CN101148501A - Method for preparing polyhydroxy fatty acid ester with high thermal stability - Google Patents
Method for preparing polyhydroxy fatty acid ester with high thermal stability Download PDFInfo
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Abstract
The present invention relates to preparation process of high heat stability polyhydroxy fatty acid ester. The preparation process includes dissolving polyhydroxy fatty acid ester in organic solvent, and reacting with modifier bis(2-oxazolinyl) at 85-125 deg.c for 1-16 hr, with the molar ratio between polyhydroxy fatty acid ester and bis(2-oxazolinyl) being 0.5-2.0. The high heat stability polyhydroxy fatty acid ester has high heat stability, wide machining window, and expanded application range in common plastic, biomedicine and other fields.
Description
Technical field
The invention belongs to the preparation field of modification polyhydroxyalkanoate, particularly relate to a kind of preparation method of polyhydroxy fatty acid ester with high thermal stability.
Background technology
Polyhydroxyalkanoate is a class by the biological polyester of microorganism synthetic, is the unique class performance thermal plasticity high polymer suitable with the synthetic high polymer performance in the natural high polymer of finding up to now.Poly 3-hydroxy butyrate and poly-(3-butyric ester-co-3-hydroxyl valerate) are most important kind, suitability for industrialized production in the polyhydroxyalkanoate.It is renewable that it has excellent biological compatibility, biodegradability and resource.But its (1) taxis is good, and crystallization trend is big; (2) second-order transition temperature is low, and secondary crystal easily takes place in the storage process; (3) in poly-(3-butyric ester-co-3-hydroxyl valerate), there be " isodimorphism "; (4) in the lattice of poly 3-hydroxy butyrate, there is interactional hydrogen bond between the methyl in spirane structure and the carbon back of another spirane structure.These factors have determined polyhydroxyalkanoate degree of crystallinity height, crystalline structure is complete, thereby [poly 3-hydroxy butyrate and hydroxypentanoic acid HV content are less than 15mol% poly-(3-butyric ester-3-hydroxyl valerate) suitability for industrialized production for the fusing point height, poly-(3-butyric ester) fusing point is 178 ℃, HV content is that the fusing point of 13mol% is 157 ℃], but when temperature is higher than 160 ℃, thermal degradation reaction can take place because of the elimination of β hydrogen in polyhydroxyalkanoate, causes the melt-processed window narrows of polyhydroxyalkanoate.Have great importance so improve the thermostability of polyhydroxyalkanoate, will improve the fusion workability of polyhydroxyalkanoate greatly, thereby widen the application prospect of polyhydroxyalkanoate at aspects such as common plastics field and bio-medicals.
Up till now for this reason, both at home and abroad also not about improving the patent of polyhydroxyalkanoate thermostability.The method that improves the polyhydroxyalkanoate thermostability according to bibliographical information mainly contains blend and graft modification etc.MOO SUNG LEE etc. utilizes poly (glycidylmethacrylate--co-ethylene dimethacrylate) (PGMA) and the thermostability of poly 3-hydroxy butyrate blend with the raising poly 3-hydroxy butyrate, and when the blend ratio of PGMA was less, the thermostability of poly 3-hydroxy butyrate improved not obvious; Improve more for a long time and work as thermostability, the content of PGMA needs higher, when for example the temperature when poly 3-hydroxy butyrate thermal destruction speed is maximum improves 32 ℃, the content of PGMA needs up to 70%, and the introducing of a large amount of superpolymer will have a strong impact on biological nature [the SEUNG NO LEE of poly-(3-butyric ester), MOON YEON LEE, WON HO PARK, Thermal Stabilization ofPoly (3-hydroxybutyrate) by Poly (glycidyl methacrylate), Journal of Applied Polymer Science, 83:2945-2952 (2002)].Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences utilizes multi-walled carbon nano-tubes to improve the thermostability of poly-(3-butyric ester-3-hydroxyl valerate), make the temperature the when weight loss rate that gathers (3-butyric ester-3-hydroxyl valerate) is maximum improve 16 ℃ of [Lai MD, Li J, Yang J, Liu JJ, Tong X, Cheng HM, The morphologyand thermal properties of multi-walled carbon nanotube andpoly (hydroxybutyrate-co-hydroxyvalerate) composite, polymer International, 53 (10): 1479-1484 (2004)].In addition, trials such as Won Mook Choi utilize organic clay to improve the thermostability of poly-(3-butyric ester-3-hydroxyl valerate), make the thermostability of poly-(3-butyric ester-3-hydroxyl valerate) [the Won Mook Choi that improves, Tae Wan Kim, O Ok Park, Yong Keun Chang, Jin Woo Lee, Preparationand Characterization of Poly (hydroxybutyrateco-hydroxyvalerate)-Organoclay Nanocomposites, Journal ofApplied Polymer Science, 90:525-529 (2003)].But the adding of multi-walled carbon nano-tubes and organic clay has influenced the biological degradability of poly-(3-butyric ester-3-hydroxyl valerate).Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences is initiator with BPO, with maleic anhydride poly 3-hydroxy butyrate is carried out graft modification, though temperature improves often.But there are the homopolymer of maleic anhydride and separation problem [the Chen C between the modification poly 3-hydroxy butyrate, Peng SW, Fei B, Zhuang YG, Dong LS, Feng ZL, Chen S, Xia HM, Synthesis and characterization of maleatedpoly (3-hydroxybutyrate), Journal OF Applied Polymer Science, 88 (3): 659-668 (2003)] in sum, up till now for this reason, also there is not a kind of heat-staple approach of polyhydroxyalkanoate that improves effectively.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyhydroxy fatty acid ester with high thermal stability.By adopting two (2-oxazoline) to prepare polyhydroxy fatty acid ester with high thermal stability as properties-correcting agent, polyhydroxyalkanoate poor heat stability, the narrow problem of process window have been solved, overcome in the existing blending technology, second component is to the influence of polyhydroxyalkanoate biological nature, having remedied in the graft modification homopolymer and modification polyhydroxyalkanoate can't isolating deficiency, has expanded the range of application of polyhydroxyalkanoate at aspects such as common plastics field and bio-medicals.
The method for preparing polyhydroxy fatty acid ester with high thermal stability of the present invention comprises the following steps:
(1) polyhydroxyalkanoate and organic solvent are inserted in the reactor, the weightmeasurement ratio of polyhydroxyalkanoate and organic solvent (w/v) is 0.02g/mL～0.05g/mL;
(2) in reactor, fed nitrogen 5-15 minute, remove the air in the reactor, continue logical nitrogen, be heated to 60 ℃～80 ℃, stirred 0.5～2 hour, polyhydroxyalkanoate is fully dissolved;
(3) reacting by heating still to 85 ℃～125 ℃ is continued in polyhydroxyalkanoate dissolving back, adds two (2-oxazoline) properties-correcting agent, stirring reaction 1～16 hour, and the mol ratio of two (2-oxazoline) properties-correcting agent and polyhydroxyalkanoate is 0.5～2.0;
(4) stop heating, continue logical nitrogen to temperature and drop to 0-50 ℃, take out reaction product, with dehydrated alcohol precipitation and vacuum filtration;
(5) products therefrom is removed residual solvent in 12 hours～24 hours in 50 ℃～60 ℃ dryings of vacuum, get polyhydroxy fatty acid ester with high thermal stability.
Described polyhydroxyalkanoate is poly 3-hydroxy butyrate or poly-(3-butyric ester-co-3-hydroxyl valerate), its weight-average molecular weight is 100,000～600,000, molecular weight distribution is 1.2～5.0, hydroxypentanoic acid HV content is 1.0～15.0mol% in poly-(3-butyric ester-co-3-hydroxyl valerate), the general structure of polyhydroxyalkanoate:
Wherein R is CH
3, work as R ' and be-CH
3The time, represent poly 3-hydroxy butyrate; Working as R ' is-CH
2-CH
3, representative poly-(3-butyric ester-co-3-hydroxyl valerate);
Described organic solvent is 1,2-ethylene dichloride, N, a kind of in N '-dimethyl formamide or the diethylene glycol dimethyl ether.
