CN1425729A - Propylenyl pimaric acid diglycidic ester and its epoxy resin and their preparation - Google Patents
Propylenyl pimaric acid diglycidic ester and its epoxy resin and their preparation Download PDFInfo
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- CN1425729A CN1425729A CN 02149777 CN02149777A CN1425729A CN 1425729 A CN1425729 A CN 1425729A CN 02149777 CN02149777 CN 02149777 CN 02149777 A CN02149777 A CN 02149777A CN 1425729 A CN1425729 A CN 1425729A
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- acrylic acid
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- epoxy
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- -1 Propylenyl pimaric acid Chemical compound 0.000 title claims abstract description 13
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 title abstract description 6
- 229920000647 polyepoxide Polymers 0.000 title abstract description 6
- 150000002148 esters Chemical class 0.000 title abstract 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 113
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 112
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 112
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 98
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 43
- 239000004593 Epoxy Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003444 phase transfer catalyst Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003849 aromatic solvent Substances 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- 150000001253 acrylic acids Chemical class 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000005445 natural material Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 241000370738 Chlorion Species 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Abstract
The present invention relates to modified rosin and is propylenyl pimaric acid diglycidic ester and acrylic acid modified rosin epoxy resin containing propylenyl pimaric acid diglycidic ester in 40-100 wt%. The present invention also provides their preparation process. The propylenyl pimaric acid diglycidic ester and acrylic acid modified rosin epoxy resin are prepared with cheap natural material and are new environment friendly adhesive material with high epoxide number. The may be used also as the intermediate for preparing rosin surfactant, and has simple preparation process easy to use in industry.
Description
Technical field
The present invention relates to the modified rosin field, especially rosin acrylic acid 2-glycidyl ester, rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy and their preparation method.
Technical background
China's rosin (rosin) aboundresources, cheap, be the basic raw material of chemical industry, be widely used in industry such as coating, printing ink, synthetic rubber, papermaking, soap, metal processing.Resins, epoxy (epoxy resins) is because of its distinctive electrical property, mechanical property, erosion resistance and chemical stability, now obtain to use widely at coating, electronic apparatus, matrix material and adhesives industries, become the very fast class thermosetting resin of development in recent years.But general bisphenol A type epoxy resin can not satisfy the needs of modern industry development.The Resins, epoxy product innovation that exploitation has resistance to elevated temperatures, anti-ultraviolet and obdurability has become the new problem that Resins, epoxy is studied.Wang Dingxuan, the Kong Zhenwu of Nanjing forest chemical institute is that raw material has synthesized maleopimaric acid Resins, epoxy with the maleated rosin, and this based epoxy resin is a three-functionality-degree Racemic glycidol type Resins, epoxy, has better heat-resisting performance and good mechanical property.Guangzhou chemistry the Kazakhstan become bravely, Shen Minmin is that raw material has synthesized TEG-99 Resins, epoxy with turps.
Summary of the invention
The purpose of this invention is to provide with the acrylic acid modified rosin is the rosin acrylic acid 2-glycidyl ester of feedstock production, because it has the epoxy group(ing) of hyperergy, both can be used as Resins, epoxy and directly used, also can be used as the reaction intermediate of preparation rosin based tensio-active agent.
Another object of the present invention provides cheap high performance rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy.
Also purpose of the present invention provides their preparation method.
The chemical structural formula of rosin acrylic acid 2-glycidyl ester provided by the invention is as follows:
The rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy that provides, it is characterized in that by acrylic acid modified rosin and/or rosin acrylic acid and epichlorohydrin reaction and obtain, in this Resins, epoxy by gross weight, contain described rosin acrylic acid 2-glycidyl ester 40～100%, preferred 60～90%.
The preparation method of rosin acrylic acid 2-glycidyl ester provided by the invention is to count by weight, with 100 parts of rosin acrylic acids, 45～150 parts of epoxy chloropropane, 100～400 parts of organic solvents, 0.05～5 part of phase-transfer catalyst, 80～150 parts of weak base, back flow reaction 50～180 hours is filtered, and boils off solvent, residue is through aromatic solvent extraction, drying, boil off solvent, after recrystallization or column chromatography methods separation and purification, obtain the rosin acrylic acid 2-glycidyl ester, oxirane value 0.38～0.40.
