CN103387881B - Preparation method of orange oil based unsaturated resin monomer - Google Patents
Preparation method of orange oil based unsaturated resin monomer Download PDFInfo
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Abstract
The invention discloses a preparation method of orange oil based unsaturated resin monomer. The preparation method comprises the following steps of: reacting a certain amount of orange essential oil with unsaturated carboxylic acid or acid anhydride to prepare orange oil based unsaturated carboxylic acid or acid anhydride; and converting the prepared orange oil based unsaturated carboxylic acid or acid anhydride into salt, and reacting the salt with chloropropene to synthesize the orange oil based unsaturated resin monomer. The orange oil based unsaturated resin monomer which is prepared from the preparation method disclosed by the invention is applied to the unsaturated resin field, and can be used for preparing the corresponding products and materials by ultraviolet curing and heating curing after being mixed with other unsaturated resin monomers in a certain proportion. The unsaturated resin monomer which is prepared by using the orange essential oil as the base body material has low viscosity (500mPa.s-1000mPa.s), a high iodine value (200-270) and the potential of replacing normal non-environment-friendly diluent styrene, and therefore, the product is expected to improve the defect that the conventional unsaturated resin has poor toughness and weather resistance. Meanwhile, the comprehensive performances of the unsaturated resin copolymerized material are improved.
Description
Technical field
The present invention relates to a kind of preparation method of unsaturated polyester monomer, relate generally to by D-A and react to prepare orange oil base unsaturated carboxylic acid (acid anhydride), and then utilize sodium hydroxide to react and make orange oil base unsaturated carboxylic acid sodium salt with the orange oil base unsaturated carboxylic acid (acid anhydride) of gained, finally react to prepare again the method for orange oil base unsaturated polyester monomer with propenyl chloride.
Background technology
Unsaturated polyester generally refers to a resinoid that contains unsaturated double-bond in molecular structure, such as unsaturated polyester resin, vinyl ester resin etc., is all common unsaturated polyester.The vinyl monomer that the raw material of synthetic unsaturated polyester generally comprises undersaturated diprotic acid, dibasic alcohol, dihydroxyphenyl propane and contains carbonyl etc.The synthetic method of monomer whose generally has addition, condensation etc., if the synthetic of unsaturated polyester resin monomer is to obtain by the condensation between diprotic acid and dibasic alcohol.The unsaturated polyester monomer of gained is generally the liquid of semisolid or thickness, during use, need to add a certain amount of thinner, and the thinner of conventional unsaturated polyester is the thinner that contains vinyl monomer.Unsaturated resin products has the performance of many excellences, such as good erosion resistance, excellent electrical insulating property, unique thermal characteristics, excellent processing technology etc., has been widely used in the industries such as building, chemical industry metallurgical, plating, papermaking, chlor-alkali, medicine, food product pack.
At present business is with containing a large amount of rigidity benzene ring structures in unsaturated polyester diluent monomer vinylbenzene, and its cured article fragility is very large, and cured article ubiquity toughness is bad, and the shortcoming that shock resistance is not high is subject to uneven in temperature or External Force Acting to be easy to break; In conventional diluent monomer vinylbenzene, contain a large amount of benzene ring structures in addition, easily absorb UV-light generation photodestruciton, produce free radical and oxidative degradation, under photooxidation out of doors, easily there is xanthochromia and powder phenomenon-tion in unsaturated polyester resin cured article; Now the raw material major part of the unsaturated polyester of use comes from petrochemical materials in addition, and the thinner using in building-up process also mostly comes from petrochemicals, and styrenic thinner, irritant gas, and Long Term Contact is to healthy unfavorable.Therefore, day by day serious along with the day by day exhausted and environmental pollution of petroleum resources, searching high-quality, cheapness, reproducible oil substitute become focus and the development trend of world today's scientific research field.
