CN102250318A - Full-rosinyl epoxy resin composite and condensate thereof - Google Patents
Full-rosinyl epoxy resin composite and condensate thereof Download PDFInfo
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Abstract
The invention discloses a full-rosinyl epoxy resin composite which is composed of 100 parts by weight of rosinyl epoxy resin base material, 30-80 parts by weight of rosinyl curing agent and 1-12 parts by weight of catalyst. After the full-rosinyl epoxy resin composite is solidified, the full-rosinyl epoxy resin condensate can be obtained and has the characteristics of high strength, high modulus, high glass-transition temperature and the like and is especially suitable for preparing the biobased composite material substrate resin and outdoor electrical engineering insulation materials. The invention also discloses a preparation method of the full-rosinyl epoxy resin condensate, the preparation method has the advantages of simple preparation technology, strong operability and good process controllability and is easy for industrial implementation.
Description
Technical field
The present invention relates to bio-based macromolecule resin field, particularly a kind of full rosinyl composition epoxy resin and cured article thereof.
Background technology
The double effects that the bio-based macromolecular material has the protection environment and economizes on resources is a focus of at present domestic and international investigation of materials.Early several years ago, the U.S., Japan, European Union etc. have just successively passed through strategic bill such as " biomass research and development bill ", " biotechnology strategy outline ", European environmental standard EN13432 and standard promotes its sound development.In China, Premier Wen Jiabao will make the formal commitment to the world for the end of the year 2009, to reduce 40%～45% on basis in 2005 to the year two thousand twenty China per GDP CO2 emissions, the use of bio-based materials is considered to one of important means of development " low-carbon economy ".As seen, be raw material with the regeneration biological resource, research and development novel high-performance material is complied with era development trend, meets national strategy demand, and important application value and vast potential for future development are arranged.
Rosin is a kind of important natural reproducible resource of China.China produces rosin 50～600,000 ton per year, is the country of rosin output maximum in the world, has the power to make decision of world's rosin price.Two keys in the sylvic acid and carboxyl isoreactivity functional group conveniently carry out number of chemical reactions such as addition, esterification, condensation, its huge hydrogen phenanthrene ring structure has higher mechanics rigidity simultaneously, can match in excellence or beauty with petroleum base aliphatics or aromatic series ring-type monomer, be applied to the Polymer Synthesizing field so rosin and derivative thereof have been used as the surrogate of some industrial chemicals.As application number is that the Chinese patent application of 02149777.X has been introduced and used acrylic acid rosin and epichlorohydrin reaction to prepare the method for rosin acrylic acid 2-glycidyl ester type Resins, epoxy; Application number is a kind of three-glycidyl ester epoxy resin based on maleopimaric anhydride and epoxy chloropropane for the 01108250.X Chinese patent application discloses; Application number is that 200710032534.2 Chinese patent application and application number are that 200810198059.0 Chinese patent application discloses a kind of method of using polymerized rosin and formaldehyde modified rosin to prepare Resins, epoxy respectively.Simultaneously, also having with rosin is raw material synthetic epoxy resin solidifying agent, improves report (Green Chemistry 2009,11, the 1018-1025 of epoxy resin cured product second-order transition temperature and mechanical strength in the hope of utilizing hydrogen phenanthrene ring structure huge in the sylvic acid; BioresourceTechnology, 2010,101,2520-2524).
But, up to the present, utilize the rosinyl epoxy hardener to solidify document and patent report that rosinyl Resins, epoxy obtains full rosinyl epoxy resin cured product thereby yet there are no.
Summary of the invention
The invention provides a kind of full rosinyl composition epoxy resin, adopted the rosinyl epoxy hardener to solidify rosinyl Resins, epoxy.
The present invention also provides a kind of full rosinyl epoxy resin cured product, has high glass-transition temperature, high strength and high-modulus characteristics, is particularly useful for making high-performance bio-based composite material matrix resin and outdoor electrical insulating material.
The present invention also provides a kind of preparation method of full rosinyl epoxy resin cured product, and its preparation technology is simple, workable, the process controllability is good, is easy to industrializing implementation.
