bio-based and biological degradation based polyalcohol, particularly the preparation method of a kind of epoxy-functional chainextender, epoxy-functional chainextender and application thereof.
Background technology
Green and low-carbon economy is the theme of world today's development, and the trend that bio-based and biodegradable plastic substitute fossil base (oil and coal etc.) plastics is irreversible.Poly(lactic acid) (PLA), polypropylene carbonate (PPC) etc. have the concern that the bio-based of fatty group polyester construction and biodegradable plastic development are more and more subject to global range, the industrialization technology trend of synthetic resins is ripe on the one hand, and industrialized scale improves rapidly; Processing and modification technology exploitation enliven on the other hand, and the Application Areas of goods is constantly expanded.Compared with traditional fossil base plastics, bio-based and biodegradable polyester resin intrinsic to thermo-responsive, facile hydrolysis, melt strength difference and the drawback such as mechanical property is not enough, even can not be used alone.But, bio-based and biodegradable polyester resin belong to polycondensation base polymer, hydroxyl, carboxyl isoreactivity group is often comprised in its structure, can the growth of molecular chain be realized by chainextender and be cross-linked, and then improve the processing of goods and application performance, realize bio-based and biodegradable resin is practical and the variation of goods processing mode and Application Areas.
R and D are applicable to the heat subject that bio-based and the resinoid chainextender of biodegradable polyesters have become world today's plastic working and modification field.
Take a broad view of status both at home and abroad, the focus of chainextender research and development so far concentrates on epoxy functionalized polymers aspect substantially, following subject matter is there is in existing technology, first, in order to chain extension under the residence time suitable in extrusion reaction system is sufficient, bio-based and biodegradable based polyalcohol must in advance dry, operate under condition of high vacuum degree, catalyzer and stablizer must be used between processing period.If do not possess these features, the limitation that molecular weight increases, product does not reach desired performance.Secondly, because the functionality of chainextender increases, the degree of branching of made product and the potential of gel also increase.Large-scale branching has very strong negative impact to degree of crystallinity, and the gel existed in product all has very large negative effect to the mechanical property of bio-based and biodegradable based polyalcohol.The second-order transition temperature Tg of the styrene acrylic chainextender of the 3rd epoxy-functional is generally 50 ~ 70 DEG C, and the processing temperature of bio-based and biodegradable based polyalcohol is general all at about 200 DEG C.Therefore when the styrene acrylic series chain extender of epoxy-functional is introduced directly into the intake zone of processing units, chainextender realize dispersed before just local produced reaction, define gel.And due to the second-order transition temperature Tg of the styrene acrylic series chain extender of epoxy-functional lower, easily block opening for feed, cause formula uneven, produce unstable.
Publication number is the preparation method that the Chinese patent of CN101157739 discloses a kind of macromolecule material chain extender, relate to a kind of macromolecular material chainextender and preparation method thereof, the component of this chainextender and content (weight part) comprising: styrene monomer 50-75, glycerol acrylate class monomer 50-25, initiator 0.1-1.2, dispersion agent 0.1-1.0, other auxiliary agent 0.1-0.3; The preparation method of this chainextender comprises the above-mentioned reaction monomers of selection and auxiliary agent, adds reactor, at suitable temperature and stirring velocity, carry out copolyreaction according to setting order; Reaction product becomes product after washing, drying.The method of this patent disclosure comprises dispersion agent and other auxiliary agents, and reaction solvent aspect uses ionized water, and reaction approximately needs 7-10h.
Summary of the invention
Based on this, the object of the invention is to overcome defect that prior art exists and the preparation method of the epoxy-functional chainextender product that a kind of technique is simple, molecular weight distribution is narrower, second-order transition temperature is high, easy to use that provides and epoxy-functional chainextender, it is applied in the bio-based and biodegradable plastic that poly(lactic acid) (PLA), polypropylene carbonate (PPC) etc. have fatty group polyester construction, second-order transition temperature is high, and the course of processing is stablized.
The present invention adopts following technical scheme: a kind of epoxy-functional chainextender, is made up of (by mass fraction) following composition of raw materials:
Styrene monomer: 50 ~ 75;
Glycerol acrylate class monomer: 25 ~ 50;
Initiator: 2 ~ 12.
Preferably, described styrene monomer is vinylbenzene.
Preferably, described glycerol acrylate class monomer is glycidyl methacrylate
Preferably, described initiator refers to benzoyl peroxide.
