CN104479317B - A kind of Biodegradable aliphatic-aromatic copolyester compositions and application thereof - Google Patents
A kind of Biodegradable aliphatic-aromatic copolyester compositions and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of biodegradable fatty race aromatic copolyester compositions and application thereof, by mass percentage, comprise following components: A:60% ~ 89% contains alkyl/alkyloxy side chain aliphatic aromatic copolyesters；B:10% ~ 39% thermoplastic starch；C:1% ~ 10% polyhydric alcohol；Described A by mass percentage, comprises following components: A1:44% ~ 60% aromatic polyester unit；A2:39% ~ 55% straight-chain aliphatic polyester unit；A3:0.3% ~ 3% contains alkyl/alkyloxy side chain fatty group dibasic acid unit；In the biodegradable fatty race aromatic copolyester compositions of the present invention due to add specific proportioning containing alkyl/alkyloxy side chain fatty group dibasic acid unit, the yield strength making the thin film made is improved, be conducive to improving agricultural mulching tolerant crops and the puncture resistance of weeds, reduce the probability that holes phenomenon occurs；And OTR oxygen transmission rate improves, moisture-vapor transmission reduces, and the thin film made is used as during agricultural mulching have preferably insulation, moisture-keeping function.
Description
Technical field
The invention belongs to polymer blend technical field, particularly to a kind of biodegradation containing alkyl/alkyloxy side chain
Aliphatic-aromatic copolyester compositions and the application in agricultural film industry thereof.
Background technology
At present, the mulch film great majority used in agricultural production are synthetic polymers, such as polyethylene (PE), polrvinyl chloride
(PVC) etc..While using these film material to bring certain economic benefit to agricultural, also cause serious to environment
White pollution.These materials are the long-term stable existence of meeting in natural environment, remains in the mulch film debris damage soil in soil in a large number
Earth structure, makes soil hardening, hinders crop to absorb water and fertilizer from soil, and life-time service causes crop production reduction.From Tanaka
Mulch film workload is big, cost is high in recovery, and is difficult to reclaim mulch film completely.Through long-time accumulation, mulch film relic can drop significantly
The quality of low soil, causes serious pollution to environment.Biodegradable plastic can comparatively fast be degraded in natural environment, finally produces
Thing is water and carbon dioxide, is the effective way solving plastic refuse environmental pollution, causes the extensive concern of people.
At present, biodegradable plastic mainly has following several: the equal polyester of biodegradation, such as polyhydroxyalkanoate, poly-breast
Hydroxybutyl ester sour, poly-, polycaprolactone；Biodegradable Copolyester, as poly butylene succinate, poly butylene succinate-
Co-tetramethylene adipate, according to p-phthalic acid butanediol-co-poly adipate succinic acid ester etc.；Or there is polysaccharide structures
Natural product, such as thermoplastic starch, cellulose acetate etc..Above-mentioned degradative plastics has a good biodegradability, but due to
Certain defect himself is had to limit and be used alone.By blending and modifying, choose the suitable biodegradation material of performance, and
Regulating the proportioning between each component, the material taking suitable process exploitation to meet use requirement is that current biological degradable material grinds
One of focus studied carefully.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention be to provide one containing alkyl/
The Biodegradable aliphatic-aromatic copolyester compositions of alkyloxy side chain.
Another object of the present invention is to provide above-mentioned biodegradable fatty race-aromatic series containing alkyl/alkyloxy side chain common
Polymer blend application in agricultural mulching industry.
The purpose of the present invention realizes by following technical solution:
A kind of Biodegradable aliphatic-aromatic copolyester compositions, by mass percentage, comprises following components:
A: containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester 60% ~ 89%；
B: thermoplastic starch 10% ~ 39%；
C: polyhydric alcohol 1% ~ 10%；
Described A by mass percentage, comprises following components:
A1: aromatic polyester unit 44% ~ 60%；
A2: straight-chain aliphatic polyester unit 39% ~ 55%；
A3: containing alkyl/alkyloxy side chain fatty group dibasic acid unit 0.3% ~ 3%.