Orange essential oil is the natural product of a kind of environmental protection of extracting from orange skin.In orange essential oil, contain a large amount of unsaturated double-bonds, so can there are many chemical reactions in it, as oxidation, hydrogenation, isomerization, sulfation, sulfonation, polymerization, pyrolysis etc.So can utilize unsaturated double-bond structure active in orange essential oil to be introduced in unsaturated polyester monomer, make orange oil base unsaturated polyester.China's orange annual production is 1,400 ten thousand tons, so orange essential oil has the abundant advantage in source, and orange essential oil also has the advantages such as asepsis environment-protecting, pleasant aroma in addition, therefore in industries such as chemical industry, agricultural, food, makeup, has a wide range of applications.Orange essential oil can replace many poisonous solvents aspect chemical industry, for example it can replace dimethylbenzene to be used for natural resin and synthetic resins, can also can greatly reduce the wherein content of hazardous and noxious substances as various coating, painting and thinner or additive, reach the requirement of environmental protection.In this research, take orange essential oil as a kind of novel orange oil base unsaturated polyester of development of raw materials, in today of emphasizing away sustainable development path, utilize the feature exploitation of orange essential oil natural environmental-protective to can be used as the orange oil base unsaturated polyester of materials'use significant.
Summary of the invention
the technical problem solving:
In order to improve the shortcomings such as the poor and toxic ingredient content height of the poor toughness, the weathering resistance that exist in traditional unsaturated polyester, the invention provides a kind of preparation method of synthesizing new orange oil base unsaturated polyester monomer, adopting orange essential oil is raw material, first through carrying out D-A with unsaturated carboxylic acid or acid anhydrides, reacts to change into after sodium salt again and reacts with propenyl chloride and make orange oil base unsaturated polyester monomer.The method has the advantages such as reaction conditions gentleness, process efficiency is high, product stability is good.
technical scheme:a preparation method for orange oil base unsaturated polyester monomer, is made by following steps:
The first step: unsaturated carboxylic acid or acid anhydrides are joined in reactor, be warmed up to 45 ~ 60 ℃, it is dissolved completely, drip orange essential oil, wherein orange essential oil and unsaturated carboxylic acid or acid anhydrides mol ratio are 1.2 ~ 1:1, add the catalyst A of reaction system total mass 0.25 ~ 2.0%, be warmed up to 70 ~ 150 ℃, reaction 4 ~ 6h, unreacted orange essential oil, unsaturated carboxylic acid or acid anhydrides and by product are removed in underpressure distillation, obtain intermediate product orange oil base unsaturated carboxylic acid or acid anhydrides; Catalyst A used is a kind of in titanium tetrachloride, divinyl amine, aluminum chloride, boron trifluoride diethyl etherate;
Second step: orange oil base unsaturated carboxylic acid or acid anhydrides that the first step is made are dissolved in water, then drip wherein the aqueous solution of sodium hydroxide, dropwise rear continuation reaction 1 ~ 3h, steam after completion of the reaction water, and vacuum-drying obtains mandarin oil yl carboxylic acid sodium salt;
The 3rd step: the ratio that is 1 ~ 2.4:1 according to mol ratio by propenyl chloride and mandarin oil yl carboxylic acid sodium salt is dissolved in organic solvent, then add the quaternary ammonium salt catalyst B that accounts for orange oil base unsaturated carboxylic acid sodium salt molar mass 0.5% ~ 1.5%, account for the stopper of orange oil base unsaturated carboxylic acid sodium salt molar mass 0.2 ~ 0.5%, at 45 ~ 60 ℃, react 5 ~ 7h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
Selected unsaturated carboxylic acid is: butenoic acid, vinylformic acid, methacrylic acid, 2-phenylacrylic acid or styracin.
Selected acid anhydrides is cis-1, fumaroyl acid anhydride or crotonic anhydride.
The molar weight of the sodium hydroxide that drips equates with carboxyl mole number in system.
Described organic solvent is a kind of in DMF, acetone, ethanol, sherwood oil, tetracol phenixin, methylene dichloride, chloroform, ethyl acetate and dioxane.
Selected quaternary ammonium salt catalyst B is any one in tetramethyl ammonium chloride, 4 bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide.
Selected stopper is a kind of in Resorcinol, para benzoquinone, toluhydroquinone, di-tert-butyl hydroquinone, MEHQ.
beneficial effect:
1 compares with traditional unsaturated polyester, and the orange oil base unsaturated polyester of preparing in the present invention utilizes orange essential oil for raw material, and raw material sources are abundant, product environmental protection, cheap, and broken away from the dependence to petrochemical complex resource.
