CN102329309A - Rosin epoxy resin and preparation method thereof - Google Patents
Rosin epoxy resin and preparation method thereof Download PDFInfo
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- CN102329309A CN102329309A CN2010102252795A CN201010225279A CN102329309A CN 102329309 A CN102329309 A CN 102329309A CN 2010102252795 A CN2010102252795 A CN 2010102252795A CN 201010225279 A CN201010225279 A CN 201010225279A CN 102329309 A CN102329309 A CN 102329309A
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Abstract
The invention discloses a rosin epoxy resin for the solidification of polyester powdery paints. The rosin epoxy resin is a compound with the structure of formula I or formula II. In the formula I or the formula II, R is an aliphatic chain segment or an aromatic chain segment. The invention also discloses a preparation method of the rosin epoxy resin. The preparation method comprises the following steps: 1, treating rosin as a raw material, adding with a catalyst I and maleic anhydride, and carrying out a Diels-Alder reaction to obtain maleopimaric acid anhydride (MPA); 2, reacting a compound containing amino and carboxyl with the MPA to prepare a rosin polyprotic acid; and 3, carrying out a series of chemical reactions on the rosin polyprotic acid, an epoxy alkylogen, a catalyst II, and an alkali to prepare the rosin epoxy resin. The rosin epoxy resin of the invention which has the advantages of environmentally friendly preparation technology, and low manufacture cost is mainly used for solidifying the polyester powdery paints.
Description
Technical field
The present invention relates to bio-based epoxy resin field, be specifically related to a kind of rosinyl epoxy resin and preparation method thereof.
Background technology
At present, Along with people's is to the pay attention to day by day of environmental problem, and towards low pollutions such as Water-borne modification, powderised, solvent frees, non-harmful direction develops world's coating, and the traditional coating that the solvent evaporates amount is big, environmental pollution is serious is being faced with great challenge.Compare with traditional coating; Powder coating is a kind of zero VOC coating products that contains 100% solids component; Because characteristics such as its resource-saving, nuisanceless, labor productivity height; Be acknowledged as that a kind of accords with production efficient is high, film performance is good, ecological, environmental protective and economic and practical product, become in world today's scope one of coating variety of tool development prospect.
Polyester powder coating is a kind of thermosetting powder coating(s) that after epoxy and epoxy-polyester powder coating, grows up, because of its excellent weathering resistance has irreplaceable importance.Its output accounts for about 40% of all thermosetting powder coating(s)s, has been widely used in the application of outdoor products such as traffic sign, agricultural equipment, the vehicles, barred window fence.From principle, polyester powder coating mainly is by the end carboxyl of certain molecular weight or the hydroxyl telechelic polyester resin is cured with the solidifying agent that has epoxy group(ing), isocyano or hydroxyl or condensation reaction forms filming of macromolecular compound.
At present, be used for the trimellitic acid 1,2-anhydride three-glycidyl ester (PT910) that polyester powder coating solidified epoxies solidifying agent mainly is limited to isocyanuric acid three-glycidyl ester (TGIC) and the exploitation of CIBA company.Wherein, TGIC is to use the longest, the maximum a kind of traditional polyester powder coating solidifying agent of consumption of time.Its defective is that the TGIC production technique can produce a large amount of waste water and waste residue, and environmental pollution is serious, and simultaneously, it is biological that TGIC has been considered to a kind of mutagen, and very big physiology toxicity is arranged, and is used by the strictness restriction.PT910 is by a kind of trimellitic acid 1,2-anhydride three-glycidyl ester of Switzerland CIBA company research and development and the mixture of di-carboxylic acid glyceryl ester; Its defective is; Though do not have physiology toxicity, but still have certain contact toxicity and serious pungency, and because its stable storing performance is relatively poor; Need select higher resin dedicated of second-order transition temperature during powder process for use, also relatively poor by polyester powder coating thermotolerance, weathering resistance that PT910 prepares.
