CN103435576B - A kind of Malic acid radical water-borne epoxy resin and preparation method thereof - Google Patents
A kind of Malic acid radical water-borne epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Malic acid radical water-borne epoxy resin (shown in I) and preparation method thereof.This Malic acid radical water-borne epoxy resin first under the existence of acid binding agent, obtains a kind of oxysuccinic acid diallyl ester (shown in II) by oxysuccinic acid and allylation reagent by dehydrohalogenation; Reacted by oxysuccinic acid diallyl ester and peralcohol and obtained again.This Malic acid radical water-borne epoxy resin for raw material, is conducive to reducing macromolecular material to the consumption of petroleum resources and reduce CO with the abundant oxysuccinic acid of biogenetic derivation
2discharge, open new approach for preparing aqueous epoxy resins simultaneously.This Malic acid radical water-borne epoxy resin has water miscible feature, being applied using water as the field of solvent, can have broad application prospects.
Description
Technical field
The present invention relates to bio-based polymeric material field, be specifically related to a kind of Malic acid radical water-borne epoxy resin and preparation method thereof.
Background technology
Along with petroleum resources are day by day exhausted, finding sustainable, high-quality, cheapness oil substitute is the key of polymer industry Existence and development.Bio-based macromolecular material take renewable resources as main raw material, reduce plastic industry to while petrochemicals consumption, also reduce the pollution to environment in petroleum-based feedstock production process, be an important development direction of current macromolecular material, there is important actual value and wide development space.
Oxysuccinic acid is one of intermediate of tricarboxylic acid cycle, be present in the multiple fruits such as apple, grape, hawthorn, along with its raw materials fumaroyl can by Wood Adhesives from Biomass, the oxysuccinic acid of bio-based not only can obtain by extracting directly from plant, indirectly can also be obtained from biomass by Degradation and Transformation.And along with biomass ferment method directly obtains the continuous maturation of oxysuccinic acid, with biomass be from now on raw material prepare oxysuccinic acid can be more and more easier.Current oxysuccinic acid is mainly applied to food and field of medicaments with the form of additive, and demand is relatively less.And hydroxyl in oxysuccinic acid molecular structure and carboxyl isoreactivity functional group conveniently carry out number of chemical reaction, are applicable to being applied to polymeric material field.Polymalic acid material and the polyester containing oxysuccinic acid are the main application of current oxysuccinic acid in field of polymer technology.
Application publication number is CN 102002148A(application number is 201010547712.7) Chinese invention patent application disclose a kind of preparation method of biodegradable polymalic acid material.Publication number is 101041711A(application number is 200710027397.3) Chinese invention patent application disclose the method for the preparation of biological catalyst in a kind of organic medium containing malic acid unit functional polyester, with dibasic alcohol and oxysuccinic acid for monomer, utilize the direct polymerization of lipase-catalyzed dibasic alcohol and oxysuccinic acid to react, prepare the functional polyester containing malic acid unit.Application publication number is CN 102127211A(application number is 201110040215.2) Chinese invention patent application disclose a kind of biomass polyester, comprise glycerine, Xylitol etc. with the oxysuccinic acid of biomass source, methylene-succinic acid, citric acid etc. with the polyvalent alcohol of biomass source and prepare a kind of full biomass polyester, mainly for the preparation of environment-friendly material and biomedical material.
Above-mentioned patent application has certain pushing effect to oxysuccinic acid in the extensive application of field of polymer technology.But based on the special construction of oxysuccinic acid, being not limited only to above-mentioned polymalic acid material or biomass polyester makes oxysuccinic acid be applied preparing in macromolecular material, need the oxysuccinic acid based compound that more structures are provided further, oxysuccinic acid based compound is used widely preparing in macromolecular material.
Up to the present, yet there are no the document directly utilizing oxysuccinic acid synthetic epoxy resin and patent report in prior art.
Summary of the invention
The invention provides a kind of Malic acid radical water-borne epoxy resin, there is epoxide group.
A kind of Malic acid radical water-borne epoxy resin is the compound of formula I structure;
Present invention also offers a kind of preparation method of Malic acid radical water-borne epoxy resin, reacted by oxysuccinic acid and allylation reagent and prepare oxysuccinic acid diallyl ester, again oxysuccinic acid diallyl ester and peralcohol are obtained by reacting epoxy resin, its preparation is simple, easy to implement and control.