Described A3 is to react prepared containing alkyl/alkyloxy side chain aliphatic dibasic acid or ester with dihydroxy compounds；Institute
State and containing alkyl/alkyloxy side chain aliphatic dibasic acid there is following structure:
Wherein R1For alkyl or alkoxyl；
R1During for alkyl, R1For the alkyl of C4 ~ C12, R1 can be less than containing carbon number the side chain of 2, R1In contain
0 ~ 1 carbon-carbon double bond, carbon-carbon double bond can be at R1Any position；N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤
n1+n2≤9；
R1During for alkoxyl, there is following structure:
Wherein R3For the one in hydrogen atom, methyl or ethyl, a is the integer of 2 ~ 4, and b is the integer of 1 ~ 6, and 4≤
a×b≤12。
Described A1 is that aromatic acid or ester react with dihydroxy compounds and prepare；Described aromatic acid is selected from
One or more kinds of mixture in p-phthalic acid, M-phthalic acid, phthalic acid or its carboxylate.
Described A2 is that straight-chain aliphatic binary acid or ester react with dihydroxy compounds and prepare；Described straight-chain aliphatic two
Unit's acid is selected from the Straight chain diatomic acid containing 3 ~ 10 carbon atoms, preferably malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, heptan two
One or more kinds of mixture in acid, suberic acid, Azelaic Acid, decanedioic acid.
Described dihydroxy compounds is selected from the alkyl diol of C2 ~ C6, preferably ethylene glycol, 1,3-PD, Isosorbide-5-Nitrae-fourth two
One or more kinds of mixture in alcohol, 1,5-pentanediol, 1,6-HD.
Described thermoplastic starch is selected from deriving from the native starch of plant and/or using physics or chemical method by natural
Starch after starch conversion；The described native starch of plant that derives from is selected from potato starch, tapioca, corn starch, rice
One or more kinds of mixture in starch, rye starch, wheaten starch；Described use physics or chemical method will
Native starch modified starch one or two kinds of in branched starch, cationic starch, Oxytarch, crosslinked starch
Above mixture.
Described polyhydric alcohol selected from glycerol, polyglycereol, trimethylolpropane, ethylene glycol, propylene glycol, butanediol, neopentyl glycol,
Tetramethylolmethane, sorbitol, the oligomer of xylitol and/or polymer；Described polyhydric alcohol uses as plasticizer.
The described degree of randomness containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 0.8 ~ 1.2, described degree of randomness
Obtained by 1H NMR test result calculations, method of testing reference computational methods reference " New Chemical Materials " volume 2012,40,12
Phase, p85 ~ 93.
The described intrinsic viscosity containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, described
Intrinsic viscosity records with reference to GB/T1632.5-2008, and test temperature is 25oC, solvent is phenol/o-dichlorohenzene (60/40, wt/
Wt), the concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
The described melt mass flow rate containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 2 ~ 5g/
10min, described melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190oC, load is 2.16Kg.
The described fusing point containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 115oC~150oC；Described fusing point is joined
Record according to GB/T 19466.3-2004.
The above-mentioned preparation method containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester:
1) Biodegradable aliphatic-aromatic copolyester can directly be prepared by conventional vacuum fusion polymerization；
2) can also first prepare the prepolymer P0 that intrinsic viscosity is 0.9 ~ 1.1dL/g, then obtain biological by chain extension legal system
Degrading aliphatic-aromatic copolyester.Wherein, chain extender can use difunctional isocyanates；Described difunctional isocyanide
Acid esters is selected from 2,6-toluene di-isocyanate(TDI), 2,4 toluene diisocyanate, '-diphenylmethane diisocyanate, 1,6-hexa-methylene
The mixture of one or more in diisocyanate, isoflurane chalcone diisocyanate.