Rosin is a kind of important renewable resources of China, and it is mainly by accounting for the sylvic acid C of total mass more than 90%
19H
29COOH forms with a small amount of neutral substance.Two keys in the sylvic acid and carboxyl isoreactivity functional group conveniently carry out addition; Esterification, the reaction of number of chemical such as condensation, its huge hydrogen phenanthrene ring structure has higher mechanics rigidity; Can match in excellence or beauty with petroleum base aliphatics or aromatic series ring-type monomer; And price is relatively low, and in bio-based materials flourish today, rosin and verivate thereof have been used as industrial chemicals and have been widely used in polymeric material field.But, the relevant report that is suitable for polyester powder coating solidified bio-based epoxy resin is not also arranged at present.
Summary of the invention
The invention provides a kind of polyester powder coating solidified rosinyl epoxy resin that is suitable for.
The present invention also provides a kind of preparation method of rosinyl epoxy resin, and this method is easy and simple to handle, is suitable for suitability for industrialized production.
A kind of rosinyl epoxy resin is the compound of structure shown in formula I or the formula II:
Wherein, R is aromatic series segment or aliphatics segment; As preferably, R is selected from phenyl or C
1～C
10The alkyl segment, in I, R can be selected from
-(CH2)
n-, n is 1～10 positive integer; In the formula II, R can be selected from
M is 0～9 integer.
The preparation method of described rosinyl epoxy resin comprises step:
(1) under protection of inert gas, rosin is carried out diene addition reaction (being Diels-Alder reaction (Diels-Alder reaction)) in the presence of catalyst A and maleic anhydride, make maleopimaric anhydride (MPA);
(2) above-mentioned maleopimaric anhydride and the compound that contains amino and carboxyl are simultaneously carried out imidization reaction in organic solvent, prepare the rosinyl polyprotonic acid;
(3) in protection of inert gas, above-mentioned rosinyl polyprotonic acid and epoxy haloalkane are reacted in the presence of catalyst B and alkali, make the rosinyl epoxy resin shown in formula I or the formula II.
As preferably:
In the step (1), described catalyst A is selected from one or both in p-methyl benzenesulfonic acid, the Resorcinol; The consumption of catalyst A can be according to the adjustment of reaction raw materials amount, and catalyzed reaction being as the criterion, in order when economizing in raw materials, to play catalytic effect better, the quality optimization of catalyst A is 0.3%～3% of a rosin quality.
In the step (2); Describedly contain amino compound simultaneously and be selected from aliphatic amino monoprotic acid, aliphatic dibasic amino acid, aromatic amino monoprotic acid or aromatic dibasic amino acid, further preferably contain in the compound of amino and carboxyl any one as follows with carboxyl:
Described organic solvent is selected N for use, one or more in dinethylformamide (DMF), DMSO 99.8MIN. (DMSO), benzene, the toluene.
In the step (3), described catalyst B is selected the aliphatics ammonium halide for use, one or more in further preferred tetramethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, the hexamethylenetetramine; The consumption of catalyst B can be according to the adjustment of reaction raw materials amount, and catalyzed reaction being as the criterion, in order when economizing in raw materials, to play catalytic effect better, the quality optimization of catalyst B is 1.0%～6% of a rosinyl polyprotonic acid quality.
Described epoxy haloalkane is one or both in epoxy chloropropane, the epoxy bromopropane.
Described alkali mainly is meant inorganic strong alkali property compound; Select in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, hydrated barta, Marinco H, the Lithium Hydroxide MonoHydrate one or more for use; So that contain the rosinyl polyprotonic acid salify of bismaleimide amine structure; Improve its Electron Affinities, be beneficial to the epoxy haloalkane and react.
Described rare gas element is selected the rare gas element of this area broad scope for use, can select a kind of in nitrogen, argon gas, the helium etc. for use, considers nitrogen from the angle of practicing thrift cost.
In the step (1), the condition optimization of described diene addition reaction was: 150 ℃～220 ℃ reactions 2 hours～5 hours.
In the step (2), the condition optimization of described imidization reaction is: stirred 3 hours～24 hours at 15 ℃～35 ℃ in advance, stirred 2 hours～8 hours cooling again at 110 ℃～170 ℃.
In the step (3), the condition optimization of described reaction is: with rosinyl polyprotonic acid and epoxy haloalkane in the presence of catalyst B in 90 ℃～120 ℃ reactions 4 hours～5 hours, be cooled to 65 ℃～75 ℃, added alkali reaction 4 hours～6 hours.
