CN103951814B - A kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester - Google Patents
A kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester Download PDFInfo
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- CN103951814B CN103951814B CN201410221360.4A CN201410221360A CN103951814B CN 103951814 B CN103951814 B CN 103951814B CN 201410221360 A CN201410221360 A CN 201410221360A CN 103951814 B CN103951814 B CN 103951814B
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- branched polyester
- end carboxyl
- super branched
- carboxyl super
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- 229920000728 polyester Polymers 0.000 title claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 12
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011090 malic acid Nutrition 0.000 claims abstract description 12
- 239000001630 malic acid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 229920000587 hyperbranched polymer Polymers 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 7
- -1 polyphenylene Polymers 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester.Oxysuccinic acid is joined in organic solvent, stir and make it fully dissolve, obtained malic acid solution; By catalyst dissolution in DMF, at N
2progressively be added drop-wise in malic acid solution under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester; Described organic solvent is one or more in tetrahydrofuran (THF), acetone, methyl alcohol, DMF and N,N-dimethylacetamide; Described catalyzer is one or both in N, N-dicyclohexylcarbodiimide and N, N-DIC.The inventive method raw material sources are extensive, and price is low, pollutes little, and technique is simple, and products therefrom excellent property, can significantly improve composite materials property, and promote curing reaction.
Description
Technical field
The invention belongs to field of high polymer material modification, particularly relating to a kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester.
Background technology
Hyperbranched polymer (Hyperbranchedpolymer, HBP) is the emerging macromolecular material of a class, and it is a kind of random multi-level branched polymkeric substance of height with three-dimensional globular three-dimensional arrangement.Hyperbranched polymer theory is proposed by Flory in nineteen fifty-two, he describes this possibility that is noncrystalline, that synthesize without the hyperbranched polymer be wound around, also done some predictions to its characteristic simultaneously, but do not caused enough attention.1987, E.I.Du Pont Company Kim has applied for first patent about Hyperbranched polyphenylene synthesis, within 1988, in the American Chemical Society of Los Angeles, disclose this achievement, nineteen ninety reports the syntheses and properties method about hyperbranched polymer, and proposes this noun of " hyperbranched " (hyperbranched).From then on, hyperbranched polymer to become in polymer chemistry an important branch gradually.Up to now, the multiple hyperbranched polymers such as the superbranched polystyrene of Hyperbranched polyphenylene, polyester, polyethers, polyamine, polymeric amide, urethane, polysiloxane and vinyl monomer have been synthesized.Particularly recently, researchist more and more payes attention to the synthesis of hyperbranched polymer, stuctures and properties, has become the another focus in field of polymer technology.
Hyperbranched polymer is the macromole with " nucleocapsid " structure, and " shell " of molecule is highly branched, and end assembles a large amount of active function groups, without tangling between molecule.Therefore, show the property that simple linear polymer does not have, as good solubility, low solution viscosity, high reaction activity etc., and by end capping in addition modification, the performance of tailoring can be reached.Hyperbranched polymer synthesis technique is simple, be easy to industrialization, these performances make hyperbranched polymer demonstrate tempting application prospect in polymer blending, tamanori, coating, high molecule liquid crystal, medicament slow release, nanometer and hybrid inorganic-organic materials etc. are many.
Epoxy resin (EP) has chemical resistance, electrical property, electrical insulating property, bonding force is strong, good stability and the premium properties such as shrinking percentage is little, and it is with low cost, be made up of and the advantage such as processing means flexible formula again, being widely used in the fields such as tackiness agent, coating, potting compound, structured material and fibre reinforced composites, is one of most widely used matrix resin in polymer matrix composite.But because the cross linking of epoxy resin density after solidification is high, internal stress is large, and thus there is the shortcomings such as matter is crisp, resistance to fatigue is poor, thermotolerance is low, be difficult to the requirement meeting modern high technology, the application in high-tech area is subject to certain restrictions.Sun will to have etc. and reports patent of invention " a kind of preparation method containing the low branched polyester liquid crystal of xenyl " (ZL201110049224.8), utilize this low branched polyester liquid crystal modified epoxy, research shows that a small amount of hyper-branched polyester liquid crystal can the toughness of raising epoxy resin by a relatively large margin, modulus and thermotolerance.Meanwhile, also show mechanical property and thermal characteristics that hyperbranched polymer effectively can improve matrix material.