55～80 parts of wherein preferred epoxy chloropropane, 200～300 parts of organic solvents, 0.5～4 part of phase-transfer catalyst, 100～120 parts of reactions of weak base 60～80 hours.
Described organic solvent comprises ketone such as acetone, butanone, amides such as N, dinethylformamide, N, N-diethylformamide, nitrile such as acetonitrile, butyronitrile etc.
Phase-transfer catalyst comprises 18-hat-6, polyoxyethylene glycol, Tetrabutyl amonium bromide etc.
Weak base comprises salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate etc.
The preparation method of described rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy, be to count by weight, with 100 parts of acrylic acid modified rosin and/or rosin acrylic acids, 150～350 parts of epoxy chloropropane, 15～40 parts of inorganic strong alkalis, 0.05～5 part of phase-transfer catalyst, be heated to 60～120 ℃ of reactions after 5～20 hours, remove residual epoxy chloropropane, then under room temperature or ice-water bath condition, add 50～400 parts of aromatic solvents, add 15～40 parts of inorganic strong alkali ring-closure reactions, reaction is used the distilled water wash reaction solution after finishing, collected organic layer, drying boils off solvent, vacuum-drying, get yellow thick acrylic acid modified rosin Resins, epoxy, oxirane value 0.20～0.39.
100 parts of wherein preferred acrylic acid modified rosin and/or rosin acrylic acids, 250～300 parts of epoxy chloropropane, 15～25 parts of inorganic strong alkalis, 0.5～4 part of phase-transfer catalyst, be heated to 95～105 ℃ of reactions after 6～10 hours, remove residual epoxy chloropropane, then under the ice-water bath condition, add 250～350 parts of aromatic solvents, add 15～30 parts of inorganic strong alkali ring-closure reactions.
The another kind of preparation method of rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy, be to count by weight, with 100 parts of acrylic acid modified rosin and/or rosin acrylic acids, 50～90 parts of epoxy chloropropane, 14～40 parts of inorganic strong alkalis, 0.05～5 part of phase-transfer catalyst, 200～500 parts of aromatic solvents are heated to 60～120 ℃ of reactions 6～20 hours, after reaction finishes, use the distilled water wash reaction solution, collected organic layer, drying, boil off solvent, vacuum-drying gets yellow thick acrylic acid modified rosin Resins, epoxy, oxirane value 0.18～0.38.
100 parts of wherein preferred acrylic acid modified rosin and/or rosin acrylic acids, 60～80 parts of epoxy chloropropane, 24～30 parts of inorganic strong alkalis, 0.5～4 part of phase-transfer catalyst, 260～330 parts of aromatic solvents are heated to 90～110 ℃ of reactions 8～10 hours.
Among the preparation method of the above rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy, described phase-transfer catalyst comprises 18-hat-6, polyoxyethylene glycol, Tetrabutyl amonium bromide etc.
Aromatic solvent comprises toluene, dimethylbenzene etc.
Inorganic strong alkali comprises sodium hydroxide, potassium hydroxide etc.
The present invention is to be the method synthesizing propylene pimaric acid 2-glycidyl ester and the acrylic acid modified rosin Resins, epoxy of raw material use phase-transfer-catalyzed reactions with rosin acrylic acid, acrylic acid modified rosin resin and epoxy chloropropane.Acrylic acid modified rosin described in rosin acrylic acid 2-glycidyl ester and the preparation of rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy is the acrylic acid modified rosin of common rosin or resin and vinylformic acid generation addition reaction generation, wherein effective constituent is rosin acrylic acid, and its preparation method can adopt the existing conventional technology.The acrylic acid modified rosin purification can be obtained rosin acrylic acid.The acrylic acid modified rosin that is used to prepare the rosin acrylic acid 2-glycidyl ester must contain higher amount to pure vinylformic acid pimaric acid.The vinylformic acid pimaric acid is high more in the acrylic acid modified rosin, the oxirane value of rosin acrylic acid 2-glycidyl ester that makes and rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy is also high more, illustrates that the content of rosin acrylic acid 2-glycidyl ester wherein is high more.
