CN103145980A - Unsaturated biology-based polyesteramide and preparation method thereof - Google Patents
Unsaturated biology-based polyesteramide and preparation method thereof Download PDFInfo
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- CN103145980A CN103145980A CN2013100849748A CN201310084974A CN103145980A CN 103145980 A CN103145980 A CN 103145980A CN 2013100849748 A CN2013100849748 A CN 2013100849748A CN 201310084974 A CN201310084974 A CN 201310084974A CN 103145980 A CN103145980 A CN 103145980A
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Abstract
The invention discloses an unsaturated polyesteramide and a preparation method thereof. The aliphatic dihydric alcohol, aliphatic diamine, aliphatic saturated binary acid and unsaturated binary acid from regenerative resource are used as the raw material, and the unsaturated aliphatic polyesteramide having number-average molecular weight between 19365-29452 and weight-average molecular weight between 39961-61214 is synthesized through a direct polycondensation method. The raw material of the polyesteramide is independent from fossil resource, the preparation process is simple, and the material performance can be improved through further crosslinking.
Description
Technical field:
The present invention relates to a kind of unsaturated biological poly esteramides and preparation method thereof, but a kind of polyesteramide preparation method based on the bio-based renewable resource particularly.
Background technology:
All be subject to today of serious challenge at the energy, resource and environment, the chemical engineering industry take the mass energy resource consumption as cost is being faced with acid test.Take full advantage of renewable resources, minimizing has very great meaning to the dependence of the non-renewable fossil resource such as oil to the Sustainable development that promotes global economy, and turning to reproducible starting material from fossil resource is ultimate challenge and opportunities to develop that in 50 years from now on, people face.
The applicant discloses a kind of origin " a kind of poly-cruel type biological engineering rubber and preparation method thereof " in (ZL200910076032.9) and has come from the synthetic unsaturated aliphatic polyester base biological engineering rubber of reproducible Biological resources aliphatic dihydroxy alcohol, aliphatic dicarboxylic acid and the polycondensation of aliphatics unsaturated dibasic acid, has obtained certain breakthrough.But the polyester based biological engineering rubber is Shortcomings also, and is as not good in mechanical property and processing characteristics, and purpose of the present invention just is to provide a kind of novel material of dealing with problems.
Polyesteramide is a kind of novel biodegradable polymer, the existence of the intermolecular hydrogen bond of acid amides segment makes polyesteramide material when molecular weight is low also have higher thermomechanical property and intensity, and the existence of ester bond simultaneously gives again material good biodegradable.
And traditional polyester-amide material generally adopts multistep processes, and the present invention selects the biogenetic derivation raw material, synthesizes a kind of method of random unsaturated polyester amide through single stage method, at home and abroad all without report.
Summary of the invention:
The purpose of this invention is to provide unsaturated polyester amide of a kind of Non oil-based route and preparation method thereof, dibasic alcohol, diamine and diprotic acid polycondensation that employing derives from reproducible Biological resources form, and the material that makes has good physical and mechanical properties and biodegradability.
A kind of unsaturated polyester amide material provided by the invention, that aliphatic diamine, aliphatic dihydroxy alcohol, representative examples of saturated aliphatic diprotic acid and the unsaturated aliphatic diprotic acid that origin comes from reproducible Biological resources forms through direct polymerization, it is characterized in that number-average molecular weight is 19365～29452, weight-average molecular weight is 39961～61214.Its structural formula is:
（k,l,m,n=1,2,3…）
The present invention also provides the preparation method of above-mentioned bio-based unsaturated polyester amide, aliphatic diamine, aliphatic dihydroxy alcohol, representative examples of saturated aliphatic diprotic acid and unsaturated aliphatic diprotic acid that employing derives from reproducible Biological resources make through direct polymerization, and concrete reaction conditions and step are as follows:
be the aliphatic dihydroxy alcohol of 1～1.3:1 with the alkohol and amine total amount with mixing the total amount mol ratio of calculating acid, aliphatic diamine, aliphatic dicarboxylic acid and aliphatics unsaturated dibasic acid mix, wherein the mol ratio of aliphatic dihydroxy alcohol and aliphatic diamine is 9:1～3:7, the mol ratio of aliphatics unsaturated dibasic acid and monounsaturated dicarboxylic acid is 1.5:8.5, the stopper that adds monomer total mass 0.2%～0.5%, the stablizer that adds monomer total mass 0.05～0.1%, in nitrogen atmosphere, be warming up to 120 ℃ of reactions 1～3 hour under the condition that stirs, make material melting and preliminary pre-polymerization, increase the temperature to 170～190 ℃ of reactions 1～3 hour, obtain prepolymer product.
Described aliphatic dihydroxy alcohol is Isosorbide-5-Nitrae-butyleneglycol, and aliphatic diamine is 1,10-decamethylene diamine.
Described aliphatic dibasic acid is 1,10-sebacic acid, and the aliphatics unsaturated dibasic acid is methylene-succinic acid.
