CN104987499A - Water-soluble maleopimaric acid hyperbranched polyester and preparation method therefor - Google Patents
Water-soluble maleopimaric acid hyperbranched polyester and preparation method therefor Download PDFInfo
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Abstract
The present invention discloses a water-soluble maleopimaric acid hyperbranched polyester and a preparation method therefor. A maleopimaric acid and a polyhydric alcohol are added to a reactor; under the protection of nitrogen, a proper amount of catalyst is added, and these substances react at 180-240 DEG C for 0.5-24 h; then the reactor is vacuumed and the substances continue to react at the vacuum degree of 0.1-100 KPa for 0.5-5 h to obtain a hyperbranched polyester. The molar ratio of the maleopimaric acid to the polyhydric alcohol is 1: (1.0 to 2.0). According to the present invention, melt polymerization is used without using any solvent and is mild in reaction condition, simple in process, low in cost, and easy in mass production. The water-soluble maleopimaric acid hyperbranched polyester provided by the invention is high in reactivity, good in solubility, and suitable for fields such as paints, plasticizers and adhesives, and has a wide application prospect.
Description
Technical field
The present invention relates to a kind of method preparing hyper-branched polyester, particularly relate to a kind of preparation method of water-soluble maleopimaric acid hyper-branched polyester.
Technical background
Hyperbranched polymer has the polymkeric substance of highly branched, three-dimensional netted molecular structure, there is the superiority that linear polymer does not possess, as low viscosity, good solvability, the features such as polyfunctional group, wherein hyper-branched polyester is a series products important in hyperbranched polymer.Hyper-branched polyester take ester group as the hyperbranched polymer of repeating unit, and end group is generally containing a large amount of free hydroxyl group.The synthesis of hyper-branched polyester mainly contains the methods such as ABx type monomer autohemagglutination, ring-opening polymerization and multifunctional groups monomer copolymerization, and the structure according to monomer can be divided into again Aromatic Hyperbranched Polyesters and aliphatics hyper-branched polyester.Compared with linear polyester, there is the advantages such as good mobility, low viscosity, multifunctionality and good solubility, make it be widely used research in fields such as biological medicine, photo-cured coating, polymer blending, polymeric membranes.
There is abundant rosin resource in China, is mainly gum resin.Rosin is very important natural product, is also a kind of very important renewable resources.Along with the exhaustion of the fossil resources such as oil, each state is all at the substitution of research oil, and rosin and derivative thereof receive to be paid close attention to widely, becomes the important source material preparing a lot of product.
Rosinyl hyper-branched polyester is the type material just begun one's study in recent years, Diels-Alder Reactive Synthesis is there is in maleopimaric acid by levopimaric acid in rosin and maleic anhydride, there is condensed cyclic structure and similar trimellitic anhydride structure, be introduced in resin and can improve resin hardness, intensity etc., obtain the material of property.At present, little with the research report of maleopimaric acid synthesis of super branched polyester aspect.Sun Liting [chemistry of forest product and industry, 2013,33 (3): 1-6] etc. utilizes maleopimaric acid to be polymerized with open loop of epoxy compound and obtains performance preferably new rosin base hyper-branched polyester; Ma Xiaoshu etc. [thermosetting resin, 2010,25 (1): 40-42,47] utilize maleopimaric acid and epichlorohydrin reaction obtain hyper-branched polyester and are applied at curing field; But all need to use solvent in building-up process, and epoxy compounds market value is higher.Therefore, development technology is simple, the method utilizing rosin synthesis of super branched polyester of low cost, can not only widen the purposes of rosin, also will improve the utility value of rosin.