The solidifying agent that described rosinyl epoxy resin can be used as polyester powder coating is applied to the preparation of polyester powder coating, and the polyester powder coating that adopts rosinyl epoxy resin of the present invention to make as solidifying agent has good weather resistance.
The not strict qualification of the consumption of reaction raw materials generally measure than react according to chemical reaction, but also maleic anhydride, the compound that contains amino and carboxyl, epoxy haloalkane or base excess reacts among the present invention.
The not strict qualification of organic solvent, catalyst consumption among the present invention can be adjusted according to the consumption of reaction raw materials: more increase organic solvent of reaction raw materials and catalyst consumption, less minimizing organic solvent of reaction raw materials and catalyst consumption.
Of the present invention have a following advantage:
The present invention is starting raw material with the natural rosin; Developed the simple bio-based epoxy resin of a kind of environmental protection, health and preparation process; This rosinyl epoxy resin can be used for the curing of polyester powder coating, can substitute existing industrialization product TGIC or PT910, has good application prospects.
The present invention is a raw material with natural reproducible rosin, has opened up new raw material and new way for preparing novel rosinyl epoxy resin, also for the deep processing of China's rosin resource provides new way, helps further bringing into play the rosiny economic worth.
The preparation method of rosinyl epoxy resin of the present invention, environment protection health, easy and simple to handle, be suitable for suitability for industrialized production.
Embodiment
Can further clearly understand content of the present invention through specific embodiment of the present invention given below.
Embodiment 1
(1) 100 weight part rosin is heated to 150 ℃ under nitrogen protection; Add the Resorcinol of 0.3 weight part and the maleic anhydride of 30 weight parts then, temperature rises to 190 ℃, reacts 4 hours; Cooling; Add Glacial acetic acid min. 99.5 and carry out recrystallization, vacuum-drying obtains 78 weight part purity and is 96% maleopimaric anhydride (MPA).
(2) above-mentioned 78 weight part maleopimaric anhydrides (MPA) are dissolved in an amount of N, in the dinethylformamide (DMF), and add 46 weight part para-amino benzoic acid; After stirring 3 hours under 25 ℃ of room temperatures, be warming up to 150 ℃ and stirred 4 hours, be cooled to room temperature; Become the yellowish brown solid; The zero(ppm) water that adds 150 an amount of weight parts stirs, and has yellow mercury oxide to produce.Filter, washing, vacuum-drying 3 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains 90 weight part rosinyl diprotic acid.
(3) under the nitrogen gas shiled, the epoxy bromopropane of 90 weight part rosinyl diprotic acid that obtain in the step 2 and 40 weight parts added have in the churned mechanically there-necked flask, heating for dissolving becomes homogeneous phase; Add cetyl trimethylammonium bromide 3 weight parts in 90 ℃ of reactions 5 hours, be cooled to 70 ℃, divide 3 times and add sodium hydroxide 15 weight parts; Each 5 weight parts; Keep reaction 4 hours, remove by filter the NaCl of generation, excessive epoxy chloropropane is reclaimed in underpressure distillation; Crude product water/ether system (volume ratio of water and ether is 1: 1) extraction, vacuum-drying gets product 42 weight parts.This epoxy resin contains 2 epoxy-functionals.
Above-mentioned MPA is carried out structure identify that qualification result is: nuclear magnetic spectrogram
1H-NMR (CDCl
3, δ ppm) and 5.5,3.1-3.0,2.7-2.8,2.47-2.52,2.1-2.3,1.7-0.5; Fourier's ir spectra FT-IR (cm
-1) 795,850,926,944,1010,1086,1140,1279,1234,1388,1465,1690,1780,1844,2860,2942,3500-3100; Acid number: be in theory: 420mg KOH/g; Actual being measured as: 420mg KOH/g..The structural formula that shows above-mentioned MPA is:
Above-mentioned rosinyl diprotic acid is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [DMSO-d6, δ ppm]: 7.97-8.0,7.18-7.21,5.49,3.10-3.06,2.68-2.72; FT-IR (cm
-1) 1708,1776,2860,2942,3500-3100. acid number: be in theory: 215mg KOH/g; Actual being measured as: 214mg KOH/g.The structural formula that shows above-mentioned rosinyl diprotic acid is:
Above-mentioned rosinyl epoxy resin is carried out structure identifies that qualification result is:
1H-NMR (CDCl
3, ppm) 8.06-8.09,7.22-7.25,5.49,4.59-4.63,4.48-4.39,4.10-4.16,3.82-3.89,3.30,3.10-3.06,2.52-2.86.FT-IR (cm
-1) 853,901,1100,1178,1705,1778. molar mass 623g/mol. show that above-mentioned rosinyl epoxy resin has following structure:
Embodiment 2
(1) 100 weight part rosin is heated to 150 ℃ under nitrogen protection; Add the p-methyl benzenesulfonic acid of 2.6 weight parts and the maleic anhydride of 35 weight parts then, temperature rises to 220 ℃, reacts 3 hours; Cooling; Add Glacial acetic acid min. 99.5 and carry out recrystallization, vacuum-drying, obtaining 70 weight part purity is the maleopimaric anhydride (MPA) more than 95%.
