CN102604348A - Degradable resin composition and preparation method thereof - Google Patents
Degradable resin composition and preparation method thereof Download PDFInfo
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- CN102604348A CN102604348A CN2012100626444A CN201210062644A CN102604348A CN 102604348 A CN102604348 A CN 102604348A CN 2012100626444 A CN2012100626444 A CN 2012100626444A CN 201210062644 A CN201210062644 A CN 201210062644A CN 102604348 A CN102604348 A CN 102604348A
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- oxazoline
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Abstract
Disclosed are degradable resin composition and a preparation method thereof. The degradable resin composition can be obtained by melting and mixing polylactic acid (PLA), terephthalic acid-adipic acid-1,4-poly butylene adipate (PBAT), dioxins-like compounds and anhydride-like compounds according a certain proportion. The degradable resin composition prepared has excellent flexibility, high strength, degradability, fine product stability and can be used for fibers and package materials. The degradable resin composition is simple in preparation process and easy to produce.
Description
Technical field
The present invention relates to a kind of POLYACTIC ACID (A component) and terephthalic acid-hexanodioic acid-1 of containing, the degradable resin composition and method of making the same of 4-butyleneglycol three-element copolymerized ester (B component).
Background technology
POLYACTIC ACID (PLA) is a kind of the have good biocompatibility and macromolecular material of biodegradable, under the occurring in nature microbial process, can resolve into water and carbonic acid gas fully, can not produce environment and pollute.PLA is a kind of thermoplastic polymer, can adopt method in common to process, as extrude, moulding, casting, melt spun, solution spin, blowing etc., and are widely used in fields such as health care, clothes, family expenses decoration, industry.But there is poor toughness in POLYACTIC ACID, lacks flexibility and flexibility, and these shortcomings make its application receive certain restriction.
Terephthalic acid-hexanodioic acid-1; 4-butyleneglycol three-element copolymerized ester (PBAT) also belongs to a kind of Biodegradable Polymers; PBAT has good tensile property and snappiness; Utilizing PBAT to carry out toughness reinforcing to PLA also is a kind of effective method for toughening that adopts at present, but the simple blend of PLA/PBAT is the incompatible system of thermodynamics.Therefore, need to introduce expanding material and improve the consistency between them, thereby improve the tensile property of composite blend.
For the PLA/PBAT co-mixing system, existing bibliographical information adopts the epoxies expanding material to carry out increase-volume, as adopts the Lotader AX8900 (" research of AX8900 increase-volume POLYACTIC ACID/PBAT co-mixing system " of French Arkema; Plastics industry, 2009,3:75-77); But; The processing temperature of PLA/PBAT blend is generally 175 ℃, and the compatibilization effect of epoxies expanding material is not good under this temperature, and its improved performance is little.
Summary of the invention
The compounds that oxazoline (Oxazoline) is meant the five-ring heterogeneous ring compound and comprises this type ring, its chemical property is active, can carry out ring-opening reaction with carboxyl, acid anhydrides, amino, epoxy group(ing), coloured glaze base, phenolic hydroxyl group, isocyano etc. at a certain temperature.Therefore the ， bisoxazoline usually can be used as the chainextender or the linking agent of superpolymer, also is a kind of compatilizer of blend polymer simultaneously.As 2,2 '-two-(2-oxazoline) (a), 2,2-(1, the 3-phenylene)-bisoxazolines (1,3-PBO) (b), 2,2 '-(1, the molecular structural formula of 4-phenylene) bisoxazoline (c) is following:
The bisoxazoline compounds has the effect of tangible line style addition chain extension to the chain extending reaction of polyester, and is high with the reactive behavior of terminal carboxyl polyester, and the molecular weight of polyester is improved, and is suitable for reactively blending.
Bisoxazoline is a kind of carboxyl add-on type polyester chainextender, in theory under the melt processing temperature condition, can with the end carboxyl generation chemical reaction of PLA in the blend and PBAT molecule, the molecular chain of polymkeric substance is increased.Because PLA and PBAT not only contain carboxyl but also contain hydroxyl, Er bisoxazoline only with hold carboxyl reaction, can not react with terminal hydroxy group, thereby its compatibilization effect is not good.And the terminal hydroxy group of anhydrides compound and PLA, PBAT reaction generates new carboxyl, therefore, both composite uses can be played better increase-volume chain extension effect as the chainextender of polyester.
Cai Yong bisoxazoline of the present invention and the composite increase-volume PLA/PBAT of anhydrides compound co-mixing system prepare a kind of degradable resin compsn.
