CN104387564A - Method for preparing flame-retardant orange essential oil-based vinyl ester resin monomer - Google Patents
Method for preparing flame-retardant orange essential oil-based vinyl ester resin monomer Download PDFInfo
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Abstract
The invention discloses a method for preparing a flame-retardant orange essential oil-based vinyl ester resin monomer. The method comprises the following steps: adding an unsaturated anhydride into a reactor so as to be completely fused, and dripping orange essential oil; performing reduced pressure distillation to remove impurities, thereby obtaining an intermediate product orange essential oil-based anhydride; dripping distilled water, carrying out a condensate reflux reaction, thereby preparing an orange essential oil-based dicarboxylic acid; adding DOPO into the orange essential oil-based dicarboxylic acid prepared in the first step, and heating and reacting so as to obtain a flame-retardant orange essential oil-based dicarboxylic acid; adding the flame-retardant orange essential oil-based dicarboxylic acid and epoxy chloropropane into a reactor, adding a catalyst A, adding sodium hydroxide and calcium oxide with the same mole number as carboxyl, stirring, performing suction filtration so as to obtain the filtrate, and performing rotary evaporation to remove excessive epoxy chloropropane, thereby obtaining flame-retardant orange essential oil-based epoxy resin; and adding the flame-retardant orange essential oil-based epoxy resin, a catalyst B and a polymerization inhibitor into a reactor, heating, and dripping acrylic acid into the reactor, thereby preparing the flame-retardant orange essential oil-based vinyl ester resin monomer.
Description
Technical field
The present invention relates to a kind of preparation method of flame retardant type bio-based vinyl ester resin monomer, relate generally to by epoxy resin route to prepare the method for flame retardant type orange essential oil base vinyl ester resin monomer.
Background technology
Vinyl ester resin is the common resin of a class in unsaturated polyester, the solidifying product of vinyl ester resin has good erosion resistance, excellent electrical insulating property, excellent processing technology etc., has been widely used in the industries such as building, chemical industry metallurgical, medicine, food product pack.
Usually containing a large amount of rigidity benzene ring structure in conventional ethylene base ester resin monomer, the cured article fragility after resin solidification is very large, breaks by External Force Acting or uneven in temperature being easy to.In addition, curing system is limited to the self-curing characteristic of monomer reactivity group, and the handiness that mixed with resin proportioning is adjustable is little, is difficult to carry out free allotment according to the hard and soft characteristic of practical application to cured article.The most flame retardant properties of conventional ethylene base ester resin is poor, and the easy temperature distortion of solidified coating is even caught fire, and common solution adds appropriate fire retardant.The conventional fire retardant being coated with material flame-retardant and mostly belonging to non-reactive, there is the phenomenons such as flame retardant properties is low, fire retardant is easily separated out in modified curing system.The interpolation of single type fire retardant also can cause coating flame retardant properties to improve the problems such as not obvious, solidification and adhesive property reduction.
The raw material major part of vinyl ester resin present in addition comes from fossil feedstock, and product and middle product have strong impulse smell, and Long Term Contact is to healthy seriously unfavorable.Along with the exhaustion day by day of petroleum resources and the day by day serious of environmental pollution, searching high-quality, cheapness, reproducible petroleum substitute become focus and the development trend of world today's scientific research field.
Along with the development of domestic economy and the growth in the living standard of people, the consciousness of people to aspects such as materials'use weather resistance, material fire prevention, health environment-friendlies strengthens gradually, improves researched and proposed many new problems to the flame-retardant modified of the type product and performance.
Orange essential oil is the natural product of a kind of environmental protection extracted from orange skin, abundance and asepsis environment-protecting, in industry extensive application such as chemical industry, agricultural, food, makeup.Containing a large amount of unsaturated double-bonds in orange essential oil, can there is many chemical reactions in it, as oxidation, hydrogenation, isomerization, sulfation, sulfonation, polymerization, pyrolysis etc.So unsaturated double-bond structure active in orange essential oil can be utilized to introduce new active group and final obtained novel flame-retardant vinyl ester resin monomer through isomerization polymerization.Developing safety, environmental protection and energy-conservation flame retardant type bio-based vinyl ester resin is one of the main development direction in future, and the exploitation of flame retardant type bio-based vinyl ester resin monomer adapts to the demand for development in epoch.
