CN107141459A - The preparation method of aliphatic polyester-b- polycarbonate block Biodegradable polyesters - Google Patents
The preparation method of aliphatic polyester-b- polycarbonate block Biodegradable polyesters Download PDFInfo
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- CN107141459A CN107141459A CN201610115368.1A CN201610115368A CN107141459A CN 107141459 A CN107141459 A CN 107141459A CN 201610115368 A CN201610115368 A CN 201610115368A CN 107141459 A CN107141459 A CN 107141459A
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- acid
- aliphatic
- pcdl
- polyester
- hydroxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The preparation method of aliphatic polyester b polycarbonate block Biodegradable polyesters, belongs to polyester technical field.First with aliphatic dibasic acid and excessive dihydric alcohol melt polycondensation, synthesize the polyester oligomer of terminal hydroxy group, then with the further polycondensation of PCDL prepolymer, obtain aliphatic polyester b polycarbonate block Biodegradable polyesters.This method is easy to operate, pollution-free, environmental protection, and gained block biodegradable polyester is easily crystallized, and is easy to structure regulating, with higher fusing point, good hot property and mechanical property.
Description
Technical field
The present invention relates to a kind of aliphatic polyester-b- polycarbonate block Biodegradable polyesters
Melt polycondensation preparation method, first synthesizes the poly- of terminal hydroxy group with aliphatic dibasic acid and diol reaction
Ester oligomer, then reacted with PCDL oligomer, synthesizing biological degradable polyester-b-
Polycarbonate block polyester, the number-average molecular weight of resulting polymers may be up to 36779g/mol,
Belong to polyester technical field.
Technical background
Poly butylene succinate (PBS) is typical Biodegradable aliphatic polyester, tool
There is excellent molding processibility and physical and mechanical property and good biological degradability.With PLA
(PLA), the degradative plastics such as polyhydroxy-alkanoate (PHA) is compared, and PBS is cheap, system
Preparation Method is easy, has a good promotion prospects.The centre that PBS degrades in the environment
Product succinic acid is the important intermediate material of tricarboxylic acid cycle in life entity, and degraded final product is
Carbon dioxide and water, due to can be degradable and product is nontoxic, PBS be ground as biomaterial
Study carefully the extensive concern for causing domestic and foreign scholars.
PBS can be prepared by the direct melt polycondensation of succinic acid, butanediol, but be needed very high
Vacuum, otherwise molecular weight is not high enough, more crisp.The flat 6-59801 of Japanese Laid Open Patent is
Using binary acid and dihydric alcohol polycondensation under condition of high vacuum degree, the aliphatic poly of HMW is prepared
Ester.In addition, the flat 6-322091 of Japanese Laid Open Patent uses tetra-atomic acid dicarboxylic anhydride, put down
6-256461 uses diisocyanate to carry out chain extension for chain extender, prepares high-molecular-weight aliphatic and gathers
Ester.And isocyanates is poisonous, side reaction is more in chain extension process, and other chain extenders, which are existed, to be difficult
The defects such as preparation.
The invention provides a kind of high tenacity PBS preparation method, PBS is synthesized first oligomeric
Thing and PCDL oligomer, will the two further polycondensation, the fat of acquisition HMW
Adoption ester-b- polycarbonate block Biodegradable polyesters；By adjusting PBS and makrolon
The molecular weight and ratio of oligomers of glycols, to regulate and control fusing point, mechanical property and the biology of polymer
Degradability, with reaction condition is gentle, environmental protection, it is efficient the characteristics of；The thermoplasticity of acquisition
Polyester material, with higher fusing point, good mechanical property and pliability, belongs to polyester skill
Art field.
The content of the invention：
The purpose of the present invention is that there is provided one kind is easy to operate, green in view of the shortcomings of the prior art
Colour circle is protected, efficient melt polycondensation prepares aliphatic polyester-b- polycarbonate blocks and biological can dropped
The method for solving polyester.This method raw material is easy to get, and preparation method is easy, and resulting polymers have good
Good thermal property and mechanical property.
The present invention prepares aliphatic polyester-b- polycarbonate blocks using the method for melt polycondensation can
Biodegradable polyester.First with aliphatic dibasic acid and excessive dihydric alcohol melt polycondensation, close
Into the polyester oligomer of terminal hydroxy group, then with the further polycondensation of PCDL, prepare number and divide equally
Son amount reaches 36779g/mol aliphatic polyester-b- polycarbonate block Biodegradable polyesters,
Comprise the following steps that：
(1) synthesis of aliphatic polyester performed polymer：By aliphatic dibasic acid and dihydric alcohol according to
1：The mol ratio of (1.1~1.5), add total monomer weight 0.002~0.3% catalyst and
0.02~0.3% phosphorous acid antioxidant, melts at 150 DEG C and is reacted, then progressively
200 DEG C are warming up to, water byproduct is steamed and unnecessary aliphatic dihydroxy alcohol, then at 200 DEG C
Lower decompression step by step reacts 4h, and reacts at least 4h in the case where vacuum is 1~5mmHg, until
Acid number drops to less than 2, obtains terminal hydroxy group aliphatic polyester oligo.