2, take unsaturated polyester monomer viscosity low (500 ~ 1000 mPas), the iodine number high (200-270) that orange essential oil makes as matrix material, there are the cinnamic potentiality of conventional non-environment-friendly type thinner of substituting, product is expected to improve traditional unsaturated polyester poor toughness and the poor shortcoming of weathering resistance, and improves the over-all properties of unsaturated polyester copolymeric material simultaneously.
3, the product stability that this preparation method's reaction conditions is gentle, process efficiency is high and make is good.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of orange oil base unsaturated polyester monomer.
Embodiment
following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the modification that the inventive method, step or condition are done and replacement, all belong to scope of the present invention.
if do not specialize, the conventional means that in embodiment, technique means used is well known to those skilled in the art.
Orange essential oil is purchased from Huaian Jia Yi Trade Co., Ltd., brown liquid, and purity is 99%.
embodiment 1
The MALEIC ANHYDRIDE of certain mass is joined in reactor, be warmed up to 45 ℃, it is dissolved completely, in being 1:1 with MALEIC ANHYDRIDE mol ratio, ratio drips orange essential oil, add the catalyzer titanium tetrachloride that accounts for reactant total mass 0.25%, be warmed up to 70 ℃, reaction 6h, unreacted orange essential oil, MALEIC ANHYDRIDE and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base MALEIC ANHYDRIDE.The orange oil base MALEIC ANHYDRIDE making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 3h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil MALEIC ANHYDRIDE.The ratio that is 1:2.4 according to mol ratio by the sodium salt of orange oil base MALEIC ANHYDRIDE and propenyl chloride is dissolved in solvent N, dinethylformamide, then add the catalyzer palmityl trimethyl ammonium chloride that accounts for orange oil base MALEIC ANHYDRIDE sodium salt molar mass 0.5%, account for the hydroquinone of polymerization retarder of the sodium salt molar mass 0.2% of mandarin oil MALEIC ANHYDRIDE, at 45 ℃, react 7h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 2
The FUMARIC ACID TECH GRADE acid anhydride of certain mass is joined in reactor, be warmed up to 60 ℃, it is dissolved completely, in being 1.2:1 with FUMARIC ACID TECH GRADE acid anhydride mol ratio, ratio drips orange essential oil, add the catalyzer titanium tetrachloride that accounts for reactant total mass 0.25%, be warmed up to 150 ℃, reaction 4h, unreacted orange essential oil, FUMARIC ACID TECH GRADE acid anhydride and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base FUMARIC ACID TECH GRADE acid anhydride.The orange oil base FUMARIC ACID TECH GRADE acid anhydride making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 1h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil FUMARIC ACID TECH GRADE acid anhydride.The ratio that is 1:2 according to mol ratio by the sodium salt of orange oil base FUMARIC ACID TECH GRADE acid anhydride and propenyl chloride is dissolved in solvent sherwood oil, then add the catalyzer tetramethyl ammonium chloride that accounts for orange oil base FUMARIC ACID TECH GRADE acid anhydride sodium salt molar mass 1.5%, account for the stopper para benzoquinone of the sodium salt molar mass 0.5% of orange oil base FUMARIC ACID TECH GRADE acid anhydride, at 60 ℃, react 5h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 3
The butenoic acid of certain mass is joined in reactor, be warmed up to 55 ℃, it is dissolved completely, in being 1.1:1 with butenoic acid mol ratio, ratio drips orange essential oil, add the catalyzer divinyl amine that accounts for reactant total mass 0.5%, be warmed up to 90 ℃, reaction 5h, unreacted orange essential oil, butenoic acid and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base butenoic acid.The orange oil base butenoic acid making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 2h.Steam after completion of the reaction etoh solvent, and vacuum-drying obtains the sodium salt of mandarin oil butenoic acid.The ratio that is 1:2.2 according to mol ratio by the sodium salt of orange oil base butenoic acid and propenyl chloride is dissolved in solvent tetracol phenixin, then add the catalyzer 4 bromide that accounts for orange oil base butenoic acid sodium salt molar mass 1%, account for the stopper para benzoquinone of the sodium salt molar mass 0.3% of mandarin oil butenoic acid, at 50 ℃, react 5h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 4