Through infrared, ultimate analysis, nuclear-magnetism (hydrogen spectrum, carbon spectrum), mass spectrometric measurement, the physical constant of rosin acrylic acid 2-glycidyl ester is as follows:
EA (ultimate analysis): C (71.93%), H (8.01%), O (20.06%); IR:(v
Max KBr(cm
-1)): 2933,2867,1725,1644,
910,
846, 761; NMR:61H (CDCl
3): 5.28 (1H, s, 14-H), 4.35～3.40 (10H, m, 24-H, 25-H, 26-H, 27-H, 28-H, 29-H), 2.54 (1H, m, 21-H), 2.34 (2H, d, 22-H), 1.90～0.80 (16H, m, 1-H, 2-H, 3-H, 5-H, 6-H, 7-H, 9-H, 11-H, 12-H, 15-H), 1.125 (3H, s, 19-CH
3), 1.03 (3H, s, 16-CH
3), 1.02 (3H, s, 17-CH
3), 0.58 (3H, s, 20-CH
3); δ 13C (CDCl
3): 179.0 (C
18=O), 175.5 (C
23=O), 149.0 (C
13), 122.8 (C
14), 70.3 (C
27), 65.2 (C
24), 64.8 (C
28), 63.7 (C
25), 55.4 (C
21), 52.1 (C
9), 49.7 (C
29), 49.3 (C
5), 47.4 (C
4), 44.6 (C
26), 40.7 (C
8), 37.8 (C
1), 36.8 (C
10), 35.0 (C
12), 32.8 (C
7), 31.5 (C
3), 27.5 (C
11), 22.6 (C
22), 20.5 (C
16+17), 17.0 (C
2), 16.7 (C
19), 16.0 (C
20); M/z:486,
358, 133,91,55,43,29.
Rosin acrylic acid 2-glycidyl ester provided by the invention and acrylic acid modified rosin Resins, epoxy, raw material is a natural product cheap and easy to get, the oxirane value height is eco-friendly novel bonding material, also can be used as the reaction intermediate of preparation rosin based tensio-active agent.And their preparation method is simple, is easy to industrialization, has broad application prospects.
Preferred forms
Embodiment 1
The preparation of rosin acrylic acid 2-glycidyl ester:
In the 100ml reactor, add 3.74g (10mmol) rosin acrylic acid, the epoxy chloropropane of 1.87 (20mmol) and 3.74g (27mmol) salt of wormwood, and 0.0187g (0.07mmol) 18-hat-6 ethers, 80ml acetone is heated to 55～60 ℃ of backflows, reacts 60 hours.After cooling, use the Rotary Evaporators removal of solvent under reduced pressure.Add the dissolving of 15ml toluene, repeatedly wash, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water.Collect toluene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin, oxirane value 0.38, cl content 0.036% (molar content); Behind normal hexane and acetone recrystallization, promptly getting the rosin acrylic acid 2-glycidyl ester is white solid, oxirane value 0.395.
Embodiment 2
The preparation of rosin acrylic acid 2-glycidyl ester:
In the 100ml reactor, add 3.74g (10mmol) rosin acrylic acid, the epoxy chloropropane of 2.24g (24mmol) and 4.11g (30mmol) saleratus, and 0.075g (0.28mmol) Tetrabutyl amonium bromide, 70ml acetone is heated to 55～60 ℃ of backflows, reacts 70 hours.After cooling, use the Rotary Evaporators removal of solvent under reduced pressure.Add the dissolving of 20ml toluene, repeatedly wash, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water.Collect toluene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin, oxirane value 0.385, cl content 0.042% (molar content); Behind normal hexane and acetone recrystallization, promptly getting the rosin acrylic acid 2-glycidyl ester is white solid, oxirane value 0.396.
Embodiment 3
The preparation of rosin acrylic acid 2-glycidyl ester:
In the 100ml reactor, add 3.74g (10mmol) rosin acrylic acid, the epoxy chloropropane of 3.0g (32mmol) and 4.49g (34mmol) salt of wormwood, and 0.15g (0.56mmol) 18-hat-6 ethers, the 60ml butanone is heated to 75～80 ℃, reacts 80 hours.After cooling, use the Rotary Evaporators removal of solvent under reduced pressure.Add the dissolving of 20ml toluene, repeatedly wash, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water.Collect toluene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin, oxirane value 0.39, cl content 0.03% (molar content); Column chromatography is separated back normal hexane and acetone recrystallization, and promptly getting the rosin acrylic acid 2-glycidyl ester is white solid, oxirane value 0.415.