In conventional art, with maleopimaric acid and polyol reaction, mainly generate polyester polyol, further deriving becomes urethane, tensio-active agent etc.Liu He etc. [coatings industry, 2013,43 (1): 53-55] utilize maleopimaric acid and ethylene glycol, glycol ether, triglycol and BDO synthesizing polyester polyvalent alcohol, and then have prepared aqueous polyurethane; Yang Chengwu etc. [Nanjing University of Technology's journal, 2007,29 (1): 85-88] utilize maleopimaric acid and neopentyl glycol to be obtained by reacting high hydroxyl value polyester; Zhou Guoyong [chemical science and technology, 2011,19 (6): 26-30] rosin and polyoxyethylene glycol is utilized to be obtained by reacting rosin macrogol ester, again with the third three acid-responss, prepare a kind of tensio-active agent, gentle and quiet [petrochemical complex, 2004 such as to defend, 33 (3): 249-251] use rosin and Polyglycerine to be obtained by reacting polyglycerol rosin ester, and then prepare tensio-active agent of good performance.But, can not obtain the product with dissaving structure feature by these reactions.
Summary of the invention
The object of the invention is water-soluble maleopimaric acid hyper-branched polyester of open one and preparation method thereof, synthesizes the water-soluble ultrabranching polyester with wide application prospect with maleopimaric acid and polyvalent alcohol.
Technical scheme of the present invention is: a kind of water-soluble maleopimaric acid hyper-branched polyester; adopt solvent-free polymeric legal system standby; under nitrogen protection; with maleopimaric acid and polyoxyethylene glycol for raw material; under catalyst after temperature reaction to acid number≤15mg/g, then the sufficient reacting under vacuum tightness is 0.1 ~ 100kPa condition that reduces pressure.
The preparation method of described water-soluble maleopimaric acid hyper-branched polyester; adopt solvent-free polymeric legal system standby; under nitrogen protection; with maleopimaric acid and polyoxyethylene glycol for raw material; under catalyst after temperature reaction to acid number≤15mg/g, then the sufficient reacting under vacuum tightness is 0.1 ~ 100kPa condition that reduces pressure.
Maleopimaric acid and polyoxyethylene glycol in molar ratio 1: (1.0 ~ 2.0) mix.
Described polyoxyethylene glycol comprises the mixture of any one or any several composition in Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, cetomacrogol 1000.
Described catalyzer is the mixture of the one or any several composition in stannous oxalate, Mono-n-butyltin, tetrabutyl titanate, titanium isopropylate, zinc oxide.
Temperature of reaction is 180 DEG C ~ 240 DEG C.
Beneficial effect:
The present invention adopts the preparation method of solvent-free polymeric.Reaction is divided into two sections, and preceding polymerization reacts at ambient pressure, just reacts under vacuum conditions after acid number drops to below 15mg/g, finally obtains water-soluble maleopimaric acid hyper-branched polyester.
The present invention prepares the main raw material of hyper-branched polyester and maleopimaric acid derives from rosin, and not only synthetic method is simple, cost is low, be easy to suitability for industrialized production, and aboundresources.
Hyperbranched poly ester terminal prepared by the present invention contains great amount of hydroxy group.
Hyper-branched polyester viscosity prepared by the present invention is low, has good water-soluble, organic solvent solubility and thermotolerance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram that water-soluble maleopimaric acid hyper-branched polyester (a) of embodiment 1 products therefrom contrasts with raw material maleopimaric acid (b).In figure, maleopimaric acid infrared spectrum (curve b) 1771,1845cm
-1for acid anhydrides carbonylic stretching vibration absorption peak, 1080cm
-1for-C-O-C-stretching vibration absorption peak; Contrast with MPA, from water-soluble maleopimaric acid hyper-branched polyester collection of illustrative plates, (curve a) obviously can see 3486cm
-1place's hydroxyl peak, acid anhydrides carbonyl characteristic peak 1771cm
-1disappear, and occur 1720cm
-1ester group characteristic peak, illustrates that in maleopimaric acid, acid anhydrides reacts, and obtains superbrnaching end-hydroxy polyester.
