CN102250318B - A kind of all-rosin-based epoxy resin composition and cured product thereof - Google Patents

Abstract

The invention discloses a full rosin-based epoxy resin composition, which consists of 100 parts by weight of a rosin-based epoxy resin substrate, 30-80 parts by weight of a rosin-based curing agent and 1-12 parts by weight of a catalyst. After the rosin-based epoxy resin composition is cured, a cured product of the all-rosin-based epoxy resin can be obtained, which has the characteristics of high strength, high modulus and high glass transition temperature, and is especially suitable for the preparation of bio-based composite material matrix resin and outdoor electrician Insulation Materials. The invention also discloses a method for preparing the cured product of the full rosin-based epoxy resin, which has the advantages of simple preparation process, strong operability, good process controllability and easy industrial implementation.

Description

A kind of all-rosin-based epoxy resin composition and cured product thereof

technical field

The invention relates to the field of bio-based polymer resins, in particular to an all-rosin-based epoxy resin composition and its cured product.

Background technique

Bio-based polymer materials have dual effects of protecting the environment and saving resources, and are currently a hot spot in material research at home and abroad. As early as a few years ago, the United States, Japan, and the European Union successively passed strategic bills and standards such as the Biomass Research and Development Act, the Biotechnology Strategy Outline, and the European environmental standard EN13432 to promote its healthy development. In my country, Premier Wen Jiabao made a solemn promise to the world at the end of 2009 that by 2020, my country's unit GDP carbon dioxide emissions will be reduced by 40% to 45% on the basis of 2005. The use of bio-based materials is considered to be the key to developing a "low-carbon economy". One of the important means. It can be seen that using renewable biological resources as raw materials to research and develop new high-performance materials conforms to the development trend of the times and meets the national strategic needs, and has important practical application value and broad development prospects.

Rosin is an important natural renewable resource in my country. With an annual output of 500,000 to 600,000 tons of rosin, my country is the country with the largest rosin production in the world and has the right to determine the price of rosin in the world. The active functional groups such as double bonds and carboxyl groups in rosin acid are convenient for various chemical reactions such as addition, esterification, and condensation. Cyclic monomers are comparable, so rosin and its derivatives have been used as substitutes for some chemical raw materials in the field of polymer synthesis. For example, the Chinese patent application whose application number is 02149777.X introduces the method of using acrylic acid rosin and epichlorohydrin to react to prepare acrylic acid diglycidyl ester type epoxy resin; the application number is 01108250.X Chinese patent application discloses a Triglycidyl ester epoxy resin based on maleopimaric anhydride and epichlorohydrin; the Chinese patent application with the application number 200710032534.2 and the Chinese patent application with the application number 200810198059.0 respectively disclose a preparation using polymerized rosin and formaldehyde-modified rosin Epoxy method. Simultaneously, there is also the report of using rosin as a raw material to synthesize epoxy resin curing agent, in order to improve the glass transition temperature and mechanical strength of epoxy resin cured product by utilizing the huge hydrophenanthrene ring structure in abietic acid (Green Chemistry 2009, 11, 1018-1025 ; BioresourceTechnology, 2010, 101, 2520-2524).

However, so far, there are no literature and patent reports on using a rosin-based epoxy curing agent to cure a rosin-based epoxy resin to obtain a cured product of a full-rosin-based epoxy resin.

Contents of the invention

The invention provides a full rosin-based epoxy resin composition, which uses a rosin-based epoxy curing agent to cure the rosin-based epoxy resin.

The invention also provides a cured product of full rosin-based epoxy resin, which has the characteristics of high glass transition temperature, high strength and high modulus, and is especially suitable for preparing high-performance bio-based composite material matrix resin and outdoor electrical insulation material.

The invention also provides a method for preparing the cured product of the full rosin-based epoxy resin, which has the advantages of simple preparation process, strong operability, good process controllability and easy industrial implementation.

A kind of full rosin-based epoxy resin composition, is made up of the raw material of following weight part:

Rosin-based epoxy resin 100 parts by weight;

Rosin-based epoxy resin curing agent 30-80 parts by weight;

Catalyst 1-12 parts by weight.

Generally speaking, the final performance of the cured epoxy resin is determined by the epoxy resin monomer and the type of curing agent selected and the ratio between the two, that is, the composition and ratio of the full rosin-based epoxy resin composition . The cured product of the full rosin-based epoxy resin prepared from the full-rosin-based epoxy resin composition through a curing process has excellent comprehensive performance.