A preparation method for Malic acid radical water-borne epoxy resin, comprises following two steps:
1) by the acid binding agent of the first organic solvent of the oxysuccinic acid of 100 mass parts, 100 ~ 1500 mass parts, the allylation reagent of 40 ~ 800 mass parts and 25 ~ 400 mass parts, 0 ~ 80 DEG C of reaction 0.5 ~ 72 hour, obtain the oxysuccinic acid diallyl ester of formula II structure through the first aftertreatment;
2) by the second organic solvent of the oxysuccinic acid diallyl ester of 100 mass parts, the peralcohol of 30 ~ 700 mass parts, the catalyzer of 0 ~ 300 mass parts and 50 ~ 2500 mass parts, 0 ~ 80 DEG C of reaction 1 ~ 200 hour, after the second aftertreatment, then obtain the Malic acid radical water-borne epoxy resin of formula I structure.
In step 1), as preferably, described allylation reagent is chlorallylene or allyl bromide 98.This allylation reagent can react with oxysuccinic acid, the oxysuccinic acid diallyl ester of production II structure.
Described acid binding agent is one or both in mineral alkali, organic bases, as preferably, described acid binding agent is salt of wormwood, one or more (comprising two kinds) in sodium hydroxide, sodium carbonate, potassium hydroxide, lithium hydroxide, calcium oxide, calcium hydroxide, magnesium hydroxide, pyridine, triethylamine, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene.Acid binding agent can absorption reaction generate hydrogenchloride, hydrogen bromide, reaction is carried out smoothly.
As preferably, the first described organic solvent is tetrahydrofuran (THF), dioxane, ether, acetone, butanone, N, N '-dimethyl methane amide, N, one or more (comprising two kinds) in N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO).First organic solvent plays the effect of dissolving and diluting reaction thing, and reaction is carried out smoothly.
As preferably, the first described aftertreatment comprises filtration, washing and underpressure distillation desolventizes and water, obtains oxysuccinic acid diallyl ester after the first aftertreatment.
Step 2) in, as preferably, described peralcohol is hydrogen peroxide, metachloroperbenzoic acid, Peracetic Acid or the hydrogen peroxide trimethyl carbinol.Oxysuccinic acid diallyl ester and peralcohol are obtained by reacting Malic acid radical water-borne epoxy resin.
As preferably, described catalyzer is one or more (comprising two kinds) in formic acid, acetic acid, sulfuric acid, hydrochloric acid or ion exchange resin, the Amberlite sequence of ion exchange resin that ion exchange resin specifically can select Rhom and Hass to produce.
As preferably, the second described organic solvent is one or more (comprising two kinds) in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, acetone, butanone.Second organic solvent plays the effect of dissolving and diluting reaction thing, and reaction is carried out smoothly.
As preferably, the second described aftertreatment comprises: first adopt the reductibility compound water solution of mass percent 5% ~ 20% to wash 0 ~ 5 time, adopt the basic cpd solution washing 1 ~ 5 time of mass percent 5% ~ 20% again, adopt washing afterwards, finally remove solvent and water etc. under reduced pressure, after the second aftertreatment, obtain Malic acid radical water-borne epoxy resin.
Further preferably, described reductibility compound is S-WAT, sodium bisulfite, Sodium Pyrosulfite or V-Brite B, is mainly used for reducing unreacted peralcohol.Described basic cpd is sodium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, potassium hydroxide or saleratus, is mainly used for washing away acidic substance.
Described Malic acid radical water-borne epoxy resin can be used for preparing cured article, has good second-order transition temperature and good hardness.
Malic acid radical water-borne epoxy resin, water and polyetheramine are mixed, is coated on matrix, after solidification, form cured article.
The present invention has following advantage relative to prior art:
One, the present invention with reproducible oxysuccinic acid for Material synthesis prepares bio-based glycidyl ester epoxy resin; the new source of epoxy resin raw materials, new variety are opened up; enrich the structure of epoxy resin; reduce from synthesis source or avoid the use of petroleum chemicals, there is the double effects economized on resources with protection of the environment.
Two, containing hydroxyl in the bio-based epoxy resin synthesized in the present invention, adding epoxy group(ing), the existence of ester bond etc., make it have water miscible feature, being applied using water as the field of solvent, can have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of oxysuccinic acid diallyl ester prepared by embodiment 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of Malic acid radical water-borne epoxy resin prepared by embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
1) 100g oxysuccinic acid, 1200g dioxane, 800g chlorallylene and 60g sodium hydroxide mixing, 80 DEG C of reactions 8 hours, filters, washing, underpressure distillation desolventizes, obtains oxysuccinic acid diallyl ester after water etc.