Described two (2-oxazoline) properties-correcting agent is 1, two (2-oxazoline-2) ethane, 1 of 2-, two (2-oxazoline-2) butane, 1 of 4-, two (2-oxazoline-2) hexanes, 1 of 6-, two (2-oxazoline-2) octanes and 1 of 8-, two (2-oxazoline-2) hexanaphthenes of 4-, 1, two (2-oxazoline-2) benzene, 1 of 2-, two (2-oxazoline-2) benzene, 1 of 3-, two (2-oxazoline-2) benzene or 2 of 4-, a kind of in 2 '-two (2-oxazolines), the general structure of two (2-oxazoline) properties-correcting agent:
Beneficial effect of the present invention:
Adopt the polyhydroxyalkanoate of the inventive method modification to compare with former polyhydroxyalkanoate, the initial degradation temperature of polyhydroxy fatty acid ester with high thermal stability, rate of weight loss are that 5% o'clock temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum can improve 9.8 ℃～38.7 ℃, 10.2 ℃～49.2 ℃, 7.6 ℃～30.5 ℃, 8.6 ℃～33.8 ℃ and 55.7KJ/mol～350.7KJ/mol respectively.That sign is selected for use is thermogravimetric analyzer (NETZSCH TG 209 F1), and promptly the TGA test analysis is tested and carried out under the condition of nitrogen protection, and temperature rise rate is 10 ℃/min.
The present invention uses the starting material that extensively are easy to get, the polyhydroxy fatty acid ester with high thermal stability material Heat stability is good that makes, and process window is wide; The properties-correcting agent add-on is few, and preparation technology is simple, and side reaction is few, does not have the separation problem of other product or homopolymer and polyhydroxy fatty acid ester with high thermal stability;
It is less that the prepared polyhydroxy fatty acid ester with high thermal stability biocompatibility of the present invention and biological natures such as biological degradability and former polyhydroxyalkanoate are compared difference.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 40 milliliters of N; N '-dimethyl formamide; weight-average molecular weight and molecular weight distribution are respectively 100,000 and 3.2; HV content is that poly-(the 3-butyric ester-co-3-hydroxyl valerate) 1.0 of 2.6mol% restrains in three mouthfuls of round-bottomed flasks that join 100 milliliters; feed nitrogen after 5 minutes; 70 ℃ of oil bath heated and stirred made poly-(3-butyric ester-co-3-hydroxyl valerate) to dissolve fully in 50 minutes; be heated to 95 ℃ then; by poly-(3-butyric ester-co-3-hydroxyl valerate) and 2; 2 '-two (2-oxazoline) mol ratio is 2.0 ratio adding 2; 2 '-two (2-oxazolines), react 3 hours (be reflected under the condition of nitrogen protection and carry out), stop heating; continuing logical nitrogen to temperature drops to below 50 ℃; take out reaction product and precipitate with dehydrated alcohol, vacuum filtration is then 50 ℃ of vacuum-dryings 24 hours.Record by TGA, the initial degradation temperature of poly-(3-butyric ester-3-hydroxyl valerate) after the modification, temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum that rate of weight loss is at 5% o'clock have increased by 18.5 ℃, 30.3 ℃, 10.7 ℃, 13.2 ℃ and 109.8KJ/mol respectively.
Embodiment 2
With 20 milliliter 1; the 2-ethylene dichloride; weight-average molecular weight and molecular weight distribution are respectively 140,000 and 1.2; HV content is that poly-(the 3-butyric ester-co-3-hydroxyl valerate) 1.0 of 1.0mol% restrains in three mouthfuls of round-bottomed flasks that join 100 milliliters; feed nitrogen after 15 minutes; 60 ℃ of oil bath heated and stirred made poly-(3-butyric ester-co-3-hydroxyl valerate) to dissolve fully in 30 minutes; be heated to 85 ℃ then; by poly-(3-butyric ester-co-3-hydroxyl valerate) and 1; two (2-oxazoline-2) the ethane mol ratios of 2-are 1.0 ratio adding 1; two (2-oxazoline-2) ethane of 2-reacts 6 hours (be reflected under the condition of nitrogen protection and carry out), stop to heat; continuing logical nitrogen to temperature drops to below 50 ℃; take out reaction product and precipitate with dehydrated alcohol, vacuum filtration, then 50 ℃ of vacuum-dryings 24 hours to constant weight.Record by TGA, the initial degradation temperature of poly-(3-butyric ester-co-3-hydroxyl valerate) after the modification, temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum that rate of weight loss is at 5% o'clock have increased by 32.5 ℃, 34.0 ℃, 26.2 ℃, 26.7 ℃ and 232.3KJ/mol respectively.