(2) synthesis of PCDL：By a certain amount of dihydric alcohol and ethylene carbonate,
The catalyst of addition gross weight 0.002~0.3%, the synthesis under normal pressure 4h at 180 DEG C, then
With water pump 1.5~7h of Depressor response, PCDL prepolymer is obtained；
(3) the hydroxyl telechelic polyester performed polymer that will be prepared in step (1), and in step (2)
The PCDL oligomer of preparation, in 180 DEG C in N2Stirred under protection, catalysts conditions
Mixing is mixed, Depressor response is obtained untill viscosity is not further added by under 1~5mmHg vacuums
To aliphatic polyester-b- polycarbonate block Biodegradable polyesters；Wherein, with 100 weight
The aliphatic polyester performed polymer meter of part, the consumption of PCDL is 30~130 parts by weight,
It is preferably 0.002~0.3% that catalyst quality, which accounts for gross mass percentage,.
Wherein, the terminal hydroxy group aliphatic polyester oligo described in step (1), preferably has
There is the structure shown in formula (I)：
L=2~12, m=2~10, p=6~21 in above formula；Fat described in step (1)
The formula of race's dihydric alcohol is HO (CH2)lOH, l=2~12, it is conventional for ethylene glycol, 1,3-
One or both of propane diols, 1,4- butanediols, 1,6-HD etc.；Institute in step (1)
The formula for the aliphatic dibasic acid stated is HOOC (CH2)mCOOH, m=2~10, it is conventional
For one kind in succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, decanedioic acid etc. or
Two kinds.
PCDL prepolymer described in step (2), its general structure such as (II)
It is shown：
R is-(CH in above formula2)n-, n=2~12, q=2~15, conventional PCDL is end
The poly- ethylene carbonate ester of hydroxyl, terminal hydroxy group polytrimethylene carbonate, the poly- carbonic acid butanediol of terminal hydroxy group
The poly- carbonic acid hexylene glycol ester of ester, terminal hydroxy group.
Step (1), (2), the catalyst described in (3) are stannous chloride, tin oxide, oxygen
Change zinc, zinc acetate, zinc chloride, aluminium chloride, aluminum carboxylate, titanium complex, butyl titanate or
One or more in the catalyst such as tetraisopropyl titanate, preferable amount is total monomer weight
0.002~0.3%.
Advantages of the present invention and its effect：
The present invention is led to using PCDL prepolymer with terminal hydroxy group aliphatic polyester oligo
Cross melt-polycondensation, synthctic fat adoption ester-b- polycarbonate block Biodegradable polyesters,
Thus obtained polyester has linear structure, shown in concrete structure such as formula (III)：
Wherein l=2~12, m=2~10, p=6~21；R is-(CH2)n-, n=2~12, q=2~
15。
This method is easy to operate, green, clean, efficiently, obtains product for biodegradable heat
Plasticity polyester, with higher fusing point, good mechanical property and pliability.
Embodiment：
The present invention presses 1 using aliphatic dibasic acid and excessive aliphatic dihydroxy alcohol:(1.1~
1.5) mol ratio carries out melt polycondensation, and synthesis carries the aliphatic polyester oligo of terminal hydroxy group,
Again with PCDL polycondensation, number-average molecular weight is prepared up to more than 20000, Weight-average molecular
The biodegradable aliphatic thermoplastic polyester of amount reachable more than 40000.
In the above embodiments, preferable embodiment is exemplified below to carry out in detail the present invention
Illustrate, but the realization of the present invention is not limited to following instance.
Embodiment 1：
1) preparation of terminal hydroxy group poly butylene succinate oligomer (PrePBS)：With parts by weight
Weigh 23.32 parts of succinic acid, 26.68 parts of BDOs, 0.14 part of phosphorous acid, 0.1 part is urged
Agent, after 150 DEG C are reacted 1h, is gradually heating to 200 DEG C, treats that the water amount of steaming reaches theory
Value, is first reacted 4 hours with water pump decompression step by step, then with oil pump to be decompressed to 1~5mmHg anti-
Answer 4 hours, it is the poly- fourth that 1.4mgKOH/g, hydroxyl value are 32.96mgKOH/g to obtain acid number
Succinate adipate performed polymer PrePBS.
