CN104987499B - 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, more particularly, to a kind of water solublity maleopimaric acid is hyperbranched
The preparation method of polyester.
Technical background
Dissaving polymer has the polymer of highly branched, three-dimensional netted molecular structure, has linear polymer and does not have
Standby superiority, such as low viscosity, preferable dissolubility, the features such as polyfunctional group, wherein hyper-branched polyester is dissaving polymer
In an important class product.Hyper-branched polyester is the dissaving polymer with ester group as repetitives, and end group typically contains in a large number
Free hydroxyl group.The synthesis of hyper-branched polyester mainly has the side such as abx type monomer autohemagglutination, ring-opening polymerisation and multifunctional groups monomer copolymerization
Method, the structure according to monomer can be divided into Aromatic Hyperbranched Polyesters and aliphatic hyper-branched polyester again.Compared with linear polyester, tool
There are good mobility, low viscosity, multifunctionality and good dissolubility so as to apply in biological medicine, photocuring
The fields such as material, polymer blending, polymeric membrane are widely used research.
There are abundant Colophonium resource, predominantly gum rosin in China.Colophonium is highly important natural product, is also a kind of
Highly important Renewable resource.With the exhaustion of the fossil resources such as oil, each state is all in the substitution of research oil, pine
Fragrant and its derivant is of great interest, becomes the important source material preparing a lot of products.
Abietyl hyper-branched polyester is the new material just having begun one's study in recent years, and maleopimaric acid is by sea left-handed in Colophonium
Pine acid and maleic anhydride occur diels-alder to be synthesized, and have condensed cyclic structure and similar trimellitic anhydride structure, by it
It is incorporated in resin and can improve resin hardness, intensity etc., obtain the material of property.At present, synthesized with maleopimaric acid
The research report of hyper-branched polyester aspect is seldom.Sun Liting [chemistry of forest product and industry, 2013,33 (3): 1-6] etc. utilizes Malaysia
Dextropimaric acid is polymerized with open loop of epoxy compound and obtains performance preferably new rosin base hyper-branched polyester；[the thermosettings such as Ma Xiaoshu
Resin, 2010,25 (1): 40-42,47] obtain hyper-branched polyester solid in light using maleopimaric acid and epichlorohydrin reaction
Change field is applied；But it is both needed to use solvent in building-up process, and the epoxide market price is higher.Therefore, develop
Process is simple, the method for the utilization Colophonium synthesis of super branched polyester of low cost, can not only widen the purposes of Colophonium, also will improve pine
Fragrant value.
In conventional art, with maleopimaric acid and polyol reaction, mainly generate PEPA, further derive
Become polyurethane, surfactant etc..Liu He etc. [coatings industry, 2013,43 (1): 53-55] utilizes maleopimaric acid and second two
Alcohol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol). and BDO synthesizing polyester polyhydric alcohol, and then it is prepared for aqueous polyurethane；[the south such as Yang Chengwu
Capital polytechnical university journal, 2007,29 (1): 85-88] reacted using maleopimaric acid and neopentyl glycol and obtain high hydroxyl value polyester；Week
[chemical science and technology, 2011,19 (6): 26-30] is reacted using Colophonium and Polyethylene Glycol and obtains Colophonium macrogol ester forever for state, then with
The third three acid reactions, are prepared for a kind of surfactant, and gentle and quiet defend etc. [petrochemical industry, 2004,33 (3): 249-251] uses Colophonium
Obtain polyglycerol rosin ester with polyglycereol reaction, and then be prepared for surfactant of good performance.But, by these reactions
The product with dissaving structure feature can not obtained.
Content of the invention
Present invention aim at disclosing a kind of water solublity maleopimaric acid hyper-branched polyester and preparation method thereof, use Ma Laihai
Pine acid has the water-soluble ultrabranching polyester of wide application prospect with polyhydric alcohol synthesis.
The technical scheme is that a kind of water solublity maleopimaric acid hyper-branched polyester, using solvent-free polymeric legal system
Standby, under nitrogen protection, with maleopimaric acid and Polyethylene Glycol as raw material, under catalyst temperature reaction to acid number≤
After 15mg/g, then reaction under the conditions of vacuum is 0.1～100kpa of reducing pressure is abundant.
The preparation method of described water solublity maleopimaric acid hyper-branched polyester, using the preparation of solvent-free polymeric method, nitrogen
Under protection, with maleopimaric acid and Polyethylene Glycol as raw material, under catalyst temperature reaction to acid number≤15mg/g, then
Decompression reaction under the conditions of vacuum is 0.1～100kpa is abundant.
Maleopimaric acid and Polyethylene Glycol in molar ratio 1: (1.0～2.0) mix.
