阅读说明：本技术 一种改性环氧树脂及其制备方法 (Modified epoxy resin and preparation method thereof ) 是由 王世茸 于 2019-08-31 设计创作，主要内容包括：本发明提供了一种改性环氧树脂,属于高分子领域。本发明提供的改性环氧树脂通过以妥尔油脂肪酸为单体在强碱的存在下电解,再使用环氧化试剂进行环氧化,得到妥尔油环氧脂肪酸,向妥尔油环氧脂肪酸中添加交联剂反应制备而成。本发明的有益之处在于：本发明的原料采用环保的妥尔油脂肪酸,创造性地将工业上用处不大的妥尔油脂肪酸制成工业价值较高的改性环氧树脂。得到的改性环氧树脂具有良好的耐热性、热稳定性及抗变形能力。在改性环氧树脂的制备过程中,采用了环境友好型溶剂,采用电解方式可以避免使用或减少使用重金属和对环境有害的溶剂。整个制备流程操作方便,在低能耗的基础上却大大增加了产能。(The invention provides a modified epoxy resin, belonging to the field of macromolecules. The modified epoxy resin provided by the invention is prepared by electrolyzing tall oil fatty acid serving as a monomer in the presence of strong alkali, carrying out epoxidation by using an epoxidation reagent to obtain tall oil epoxy fatty acid, and adding a crosslinking agent into the tall oil epoxy fatty acid for reaction. The invention has the advantages that: the raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value. The obtained modified epoxy resin has good heat resistance, thermal stability and deformation resistance. In the preparation process of the modified epoxy resin, an environment-friendly solvent is adopted, and the use of heavy metals and solvents harmful to the environment can be avoided or reduced by adopting an electrolysis mode. The whole preparation process is convenient to operate, and the capacity is greatly increased on the basis of low energy consumption.)

1. The preparation method of the modified epoxy resin is characterized by comprising the following steps:

s1, electrolyzing by taking tall oil fatty acid as a monomer in the presence of strong alkali,

s2, epoxidizing by using an epoxidizing agent to obtain tall oil epoxy fatty acid,

s3, adding a cross-linking agent into the tall oil epoxy fatty acid to react to obtain the modified epoxy resin.

2. The method for preparing modified epoxy resin according to claim 1, wherein the strong base is selected from any one or more of sodium methoxide, sodium ethoxide, sodium hydride and potassium tert-butoxide.

3. The method for preparing a modified epoxy resin according to claim 1, wherein the parameters of the electrolysis are as follows: performing constant current electrolysis at 40-60 deg.C with graphite electrode and current density of 15-30mA/cm²The current is 5-10A, the voltage is 4-6V, and the electrolysis time is 10-20 s.

4. The method for producing a modified epoxy resin according to claim 1, wherein the epoxidizing agent is potassium hydrogen peroxymonosulfate, triphenylmethyl hydroperoxide, t-butyl peroxy-alcohol or t-butyl peroxy-tetraalkyl titanate complex.

5. The method of claim 4, wherein the trialkyl titanate is tetraisopropyl titanate or tetra-tert-butyl titanate.

6. The method for preparing modified epoxy resin according to claim 1, wherein the cross-linking agent is selected from one or more of amine cross-linking agent, polylysine, polyamide cross-linking agent and fibroin.

7. The method for preparing modified epoxy resin according to claim 6, wherein the amine crosslinking agent is selected from any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, m-aminobenzylamine, and biphenyldiamine.

8. The process for producing a modified epoxy resin according to claim 6, wherein the polyamide-based crosslinking agent is a polyether fatty acid amide;

the preparation method of the polyether fatty acid amide comprises the following steps:

s1, dissolving 200 parts by weight of epoxy fatty acid ester in 200 parts by weight of 1, 4-dioxane in 300 parts by weight of 200 parts by weight of 1, 4-dioxane, adding 0.5-3 parts by weight of boron trifluoride diethyl etherate solution under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring for 1-3 hours at 30-50 ℃ after the boron trifluoride diethyl etherate solution is added, adding 2-3 parts by weight of 30-80 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;

s2, adding 150 parts by weight of poly fatty acid methyl ester into a reaction vessel, dropwise adding 50-80 parts of diamine compound into the system within 15-30 minutes, and heating to 180-200 ℃ for refluxing for 1-3 hours after dropwise addition is finished.

9. The process for producing a modified epoxy resin according to any one of claims 1 to 8, which comprises the steps of:

s1, dissolving tall oil fatty acid in methanol, adding strong base with the molar weight of 0.8-1.2 times of that of the tall oil fatty acid for constant current electrolysis, removing the solvent, adding water, adjusting the pH value to 2-3 with hydrochloric acid aqueous solution, washing with ethyl acetate for 1-3 times, combining organic phases, drying, and removing the solvent to obtain a crude product;

s2, dissolving the crude product in 2-butanone, adding sodium bicarbonate with the mass 2-4 times that of the crude product and tetrabutylammonium bisulfate with the mass 0.2-0.5 time that of the crude product, slowly adding an epoxidation reagent to carry out epoxidation reaction, after the epoxidation reaction is finished, adding water with the volume 2-3 times that of the 2-butanone to carry out quenching reaction, extracting by using diethyl ether, combining organic phases, drying and concentrating to obtain uncured resin;

and S3, dissolving the uncured resin in a solvent, adding a cross-linking agent for curing, and obtaining the modified epoxy resin after curing.

10. A modified epoxy resin obtained by the production method according to any one of claims 1 to 9.

Technical Field

The invention relates to a modified epoxy resin and a preparation method thereof, belonging to the field of macromolecules.

