CN102276788A - Epoxy resin based on gallic acids as well as preparation method and application thereof - Google Patents
Epoxy resin based on gallic acids as well as preparation method and application thereof Download PDFInfo
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- CN102276788A CN102276788A CN 201110118776 CN201110118776A CN102276788A CN 102276788 A CN102276788 A CN 102276788A CN 201110118776 CN201110118776 CN 201110118776 CN 201110118776 A CN201110118776 A CN 201110118776A CN 102276788 A CN102276788 A CN 102276788A
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Abstract
The invention discloses an epoxy resin based on gallic acids with a structure shown as the formula I, which has high epoxy values and also has higher crosslinking density after being cured, thus having good mechanical property and thermal property. The invention also discloses a preparation method of the epoxy resin based on the gallic acids, comprising the following steps: mixing the gallic acids, epoxy halogenopropane and a catalyst and reacting for 2-5 hours at the temperature of 100-120 DEG C; cooling to 20-40 DEG C; adding alkaline compounds and water and continuing to react for 2-5 hours; and washing, removing a solvent and drying to obtain the epoxy resin based on the gallic acids. The preparation method is simple in process, good in controllability and easy to implement industrially. The invention also provides an application of the epoxy resin based on the gallic acids. The epoxy resin based on the gallic acids is particularly applied to preparing composite materials, epoxy adhesives and coatings.
Description
Technical field
The present invention relates to preparation of Resins, epoxy, Resins, epoxy and Application Areas, particularly a kind of Resins, epoxy based on gallic acid and its production and application.
Background technology
The bio-based macromolecular material is main raw material with the renewable resources; it is when the minimizing plastic industry is to petroleum resource consumption; also reduce the petroleum base industrial chemicals in process of production to the pollution of environment, had the double effects of saving petroleum resources and protection environment.Early several years ago, the U.S., Japan, European Union etc. have just successively passed through the sound development that strategic bill such as " biomass research and development bill ", " biotechnology strategy outline ", European environmental standard EN13432 and standard promote economy and environment.In China, Premier Wen Jiabao will make the formal commitment to the world for the end of the year 2009, to reduce 40%～45% on basis in 2005 to the year two thousand twenty China per GDP CO2 emissions, and reach above-mentioned target, the use of bio-based materials is considered to one of important means of development " low-carbon economy ".
Just at present, the research of bio-based macromolecular material mainly is confined to starch plastic, Mierocrystalline cellulose, polycaprolactone (PCL), poly(lactic acid) (PLA), poly butylene succinate (PBS), polyhydroxyalkanoate (PHA), polyvinyl alcohol (PVA) waits some natural polymers or thermoplastic material, then is in the starting stage for the research of thermoset bio-based plastics.Thermosetting resin is being brought into play irreplaceable vital role because of it has good dimensional stability, good thermotolerance and good processibility etc. in all respects of national economy, is a class wide application, macromolecular material that consumption is big.With renewable plant resources is raw material, research and develop novel bio-based thermosetting epoxy resin and be used for substituting existing petroleum-based products, no matter be development trend,, all seem significant and have a extensive future still from the present Research of bio-based plastics from domestic and international bio-based plastics.
Dihydroxyphenyl propane is one of most popular petrochemical materials in the world, is mainly used in macromolecular materials such as producing polycarbonate, Resins, epoxy, polysulfone resin, polyphenylene oxide resin, unsaturated polyester resin.But dihydroxyphenyl propane is suspected that by food and drug administration (FDA) physiology toxicity is arranged, especially dihydroxyphenyl propane class material and Food Contact (as the epoxy coat of can inwall) process in can discharge a small amount of dihydroxyphenyl propane compounds in food so that HUMAN HEALTH is constituted a threat to.In this case, seek and use new raw material, especially substitute traditional petroleum base dihydroxyphenyl propane with renewable resources, materials such as the Resins, epoxy of synthesizing new or polycarbonate seem significant.