Described stopper is Resorcinol.Adding of Resorcinol is in order to prevent that two keys in unsaturated binary of fatty acids are in thermopolymerization.
Then add the catalyzer of monomer total mass 0.01%～2% in above-mentioned reaction system, be warming up to 210～220 ℃, in 1 hour, reactor pressure is reduced to 0.3MPa gradually, and react 2～4 hours under the 0.3MPa condition, obtain unsaturated polyester amide.Its number-average molecular weight can reach 19365～29452, and weight-average molecular weight can reach 39961～61214.
Described catalyzer is tetrabutyl titanate, can be with tetrabutyl titanate and with 1 when adding catalyzer, 4-butyleneglycol is made into the solution that volume ratio is 1:20, add in reaction system, the raw material monomer that volatilizees in can the postreaction process is simultaneously due to the tetrabutyl titanate facile hydrolysis, with 1, add after 4-butyleneglycol wiring solution-forming, catalytic effect is also better.
The preparation method of bio-based unsaturated polyester amide of the present invention adopts nitrogen protection, is in order to prevent the generation of side reaction heat oxidative degradation on the one hand, is the micromolecular water that generates in condensation polymerization in order to remove on the other hand, and balance is moved to positive dirction.In order to prevent the generation of thermal oxidative reaction in polycondensation, add appropriate phosphorous acid as stablizer in addition, the add-on of phosphorous acid is 0.05%～0.1% of monomer total mass.
The unsaturated bio-based polyester-amide material of the present invention's preparation, the material of selecting all derives from biological renewable resources, be of value to the challenge that solves the petroleum resources exhaustion, and its physical and mechanical properties is better than polyester material, close to polyamide material, and has the not available biodegradability of polyamide material.And it prepares the technique of polyesteramide by direct single stage method, has also reduced the energy consumption of production process.And the two keys in material can adopt peroxide crosslinking, provide possibility for further improving in the future material property.
Description of drawings:
Fig. 1 is the unsaturated biological poly esteramides of embodiment 1 preparation
1The H-NMR spectrogram.
Fig. 2 is the FT-IR spectrogram of the unsaturated biological poly esteramides of embodiment 1 preparation.
Embodiment:
The methylene-succinic acid that adopts in the embodiment of the present invention, sebacic acid, decamethylene diamine, butyleneglycol all adopt commercially available chemicals.
Embodiment 1:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 8.92g (0.099mol) butyleneglycol, 1.90g(0.011mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 22107, and weight-average molecular weight is 39961, and polydispersity coefficient is 1.8076.
Embodiment 2:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 6.94g (0.077mol) butyleneglycol, 5.69g(0.033mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 25217, and weight-average molecular weight is 52145, and polydispersity coefficient is 2.0679.
Embodiment 3:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 4.96g (0.055mol) butyleneglycol, 9.48g(0.055mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 29414, and weight-average molecular weight is 63215, and polydispersity coefficient is 2.1490.
Embodiment 4:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 2.97g (0.033mol) butyleneglycol, 13.27g(0.077mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 29452, and weight-average molecular weight is 61214, and polydispersity coefficient is 2.0784.
Embodiment 5:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 9.73g (0.108mol) butyleneglycol, 2.07g(0.012mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 19365, and weight-average molecular weight is 40157, and polydispersity coefficient is 2.074.
Embodiment 6:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 4.96g (0.055mol) butyleneglycol, 9.48g(0.055mol) decamethylene diamine, 0.040g Resorcinol, 0.020g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 190 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.02% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 210 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 26451, and weight-average molecular weight is 61542, and polydispersity coefficient is 2.3266.
Embodiment 7:
In the reaction unit that mechanical stirring, nitrogen gangway, heating unit, thermometer and prolong are housed, add 17.19g (0.085mol) 1,10-sebacic acid, 1.95g (0.015mol) methylene-succinic acid, 4.96g (0.055mol) butyleneglycol, 9.48g(0.055mol) decamethylene diamine, 0.050g Resorcinol, 0.025g phosphorous acid, in nitrogen atmosphere, under the condition that stirs, be warming up to 120 ℃, molten prepolymer polymerization 2 hours.Temperature rises to 180 ℃, reacts 2 hours, obtains preliminary prepolymerization product.Then add monomer total mass 0.5% tetrabutyl titanate and with solution that butyleneglycol is made into volume ratio 1:20 be catalyzer, rising temperature to 220 ℃, last 1 hour reactor pressure and be decompressed to 0.3MPa, then reacted 2 hours under the 0.3MPa condition, obtain unsaturated polyester amide.The number-average molecular weight that records unsaturated polyester amide is 27412, and weight-average molecular weight is 62541, and polydispersity coefficient is 2.2815.
Comparative Examples:
Poly-(Isosorbide-5-Nitrae-butyleneglycol/1.10-sebacic acid/methylene-succinic acid) copolyesters of 10g is in blocks with the mold pressing of vacuum tabletting machine.
