CN103073709B - A kind of preparation method of poly-2-dimethyl succinic acid DOPCP - Google Patents
A kind of preparation method of poly-2-dimethyl succinic acid DOPCP Download PDFInfo
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- CN103073709B CN103073709B CN201310014842.8A CN201310014842A CN103073709B CN 103073709 B CN103073709 B CN 103073709B CN 201310014842 A CN201310014842 A CN 201310014842A CN 103073709 B CN103073709 B CN 103073709B
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Abstract
The preparation method that the present invention relates to a kind of poly-2-dimethyl succinic acid DOPCP, catalyst, 2-dimethyl succinic acid and neopentyl glycol are esterified by described method under normal pressure, first prepare estrodur performed polymer, at reduced pressure conditions performed polymer polycondensation is obtained polyester again, be eventually adding chain extender and carry out chain extension and secure satisfactory grades the poly-2-dimethyl succinic acid DOPCP of sub-amount.The poly-2-dimethyl succinic acid DOPCP molecular weight that the present invention makes can reach 13.8 × 104G/mol, and in dimethyl succinic acid and neopentyl glycol, the introducing of pending methyl group destroys the symmetry of strand, therefore to be expected to the degradation speed of poly butylene succinate more widely studied fast for this polyester.
Description
Technical field
The invention belongs to macromolecule preparing technical field, the preparation method being specifically related to a kind of poly-2-dimethyl succinic acid DOPCP.
Background technology
Along with expanding day and mankind's concern to environmental problem of macromolecular material application, " white pollution " problem that environment is caused by difficult degradation macromolecular material has needed solution badly.Substitute with Biodegradable polymer material and be currently being widely used Nondegradable plastics, be a kind of effective way solving " white pollution " problem at present.
Biodegradated polymer materal, owing to reverting to nature by microorganism after can being decomposed in natural environment again, has caused the common concern of people.At present in the biodegradable polymers of research, aliphatic polyester is owing to having the biological degradability of uniqueness, biocompatibility and Bioabsorbable, obtain deep research in fields such as bio-medical, drug packages, agricultural productions, be that a class is of many uses, the macromolecular material of excellent performance.The main chain of this kind polyester is formed by connecting by the ester bond of facile hydrolysis by aliphatic structure unit mostly, main chain is submissive, easily by the multiple-microorganism in nature or the decomposition of animal and plant body endoenzyme, metabolism, ultimately form carbon dioxide and water and go back to nature, be biodegradable plastic most with prospects.
At present, the synthesis of high-molecular aliphatic polyester is a key difficulties all the time, and this kind polyester physical and mechanical properties low-molecular-weight is poor, and fusing point is below greatly 100 DEG C, it is impossible to use separately as plastic.Under normal circumstances, the fusing point of polyester is only higher than 100 DEG C, and after processing and forming, the plastic obtained just has actual application value.At present for the study on the synthesis of degradable polyester more be poly butylene succinate (PBS), PGA (PGA), polylactic acid (PLA), polycaprolactone (PCL) etc., yet there are no with report that 2-dimethyl succinic acid, neopentyl glycol are the poly-2-dimethyl succinic acid DOPCP of raw material preparation.In addition, the raw materials for production of existing aliphatic polyester product generally extract from oil, although so this kind polyester has biological degradability, but be not biological basis material, evaluation of life cycle shows, this polyester utilizing Petroleum Production can reduce carrying capacity of environment hardly.Above-mentioned reason all makes it apply to be limited by very large.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, it is proposed that the preparation method of a kind of poly-2-dimethyl succinic acid DOPCP, the poly-2-dimethyl succinic acid butanediol ester that described method is prepared, and adopts GPC method to carry out molecular weight test, and its weight average molecular weight is up to 13.8 × 104G/mol, has good moulding processability and biodegradability.