Therefore, the purpose of this invention is to provide a kind of PLA/PBAT resin combination that contains bisoxazoline compounds and the composite expanding material of anhydrides compound, this resin combination has good toughness, intensity, processibility and degradability.
Another object of the present invention provides the preparation method of said resin combination.
Said resin combination of the present invention; It is characterized in that including in this kind resin combination the following component of blend: POLYACTIC ACID (A component), terephthalic acid-hexanodioic acid-1; 4-butyleneglycol three-element copolymerized ester (B component) 、 bisoxazoline compounds and anhydrides compound; Wherein, POLYACTIC ACID, terephthalic acid-hexanodioic acid-1, the weight ratio of 4-butyleneglycol three-element copolymerized ester 、 bisoxazoline compounds and anhydrides compound is (95～50): (5～50): (0.1～5): (0.1～5).
Among the present invention in the compsn De bisoxazoline compounds comprise 2,2 '-two (2-oxazolines), 2,2 '-two (4-methyl-2-oxazoline), 2,2 '-two (4-butyl-2-oxazoline), 2; 2 '-(1, the 3-phenylene)-bisoxazolines, 2,2 '-(1; The 4-phenylene)-bisoxazolines, 2,2 '-p-phenylene two (4-methyl-2-oxazoline), 2,2 '-p-phenylene two (4; 4 '-dimethyl--2-oxazoline), 2,2 '-ethylenebis (2-oxazoline), 2,2 '-butylidene two (2-oxazolines), 2; 2 '-hexylidene two (2-oxazoline), 2,2 '-ethylenebis (4-methyl-2-oxazoline), 2,2 '-butylidene two (4; 4 '-dimethyl--2-oxazoline), 2,2 '-cyclohexylene two (2-oxazolines), 2, at least a in 2 '-diphenylene two (4-methyl-2-oxazoline).
Anhydrides compound among the present invention in the compsn comprise Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Jia Qiao-Nei-Tetra Hydro Phthalic Anhydride, methyl first bridge-Nei-Tetra Hydro Phthalic Anhydride, 4-tert-butyl o phthalate anhydride, methyl tetrahydrophthalic anhydride, pyromellitic dianhydride, trimellitic acid 1,2-anhydride, 4,4 '-at least a in the two Tetra hydro Phthalic anhydrides of oxygen, UVNUL MS-40 tetracarboxylic acid dicarboxylic anhydride, terephthalic anhydride.
In the preparation process, the blending temperature of material is the temperature of the used melt blending of PLA plastic working in the prior art, can decide according to the melt temperature of matrix PLA, selects in the scope that should not only guarantee the complete fusion of PLA plastics but also PLA is decomposed.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent of PLA plastic working in right amount.The employed melt blending equipment of present method is the general blending equipment of rubber and plastic processing industry kind, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
The present invention also provide a kind of preparation method of this resin combination.
Beneficial effect of the present invention:
(1) tensile property of the prepared resin combination of the present invention is better than the tensile property that does not add any chain-expanding agent, also is better than the tensile property of independent interpolation bisoxazoline compounds, and this resin combination is used for various moulding article.
(2) this method technology is simple, easy handling
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention does not receive the restriction of these embodiment.
Scope of the present invention proposes in claims.
Embodiment 1:
POLYACTIC ACID (Natural Works produces, trade mark 2002D), terephthalic acid-hexanodioic acid-1, (the prosperous rich medicine company production of Zhejiang Hangzhou of 4-butyleneglycol three-element copolymerized ester; The Biocosafe resin), 2; 2 '-two-(2-oxazoline) (Wuhan one-tenth far away is created Science and Technology Ltd.) and Tetra hydro Phthalic anhydride (ltd is learned in fluorine Dehua, Shanghai) mix, it specifically consists of: 80 parts of POLYACTIC ACIDs, terephthalic acid-hexanodioic acid-1; 20 parts of 4-butyleneglycol three-element copolymerized esters; 2,2 '-two-(2-oxazoline) 1 part, 0.5 part of Tetra hydro Phthalic anhydride.Times Long Keya Nanjing machinery CTE35 of the ltd twin screw extruder blend granulation of employing section, each section of forcing machine temperature is respectively: 160 ℃, 170 ℃, 175 ℃, 175 ℃, 175 ℃ and 170 ℃ (head temperature).Pellet is processed the standard batten through injection, carries out the tensile property test, and its result is as shown in table 1.
Embodiment 2:
Remove with the Tetra hydro Phthalic anhydride among the embodiment 11 especially, all the other conditions are identical with embodiment 1.The pellet that melt blending obtains is processed the standard batten through injection, carries out the tensile property test, and the result lists in table 1.