2) synthesis of PCDL：42.34 parts of ethylene carbonates are weighed with parts by weight,
37.658 parts of 1,6- hexylene glycols, 0.16 part of catalyst, the synthesis under normal pressure 4h at 180 DEG C, then
With water pump Depressor response 3.5h, hydroxyl value 137.51mgKOH/g PCDL is obtained.
3) step 1 is weighed with parts by weight) middle 4 parts of PrePBS, the steps 2 prepared) middle preparation
1 part of PCDL, 0.01 part of titanium catalyst, be decompressed to 1~5mmHg at 180 DEG C
Reaction, untill polymer viscosity is not further added by, the number-average molecular weight of gained polyester is
33700, weight average molecular weight is 74700, and fusing point Tm is 81.8 DEG C.Its tensile strength is 19.897
MPa, elongation at break is 570.17%.
Embodiment 2：
1) synthesis of PCDL：47.89 parts of ethylene carbonates, 32.1 are weighed with parts by weight
Part 1,6- hexylene glycols, 0.16 part of catalyst, synthesis under normal pressure 4h, then uses water pump at 180 DEG C
Depressor response 3h, obtains hydroxyl value 189.29mgKOH/g PCDL.
2) weigh the step 1 of embodiment 1 with parts by weight) in prepare 5.5 parts of PrePBS, implement
The step 1 of example 2) middle 1 part and 0.012 part catalyst of PCDL prepared, at 180 DEG C
Under with oil pump be decompressed to 1~5mmHg reaction, untill polymer viscosity is not further added by,
The number-average molecular weight of gained polyester is 26676, and weight average molecular weight is 28900, and fusing point Tm is
88.45 DEG C, its tensile strength is 22.48MPa, and elongation at break is 429.35%.
Embodiment 3：
1) preparation of terminal hydroxy group poly butylene succinate oligomer (PrePBS)：With parts by weight
Weigh 28 parts of succinic acid, 32 parts of BDOs, 0.14 part of phosphorous acid, 0.12 part of catalyst,
After 150 DEG C are reacted 1h, 200 DEG C are gradually heating to, treats that the water amount of steaming reaches theoretical value, first
Reacted 4 hours with water pump decompression step by step, then to be decompressed to oil pump 1~5mmHg reactions 4.5 small
When, it is the poly-succinic fourth that 0.7mgKOH/g, hydroxyl value are 29.5mgKOH/g to obtain acid number
Diol ester performed polymer PrePBS.
2) weigh the step 1 of embodiment 3 with parts by weight) in prepare 5.74 parts of PrePBS and reality
Apply the step 2 of example 1) in prepare 1.26 parts of PCDLs, 0.014 part of catalyst,
180 DEG C with oil pump be decompressed to 1~5mmHg reaction, until polymer viscosity be not further added by for
Only, the number-average molecular weight of gained polyester is 36779, and weight average molecular weight is 63900, fusing point Tm
For 85.82 DEG C.Its tensile strength is 17.12MPa, and elongation at break is 14.53%.
Embodiment 4：
1) weigh the step 1 of embodiment 3 with parts by weight) in prepare 6.27 parts of PrePBS and reality
Apply the step 1 of example 2) in prepare 1 part of PCDL, 0.014 part of catalyst, at 180 DEG C
1~5mmHg reactions, untill polymer viscosity is not further added by, institute are decompressed to oil pump
The number-average molecular weight for obtaining polyester is 17558, and weight average molecular weight is 23800, and fusing point Tm is
95.88℃.Its tensile strength is 25.06MPa, and elongation at break is 19.18%.
Embodiment 5：
1) synthesis of PCDL：33 parts of ethylene carbonates, 17 are weighed with parts by weight
Part 1,6- hexylene glycols, 0.15 part of catalyst, synthesis under normal pressure 4h, then uses water pump at 180 DEG C
Depressor response 3h, obtains hydroxyl value 201.3mgKOH/g PCDL.
2) weigh the step 1 of embodiment 3 with parts by weight) in prepare 6.66 parts of PrePBS and reality
Apply the step 1 of example 5) in prepare 1 part of PCDL, 0.014 part of catalyst, at 180 DEG C
1~5mmHg reactions, untill polymer viscosity is not further added by, institute are decompressed to oil pump
The number-average molecular weight for obtaining polyester is 27192, and weight average molecular weight is 41290, and fusing point Tm is
103.94℃.Its tensile strength is 31.03MPa, and elongation at break is 308.44%.
