CN101597373A - The processing method of preparation aliphatic copolyester - Google Patents
The processing method of preparation aliphatic copolyester Download PDFInfo
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- CN101597373A CN101597373A CNA2008101111129A CN200810111112A CN101597373A CN 101597373 A CN101597373 A CN 101597373A CN A2008101111129 A CNA2008101111129 A CN A2008101111129A CN 200810111112 A CN200810111112 A CN 200810111112A CN 101597373 A CN101597373 A CN 101597373A
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Abstract
A kind of aliphatic copolyester and preparation method thereof, relating to a series of is copolyesters of monomer polymerization and preparation method thereof with aliphatic dibasic acid and aliphatic dihydroxy alcohol A and dibasic alcohol B, belongs to multicomponent copolyester product and preparation method's technical field.Wherein, dibasic alcohol A is alkane or the cycloalkanes dibasic alcohol that only contains straight chained alkyl, and dibasic alcohol B is alkane or the cycloalkanes dibasic alcohol that contains branched-chain alkyl.The present invention adopts the efficient catalytic system, need not chain extending reaction and prepares weight-average molecular weight and reach 200,000 biodegradable copolyesters.
Description
Technical field
The invention belongs to the condensation polymerization legal system and be equipped with the method field of fully biodegradable copolyesters.Relating to a kind of is monomeric with aliphatic dibasic acid and dibasic alcohol and the dibasic alcohol that contains alkyl branches, prepares the method for high molecular diprotic acid dibasic alcohol copolyesters.
Background technology
The fully biodegradable polymer materials is considered to solve one of main path of " white pollution " problem that is on the rise that the conventional plastic goods cause always at recent two decades.Aliphatic polyester is to study maximum fully biodegradable polymer materialss at present.Condensation polymerization method synthetic is the polyester of main polymerization single polymerization monomer with aliphatic dibasic acid and aliphatic dihydroxy alcohol,, can carry out molecular designing, can reduce production costs, be expected in some field to substitute conventional plastic, alleviate the problem of environmental pollution that causes by conventional plastic.
In biodegradable diprotic acid dibasic alcohol polyester: poly-succinic fourth diester (PBS) fusing point is higher, has mechanical property and favorable biological degradability preferably, and it can finally be converted into carbonic acid gas and water under the effect of bacterium or enzyme.Eighties of last century nineties, Japanese Showa highpolymer company is at first with Succinic Acid, 1, and the 4-butyleneglycol is a raw material, adopts the synthetic method of vulcabond chain extension, has developed biodegradable polyesters Bionolle, is mainly used to Production and Packaging bottle, film etc.
In order to expand the range of application of PBS, often take the method for copolymerization or blend to carry out modification.Japan Showa highpolymer company is with hexanodioic acid and Succinic Acid, 1, and the 4-butyleneglycol carries out copolymerization, obtains the better PBSA polyester of tensile property and degradation property, and trade(brand)name Bionolle 3001.Germany BASF AG, with hexanodioic acid, terephthalic acid, 1, the copolymerization of 4-butyleneglycol obtains Biodegradable polyester Ecoflex, can be used for fields such as injection moulding, blown film.Lin Xiangchun etc. have synthesized Succinic Acid, terephthalic acid and 1, the series copolymer of 4-butyleneglycol, raising with terephthaldehyde's acid content, tensile property and notch shock performance all increase, (the Lin Xiangchun but degradation property descends to some extent, Journal of Korean ChemicalSociety, 1996,40:1-9).Guo Baohua etc. are that raw material directly carries out melt polymerization with diprotic acid, dibasic alcohol and the diprotic acid that contains side chain, obtain weight-average molecular weight 40,000-50,000 copolyesters (CN200610012284.1).In addition, also has the copolymerization of poly butylene succinate and ethylene glycol, hexylene glycol or 1,4 cyclohexane dimethanol.Though elongation at break and biological degradability significantly improve, fusing point and tensile strength etc. all descend to some extent.