Embodiment 3:
Remove with the Tetra hydro Phthalic anhydride among the embodiment 12 especially, all the other conditions are identical with embodiment 1.The pellet that melt blending obtains is processed the standard batten through injection, carries out the tensile property test, and the result lists in table 1.
Embodiment 4:
POLYACTIC ACID (Natural Works produces, trade mark 2002D), terephthalic acid-hexanodioic acid-1, (the prosperous rich medicine company production of Zhejiang Hangzhou of 4-butyleneglycol three-element copolymerized ester; The Biocosafe resin), 2; 2 '-two-(2-oxazoline) (Wuhan one-tenth far away is created Science and Technology Ltd.) and pyromellitic dianhydride (ltd is learned in fluorine Dehua, Shanghai) mix, it specifically consists of: 70 parts of POLYACTIC ACIDs, terephthalic acid-hexanodioic acid-1; 30 parts of 4-butyleneglycol three-element copolymerized esters; 2,2 '-two-(2-oxazoline) 3 parts, 1 part of pyromellitic dianhydride.Times Long Keya Nanjing machinery CTE35 of the ltd twin screw extruder blend granulation of employing section, each section of forcing machine temperature is respectively: 160 ℃, 170 ℃, 175 ℃, 175 ℃, 175 ℃ and 170 ℃ (head temperature).Pellet is processed the standard batten through injection, carries out the tensile property test, and its result is as shown in table 1.
Embodiment 5:
Remove with the pyromellitic dianhydride among the embodiment 43 especially, all the other conditions are identical with embodiment 4.The pellet that melt blending obtains is processed the standard batten through injection, carries out the tensile property test, and the result lists in table 1.
Comparative example 1:
(Natural Works produces POLYACTIC ACID; Trade mark 2002D) with terephthalic acid-hexanodioic acid-1; 4-butyleneglycol three-element copolymerized ester (the prosperous rich medicine company production of Zhejiang Hangzhou, Biocosafe resin) mix, it specifically consists of: 80 parts of POLYACTIC ACIDs; Terephthalic acid-hexanodioic acid-1,20 parts of 4-butyleneglycol three-element copolymerized esters.Times Long Keya Nanjing machinery CTE35 of the ltd twin screw extruder blend granulation of employing section, each section of forcing machine temperature is respectively: 160 ℃, 170 ℃, 175 ℃, 175 ℃, 175 ℃ and 170 ℃ (head temperature).Pellet is processed the standard batten through injection, carries out the tensile property test, and its result is as shown in table 1.
Comparative example 2:
POLYACTIC ACID (Natural Works produces, trade mark 2002D) and terephthalic acid-hexanodioic acid-1, (the prosperous rich medicine company production of Zhejiang Hangzhou of 4-butyleneglycol three-element copolymerized ester; The Biocosafe resin) and 2,2 '-two-(2-oxazoline) (Wuhan far away become to create Science and Technology Ltd.) mix, it specifically consists of: 80 parts of POLYACTIC ACIDs; Terephthalic acid-hexanodioic acid-1; 20 parts of 4-butyleneglycol three-element copolymerized esters, 2,2 '-two-(2-oxazoline) 1 part.Times Long Keya Nanjing machinery CTE35 of the ltd twin screw extruder blend granulation of employing section, each section of forcing machine temperature is respectively: 160 ℃, 170 ℃, 175 ℃, 175 ℃, 175 ℃ and 170 ℃ (head temperature).Pellet is processed the standard batten through injection, carries out the tensile property test, and its result is as shown in table 1.
Comparative example 3:
Remove and to change the POLYACTIC ACID in the comparative example 2 into 70 parts, terephthalic acid-hexanodioic acid-1,4-butyleneglycol three-element copolymerized ester changes 30 parts into, 2,2 '-two-(2-oxazoline) 3 especially, all the other conditions are identical with comparative example 2.The pellet that melt blending obtains is processed the standard batten through injection, carries out the tensile property test, and the result lists in table 1.
Compare with comparative example 2 (only adding 1 part of chain-expanding agent-bisoxazoline compounds) with comparative example 1 (not adding chain-expanding agent); Owing to add Tetra hydro Phthalic anhydride among the embodiment 1, embodiment 2, embodiment 3 with bisoxazoline compounds composite; Tensile strength among the embodiment 1 changes little, and tension fracture elongation rate improves, and; Increase the umber of Tetra hydro Phthalic anhydride, its modified effect is constant.Compare with comparative example 3 (only adding 3 parts of chain-expanding agent-bisoxazoline compounds), owing to add pyromellitic dianhydride among embodiment 4 and the embodiment 5 with bisoxazoline compounds composite, its tensile strength changes little, and tension fracture elongation rate obviously improves.