The preparation method of described Biodegradable aliphatic-aromatic copolyester compositions:
By above-mentioned containing the thermoplastic starch after alkyl/alkyloxy side chain aliphatic-aromatic copolyester, drying and polyhydric alcohol
In high mixer after mixing, add in double screw extruder with weighing balance, in 170 ~ 220oThe i.e. available biology fall of C extruding pelletization
Solve aliphatic-aromatic copolyester compositions.
Can be containing the stabilizer of not more than 1% in Biodegradable aliphatic-aromatic copolyester compositions, stabilizer selects
More than the one or two kinds of in Hinered phenols stabilizer, phosphite-type stabilisers, amines stabilizer, thioether class stabilizer
Mixture.
Above-mentioned Biodegradable aliphatic-aromatic copolyester compositions can by the processing modes such as blowing make thin film,
Sack etc..The thin film made by Biodegradable aliphatic-aromatic copolyester compositions can serve as agricultural mulching.
The present invention compared with prior art, has the advantages that
1) in the Biodegradable aliphatic-aromatic copolyester compositions of the present invention due to add specific proportioning containing alkane
Base/alkyloxy side chain fatty group dibasic acid unit so that the yield strength of the thin film made is improved, and is conducive to improving agriculture
With mulch film tolerant crops and the puncture resistance of weeds, reduce the probability that holes phenomenon occurs；
2) the tear-resistant intensity of the thin film that the Biodegradable aliphatic-aromatic copolyester compositions of the present invention is made and falling
The damaged quality of mark impact is improved, and prevents thin film from holes occur during being conducive to using；
3) OTR oxygen transmission rate of the Biodegradable aliphatic-aromatic copolyester compositions of the present invention improves, and steam is saturating
Rate of crossing reduces, and the thin film made is used as during agricultural mulching have preferably insulation, moisture-keeping function.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
Now the raw material used by embodiment and comparative example is done as described below, but is not limited to these materials:
P-phthalic acid (PTA): high-class product, raises sub-petrochemical industry and produces；
Dimethyl terephthalate (DMT) (DMT): high-class product, Japan Supreme Being people produces；
BDO (BDO): top grade product, Shanxi three-dimensional is produced；
Adipic acid (AA): top grade product, Daqing petrochemical is produced；
Thermoplastic starch (TPS): purchased from National Starch；
Polyol plasticiser is commercially available analytical pure；
Synthesize with reference to the method for " petrochemical industry " 1993,10, p675 ~ 678 containing alkyl/alkyloxy side chain aliphatic diacid
Other raw material, if titanate catalyst, stabilizer etc. are commercially available technical grade product.
Preparation containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester A:
Embodiment A1
By dimethyl terephthalate (DMT) 8.73 Kg, BDO 9 Kg, put in reactor, use nitrogen displacement reaction
After air in still, it is warming up to 170 DEG C, after dimethyl terephthalate (DMT) is completely melt, adds isopropyl titanate 10 g, gradually
It is warming up to 180 DEG C and carries out esterification.After the methanol slipped out reaches theoretical amount, add adipic acid 7.96 Kg, laurylene base fourth
Diacid 142 g, continues reaction to slipping out after water reaches theoretical amount, adds isopropyl titanate 10g, be gradually heating to 230 ~ 250 DEG C,
Reacting kettle inner pressure is reduced to below 60Pa by about 30min, and continuation reaction reaches to set to stirring motor power with this understanding
Definite value.In reactor, it is filled with high pure nitrogen, obtains containing alkyl/alkoxyl side through tie rod, pelletizing after melt per os is molded out
Chain fatty race-aromatic copolyester.
Embodiment A2
By dimethyl terephthalate (DMT) 11.64Kg, 1,4-butanediol 9Kg, adipic acid 5.40Kg, octenyl succinic anhydride
630g puts in reactor, is gradually heating to 170oC, adds tetrabutyl titanate 20g, and first alcohol and water to be slipped out reaches theoretical amount
After, it is gradually heating to 230 ~ 250oReacting kettle inner pressure is reduced to below 60Pa by C, about 30min, and continues anti-with this understanding
Setting value should be reached to stirring motor power；In reactor, be filled with high pure nitrogen, after melt per os is molded out through tie rod, cut
Grain obtains copolyesters base material A 20；After A20 is dried, at double screw extruder after mixing with 0.6% hexamethylene diisocyanate
Middle reaction, obtains containing alkyl side chain aliphatic-aromatic copolyester through pelletizing.
