CN103951814A - Method for preparing carboxyl-terminated hyperbranched polyester by taking malic acid as main raw material - Google Patents
Method for preparing carboxyl-terminated hyperbranched polyester by taking malic acid as main raw material Download PDFInfo
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- CN103951814A CN103951814A CN201410221360.4A CN201410221360A CN103951814A CN 103951814 A CN103951814 A CN 103951814A CN 201410221360 A CN201410221360 A CN 201410221360A CN 103951814 A CN103951814 A CN 103951814A
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- CN
- China
- Prior art keywords
- malic acid
- raw material
- branched polyester
- main raw
- hyperbranched polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 title claims abstract description 16
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 235000011090 malic acid Nutrition 0.000 title claims abstract description 16
- 239000001630 malic acid Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 229920006150 hyperbranched polyester Polymers 0.000 title abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000002904 solvent 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
- 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 6
- -1 polyphenylene Polymers 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920000642 polymer Polymers 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
- 229910000831 Steel Inorganic materials 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
- 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
- 230000015572 biosynthetic process Effects 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
- 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
- 238000003786 synthesis reaction Methods 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 method for preparing carboxyl-terminated hyperbranched polyester by taking malic acid as a main raw material. The method comprises the steps of adding malic acid into an organic solvent, stirring to enable the malic acid to be sufficiently dissolved to prepare a malic acid liquid; dissolving a catalyst into N, N-dimethylformamide, gradually and dropwise adding the liquid into the malic acid liquid under the protection of N2, reacting for 12h under stirring at normal temperature, then, filtering to remove grey white sediments, distilling filtrate to remove the solvent to obtain a faint yellow oily viscous liquid, i.e., the carboxyl-terminated hyperbranched polyester. The organic solvent is one or more selected from tetrahydrofuran, acetone, methanol, N, N-dimethylformamide and N, N-dimethylacetamide; and the catalyst is one or both selected from N, N-dicyclohexylcarbodiimide and N, N-diisopropylcarbondiimide. The method disclosed by the invention is wide in raw material source, low in price, little in pollution and simple in process; and in addition, the obtained product is favorable in performance and capable of remarkably improving the mechanical performance of a composite and accelerating curing reaction.
Description
Technical field
The invention belongs to polymer modification technical field, particularly relate to and a kind ofly take oxysuccinic acid and prepare the method for end carboxyl super branched polyester as main raw material.
Background technology
Hyperbranched polymer (Hyperbranched polymer, 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 spherical three-dimensional arrangement.Hyperbranched polymer theory is to be proposed by Flory in nineteen fifty-two, he described this noncrystalline, without the synthetic possibility of hyperbranched polymer being wound around, also its characteristic has been done to some predictions simultaneously, but has not caused enough attention.1987, the Kim of E.I.Du Pont Company has applied for that first is about the synthetic patent of Hyperbranched polyphenylene, in 1988 Nian Los Angeles American Chemical Societies, announced this achievement, nineteen ninety has been reported the synthetic and characterizing method about hyperbranched polymer, and has proposed " hyperbranched " (hyperbranched) this noun.From then on, hyperbranched polymer becomes an important branch in polymer chemistry gradually.Up to now, the multiple hyperbranched polymers such as superbranched polystyrene that synthesized Hyperbranched polyphenylene, polyester, polyethers, polyamine, polymeric amide, urethane, polysiloxane and vinyl monomer.Particularly recently, researchist more and more payes attention to synthetic, the structure of hyperbranched polymer and performance, 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 is assembled a large amount of active function groups, and between molecule, nothing is tangled.Therefore, show the property that simple linear polymer does not have, as good solubility, low solution viscosity, high reaction activity etc., and can, by addition modification of end capping, reach the performance of tailoring.Hyperbranched polymer synthesis technique is simple, be easy to industrialization, these performances make hyperbranched polymer demonstrate tempting application prospect at polymer blending, tamanori, coating, high molecule liquid crystal, medicament slow release, nanometer and hybrid inorganic-organic materials etc. aspect many.