Table 1
Claims (7)
1.1 degradable resin compsn, its characteristic comprise POLYACTIC ACID (A component), terephthalic acid-hexanodioic acid-1,4-butyleneglycol three-element copolymerized ester (B component) 、 bisoxazoline compounds and anhydrides compound.
2. degradable resin compsn according to claim 1 wherein, adds up to 100 weight parts with respect to A component and B component, contains 50～95 parts of A components.
3. degradable resin compsn according to claim 1 wherein, adds up to 100 weight parts with respect to A component and B component, contains 0.5～5 part of bisoxazoline compounds component.
4. degradable resin compsn according to claim 1 wherein, adds up to 100 weight parts with respect to A component and B component, contains 0.5～5 part of anhydrides compound component.
5. degradable resin compsn according to claim 1 is characterized in that De bisoxazoline compounds comprises 2 in the compsn, 2 '-two (2-oxazolines), 2; 2 '-two (4-methyl-2-oxazoline), 2,2 '-two (4-butyl-2-oxazoline), 2,2 '-(1; The 3-phenylene)-bisoxazolines, 2,2 '-(1, the 4-phenylene)-bisoxazolines, 2; 2 '-p-phenylene two (4-methyl-2-oxazoline), 2,2 '-p-phenylene two (4,4 '-dimethyl--2-oxazoline), 2; 2 '-ethylenebis (2-oxazoline), 2,2 '-butylidene two (2-oxazoline), 2,2 '-hexylidene two (2-oxazoline), 2; 2 '-ethylenebis (4-methyl-2-oxazoline), 2,2 '-butylidene two (4,4 '-dimethyl--2-oxazoline), 2; 2 '-cyclohexylene two (2-oxazolines), 2, at least a in 2 '-diphenylene two (4-methyl-2-oxazoline).
6. degradable resin compsn according to claim 1; It is characterized in that anhydrides compound in the compsn comprise Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Jia Qiao-Nei-Tetra Hydro Phthalic Anhydride, methyl first bridge-Nei-Tetra Hydro Phthalic Anhydride, 4-tert-butyl o phthalate anhydride, methyl tetrahydrophthalic anhydride, pyromellitic dianhydride, trimellitic acid 1,2-anhydride, 4,4 '-at least a in the two Tetra hydro Phthalic anhydrides of oxygen, UVNUL MS-40 tetracarboxylic acid dicarboxylic anhydride, terephthalic anhydride.
7. according to the described degradable resin preparation of compositions of one of claim 1～6 method; It is characterized in that with polylactic resin, terephthalic acid-hexanodioic acid-1 4-butyleneglycol three-element copolymerized ester 、 bisoxazoline compounds and anhydrides compound melt blending make the degradable resin compsn.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304958A (en) * | 2013-05-14 | 2013-09-18 | 泉州特米斯高环保科技有限公司 | Production method of biodegradable resin |
| CN108102323A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of complete biodegradable refuse bag and preparation method thereof |
| CN113462002A (en) * | 2021-06-29 | 2021-10-01 | 北京化工大学常州先进材料研究院 | Preparation method of degradable flame-retardant foamed beads |
| CN115678083A (en) * | 2022-11-17 | 2023-02-03 | 苏州和塑美科技有限公司 | Preparation method of PBAT high-resilience sheet with adjustable multiplying power and product thereof |
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- 2012-03-12 CN CN2012100626444A patent/CN102604348A/en active Pending
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| CN101245178A (en) * | 2008-03-06 | 2008-08-20 | 同济大学 | Method for manufacturing biologically degradable polyester composite material with capacity increasing function |
| WO2011054892A1 (en) * | 2009-11-05 | 2011-05-12 | Novamont S.P.A. | Mixtures of biodegradable polyesters with at least one polymer of natural origin |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304958A (en) * | 2013-05-14 | 2013-09-18 | 泉州特米斯高环保科技有限公司 | Production method of biodegradable resin |
| CN108102323A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of complete biodegradable refuse bag and preparation method thereof |
| CN113462002A (en) * | 2021-06-29 | 2021-10-01 | 北京化工大学常州先进材料研究院 | Preparation method of degradable flame-retardant foamed beads |
| CN115678083A (en) * | 2022-11-17 | 2023-02-03 | 苏州和塑美科技有限公司 | Preparation method of PBAT high-resilience sheet with adjustable multiplying power and product thereof |
| CN115678083B (en) * | 2022-11-17 | 2023-09-19 | 苏州和塑美科技有限公司 | Preparation method of PBAT high-resilience sheet with adjustable multiplying power and product thereof |
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Application publication date: 20120725 |