This oxysuccinic acid diallyl ester
1h NMR spectrogram as shown in Figure 1, occur in Fig. 1 that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) by the Amberlite sequence of ion exchange resin of the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, 30g hydrogen peroxide, 20g formic acid, the production of 5gAmberlite-120(Rhom and Hass) and the mixing of 50g dioxane, 60 DEG C of reactions 60 hours, 2 times are washed again with the aqueous sodium hydroxide solution of mass percent 5%, adopt washing afterwards, after finally removing solvent and water etc. under reduced pressure, obtain Malic acid radical water-borne epoxy resin.
This Malic acid radical water-borne epoxy resin
1h NMR spectrogram as shown in Figure 2, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.811(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Embodiment 2
1) 100g oxysuccinic acid, 900g tetrahydrofuran (THF), 400g chlorallylene and 400g salt of wormwood mixed, 40 DEG C of reactions 72 hours, filter, washing, underpressure distillation desolventizes, obtain oxysuccinic acid diallyl ester after water etc.
According to this oxysuccinic acid diallyl ester
1h NMR spectrogram is known, occur in figure that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, 700g metachloroperbenzoic acid and 2500g methylene dichloride are mixed, 25 DEG C of reactions 200 hours, 5 times are washed again with the sodium sulfite aqueous solution of mass percent 5%, then 5 times are washed with the aqueous sodium carbonate of mass percent 15%, adopt washing afterwards, after finally removing solvent and water etc. under reduced pressure, obtain Malic acid radical water-borne epoxy resin.
According to this Malic acid radical water-borne epoxy resin
1h NMR spectrogram is known, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.809(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Embodiment 3
1) by 100g oxysuccinic acid, 100g dimethyl sulfoxide (DMSO), 300g allyl bromide 98 and 300g1,8-diazabicylo [5.4.0] 11 carbon-7-alkene mixes, and 0 DEG C of reaction 0.5 hour, filters, washing, underpressure distillation desolventizes, obtain oxysuccinic acid diallyl ester after water etc.
According to this oxysuccinic acid diallyl ester
1h NMR spectrogram is known, occur in figure that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, 400g hydrogen peroxide, 120g formic acid, 180g sulfuric acid and 900g butanone are mixed, 70 DEG C of reactions 10 hours, adopt the V-Brite B solution washing 1 time of mass percent 20% again, then the potassium hydroxide aqueous solution washing of mass percent 5% is adopted, adopt washing afterwards, after finally removing solvent and water etc. under reduced pressure, obtain Malic acid radical water-borne epoxy resin.
According to this Malic acid radical water-borne epoxy resin
1h NMR spectrogram is known, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.808(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Embodiment 4
1) 100g oxysuccinic acid, 700g butanone, 180g allyl bromide 98 and 200g triethylamine mixed, 20 DEG C of reactions 18 hours, filter, washing, underpressure distillation desolventizes, obtain oxysuccinic acid diallyl ester after water etc.
According to oxysuccinic acid diallyl ester
1h NMR spectrogram is known, occur in figure that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, the 600g hydrogen peroxide trimethyl carbinol, 800g acetone and 1200g trichloromethane are mixed, 10 DEG C of reactions 150 hours, the metabisulfite solution of mass percent 15% is adopted to wash 4 times again, then 4 times are washed with the wet chemical that mass percent is 10%, adopt washing afterwards, after finally removing solvent and water etc. under reduced pressure, obtain Malic acid radical water-borne epoxy resin.
According to this Malic acid radical water-borne epoxy resin
1h NMR spectrogram is known, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.814(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Embodiment 5
1) by 100g oxysuccinic acid, 400g N, N '-dimethyl methane amide, 100g chlorallylene and 150g pyridine mix, and 65 DEG C of reactions 32 hours, filter, washing, underpressure distillation desolventizes, obtain oxysuccinic acid diallyl ester after water etc.
According to oxysuccinic acid diallyl ester
1h NMR spectrogram is known, occur in figure that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, 200g Peracetic Acid and 1500g tetrahydrofuran (THF) are mixed, 80 DEG C of reactions 1 hour, adopt again mass percent be 10% aqueous solution of sodium bisulfite wash 2 times, then adopt mass percent be 20% sodium bicarbonate aqueous solution wash 2 times, adopt washing afterwards, finally adopt after removing solvent and water etc. under reduced pressure and obtain Malic acid radical water-borne epoxy resin.