Epoxy resin (EP) has chemical resistance, electrical property, electrical insulating property, bonding force is strong, the premium propertiess such as good stability and shrinking percentage are little, and with low cost, by formula, is formed again and the flexible advantage such as easy variation of processing means, 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 solidifying is high, internal stress is large, thereby has the shortcomings such as matter is crisp, resistance to fatigue is poor, thermotolerance is low, is difficult to meet the requirement of modern high technology, and the application in high-tech area is subject to certain restrictions.Sun will has etc. has reported patent of invention " a kind of preparation method who contains the low branched polyester liquid crystal of xenyl " (ZL201110049224.8), utilize this low branched polyester liquid crystal modified epoxy, research shows toughness, modulus and the thermotolerance of the raising epoxy resin that a small amount of hyper-branched polyester liquid crystal can be by a relatively large margin.Meanwhile, also shown that hyperbranched polymer can effectively improve mechanical property and the thermal characteristics of matrix material.
Take oxysuccinic acid as main raw material, utilize the end carboxyl super branched polyester of polycondensation synthesizing biological degradable, have no at present report.
Summary of the invention
The object of this invention is to provide and a kind ofly take oxysuccinic acid and prepare the method for end carboxyl super branched polyester as main raw material.
Concrete steps are:
(1) 2 ~ 6 grams of oxysuccinic acid are joined in 6 ~ 10 milliliters of organic solvents, stir it is fully dissolved, make malic acid solution.
(2) by 1 ~ 4 gram of catalyst dissolution in 3 ~ 8 milliliters of DMFs, at N
2under protection, be progressively added drop-wise in the malic acid solution that step (1) makes, stirring at normal temperature reaction, after 12 hours, is filtered, and removes pale precipitation thing, and 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 N, N-dicyclohexylcarbodiimide and N, one or both in 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 simpler, is applicable to fairly large production and popularization.
(3) prepared end carboxyl super branched polyester consistency in matrix resin is good, can effectively improve the mechanical property of matrix material, and holds carboxyl also to participate 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 '-diaminodiphenylsulfone(DDS) (DDS, technical grade).
embodiment 1:
(1) 3 grams of oxysuccinic acid are joined in 7 milliliters of tetrahydrofuran (THF)s, stir it is fully dissolved, make malic acid solution.
(2), by 1 gram of N, N-dicyclohexylcarbodiimide is dissolved in 8 milliliters of DMFs, at N
2under protection, be progressively added drop-wise in the malic acid solution that step (1) makes, stirring at normal temperature reaction, after 12 hours, is filtered, and removes pale precipitation thing, and filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
Getting the end carboxyl super branched polyester that 0.26 gram of the present embodiment makes joins in 26 grams of epoxy resin-bases, decompression is bled, add again 7.8 grams of DDS solidifying agent, after mixed dissolution, pour in the steel die that scribbles estersil, in 120 ℃/2 hours+160 ℃/2 hours+180 ℃/2 hours lower curing moldings, make end carboxyl super branched polyester modified epoxy resin matrix material.
Epoxy resin after the end carboxyl super branched polyester making through the present embodiment (consumption is only the 1wt% of epoxy resin) modification, its shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 24.2kJ/m
2, having improved 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 it is fully dissolved, make malic acid solution.
(2), by 1.5 grams of N, N-dicyclohexylcarbodiimide is dissolved in 8 milliliters of DMFs, at N
2under protection, be progressively added drop-wise in the malic acid solution that step (1) makes, stirring at normal temperature reaction, after 12 hours, is filtered, and removes pale precipitation thing, and filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
Getting the end carboxyl super branched polyester that 0.78 gram of the present embodiment makes joins in 26 grams of epoxy resin-bases, decompression is bled, add again 7.8 grams of DDS solidifying agent, after mixed dissolution, pour in the steel die that scribbles estersil, in 120 ℃/2 hours+160 ℃/2 hours+180 ℃/2 hours lower curing moldings, make end carboxyl super branched polyester modified epoxy resin matrix material.