Gallic acid has another name called gallic acid, gallate, chemistry by name 3,4, the 5-trihydroxybenzoic acid, generally the form with tannin is present in Turkey-galls, oak bark, tealeaves and the pomegranate etc., be a kind of important natural reproducible resource of China, be widely used in industries such as chemical industry, medicine, food, fuel, light industry and electronics at present.As being that raw material synthetic Tenox PG is a kind of good food antioxidant with the gallic acid, use at many state approvals such as Japan, the U.S., Germany; Be that products such as raw material synthetic salt, amides are the important synthetic intermediates of synthetic antimicrobial, cardiovascular disease resistant, medicine such as anticancer with the gallic acid.Contain a plurality of phenolic hydroxyl groups in the gallic acid, it is comparatively similar with present industrial dihydroxyphenyl propane chemical structure, and the structural formula of gallic acid and the structural formula of dihydroxyphenyl propane are as shown below, and structural similarity demonstrates the potential of synthetic preparation neo-epoxy resin.
The gallic acid dihydroxyphenyl propane
Based on this, present development trend presses for the dihydroxyphenyl propane based epoxy resin that a kind of novel thermosetting epoxy resin replaces tradition to use, so that reach harmonious development between economy and the environment, in the prior art, do not see with the gallic acid to be Resins, epoxy document and the patent report of starting raw material preparation based on gallic acid.
Summary of the invention
The invention provides a kind of Resins, epoxy based on gallic acid, this Resins, epoxy has very high oxirane value, will have higher cross-linking density after solidifying, thereby possess good mechanical performance and thermal property.
The present invention also provides a kind of method of the Resins, epoxy based on gallic acid, and its preparation technology is simple, workable, the process controllability is good, is easy to industrializing implementation.
The present invention also provides a kind of application of the Resins, epoxy based on gallic acid, is specially adapted in matrix material, epoxy adhesive and the coating.
A kind of Resins, epoxy based on gallic acid, the structure of described Resins, epoxy based on gallic acid is a formula I structure:
Resins, epoxy based on gallic acid at room temperature is colourless to light yellow transparent liquid, and 2960cm is arranged in infrared spectrogram
-1, 1720cm
-1, 1580cm
-1, 1205cm
-1, 1080cm
-1, 853cm
-1Deng charateristic avsorption band;
1H nucleus magnetic resonance (CD
3Cl is a solvent) in the characterization displacement study of 7.3ppm, 4.0～4.5ppm, 3.7ppm, 3.1～2.9ppm, 2.7～2.8ppm is arranged, by infrared spectrogram and
1The H nmr spectrum can clearly characterize, and is specially formula I structure; Oxirane value is 0.3～0.72 epoxy equivalent (weight)/100 gram resins.
Contain four active function groups that can be replaced by epoxide group in the gallic acid, by epoxide group it is replaced, so that higher oxirane value, cross-linking density and mechanical strength are arranged behind the epoxy resin cure based on gallic acid.
The preparation method of described Resins, epoxy based on gallic acid may further comprise the steps:
After gallic acid 100 weight parts, epoxy halogenopropane 250～900 weight parts and catalyst mix, at 100 ℃～120 ℃ reaction 2h～5h, be cooled to 20 ℃～40 ℃ then, add basic cpd and water, form reaction system, continue reaction 2h～5h at 20 ℃～40 ℃, through washing, remove and desolvate, obtain after the drying Resins, epoxy based on gallic acid.
For preparation method of the present invention reaches better invention effect, carry out further preferred:
Described epoxy halogenopropane is one or both in epoxy chloropropane, the epoxy bromopropane.The epoxy halogenopropane replaces by different reactions with three hydroxyls and a carboxyl on the gallic acid.
Described catalyzer is one or more in tetramethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, six methynes, four ammoniums, and described catalyst consumption is 5～20 weight parts.
