CN115894862A - Low-viscosity TOFA modified epoxy resin and preparation method thereof - Google Patents

Low-viscosity TOFA modified epoxy resin and preparation method thereof Download PDF

Info

Publication number
CN115894862A
CN115894862A CN202211620921.9A CN202211620921A CN115894862A CN 115894862 A CN115894862 A CN 115894862A CN 202211620921 A CN202211620921 A CN 202211620921A CN 115894862 A CN115894862 A CN 115894862A
Authority
CN
China
Prior art keywords
epoxy resin
tofa
viscosity
liquid epoxy
fatty acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211620921.9A
Other languages
Chinese (zh)
Inventor
奚羽
杨颖�
俞孝伟
苏红丹
陈铭铸
金顺中
孙祥
徐晓虎
鉏瑞杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Yangnong Kumho Chemical Co ltd
Jiangsu Yangnong Chemical Group Co Ltd
Original Assignee
Jiangsu Yangnong Kumho Chemical Co ltd
Jiangsu Yangnong Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Yangnong Kumho Chemical Co ltd, Jiangsu Yangnong Chemical Group Co Ltd filed Critical Jiangsu Yangnong Kumho Chemical Co ltd
Priority to CN202211620921.9A priority Critical patent/CN115894862A/en
Publication of CN115894862A publication Critical patent/CN115894862A/en
Pending legal-status Critical Current

Links

Landscapes

  • Epoxy Resins (AREA)

Abstract

The invention provides a low-viscosity TOFA modified epoxy resin and a preparation method thereof, belonging to the technical field of epoxy resins. Tall Oil Fatty Acid (TOFA) is adopted to modify liquid epoxy resin, a flexible chain segment (long carbon chain structure can improve the toughness and impact strength of the material) contained in the tall oil fatty acid is introduced into a molecular chain of low-molecular liquid epoxy resin, the toughness of the epoxy resin is improved, the viscosity of the epoxy resin and the cross-linking density of the cured resin are reduced, the resin fluidity and the coating toughness are improved, and the adhesive force of the coating to a metal substrate is improved; the TOFA modified epoxy resin prepared by the invention has no reduced reactivity, can be cured at normal temperature, can be added with various fillers at the later stage, meets the construction requirements of most coatings, and effectively solves the problem that the subsequent processing of downstream industries is difficult due to high viscosity and poor fluidity of liquid epoxy resin.