Embodiment 3
With 50 milliliters of diethylene glycol dimethyl ethers; weight-average molecular weight and molecular weight distribution are respectively 150,000 and 2.8; HV content is that poly-(the 3-butyric ester-co-3-hydroxyl valerate) 1.0 of 15.0mol% restrains in three mouthfuls of round-bottomed flasks that join 100 milliliters; feed nitrogen after 8 minutes; 80 ℃ of oil bath heated and stirred made poly-(3-butyric ester-co-3-hydroxyl valerate) to dissolve fully in 1 hour; be heated to 100 ℃ then; by poly-(3-butyric ester-co-3-hydroxyl valerate) and 1; two (2-oxazoline-2) the butane mol ratios of 4-are 0.7 ratio adding 1; two (2-oxazoline-2) butane of 4-;, react 4 hours (be reflected under the condition of nitrogen protection and carry out), stop heating; continuing logical nitrogen to temperature drops to below 50 ℃; take out reaction product and precipitate with dehydrated alcohol, vacuum filtration is then 50 ℃ of vacuum-dryings 22 hours.Record by TGA, the initial degradation temperature of poly-(3-butyric ester-co-3-hydroxyl valerate) after the modification, temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum that rate of weight loss is at 5% o'clock have increased by 35.8 ℃, 45.7 ℃, 30.0 ℃, 29.6 ℃ and 305.8KJ/mol respectively.
Embodiment 4
With 20 milliliter 1; the 2-ethylene dichloride; weight-average molecular weight and molecular weight distribution are respectively 600,000 and 1.8; HV content is that poly-(the 3-butyric ester-co-3-hydroxyl valerate) 1.0 of 3.5mol% restrains in three mouthfuls of round-bottomed flasks that join 100 milliliters; feed nitrogen after 12 minutes; 60 ℃ of oil bath heated and stirred made poly-(3-butyric ester-co-3-hydroxyl valerate) to dissolve fully in 30 minutes; be heated to 90 ℃ then; then by poly-(3-butyric ester-co-3-hydroxyl valerate) and 1; two (2-oxazoline-2) the hexane mol ratios of 6-are 0.8 ratio adding 1; two (2-oxazoline-2) hexanes of 6-reacts 16 hours (be reflected under the condition of nitrogen protection and carry out), stop to heat; continuing logical nitrogen to temperature drops to below 50 ℃; take out reaction product and precipitate with dehydrated alcohol, vacuum filtration is then 60 ℃ of vacuum-dryings 20 hours.Record by TGA, the initial degradation temperature of poly-(3-butyric ester-co-3-hydroxyl valerate) after the modification, temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum that rate of weight loss is at 5% o'clock have increased by 33.3 ℃, 28.4 ℃, 29.0 ℃, 29.5 ℃ and 116.5KJ/mol respectively.
Embodiment 5
With 40 milliliters of N; N '-dimethyl formamide; weight-average molecular weight and molecular weight distribution are respectively 120,000 and 2.0 poly 3-hydroxy butyrate, 1.0 grams and join in three mouthfuls of round-bottomed flasks of 100 milliliters; feed nitrogen after 10 minutes; 70 ℃ of oil bath heated and stirred dissolved poly 3-hydroxy butyrate in 50 minutes fully; be heated to 105 ℃ then; press poly 3-hydroxy butyrate and 1; two (2-oxazoline-2) the octane mol ratios of 8-are 1.8 ratio adding 1; two (2-oxazoline-2) octanes of 8-; react 2 hours (be reflected under the condition of nitrogen protection and carry out); stop heating, continue logical nitrogen to temperature and drop to below 50 ℃, take out reaction product and precipitate with dehydrated alcohol; vacuum filtration is then 60 ℃ of vacuum-dryings 12 hours.Record by TGA, the initial degradation temperature of poly 3-hydroxy butyrate, rate of weight loss are that 5% o'clock temperature, degradation rate temperature, thermal destruction final temperature and the thermal degradation activation energy when maximum increased by 19.5 ℃, 18.7 ℃, 13.5 ℃, 15.8 ℃ and 89.5KJ/mol respectively after the modification.
Embodiment 6
With 40 milliliters of N; N '-dimethyl formamide; weight-average molecular weight and molecular weight distribution are respectively 500,000 and 3.9 poly 3-hydroxy butyrate, 1.0 grams and join in three mouthfuls of round-bottomed flasks of 100 milliliters; feed nitrogen after 9 minutes; 70 ℃ of oil bath heated and stirred dissolved poly 3-hydroxy butyrate in 50 minutes fully; be heated to 95 ℃ then; press poly 3-hydroxy butyrate and 1; the mol ratio of two (2-oxazoline-2) hexanaphthenes of 4-is 1.5 ratio adding 1; two (2-oxazoline-2) hexanaphthenes of 4-; react 1 hour (be reflected under the condition of nitrogen protection and carry out); stop heating, continue logical nitrogen to temperature and drop to below 50 ℃, take out reaction product and precipitate with dehydrated alcohol; vacuum filtration is then 60 ℃ of vacuum-dryings 12 hours.Record by TGA, the initial degradation temperature of poly-poly 3-hydroxy butyrate after the modification, temperature, temperature, thermal destruction final temperature and thermal degradation activation energy when degradation rate is maximum that rate of weight loss is at 5% o'clock have increased by 9.8 ℃, 10.2 ℃, 7.6 ℃, 8.6 ℃ and 55.7KJ/mol respectively.