The technical scheme is that, a kind of preparation method of poly-2-dimethyl succinic acid DOPCP, catalyst, 2-dimethyl succinic acid and neopentyl glycol are esterified by described method under normal pressure, first prepare estrodur performed polymer, at reduced pressure conditions performed polymer polycondensation is obtained polyester again, be eventually adding chain extender and carry out chain extension and secure satisfactory grades the poly-2-dimethyl succinic acid DOPCP of sub-amount；It specifically comprises the following steps that
1) first by a certain amount of neopentyl glycol in 250ml there-necked flask; melt as molten condition at 140 DEG C; in proportion 2-dimethyl succinic acid is joined in 250ml flask again; add catalyst; the mol ratio making neopentyl glycol and 2-dimethyl succinic acid is 1: 1～3: 1; the mol ratio of catalyst and 2-dimethyl succinic acid is 0.001: 1～0.25: 1, is warming up at 140～170 DEG C under nitrogen protection and carries out normal pressure esterification reacts to obtain estrodur performed polymer；
2) estrodur performed polymer obtained is decompressed to below 500Pa, and is warming up to 180～250 DEG C and carries out polycondensation reaction, 300-350 minute time, obtain poly-2-dimethyl succinic acid DOPCP；
3) mol ratio that the poly-2-dimethyl succinic acid DOPCP obtained a certain amount of chain extender of addition carries out chain extension, chain extender and 2-dimethyl succinic acid is 0.001: 1～0.7: 1, reaction temperature 170～230 DEG C, 300-340 minute response time.
Described catalyst is the one in p-methyl benzenesulfonic acid, stannous chloride, antimony oxide, zinc acetate, magnesium acetate, cerous sulfate, cerous nitrate or butyl titanate.
Described chain extender be malonic anhydride, succinic anhydride, phthalic anhydride, 2,2-dimethyl-butyrylchlorine, ethanedioly chloride, Adipoyl Chloride, terephthalyl chloride, 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), 1, one in hexamethylene-diisocyanate or 4,4-methyl diphenylene diisocyanates.
The poly-2-dimethyl succinic acid butanediol ester that the present invention prepares, adopts GPC method to carry out molecular weight test, and its weight average molecular weight is up to 13.8 × 104G/mol, has good moulding processability and biodegradability.
Beneficial effects of the present invention:
The poly-2-dimethyl succinic acid DOPCP molecular weight that the present invention makes can reach 13.8 × 104G/mol, and in dimethyl succinic acid and neopentyl glycol, the introducing of pending methyl group destroys the symmetry of strand, therefore to be expected to the degradation speed of poly butylene succinate more widely studied fast for this polyester.
Detailed description of the invention
Embodiment 1:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 1: 1 being placed in 250ml flask, and add catalyst p-methyl benzenesulfonic acid, its addition is the 1% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 140 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 180 DEG C, is decompressed to 500Pa and carries out polycondensation reaction, 3 hours response time.Be cooled to room temperature in a nitrogen environment, in reaction unit add chain extender malonic anhydride, its addition is the 10% of 2-dimethyl succinic acid amount of substance, and 190 DEG C, below 600Pa react 5h, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid butanediol ester of gained is detected, its weight average molecular weight MwIt is 8.4 × 104g/mol。
Embodiment 2:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 3: 1 being placed in 250ml flask, and add catalyst p-methyl benzenesulfonic acid, its addition is the 10% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 170 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 180 DEG C, is decompressed to 500Pa and carries out polycondensation reaction, 6 hours response time.Being cooled to room temperature in a nitrogen environment, add chain extender phthalic anhydride in reaction unit, its addition is the 40% of 2-dimethyl succinic acid amount of substance, and at 220 DEG C, reaction 5h under 600Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 12.6 × 104g/mol。
Embodiment 3:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 2: 1 being placed in 250ml flask, and add catalyst butyl titanate, its addition is the 0.5% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 150 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 230 DEG C, is decompressed to 500Pa and carries out polycondensation reaction, 6 hours response time.After cooling, adding chain extender succinic anhydride in reaction unit, its addition is the 20% of 2-dimethyl succinic acid amount of substance, and at 200 DEG C, reaction 5h under 300Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 10.7 × 104g/mol。