The middle aromatic acid that feeds intake, aliphatic dibasic acid is changed fatty with containing alkyl/alkyloxy side chain by the proportioning of table 1
The ratio of race's diacid, according to above-described embodiment A1 or the preparation method of embodiment A2, can prepare different containing alkyl/alkane
Epoxide pendent fatty race-aromatic copolyester A.
Table 1 contains proportioning and the performance test results of alkyl/alkyloxy side chain aliphatic-aromatic copolyester A
Wherein, the preparation method of B4 is: prepare polybutylene terephthalate (PBT) prepolymer, polyadipate fourth the most respectively
Diol ester prepolymer, the prepolymer of poly-dodecenylsuccinic acid butanediol, be subsequently adding hexamethylene diisocyanate at double spiral shells
Bar extruder carries out chain extending reaction prepare.
Embodiment 1 ~ 9 and comparative example 1 ~ 4:
By the proportioning of table 2 by containing the thermoplastic starch after alkyl/alkyloxy side chain aliphatic-aromatic copolyester A, drying
After mixing in high mixer with the polyhydric alcohol as plasticizer, add in double screw extruder with weighing balance, in 170 ~ 220oC squeezes
Go out pelletize and obtain Biodegradable aliphatic-aromatic copolyester compositions.
The proportioning of table 2 Biodegradable aliphatic-aromatic copolyester compositions P
The performance test results of table 3 Biodegradable aliphatic-aromatic copolyester compositions P
From table 2 and table 3 it can be seen that due to add specific proportioning containing alkyl/alkyloxy side chain aliphatic dibasic acid
Ester units, the thin film yield strength that Biodegradable aliphatic-aromatic copolyester compositions prepares is improved, and is conducive to improving
Agricultural mulching tolerant crops and the puncture resistance of weeds, reduce the probability that holes phenomenon occurs；And the thin film that said composition prepares
Tear-resistant intensity and the mark damaged quality of impact that falls be improved, prevent thin film from holes occurring during being conducive to using；
The OTR oxygen transmission rate of Biodegradable aliphatic-aromatic copolyester compositions improves, and moisture-vapor transmission reduces, system
The thin film become is used as during agricultural mulching have preferably insulation, moisture-keeping function.
Each performance test standard or method:
Intrinsic viscosity records with reference to GB/T1632.5-2008, and test temperature is 25oC, solvent is phenol/o-dichlorohenzene
(60/40, wt/wt), copolyesters A concentration is 0.5g/100mL, records with Ubbelohde viscometer；
Copolyesters1H NMR VARIAN company Mercury300 nuclear magnetic resonance chemical analyser records, and solvent is CDCl3/
CD3COOD(9/1)；
The degree of randomness of copolyesters A by1H NMR test result calculations obtains, and method of testing is with reference to computational methods reference " chemical industry
New material " volume 2012,40,12 phases, p85 ~ 93；
Melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190oC, load is 2.16Kg；
Fusing point records with reference to GB/T 19466.3-2004；
Film stretchability can record with reference to GB/T 1040.3-2006；
The tear-resistant intensity of thin film records with reference to GB/T 16578.2-2009；
Thin film shock resistance records with reference to GB/T 9639.1-2008；
Film water vapor transmission rates records with reference to ASTM F 1249；
Thin-films Oxygen vapor permeability records with reference to ASTM D 3985.
Film thickness records with reference to GB/T 20220-2006.