The present invention also provides a kind of preparation method of epoxy-functional chainextender, comprises the following steps:
First, by mass fraction proportioning, following raw material will be prepared:
Styrene monomer: 50 ~ 75;
Glycerol acrylate class monomer: 25 ~ 50;
Initiator: 2 ~ 12;
Solvent: 150 ~ 200;
Then, by joining in solvent after above-mentioned styrene monomer, glycerol acrylate class monomer, initiator mixing, being warming up to backflow in the reactor, keeping 2.5-5h;
Finally, recycling design, blowing obtains epoxy-functional chainextender.
Preferably, described reactor is the there-necked flask that band stirs and refluxes.
Preferably, described solvent is toluene.
Preferably, the temperature 110-120 DEG C after heating up in the reactor.
And as a kind of novelty teabag of the present invention, wherein said epoxy-functional chainextender is in the application improving poly(lactic acid) (PLA) Tg, molecular weight, moment of torsion and optimize in melting index.
And as a kind of novelty teabag of the present invention, wherein said epoxy-functional chainextender is in the application improving polypropylene carbonate (PPC) Tg, molecular weight, moment of torsion and optimize in melting index.
The present invention has following beneficial effect: the feature of epoxy-functional chainextender of the present invention is that molecular weight distribution is narrower, second-order transition temperature is high, its manufacturing process simple, and react under whole raw materials being blended in the temperature of solvent refluxing, the reaction times shortens.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail.
Embodiment 1
1), the formula of epoxy-functional chainextender is:
| Component | Mass fraction |
| Styrene monomer | 50 |
| Glycerol acrylate class monomer | 25 |
| Initiator | 2 |
2), the preparation process of epoxy-functional chainextender
In 5000ML there-necked flask, add 500ml toluene, 350g vinylbenzene, 175g glycidyl acrylate, 14g benzoyl peroxide, be warming up to 110 DEG C, keep 5h, recycling design, blowing obtains product.
3), recording product second-order transition temperature Tg is 73 DEG C
The foundation of its test is GB/T 19466.2-2004 plastics dsc (DSC) part 2s: the mensuration of second-order transition temperature.
Embodiment 2
1) formula of epoxy-functional chainextender is:
| Component | Mass fraction |
| Styrene monomer | 75 |
| Glycerol acrylate class monomer | 50 |
| Initiator | 12 |
2), the preparation process of epoxy-functional chainextender
In 5000ML there-necked flask, add 500ml toluene, 375g vinylbenzene, 250g glycidyl acrylate, 60g benzoyl peroxide, be warming up to 110 DEG C, keep 2.5h, recycling design, blowing obtains product.
3), recording product second-order transition temperature Tg is 76 DEG C.
The foundation of its test is GB/T 19466.2-2004 plastics dsc (DSC) part 2s: the mensuration of second-order transition temperature.
Embodiment 3
And use twin screw extruder to carry out modification granulation according to the processing method of routine to poly(lactic acid) (PLA), concrete formula is as follows:
1), comparative example: poly(lactic acid) (PLA) 4032D of the chainextender ADR4370 and 99.75% of 0.25%.
Wherein, German BASF chainextender ADR4370 can buy from market and obtain.
2), experimental example: the epoxy-functional chainextender in 0.25% embodiment 1 and 99.75% poly(lactic acid) (PLA) 4032D.
The result of experiment shows, produced and gathered materials after comparative example charging opening entered tens minutes, and greatly, head discharging is unstable in melt pressure change; Experimental example charging immediate stability, melt pressure is always constant, and head discharging is stablized.
Embodiment 4
The application of epoxy-functional chain extender composition in poly(lactic acid) (PLA) (natures4032D) in embodiment 1, epoxy-functional chainextender and 99% poly(lactic acid) of the embodiment 1 by 1% are carried out mixing on torque rheometer, time 900S, temperature 180 DEG C.
| Pure PLA | Modification PLA | |
| Moment of torsion NM | 12.3 | 25.0 |
| Second-order transition temperature DEG C | 60 | 64 |
| Melting index g/10min | 6.7 | 0.57 |
Wherein:
1), moment of torsion is the data final after mixing 900s at 180 DEG C of torque rheometer.
2), according to GB/T 19466.2-2004 plastics dsc (DSC) part 2: the mensuration of second-order transition temperature.
3), melting index is at 210 DEG C, measures under counterweight 2.16kg condition.