A kind of full rosinyl composition epoxy resin, form by the raw material of following weight part:
Rosinyl Resins, epoxy 100 weight parts;
Rosinyl epoxy curing agent 30～80 weight parts;
Catalyzer 1～12 weight part.
In general, the final performance of epoxy resin cured product is decided by epoxy monomer and selected solidifying agent kind and the proportioning between the two, the i.e. composition and the proportioning of full rosinyl composition epoxy resin.By the comprehensive use properties excellence of full rosinyl composition epoxy resin by the full rosinyl epoxy resin cured product of curing process preparation.
In order to reach better invention effect, carry out further preferred:
Described rosinyl Resins, epoxy is one or more in the rosinyl epoxy monomer; Described rosinyl epoxy monomer is preferably the monomer of formula I structure, formula II structure, formula III structure or formula IV structure:
Formula I formula II
Formula III, formula IV.
Wherein, the rosinyl epoxy monomer of formula I structure is prepared by a series of existing chemical reactions by rosin derivative maleopimaric anhydride and epoxy chloropropane, and concrete preparation process can be the Chinese patent application of 01108250.X with reference to application number;
The rosinyl epoxy monomer of formula II structure is prepared by a series of existing chemical reactions by acrylic acid modified rosin and epoxy chloropropane, and concrete preparation process can be the Chinese patent application of 02149777.X with reference to application number;
The rosinyl epoxy monomer of formula III structure is prepared by a series of existing chemical reactions by polymerized rosin and epoxy chloropropane, and concrete preparation process can be 200710032534.2 Chinese patent application with reference to application number;
The rosinyl epoxy monomer of formula IV structure is prepared by a series of existing chemical reactions by formaldehyde modified rosin and epoxy chloropropane, and concrete preparation process can be 200810198059.0 Chinese patent application with reference to application number.
Described rosinyl epoxy curing agent is preferably the maleopimaric anhydride of formula V structure:
Formula V.
Maleopimaric anhydride is prepared by the D-A addition reaction by rosin and maleic anhydride, but concrete preparation process reference literature report (Green Chemistry 2009,11,1018-1025 or " chemistry circular " 2011,1,607-609) or with reference to application number 201010225279.5 Chinese patent application.
Described catalyzer can be selected one or more in imdazole derivatives, tertiary amine, quaternary ammonium salt, boron trifluoride complex, the metal halide for use; In preferred 1-methyl-2-ethyl imidazol(e), triethylamine, tetramethyl ammonium chloride, etamon chloride, the boron trifluoride ethyl ether complex one or more.
The preparation method of described full rosinyl composition epoxy resin is: rosinyl Resins, epoxy, rosinyl epoxy hardener and catalyzer are mixed by proportioning, obtain full rosinyl composition epoxy resin.
Described full bio-based composition epoxy resin can be applicable to prepare Weather-resistant epoxy sizing agent, epoxy resin-based paint and epoxypaint, has a good application prospect.
Described full rosinyl composition epoxy resin can obtain full rosinyl epoxy resin cured product after solidifying.
Described full rosinyl composition epoxy resin prepares the method for full rosinyl epoxy resin cured product, may further comprise the steps:
Rosinyl Resins, epoxy, rosinyl epoxy curing agent and catalyst mix are obtained mixture after evenly; Mixture at 60 ℃～100 ℃ following Procuring 1h～2h, at 140 ℃～180 ℃ following after fixing 2～4h, is obtained full rosinyl epoxy resin cured product again.
Described full rosinyl epoxy resin cured product can be used for preparing composite matrix resin and outdoor electrical insulating material.
Compared with prior art, advantage of the present invention and beneficial effect are as follows:
(1) prescription of full rosinyl epoxy resin cured product of the present invention and preparation method just so far, thereby yet there are no document and the patent report that utilizes the rosinyl solidifying agent to solidify rosinyl Resins, epoxy preparation rosinyl epoxy resin cured product;
(2) rosin belong to China's characteristic cheapness, renewable resources is easy to get, through rosin (being rosinyl epoxy monomer and rosinyl epoxy curing agent) alternative petroleum base aliphatics or aromatic epoxy resin or the epoxy curing agent after the modification, on the one hand, raw material adopts renewable resources, has good environmental benefit; On the other hand, the present invention provides new approach for rosiny deep processing and high value added utilization;
(3) the utilization of the present invention rosinyl epoxy hardener that contains hydrogen phenanthrene ring structure solidifies the rosinyl Resins, epoxy that contains hydrogen phenanthrene ring structure, solidifying agent that has huge rigid annular structure and the Resins, epoxy that has huge rigid annular structure have been adopted simultaneously, more fully and effectively utilize in the rosin huge hydrogen phenanthrene ring structure in the advantage that improves on thermosetting resin glass transition temperature and the mechanical strength, prepared high glass-transition temperature, the full rosinyl epoxy resin cured product of high strength and high-modulus, the comprehensive use properties excellence of the feasible full rosinyl epoxy resin cured product that makes.