Summary of the invention
The objective of the invention is to poly butylene succinate (PBS) at present homopolymerization and some limitation on the copolymer material performance thereof, a kind of have practical value and the lower biodegradable copolyesters of preparation cost are provided.
Another order of the present invention is to provide a kind of processing method of capable of being industrialized, the described biodegradable copolyester of preparation that need not chain extending reaction.
Biodegradable copolyesters of the present invention is that the dibasic alcohol B of binary aliphatic acid mixture and a kind of aliphatic dihydroxy alcohol A and a kind of containg branched alkyl radical carries out copolymerization, finally obtains linear copolyester.Wherein, the binary aliphatic acid mixture is the mixing of any two kinds of aliphatic dibasic acids, and its mol ratio can be regulated arbitrarily in 0: 100 to 100: 0 scope.The mol ratio of the dibasic alcohol of aliphatic dihydroxy alcohol and containg branched alkyl radical can be regulated arbitrarily in 1: 99 to 99: 1 scope.
The method of the above-mentioned Biodegradable polyester of preparation provided by the invention, its processing step and condition are as follows:
(1) esterification, the preparation of prepolymer
Diprotic acid mixture, diol mixture will and catalyzer (C1) are added in the polymerizing reactor, and wherein, total mol ratio of dibasic alcohol and diprotic acid is 1.01-1.25: 1.Under nitrogen protection, slowly heat and stir, treat that temperature surpasses 140 ℃ of monomers and melts fully after, strengthen stirring velocity rapidly and continue to be heated to 170-180 ℃, keep isothermal reaction 30min this moment; Subsequently, heat up with 10 ℃/30min; At last the temperature control interval is fixed on 210-220 ℃, distillate until no longer including moisture.The terminal point of this step reaction distillates as judging criterion fully with theoretical esterification water growing amount.Wherein, the consumption of catalyzer (C1) is the 0.01%-1% of diprotic acid mixture total mole number.
(2) polycondensation, the preparation of high molecular weight polyesters
After esterification finishes, add catalyzer (C2) after, vacuumize after stirring 10min fast, in 1 hour, be evacuated to below the 20Pa, and under high-speed stirring, be warming up to 240-250 ℃ from normal pressure.Isothermal reaction 3-4h promptly obtains product.Wherein, the consumption of catalyzer (C2) is the 0.01%-1% of diprotic acid mixture total mole number.
Described catalyzer (C2) is catalyzer (C1) one package stabilizer (W1).
Described catalyzer (C1) is the compound that contains following metal, for example, and main group element (for example tin, bismuth, antimony, germanium), transition element (lead, zinc, cadmium, manganese, cobalt, zirconium, titanium, niobium, iron).Preferred titanium-containing compound, germanium-containing compound.
Described titanium-containing compound, germanium-containing compound are four titanium butoxide, four butoxy germanium, tetraisopropoxy titanium, tetraisopropoxide germanium, titanium ethylene glycolate, ethylene glycol germanium, titania/silica mixture.Preferred catalyst is four butoxy germanium, titanium ethylene glycolate, ethylene glycol germanium.
Described stablizer (W1) is a P contained compound, mainly is phosphoric acid or phosphorons acid compound.Proper phosphorus-containing stabilizers has triphenylphosphate, triphenyl phosphite, tributyl phosphate, tributyl phosphate, trimethyl phosphite 99.
Described aliphatic dibasic acid is C
2-C
12Alkane or cycloalkanes diacid are as oxalic acid, Succinic Acid, pyrovinic acid, hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid etc.
Described aliphatic dihydroxy alcohol A can be C
2-C
12Straight chained alkyl or cycloalkyl glycol, as ethylene glycol, 1, ammediol, 1,4-butyleneglycol, pentanediol, 1,6-hexylene glycol, decanediol, 1,4 cyclohexane dimethanol, also can be the etherate of above-mentioned aliphatic dihydroxy alcohol, as glycol ether, Triethylene glycol etc.
