CN102702702A - Polylactic acid mixed resin modified by polycarboxylic polymer, preparation method and application - Google Patents
Polylactic acid mixed resin modified by polycarboxylic polymer, preparation method and application Download PDFInfo
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- CN102702702A CN102702702A CN2012101921989A CN201210192198A CN102702702A CN 102702702 A CN102702702 A CN 102702702A CN 2012101921989 A CN2012101921989 A CN 2012101921989A CN 201210192198 A CN201210192198 A CN 201210192198A CN 102702702 A CN102702702 A CN 102702702A
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Abstract
The invention discloses a polylactic acid mixed resin modified by a polycarboxylic polymer. The polylactic acid mixed resin is formed by a polylactic acid resin and the polycarboxylic polymer, and is characterized in that 0.1 g to 50 g of polycarboxylic polymer is added into each 100 g of polylactic acid resin. The invention further discloses a preparation method of the polylactic acid mixed resin modified by the polycarboxylic polymer and application. In comparison with a pure polylactic acid film, the blow-up ratio, the elongation at break and the intensity of the film are remarkably improved. After the polylactic acid resin is modified by the polycarboxylic polymer, the toughness and the intensity of the mixed resin film are remarkably improved, the improvement effect is not limited by types and sources of the polylactic acid and the polycarboxylic polymer, and the polycarboxylic polymer provided in the method is easy to popularize and apply.
Description
Technical field
The present invention relates to a kind of polylactic acid blend resin, be specifically related to a kind of polylactic acid blend resin of novel more carboxyl polymer modification, the invention still further relates to the preparation method and the application of said polylactic acid blend resin.
Background technology
But in numerous Natural Degradations and twice-laid stuff, POLYACTIC ACID is abundant because of its source, environmental friendliness, excellent performance, easy-formation processing and biocompatibility well receive much concern.Therefore, POLYACTIC ACID more will become one of the good substitute products of many synthesized polymer materials of potentiality, if can big area promote the use of, will definitely make huge contribution for slowing down environmental stress, also will definitely become the focus that Recent study is used.Yet owing to polylactic acid melt intensity is crossed the low blowing film forming that is difficult for, and since the thin-film material of its blowing gained also since under the normal temperature property crisp and can't meet the demands of production and living, this has greatly limited the application of POLYACTIC ACID, especially in the packaging film field.
Main at present through POLYACTIC ACID being carried out melt strength and the toughness that physical blending or chemical reaction modification improve POLYACTIC ACID.Wherein physical blending mainly comprises: with elastomer blended (Korea-Australia Rheology Journal 19 (3): 125-131.); With the polymer blending of flexibility (like new LDPE (film grade) (LDPE) (Journal of Applied Polymer Science 89 (14): 3757-3768.); Poly butylene succinate (PBS) (Korea-Australia Rheology Journal 19 (3): 125-131.) or gather (succinic acid-butanediol ester-co-l-lactate) (PBSL) (Polymer 47 (10): 3557-3564.); (Polymer 49 (2): 599-609.) for polycaprolactone (PCL); Polyoxyethylene glycol (PEG) (Journal of Applied Polymer Science 66 (8): 1495-1505.) and Z 150PH (Journal of Applied Polymer Science 114 (4): 2481-2487.) etc.); ((Polymer 46 (25): 11716-11727.) to comprise layered silicate to add softening agent; Citrate trianion (Journal of Applied Polymer Science 66 (8): 1507-1513.); Low malonic ester polymkeric substance (Journal of Applied Polymer Science 96 (4): 992-1002.) and lact-acid oligomer (Polymer 42 (14): 6209-6219.) etc.).The chemical reaction modification then has the following aspects: as (Polymer 47 (1): 429-434.) with POLYACTIC ACID branching; Crosslinked (Carbohydrate Polymers 72 (4): 673-681.) with POLYACTIC ACID; And with other materials (Biomacromolecules 5 (3): 1124-1134.) as gathering in oneself acid esters; Poly butylene succinate (Biomacromolecules 4 (6): 1827-1834.) and PEG (Macromolecular Bioscience 5 (11): 1125-1131.) etc. carry out copolymerization etc.In addition, Shu Ying etc. is through adding chainextender (Polymer International:982-986.) and Kim etc. then through improving the molecular weight that polymerization route and method improve POLYACTIC ACID (Macromolecular Chemistry and Physics 203 (15): 2245-2250.) with the melt strength and the performance of raising POLYACTIC ACID.Yu etc. then adopt technologies such as stretching and quenching to increase orientation to improve mechanical property (the Polymer Engineering and Science 48 (4): 634-641.) of poly-lactic acid material.
