CN104497293A - Biodegradable aliphatic-aromatic copolyester and application thereof - Google Patents
Biodegradable aliphatic-aromatic copolyester and application thereof Download PDFInfo
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- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
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Abstract
The invention discloses a biodegradable aliphatic-aromatic copolyester and application thereof. The biodegradable aliphatic-aromatic copolyester comprises the following components: component 1: an aromatic polyester unit comprising 45-60 mol% of aromatic diacid residues A1 and dihydroxy compound residues B; component 2: a linear aliphatic polyester unit comprising 37-54.7 mol% of linear aliphatic diacid residues A2 and the dihydroxy compound residues B; and component 3: an alkyl-containing side chain aliphatic polyester unit comprising 0.3-3 mol% of alkyl-containing side chain aliphatic diacid residues A3 and the dihydroxy compound residues B. As the biodegradable aliphatic-aromatic copolyester disclosed by the invention comprises the alkyl-containing side chain aliphatic polyester unit, the yield strength of a thin film prepared from the biodegradable aliphatic-aromatic copolyester is improved, thereby being favorable for improving the performance of tolerating puncture of crops and weeds of an agricultural plastic mulching film and reducing the probability of causing a hole breaking phenomenon; and the oxygen transmission rate is improved, the water vapor transmission rate is reduced, and when the prepared thin film is used as the agricultural plastic mulching film, better heat preservation and moisture preservation effects are realized.
Description
Technical field
The invention belongs to polyester technical field, particularly a kind of containing the Biodegradable aliphatic-aromatic copolyester of alkyl group side chain and the application in agricultural film industry thereof.
Background technology
At present, the mulch film great majority used in agriculture production are synthetic polymers, as polyethylene (PE), polyvinyl chloride (PVC) etc.While using these film material to bring certain economic benefit to agricultural, also cause serious white pollution to environment.These materials are the long-term stable existence of meeting in physical environment, remains in the mulch film debris damage Soil structure in soil in a large number, makes soil hardening, and hinder crop from soil, absorb water and fertilizer, life-time service can cause crop production reduction.In addition, reclaim from field that mulch film workload is large, cost is high, and be difficult to mulch film to reclaim completely.Therefore, through accumulating for a long time, mulch film relic greatly can reduce the quality of soil.
Biodegradable polyester can in the physical environment in field, by the effect of water and microorganism, can be degradable in the time about some months to several years, and final product is water and carbonic acid gas, is the ideal material making mulch film.CN1071342C discloses terephthalic acid, hexanodioic acid, the Biodegradable Copolyester that obtains containing sulfonic acid group diprotic acid and glycol copolymerization, it has good biodegradability, but when being used as film material, under crop and weeds effect, easily there is the problems such as holes, cause insulation, humidity-holding effect is undesirable, thus limit the application of Biodegradable polyester mulch film.CN102344556 discloses a kind of biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer, its aromatic polyester prepolymer by difference synthesis of hydroxy end-blocking, hydroxy-end capped aliphatic polyester prepolymer and hydroxy-end capped straight-chain aliphatic polyester prepolyer, then prepare biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer by the mode of chain extension.This multipolymer needs to synthesize three kinds of prepolymers respectively, and preparation process is loaded down with trivial details, is unfavorable for suitability for industrialized production.And this copolyesters is block structure, the tear-resistant intensity of the film made is lower, when reality uses, occurs easily occurring large-area film breaks after holes, thus limits its application in agricultural mulching industry.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of Biodegradable aliphatic-aromatic copolyester.
Another object of the present invention is to provide the application of above-mentioned Biodegradable aliphatic-aromatic copolyester in agricultural mulching industry.
Object of the present invention realizes by following technical solution:
A kind of Biodegradable aliphatic-aromatic copolyester, comprises following component:
Component 1: the aromatic polyester unit be made up of 45 ~ 60mol% aromatic diacid residues A1 and dihydroxy compound residue B;
Component 2: the linear aliphatic adoption ester units be made up of 37 ~ 54.7mol% linear aliphatic race diacid residues A2 and dihydroxy compound residue B;
Component 3: what be made up of containing alkyl group side chain aliphatic diacid residue A 3 and dihydroxy compound residue B 0.3 ~ 3mol% contains alkyl group side chain aliphatic poly ester units.