(4) the full rosinyl epoxy resin cured product of the present invention preparation method, its preparation technology is simple, workable, the process controllability is good, is easy to industrializing implementation.
Embodiment
Embodiment 1 (maleopimaric anhydride preparation method 1):
100 weight part rosin are heated to 150 ℃ under nitrogen protection; add the p-methyl benzenesulfonic acid of 3 weight parts and the maleic anhydride of 35 weight parts then; temperature rises to 220 ℃; reacted 3 hours; cooling; add Glacial acetic acid and carry out recrystallization, vacuum-drying obtains 70 weight part purity (mass percent) and is 95% maleopimaric anhydride.
Embodiment 2 (maleopimaric anhydride preparation method 2):
100 weight part rosin are heated to 150 ℃ under nitrogen protection; add the Resorcinol of 0.4 weight part and the maleic anhydride of 30 weight parts then; temperature rises to 190 ℃; reacted 4 hours; cooling; add Glacial acetic acid and carry out recrystallization, vacuum-drying obtains 62 weight part purity (mass percent) and is 95% maleopimaric anhydride.
Embodiment 3
(1) maleopimaric anhydride 400 grams that embodiment 1 made, epoxy chloropropane 300 grams and water 20 grams mix, add 9 gram 4 bromides, reacted 1 hour down at 75 ℃, the remaining epoxy chloropropane of reaction is reclaimed in underpressure distillation, adds 50 milliliters of toluene then, and is 180 to restrain sodium hydroxide 100 ℃ of following minutes 4 times equivalent adding total amounts, keep reaction 2 hours, filter also washing to neutral, vacuum distillation recovered solvent obtains the light yellow collophony basic ring epoxy resins monomer of formula I structure;
The rosinyl epoxy monomer of formula I structure
(2) with maleopimaric anhydride 80 grams of rosinyl epoxy monomer 100 gram of above-mentioned formula I structure, embodiment 1 preparation with after catalyzer 1-methyl-2-ethyl imidazol(e) 3 grams mix, obtain mixture, promptly full rosinyl composition epoxy resin;
(3) with said mixture 60 ℃ of following Procuring 2 hours, 160 ℃ of following after fixing 4 hours, obtain full rosinyl epoxy resin cured product again.
After tested, preparation-obtained full rosinyl epoxy resin cured product has following performance: tensile strength: 56MPa; Tensile modulus: 2845MPa; 152 ℃ of second-order transition temperatures.
Embodiment 4
(1) formaldehyde modified rosin 100 gram and epoxy chloropropane 470 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong and mix, add tetramethyl ammonium chloride 0.5 gram after being warming up to 75 ℃, reacted 5 hours, the cooling back adds benzene 80 grams and sodium hydroxide 30 grams, controlled temperature then reacted 3.5 hours at 73 ℃.Filter, be washed to the halogen ion, removal of solvent under reduced pressure, 60 ℃ of vacuum-dryings obtained the rosinyl epoxy monomer of formula IV structure in 6 hours;
The rosinyl epoxy monomer of formula IV structure
(2) rosinyl epoxy monomer 100 grams of above-mentioned formula IV structure, maleopimaric anhydride 70 grams and catalyst of triethylamine 1 gram of embodiment 2 preparations are mixed, obtain mixture, promptly full rosinyl composition epoxy resin;
(3) mixture at 180 ℃ of following after fixing 2h, obtains full rosinyl epoxy resin cured product again at 80 ℃ of following Procuring 1.5h.