Embodiment 5
The application of epoxy-functional chainextender in embodiment 1 in polypropylene carbonate (PPC) (covering west).Epoxy-functional chainextender and 99% polypropylene carbonate of the example 1 by 1% carry out mixing on torque rheometer, time 300S, temperature 130 DEG C.
| Pure PPC | MODIFIED PP C | |
| Moment of torsion NM | 7.3 | 29.5 |
| Second-order transition temperature DEG C | 12.8 | 29.8 |
| Molecular weight | 33000 | 55000 |
| Melting index g/10min | 0.3 |
Wherein:
1), moment of torsion is the data final after mixing 300s at 130 DEG C of torque rheometer;
2), GB/T 19466.2-2004 plastics dsc (DSC) part 2: the mensuration of second-order transition temperature;
3), molecular weight gel chromatography records;
4), melting index is at 160 DEG C, measures under counterweight 2.16kg condition.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; and other any do under not deviating from spirit of the present invention and principle change, modification, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. an epoxy-functional chainextender, it is characterized in that, 500ml toluene, 350g vinylbenzene, 175g glycidyl acrylate is added in 5000ML there-necked flask, 14g benzoyl peroxide, be warming up to 110 DEG C, keep 5h, recycling design, blowing obtains product, and recording product second-order transition temperature Tg is 73 DEG C.
2. a preparation method for epoxy-functional chainextender, is characterized in that, adds 500ml toluene, 350g vinylbenzene, 175g glycidyl acrylate in 5000ML there-necked flask, 14g benzoyl peroxide, is warming up to 110 DEG C, keeps 5h, recycling design, blowing obtains product.
3. an application for epoxy-functional chainextender according to claim 1, is characterized in that, described epoxy-functional chainextender is in the application improving poly(lactic acid) (PLA) Tg, molecular weight, moment of torsion and optimize in melting index.
4. an application for epoxy-functional chainextender according to claim 1, is characterized in that, described epoxy-functional chainextender is in the application improving polypropylene carbonate (PPC) Tg, molecular weight, moment of torsion and optimize in melting index.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103724522B (en) * | 2013-12-31 | 2016-04-13 | 内蒙古蒙西高新技术集团有限公司 | Containing terpolymer and the copolymerization process of the material of multiple epoxy-functional, its preparation method, itself and carbonic acid gas and propylene oxide |
| WO2015100517A1 (en) * | 2013-12-31 | 2015-07-09 | 内蒙古蒙西高新技术集团有限公司 | Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor |
| CN103881001A (en) * | 2014-03-27 | 2014-06-25 | 杭州曦茂新材料科技有限公司 | Preparation method and application of comb-type epoxy capacity-increasing chain extender for polymer material |
| CN104193879B (en) * | 2014-08-23 | 2016-06-08 | 山西省化工研究所（有限公司） | With functional group's melt reinforcing agent, preparation and application thereof |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
| CN105837722A (en) * | 2016-06-20 | 2016-08-10 | 王金明 | Preparation method of hydrophilic capacity-increasing chain extender |
| CN105859939A (en) * | 2016-06-20 | 2016-08-17 | 王金明 | Preparation method of organic silicon capacity increasing chain extender |
| CN106065043B (en) * | 2016-07-28 | 2018-09-18 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
| CN106188369A (en) * | 2016-07-28 | 2016-12-07 | 王金明 | A kind of preparation method of the chain-expanding agent containing organic fluorinated silicone |
| CN109575196B (en) * | 2018-12-12 | 2022-04-05 | 温州大学新材料与产业技术研究院 | Polylactic acid chain extender, preparation method thereof and modified polylactic acid |
| CN110452325A (en) * | 2019-07-26 | 2019-11-15 | 广州华新科智造技术有限公司 | Terpolymer and preparation method thereof |
| CN111499789B (en) * | 2020-04-17 | 2021-01-12 | 佳易容聚合物(上海)有限公司 | Solvent-free tackifying chain extender and preparation method and application thereof |
| CN112279985A (en) * | 2020-11-01 | 2021-01-29 | 福建师范大学 | Degradable chain extender and preparation method and application thereof |
| CN112778454B (en) * | 2021-01-22 | 2022-03-08 | 上海涵点科技有限公司 | Polyepoxy chain extender and preparation method and application thereof |
| CN114621570B (en) * | 2022-03-29 | 2023-09-19 | 湖北中烟工业有限责任公司 | Regeneration method and application of residual materials in flue gas cooling section |
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| CN101440141A (en) * | 2007-11-23 | 2009-05-27 | 佛山市顺德区汉达精密电子科技有限公司 | Compatibilization chain extender for recycling engineering plastics |
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| US7855252B2 (en) * | 2008-06-16 | 2010-12-21 | Basf Corporation | End capping additive for polycondensate polymer resins |
| EP2456792B1 (en) * | 2009-07-21 | 2014-03-12 | BASF Corporation | Process for the production of condensation polymers via in-reactor chain extension and products thereof |
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| CN101157739A (en) * | 2006-10-08 | 2008-04-09 | 周小雯 | Method for preparing macromolecule material chain extender |
| CN101440141A (en) * | 2007-11-23 | 2009-05-27 | 佛山市顺德区汉达精密电子科技有限公司 | Compatibilization chain extender for recycling engineering plastics |
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