Aforesaid method is in the progress that has obtained in recent years to a certain degree; But chemical reactions such as grafting and block copolymerization are consuming time, productive rate is low because other polymkeric substance or non-degradable or, monomerics relatively poor with the POLYACTIC ACID consistency are prone to migration and problem such as cost height, make aforesaid method not drop in the middle of the actual production on a large scale.Thereby, seek new material or new approach become numerous investigators with the simple and effective blown film performance of improving POLYACTIC ACID new challenge.As far as we know; Although people such as Li once improved the melt rheological property ability (Macromolecules of PLA by hyper-branched polyester (HBP) and the intermolecular ydrogen bonding reactive force of PLA; Vol. 40, No. 16,2007); But HBP/PLA blending and modifying effect is limited and be not applied in preparation and the performance examination of blown film material of PLA; Although HBP class material is limited to the PLA modified effect then mainly to be because HBP contains a plurality of carboxyls owing to belong to hyperbranched type material, the steric effect that its structure is brought make the carboxyl of HBP fully to contact with the PLA molecular chain and cause the hydrogen bond action of system inside limited due to.Simultaneously, nobody source directly melt blended melt rheological characteristics and blown film performance of coming polydactyl acid of other types more carboxyl polymer resin and polylactic resin widely of utilizing non-HBP still so far.And the present invention proves that through testing repeatedly more carboxyl polymer has significant improvement to the melt rheological property ability and the blown film performance of polylactic resin; Its principle is that the hydrogen bond and the carbonyl on the polylactic acid molecule chain of more carboxyl polymer forms hydrogen bond and in whole system, form the hydrogen bond network structure, thereby realizes toughness reinforcing to the enhancing of POLYACTIC ACID.Compare with HBP class material, more carboxyl polymer not only can form the hydrogen bond network structure with PLA and realize strengthen toughness reinforcingly, can also select as required and have varying strength and the flexible more carboxyl polymer comes further toughness reinforcing to the PLA enhancing.In view of the above; The present invention is then through with the more carboxyl polymer of non-HBP and the direct melt blended preparation modified polylactic resin of polylactic resin and it is extruded blown film to make a kind of novel POLYACTIC ACID blown film material modified; Thereby realize the POLYACTIC ACID optimization in Properties; Its preparation process simple controllable, production efficiency is high, and is with low cost.
Summary of the invention
One of purpose of embodiments of the invention is to cause POLYACTIC ACID on blowfilm shaping technology, to have all drawbacks to the intrinsic deficiency on the existing existing above-mentioned performance of POLYACTIC ACID; A kind of novel polylactic acid blend modified resin and preparation method thereof is provided, promptly utilizes the blow molding after extruding blend commercially available polylactic resin is carried out modification of commercially available more carboxyl polymer to make degradable polydactyl acid film.This method is the technology simple controllable not only, and production efficiency is high, and cost is also cheaper simultaneously.
The present invention is achieved in that
A kind of polylactic acid blend resin of more carboxyl polymer modification is made up of polylactic resin and more carboxyl polymer.
Scheme further is: the more carboxyl polymer that adds 0.1 g to 50 g in per 100 g polylactic resin.
Scheme further is: described more carboxyl polymer is meant the carboxyl number purpose more carboxyl polymer that in 1 polymer molecule, has more than 7.(PAA: the algorithm of carboxyl limits value: the required lowest molecular weight 500 of PAA that sets with experiment calculates, and its carboxyl number is: 500/72 ≌ 7 (individual))
Scheme further is: said polylactic resin is any in the commercially available prod.
Another object of the present invention is to provide the preparation method of the polylactic acid blend resin of said more carboxyl polymer modification, is specially:
Place baking oven to be dried to constant weight polylactic resin; More carboxyl polymer is joined in the dried polylactic resin by the composition proportioning of adding the more carboxyl polymer of 0.1 g to 50 g in per 100 g polylactic resin; Mix, prepare POLYACTIC ACID/more carboxyl polymer pre-composition.
POLYACTIC ACID/more carboxyl polymer pre-composition is joined twin screw extruder carry out blend and extrude, promptly make the polylactic acid blend resin of more carboxyl polymer modification.
A further object of the present invention is to provide the application of said more carboxyl polymer polydactyl acid blending resin, said being applied on the preparation film.Polylactic acid blend resin with said more carboxyl polymer modification makes more carboxyl polymer polydactyl acid blending resin film through blowfilm shaping exactly.Blowfilm shaping can adopt single screw rod extrusion blow molding machine.When the present invention can overcome common POLYACTIC ACID blowfilm shaping owing to molecular weight is low, chain entanglement is counted out very few big, the flexible problems such as differ from of its thin-film material fragility that cause.The purer polylactic resin of performance such as its elongation at break, blow-up ratio all increase.