After tested, preparation-obtained full rosinyl epoxy resin cured product has following performance: tensile strength: 62MPa; Tensile modulus: 3200MPa; 172 ℃ of second-order transition temperatures.
Embodiment 5
(1) polymerized rosin 100 grams and epoxy chloropropane 74 gram addings are had in the four-hole boiling flask of thermometer, agitator and prolong, be warming up to 90 ℃, add tetramethyl ammonium chloride 0.2 gram reaction and be cooled to 50 ℃ after 3.5 hours, add 75 gram benzene and 24 gram sodium hydroxide then, be warming up to 70 ℃ of reactions 3 hours, filter, be washed with distilled water to the halogen ion, remove and to desolvate, 60 ℃ of vacuum-drying 6 hours obtains the rosinyl epoxy monomer of formula III structure;
The rosinyl epoxy monomer of formula III structure
(2) rosinyl epoxy monomer 100 grams of above-mentioned formula III structure, maleopimaric anhydride 40 grams and catalyzer boron trifluoride ethyl ether complex 12 grams of embodiment 1 preparation are mixed, obtain mixture, promptly full rosinyl composition epoxy resin;
(3) with said mixture 100 ℃ of following Procuring 2 hours, 140 ℃ of following after fixing 4 hours, obtain full rosinyl epoxy resin cured product again.
After tested, preparation-obtained full rosinyl epoxy resin cured product has following performance: tensile strength: 37MPa; Tensile modulus: 2540MPa; 127 ℃ of second-order transition temperatures.
Embodiment 6
(1) add rosin acrylic acid 370 grams in 100 milliliters of four-hole bottles, 75 milliliters in epoxy chloropropane 230 grams, saleratus 410 grams, Tetrabutyl amonium bromide 6.5 grams and acetone were heated to 60 ℃ of back flow reaction 10 hours, and the pressurization of cooling back removes desolvates.Add the dissolving of 25 milliliters of toluene then, repeatedly washing with distilled water does not have chlorion to water layer and exists.Collect toluene layer, 80 ℃ of vacuum-dryings 4 hours, obtain the rosinyl epoxy monomer of formula II structure behind the removal solvent;
The rosinyl epoxy monomer of formula II structure
(2) maleopimaric anhydride 72 grams of rosinyl epoxy monomer 100 gram of above-mentioned formula II structure, embodiment 2 preparations and the catalyst mix be made up of tetramethyl ammonium chloride 2 grams and triethylamine 1 gram are even, obtain mixture, promptly full rosinyl composition epoxy resin;
(3) with said mixture 100 ℃ of following Procuring 2 hours, 160 ℃ of following after fixing 4 hours, obtain full rosinyl epoxy resin cured product again;
After tested, preparation-obtained full rosinyl epoxy resin cured product has following performance: tensile strength: 49MPa; Tensile modulus: 2720MPa; Second-order transition temperature: 132 ℃.
Embodiment 7
(1) be prepared as follows the rosinyl epoxy monomer of the formula I structure shown in the figure and the rosinyl epoxy monomer of formula III structure according to the preparation process among embodiment 3 and the embodiment 5 respectively:
The rosinyl epoxy monomer of the rosinyl epoxy monomer formula III structure of formula I structure
(2) rosinyl epoxy monomer and each 50 gram of rosinyl epoxy monomer of formula III structure, maleopimaric anhydride 62 grams and catalyzer etamon chloride 5 grams of embodiment 2 preparations with formula I structure mix, obtain mixture, promptly full rosinyl composition epoxy resin;
(3) with said mixture 90 ℃ of following Procuring 2 hours, 180 ℃ of following after fixing 3 hours, obtain full rosinyl epoxy resin cured product again.
After tested, preparation-obtained full rosinyl epoxy resin cured product has following performance: tensile strength: 46MPa; Tensile modulus: 2750MPa; Second-order transition temperature: 145 ℃.
The full rosinyl epoxy resin cured product of embodiment of the invention preparation has high tensile, high tensile modulus and high glass transition, obviously, used as composite matrix resin and outdoor electrical insulating material, still have above-mentioned various excellent properties.
Above-mentioned is in conjunction with the embodiments the present invention to be elaborated; but embodiments of the present invention are not restricted to the described embodiments, and other any change of being done under patent core guiding theory of the present invention, replacement, combination simplification etc. are included within the protection domain of patent of the present invention.