Fig. 2 is thermal weight loss (TG) curve of the water-soluble maleopimaric acid hyper-branched polyester of embodiment 1 products therefrom.In figure, the temperature of water-soluble maleopimaric acid hyper-branched polyester rate of weight loss 10%, 50%, 90% time is respectively 328 DEG C, 415 DEG C, 453 DEG C, the thermolysis of water-soluble maleopimaric acid hyper-branched polyester mainly concentrates on 350 DEG C ~ 450 DEG C, and this shows that product has good thermotolerance.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
A kind of preparation method of water-soluble maleopimaric acid hyper-branched polyester, adopt solvent-free polymeric method, concrete steps are: under normal pressure, under nitrogen protection, by maleopimaric acid and polyvalent alcohol in molar ratio 1.0: (1.0 ~ 2.0) mix, add proper catalyst, 0.5h ~ 24h at 180 DEG C ~ 240 DEG C temperature; As acid number≤15mg/g, continue under vacuum tightness is 0.1 ~ 100kPa condition, continue reaction 0.5h ~ 5h, obtain water-soluble ultrabranching polymkeric substance.
Polyvalent alcohol used of the present invention is polyoxyethylene glycol series, as the mixture of a kind of in Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, cetomacrogol 1000 or its two kinds and two or more composition.
Catalyst levels of the present invention is 0.05% ~ 2% of maleopimaric acid quality.
Temperature of reaction of the present invention is 180 DEG C ~ 240 DEG C.
Catalyzer of the present invention is the mixture of one or both and two or more composition in organic tin catalyzer, titanate ester catalyzer, zinc oxide.Described catalyzer is the mixture of the one or any several composition in stannous oxalate, Mono-n-butyltin, tetrabutyl titanate, titanium isopropylate, zinc oxide.
The present invention's maleopimaric acid used is self-control, method reference literature: Wang Hongxiao etc. [chemical reagent, 2009,31 (3): 177-202].
Embodiment 1
Under normal pressure; 0.20mol (80g) maleopimaric acid, 0.33mol (132g) poly(oxyethylene glycol) 400 is added in reaction flask; add stannous oxalate 0.40g (0.5% of maleopimaric acid quality), under nitrogen protection, be warmed up to about 230 DEG C.As acid number≤15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyperbranched polymer, yield 83%.
Table 1 is the limiting viscosity of embodiment 1 products therefrom, second-order transition temperature and solvability test result.
The limiting viscosity of table 1 hyper-branched polyester, second-order transition temperature and solvability
Note :+represent solvable;-represent insoluble.
Embodiment 2
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.36mol (144g) poly(oxyethylene glycol) 400, add stannous oxalate 0.40g (0.5% of maleopimaric acid quality), under nitrogen protection, be warmed up to about 240 DEG C.As acid number≤15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain deep yellow water-soluble ultrabranching polymkeric substance, yield 87%.
Embodiment 3
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.39mol (156g) poly(oxyethylene glycol) 400, add tetrabutyl titanate 0.80g (1% of maleopimaric acid quality), under nitrogen protection, be warmed up to about 230 DEG C.As acid number≤15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyperbranched polymer, yield 88%.
Embodiment 4
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.39mol (78g) Macrogol 200, add stannous oxalate 0.40g (0.5% of maleopimaric acid quality), at N
2slowly be warming up to 220 DEG C under protection, as acid number≤about 15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyper-branched polyester, yield 85%.
Embodiment 5
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.39mol (234g) Polyethylene Glycol-600, add stannous oxalate 0.40g (0.5% of maleopimaric acid quality), at N
2slowly be warming up to 220 DEG C under protection, as acid number≤about 15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyper-branched polyester, yield 80%.
Embodiment 6
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.39mol (234g) poly(oxyethylene glycol) 400, add zinc oxide 0.40g (0.5% of maleopimaric acid quality), at N
2slowly be warming up to 220 DEG C under protection, as acid number≤about 15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyper-branched polyester, yield 87%.
Embodiment 7
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.30mol (120g) poly(oxyethylene glycol) 400, add Mono-n-butyltin 0.40g (0.5% of maleopimaric acid quality), at N
2slowly be warming up to 220 DEG C under protection, as acid number≤about 15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyper-branched polyester, yield 82%.