Embodiment 7
With 40 milliliters of N; N '-dimethyl formamide; weight-average molecular weight and molecular weight distribution are respectively 390,000 and 5.0 poly 3-hydroxy butyrate, 1.0 grams and join in three mouthfuls of round-bottomed flasks of 100 milliliters; feed nitrogen after 6 minutes; 70 ℃ of oil bath heated and stirred dissolved poly 3-hydroxy butyrate in 50 minutes fully; be heated to 115 ℃ then; press poly 3-hydroxy butyrate and 1; two (2-oxazoline-2) benzene moles of 2-add 1 than the ratio that is 1.0; two (2-oxazoline-2) benzene of 2-; react 4 hours (be reflected under the condition of nitrogen protection and carry out); stop heating, continue logical nitrogen to temperature and drop to below 50 ℃, take out reaction product and precipitate with dehydrated alcohol; vacuum filtration is then 60 ℃ of vacuum-dryings 15 hours.Record by TGA, the initial degradation temperature of poly 3-hydroxy butyrate, rate of weight loss are that 5% o'clock temperature, degradation rate temperature, thermal destruction final temperature and the thermal degradation activation energy when maximum increased by 38.7 ℃, 49.2 ℃, 30.5 ℃, 33.8 ℃ and 350.7KJ/mol respectively after the modification.
Embodiment 8
With 50 milliliters of diethylene glycol dimethyl ethers; weight-average molecular weight and molecular weight distribution are respectively 250,000 and 3.7 poly 3-hydroxy butyrate, 1.0 grams and join in three mouthfuls of round-bottomed flasks of 100 milliliters; feed nitrogen after 13 minutes; 80 ℃ of oil bath heated and stirred dissolved poly 3-hydroxy butyrate in 60 minutes fully; be heated to 125 ℃ then; press poly 3-hydroxy butyrate and 1; two (2-oxazoline-2) benzene moles of 3-add 1 than the ratio that is 1.2; two (2-oxazoline-2) benzene of 3-; react 5 hours (be reflected under the condition of nitrogen protection and carry out); stop heating; continuing logical nitrogen to temperature drops to below 50 ℃; take out reaction product and precipitate with dehydrated alcohol, vacuum filtration is then 60 ℃ of vacuum-dryings 14 hours.Record by TGA, the initial degradation temperature of poly 3-hydroxy butyrate, rate of weight loss are that 5% o'clock temperature, degradation rate temperature, thermal destruction final temperature and the thermal degradation activation energy when maximum increased by 28.5 ℃, 29.9 ℃, 27.6 ℃, 31.6 ℃ and 309.9KJ/mol respectively after the modification.
Embodiment 9
With 40 milliliters of N; N '-dimethyl formamide; weight-average molecular weight and molecular weight distribution are respectively 450,000 and 4.3 poly 3-hydroxy butyrate, 1.0 grams and join in three mouthfuls of round-bottomed flasks of 100 milliliters; feed nitrogen after 11 minutes; 70 ℃ of oil bath heated and stirred dissolved poly 3-hydroxy butyrate in 50 minutes fully; be heated to 95 ℃ then; press poly 3-hydroxy butyrate and 1; two (2-oxazoline-2) benzene moles of 4-add 1 than the ratio that is 1.1; two (2-oxazoline-2) benzene of 4-; react 8 hours (be reflected under the condition of nitrogen protection and carry out); stop heating, continue logical nitrogen to temperature and drop to below 50 ℃, take out reaction product and precipitate with dehydrated alcohol; vacuum filtration is then 60 ℃ of vacuum-dryings 16 hours.Record by TGA, the initial degradation temperature of poly 3-hydroxy butyrate, rate of weight loss are that 5% o'clock temperature, degradation rate temperature, thermal destruction final temperature and the thermal degradation activation energy when maximum increased by 32.2 ℃, 30.8 ℃, 30.2 ℃, 33.5 ℃ and 320.6KJ/mol respectively after the modification.