(2) above-mentioned 70 weight part maleopimaric anhydrides (MPA) are dissolved in an amount of N, in the dinethylformamide (DMF), and add the amino m-phthalic acid of 60 weight part 5-; After stirring 12 hours under 25 ℃ of room temperatures, be warming up to 130 ℃ and stirred 4 hours, be cooled to room temperature; Become the yellowish brown solid; The zero(ppm) water that adds 150 an amount of weight parts stirs, and has yellow mercury oxide to produce.Filter, washing, vacuum-drying 5 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains 90 weight part rosinyl triprotic acids.
(3) under the nitrogen protection, the epoxy chloropropane of above-mentioned 90 weight part rosinyl triprotic acids and 60 weight parts added have in the churned mechanically there-necked flask, heating for dissolving becomes homogeneous phase; Add catalyzer 4.5 weight part octadecyl trimethylammonium bromides in 90 ℃ of reactions 5 hours, be cooled to 70 ℃, divide three times and add sodium hydroxide 21 weight parts; Each 7 weight parts; Keep reaction 6 hours, remove by filter the NaCl of generation, excessive epoxy chloropropane is reclaimed in underpressure distillation; Crude product water/ether system (volume ratio of water and ether is 1: 1) extraction, vacuum-drying gets product 54 weight parts.This epoxy resin contains 3 epoxy-functionals.
The qualification result of MPA is said identical with the foregoing description 1 with structural formula;
Above-mentioned rosinyl triprotic acid is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [CDCl
3, δ ppm]: 8.8,8.4,5.3,2.68-2.72; FT-IR (cm
-1) 1710,1778,2864,2945,3500-3100. acid number: be in theory: 257mg KOH/g; Actual being measured as: 259mg KOH/g.The structural formula that shows above-mentioned rosinyl triprotic acid is:
Above-mentioned rosinyl epoxy resin is carried out structure identifies that qualification result is:
1H-NMR (CDCl
3, ppm) 8.8,8.4,5.3,4.4-4.6,4.1-4.2,3.8-3.9,2.68-2.72; FT-IR (cm
-1) 1105,1180,1710,1778. molar mass: 731g/mol; Show that above-mentioned rosinyl epoxy resin has following structure:
Embodiment 3
(1) 100 weight part rosin is heated to 150 ℃ under nitrogen protection, adds the p-methyl benzenesulfonic acid and the Resorcinol mixture (wherein, the mass ratio of p-methyl benzenesulfonic acid and Resorcinol is 1: 1) of 3 weight parts; The maleic anhydride of 35 weight parts, temperature rise to 200 ℃, react 2.5 hours; Cooling; Add Glacial acetic acid min. 99.5 and carry out recrystallization, vacuum-drying, obtaining 71 weight part purity is the maleopimaric anhydride (MPA) more than 95%.
(2) above-mentioned 71 weight part maleopimaric anhydrides (MPA) are dissolved in an amount of N, in the dinethylformamide (DMF), and add the amino terephthalic acid of 60 weight part 2-; After stirring 18 hours under 25 ℃ of room temperatures, be warming up to 150 ℃ and stirred 4 hours, be cooled to room temperature; Become the yellowish brown solid; The zero(ppm) water that adds 150 an amount of weight parts stirs, and has yellow mercury oxide to produce.Filter, washing, vacuum-drying 4 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains 78 weight part rosinyl triprotic acids.