The dibasic alcohol B of described containg branched alkyl radical is the C of containg branched alkyl radical
2-C
12Alkane or cycloalkanes glycol, as 1,2-propylene glycol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol, neopentyl glycol etc.
In the present invention, the dibasic alcohol and aliphatic dibasic acid, the aliphatic dihydroxy alcohol that add the band branched-chain alkyl carry out copolymerization, have developed the novel polyester products that has branched-chain alkyl.Compare with the product of having reported, the introducing of novel monomeric has given the binary aliphatic alkyd polyester new performance, for the expansion of PBS kind polyester range of application provides the foundation.
The present invention need not chain extending reaction, both can prepare the molecular weight height thermoplastic resin of (weight-average molecular weight is higher than 200,000).This thermoplastic resin has good moulding processability, can process with the contour machining equipment of general purpose polyolefin.Plastic goods comprise film, slush molding goods, foam, monofilament, thin plate, tension belt and injection moulded products etc.This class material can be used for the production of all kinds of environmental protection plastic products, relates to the plastics of environmental protection as refuse bag, packing bag, bottle for cosmetics, beverage bottle, plastic cards, baby diaper, agricultural materials, packaging material for food, medicament slow release material and other.
Molecular weight of the present invention and molecular weight distribution are measured by gel permeation chromatography (GPC).Specifically be elutriant with the chloroform, polystyrene is that standard substance is measured.
Embodiment
Embodiment 1:
In having the 10L stainless steel cauldron of agitator, separation column, condenser, 1 of the Succinic Acid of adding 3000g, 2000g, 1 of 4-butyleneglycol, 420g, 2-propylene glycol and titanium ethylene glycolate 2g.Under logical condition of nitrogen gas, slowly stirring and be heated to temperature is 170 ℃, reaction 30min, and the speed with 10 ℃/30min is heated to 210 ℃ then, carries out the normal pressure esterification reaction, distillates to theoretical amount until esterification water.Be under 210 ℃ in temperature then, take out rough vacuum, remove not distilled esterification water of remnants to the following 10min of 3000Pa.Add catalyst glycol titanium 3g, triphenyl phosphite 1.2g, reacted 1 hour; Be rapidly heated to 240 ℃, and pumping high vacuum reacts and was gathered (Succinic Acid 1,4-butyleneglycol-co-Succinic Acid 1,2-propylene glycol) ester, the weight-average molecular weight M of products therefrom in 3 hours to 10Pa
wBe 23.2 ten thousand, molecular weight distribution M
w/ M
nBe 2.3.
Embodiment 2:
In having the 10L stainless steel cauldron of agitator, separation column, condenser, 1 of the Succinic Acid of adding 3000g, 2000g, the 1,3 butylene glycol of 4-butyleneglycol, 500g and four butoxy germanium 2g.Under logical condition of nitrogen gas, slowly stirring and be heated to temperature is 180 ℃, reaction 30min, and the speed with 10 ℃/30min is heated to 220 ℃ then, carries out the normal pressure esterification reaction, distillates to theoretical amount until esterification water.Be under 220 ℃ in temperature then, take out rough vacuum, remove not distilled esterification water of remnants to the following 10min of 3000Pa.Add catalyzer four butoxy germanium 3g, triphenyl phosphite 1.2g, reacted 1 hour; Be rapidly heated to 245 ℃, and pumping high vacuum reacts and was gathered (Succinic Acid 1,4-butyleneglycol-co-Succinic Acid 1,3 butylene glycol) ester, the weight-average molecular weight M of products therefrom in 3 hours to 10Pa
wBe 25.6 ten thousand, molecular weight distribution M
w/ M
nBe 1.9.