Described have following structure containing alkyl group side chain aliphatic diacid residue A 3:
Wherein R
1for carbonatoms is the alkyl of 4 ~ 12, R
1in containing carbonatoms be no more than 2 side chain, R
1in containing 0 ~ 1 carbon-carbon double bond, carbon-carbon double bond is at R
1any position; N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤n1+n2≤9.
Described aromatic diacid residues A1 is selected from the one or more kinds of mixtures in terephthalic acid, dimethyl terephthalate (DMT), pure terephthalic acid, m-phthalic acid, phthalic acid residue.
Described linear aliphatic race diacid residues A2 is selected from the Straight chain diatomic acid residue containing 3 ~ 10 carbon atoms, is preferably the mixture of a kind of or two or more residue in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid.
Described dihydroxy compound residue B is selected from the alkyl diol residue of C2 ~ C8, is preferably ethylene glycol, 1,3-PD, 1,4-butyleneglycol, 1,5-pentanediol, 1, the mixture of a kind of or two or more residue in 6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol.
The degree of randomness r of described Biodegradable aliphatic-aromatic copolyester is 0.8 ~ 1.2, and described degree of randomness passes through
1h NMR test result calculations obtains.
The limiting viscosity of described Biodegradable aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, and described limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), and the concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
The melt mass flow rate of described Biodegradable aliphatic-aromatic copolyester is 1 ~ 6g/10min, and described melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg.
The fusing point of described Biodegradable aliphatic-aromatic copolyester is 115
oc ~ 150
oc; Described fusing point records with reference to GB/T 19466.3-2004.
The preparation method of above-mentioned Biodegradable aliphatic-aromatic copolyester:
1) can by conventional vacuum fusion polymerization directly obtained Biodegradable aliphatic-aromatic copolyester;
2) also first can obtain the prepolymer P0 that limiting viscosity is 0.9 ~ 1.1dL/g, then obtain Biodegradable aliphatic-aromatic copolyester by chain extension legal system.Wherein, chainextender can use bifunctional isocyanic ester; Described bifunctional isocyanic ester is selected from the mixture of one or more in 2,6-tolylene diisocyanate, 2,4 toluene diisocyanate, '-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isoflurane chalcone diisocyanate.
Above-mentioned Biodegradable aliphatic-aromatic copolyester can make film, sack etc. by processing modes such as blowings.The film made by Biodegradable aliphatic-aromatic copolyester can be used as agricultural mulching.
The present invention compared with prior art, has following beneficial effect:
1) in Biodegradable aliphatic-aromatic copolyester of the present invention due to add specific proportioning containing alkyl group side chain aliphatic poly ester units, the yield strength of the film made is improved, be conducive to the puncture resistance improving agricultural mulching tolerant crops and weeds, reduce the probability that holes phenomenon occurs;
2) in Biodegradable aliphatic-aromatic copolyester of the present invention because degree of randomness is higher, make the tear-resistant intensity of the film made and fall mark impact damaged quality be improved, be conducive in use procedure, preventing film from occurring holes;
3) OTR oxygen transmission rate of Biodegradable aliphatic-aromatic copolyester of the present invention improves, and water vapor transmission rate (WVTR) reduces, and has better insulation, moisture-keeping function when the film made is used as agricultural mulching.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Now following explanation is done to embodiment and comparative example starting material used, but is not limited to these materials:
Pure terephthalic acid (PTA): premium grads, raises sub-petrochemical industry and produces;
Dimethyl terephthalate (DMT) (DMT): premium grads, Japanese Supreme Being people produces;
BDO (BDO): top grade product, Shanxi three-dimensional is produced;
Hexanodioic acid (AA): top grade product, Daqing petrochemical is produced;
Other raw material, if butyl (tetra) titanate, antioxidant, stablizer, dodecenylsuccinic acid (T746), octenyl Succinic anhydried (ASA), aliphatic dibasic acid, aliphatic dihydroxy alcohol etc. are commercially available technical grade product;
Other alkyl replaces aliphatic diacid and synthesizes with reference to the method for " petrochemical complex " 1993,10, p675 ~ 678.