Claims (8)
1. the method for aliphatic polyester-b- polycarbonate block Biodegradable polyesters is prepared using melt polycondensation, it is characterized in that, first with aliphatic dibasic acid and excessive dihydric alcohol melt polycondensation, synthesize the polyester oligomer of terminal hydroxy group, again with PCDL copolycondensation, aliphatic polyester-b- polycarbonate block Biodegradable polyesters are prepared, are comprised the following steps that：
(1) synthesis of aliphatic polyester performed polymer：By aliphatic dibasic acid and dihydric alcohol according to 1：The mol ratio of (1.1~1.5), add the catalyst and 0.02~0.3% phosphorous acid antioxidant of total monomer weight 0.002~0.3%, melt and reacted at 150 DEG C, then 200 DEG C are progressively warming up to, steam water byproduct and unnecessary aliphatic dihydroxy alcohol, then decompression step by step reacts 4h at 200 DEG C, and reacts at least 4h in the case where vacuum is 1~5mmHg, until acid number drops to less than 2, terminal hydroxy group aliphatic polyester oligo is obtained；
(2) synthesis of PCDL：By a certain amount of dihydric alcohol and ethylene carbonate, the catalyst of gross weight 0.002~0.3% is added, the synthesis under normal pressure 4h at 180 DEG C, then with water pump 1.5~7h of Depressor response, obtains PCDL prepolymer；
(3) will the middle hydroxyl telechelic polyester performed polymer prepared of step (1), the PCDL oligomer with preparation in step (2), in 180 DEG C in N2Mixing is stirred under protection, catalysts conditions, Depressor response obtains aliphatic polyester-b- polycarbonate block Biodegradable polyesters untill viscosity is not further added by under 1~5mmHg vacuums；Wherein, in terms of the aliphatic polyester performed polymer of 100 parts by weight, the consumption of PCDL is 30~130 parts by weight.
2. according to the method for claim 1, it is characterised in that the step of (1) described in terminal hydroxy group aliphatic polyester oligo, with the structure shown in formula (I)：
L=2~12, m=2~10, p=6~21 in above formula.
3. according to the method for claim 1, it is characterised in that the PCDL prepolymer described in step (2), its general structure is such as shown in (II)：
R is-(CH in above formula2)n-, n=2~12, q=2~15.
4. according to the method for claim 1, it is characterised in that the formula of the aliphatic dihydroxy alcohol described in step (1) is HO (CH2)lOH, l=2~12.
5. according to the method for claim 1, it is characterised in that the formula of step (1) aliphatic dibasic acid is HOOC (CH2)mCOOH, m=2~10.
6. according to the method for claim 1, it is characterized in that, step (1), (2), the catalyst described in (3) are one or more of mixing in stannous chloride, tin oxide, zinc oxide, zinc acetate, zinc chloride, aluminum carboxylate, aluminium chloride, titanium complex, butyl titanate or tetraisopropyl titanate, and consumption is the 0.002~0.3% of total monomer weight.
7. according to the method for claim 1, it is characterised in that PCDL is selected from the poly- ethylene carbonate ester of terminal hydroxy group, terminal hydroxy group polytrimethylene carbonate, terminal hydroxy group polytetramethylene carbonate diol, the poly- carbonic acid hexylene glycol ester of terminal hydroxy group.
8. according to the method for claim 1, it is characterised in that aliphatic dihydroxy alcohol is one or both of ethylene glycol, 1,3-PD, BDO, 1,6- hexylene glycols etc.；Aliphatic dibasic acid is one or both of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, decanedioic acid etc..
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3907250A1 (en) * | 2020-05-06 | 2021-11-10 | Universitaet Konstanz | Polyeester or polycarbonate-like materials, their solvolysis and production of finished parts from same |
| CN115232297A (en) * | 2022-06-30 | 2022-10-25 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735434A (en) * | 2009-12-29 | 2010-06-16 | 徐玉华 | Poly(alkene carbonate) diol-polybutylene succinate copolymer and preparation method thereof |
| CN102241814A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Poly(alkene carbonate)diol-poly(butylene succinate) copolymer and preparation method thereof |
| CN102796251A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院化学研究所 | Biodegradable polyester-polycarbonate multi-block copolymer and preparation method and application thereof |
-
2016
- 2016-03-01 CN CN201610115368.1A patent/CN107141459A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735434A (en) * | 2009-12-29 | 2010-06-16 | 徐玉华 | Poly(alkene carbonate) diol-polybutylene succinate copolymer and preparation method thereof |
| CN102241814A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Poly(alkene carbonate)diol-poly(butylene succinate) copolymer and preparation method thereof |
| CN102796251A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院化学研究所 | Biodegradable polyester-polycarbonate multi-block copolymer and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3907250A1 (en) * | 2020-05-06 | 2021-11-10 | Universitaet Konstanz | Polyeester or polycarbonate-like materials, their solvolysis and production of finished parts from same |
| WO2021224303A3 (en) * | 2020-05-06 | 2021-12-30 | Universität Konstanz | Polyethylene-type materials, the solvolysis thereof and production of finished parts therefrom |
| CN115232297A (en) * | 2022-06-30 | 2022-10-25 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof |
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