In order to achieve better invention effect, carry out further optimization:

Described rosin-based epoxy resin is one or more in rosin-based epoxy resin monomer; Described rosin-based epoxy resin monomer is preferably formula I structure, formula II structure, formula III structure or formula IV Monomer of the structure:

Among them, the rosin-based epoxy resin monomer with the structure of formula I is prepared from rosin derivative maleopimaric anhydride and epichlorohydrin through a series of existing chemical reactions. The specific preparation process can refer to the Chinese patent application number 01108250.X patent application;

The rosin-based epoxy resin monomer with the structure of formula II is prepared from acrylic acid-modified rosin and epichlorohydrin through a series of existing chemical reactions. For the specific preparation process, please refer to the Chinese patent application with application number 02149777.X;

The rosin-based epoxy resin monomer with the structure of formula III is prepared by polymerizing rosin and epichlorohydrin through a series of existing chemical reactions. For the specific preparation process, please refer to the Chinese patent application with application number 200710032534.2;

The rosin-based epoxy resin monomer with the structure of formula IV is prepared from formaldehyde-modified rosin and epichlorohydrin through a series of existing chemical reactions. For the specific preparation process, please refer to the Chinese patent application with application number 200810198059.0.

Described rosin-based epoxy resin curing agent is preferably the maleopimaric anhydride of formula V structure:

Maleopimaric anhydride is prepared by D-A addition reaction of rosin and maleic anhydride. The specific preparation process can refer to the literature report (Green Chemistry 2009, 11, 1018-1025 or "Chemical Bulletin" 2011, 1, 607-609) or refer to Chinese patent application with application number 201010225279.5.

The catalyst can be selected from one or more of imidazole derivatives, tertiary amines, quaternary ammonium salts, boron trifluoride complexes, and metal halides; preferably 1-methyl-2-ethylimidazole, tris One or more of ethylamine, tetramethylammonium chloride, tetraethylammonium chloride, boron trifluoride etherate complex.

The preparation method of the full rosin-based epoxy resin composition is: uniformly mixing the rosin-based epoxy resin, the rosin-based epoxy curing agent and the catalyst according to the proportion to obtain the full rosin-based epoxy resin composition.

The full bio-based epoxy resin composition can be applied to prepare weather-resistant epoxy adhesives, epoxy resin paints and epoxy resin coatings, and has good application prospects.

After the full rosin-based epoxy resin composition is cured, a cured product of the full-rosin-based epoxy resin can be obtained.

Described full rosin-based epoxy resin composition prepares the method for full rosin-based epoxy resin cured product, comprises the following steps:

Mix rosin-based epoxy resin, rosin-based epoxy resin curing agent and catalyst evenly to obtain a mixture; pre-cure the mixture at 60°C-100°C for 1h-2h, and then post-cure at 140°C-180°C for 2-4h , to obtain a full rosin-based epoxy resin cured product.

The cured product of the full rosin-based epoxy resin can be used to prepare composite material matrix resin and outdoor electrical insulation material.

Compared with prior art, advantage and beneficial effect of the present invention are as follows:

(1) The formula and the preparation method of the full rosin-based epoxy resin cured product of the present invention, so far, there are no documents and documents that utilize a rosin-based curing agent to solidify a rosin-based epoxy resin to prepare a rosin-based epoxy resin cured product. patent reports;

(2) Rosin is a cheap and easy-to-get renewable resource with Chinese characteristics. Modified rosin (ie, rosin-based epoxy resin monomer and rosin-based epoxy resin curing agent) can replace petroleum-based aliphatic or aromatic rings Oxygen resin or epoxy resin curing agent, on the one hand, the raw material adopts renewable resources, which has good environmental benefits; on the other hand, the present invention provides a new approach for the deep processing and high value-added utilization of rosin;

(3) The present invention utilizes the rosin-based epoxy curing agent containing the hydrophenanthrene ring structure to solidify the rosin-based epoxy resin containing the hydrophenanthrene ring structure, and simultaneously adopts a curing agent with a huge rigid ring structure and has a huge rigidity Epoxy resins with a ring structure make full and effective use of the advantages of the large hydrophenanthrene ring structure in rosin in improving the glass transition temperature and mechanical strength of thermosetting resins, and prepare high glass transition temperature, high strength and high modulus The cured product of full rosin-based epoxy resin has excellent comprehensive performance.

(4) The preparation method of the all-rosin-based epoxy resin cured product of the present invention has the advantages of simple preparation process, strong operability, good process controllability, and easy industrial implementation.

Detailed ways

Embodiment 1 (preparation method 1 of maleopimaric anhydride):

Heat 100 parts by weight of rosin to 150°C under nitrogen protection, then add 3 parts by weight of p-toluenesulfonic acid and 35 parts by weight of maleic anhydride, raise the temperature to 220°C, react for 3 hours, cool, and add glacial acetic acid Perform recrystallization and vacuum drying to obtain 70 parts by weight of maleopimaric anhydride with a purity (mass percentage) of 95%.