Claims (4)
1. the preparation method of a polyhydroxy fatty acid ester with high thermal stability comprises the following steps:
(1) polyhydroxyalkanoate and organic solvent are inserted in the reactor, the weightmeasurement ratio of polyhydroxyalkanoate and organic solvent is 0.02g/mL～0.05g/mL;
(2) in reactor, fed nitrogen 5-15 minute, remove the air in the reactor, continue logical nitrogen, and be heated to 60 ℃～80 ℃, stirred 0.5～2 hour, polyhydroxyalkanoate is fully dissolved;
(3) reacting by heating still to 85 ℃～125 ℃ is continued in polyhydroxyalkanoate dissolving back, adds two (2-oxazoline) properties-correcting agent, stirring reaction 1～16 hour, and the mol ratio of two (2-oxazoline) properties-correcting agent and polyhydroxyalkanoate is 0.5～2.0; (4) stop heating, continue logical nitrogen to temperature and drop to 0-50 ℃, take out reaction product, with dehydrated alcohol precipitation and vacuum filtration;
(5) products therefrom is removed residual solvent in 12 hours～24 hours in 50 ℃～60 ℃ dryings of vacuum, get polyhydroxy fatty acid ester with high thermal stability.
2. the preparation method of polyhydroxy fatty acid ester with high thermal stability according to claim 1, it is characterized in that, described polyhydroxyalkanoate is poly 3-hydroxy butyrate or poly-(3-butyric ester-co-3-hydroxyl valerate), its weight-average molecular weight is 100,000～600,000, molecular weight distribution is 1.2～5.0, hydroxypentanoic acid HV content is 1.0～15.0mol% in poly-(3-butyric ester-co-3-hydroxyl valerate), the general structure of polyhydroxyalkanoate:
Wherein R is CH
3, work as R ' and be-CH
3The time, represent poly 3-hydroxy butyrate; Working as R ' is-CH
2-CH
3, representative poly-(3-butyric ester-co-3-hydroxyl valerate).
3. the preparation method of polyhydroxy fatty acid ester with high thermal stability according to claim 1 is characterized in that, described organic solvent is 1,2-ethylene dichloride, N, a kind of in N '-dimethyl formamide or the diethylene glycol dimethyl ether.
4. the preparation method of a kind of polyhydroxy fatty acid ester with high thermal stability as claimed in claim 1, it is characterized in that, described two (2-oxazoline) properties-correcting agent is 1, two (2-oxazoline-2) ethane, 1 of 2-, two (2-oxazoline-2) butane, 1 of 4-, two (2-oxazoline-2) hexanes, 1 of 6-, two (2-oxazoline-2) octanes and 1 of 8-, two (2-oxazoline-2) hexanaphthenes of 4-, 1, two (2-oxazoline-2) benzene, 1 of 2-, two (2-oxazoline-2) benzene, 1 of 3-, two (2-oxazoline-2) benzene or 2 of 4-, a kind of in 2 '-two (2-oxazolines).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450989B (en) * | 2008-12-19 | 2011-11-23 | 东华大学 | Method for synthesizing poly hydroxy fatty acid ester block copolymers in situ |
| CN105504663A (en) * | 2016-01-26 | 2016-04-20 | 苏州羽帆新材料科技有限公司 | Heat-resistant and aging-resistant plastic material and preparation method thereof |
| CN106220836A (en) * | 2016-08-30 | 2016-12-14 | 无锡市兴盛新材料科技有限公司 | A kind of preparation method of high viscosity resistance to thermal degradation PBT polyester |
-
2007
- 2007-10-19 CN CN2007100472784A patent/CN101148501B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450989B (en) * | 2008-12-19 | 2011-11-23 | 东华大学 | Method for synthesizing poly hydroxy fatty acid ester block copolymers in situ |
| CN105504663A (en) * | 2016-01-26 | 2016-04-20 | 苏州羽帆新材料科技有限公司 | Heat-resistant and aging-resistant plastic material and preparation method thereof |
| CN106220836A (en) * | 2016-08-30 | 2016-12-14 | 无锡市兴盛新材料科技有限公司 | A kind of preparation method of high viscosity resistance to thermal degradation PBT polyester |
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| CN101148501B (en) | 2010-06-16 |
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