Summary of the invention
the technical problem solved:in order to improve the shortcomings such as poor fire, weathering resistance difference and toxic ingredient content that conventional vinyl ester resin exists are high, the invention provides a kind of preparation method of flame retardant type orange essential oil base vinyl ester resin monomer, orange essential oil is adopted to be raw material, first through changing into fire-retardant epoxy resin with unsaturated acid anhydride again through D-A addition reaction, finally by the vinylated obtained orange essential oil base flame-retardant vinyl ester resin of epoxy addition.Present method has that reaction conditions gentleness, product stability are good, yield advantages of higher.
technical scheme:the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer, obtained by following steps: the first step: unsaturated acid anhydride is joined in reactor, be warming up to 60 ~ 80 DEG C, make its complete melting, drip orange essential oil, described dropping orange essential oil and unsaturated acid anhydride mol ratio are 1.2 ~ 1.4:1; Be warmed up to 160 ~ 200 DEG C, reaction 4 ~ 6h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, condensing reflux reaction 1.5 ~ 2.5h under 95 ~ 105 DEG C of conditions, obtained orange essential oil base di-carboxylic acid; Second step: add DOPO in the orange essential oil base di-carboxylic acid that the first step is obtained, described DOPO and orange essential oil base di-carboxylic acid mol ratio are 0.2 ~ 1.0:1, are heated to 140 ~ 180 DEG C, reaction 2 ~ 4h, obtains flame retardant type orange essential oil base di-carboxylic acid; 3rd step: join in reactor according to the ratio that mol ratio is 1:8 by flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane, adds the catalyst A accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.5 ~ 1.5wt%, 100 DEG C of reaction 2h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole number such as carboxyl and calcium oxide, at 60 DEG C, stir 3h, after suction filtration filtrate, revolve and to steam after the unnecessary epoxy chloropropane of removing i.e. obtained flame retardant type orange essential oil base epoxy; 4th step: by flame retardant type orange essential oil base epoxy and account for the catalyst B of reactant total mass 0.5 ~ 1.5 %, the stopper of 0.1 ~ 0.25 % joins in reactor, be warming up to 60 ~ 80 DEG C, then drip vinylformic acid wherein, the mol ratio of described vinylformic acid and orange essential oil base epoxy is 2:1; After dropwising, 100 ~ 120 DEG C of reaction 2 ~ 4h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
Selected unsaturated acid anhydride is any one in cis-1, fumaroyl acid anhydride, itaconic anhydride.
Selected catalyst A is any one in benzyltrimethylammonium bromide, tetraethylammonium bromide, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, 4 bromide, cetyl trimethylammonium bromide.
Selected catalyst B is any one in N, N-dimethyl benzylamine, triphenylphosphine, benzyltrimethylammonium bromide, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide.
Selected stopper is any one in toluhydroquinone, para benzoquinone, Resorcinol, di-tert-butyl hydroquinone.
beneficial effect:
(1) with orange essential oil for the obtained bio-based vinyl ester resin viscosity of matrix material and flame retardant resistance is controlled, iodine number is high, product is expected to the shortcoming improving traditional unsaturated polyester poor fire and weathering resistance difference, and improves the over-all properties of its cured article simultaneously;
(2) devise organophosphine modified orange essential oil base vinyl ester resin monomer, formulate out the bio-based vinyl ester resin that flame retardant resistance is controlled;
(3) this preparation method's reaction conditions is gentle, product stability is good, yield is high;
(4) compare with traditional Vinylite, the flame retardant type orange essential oil base unsaturated polyester prepared in the present invention utilizes orange essential oil for raw material, abundant raw material source, product environmental protection, cheap, and has broken away from the dependence to petrochemical complex resource.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of flame retardant type orange essential oil base vinyl ester resin monomer.