Embodiment 3:
In having the 10L stainless steel cauldron of agitator, separation column, condenser, add Succinic Acid, the 1410g1 of 2800g, the neopentyl glycol of 4-butyleneglycol, 480g and ethylene glycol germanium 2g.Under logical condition of nitrogen gas, slowly stirring and be heated to temperature is 180 ℃, reaction 30min, and the speed with 10 ℃/30min is heated to 220 ℃ then, carries out the normal pressure esterification reaction, distillates to theoretical amount until esterification water.Be under 220 ℃ in temperature then, take out rough vacuum, remove not distilled esterification water of remnants to the following 10min of 3000Pa.Add catalyst glycol germanium 3g, tributyl phosphate 1.2g, reacted 1 hour; Be rapidly heated to 245 ℃, and pumping high vacuum reacts and was gathered (Succinic Acid 1,4-butyleneglycol-co-Succinic Acid neopentyl glycol) ester, the weight-average molecular weight M of products therefrom in 3 hours to 10Pa
wBe 22.4 ten thousand, molecular weight distribution M
w/ M
nBe 1.7.
Claims (9)
1. processing method for preparing the aliphatic dibasic acid dibasic alcohol copolyesters of containg branched alkyl radical, it is characterized in that: the dibasic alcohol B by binary aliphatic acid mixture and a kind of aliphatic dihydroxy alcohol A and a kind of containg branched alkyl radical carries out copolymerization, wherein, the binary aliphatic acid mixture is the mixing of any two kinds of aliphatic dibasic acids, and its mol ratio can be regulated arbitrarily in 0: 100 to 100: 0 scope; The mol ratio of the dibasic alcohol of aliphatic dihydroxy alcohol and containg branched alkyl radical can be regulated arbitrarily in 1: 99 to 99: 1 scope.Its processing step and condition are as follows:
(1) esterification, the preparation of prepolymer
Diprotic acid mixture, diol mixture will and catalyzer (C1) are added in the polymerizing reactor, and wherein, total mol ratio of dibasic alcohol and diprotic acid is 1.01-1.25: 1; Under nitrogen protection, slowly heat and stir, treat that temperature surpasses 140 ℃ of monomers and melts fully after, strengthen stirring velocity rapidly and continue to be heated to 170-180 ℃, keep isothermal reaction 30min this moment; Subsequently, heat up with 10 ℃/30min; At last the temperature control interval is fixed on 210 ~ 220 ℃, distillate until no longer including moisture; The terminal point of this step reaction distillates as judging criterion fully with theoretical esterification water growing amount, and the consumption of catalyzer (C1) is the 0.01%-1% of binary aliphatic acid mixture total mole number,
(2) polycondensation, the preparation of high molecular weight polyesters
After esterification finishes, take out rough vacuum 10min and remove residual moisture in the system; After adding catalyzer (C2), vacuumize after stirring 10min fast, be evacuated to below the 20Pa from normal pressure in 1 hour, and be warming up to 240-250 ℃ under high-speed stirring, isothermal reaction 3-4h promptly obtains product; Wherein said catalyzer (C2) is main group element or transition element compound, and catalyzer (C2) is catalyzer (C1) one package stabilizer (W1), and the consumption of catalyzer (C2) is the 0.01%-1% of binary aliphatic acid mixture total mole number.
2. processing method as claimed in claim 1, it is characterized in that: described catalyzer (C1) is the compound of the compound of main group element tin, bismuth, antimony, germanium or transition element lead, zinc, cadmium, manganese, cobalt, zirconium, titanium, niobium, iron, preferred titanium-containing compound, germanium-containing compound.
3. processing method as claimed in claim 2 is characterized in that: described catalyzer (C1) is four titanium butoxide, four butoxy germanium, tetraisopropoxy titanium, tetraisopropoxide germanium, titanium ethylene glycolate, ethylene glycol germanium.Preferred catalyst is titanium ethylene glycolate, ethylene glycol germanium, four butoxy germanium.
4. as each described processing method of claim 1-3, it is characterized in that: described stablizer (W1) is phosphoric acid or phosphorons acid compound.