Claims (9)
1. a full rosinyl composition epoxy resin is characterized in that, is made up of the raw material of following weight part:
Rosinyl Resins, epoxy 100 weight parts;
Rosinyl epoxy curing agent 30～80 weight parts;
Catalyzer 1～12 weight part.
2. full rosinyl composition epoxy resin according to claim 1 is characterized in that, described rosinyl Resins, epoxy is one or more in the rosinyl epoxy monomer.
3. full rosinyl composition epoxy resin according to claim 2 is characterized in that, described rosinyl epoxy monomer is the monomer of formula I structure, formula II structure, formula III structure or formula IV structure:
Formula I formula II
Formula III formula IV.
4. full rosinyl composition epoxy resin according to claim 1 is characterized in that, described rosinyl epoxy curing agent is the maleopimaric anhydride of formula V structure:
5. full rosinyl composition epoxy resin according to claim 1 is characterized in that described catalyzer is one or more in imdazole derivatives, tertiary amine, quaternary ammonium salt, boron trifluoride complex, the metal halide.
6. complete according to claim 1 or 5 rosinyl composition epoxy resin, it is characterized in that described catalyzer is one or more in 1-methyl-2-ethyl imidazol(e), triethylamine, tetramethyl ammonium chloride, etamon chloride, the boron trifluoride ethyl ether complex.
7. prepare the method for full rosinyl epoxy resin cured product according to each described full rosinyl composition epoxy resin of claim 1～6, it is characterized in that, may further comprise the steps:
Rosinyl Resins, epoxy, rosinyl epoxy curing agent and catalyst mix are obtained mixture after evenly; Mixture at 60 ℃～100 ℃ following Procuring 1h～2h, at 140 ℃～180 ℃ following after fixing 2～4h, is obtained full rosinyl epoxy resin cured product again.
8. the full rosinyl epoxy resin cured product of method preparation according to claim 7.
9. the application of full rosinyl epoxy resin cured product according to claim 8 in preparation composite matrix resin and outdoor electrical insulating material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702683A (en) * | 2012-06-04 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin for prepreg and preparation method thereof |
| CN102863610A (en) * | 2012-09-07 | 2013-01-09 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin system and preparation method of maleated rosin imidazolium salt accelerator |
| CN103203568A (en) * | 2013-03-03 | 2013-07-17 | 石盛华 | Rapidly shrinking fusing auxiliary |
| CN105482078A (en) * | 2015-11-27 | 2016-04-13 | 中国科学院宁波材料技术与工程研究所 | Rosin-based epoxy resin curing agent and its preparation method and use |
| CN105778048A (en) * | 2016-03-14 | 2016-07-20 | 山东科技大学 | Rosin epoxy resin composition and preparation method thereof |
| 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 |
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| CN102702683A (en) * | 2012-06-04 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin for prepreg and preparation method thereof |
| CN102702683B (en) * | 2012-06-04 | 2015-02-11 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin for prepreg and preparation method thereof |
| CN102863610A (en) * | 2012-09-07 | 2013-01-09 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin system and preparation method of maleated rosin imidazolium salt accelerator |
| CN102863610B (en) * | 2012-09-07 | 2015-02-11 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin system and preparation method of maleated rosin imidazolium salt accelerator |
| CN103203568A (en) * | 2013-03-03 | 2013-07-17 | 石盛华 | Rapidly shrinking fusing auxiliary |
| CN105482078A (en) * | 2015-11-27 | 2016-04-13 | 中国科学院宁波材料技术与工程研究所 | Rosin-based epoxy resin curing agent and its preparation method and use |
| CN105482078B (en) * | 2015-11-27 | 2017-06-23 | 中国科学院宁波材料技术与工程研究所 | Rosin epoxy resin curing agent, its preparation method and application |
| CN105778048A (en) * | 2016-03-14 | 2016-07-20 | 山东科技大学 | Rosin epoxy resin composition and preparation method thereof |
| CN105778048B (en) * | 2016-03-14 | 2018-04-10 | 山东科技大学 | A kind of rosin and epoxy resin composition and preparation method thereof |
| 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 |
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