Embodiment
Provide section Example below so that the invention will be further described; but following examples are not construed as limiting the scope of the present invention explanation, these those skilled in the art make some nonessential improvement according to content of the present invention and adjustment still belongs to scope.
embodiment 1
Cis-1 is joined in reactor, be warming up to 70 DEG C, make its complete melting, the ratio being 1.3:1 in orange essential oil and maleic acid anhydride mol ratio drips orange essential oil, is warmed up to 180 DEG C, reacts 5 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 100 DEG C of conditions, condensing reflux reacts 2.0 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.6:1, be heated to 160 DEG C, react 3 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the benzyltrimethylammonium bromide accounting for flame retardant type orange essential oil base di-carboxylic acid quality 1.0 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and account for the benzyltrimethylammonium bromide of reactant total mass 1.0 %, the toluhydroquinone of 0.15 % joins in reactor, be warming up to 70 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 110 DEG C of reaction 3 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 2
Fumaroyl acid anhydride is joined in reactor, be warming up to 65 DEG C, make its complete melting, the ratio being 1.25:1 in orange essential oil and FUMARIC ACID TECH GRADE acid anhydride mol ratio drips orange essential oil, be warmed up to 170 DEG C, react 4.5 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 100 DEG C of conditions, condensing reflux reacts 2.0 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.4:1, be heated to 155 DEG C, react 3.5 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the tetraethylammonium bromide accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.75 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and the N accounting for reactant total mass 0.75 %, the para benzoquinone of N-dimethyl benzylamine, 0.15 % joins in reactor, be warming up to 65 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 120 DEG C of reaction 2 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 3
Itaconic anhydride is joined in reactor, be warming up to 75 DEG C, make its complete melting, the ratio being 1.2:1 in orange essential oil and itaconic anhydride mol ratio drips orange essential oil, is warmed up to 200 DEG C, reacts 4 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 105 DEG C of conditions, condensing reflux reacts 1.5 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.75:1, be heated to 180 DEG C, react 2 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the tetramethyl ammonium chloride accounting for flame retardant type orange essential oil base di-carboxylic acid quality 1.2 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and the N accounting for reactant total mass 1.5 %, the Resorcinol of N-dimethyl benzylamine, 0.25 % joins in reactor, be warming up to 60 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 120 DEG C of reaction 2 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 4
Cis-1 is joined in reactor, be warming up to 60 DEG C, make its complete melting, in being 1.4:1 with cis-1 mol ratio, ratio drips orange essential oil, is warmed up to 160 DEG C, reacts 6 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 95 DEG C of conditions, condensing reflux reacts 2.5 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.2:1, be heated to 140 DEG C, react 4 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the benzyl trimethyl ammonium chloride accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.5 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and account for the cetyl trimethylammonium bromide of reactant total mass 0.5 %, the di-tert-butyl hydroquinone of 0.1 % joins in reactor, be warming up to 60 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 100 DEG C of reaction 4 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 5
Fumaroyl acid anhydride is joined in reactor, is warming up to 80 DEG C, make its complete melting, in being 1.35:1 with fumaroyl acid anhydride mol ratio, ratio drips orange essential oil, is warmed up to 165 DEG C, reacts 5.5 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 105 DEG C of conditions, condensing reflux reacts 1.5 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 1:1, be heated to 170 DEG C, react 3 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the palmityl trimethyl ammonium chloride accounting for flame retardant type orange essential oil base di-carboxylic acid quality 1.5 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and account for the benzyl trimethyl ammonium chloride of reactant total mass 1.0 %, the di-tert-butyl hydroquinone of 0.20 % joins in reactor, be warming up to 70 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 120 DEG C of reaction 2 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 6