Described Polyethylene Glycol include polyethylene glycol 200, PEG400, Macrogol 600, in Macrogol 1000
Any one or arbitrarily several composition mixture.
Described catalyst is stannous oxalate, Mono-n-butyltin, butyl titanate, tetraisopropyl titanate, in zinc oxide
One or any several compositions mixture.
Reaction temperature 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 is to react at ambient pressure, when
Acid number is just reacted after dropping to below 15mg/g under vacuum conditions, finally gives water solublity maleopimaric acid hyperbranched poly
Ester.
The primary raw material that the present invention prepares hyper-branched polyester is that maleopimaric acid derives from Colophonium, not only synthetic method letter
List, low cost, it is easy to industrialized production, and aboundresources.
The hyperbranched poly ester terminal of present invention preparation contains great amount of hydroxy group.
The hyper-branched polyester viscosity of present invention preparation is low, has good water solublity, organic solvent solubility and thermostability.
Brief description
Fig. 1 is embodiment 1 products therefrom water solublity maleopimaric acid hyper-branched polyester (a) and raw material maleopimaric acid (b)
The infrared spectrogram of comparison.In figure, maleopimaric acid infrared spectrum (curve b) 1771,1845cm-1For anhydride carbonylic stretching vibration
Absworption peak, 1080cm-1For c-o-c stretching vibration absworption peak；Contrast with mpa, from water solublity maleopimaric acid hyperbranched poly
(curve a) can be clearly visible 3486cm to ester collection of illustrative plates-1Place's hydroxyl peak, anhydride carbonyl characteristic peak 1771cm-1Disappear, and occur
1720cm-1Ester group characteristic peak, illustrates that in maleopimaric acid, anhydride is reacted, obtains superbrnaching end-hydroxy polyester.
Fig. 2 is thermal weight loss (tg) curve of embodiment 1 products therefrom water solublity maleopimaric acid hyper-branched polyester.In figure,
The temperature when 10%, 50%, 90% for the water solublity maleopimaric acid hyper-branched polyester weight-loss ratio be respectively 328 DEG C, 415 DEG C, 453
DEG C, the thermal decomposition of water solublity maleopimaric acid hyper-branched polyester is concentrated mainly on 350 DEG C～450 DEG C, and it is good that this shows that product has
Good thermostability.
Specific embodiment
The following examples are that the present invention is further illustrated, rather than limit the scope of the present invention.
A kind of preparation method of water solublity maleopimaric acid hyper-branched polyester, using solvent-free polymeric method, concretely comprises the following steps:
Under normal pressure, under nitrogen protection, by maleopimaric acid and polyhydric alcohol in molar ratio 1.0: (1.0～2.0) mix, and add and urge in right amount
Agent, 0.5h～24h at a temperature of 180 DEG C～240 DEG C；As acid number≤15mg/g, continuing in vacuum is 0.1～100kpa bar
Under part, continue reaction 0.5h～5h, obtain water-soluble ultrabranching polymer.
The polyhydric alcohol used of the present invention is Polyethylene Glycol series, such as polyethylene glycol 200, PEG400, Polyethylene Glycol
600th, the mixture of one of Macrogol 1000 or its two kinds and two or more composition.
Catalyst amount of the present invention is the 0.05%～2% of maleopimaric acid quality.
Reaction temperature of the present invention is 180 DEG C～240 DEG C.
Catalyst of the present invention is one of organic tin catalyst, titanate ester catalyst, zinc oxide or two kinds and two
Plant the mixture of composition described above.Described catalyst is stannous oxalate, Mono-n-butyltin, butyl titanate, metatitanic acid four isopropyl
One of ester, zinc oxide or the mixture of arbitrarily several composition.
Maleopimaric acid used by the present invention is self-control, and method reference literature: Wang Hongxiao etc. [chemical reagent, 2009,31
(3):177-202].
Embodiment 1
Under normal pressure, in reaction bulb, add 0.20mol (80g) maleopimaric acid, 0.33mol (132g) PEG400,
Add stannous oxalate 0.40g (the 0.5% of maleopimaric acid quality), under nitrogen protection, be warmed up to 230 DEG C about.When acid number≤
15mg/g, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains the hyperbranched polymerization of yellow water-soluble
Thing, yield 83%.
Table 1 is intrinsic viscosity, glass transition temperature and the dissolubility test result of embodiment 1 products therefrom.
The intrinsic viscosity of table 1 hyper-branched polyester, glass transition temperature and dissolubility
Note :+represent solvable；Represent insoluble.