(3) under the nitrogen protection, the epoxy bromopropane of above-mentioned 78 weight part rosinyl triprotic acids and 60 weight parts added have in the churned mechanically there-necked flask, heating for dissolving becomes homogeneous phase; Add 1.2 weight part tetramethyl ammonium chlorides in 90 ℃ of reactions 3 hours, be cooled to 65 ℃, divides three adding sodium hydroxide 18 weight parts; Each 6 weight parts that add; Keep reaction 6 hours, remove by filter the NaCl of generation, excessive epoxy chloropropane is reclaimed in underpressure distillation; Crude product water/ether system (volume ratio of water and ether is 1: 1) extraction, vacuum-drying gets product 38 weight parts.This epoxy resin contains 3 epoxy-functionals.
The qualification result of MPA is said identical with the foregoing description 1 with structural formula;
Above-mentioned rosinyl triprotic acid is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [CDCl
3, δ ppm]: 8.4,8.0,7.6,5.3,2.68-2.7; FT-IR (cm
-1) 1715,1780,2870,29473500-3100. acid number: be in theory: 257mg KOH/g; Actual being measured as: 259mgKOH/g.The structural formula that shows above-mentioned rosinyl triprotic acid is:
Above-mentioned rosinyl epoxy resin is carried out structure identifies that qualification result is:
1H-NMR (CDCl
3, ppm) 8.4,8.0,7.6,5.3,4-4.6,4.1-4.2,3.8-3.9,2.68-2.72; FT-IR (cm
-1) 1105,1176,1707,1788. molar mass: 731g/mol; Show that above-mentioned rosinyl epoxy resin has following structure:
Embodiment 4
(1) 100 weight part rosin is heated to 150 ℃ under nitrogen protection; Add the p-methyl benzenesulfonic acid of 2.6 weight parts and the maleic anhydride of 35 weight parts then, temperature rises to 220 ℃, reacts 3 hours; Cooling; Add Glacial acetic acid min. 99.5 and carry out recrystallization, vacuum-drying, obtaining 68 weight part purity is the maleopimaric anhydride (MPA) more than 95%.
(2) above-mentioned 68 weight part maleopimaric anhydrides (MPA) are dissolved in an amount of N, in the dinethylformamide (DMF), and add 35 weight part 4-propalanines; After stirring 8 hours under 25 ℃ of room temperatures; Be warming up to 150 ℃ and stirred 4 hours, be cooled to room temperature, add the zero(ppm) water of 150 an amount of weight parts; Stir, have yellow mercury oxide to produce.Filter, washing, vacuum-drying 5 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains 53 weight part rosinyl diprotic acid.
(3) under the nitrogen protection; The epoxy chloropropane adding of above-mentioned 53 weight part rosinyl diprotic acid and 100 weight parts is had in the churned mechanically there-necked flask, and heating for dissolving becomes homogeneous phase, and the mixture (mass ratio of tetramethyl ammonium chloride and cetyl trimethylammonium bromide is 1: 2) that adds 5 weight part tetramethyl ammonium chlorides and cetyl trimethylammonium bromide was in 100 ℃ of reactions 5 hours; Be cooled to 70 ℃; Divide 3 times and add sodium hydroxide 15 weight parts, each 5 weight parts are kept reaction 6 hours; Remove by filter the NaCl of generation; Excessive epoxy chloropropane is reclaimed in underpressure distillation, crude product water/ether system (volume ratio of water and ether is 1: 1) extraction, and vacuum-drying gets product 30 weight parts.This epoxy resin contains 2 epoxy-functionals.
The qualification result of MPA is said identical with the foregoing description 1 with structural formula;
Above-mentioned rosinyl diprotic acid is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [DMSO-d6, δ ppm]: 5.5,3.5,3.1-3.06,2.2-2.72,1.8; FT-IR (cm
-1) 1712,1770,2865,2947,3500-3100. acid number: be in theory: 231mg KOH/g; Actual being measured as: 231mg KOH/g.The structural formula that shows above-mentioned rosinyl diprotic acid is:
Above-mentioned rosinyl epoxy resin is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [DMSO-d6, δ ppm]: 5.5,4.3,4.1,3.5,3.1-3.06,2.2-2.72,1.9; FT-IR (cm
-1) 1040,1180,1712,1770; Molar mass: 597g/mol; Show that above-mentioned rosinyl epoxy resin has following structure:
Embodiment 5
(1) 100 weight part rosin is heated to 150 ℃ under nitrogen protection; Add the Resorcinol of 0.3 weight part and the maleic anhydride of 30 weight parts then, temperature rises to 190 ℃, reacts 4 hours; Cooling; Add Glacial acetic acid min. 99.5 and carry out recrystallization, vacuum-drying, obtaining 62 weight part purity is the maleopimaric anhydride (MPA) more than 95%.