embodiment 1
By dimethyl terephthalate (DMT) 8.73 Kg, BDO 9 Kg, drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add hexanodioic acid 7.96 Kg, dodecenylsuccinic acid 142 g, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P1.
embodiment 2
Dimethyl terephthalate (DMT) 11.64Kg, BDO 9Kg, hexanodioic acid 5.40Kg, octenyl Succinic anhydried 684g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.High pure nitrogen is filled with in reactor, obtain copolyesters base-material P20 through tie rod, pelletizing after the mold pressing of melt per os being gone out, after P20 is dried, react in twin screw extruder after mixing with 0.6% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P2.
embodiment 3
By pure terephthalic acid 8.3Kg, 1,3-PD 8Kg, drops in reactor, in 230
oc reaction reaches theoretical value to slipping out the water yield, adds hexanodioic acid 7Kg, butenyl succinic acid 344g, continues reaction and reaches theoretical value to slipping out the water yield.Add tetrabutyl titanate 20g, and be warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P3.
embodiment 4
Dimethyl terephthalate (DMT) 10.67Kg, BDO 9Kg, sebacic acid 6.28Kg, octyl group nonane diacid 600g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P4.
embodiment 5
Dimethyl terephthalate (DMT) 9.31Kg, 1,9-nonanediol 16Kg, propanedioic acid 5.3Kg, pentenyl succinic acid 186g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P50 through tie rod, pelletizing, react in twin screw extruder after P50 and 0.8% '-diphenylmethane diisocyanate are mixed, obtain copolyesters through pelletizing and be labeled as P5.
embodiment 6
By dimethyl terephthalate (DMT) 11.64 Kg, BDO 9 Kg, drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add nonane diacid 7.24Kg, octenyl pimelic acid 315 g, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P6.
embodiment 7
Dimethyl terephthalate (DMT) 11.25Kg, 1,8-ethohexadiol 14.6Kg, 1,8-suberic acid 6.87Kg, undecyl succinic acid 680g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P7.
embodiment 8
Dimethyl terephthalate (DMT) 10.09Kg, BDO 9Kg, hexanodioic acid 6.64Kg, octenyl Succinic anhydried 525g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P8.
embodiment 9
Dimethyl terephthalate (DMT) 11.06Kg, BDO 9Kg, hexanodioic acid 5.84Kg, dodecenylsuccinic acid 852g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P9.
embodiment 10
Dimethyl terephthalate (DMT) 11.45Kg, 1,6-hexylene glycol 12Kg, suberic acid 6.97Kg, n-amyl malonic acid 174g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P100 through tie rod, pelletizing.After P100 is dried, react in twin screw extruder after mixing with 0.64% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P10.
embodiment 11
Dimethyl terephthalate (DMT) 10.67Kg, 1,3-PD 8Kg, pentanedioic acid 5.9Kg, decyl suberic acid 807g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P110 through tie rod, pelletizing.After P110 is dried, react in twin screw extruder after mixing with 0.65% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P11.
embodiment 12
Dimethyl terephthalate (DMT) 10.86Kg, 1,5-PD 12Kg, pimelic acid 7Kg, hendecene base pentanedioic acid 85.2g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P120 through tie rod, pelletizing.After P20 is dried, react in twin screw extruder after mixing with 0.67% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P12.
embodiment 13
Dimethyl terephthalate (DMT) 10.48Kg, 1,7-heptanediol 14Kg, succinic acid 5.25Kg, nonyl hexanodioic acid 136g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, and after slipping out first alcohol and water and reaching theoretical amount, be warming up to 230 ~ 250oC gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P130 through tie rod, pelletizing.After P20 is dried, react in twin screw extruder after mixing with 0.68% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P13.