Embodiment 4
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 1.87g (3.8mmol) acrylic acid modified rosin, 4.6g (50mmol) epoxy chloropropane, 0.28g (7.0mmol) sodium hydroxide and 0.0094g (0.029mmol) Tetrabutyl amonium bromide heat 95～105 ℃ of reactions 6 hours.After cooling, remove the remaining epoxy chloropropane of dereaction with the Rotary Evaporators decompression.Then under the ice-water bath condition, add 55ml dimethylbenzene and the ring-closure reaction of 0.28g (7.0mmol) sodium hydrate solid 2 hours.After reaction finishes,, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water washing reaction liquid repeatedly.Collect the dimethylbenzene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin be acrylic acid modified rosin Resins, epoxy 2.16g, oxirane value 0.2.
Embodiment 5
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 1.87g (3.8mmol) acrylic acid modified rosin, 5.2g (56mmol) epoxy chloropropane, 0.4g (10mmol) sodium hydroxide and 0.02g polyoxyethylene glycol heat 95～105 ℃ of reactions 8 hours.After cooling, remove the remaining epoxy chloropropane of dereaction with the Rotary Evaporators decompression.Then under the room temperature, add 50ml toluene and the ring-closure reaction of 0.4g (10mmol) sodium hydrate solid 6 hours.After reaction finishes,, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water washing reaction liquid repeatedly.Collect toluene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin be acrylic acid modified rosin Resins, epoxy 2.15g, oxirane value 0.29.
Embodiment 6
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 1.87g (3.8mmol) acrylic acid modified rosin, 5.6g (60mmol) epoxy chloropropane, 0.468g (11.6mmol) sodium hydroxide and 0.05g (0.23mmol) Tetrabutyl amonium bromide heat 95～105 ℃ of reactions 10 hours.After cooling, remove the remaining epoxy chloropropane of dereaction with the Rotary Evaporators decompression.Then under the ice-water bath condition, add 60ml toluene and the ring-closure reaction of 0.36g (9mmol) sodium hydrate solid 2 hours.After reaction finishes,, vibrate, leave standstill, do not have chlorion with Silver Nitrate check water layer after the layering and exist with distilled water washing reaction liquid repeatedly.Collect toluene layer, remove with Rotary Evaporators behind the anhydrous magnesium sulfate drying and desolvate, 80 ℃ of vacuum-drying 3～4 hours, yellow thick resin be acrylic acid modified rosin Resins, epoxy 2.03g, oxirane value 0.36.
Embodiment 7
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 3.75g (7.6mmol) acrylic acid modified rosin, 2.25g (24.3mmol) epoxy chloropropane, 18-hat-6 ethers of 0.935g (23.4mmol) sodium hydrate solid and 0.0187g (0.07mmol), add 15ml dimethylbenzene, heat 90～100 ℃ of reactions 8 hours.After reaction finishes,, vibrate, leave standstill with distilled water washing reaction liquid repeatedly, collected organic layer, anhydrous magnesium sulfate drying removes with Rotary Evaporators and to desolvate, vacuum-drying gets yellow thick resin and is acrylic acid modified rosin Resins, epoxy 5.12g, oxirane value 0.32.
Embodiment 8
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 3.75g (7.6mmol) acrylic acid modified rosin, 3.0g (32mmol) epoxy chloropropane, the polyoxyethylene glycol of 0.468g (11.6mmol) sodium hydrate solid and 0.04g adds 20ml toluene, adds 90～100 ℃ of thermal responses 9 hours.After reaction finishes,, vibrate, leave standstill with distilled water washing reaction liquid repeatedly, collected organic layer, anhydrous magnesium sulfate drying removes with Rotary Evaporators and to desolvate, vacuum-drying gets yellow thick resin and is acrylic acid modified rosin Resins, epoxy 5.04g, oxirane value 0.28.