Epoxy resin after the end carboxyl super branched polyester making through the present embodiment (consumption is only the 3wt% of epoxy resin) modification, shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 29.6kJ/m
2, having improved 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 it is fully dissolved, make malic acid solution.
(2), by 1.5 grams of N, N-dicyclohexylcarbodiimide is dissolved in 8 milliliters of DMFs, at N
2under protection, be progressively added drop-wise in the malic acid solution that step (1) makes, stirring at normal temperature reaction, after 12 hours, is filtered, and removes pale precipitation thing, and filtrate obtains faint yellow oily thick liquid through distillation except after desolventizing, is end carboxyl super branched polyester.
Getting the end carboxyl super branched polyester that 1.3 grams of the present embodiment make joins in 26 grams of epoxy resin-bases, decompression is bled, add again 7.8 grams of DDS solidifying agent, after mixed dissolution, pour in the steel die that scribbles estersil, in 120 ℃/2 hours+160 ℃/2 hours+180 ℃/2 hours lower curing moldings, make end carboxyl super branched polyester modified epoxy resin matrix material.
Epoxy resin after the end carboxyl super branched polyester making through the present embodiment (consumption is only the 5wt% of epoxy resin) modification, shock strength is by the 17.5kJ/m of pure epoxy resin
2bring up to 34.3 kJ/m
2, having improved 96%, tensile strength improves 43%, and flexural strength increases by 58%.
Claims (1)
1. the oxysuccinic acid of take is prepared the method for end carboxyl super branched polyester as main raw material, 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 it is fully dissolved, make malic acid solution;
(2) by 1 ~ 4 gram of catalyst dissolution in 3 ~ 8 milliliters of DMFs, at N
2under protection, be progressively added drop-wise in the malic acid solution that step (1) makes, stirring at normal temperature reaction, after 12 hours, is filtered, and removes pale precipitation thing, and 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 N, N-dicyclohexylcarbodiimide and N, one or both in N-DIC.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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|---|---|---|---|
| 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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| CN103951814A true CN103951814A (en) | 2014-07-30 |
| CN103951814B CN103951814B (en) | 2015-12-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610532A (en) * | 2014-12-15 | 2015-05-13 | 威海晨源分子新材料有限公司 | New biodegradable dendritic scale inhibitor |
| CN110218331A (en) * | 2019-06-13 | 2019-09-10 | 烟台正海合泰科技股份有限公司 | A kind of hyperbranched aldehyde remover of biology base and preparation method thereof |
| CN113336888A (en) * | 2021-05-28 | 2021-09-03 | 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 |
-
2014
- 2014-05-25 CN CN201410221360.4A patent/CN103951814B/en active Active
Patent 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 |
Non-Patent Citations (1)
| Title |
|---|
| 李睿颖等: "聚苹果酸及其衍生物的研究与发展", 《食品工程》, no. 2, 30 June 2009 (2009-06-30), pages 6 - 9 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610532A (en) * | 2014-12-15 | 2015-05-13 | 威海晨源分子新材料有限公司 | New biodegradable dendritic scale inhibitor |
| CN104610532B (en) * | 2014-12-15 | 2017-01-11 | 威海金泓集团有限公司 | Biodegradable dendritic scale inhibitor |
| CN110218331A (en) * | 2019-06-13 | 2019-09-10 | 烟台正海合泰科技股份有限公司 | A kind of hyperbranched aldehyde remover of biology base and preparation method thereof |
| CN113336888A (en) * | 2021-05-28 | 2021-09-03 | 华南农业大学 | Super-hydrophilic oil-water separation membrane with response of alkaloid and preparation method and application thereof |
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| CN103951814B (en) | 2015-12-30 |
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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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