Embodiment 8
In reaction flask, add 0.20mol (80g) maleopimaric acid, 0.20mol (120g) Polyethylene Glycol-600, add titanium isopropylate 0.40g (0.5% of maleopimaric acid quality), at N
2slowly be warming up to 220 DEG C under protection, as acid number≤about 15mg/g, continue decompression under vacuum tightness is 0.1 ~ 100kPa and continue reaction 0.5h, obtain yellow water-soluble hyper-branched polyester, yield 86%.
Claims (6)
1. a water-soluble maleopimaric acid hyper-branched polyester; it is characterized in that; adopt solvent-free polymeric legal system standby; under nitrogen protection; with maleopimaric acid and polyoxyethylene glycol for raw material; under catalyst after temperature reaction to acid number≤15mg/g, then the sufficient reacting under vacuum tightness is 0.1 ~ 100kPa condition that reduces pressure.
2. the preparation method of water-soluble maleopimaric acid hyper-branched polyester according to claim 1; it is characterized in that; adopt solvent-free polymeric legal system standby; under nitrogen protection; with maleopimaric acid and polyoxyethylene glycol for raw material; under catalyst after temperature reaction to acid number≤15mg/g, then the sufficient reacting under vacuum tightness is 0.1 ~ 100kPa condition that reduces pressure.
3. the preparation method of water-soluble maleopimaric acid hyper-branched polyester according to claim 2, is characterized in that, maleopimaric acid and polyoxyethylene glycol in molar ratio 1: (1.0 ~ 2.0) mix.
4. the preparation method of water-soluble maleopimaric acid hyper-branched polyester according to claim 2, it is characterized in that, described polyoxyethylene glycol comprises the mixture of any one or any several composition in Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, cetomacrogol 1000.
5. the preparation method of water-soluble maleopimaric acid hyper-branched polyester according to claim 2, it is characterized in that, described catalyzer is the mixture of the one or any several composition in stannous oxalate, Mono-n-butyltin, tetrabutyl titanate, titanium isopropylate, zinc oxide.
6. the preparation method of water-soluble maleopimaric acid hyper-branched polyester according to claim 2, is characterized in that, temperature of reaction is 180 DEG C ~ 240 DEG C.
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| CN106519188A (en) * | 2016-09-29 | 2017-03-22 | 中南民族大学 | Abietyl hyper branched epoxy resin and preparation method and application thereof |
| CN106514056A (en) * | 2016-10-06 | 2017-03-22 | 常州市鼎升环保科技有限公司 | Preparation method for electronic substrate welding assistant |
| CN111138278A (en) * | 2019-12-27 | 2020-05-12 | 广州星业科技股份有限公司 | Preparation method of butanediol caprylate |
| CN115322329A (en) * | 2022-08-29 | 2022-11-11 | 南京林业大学 | Preparation method of high-strength easily-degradable and renewable antibacterial polyurethane with dynamic covalent bond and degradation and regeneration method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519188A (en) * | 2016-09-29 | 2017-03-22 | 中南民族大学 | Abietyl hyper branched epoxy resin and preparation method and application thereof |
| CN106514056A (en) * | 2016-10-06 | 2017-03-22 | 常州市鼎升环保科技有限公司 | Preparation method for electronic substrate welding assistant |
| CN111138278A (en) * | 2019-12-27 | 2020-05-12 | 广州星业科技股份有限公司 | Preparation method of butanediol caprylate |
| CN111138278B (en) * | 2019-12-27 | 2023-03-10 | 广州星业科技股份有限公司 | Preparation method of butanediol caprylate |
| CN115322329A (en) * | 2022-08-29 | 2022-11-11 | 南京林业大学 | Preparation method of high-strength easily-degradable and renewable antibacterial polyurethane with dynamic covalent bond and degradation and regeneration method thereof |
| CN115322329B (en) * | 2022-08-29 | 2023-10-27 | 南京林业大学 | Preparation method of high-strength antibacterial polyurethane with dynamic covalent bonds and easy degradation and regeneration method thereof |
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