The crotonic anhydride of certain mass is joined in reactor, be warmed up to 50 ℃, it is dissolved completely, in being 1.1:1 with crotonic anhydride mol ratio, ratio drips orange essential oil, add the catalyzer titanium tetrachloride that accounts for reactant total mass 1%, be warmed up to 120 ℃, reaction 4h, unreacted orange essential oil, crotonic anhydride and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base crotonic anhydride.The orange oil base crotonic anhydride making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 1h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of orange oil base crotonic anhydride.The ratio that is 1:2.2 according to mol ratio by the sodium salt of orange oil base crotonic anhydride and propenyl chloride is dissolved in solvent acetone, then the catalyzer tetrabutylammonium chloride that adds the sodium salt molar mass 1% that accounts for orange oil base crotonic anhydride, account for the stopper toluhydroquinone of orange oil base crotonic anhydride sodium salt molar mass 0.3%, at 50 ℃, react 6h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 5
The 2-phenylacrylic acid of certain mass is joined in reactor, be warmed up to 55 ℃, it is dissolved completely, in being 1.2:1 with 2-phenylacrylic acid mol ratio, ratio drips orange essential oil, add the catalyzer aluminum chloride that accounts for reactant total mass 0.3%, be warmed up to 120 ℃, reaction 4h, unreacted orange essential oil, 2-phenylacrylic acid and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base 2-phenylacrylic acid.The orange oil base 2-phenylacrylic acid making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 1h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil 2-phenylacrylic acid.The ratio that is 1:2.4 according to mol ratio by the sodium salt of orange oil base 2-phenylacrylic acid and propenyl chloride is dissolved in etoh solvent, then add the catalyzer Tetrabutyl amonium bromide that accounts for orange oil base 2-phenylacrylic acid sodium salt molar mass 1.5%, account for the stopper di-tert-butyl hydroquinone of the sodium salt molar mass 0.4% of mandarin oil 2-phenylacrylic acid, at 50 ℃, react 6h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 6
The vinylformic acid of certain mass is joined in reactor, be warmed up to 50 ℃, it is dissolved completely, in being 1.1:1 with methacrylic anhydride mol ratio, ratio drips orange essential oil, add the catalyzer boron trifluoride diethyl etherate that accounts for reactant total mass 1%, be warmed up to 100 ℃, reaction 6h, unreacted orange essential oil, vinylformic acid and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base vinylformic acid.The orange oil base vinylformic acid making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 2h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil methacrylic anhydride.The ratio that is 1:1.2 according to mol ratio by the acrylic acid sodium salt of orange oil base and propenyl chloride is dissolved in methylene chloride, then add the catalyzer tetraethylammonium bromide that accounts for mandarin oil ylmethyl acrylic anhydride sodium salt molar mass 1%, account for the stopper MEHQ of mandarin oil methacrylic anhydride sodium salt molar mass 0.3%, at 50 ℃, react 5h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 7
The methacrylic acid of certain mass is joined in reactor, be warmed up to 60 ℃, it is dissolved completely, in being 1.1:1 with methacrylic acid mol ratio, ratio drips orange essential oil, add the catalyzer boron trifluoride diethyl etherate that accounts for reactant total mass 1%, be warmed up to 120 ℃, reaction 4h, unreacted orange essential oil, methacrylic acid and a small amount of by product are removed in underpressure distillation, obtain intermediate product mandarin oil ylmethyl vinylformic acid.The mandarin oil ylmethyl vinylformic acid making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 1h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil methacrylic acid.The ratio that is 1:1.2 according to mol ratio by the acrylic acid sodium salt of mandarin oil ylmethyl and propenyl chloride is dissolved in solvent chloroform, then add the catalyzer benzyl trimethyl ammonium chloride that accounts for the acrylic acid sodium salt molar mass 0.5% of mandarin oil ylmethyl, account for the hydroquinone of polymerization retarder of mandarin oil sodium salt of methacrylic acid molar mass 0.5%, at 50 ℃, react 5h, after completion of the reaction except desolventizing, obtain orange oil base unsaturated polyester monomer, infrared spectrogram is referring to Fig. 1.