Embodiment 4:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 2: 1 being placed in 250ml flask, and add catalyst sulfuric acid cerium, its addition is the 0.1% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 140 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 200 DEG C, is decompressed to 100Pa and carries out polycondensation reaction, 4 hours response time.After cooling, adding chain extender ethanedioly chloride in reaction unit, its addition is the 30% of 2-dimethyl succinic acid amount of substance, and at 150 DEG C, reaction 5h under 500Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 12.9 × 104g/mol。
Embodiment 5:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 1: 1 being placed in 250ml flask, and add the catalytic antimony trioxide, its addition is the 0.5% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 160 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 180 DEG C, is decompressed to 300Pa and carries out polycondensation reaction, 4 hours response time.After cooling, adding chain extender 2,4 toluene diisocyanate in reaction unit, its addition is the 5% of 2-dimethyl succinic acid amount of substance, and at 210 DEG C, reaction 5h under 500Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 9.0 × 104g/mol。
Embodiment 6:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 2.5: 1 being placed in 250ml flask, and add catalyst p-methyl benzenesulfonic acid, its addition is the 1% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 160 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 180 DEG C, is decompressed to 100Pa and carries out polycondensation reaction, 6 hours response time.After cooling, adding chain extender 1, hexamethylene-diisocyanate in reaction unit, its addition is the 70% of 2-dimethyl succinic acid amount of substance, and at 220 DEG C, reaction 5h under 50Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 12.8 × 104g/mol。
Embodiment 7:
Neopentyl glycol and 2-dimethyl succinic acid that mol ratio is 1.5: 1 being placed in 250ml flask, and add catalyst stannous chloride, its addition is the 2% of 2-dimethyl succinic acid amount of substance.Connecting water knockout drum, thermometer and agitator, be warming up to 150 DEG C and strong agitation under nitrogen protection, when no longer there being water to generate in water knockout drum, esterification terminates.Changing division box is decompressor, then heats to 250 DEG C, is decompressed to 50Pa and carries out polycondensation reaction, 6 hours response time.After cooling, adding chain extender Adipoyl Chloride in reaction unit, its addition is the 10% of 2-dimethyl succinic acid amount of substance, and at 220 DEG C, reaction 5h under 100Pa, poly-2-dimethyl succinic acid DOPCP.
Adopt gel chromatography that the molecular weight of the poly-2-dimethyl succinic acid DOPCP of gained is detected, its weight average molecular weight MwIt is 13.8 × 104g/mol。
Claims (1)
1. the preparation method of a poly-2-dimethyl succinic acid DOPCP, it is characterized in that: catalyst, 2-dimethyl succinic acid and neopentyl glycol are esterified by described method under normal pressure, first prepare estrodur performed polymer, at reduced pressure conditions performed polymer polycondensation is obtained polyester again, be eventually adding chain extender and carry out chain extension and secure satisfactory grades the poly-2-dimethyl succinic acid DOPCP of sub-amount；It specifically comprises the following steps that
1) first by a certain amount of neopentyl glycol in 250mL there-necked flask; melt as molten condition at 140 DEG C; in proportion 2-dimethyl succinic acid is joined in 250mL flask again; add catalyst; the mol ratio making neopentyl glycol and 2-dimethyl succinic acid is 1: 1～3: 1; the mol ratio of catalyst and 2-dimethyl succinic acid is 0.001: 1～0.25: 1, is warming up at 140～170 DEG C under nitrogen protection and carries out normal pressure esterification reacts to obtain estrodur performed polymer；Described catalyst is stannous chloride；
2) estrodur performed polymer obtained is decompressed to below 500Pa, and is warming up to 180～250 DEG C and carries out polycondensation reaction, 300-350 minute time, obtain poly-2-dimethyl succinic acid DOPCP；
3) mol ratio that the poly-2-dimethyl succinic acid DOPCP obtained a certain amount of chain extender of addition carries out chain extension, chain extender and 2-dimethyl succinic acid is 0.001: 1～0.7: 1, reaction temperature 170～230 DEG C, 300-340 minute response time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604052A (en) * | 2012-03-07 | 2012-07-25 | 青岛科技大学 | Method for preparing poly(2-methyl butylene succinate) with high molecular weight (HMW) |
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| CN102604052A (en) * | 2012-03-07 | 2012-07-25 | 青岛科技大学 | Method for preparing poly(2-methyl butylene succinate) with high molecular weight (HMW) |
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| 生物可降解聚丁二酸丁二醇酯的合成及扩链改性;张贞浴等;《黑龙江大学自然科学学报》;20051025;第22卷(第5期);642-645 * |
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