Embodiment 9
The preparation of acrylic acid modified rosin Resins, epoxy:
In the 100ml reactor, add 3.75g (7.6mmol) acrylic acid modified rosin, 2.62g (28.3mmol) epoxy chloropropane, 1.125g (28.1mmol) sodium hydrate solid and 0.075g (0.28mmol) Tetrabutyl amonium bromide, add 30ml toluene, heat 100～110 ℃ of reactions 10 hours.After reaction finishes,, vibrate, leave standstill with distilled water washing reaction liquid repeatedly, collected organic layer, anhydrous magnesium sulfate drying removes with Rotary Evaporators and to desolvate, vacuum-drying gets yellow thick resin and is acrylic acid modified rosin Resins, epoxy 5.4g, oxirane value 0.34.
Claims (12)
1, a kind of rosin acrylic acid 2-glycidyl ester, chemical structural formula is as follows:
2, a kind of rosin acrylic acid 2-glycidyl ester type acrylic acid modified rosin Resins, epoxy, by acrylic acid modified rosin and/or rosin acrylic acid and epichlorohydrin reaction and obtain, by gross weight, contain the rosin acrylic acid 2-glycidyl ester 40～100% of claim 1 in this Resins, epoxy.
3, the Resins, epoxy of claim 2, wherein the rosin acrylic acid 2-glycidyl ester 60～90%.
4, the preparation method of the rosin acrylic acid 2-glycidyl ester of claim 1, be to count by weight, with 100 parts of rosin acrylic acids, 45～150 parts of epoxy chloropropane, 100～400 parts of organic solvents, 0.05～5 part of phase-transfer catalyst, 80～150 parts of weak base, back flow reaction 50～180 hours is filtered, and boils off solvent, residue is through aromatic solvent extraction, drying, boil off solvent, after recrystallization or column chromatography methods separation and purification, obtain the rosin acrylic acid 2-glycidyl ester, oxirane value 0.38～0.40.
5, the method for claim 4, wherein epoxy chloropropane is 55～80 parts, 200～300 parts of organic solvents, 0.5～4 part of phase-transfer catalyst, 100～120 parts of reactions of weak base 60～80 hours.
6, claim 4 or 5 method, wherein phase-transfer catalyst is selected from 18-hat-6, polyoxyethylene glycol, Tetrabutyl amonium bromide; Weak base is selected from salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate; Organic solvent is selected from acetone, butanone, N, dinethylformamide, N, N-diethylformamide, acetonitrile, butyronitrile.
7, the preparation method of claim 2 or 3 acrylic acid modified rosin Resins, epoxy, be to count by weight, with 100 parts of acrylic acid modified rosin and/or rosin acrylic acids, 150～350 parts of epoxy chloropropane, 15～40 parts of inorganic strong alkalis, 0.05～5 part of phase-transfer catalyst, be heated to 60～120 ℃ of reactions after 5～20 hours, remove residual epoxy chloropropane, then under room temperature or ice-water bath condition, add 50～400 parts of aromatic solvents, add 15～40 parts of inorganic strong alkali ring-closure reactions, reaction is used the distilled water wash reaction solution after finishing, collected organic layer, drying boils off solvent, vacuum-drying, get yellow thick acrylic acid modified rosin Resins, epoxy, oxirane value 0.20～0.39.
8, the method for claim 8.Wherein acrylic acid modified rosin and/or rosin acrylic acid are 100 parts, 250～300 parts of epoxy chloropropane, 15～25 parts of inorganic strong alkalis, 0.5～4 part of phase-transfer catalyst, be heated to 95～105 ℃ of reactions after 6～10 hours, remove residual epoxy chloropropane, then under the ice-water bath condition, add 250～350 parts of aromatic solvents, add 15～30 parts of inorganic strong alkali ring-closure reactions.
9, claim 7 or 8 method, wherein phase-transfer catalyst is selected from 18-hat-6, polyoxyethylene glycol, Tetrabutyl amonium bromide; Aromatic solvent is selected from toluene, dimethylbenzene, sherwood oil; Inorganic strong alkali is selected from sodium hydroxide, potassium hydroxide.