The present invention compared with prior art has following positively effect:
1. the present invention is based on current commercially available non-HBP class more carboxyl polymer and comes the melt processability of the current commercially available polylactic resin of modification and the final performance of blown film material.This method belongs to initiative, and adopts method of the present invention to prepare the restriction that polylactic acid film material does not receive POLYACTIC ACID and more carboxyl polymer kind and source, can choose all polylactic resin raw materials and more carboxyl polymer raw material on the market, is easy to apply.
2. the polylactic acid blend resin and the blown film material thereof of the prepared more carboxyl polymer modification of the present invention.Compare with pure polylactic resin and film thereof, at first as the most of degradables of more carboxyl polymer raw material of properties-correcting agent, the source is abundant, thereby has broad application prospects.
3. the polylactic acid blend resin and the blown film material thereof of the prepared more carboxyl polymer modification of the present invention.Its preparation technology is simple, is easy to control, less demanding to equipment, but industriallization, and reduced investment.
4. the polylactic acid blend resin and the blown film material thereof of the prepared more carboxyl polymer modification of the present invention are compared with pure polylactic resin, and its blow-up ratio obviously increases, blown film process stable and controllable more; With low cost; Natural degradable; Preparation technology's equipment is conventional equipment simultaneously, the simple control easily of production technique, and production efficiency is high; To the obvious restriction that does not also receive the POLYACTIC ACID kind of the modified effect of polylactic resin, be easy to apply.
5. the polylactic acid blend resin and the blown film material thereof of the prepared more carboxyl polymer modification of the present invention; Compare with unmodified polylactic resin; Its transparency changes little, but its intensity and toughness all is significantly improved, and this application to the expansion said material is significant.
6. because the present invention provides the polylactic acid blend resin of more carboxyl polymer modification and the preparation of blown film material thereof to fill a prescription simple; Need not add any other analog assistant except that more carboxyl polymer; And preparation process and processing unit and control thereof are all very simple and easy; Thereby production cost is low, production efficiency is high, problems such as the equipment and instrument of having avoided prior art to cause is complicated, technology controlling and process is difficult, operating process is various, production line length.
Description of drawings
The stress-strain(ed) curve of the pure POLYACTIC ACID of Fig. 1 (PLA) thin-film material.
The stress-strain(ed) curve of polydactyl acid (PLA/A1-5) thin-film material when Fig. 2 polyhydroxylated polymer addition is 5 g.
The stress-strain(ed) curve of polydactyl acid (PLA/A2-5) thin-film material when Fig. 3 polyhydroxylated polymer addition is 5 g.
The stress-strain(ed) curve of polydactyl acid (PLA/A2-1) thin-film material when Fig. 4 polyhydroxylated polymer addition is 1 g.
The stress-strain(ed) curve of polydactyl acid (PLA/A2-20) thin-film material when Fig. 5 polyhydroxylated polymer addition is 20 g.
Embodiment
Embodiment given below is to specific descriptions of the present invention; Be necessary to be pointed out that at this following examples only are used for the present invention is done further explanation; Can not be interpreted as restriction to protection domain of the present invention; This art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Mentioned more carboxyl polymer is meant the carboxyl number purpose more carboxyl polymer that in 1 polymer molecule, has more than 7 in the literary composition, and the heteropolymer that adopts among the embodiment comprises ROHM (PAA) and polymethyl acrylic acid (PMAA).
It is to be noted; The present invention can be according to final intensity and the toughness that requires of polylactic acid blend resin film material; Select different sorts, varying strength and flexible more carboxyl polymer and polylactic acid blend, polymer shared percentage composition in whole system is 0.1% to 50%.Only need more carboxyl polymer to satisfy in 1 polymer molecule and have the carboxyl number purpose more carboxyl polymer more than 7, and be that non-hyperbranched poly Ester gets final product.
The concrete preparation method that the application adopts is following:
(1) raw material drying.Place baking oven to be dried to constant weight polylactic resin, subsequent use.
(2) preparation POLYACTIC ACID/more carboxyl polymer (PLA/A1) pre-composition.More carboxyl polymer is joined by in the dried polylactic resin of step (1) by proportioning, and carry out simple mechanically mixing, the preparation pre-composition.
(3) preparation PLA/A1 resin.The pre-composition of step (2) preparation is joined twin screw extruder extrude the blend granulation, make the PLA/A1 resin granular material.
(4) drying.Place baking oven to be dried to constant weight the polydactyl acid pellet of step (3) preparation.
(5) preparation PLA/A1 film.The dried pellet of step (4) is joined single screw extrusion machine extrude blowfilm shaping, make the thin-film material (PLA/A1) of first kind of polylactic acid blend resin after the more carboxyl polymer modification.