Described basic cpd mainly is meant the inorganic strong alkali compound, can be selected from magnesium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, the hydrated barta one or more, the consumption of described basic cpd is 18～50 weight parts, the consumption of described water is 60～120 weight parts, preferred, water can be selected distilled water for use.
After reaction system reacts completely, carry out aftertreatment again after can waiting to reduce to room temperature; Washing can adopt deionization repeatedly to wash, and washs 3～4 times as each usefulness 150 weight parts～200 parts by weight of deionized water, removes modes such as solvent can adopt that Rotary Evaporators desolvates, and drying can adopt modes such as vacuum-drying.
Described Resins, epoxy based on gallic acid can be applicable to prepare in matrix material, epoxy adhesive and the coating.As Resins, epoxy and the HHPA based on gallic acid being formed cured article, this cured article has excellent mechanical property and higher decomposition temperature, is a kind of matrix material of excellence.
A kind of cured article that contains based on the Resins, epoxy of gallic acid comprises the Resins, epoxy and 10～60 weight part HHPAs based on gallic acid of 100 weight part formula I structures.
The described preparation method who contains based on the cured article of the Resins, epoxy of gallic acid may further comprise the steps:
To mix based on the Resins, epoxy and the HHPA of gallic acid, solidify 1.5h～2.5h at 110 ℃～130 ℃ successively, 140 ℃～160 ℃ solidify 1.5h～2.5h and 170 ℃～190 ℃ and solidify 1.5h～2.5h after, obtain containing cured article based on the Resins, epoxy of gallic acid.
Compared with prior art, the present invention has following advantage:
The present invention is that starting raw material prepares novel bio-based thermosetting epoxy resin with the gallic acid of natural reproducible, can substitute existing petroleum base dihydroxyphenyl propane based epoxy resin, the potential threat of when possessing environmental benefit, having avoided traditional bis-phenol category-A Resins, epoxy that HUMAN HEALTH is caused from the source;
Among the present invention based on the Resins, epoxy oxirane value height of gallic acid, cross-linking density is big after solidifying, have good mechanics and thermal property, for preparation high-performance bio-based Resins, epoxy has been opened up new raw material and new way, also the deep processing for China's gallic acid provides new way, can improve its added value;
The present invention is based on the preparation method of the Resins, epoxy of gallic acid, easy and simple to handle, controllability is good, is suitable for suitability for industrialized production.
The Resins, epoxy that the present invention is based on gallic acid can both be used in matrix material, epoxy adhesive and coating, as the cured article that will prepare based on the Resins, epoxy and the HHPA of gallic acid, have good mechanical property and higher decomposition temperature, be a kind of matrix material of excellence, have boundless application prospect.
Description of drawings
Fig. 1 is the infrared spectrogram based on the Resins, epoxy of gallic acid of preparation among the embodiment 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram based on the Resins, epoxy of gallic acid of preparation among the embodiment 1.
Embodiment
Can further clearly understand content of the present invention by specific embodiments of the invention given below.
100 gram gallic acids and 500 gram epoxy chloropropane are mixed, and temperature rises to 100 ℃, adds tetramethyl ammonium chloride 10 grams, behind 100 ℃ of reaction 5h, be cooled to 30 ℃, add 25 gram sodium hydroxide and 60 gram distilled water then, form reaction system, continue reaction 2h at 30 ℃.After the question response system is reduced to room temperature, use the 200mL deionized water wash at every turn, wash altogether 4 times, desolvate with Rotary Evaporators then, 50 ℃ of vacuum-drying 12h must be based on Resins, epoxy 60 grams of gallic acid.