Claims (14)
1. a Biodegradable aliphatic-aromatic copolyester compositions, it is characterised in that by mass percentage, comprise with
Lower component:
A: containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester 60% ~ 89%；
B: thermoplastic starch 10% ~ 39%；
C: polyhydric alcohol 1% ~ 10%；
Described A by mass percentage, comprises following components:
A1: aromatic polyester unit 44% ~ 60%；
A2: straight-chain aliphatic polyester unit 39% ~ 55%；
A3: containing alkyl/alkyloxy side chain fatty group dibasic acid unit 0.3% ~ 3%.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described A3
For reacting prepared containing alkyl/alkyloxy side chain aliphatic dibasic acid or ester with dihydroxy compounds；Described containing alkyl/alkoxyl
Pendent fatty race binary acid has a following structure:
Wherein R1For alkyl or alkoxyl；
R1During for alkyl, R1For the alkyl of C4 ~ C12, R1In can containing carbon number less than 2 side chain, R1In containing 0 ~ 1
Carbon-carbon double bond, carbon-carbon double bond can be at R1Any position；N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤n1+n2
≤9；
R1During for alkoxyl, there is following structure:
Wherein R3For the one in methyl or ethyl, a is the integer of 2 ~ 4, and b is the integer of 1 ~ 6, and 4≤a × b≤12.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described A1
React prepared for aromatic acid or ester with dihydroxy compounds；Described aromatic acid selected from p-phthalic acid,
One or more kinds of mixture in phthalic acid, phthalic acid.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described A2
React prepared for straight-chain aliphatic binary acid or ester with dihydroxy compounds；Described straight-chain aliphatic binary acid selected from containing 3 ~
The Straight chain diatomic acid of 10 carbon atoms.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 4, it is characterised in that described directly
Chain fatty race binary acid is in malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid
One or more kinds of mixture.
6., according to the Biodegradable aliphatic-aromatic copolyester compositions described in any one of claim 2 ~ 5, its feature exists
In, described dihydroxy compounds is selected from the alkyl diol of C2 ~ C6.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 6, it is characterised in that described two
Hydroxy compounds one in ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, the 1,6-HD or
Two or more mixture.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described heat
Plastic starch is selected from deriving from the native starch of plant and/or using physics or chemical method by shallow lake modified for native starch
Powder；The described native starch deriving from plant selected from potato starch, tapioca, corn starch, rice starch, rye starch,
One or more kinds of mixture in wheaten starch；Described use physics or chemical method are modified by native starch
The starch one or more kinds of mixture in branched starch, cationic starch, Oxytarch, the crosslinked starch.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described many
Unit's alcohol is selected from glycerol, trimethylolpropane, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, tetramethylolmethane, sorbitol, xylose
One or more kinds of mixture in alcohol and oligomer thereof and/or polymer.
Biodegradable aliphatic-aromatic copolyester compositions the most according to claim 1, it is characterised in that described contain
The degree of randomness of alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 0.8 ~ 1.2, and described degree of randomness is by 1H NMR test knot
Fruit is calculated, computational methods reference " New Chemical Materials " volume 2012,40 of test result, 12 phases, p85 ~ 87 and page 93.
11. Biodegradable aliphatic-aromatic copolyester compositionss according to claim 1, it is characterised in that described contain
The intrinsic viscosity of alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, and described intrinsic viscosity is with reference to GB/
T1632.5-2008 records, and test temperature is 25oC, solvent is 60 percentage by weight phenol/40 percentage by weight o-dichlorohenzenes,
The concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
12. Biodegradable aliphatic-aromatic copolyester compositionss according to claim 1, it is characterised in that described contain
The melt mass flow rate of alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 2 ~ 5g/10min, described melt quality
Flow rate records with reference to GB/T 3682-2000, and temperature is 190oC, load is 2.16Kg.
13. Biodegradable aliphatic-aromatic copolyester compositionss according to claim 1, it is characterised in that described contain
The fusing point of alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 115oC~150oC；Described fusing point is with reference to GB/T
19466.3-2004 record.
The 14. Biodegradable aliphatic-aromatic copolyester compositionss as described in any one of claim 1 ~ 13 are at agricultural mulching
Application in industry.
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| CN102344556A (en) * | 2011-08-08 | 2012-02-08 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
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