embodiment 8
The styracin of certain mass is joined in reactor, be warmed up to 50 ℃, it is dissolved completely, in being 1.2:1 with styracin mol ratio, ratio drips orange essential oil, add the catalyzer titanium tetrachloride that accounts for reactant total mass 0.75%, be warmed up to 90 ℃, reaction 6h, unreacted orange essential oil, styracin and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base styracin.The orange oil base styracin making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 2h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil styracin.The ratio that is 1:1.2 according to mol ratio by the sodium salt of mandarin oil ylmethyl styracin and propenyl chloride is dissolved in solvent ethyl acetate, then the catalyzer cetyl trimethylammonium bromide that adds the sodium salt molar mass 0.5% that accounts for orange oil base styracin, account for the stopper para benzoquinone of mandarin oil styracin sodium salt molar mass 0.5%, at 60 ℃, react 6h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
embodiment 9
The MALEIC ANHYDRIDE of certain mass is joined in reactor, be warmed up to 50 ℃, it is dissolved completely, in being 1.1:1 with MALEIC ANHYDRIDE mol ratio, ratio drips orange essential oil, add the catalyzer titanium tetrachloride that accounts for reactant total mass 0.5%, be warmed up to 120 ℃, reaction 5h, unreacted orange essential oil, MALEIC ANHYDRIDE and a small amount of by product are removed in underpressure distillation, obtain intermediate product orange oil base MALEIC ANHYDRIDE.The orange oil base MALEIC ANHYDRIDE making is dissolved in water, then drips wherein the aqueous solution (amount of sodium hydroxide equates with carboxyl mole number) of sodium hydroxide, dropwise rear continuation reaction 1h.Steam after completion of the reaction aqueous solvent, and vacuum-drying obtains the sodium salt of mandarin oil MALEIC ANHYDRIDE.The ratio that is 1:2.4 according to mol ratio by the sodium salt of orange oil base MALEIC ANHYDRIDE and propenyl chloride is dissolved in solvent dioxane, then add the catalyzer palmityl trimethyl ammonium chloride that accounts for orange oil base MALEIC ANHYDRIDE sodium salt molar mass 0.5%, account for the hydroquinone of polymerization retarder of the sodium salt molar mass 0.2% of mandarin oil MALEIC ANHYDRIDE, at 50 ℃, react 6h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
comparative example:
experimental group 1:the orange oil base unsaturated polyester monomer of embodiment 9 preparations is accurately taken to 40g, then add maleic anhydride modified epoxy soybean oil acrylate 60g, add again and account for reactant 1.5%wt initiator benzoyl peroxide, mix in the airtight grinding tool of the shape that is placed on special requirement, at 120 ℃, heat Procuring 3h, after being then increased to 160 ℃, solidify 4h, then slow cooling to normal temperature makes copolymeric material after making and solidifying again again.
experimental group 2:the orange oil base unsaturated polyester monomer of embodiment 7 preparations is accurately taken to 40g, then add maleic anhydride modified epoxy soybean oil acrylate 60g, add again and account for reactant 1.5%wt initiator benzoyl peroxide, mix in the airtight grinding tool of the shape that is placed on special requirement, at 120 ℃, heat Procuring 3h, after being then increased to 160 ℃, solidify 4h, then slow cooling to normal temperature makes copolymeric material after making and solidifying again again.
experimental group 3: take vinylbenzene 40g, then add maleic anhydride modified epoxy soybean oil acrylate 60g, add again and account for reactant 1.5%wt initiator benzoyl peroxide, mix in the airtight grinding tool of the shape that is placed on special requirement, at 120 ℃, heat Procuring 3h, after being then increased to 160 ℃, solidify 4h, then slow cooling to normal temperature makes copolymeric material after making and solidifying again again.
Above-mentioned two kinds of thermosetting materials are carried out to comprehensive mechanical property analysis, and measurement result is described in table 1.