According to this Malic acid radical water-borne epoxy resin
1h NMR spectrogram is known, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.810(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Embodiment 6
1) by 100g oxysuccinic acid, 1300g acetone, 200g N, N '-dimethyl ethanamide, 600g chlorallylene and 100g calcium oxide mix, and 50 DEG C of reactions 50 hours, filter, washing, underpressure distillation desolventizes, obtain oxysuccinic acid diallyl ester after water etc.
According to this oxysuccinic acid diallyl ester
1h NMR spectrogram is known, occur in figure that about 5.88-5.97ppm and 5.18-5.37ppm represents the H in allyl double bonds, about 4.57-4.66ppm represents the H that methylene radical adjacent with double bond on allyl group adds, H on 2.84ppm representative-OH, other peaks conform to the H proton displacement of oxysuccinic acid diallyl ester, prove that the oxysuccinic acid diallyl ester obtained has formula II structure.
2) the oxysuccinic acid diallyl ester of above-mentioned for 100g preparation, 100g hydrogen peroxide, 60g acetic acid, 10g hydrochloric acid and 200g acetone are mixed, 45 DEG C of reactions 100 hours, again with mass percent be 20% potassium bicarbonate aqueous solution washing, adopt washing afterwards, after finally removing solvent and water etc. under reduced pressure, obtain Malic acid radical water-borne epoxy resin.
According to this Malic acid radical water-borne epoxy resin
1h NMR spectrogram is known, proton peak 5.88-5.97ppm in double bond in oxysuccinic acid diallyl ester and 5.18-5.37ppm all disappears, there is the special proton peak (2.5-3.2ppm) of epoxide group, and the proton peak of-OH has moved on to 3.49ppm, add that other peaks conform to the H proton displacement of Malic acid radical water-borne epoxy resin, prove that the Malic acid radical water-borne epoxy resin prepared has formula I structure.
This Malic acid radical water-borne epoxy resin records oxirane value for 0.813(theoretical epoxy value is for 0.812 with hydrochloric acid acetone method).
Application examples
The Malic acid radical water-borne epoxy resin that 3g water, 5g embodiment 1 are prepared and 2.3g polyetheramine (D230, Aladdin provides), mix, be applied on tinplate, room temperature 25 DEG C is volatilization moisture content limit solidification 24h below, obtain cured article, the second-order transition temperature of cured article be 70 DEG C (after sample solidification, grinding powder, the test of MET type differential scanning calorimeter is produced with Mettler Toledo Inc., N2 atmosphere, temperature rise rate is 20 DEG C/min), pencil hardness is 2H.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (1)
1. a preparation method for Malic acid radical water-borne epoxy resin, is characterized in that, comprises following two steps:
1) by the acid binding agent of the first organic solvent of the oxysuccinic acid of 100 mass parts, 100 ~ 1500 mass parts, the allylation reagent of 40 ~ 800 mass parts and 25 ~ 400 mass parts, 0 ~ 80 DEG C of reaction 0.5 ~ 72 hour, obtain the oxysuccinic acid diallyl ester of formula II structure through the first aftertreatment;
Described allylation reagent is chlorallylene or allyl bromide 98;
Described acid binding agent is one or more in salt of wormwood, sodium hydroxide, sodium carbonate, potassium hydroxide, lithium hydroxide, calcium oxide, calcium hydroxide, magnesium hydroxide, pyridine, triethylamine, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene;
The first described organic solvent is tetrahydrofuran (THF), dioxane, ether, acetone, butanone, N, N '-dimethyl methane amide, N, one or more in N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO);
2) by the second organic solvent of the oxysuccinic acid diallyl ester of 100 mass parts, the peralcohol of 30 ~ 700 mass parts, the catalyzer of 0 ~ 300 mass parts and 50 ~ 2500 mass parts, 0 ~ 80 DEG C of reaction 1 ~ 200 hour, after the second aftertreatment, then obtain the Malic acid radical water-borne epoxy resin of formula I structure;
Described peralcohol is hydrogen peroxide, metachloroperbenzoic acid, Peracetic Acid or the hydrogen peroxide trimethyl carbinol;
Described catalyzer is one or more in formic acid, acetic acid, sulfuric acid, hydrochloric acid or ion exchange resin;
The second described organic solvent is one or more in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, acetone, butanone.
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