Be main raw material with oxysuccinic acid, utilize the end carboxyl super branched polyester of polycondensation synthesizing biological degradable, have no report at present.
Summary of the invention
The object of this invention is to provide a kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester.
Concrete steps are:
(1) 2 ~ 6 grams of oxysuccinic acid are joined in 6 ~ 10 milliliters of organic solvents, stir and make it fully dissolve, obtained malic acid solution.
(2) by 1 ~ 4 gram of catalyst dissolution in 3 ~ 8 milliliters of DMFs, at N
2progressively be added drop-wise in the obtained malic acid solution of step (1) under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
Described organic solvent is one or more in tetrahydrofuran (THF), acetone, methyl alcohol, DMF and N,N-dimethylacetamide.
Described catalyzer is one or both in N, N-dicyclohexylcarbodiimide and N, N-DIC.
The inventive method has the following advantages:
(1) raw material sources are extensive, and price is low, and environmental pollution is little.
(2) preparation technology is comparatively simple, is applicable to fairly large production and popularization.
(3) consistency in matrix resin of the end carboxyl super branched polyester prepared by is good, effectively can improve the mechanical property of matrix material, and end carboxyl also participates in curing reaction, plays the effect of curing catalyst.
Embodiment
The main raw material that following examples are used: oxysuccinic acid (technical grade), tetrahydrofuran (THF) (THF, analytical pure), N, N-dicyclohexylcarbodiimide (DCC, analytical pure), N, dinethylformamide (DMF, analytical pure), epoxy resin (epoxy E-44, technical grade), 4,4′ diaminodiphenyl sulfone (DDS, technical grade).
embodiment 1:
(1) 3 grams of oxysuccinic acid are joined in 7 milliliters of tetrahydrofuran (THF)s, stir and make it fully dissolve, obtained malic acid solution.
(2) 1 gram of N, N-dicyclohexylcarbodiimide is dissolved in 8 milliliters of DMFs, at N
2progressively be added drop-wise in the obtained malic acid solution of step (1) under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
The end carboxyl super branched polyester getting 0.26 gram of the present embodiment obtained joins in 26 grams of epoxy resin-bases, decompression is bled, add 7.8 grams of DDS solidifying agent again, pour into after mixed dissolution and scribble in the steel die of estersil, in 120 DEG C/2 hours+160 DEG C/2 hours+180 DEG C/2 little curing moldings at present, obtained end carboxyl super branched polyester modified epoxy resin matrix material.
Through the epoxy resin that the end carboxyl super branched polyester (consumption is only the 1wt% of epoxy resin) that the present embodiment is obtained is modified, its shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 24.2kJ/m
2, improve 38.3%, tensile strength improves 39%, and flexural strength increases by 51%.
embodiment 2:
(1) 4 grams of oxysuccinic acid are joined in 8 milliliters of tetrahydrofuran (THF)s, stir and make it fully dissolve, obtained malic acid solution.
(2) 1.5 grams of N, N-dicyclohexylcarbodiimide are dissolved in 8 milliliters of DMFs, at N
2progressively be added drop-wise in the obtained malic acid solution of step (1) under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
The end carboxyl super branched polyester getting 0.78 gram of the present embodiment obtained joins in 26 grams of epoxy resin-bases, decompression is bled, add 7.8 grams of DDS solidifying agent again, pour into after mixed dissolution and scribble in the steel die of estersil, in 120 DEG C/2 hours+160 DEG C/2 hours+180 DEG C/2 little curing moldings at present, obtained end carboxyl super branched polyester modified epoxy resin matrix material.