Fumaroyl acid anhydride is joined in reactor, is warming up to 80 DEG C, make its complete melting, in being 1.2:1 with fumaroyl acid anhydride mol ratio, ratio drips orange essential oil, is warmed up to 160 DEG C, reacts 6 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 105 DEG C of conditions, condensing reflux reacts 2.0 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.8:1, be heated to 180 DEG C, react 2.5 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the 4 bromide accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.8 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and account for the benzyltrimethylammonium bromide of reactant total mass 1.2 %, the Resorcinol of 0.8 % joins in reactor, be warming up to 80 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 105 DEG C of reaction 2 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 7
The cis-1 of certain mass is joined in reactor, be warming up to 75 DEG C, make its complete melting, the ratio being 1.3:1 in cis-1 mol ratio drips orange essential oil, be warmed up to 190 DEG C, react 4 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 95 DEG C of conditions, condensing reflux reacts 2.5 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add the DOPO of DOPO and orange essential oil base di-carboxylic acid mol ratio 0.95:1, be heated to 170 DEG C, react 3 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the cetyl trimethylammonium bromide accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.75 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and account for the triphenylphosphine of reactant total mass 0.75 %, the Resorcinol of 0.20 % joins in reactor, be warming up to 60 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 110 DEG C of reaction 3 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
embodiment 8
The itaconic anhydride of certain mass is joined in reactor, is warming up to 80 DEG C, make its complete melting, in being 1.2:1 with itaconic anhydride mol ratio, ratio drips orange essential oil, is warmed up to 160 DEG C, reacts 5 h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, and under 105 DEG C of conditions, condensing reflux reacts 2.5 h, obtained orange essential oil base di-carboxylic acid.In obtained orange essential oil base di-carboxylic acid, add DOPO and orange essential oil base di-carboxylic acid mol ratio is the DOPO of 0.9:1, be heated to 180 DEG C, react 3.5 h, obtain flame retardant type orange essential oil base di-carboxylic acid.Flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane are joined in reactor according to the ratio that mol ratio is 1:8, adds the cetyl trimethylammonium bromide accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.75 %, 100 DEG C of reaction 2 h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole numbers such as carboxyl and calcium oxide, at 60 DEG C, stir 3 h.Obtain filtrate after suction filtration, revolve after steaming the unnecessary epoxy chloropropane of removing and namely obtain flame retardant type orange essential oil base epoxy.By flame retardant type orange essential oil base epoxy and the N accounting for reactant total mass 0.5 %, the para benzoquinone of N-dimethyl benzylamine, 0.15 % joins in reactor, be warming up to 70 DEG C, then dropping vinylformic acid and orange essential oil base epoxy mol ratio are the vinylformic acid of 2:1 wherein, after dropwising, 100 DEG C of reaction 3 h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
comparative example:
experimental group 1:flame retardant type orange essential oil base vinyl ester resin monomer embodiment 6 prepared accurately takes 30g, then Viscoat 295 40g is added, add 1.5% initiator benzoyl peroxide again, mix in the closed mold of the shape being placed on special requirement, Procuring 3h is heated at 120 DEG C, 4h is solidified again, the copolymeric material then after slow cooling to normal temperature i.e. obtained solidification after being then increased to 160 DEG C again.
experimental group 2:flame retardant type orange essential oil base vinyl ester resin monomer embodiment 7 prepared accurately takes 30g, then Viscoat 295 40g is added, add 1.5% initiator benzoyl peroxide again, mix in the airtight grinding tool of the shape being placed on special requirement, Procuring 3h is heated at 120 DEG C, 4h is solidified again, the copolymeric material then after slow cooling to normal temperature i.e. obtained solidification after being then increased to 160 DEG C again.
Carry out comprehensive mechanical property analysis to above-mentioned two kinds of thermosetting materials, measurement result as described in table 1.
The thermofixation comprehensive mechanical property contrast of each experimental group got at random by table 1
| Group name | Experimental group 1 | Experimental group 2 |
| Monomer viscosity/mPas | 4500 | 5300 |
| Monomer color and luster/number | 8 | 7 |
| Tensile strength/MPa | 15.7 | 16.5 |
| Oxygen index/% | 27.8 | 29.5 |
Note: the viscosity of orange oil base unsaturated polyester monomer measures 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 extension performance is with reference to GB/T 1040.3-2006 plastic tensile test method, adopt CMT4000 type microcomputer controlled electronic universal tester (Shenzhen is newly thought carefully), the tensile property Elongation test speed measuring material is 10 mm/min, and probe temperature is 25 DEG C; Flame retardant properties GB/T 10707-2008 oxygen index measurer combustion testing method.