(2) above-mentioned 62 weight part maleopimaric anhydrides (MPA) are dissolved in an amount of N, in the dinethylformamide (DMF), and add 46 weight part gavaculines; After stirring 15 hours under 25 ℃ of room temperatures, be warming up to 130 ℃ and stirred 2 hours, be cooled to room temperature; Become the yellowish brown solid; The zero(ppm) water that adds 150 an amount of weight parts stirs, and has yellow mercury oxide to produce.Filter, washing, vacuum-drying 4 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains 64 weight part rosinyl diprotic acid.
(3) under the nitrogen protection, the epoxy chloropropane of above-mentioned 64 weight part rosinyl diprotic acid and 82 weight parts added have in the churned mechanically there-necked flask, heating for dissolving becomes homogeneous phase; Add 3.8 weight part hexamethylenetetramines in 90 ℃ of reactions 5 hours, be cooled to 70 ℃, divide 3 times and add sodium hydroxide 21 weight parts; Each about 7 weight parts; Keep reaction 6 hours, remove by filter the NaCl of generation, excessive epoxy chloropropane is reclaimed in underpressure distillation; Crude product water/ether system (volume ratio of water and ether is 1: 1) extraction, vacuum-drying gets product 48 weight parts.This epoxy resin contains 2 epoxy-functionals.
The qualification result of MPA is said identical with the foregoing description 1 with structural formula;
Above-mentioned rosinyl diprotic acid is carried out structure identify that qualification result is: nuclear magnetic spectrogram H
1-NMR [DMSO-d6, δ ppm]: 8.4,7.9,7.8,7.4,5.5,3.1-3.06,2.7-2.72; FT-IR (cm
-1) 1710,1780,2862,2945,3500-3100. acid number: be in theory: 215mg KOH/g; Actual being measured as: 214mg KOH/g.The structural formula that shows above-mentioned rosinyl diprotic acid is:
Above-mentioned rosinyl epoxy resin is carried out structure identifies that qualification result is:
1H-NMR (CDCl
3, ppm) 8.4,7.9,7.8,7.4,5.5,4.6-4.4,4.10-4.16,3.8-3.9,3.3,3.1-3.06,2.52-2.86.FT-IR (cm
-1) 856,911,1106,1172,1710,1774. molar mass 623g/mol. show that above-mentioned rosinyl epoxy resin has following structure:
Above-mentioned is to combine embodiment that the present invention is elaborated; But embodiment of the present invention is not restricted to the described embodiments, and other any change of under patent core guiding theory of the present invention, being done, replacement, combination simplification etc. are included within the protection domain of patent of the present invention.
Claims (10)
1. rosinyl epoxy resin is the compound of structure shown in formula I or the formula II:
Wherein, R is aromatic series segment or aliphatics segment.
2. rosinyl epoxy resin as claimed in claim 1 is characterized in that R is selected from phenyl or C
1～C
10The alkyl segment.
3. the preparation method of rosinyl epoxy resin as claimed in claim 1 comprises step:
(1) under protection of inert gas, rosin is carried out the diene addition reaction in the presence of catalyst A and maleic anhydride, make maleopimaric anhydride;
(2) above-mentioned maleopimaric anhydride and the compound that contains amino and carboxyl are simultaneously carried out imidization reaction in organic solvent, prepare the rosinyl polyprotonic acid;
(3) in protection of inert gas, above-mentioned rosinyl polyprotonic acid and epoxy haloalkane are reacted in the presence of catalyst B and alkali, make the rosinyl epoxy resin shown in formula I or the formula II;
The described compound that contains amino and carboxyl simultaneously is selected from aliphatic amino monoprotic acid, aliphatic dibasic amino acid, aromatic amino monoprotic acid or aromatic dibasic amino acid;
Described catalyst A is selected from one or both in p-methyl benzenesulfonic acid, the Resorcinol;
Described catalyst B is selected from the aliphatics ammonium halide;
Described epoxy haloalkane is one or both in epoxy chloropropane, the epoxy bromopropane.