10, the preparation method of claim 2 or 3 acrylic acid modified rosin Resins, epoxy, be to count by weight, with 100 parts of acrylic acid modified rosin and/or rosin acrylic acids, 50～90 parts of epoxy chloropropane, 14～40 parts of inorganic strong alkalis, 0.05～5 part of phase-transfer catalyst, 200～500 parts of aromatic solvents are heated to 60～120 ℃ of reactions 6～20 hours, after reaction finishes, use the distilled water wash reaction solution, collected organic layer, drying, boil off solvent, vacuum-drying gets yellow thick acrylic acid modified rosin Resins, epoxy, oxirane value 0.18～0.38.
11, the method for claim 10, wherein epoxy chloropropane is 60～80 parts, 24～30 parts of inorganic strong alkalis, 0.5～4 part of phase-transfer catalyst, 260～330 parts of aromatic solvents are heated to 90～110 ℃ of reactions 8～10 hours.
12, claim 10 or 11 method, wherein phase-transfer catalyst is selected from 18-hat-6, polyoxyethylene glycol, Tetrabutyl amonium bromide; Aromatic solvent is selected from toluene, dimethylbenzene, sherwood oil; Inorganic strong alkali is selected from sodium hydroxide, potassium hydroxide.
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| EP2261220A1 (en) | 2009-06-11 | 2010-12-15 | Hexion Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| CN101448862B (en) * | 2006-06-02 | 2011-12-14 | 昭和电工株式会社 | Photosensitive resin and photosensitive resin composition |
| CN102935343A (en) * | 2012-11-08 | 2013-02-20 | 中国林业科学研究院林产化学工业研究所 | Abietate alcohol ether type quaternary ammonium salt surface active agent and preparation method thereof |
| CN101544744B (en) * | 2009-04-17 | 2013-07-03 | 中国科学院广州化学研究所 | Acrylic acid rosin and epoxy resin prepolymer and preparation method thereof |
| CN105647389A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing esters with rosin acrylic acid and GMA (glycidyl methacrylate) |
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| CN111533713A (en) * | 2020-05-20 | 2020-08-14 | 中国林业科学研究院林产化学工业研究所 | Rosin-based epoxy monomer and preparation method and application thereof |
| CN112225712A (en) * | 2020-09-24 | 2021-01-15 | 仲恺农业工程学院 | Epoxidized soybean oil propylene pimaric acid ester and preparation method and application thereof |
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| CN101448862B (en) * | 2006-06-02 | 2011-12-14 | 昭和电工株式会社 | Photosensitive resin and photosensitive resin composition |
| CN101544744B (en) * | 2009-04-17 | 2013-07-03 | 中国科学院广州化学研究所 | Acrylic acid rosin and epoxy resin prepolymer and preparation method thereof |
| US8802872B2 (en) | 2009-06-11 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| WO2010142396A1 (en) | 2009-06-11 | 2010-12-16 | Momentive Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| EP2261220A1 (en) | 2009-06-11 | 2010-12-15 | Hexion Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| CN102935343A (en) * | 2012-11-08 | 2013-02-20 | 中国林业科学研究院林产化学工业研究所 | Abietate alcohol ether type quaternary ammonium salt surface active agent and preparation method thereof |
| CN102935343B (en) * | 2012-11-08 | 2014-07-02 | 中国林业科学研究院林产化学工业研究所 | Abietate alcohol ether type quaternary ammonium salt surface active agent and preparation method thereof |
| CN105647389A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing esters with rosin acrylic acid and GMA (glycidyl methacrylate) |
| CN110713797A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy grafted rosin, preparation method thereof, composition containing epoxy grafted rosin and application of composition |
| JP2022552919A (en) * | 2019-10-14 | 2022-12-20 | ヘキシオン・インコーポレイテッド | Glycidyl esters of alpha, alpha branched acids and blends thereof from renewable sources |
| CN111533713A (en) * | 2020-05-20 | 2020-08-14 | 中国林业科学研究院林产化学工业研究所 | Rosin-based epoxy monomer and preparation method and application thereof |
| CN112225712A (en) * | 2020-09-24 | 2021-01-15 | 仲恺农业工程学院 | Epoxidized soybean oil propylene pimaric acid ester and preparation method and application thereof |
| CN112225712B (en) * | 2020-09-24 | 2023-02-03 | 仲恺农业工程学院 | Epoxidized soybean oil propylene pimaric acid ester and preparation method and application thereof |
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