The Resins, epoxy based on gallic acid of above-mentioned gained is carried out the structure evaluation, and infrared spectrogram as shown in Figure 1.Qualification result is: 2960cm is arranged in infrared spectrogram
-1, 1720cm
-1, 1580cm
-1, 1205cm
-1, 1080cm
-1, 853cm
-1Deng charateristic avsorption band; Hydrogen nuclear magnetic resonance as shown in Figure 2,
1H nucleus magnetic resonance (CD
3Cl is a solvent) in the characterization displacement study of 7.3ppm, 4.0～4.5ppm, 3.7ppm, 3.1～2.9ppm, 2.7～2.8ppm is arranged; Oxirane value is 0.38 epoxy equivalent (weight)/100 gram resins.The Resins, epoxy based on gallic acid of gained has following structure:
With mixing of 100 weight parts that make based on the Resins, epoxy of gallic acid and the HHPA of 29 weight parts, solidify 2h at 120 ℃ respectively then, 150 ℃ solidify 2h and 180 ℃ and solidify 2h after, obtain containing cured article based on the Resins, epoxy of gallic acid.The modulus in flexure that contains based on the cured article of the Resins, epoxy of gallic acid of gained is 2800MPa, and flexural strength is 65MPa, and when the thermal weight loss quality was 5%, corresponding decomposition temperature was at 325 ℃.
Embodiment 2
100 gram gallic acids and 700 gram epoxy bromopropanes are mixed, and temperature rises to 110 ℃, adds octadecyl trimethylammonium bromide 20 grams, behind 110 ℃ of reaction 2h, be cooled to 30 ℃, add 30 gram potassium hydroxide and 60 gram distilled water then, form reaction system, continue reaction 3h at 30 ℃.After the question response system is reduced to room temperature, use the 200mL deionized water wash more at every turn, wash altogether 4 times, desolvate with Rotary Evaporators then, 50 ℃ of vacuum-drying 12h must be based on Resins, epoxy 80 grams of gallic acid.
The Resins, epoxy based on gallic acid of above-mentioned gained is carried out the structure evaluation, basic identical among qualification result and the embodiment 1.Oxirane value is 0.6 epoxy equivalent (weight)/100 gram resins after measured.With mixing of 100 weight parts based on the Resins, epoxy of gallic acid and 46 weight part HHPAs, solidify 2h at 120 ℃ respectively then, 150 ℃ solidify 2h and 180 ℃ and solidify 2h after, obtain containing cured article based on the Resins, epoxy of gallic acid.The modulus in flexure that contains based on the cured article of the Resins, epoxy of gallic acid of gained is 3200MPa, and flexural strength is 76MPa, and when the thermal weight loss quality was 5%, corresponding decomposition temperature was at 340 ℃.
Embodiment 3
100 gram gallic acids, 300 gram epoxy bromopropanes and 300 gram epoxy chloropropane are mixed, temperature rises to 120 ℃, add octadecyl trimethylammonium bromide 6 grams and six methynes, four ammoniums, 12 grams, behind 120 ℃ of reaction 4h, be cooled to 30 ℃, add 10 gram potassium hydroxide, 8 gram magnesium hydroxides and 60 gram distilled water then, form reaction system, continue reaction 4h at 30 ℃.After the question response system is reduced to room temperature, use the 200mL deionized water wash more at every turn, wash altogether 4 times, desolvate with Rotary Evaporators then, 50 ℃ of vacuum-drying 12h must be based on Resins, epoxy 68 grams of gallic acid.
The Resins, epoxy based on gallic acid of above-mentioned gained is identified, basic identical among qualification result and the embodiment 1.Oxirane value is 0.53 epoxy equivalent (weight)/100 gram resins after measured.100 weight parts should be mixed based on the Resins, epoxy of gallic acid and 41 weight part HHPAs, solidified 2h at 120 ℃ respectively then, 150 ℃ solidify 2h and 180 ℃ and solidify 2h after, obtain containing cured article based on the Resins, epoxy of gallic acid.The modulus in flexure that contains based on the cured article of the Resins, epoxy of gallic acid of gained is 3000MPa, and flexural strength is 62MPa, and when the thermal weight loss quality was 5%, corresponding decomposition temperature was at 336 ℃.