4. the preparation method of rosinyl epoxy resin as claimed in claim 3 is characterized in that, the described compound that contains amino and carboxyl simultaneously is selected from
H
2N-(CH
2)
n-COOH,
In a kind of; Wherein, n is 1～10 positive integer; M is 0～9 integer.
5. the preparation method of rosinyl epoxy resin as claimed in claim 3; It is characterized in that described aliphatics ammonium halide is selected from one or several in tetramethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, the hexamethylenetetramine.
6. the preparation method of rosinyl epoxy resin as claimed in claim 3 is characterized in that, described organic solvent is selected N for use, one or more in dinethylformamide, DMSO 99.8MIN., benzene, the toluene.
Perhaps, described alkali is selected one or more in Marinco H, Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, the hydrated barta for use.
7. the preparation method of rosinyl epoxy resin as claimed in claim 3 is characterized in that, in the step (1), the condition of described diene addition reaction is: 150 ℃～220 ℃ reactions 2 hours～5 hours.
8. the preparation method of rosinyl epoxy resin as claimed in claim 3; It is characterized in that in the step (2), the condition of described imidization reaction is: stirred 3 hours～24 hours at 15 ℃～35 ℃ in advance; Stirred 2 hours～8 hours cooling again at 110 ℃～170 ℃.
9. the preparation method of rosinyl epoxy resin as claimed in claim 3; It is characterized in that; In the step (3); The condition of described reaction is: with rosinyl polyprotonic acid and epoxy haloalkane in the presence of catalyst B in 90 ℃～120 ℃ reactions 4 hours～5 hours, be cooled to 65 ℃～75 ℃, added alkali reaction 4 hours～6 hours.
10. according to claim 1 or claim 2 rosinyl epoxy resin is in the application of preparation in the polyester powder coating.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN103087636A (en) * | 2013-01-28 | 2013-05-08 | 中科院广州化学有限公司 | Preparation method of maleopimaric acid |
| CN103865399A (en) * | 2014-03-14 | 2014-06-18 | 黄山锦峰实业有限公司 | Tackifying resin and preparation method thereof |
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| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN103087636A (en) * | 2013-01-28 | 2013-05-08 | 中科院广州化学有限公司 | Preparation method of maleopimaric acid |
| CN103865399A (en) * | 2014-03-14 | 2014-06-18 | 黄山锦峰实业有限公司 | Tackifying resin and preparation method thereof |
| CN103865399B (en) * | 2014-03-14 | 2015-11-18 | 黄山锦峰实业有限公司 | tackifying resin and preparation method thereof |
| RU2591193C1 (en) * | 2015-05-21 | 2016-07-10 | Федеральное государственное бюджетное учреждение науки Уфимский Институт химии РАН (УфИХ РАН) | Method of producing imides of maleopimaric acid methyl ether |
| CN108409942A (en) * | 2018-04-13 | 2018-08-17 | 西北农林科技大学 | A kind of rosin epoxy resin nanocomposite preparation method |
| CN109467674A (en) * | 2018-08-14 | 2019-03-15 | 南京大学 | A kind of resveratrol base fire retarding epoxide resin and preparation method thereof |
| CN109467674B (en) * | 2018-08-14 | 2022-02-08 | 南京大学 | Resveratrol-based flame-retardant epoxy resin and preparation method thereof |
| CN111484530A (en) * | 2020-04-22 | 2020-08-04 | 中航复材（北京）科技有限公司 | Rosin-based reactive flame-retardant curing agent and preparation method thereof |
| CN111484530B (en) * | 2020-04-22 | 2022-07-26 | 中航复材（北京）科技有限公司 | Rosin-based reactive flame-retardant curing agent and preparation method thereof |
| CN112876652A (en) * | 2021-03-01 | 2021-06-01 | 桂林理工大学 | Rosin-based epoxy glass polymer material and preparation method thereof |
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