The performance test results of the material in table 1 embodiment of the present invention and Comparative Examples
(annotate: the data in table all adopt conventional national standard testing method to obtain)
As can be seen from Table 1, the general polyester material of unsaturated biological poly esteramides contrast for preparing in the present invention has higher physical and mechanical properties, and wherein uncrosslinked two keys can be further raising performance possibility are provided, and starting material of the present invention all derive from biological renewable resources.
Claims (8)
1. unsaturated biological poly esteramides, it is characterized in that: the number-average molecular weight of described unsaturated aliphatic polyester acid amides is 19365～29452, weight-average molecular weight is 39961～61214; The structural formula of described unsaturated polyester amide is:
K wherein, l, m, n=1,2,3 ...
2. the preparation method of unsaturated polyester amide according to claim 1 is characterized in that step is:
Aliphatic dihydroxy alcohol, aliphatic diamine, aliphatic dicarboxylic acid and aliphatics unsaturated dibasic acid are mixed, wherein diamine and dibasic alcohol mole total amount is 1.3～1:1 of diprotic acid, wherein the mol ratio of aliphatic dihydroxy alcohol and aliphatic diamine is 9:1～3:7, the mol ratio of aliphatics unsaturated dibasic acid and monounsaturated dicarboxylic acid is 1.5:8.5, and above aliphatic dihydroxy alcohol, aliphatic diamine, aliphatic dicarboxylic acid and aliphatics unsaturated dibasic acid are hereinafter referred to as monomer; The stopper that adds monomer total mass 0.2%～0.5%, the stablizer that adds monomer total mass 0.05～0.1%, in nitrogen atmosphere, be warming up to 120 ℃ of reactions 1～3 hour under the condition that stirs, make material melting and preliminary pre-polymerization, increase the temperature to 170～190 ℃ of reactions 1～3 hour, obtain prepolymer product, the catalyzer that adds monomer total mass 0.01%～2% in above-mentioned reaction system, be warming up to 210～220 ℃, in 1 hour, reactor pressure is reduced to 0.3MPa gradually, and react 2～4 hours under the 0.3MPa condition, obtain unsaturated polyester amide.
3. according to claim 2 preparation method, it is characterized in that: described aliphatic dihydroxy alcohol is Isosorbide-5-Nitrae-butyleneglycol, aliphatic diamine is 1,10-decamethylene diamine.
4. according to claim 2 preparation method, it is characterized in that: described aliphatic dibasic acid is 1,10-sebacic acid, the aliphatics unsaturated dibasic acid is methylene-succinic acid.
5. according to claim 2 preparation method, it is characterized in that: described stopper is Resorcinol.
6. according to claim 2 preparation method, it is characterized in that: described catalyzer is tetrabutyl titanate.
7. according to claim 2 or 6 preparation method, it is characterized in that: catalyzer metatitanic acid four butyl esters and Isosorbide-5-Nitrae-butyleneglycol are made into the solution that volume ratio is 1:20, add in reaction system.
8. according to claim 2 preparation method, it is characterized in that: described stablizer is phosphorous acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102090A (en) * | 2016-11-24 | 2018-06-01 | 上海杰事杰新材料(集团)股份有限公司 | Ultra-toughness heat-stabilised poly amide resin and preparation method thereof |
| CN111518510A (en) * | 2020-04-23 | 2020-08-11 | 浙江恒澜科技有限公司 | Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups |
| CN117304476A (en) * | 2023-11-30 | 2023-12-29 | 广东工业大学 | All-bio-based high-performance nylon and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450985A (en) * | 2009-01-05 | 2009-06-10 | 北京化工大学 | Polyester type biological engineering rubber and preparation method thereof |
| CN102336906A (en) * | 2010-07-20 | 2012-02-01 | 东丽纤维研究所（中国）有限公司 | Polyesteramide and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450985A (en) * | 2009-01-05 | 2009-06-10 | 北京化工大学 | Polyester type biological engineering rubber and preparation method thereof |
| CN102336906A (en) * | 2010-07-20 | 2012-02-01 | 东丽纤维研究所（中国）有限公司 | Polyesteramide and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102090A (en) * | 2016-11-24 | 2018-06-01 | 上海杰事杰新材料(集团)股份有限公司 | Ultra-toughness heat-stabilised poly amide resin and preparation method thereof |
| CN111518510A (en) * | 2020-04-23 | 2020-08-11 | 浙江恒澜科技有限公司 | Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups |
| CN111518510B (en) * | 2020-04-23 | 2021-10-26 | 浙江恒澜科技有限公司 | Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups |
| CN117304476A (en) * | 2023-11-30 | 2023-12-29 | 广东工业大学 | All-bio-based high-performance nylon and preparation method thereof |
| CN117304476B (en) * | 2023-11-30 | 2024-03-26 | 广东工业大学 | All-bio-based high-performance nylon and preparation method thereof |
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