Table 1 is got the thermofixation comprehensive mechanical property contrast of each experimental group at random
| Group name | Experimental group 1 | Experimental group 2 | Experimental group 3 |
| Viscosity/mPas | 500 | 560 | 200 |
| Tensile strength/MPa | 18.2 | 15.9 | 20.2 |
| Flexural strength/MPa | 27.1 | 24.3 | 23.1 |
| Resistance to impact shock/kJm -2 | 2.65 | 3.46 | 3.46 |
Note: the viscosity of orange oil base unsaturated polyester monomer is measured with reference to GB/T 7193.1-1987; The color and luster of orange oil base unsaturated polyester monomer body, with reference to GB/T 1722-79, adopts iron cobalt colorimetry to measure; Compound system sample tensile property is with reference to GB/T 1040-1992 plastic tensile test method, flexural strength is with reference to GB/T 1043-1993, resistance to impact shock is with reference to GB/T 9341-2008, adopt CMT4000 type microcomputer controlled electronic universal tester (newly think carefully in Shenzhen), measure tensile property and the bending property of material, Elongation test speed is 10 mm/min, crooked test speed is 5 mm/min, span 50 mm, adopt XJJY-5 impact tester for simple supported beam test material resistance to impact shock, Mechanics Performance Testing temperature is 25 ℃.
Claims (5)
1. a preparation method for orange oil base unsaturated polyester monomer, is characterized in that being made by following steps:
The first step: unsaturated carboxylic acid or acid anhydrides are joined in reactor, be warmed up to 45 ~ 60 ℃, it is dissolved completely, drip orange essential oil, wherein orange essential oil and unsaturated carboxylic acid or acid anhydrides mol ratio are 1.2 ~ 1:1, add the catalyst A of reaction system total mass 0.25 ~ 2.0%, be warmed up to 70 ~ 150 ℃, reaction 4 ~ 6h, unreacted orange essential oil, unsaturated carboxylic acid or acid anhydrides and by product are removed in underpressure distillation, obtain intermediate product orange oil base unsaturated carboxylic acid or acid anhydrides; Catalyst A used is a kind of in titanium tetrachloride, divinyl amine, aluminum chloride, boron trifluoride diethyl etherate; Selected unsaturated carboxylic acid is: butenoic acid, vinylformic acid, methacrylic acid, 2-phenylacrylic acid or styracin; Selected acid anhydrides is cis-1, fumaroyl acid anhydride or crotonic anhydride;
Second step: orange oil base unsaturated carboxylic acid or acid anhydrides that the first step is made are dissolved in water, then drip wherein the aqueous solution of sodium hydroxide, dropwise rear continuation reaction 1 ~ 3h, steam after completion of the reaction water, and vacuum-drying obtains mandarin oil yl carboxylic acid sodium salt;
The 3rd step: the ratio that is 1 ~ 2.4:1 according to mol ratio by propenyl chloride and mandarin oil yl carboxylic acid sodium salt is dissolved in organic solvent, then add the quaternary ammonium salt catalyst B that accounts for orange oil base unsaturated carboxylic acid sodium salt molar mass 0.5% ~ 1.5%, account for the stopper of orange oil base unsaturated carboxylic acid sodium salt molar mass 0.2 ~ 0.5%, at 45 ~ 60 ℃, react 5 ~ 7h, except desolventizing, obtain orange oil base unsaturated polyester monomer after completion of the reaction.
2. the preparation method of a kind of orange oil base unsaturated polyester monomer according to claim 1, is characterized in that dripping the molar weight of sodium hydroxide and equates with carboxyl mole number in system.
3. the preparation method of a kind of orange oil base unsaturated polyester monomer according to claim 1, it is characterized in that described organic solvent is a kind of in DMF, acetone, ethanol, sherwood oil, tetracol phenixin, methylene dichloride, chloroform, ethyl acetate and dioxane.
4. the preparation method of a kind of orange oil base unsaturated polyester monomer according to claim 1, is characterized in that selected quaternary ammonium salt catalyst B is any one in tetramethyl ammonium chloride, 4 bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide.
5. the preparation method of a kind of orange oil base unsaturated polyester monomer according to claim 1, is characterized in that selected stopper is a kind of in Resorcinol, para benzoquinone, toluhydroquinone, di-tert-butyl hydroquinone, MEHQ.
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| CN102826995A (en) * | 2012-09-07 | 2012-12-19 | 中国林业科学研究院林产化学工业研究所 | Low-viscosity turpentine-based monoterpene vinyl ester resin monomer and preparation method and application thereof |
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