5. processing method as claimed in claim 4 is characterized in that: described phosphoric acid or phosphorons acid compound are triphenylphosphate, triphenyl phosphite, tributyl phosphate, tributyl phosphate, trimethyl phosphite 99.
6. as each described processing method of claim 1-5, it is characterized in that: described aliphatic dibasic acid is oxalic acid, Succinic Acid, hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid.
7. as each described processing method of claim 1-6, it is characterized in that: described aliphatic dihydroxy alcohol A is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, pentanediol, 1,6-hexylene glycol, decanediol, 1,4 cyclohexane dimethanol, glycol ether, Triethylene glycol.
8. as each described processing method of claim 1-7, it is characterized in that: the dibasic alcohol B of described containg branched alkyl radical is 1,2-propylene glycol, 2-methyl 1, ammediol, 1,3 butylene glycol, neopentyl glycol, 2-phenyl 1, ammediol.
9. as each described processing method of claim 1-8, it is characterized in that: the weight-average molecular weight of resulting biodegradable copolyesters is 200,000 to 400,000.
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| CNA2008101111129A CN101597373A (en) | 2008-06-06 | 2008-06-06 | The processing method of preparation aliphatic copolyester |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445592B (en) * | 2008-12-25 | 2012-03-07 | 清华大学 | Biodegradable branched co-polyester and preparation method thereof |
| CN102757550A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Preparation method of 1, 6-hexanediol modified polyester for heat shrinkable film |
| CN102757549A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Copolyester for 1, 6-hexanediol modified heat shrinkable film |
| CN103827167A (en) * | 2011-09-28 | 2014-05-28 | 阿克佐诺贝尔国际涂料股份有限公司 | Manufacturing polyesters |
| CN106977707A (en) * | 2017-05-02 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of preparation method of low-viscosity polyester |
| CN109438684A (en) * | 2018-11-14 | 2019-03-08 | 中国科学院长春应用化学研究所 | A kind of 2,5- thiophenedicarboxylic acid base polyester and preparation method thereof |
| CN110240788A (en) * | 2019-03-04 | 2019-09-17 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBSM |
| CN115197407A (en) * | 2022-08-10 | 2022-10-18 | 武汉科技大学 | Preparation and application of degradable biological copolyester and antiviral copolyester film |
| CN116102717A (en) * | 2022-02-25 | 2023-05-12 | 沈阳工业大学 | Preparation method and application of novel biodegradable aliphatic copolyester |
-
2008
- 2008-06-06 CN CNA2008101111129A patent/CN101597373A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445592B (en) * | 2008-12-25 | 2012-03-07 | 清华大学 | Biodegradable branched co-polyester and preparation method thereof |
| CN102757550A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Preparation method of 1, 6-hexanediol modified polyester for heat shrinkable film |
| CN102757549A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Copolyester for 1, 6-hexanediol modified heat shrinkable film |
| CN102757549B (en) * | 2011-04-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Copolyester for 1, 6-hexanediol modified heat shrinkable film |
| CN102757550B (en) * | 2011-04-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Preparation method of 1, 6-hexanediol modified polyester for heat shrinkable film |
| CN103827167A (en) * | 2011-09-28 | 2014-05-28 | 阿克佐诺贝尔国际涂料股份有限公司 | Manufacturing polyesters |
| CN106977707A (en) * | 2017-05-02 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of preparation method of low-viscosity polyester |
| CN109438684A (en) * | 2018-11-14 | 2019-03-08 | 中国科学院长春应用化学研究所 | A kind of 2,5- thiophenedicarboxylic acid base polyester and preparation method thereof |
| CN110240788A (en) * | 2019-03-04 | 2019-09-17 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBSM |
| CN116102717A (en) * | 2022-02-25 | 2023-05-12 | 沈阳工业大学 | Preparation method and application of novel biodegradable aliphatic copolyester |
| CN115197407A (en) * | 2022-08-10 | 2022-10-18 | 武汉科技大学 | Preparation and application of degradable biological copolyester and antiviral copolyester film |
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