embodiment 14
Dimethyl terephthalate (DMT) 10.3Kg, decamethylene-glycol 18Kg, hexanodioic acid 6.8Kg, heptyl sebacic acid 120g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base-material P130 through tie rod, pelletizing.After P20 is dried, react in twin screw extruder after mixing with 0.68% hexamethylene diisocyanate, obtain copolyesters through pelletizing, be labeled as P14.
comparative example 1
Dimethyl terephthalate (DMT) 9.7Kg, BDO 9Kg, hexanodioic acid 7.3Kg are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP1.
comparative example 2
Dimethyl terephthalate (DMT) 8.73Kg, BDO 9Kg, hexanodioic acid 7.59Kg, succinic acid 354g are dropped in reactor, is warming up to 170 ~ 210 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP2.
comparative example 3
By dimethyl terephthalate (DMT) 11.64 Kg, BDO 9 Kg, drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add hexanodioic acid 5.77Kg, succinic acid 59 g, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP3.
comparative example 4
Dimethyl terephthalate (DMT) 11.67 Kg, BDO 9 Kg are dropped in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add hexanodioic acid 5.99Kg, octenyl succinic acid 1.14Kg, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP4.
comparative example 5
Dimethyl terephthalate (DMT) 10.67 Kg, BDO 9 Kg are dropped in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add hexanodioic acid 6.54Kg, octenyl succinic acid 45.6g, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP5.
comparative example 6
By dimethyl terephthalate (DMT) 9.7Kg, BDO 7Kg drops in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 5 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP4-1.
By hexanodioic acid 7.15Kg, BDO 5Kg drops in reactor, after falling the air in reactor, is warming up to 170 DEG C, adds isopropyl titanate 5 g, be warming up to 180 DEG C gradually and carry out esterification with nitrogen replacement.After the water slipped out reaches theoretical amount, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP4-2.
Octenyl succinic acid 228g, BDO 300g are dropped in reactor, fall the air in reactor with nitrogen replacement after, is warming up to 170 DEG C, adds isopropyl titanate 5 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain copolyesters through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as DP4-3.
In twin screw extruder, carry out chain extending reaction after DP4-1, DP4-2, DP4-3 and 0.7% hexamethylene diisocyanate being mixed, obtain copolyesters through granulation, be labeled as DP6.
The performance data of table 1 copolyesters
Table 2
As can be seen from Table 1 and Table 2, due to add specific proportioning containing alkyl group side chain aliphatic poly ester units, the yield strength that Biodegradable aliphatic-aromatic copolyester obtains is improved, be conducive to the puncture resistance improving agricultural mulching tolerant crops and weeds, reduce the probability that holes phenomenon occurs;
The mark that falls of the copolyesters that random degree is higher impacts damaged quality apparently higher than the higher copolyesters (DP6) of block degree, is conducive to preventing film from occurring holes in use procedure.
The OTR oxygen transmission rate of Biodegradable aliphatic-aromatic copolyester improves, and water vapor transmission rate (WVTR) reduces, and has better insulation, moisture-keeping function when the film made is used as agricultural mulching.
each performance test standard or method:
Limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), copolyesters P concentration is 0.5g/100mL, records with Ubbelohde viscometer.
Copolyesters
1h NMR VARIAN company produces Mercury300 nuclear magnetic resonance spectrometer and records, and solvent is CDCl
3/ CD
3cOOD(9/1).
The degree of randomness of copolyesters passes through
1several sour residue hydrogen atom absorption peak area ratio of H NMR calculates.Method of calculation reference " New Chemical Materials " 2012,40 volume, 12 phases, p85 ~ 93.
Melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg.
Fusing point records with reference to GB/T 19466.3-2004 DSC method.
The Tc of copolyesters and crystalline fusion enthalpy adopt DSC method to measure, and record with reference to GB/T 19466-2004.
Film stretching performance records with reference to GB/T 1040.3-2006.
The tear-resistant intensity of film records with reference to GB/T 16578.2-2009.
Film shock resistance records with reference to GB/T 9639.1-2008.