Embodiment 2 (maleipimaric anhydride preparation method 2):

Heat 100 parts by weight of rosin to 150°C under the protection of nitrogen, then add 0.4 parts by weight of hydroquinone and 30 parts by weight of maleic anhydride, the temperature rises to 190°C, react for 4 hours, cool, add glacial acetic acid to carry out heavy Crystallized and vacuum dried to obtain 62 parts by weight of maleopimaric anhydride with a purity (mass percentage) of 95%.

Example 3

(1) Mix 400 grams of maleopimaric anhydride, 300 grams of epichlorohydrin, and 20 grams of water prepared in Example 1, add 9 grams of tetramethylammonium bromide, react at 75 ° C for 1 hour, and depressurize Distill and recover the remaining epichlorohydrin in the reaction, then add 50 ml of toluene, and add a total of 180 g of sodium hydroxide in 4 equal amounts at 100 ° C, maintain the reaction for 2 hours, filter and wash until neutral, and depressurize Distillation reclaims solvent, obtains the light yellow transparent rosin-based epoxy resin monomer of formula I structure;

Rosin-based epoxy resin monomer of formula I structure

(2) After 100 grams of rosin-based epoxy resin monomers of the above-mentioned formula I structure, 80 grams of maleopimaric anhydride prepared in Example 1 and 3 grams of catalyst 1-methyl-2-ethylimidazole were mixed uniformly, the mixture was obtained , namely full rosin-based epoxy resin composition;

(3) The above mixture was pre-cured at 60° C. for 2 hours, and then post-cured at 160° C. for 4 hours to obtain a cured product of a full rosin-based epoxy resin.

After testing, the prepared cured product of full rosin-based epoxy resin has the following properties: tensile strength: 56MPa; tensile modulus: 2845MPa; glass transition temperature: 152°C.

Example 4

(1) Add 100 grams of formaldehyde-modified rosin and 470 grams of epichlorohydrin into a four-necked flask with a thermometer, a stirrer and a condenser tube and mix evenly. After the temperature is raised to 75° C., 0.5 grams of tetramethylammonium chloride are added. React for 5 hours, add 80 grams of benzene and 30 grams of sodium hydroxide after cooling, control the temperature at 73 ° C, and then react for 3.5 hours. Filtrate, wash with water until there is no halogen ion, remove the solvent under reduced pressure, and dry in vacuum at 60° C. for 6 hours to obtain a rosin-based epoxy resin monomer of formula IV structure;

Rosin-based epoxy resin monomer of formula IV structure

(2) 100 grams of rosin-based epoxy resin monomers of the above-mentioned formula IV structure, 70 grams of maleopimaric anhydride prepared in embodiment 2 and 1 gram of catalyst triethylamine are mixed uniformly to obtain a mixture, i.e. full rosin-based epoxy resin combination;

(3) The mixture was pre-cured at 80° C. for 1.5 h, and then post-cured at 180° C. for 2 h to obtain a cured product of full rosin-based epoxy resin.

After testing, the prepared cured product of full rosin-based epoxy resin has the following properties: tensile strength: 62MPa; tensile modulus: 3200MPa; glass transition temperature: 172°C.

Example 5

(1) Add 100 grams of polymerized rosin and 74 grams of epichlorohydrin into a four-necked flask equipped with a thermometer, agitator and condenser, raise the temperature to 90°C, add 0.2 grams of tetramethylammonium chloride and react for 3.5 hours, then cool down to 50°C, then add 75 grams of benzene and 24 grams of sodium hydroxide, heat up to 70°C and react for 3 hours, filter, wash with distilled water until there is no halogen ion, remove the solvent, and dry under vacuum at 60°C for 6 hours to obtain rosin with the structure of formula III base epoxy resin monomer;

Rosin-based epoxy resin monomer of formula III structure

(2) 100 grams of rosin-based epoxy resin monomers of the above-mentioned formula III structure, 40 grams of maleopimaric anhydride prepared in Example 1, and 12 grams of catalyst boron trifluoride etherate complexes are mixed uniformly to obtain the mixture, i.e. complete Rosin-based epoxy resin composition;

(3) The above mixture was pre-cured at 100° C. for 2 hours, and then post-cured at 140° C. for 4 hours to obtain a cured product of full rosin-based epoxy resin.

After testing, the prepared cured product of full rosin-based epoxy resin has the following properties: tensile strength: 37MPa; tensile modulus: 2540MPa; glass transition temperature: 127°C.