(6) repeating step (1) to (5) makes the thin-film material (PLA/A2) of second kind of polylactic acid blend resin after the more carboxyl polymer modification.
In an embodiment, A1 representes that the more carboxyl polymer that adopts is a polymethyl acrylic acid, and A2 representes that the more carboxyl polymer that adopts is a ROHM.Concrete prescription is seen table 1, and the mechanical property and the blow-up ratio of the sample of different ingredients preparation are seen table 2.
Visible from table 2, when can overcoming common POLYACTIC ACID blowfilm shaping, the present invention very fewly causes problems such as its thin-film material fragility is big, flexibility is poor because molecular weight is low, chain entanglement is counted out.The film elongation at break of four kinds of embodiment preparations of the present invention, blow-up ratio, intensity or the like the purer polylactic resin of performance all has significantly raising.
The prescription of table 1 different sorts more carboxyl polymer blending and modifying POLYACTIC ACID (PLA/A)
| ? | Specimen coding | PLA/g | Carboxyl polymer/g | |
| | PLA | 100 | 0 | |
| Embodiment 1 | PLA/A1-5 | 100 | 5 | |
| Embodiment 2 | PLA/A2-5 | 100 | 5 | |
| Embodiment 3 | PLA/A2-1 | 100 | 1 | |
| Embodiment 4 | PLA/A2-20 | 100 | 20 |
The mechanical property of table 2 various sample and blow-up ratio
| Sample | Blow-up ratio | Intensity/MPa | Elongation at break (%) |
| PLA | 1.22 | 70.0 | 43.0 |
| PLA/A 1-5 | 1.62 | 90.0 | 60.0 |
| PLA/A2 -5 | 1.54 | 93.0 | 85.0 |
| PLA/A2 -1 | 1.72 | 100.0 | 112.0 |
| PLA/A2 -20 | 1.72 | 78.0 | 123.0 |
Claims (5)
1. the polylactic acid blend resin of a more carboxyl polymer modification is made up of polylactic resin and more carboxyl polymer, it is characterized in that: the more carboxyl polymer that adds 0.1 g to 50 g in per 100 g polylactic resin.
2. according to the polylactic acid blend resin of the said more carboxyl polymer modification of claim 1, it is characterized in that: described more carboxyl polymer is meant the carboxyl number purpose more carboxyl polymer that in 1 polymer molecule, has more than 7.
3. according to the polylactic acid blend resin of the said more carboxyl polymer modification of claim 2, it is characterized in that: described more carboxyl polymer is non-hyperbranched poly Ester.
4. the preparation method of the polylactic acid blend resin of the described more carboxyl polymer modification of the arbitrary claim of claim 1 to 3 is characterized in that:
Place baking oven to be dried to constant weight polylactic resin; More carboxyl polymer is joined in the dried polylactic resin by the composition proportioning of adding the more carboxyl polymer of 0.1 g to 50 g in per 100 g polylactic resin; Mix, prepare POLYACTIC ACID/more carboxyl polymer pre-composition; POLYACTIC ACID/more carboxyl polymer pre-composition is joined twin screw extruder carry out blend and extrude, promptly make the polylactic acid blend resin of more carboxyl polymer modification.
5. the application of the described more carboxyl polymer polydactyl acid of the arbitrary claim of claim 1 to 3 blending resin, it is characterized in that: said application is to be used to prepare film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114230992A (en) * | 2022-01-20 | 2022-03-25 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
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| CN1299393A (en) * | 1998-04-01 | 2001-06-13 | 卡吉尔公司 | Lactic acid residue contg. polymer composition, product method for prepn. and use |
| CN101225222A (en) * | 2008-02-03 | 2008-07-23 | 四川大学 | Polylactic acid as well as derivative composite material and preparation method thereof |
| CN101333332A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polylactic resin toughened and modified by acrylic ester copolymers and preparation method |
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- 2012-06-12 CN CN2012101921989A patent/CN102702702A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299393A (en) * | 1998-04-01 | 2001-06-13 | 卡吉尔公司 | Lactic acid residue contg. polymer composition, product method for prepn. and use |
| CN101225222A (en) * | 2008-02-03 | 2008-07-23 | 四川大学 | Polylactic acid as well as derivative composite material and preparation method thereof |
| CN101333332A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polylactic resin toughened and modified by acrylic ester copolymers and preparation method |
Non-Patent Citations (1)
| Title |
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| WEI ZHANG ET AL: "Modified Brittle Poly(lactic acid) by Biodegradable Hyperbranched Poly(ester amide)", 《IRANIAN POLYMER JOURNAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230992A (en) * | 2022-01-20 | 2022-03-25 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
| CN114230992B (en) * | 2022-01-20 | 2022-09-06 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
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Application publication date: 20121003 |