Embodiment 4
100 gram gallic acids and 700 gram epoxy chloropropane are mixed, and temperature rises to 116 ℃, adds cetyl trimethylammonium bromide 18 grams, behind 116 ℃ of reaction 3h, be cooled to 30 ℃, add 28 gram calcium hydroxides and 60 gram distilled water then, form reaction system, continue reaction 3h at 30 ℃.After the question response system is reduced to room temperature, use the 200mL deionized water wash more at every turn, wash altogether 4 times, desolvate with Rotary Evaporators then, 50 ℃ of vacuum-drying 12h must be based on Resins, epoxy 84 grams of gallic acid.
The Resins, epoxy based on gallic acid of above-mentioned gained is carried out the structure evaluation, basic identical among qualification result and the embodiment 1.Oxirane value is 0.72 epoxy equivalent (weight)/100 gram resins after measured.100 weight parts are mixed based on the Resins, epoxy of gallic acid and 60 weight part HHPAs, solidify 2h at 120 ℃ respectively then, 150 ℃ solidify 2h and 180 ℃ and solidify 2h after, obtain containing cured article based on the Resins, epoxy of gallic acid.The modulus in flexure that contains based on the cured article of the Resins, epoxy of gallic acid of gained is 3340MPa, and flexural strength is 82MPa, and when the thermal weight loss quality was 5%, corresponding decomposition temperature was at 342 ℃.
Above-mentioned is in conjunction with the embodiments the present invention to be elaborated; but embodiments of the present invention are not restricted to the described embodiments, and other any change of being done under patent core guiding theory of the present invention, replacement, combination simplification etc. are included within the protection domain of patent of the present invention.
Claims (10)
1. the Resins, epoxy based on gallic acid is characterized in that, the structure of described Resins, epoxy based on gallic acid is a formula I structure:
2. the preparation method of the Resins, epoxy based on gallic acid according to claim 1 may further comprise the steps:
After gallic acid 100 weight parts, epoxy halogenopropane 250～900 weight parts and catalyst mix, at 100 ℃～120 ℃ reaction 2h～5h, be cooled to 20 ℃～40 ℃ then, add basic cpd and water, form reaction system, continue reaction 2h～5h at 20 ℃～40 ℃, through washing, remove and desolvate, obtain after the drying Resins, epoxy based on gallic acid.
3. the preparation method of the Resins, epoxy based on gallic acid according to claim 2 is characterized in that described epoxy halogenopropane is one or both in epoxy chloropropane, the epoxy bromopropane.
4. the preparation method of the Resins, epoxy based on gallic acid according to claim 2, it is characterized in that described catalyzer is one or more in tetramethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, six methynes, four ammoniums.
5. according to the preparation method of claim 2 or 4 described Resins, epoxy based on gallic acid, it is characterized in that described catalyst consumption is 5～20 weight parts.
6. the preparation method of the Resins, epoxy based on gallic acid according to claim 2 is characterized in that described basic cpd is one or more in magnesium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, the hydrated barta.
7. the preparation method of the Resins, epoxy based on gallic acid according to claim 2 is characterized in that the consumption of described basic cpd is 18～50 weight parts;
The consumption of described water is 60～120 weight parts.
8. the application of Resins, epoxy in preparation matrix material, epoxy adhesive and coating based on gallic acid according to claim 1.
9. cured article that contains based on the Resins, epoxy of gallic acid comprises the Resins, epoxy and 10～60 weight part HHPAs based on gallic acid of 100 weight part formula I structures;
10. the preparation method who contains based on the cured article of the Resins, epoxy of gallic acid according to claim 9 may further comprise the steps:
After will mixing based on the Resins, epoxy of gallic acid and HHPA, solidify 1.5～2.5h at 110～130 ℃ successively, 140～160 ℃ solidify 1.5～2.5h and 170 ℃～190 ℃ and solidify 1.5～2.5h after, obtain containing cured article based on the Resins, epoxy of gallic acid.
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