Embodiment 2
Add 0.20mol (80g) maleopimaric acid, 0.36mol (144g) PEG400 in reaction bulb, add grass
Sour stannous 0.40g (the 0.5% of maleopimaric acid quality), are warmed up to 240 DEG C about under nitrogen protection.As acid number≤15mg/g,
Continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains buff water-soluble ultrabranching polymer, yield
87%.
Embodiment 3
Add 0.20mol (80g) maleopimaric acid, 0.39mol (156g) PEG400 in reaction bulb, add titanium
Sour four butyl ester 0.80g (the 1% of maleopimaric acid quality), are warmed up to 230 DEG C about under nitrogen protection.As acid number≤15mg/g,
Continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble dissaving polymer, yield
88%.
Embodiment 4
Add 0.20mol (80g) maleopimaric acid, 0.39mol (78g) polyethylene glycol 200 in reaction bulb, add oxalic acid
Stannous 0.40g (the 0.5% of maleopimaric acid quality), in n2It is to slowly warm up to 220 DEG C, when acid number≤15mg/g is left under protection
The right side, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble hyper-branched polyester, yield
85%.
Embodiment 5
Add 0.20mol (80g) maleopimaric acid, 0.39mol (234g) Macrogol 600 in reaction bulb, add grass
Sour stannous 0.40g (the 0.5% of maleopimaric acid quality), in n2It is to slowly warm up to 220 DEG C, when acid number≤15mg/g is left under protection
The right side, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble hyper-branched polyester, yield
80%.
Embodiment 6
Add 0.20mol (80g) maleopimaric acid, 0.39mol (234g) PEG400 in reaction bulb, add oxygen
Change zinc 0.40g (the 0.5% of maleopimaric acid quality), in n2It is to slowly warm up to 220 DEG C, when acid number≤15mg/g is left under protection
The right side, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble hyper-branched polyester, yield
87%.
Embodiment 7
Add 0.20mol (80g) maleopimaric acid, 0.30mol (120g) PEG400 in reaction bulb, add single
Butyl stannum oxide 0.40g (the 0.5% of maleopimaric acid quality), in n2Be to slowly warm up to 220 DEG C under protection, when acid number≤
15mg/g about, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble hyperbranched poly
Ester, yield 82%.
Embodiment 8
Add 0.20mol (80g) maleopimaric acid, 0.20mol (120g) Macrogol 600 in reaction bulb, add titanium
Sour four isopropyl ester 0.40g (the 0.5% of maleopimaric acid quality), in n2Be to slowly warm up to 220 DEG C under protection, when acid number≤
15mg/g about, continuing in vacuum is that under 0.1～100kpa, decompression continues reaction 0.5h, obtains yellow water-soluble hyperbranched poly
Ester, yield 86%.
Claims (5)
1. a kind of water solublity maleopimaric acid hyper-branched polyester is it is characterised in that using the preparation of solvent-free polymeric method, nitrogen is protected
Under, with maleopimaric acid and Polyethylene Glycol as raw material, temperature reaction under catalyst, to acid number≤15mg/g, then is reduced pressure
Under the conditions of vacuum is 0.1 ~ 100kpa, reaction is abundant；Maleopimaric acid and Polyethylene Glycol in molar ratio 1: (1.0～2.0) mix
Close.
2. the preparation method of the water solublity maleopimaric acid hyper-branched polyester described in claim 1 is it is characterised in that adopt no molten
Prepared by agent polymerization, under nitrogen protection, with maleopimaric acid and Polyethylene Glycol as raw material, under catalyst, temperature reaction is extremely
After acid number≤15mg/g, then reaction under the conditions of vacuum is 0.1 ~ 100kpa of reducing pressure is abundant；Maleopimaric acid and Polyethylene Glycol
In molar ratio 1: (1.0～2.0) mixing.
3. the preparation method of water solublity maleopimaric acid hyper-branched polyester according to claim 2 is it is characterised in that described
Polyethylene Glycol include polyethylene glycol 200, PEG400, Macrogol 600, in Macrogol 1000 any one or
The mixture of arbitrarily several composition of person.
4. the preparation method of water solublity maleopimaric acid hyper-branched polyester according to claim 2 is it is characterised in that described
Catalyst be one of stannous oxalate, Mono-n-butyltin, butyl titanate, tetraisopropyl titanate, zinc oxide or appoint
Anticipate the mixture of several compositions.
5. the preparation method of water solublity maleopimaric acid hyper-branched polyester according to claim 2 is it is characterised in that react
Temperature is 180 DEG C～240 DEG C.
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| CN106519188B (en) * | 2016-09-29 | 2018-10-02 | 中南民族大学 | Abietyl hyperbranched epoxy resin and preparation method and application |
| 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 |
| 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 |
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