Pellicular 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 (10)
1. a Biodegradable aliphatic-aromatic copolyester, is characterized in that, comprises following component:
Component 1: the aromatic polyester unit be made up of 45 ~ 60mol% aromatic diacid residues A1 and dihydroxy compound residue B;
Component 2: the linear aliphatic adoption ester units be made up of 37 ~ 54.7mol% linear aliphatic race diacid residues A2 and dihydroxy compound residue B;
Component 3: what be made up of containing alkyl group side chain aliphatic diacid residue A 3 and dihydroxy compound residue B 0.3 ~ 3mol% contains alkyl group side chain aliphatic poly ester units.
2. Biodegradable aliphatic-aromatic copolyester according to claim 1, is characterized in that, described have following structure containing alkyl group side chain aliphatic diacid residue A 3:
Wherein R
1for carbonatoms is the alkyl of 4 ~ 12, R
1in containing carbonatoms be no more than 2 side chain, R
1in containing 0 ~ 1 carbon-carbon double bond, carbon-carbon double bond is at R
1any position; N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤n1+n2≤9.
3. Biodegradable aliphatic-aromatic copolyester according to claim 1, it is characterized in that, described aromatic diacid residues A1 is selected from the one or more kinds of mixtures in terephthalic acid, dimethyl terephthalate (DMT), pure terephthalic acid, m-phthalic acid, phthalic acid residue.
4. Biodegradable aliphatic-aromatic copolyester according to claim 1, it is characterized in that, described linear aliphatic race diacid residues A2 is selected from the Straight chain diatomic acid residue containing 3 ~ 10 carbon atoms, is preferably the mixture of a kind of or two or more residue in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid.
5. Biodegradable aliphatic-aromatic copolyester according to claim 1, it is characterized in that, described dihydroxy compound residue B is selected from the alkyl diol residue of C2 ~ C8, be preferably ethylene glycol, 1,3-PD, BDO, 1,5-pentanediol, 1, the mixture of a kind of or two or more residue in 6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol.
6. Biodegradable aliphatic-aromatic copolyester according to claim 1, is characterized in that, the degree of randomness r of described Biodegradable aliphatic-aromatic copolyester is 0.8 ~ 1.2, and described degree of randomness passes through
1h NMR test result calculations obtains.
7. Biodegradable aliphatic-aromatic copolyester according to claim 1, it is characterized in that, the limiting viscosity of described Biodegradable aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, and described limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), and the concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
8. Biodegradable aliphatic-aromatic copolyester according to claim 1, it is characterized in that, the melt mass flow rate of described Biodegradable aliphatic-aromatic copolyester is 1 ~ 6g/10min, and described melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg.
9. Biodegradable aliphatic-aromatic copolyester according to claim 1, is characterized in that, the fusing point of described Biodegradable aliphatic-aromatic copolyester is 115
oc ~ 150
oc; Described fusing point records with reference to GB/T 19466.3-2004.
10. the application of the Biodegradable aliphatic-aromatic copolyester as described in any one of claim 1 ~ 9 in agricultural mulching industry.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of biodegradable thermoplastic polyester elastomer with side chain and preparation method thereof |
| CN107474230A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
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| CN113683763A (en) * | 2021-10-26 | 2021-11-23 | 江苏金发科技新材料有限公司 | Semi-aromatic polyester and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-12-01 CN CN201410711824.XA patent/CN104497293A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312165A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of biodegradable thermoplastic polyester elastomer with side chain and preparation method thereof |
| CN107312165B (en) * | 2016-04-26 | 2020-04-24 | 中国科学院理化技术研究所 | Degradable thermoplastic polyester elastomer with side chain and preparation method thereof |
| CN111320745A (en) * | 2016-09-09 | 2020-06-23 | 珠海万通化工有限公司 | PBAT resin and preparation method thereof |
| CN107474230A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
| CN107474227A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBST resins and preparation method thereof |
| CN113683763A (en) * | 2021-10-26 | 2021-11-23 | 江苏金发科技新材料有限公司 | Semi-aromatic polyester and preparation method and application thereof |
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