Claims (5)
1. the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer, is characterized in that being obtained by following steps:
The first step: joined by unsaturated acid anhydride in reactor, is warming up to 60 ~ 80 DEG C, makes its complete melting, and drip orange essential oil, described dropping orange essential oil and unsaturated acid anhydride mol ratio are 1.2 ~ 1.4:1; Be warmed up to 160 ~ 200 DEG C, reaction 4 ~ 6h, underpressure distillation removing impurity, obtains intermediate product orange essential oil base acid anhydrides; Then in being 1:1 with orange essential oil base anhydride molar ratio, ratio drips distilled water, condensing reflux reaction 1.5 ~ 2.5h under 95 ~ 105 DEG C of conditions, obtained orange essential oil base di-carboxylic acid;
Second step: add DOPO in the orange essential oil base di-carboxylic acid that the first step is obtained, described DOPO and orange essential oil base di-carboxylic acid mol ratio are 0.2 ~ 1.0:1, are heated to 140 ~ 180 DEG C, reaction 2 ~ 4h, obtains flame retardant type orange essential oil base di-carboxylic acid;
3rd step: join in reactor according to the ratio that mol ratio is 1:8 by flame retardant type orange essential oil base di-carboxylic acid and epoxy chloropropane, adds the catalyst A accounting for flame retardant type orange essential oil base di-carboxylic acid quality 0.5 ~ 1.5wt%, 100 DEG C of reaction 2h; Be cooled to 60 DEG C, add and the sodium hydroxide of the mole number such as carboxyl and calcium oxide, at 60 DEG C, stir 3h, after suction filtration filtrate, revolve and to steam after the unnecessary epoxy chloropropane of removing i.e. obtained flame retardant type orange essential oil base epoxy;
4th step: by flame retardant type orange essential oil base epoxy and account for the catalyst B of reactant total mass 0.5 ~ 1.5 %, the stopper of 0.1 ~ 0.25 % joins in reactor, be warming up to 60 ~ 80 DEG C, then drip vinylformic acid wherein, the mol ratio of described vinylformic acid and orange essential oil base epoxy is 2:1; After dropwising, 100 ~ 120 DEG C of reaction 2 ~ 4h, obtained flame retardant type orange essential oil base vinyl ester resin monomer.
2. the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer according to claim 1, is characterized in that selected unsaturated acid anhydride is any one in cis-1, fumaroyl acid anhydride, itaconic anhydride.
3. the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer according to claim 1, is characterized in that selected catalyst A is any one in benzyltrimethylammonium bromide, tetraethylammonium bromide, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, 4 bromide, cetyl trimethylammonium bromide.
4. the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer according to claim 1, it is characterized in that selected catalyst B is any one in N, N-dimethyl benzylamine, triphenylphosphine, benzyltrimethylammonium bromide, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide.
5. the preparation method of flame retardant type orange essential oil base vinyl ester resin monomer according to claim 1, is characterized in that selected stopper is any one in toluhydroquinone, para benzoquinone, Resorcinol, di-tert-butyl hydroquinone.
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| CN106008604A (en) * | 2016-05-27 | 2016-10-12 | 中国林业科学研究院林业新技术研究所 | Preparation method for anti-flaming myrcenyl dual-curing resin monomer |
| CN106188499A (en) * | 2016-07-14 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer |
| CN112608469A (en) * | 2020-12-18 | 2021-04-06 | 中国林业科学研究院林产化学工业研究所 | Orange peel essential oil based polyamide active monomer and preparation method thereof |
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| CN104086426A (en) * | 2014-07-10 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing myrcenyl vinyl ester resin monomer |
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Patent Citations (5)
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| WO2005118657A2 (en) * | 2004-05-07 | 2005-12-15 | Drexel University | Multi-modal vinyl ester resins |
| 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 |
| CN103387881A (en) * | 2013-08-02 | 2013-11-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of orange oil based unsaturated resin monomer |
| CN104031213A (en) * | 2014-05-30 | 2014-09-10 | 常州华科聚合物股份有限公司 | Low-smoke halogen-free high-temperature-resistant flame-retardant vinyl ester resin and preparation method thereof |
| CN104086426A (en) * | 2014-07-10 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing myrcenyl vinyl ester resin monomer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008604A (en) * | 2016-05-27 | 2016-10-12 | 中国林业科学研究院林业新技术研究所 | Preparation method for anti-flaming myrcenyl dual-curing resin monomer |
| CN106188499A (en) * | 2016-07-14 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer |
| CN112608469A (en) * | 2020-12-18 | 2021-04-06 | 中国林业科学研究院林产化学工业研究所 | Orange peel essential oil based polyamide active monomer and preparation method thereof |
| CN112608469B (en) * | 2020-12-18 | 2022-03-04 | 中国林业科学研究院林产化学工业研究所 | Orange peel essential oil based polyamide active monomer and preparation method thereof |
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