Through the epoxy resin that the end carboxyl super branched polyester (consumption is only the 3wt% of epoxy resin) that the present embodiment is obtained is modified, shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 29.6kJ/m
2, improve 69.2%, tensile strength improves 41%, and flexural strength increases by 53%.
embodiment 3:
(1) 6 grams of oxysuccinic acid are joined in 10 milliliters of tetrahydrofuran (THF)s, stir and make it fully dissolve, obtained malic acid solution.
(2) 1.5 grams of N, N-dicyclohexylcarbodiimide are dissolved in 8 milliliters of DMFs, at N
2progressively be added drop-wise in the obtained malic acid solution of step (1) under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
The end carboxyl super branched polyester getting 1.3 grams of the present embodiment obtained joins in 26 grams of epoxy resin-bases, decompression is bled, add 7.8 grams of DDS solidifying agent again, pour into after mixed dissolution and scribble in the steel die of estersil, in 120 DEG C/2 hours+160 DEG C/2 hours+180 DEG C/2 little curing moldings at present, obtained end carboxyl super branched polyester modified epoxy resin matrix material.
Through the epoxy resin that the end carboxyl super branched polyester (consumption is only the 5wt% of epoxy resin) that the present embodiment is obtained is modified, shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 34.3kJ/m
2, improve 96%, tensile strength improves 43%, and flexural strength increases by 58%.
Claims (1)
1. be the method that main raw material prepares end carboxyl super branched polyester with oxysuccinic acid, it is characterized in that concrete steps are:
(1) 2 ~ 6 grams of oxysuccinic acid are joined in 6 ~ 10 milliliters of organic solvents, stir and make it fully dissolve, obtained malic acid solution;
(2) by 1 ~ 4 gram of catalyst dissolution in 3 ~ 8 milliliters of DMFs, at N
2progressively be added drop-wise in the obtained malic acid solution of step (1) under protection, after stirring at normal temperature reacts 12 hours, filter, removing pale precipitation thing, filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester;
Described organic solvent is one or more in tetrahydrofuran (THF), acetone, methyl alcohol, DMF and N,N-dimethylacetamide;
Described catalyzer is one or both in N, N-dicyclohexylcarbodiimide and N, N-DIC.
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| CN201410221360.4A CN103951814B (en) | 2014-05-25 | 2014-05-25 | A kind of take oxysuccinic acid as the method that main raw material prepares end carboxyl super branched polyester |
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| CN103951814B true CN103951814B (en) | 2015-12-30 |
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| CN104610532B (en) * | 2014-12-15 | 2017-01-11 | 威海金泓集团有限公司 | Biodegradable dendritic scale inhibitor |
| CN110218331B (en) * | 2019-06-13 | 2021-03-09 | 烟台正海合泰科技股份有限公司 | Bio-based hyperbranched formaldehyde-removing agent and preparation method thereof |
| CN113336888B (en) * | 2021-05-28 | 2022-09-13 | 华南农业大学 | Super-hydrophilic oil-water separation membrane with response of alkaloid and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002148A (en) * | 2010-11-17 | 2011-04-06 | 张家港柴能生物科技有限公司 | Method for preparing biodegradable poly(malic acid) material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002148A (en) * | 2010-11-17 | 2011-04-06 | 张家港柴能生物科技有限公司 | Method for preparing biodegradable poly(malic acid) material |
Non-Patent Citations (1)
| Title |
|---|
| 聚苹果酸及其衍生物的研究与发展;李睿颖等;《食品工程》;20090630(第2期);6-9 * |
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Application publication date: 20140730 Assignee: Guilin liangwuzao Environmental Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045156 Denomination of invention: A method for preparing carboxyl terminated hyperbranched polyester using malic acid as the main raw material Granted publication date: 20151230 License type: Common License Record date: 20231102 |
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