Example 6

(1) Add 370 grams of acrylic pimaric acid, 230 grams of epichlorohydrin, 410 grams of potassium bicarbonate, 6.5 grams of tetrabutylammonium bromide and 75 milliliters of acetone in a 100 milliliter four-necked bottle, and heat to 60° C. for reflux reaction for 10 After cooling for 1 hour, the solvent was removed under pressure. Then add 25 ml of toluene to dissolve, and wash with distilled water several times until the aqueous layer is free of chloride ions. Collect the toluene layer, remove the solvent and dry in vacuum at 80°C for 4 hours to obtain the rosin-based epoxy resin monomer of the formula II structure;

Rosin-based epoxy resin monomer of formula II structure

(2) 100 grams of rosin-based epoxy resin monomers of the above-mentioned formula II structure, 72 grams of maleopimaric anhydride prepared in Example 2 and the catalyst mixed by 2 grams of tetramethylammonium chloride and 1 gram of triethylamine Uniformly, obtain mixture, i.e. full rosin-based epoxy resin composition;

(3) Pre-curing the above mixture for 2 hours at 100°C, and then post-curing for 4 hours at 160°C to obtain a cured product of full rosin-based epoxy resin;

After testing, the prepared cured product of full rosin-based epoxy resin has the following properties: tensile strength: 49MPa; tensile modulus: 2720MPa; glass transition temperature: 132°C.

Example 7

(1) prepare the rosin-based epoxy resin monomer of the formula I structure shown in the figure below and the rosin-based epoxy resin monomer of the formula III structure according to the preparation steps in embodiment 3 and embodiment 5 respectively:

Rosin-based epoxy resin monomer of formula I structure Rosin-based epoxy resin monomer of formula III structure

(2) each 50 grams of the rosin-based epoxy resin monomer of the formula I structure and the rosin-based epoxy resin monomer of the formula III structure, 62 grams of maleopimaric anhydride prepared in embodiment 2 and catalyst tetraethylammonium chloride 5 grams mix homogeneously, obtain mixture, i.e. full rosin-based epoxy resin composition;

(3) The above mixture was pre-cured at 90° C. for 2 hours, and then post-cured at 180° C. for 3 hours to obtain a cured product of full rosin-based epoxy resin.

After testing, the prepared cured product of full rosin-based epoxy resin has the following properties: tensile strength: 46MPa; tensile modulus: 2750MPa; glass transition temperature: 145°C.

The full rosin-based epoxy resin cured product prepared in the embodiment of the present invention has high tensile strength, high tensile modulus and higher glass transition temperature, obviously, it is used as composite material matrix resin and outdoor electrical insulation material, It still has the above-mentioned various excellent properties.

The above is a detailed description of the present invention in conjunction with the examples, but the implementation of the present invention is not limited by the above examples, and any other changes, replacements, combination simplifications, etc. made under the core guiding principle of the patent of the present invention are included in the present invention within the scope of patent protection.

Claims (6)

1. a full rosin-based epoxy resin composition, is characterized in that, is made up of the raw material of following weight part: Rosin-based epoxy resin 100 parts by weight; Rosin-based epoxy resin curing agent 30-80 parts by weight; Catalyst 1 to 12 parts by weight; The rosin-based epoxy resin is one or more of the rosin-based epoxy resin monomers; Described rosin-based epoxy resin monomer is a monomer of formula I structure, formula II structure, formula III structure or formula IV structure: Described rosin-based epoxy resin curing agent is the maleopimaric anhydride of formula V structure:

Formula V. 2. the full rosin-based epoxy resin composition according to claim 1, is characterized in that, described catalyst is in imidazole derivative, tertiary amine, quaternary ammonium salt, boron trifluoride complex compound, metal halide one or more of two. 3. according to claim 1 and 2 described full rosin-based epoxy resin composition, it is characterized in that, described catalyzer is 1-methyl-2-ethylimidazole, triethylamine, tetramethylammonium chloride , tetraethylammonium chloride, boron trifluoride ether complex, or one or more of them. 4. according to the method for preparing the full rosin-based epoxy resin cured product according to the full-rosin-based epoxy resin composition described in any one of claims 1 to 3, it is characterized in that, comprising the following steps: Mix rosin-based epoxy resin, rosin-based epoxy resin curing agent and catalyst evenly to obtain a mixture; pre-cure the mixture at 60°C-100°C for 1h-2h, and then post-cure at 140°C-180°C for 2-4h , to obtain a full rosin-based epoxy resin cured product. 5. the full rosin-based epoxy resin cured product prepared by the method according to claim 4. 6. the application of full rosin-based epoxy resin cured product according to claim 5 in the preparation of composite material matrix resin and outdoor electrical insulation material.