Background

The epoxy resin is a generic name of a polymer having two or more epoxy groups in a molecule. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The bisphenol A epoxy resin has the largest yield and the most complete variety, and the new modified variety is continuously increased and the quality is continuously improved. Among thermosetting polymers, epoxy resin networks have excellent mechanical, thermal and chemical stability and corrosion resistance, are the most common polymers and have wide application in the fields of coatings, adhesives, electronics, composites and the like.

The modification method of epoxy resin includes the following steps of 1, selecting a curing agent; 2. adding a reactive diluent; 3. Adding a filler; 4. adding special thermosetting or thermoplastic resin; 5. the epoxy resin itself is modified.

At present, the most widely used monomer for preparing epoxy resin is bisphenol A dimethyl ether, but bisphenol A can also cause endocrine dyscrasia and threaten the health of fetuses and children. Cancer and obesity caused by metabolic disorders are also considered to be associated therewith. In addition, epichlorohydrin used for preparing bisphenol A dimethyl ether monomer has carcinogenic effect. Accordingly, there is an urgent need in the market for non-toxic epoxy resins.

Disclosure of Invention

Due to the defects in the prior art, the invention provides a modified epoxy resin and a preparation method thereof. The raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value.

Specifically, the invention is realized by the following technical scheme:

a preparation method of modified epoxy resin comprises the following steps:

s1, electrolyzing by taking tall oil fatty acid as a monomer in the presence of strong alkali,

s2, epoxidizing by using an epoxidizing agent to obtain tall oil epoxy fatty acid,

s3, adding a cross-linking agent into the tall oil epoxy fatty acid to react to obtain the modified epoxy resin.

Preferably, the strong base is selected from any one or more of sodium methoxide, sodium ethoxide, sodium hydride and potassium tert-butoxide.

Preferably, the parameters of the electrolysis are as follows: performing constant current electrolysis at 40-60 deg.C with graphite electrode and current density of 15-30mA/cm²The current is 5-10A, the voltage is 4-6V, and the electrolysis time is 10-20 s.

Preferably, the epoxidation reagent is potassium hydrogen peroxymonosulfate, triphenylmethyl hydroperoxide, t-butyl peroxy alcohol or t-butyl peroxy alcohol-tetraalkyl titanate complexing reagent.

Preferably, the trialkyl titanate is tetraisopropyl titanate or tetra-tert-butyl titanate.

Preferably, the cross-linking agent is selected from any one or more of amine cross-linking agent, polylysine, polyamide cross-linking agent or fibroin.

Preferably, the amine cross-linking agent is selected from any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, m-aminobenzylamine, and biphenyldiamine.

Preferably, the polyamide crosslinking agent is polyether fatty acid amide;

the preparation method of the polyether fatty acid amide comprises the following steps:

s1, dissolving 200 parts by weight of epoxy fatty acid ester in 200 parts by weight of 1, 4-dioxane in 300 parts by weight of 200 parts by weight of 1, 4-dioxane, adding 0.5-3 parts by weight of boron trifluoride diethyl etherate solution under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring for 1-3 hours at 30-50 ℃ after the boron trifluoride diethyl etherate solution is added, adding 2-3 parts by weight of 30-80 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;

s2, adding 150 parts by weight of poly fatty acid methyl ester into a reaction vessel, dropwise adding 50-80 parts of diamine compound into the system within 15-30 minutes, and heating to 180-200 ℃ for refluxing for 1-3 hours after dropwise addition is finished.

Preferably, the cross-linking agent is a mixture of a polyamide cross-linking agent and polylysine in a mass ratio of (3-10): 1.

Preferably, the epoxidized fatty acid ester is trans-9, 10-epoxyoctadecanoic acid methyl ester.

Preferably, the preparation method of the modified epoxy resin comprises the following steps:

s1, dissolving tall oil fatty acid in methanol, adding strong base with the molar weight of 0.8-1.2 times of that of the tall oil fatty acid for constant current electrolysis, removing the solvent, adding water, adjusting the pH value to 2-3 with hydrochloric acid aqueous solution, washing with ethyl acetate for 1-3 times, combining organic phases, drying, and removing the solvent to obtain a crude product;

s2, dissolving the crude product in 2-butanone, adding sodium bicarbonate with the mass 2-4 times that of the crude product and tetrabutylammonium bisulfate with the mass 0.2-0.5 time that of the crude product, slowly adding an epoxidation reagent to carry out epoxidation reaction, after the epoxidation reaction is finished, adding water with the volume 2-3 times that of the 2-butanone to carry out quenching reaction, extracting by using diethyl ether, combining organic phases, drying and concentrating to obtain uncured resin;

and S3, dissolving the uncured resin in a solvent, adding a cross-linking agent for curing, and obtaining the modified epoxy resin after curing.

A modified epoxy resin is obtained by any one of the above-mentioned preparation methods.

The invention has the advantages that: the raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value. The modified epoxy resin provided by the invention has good heat resistance, thermal stability and deformation resistance. In the preparation process of the modified epoxy resin, an environment-friendly solvent is adopted, and the use of heavy metals and solvents harmful to the environment can be avoided or reduced by adopting an electrolysis mode. The whole preparation process is convenient to operate, the productivity is greatly increased on the basis of low energy consumption, and the modified epoxy resin is good in non-toxicity.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, which are provided for illustration only and are not to be construed as further limiting the invention.

The sources of the raw materials in the following examples are as follows:

tall oil fatty acid, available from Seiki-free Seiki Biotech Ltd, with an average molar mass of 280g/mol,

oligomeric Lysine, referred to Fagerland J, Finne-Wistrand A, Numata K.short One-PotChemo-enzymic Synthesis of \ r, l \ r, -Lysine and \ r, l \ r, -Alanine Diblock Co-Oligopeptides [ J ] Biomacromolecules 2014,15(3):735 + 743.