Description

Low-viscosity TOFA modified epoxy resin and preparation method thereof
Technical Field
The invention relates to the technical field of epoxy resin, in particular to low-viscosity TOFA modified epoxy resin and a preparation method thereof.
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, a plurality of compounds containing active hydrogen can be used for ring opening, curing and crosslinking to generate a network structure, so the epoxy resin is a thermosetting resin. The bisphenol A epoxy resin has the largest yield and the most complete variety, and the new modified varieties are continuously increased and the quality is continuously improved.
Among thermosetting polymers, epoxy resin networks have excellent mechanical, thermal and chemical stability, and at the same time have corrosion resistance, and they are the most common type of polymers and have wide applications in the fields of coatings, adhesives, electronics, and composite materials. However, the common epoxy resin has high viscosity and poor fluidity, and the downstream manufacturers are difficult to prepare the finish paint by using the filler. Therefore, a green and environmentally friendly epoxy resin with low viscosity is needed.
Disclosure of Invention
The invention aims to provide a low-viscosity TOFA modified epoxy resin and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of low-viscosity TOFA modified epoxy resin, which comprises the following steps:
and mixing the liquid epoxy resin, tall oil fatty acid, bisphenol A and a catalyst, and modifying to obtain the low-viscosity TOFA modified epoxy resin.
Preferably, the liquid epoxy resin, tall oil fatty acid, bisphenol a, and catalyst mixture comprises: mixing tall oil fatty acid and liquid epoxy resin, heating to 90-120 ℃, adding bisphenol A, preserving heat for 15-30 min, and adding a catalyst.
Preferably, the catalyst comprises triphenylphosphine or a triphenylphosphine derivative.
Preferably, the triphenylphosphine derivative comprises butyltriphenylphosphine bromide, ethyltriphenylphosphine chloride, ethyltriphenylphosphine bromide, or ethyltriphenylphosphine iodide.
Preferably, the mass of the catalyst is 0.1 to 0.3% of the mass of the bisphenol A.
Preferably, the liquid epoxy resin comprises liquid epoxy resin E51 or liquid epoxy resin E54; the epoxy equivalent of the liquid epoxy resin is 180-190 g/eq.
Preferably, the mass ratio of the tall oil fatty acid to the liquid epoxy resin is (5-10) to (90-100).
Preferably, the mass of the bisphenol A is 5-10% of the total mass of the tall oil fatty acid and the liquid epoxy resin.
Preferably, the modification temperature is 140-160 ℃, and the time for heating to the modification temperature is 1-2 h.
The invention provides the low-viscosity TOFA modified epoxy resin prepared by the preparation method of the technical scheme, and the viscosity of the low-viscosity TOFA modified epoxy resin is 496-856 cp.s.
The invention provides a preparation method of low-viscosity TOFA modified epoxy resin, which comprises the following steps: mixing liquid epoxy resin, tall oil fatty acid, bisphenol A and a catalyst, and modifying to obtain the low-viscosity TOFA modified epoxy resin. According to the invention, tall Oil Fatty Acid (TOFA) is adopted to modify liquid epoxy resin, a flexible chain segment (long carbon chain structure can improve the toughness and impact strength of the material) contained in the tall oil fatty acid is introduced into a liquid epoxy resin molecular chain, the density of methyl and benzene rings in resin molecules can be reduced by the flexible chain segment, the influence of steric hindrance of the methyl and the benzene rings is reduced, and the motion capability of the resin chain segment is increased, so that the toughness of the epoxy resin is improved, the viscosity of the epoxy resin and the crosslinking density of the cured resin are reduced, and the resin fluidity is improved. Moreover, the epoxy group of the TOFA modified epoxy resin prepared by the invention is not damaged, and the change of epoxy equivalent is small, so that the reactivity is not reduced, the TOFA modified epoxy resin can be cured at normal temperature, and a plurality of fillers can be added in the later period.
The method is simple, easy to operate and convenient for industrial implementation.
Detailed Description
The invention provides a preparation method of low-viscosity TOFA modified epoxy resin, which comprises the following steps:
mixing liquid epoxy resin, tall oil fatty acid, bisphenol A and a catalyst, and modifying to obtain the low-viscosity TOFA modified epoxy resin.
In the present invention, unless otherwise specified, all the required starting materials for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the liquid epoxy resin preferably includes a liquid epoxy resin E51 or a liquid epoxy resin E54; the epoxy equivalent of the liquid epoxy resin is preferably 180 to 190g/eq, more preferably 182.3 to 188.3g/eq, and still more preferably 184.2 to 186.6g/eq.
In the invention, in the tall oil fatty acid (TOFA, a mixture of oleic acid, linoleic acid and isomers thereof), the content of abietic acid is less than or equal to 2wt%, the acid value is more than or equal to 192mgKOH/g, and the content of fatty acid is more than or equal to 96wt%; the mass ratio of the Tall Oil Fatty Acid (TOFA) to the liquid epoxy resin is preferably (5-10) to (90-100), more preferably (5-9) to (91.6-95.33), and even more preferably (5-9) to (92-95). The source of the Tall Oil Fatty Acid (TOFA) is not particularly limited in the present invention and is commercially available as is well known in the art.
In the present invention, the mass of the bisphenol a is preferably 5 to 10%, more preferably 7.8 to 9.5%, and further preferably 8.0 to 8.6% of the total mass of the tall oil fatty acid and the liquid epoxy resin.
In the present invention, the catalyst preferably comprises triphenylphosphine or a triphenylphosphine derivative; the triphenylphosphine derivative preferably comprises butyltriphenylphosphine bromide, ethyltriphenylphosphine chloride, ethyltriphenylphosphine bromide or ethyltriphenylphosphine iodide.
In the present invention, the mass of the catalyst is preferably 0.1 to 0.3%, more preferably 0.13 to 0.2% of the mass of the bisphenol a.
In the present invention, the liquid epoxy resin, tall oil fatty acid, bisphenol a, and catalyst mixture preferably comprises: mixing tall oil fatty acid and liquid epoxy resin, stirring and heating to 90-120 ℃ (preferably 93-118 ℃, and more preferably 102-115 ℃), adding bisphenol A, keeping the temperature for 15-30 min (preferably 17-25 min, and more preferably 18-22 min), and adding a catalyst. The stirring temperature rise is not particularly limited in the present invention, and the temperature rise to the desired temperature may be carried out according to a stirring process well known in the art.
The method comprises the steps of mixing liquid epoxy resin with tall oil fatty acid, heating to 90-120 ℃ (preferably 93-118 ℃, and further preferably 102-115 ℃), and softening the epoxy resin by heating, so that the subsequent ring opening reaction is easy.
In the invention, the epoxy resin starts to generate ring-opening reaction after the bisphenol A is added, and the catalyst improves the reaction activity at high temperature after the catalyst is added, so that the ring-opening reaction process is accelerated, and the tall oil fatty acid is grafted on the liquid epoxy resin.
In the invention, the temperature of the modification is preferably 140-160 ℃, more preferably 145-152 ℃, and further preferably 146-147 ℃; the time for raising the temperature to the modification temperature is preferably 1 to 2 hours, more preferably 75 to 115min, and further preferably 80 to 100min; the invention preferably consists in raising the temperature from 90 to 120 ℃ to the temperature for the modification.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, tall Oil Fatty Acid (TOFA) was purchased from ingenity, having a rosin acid content of 2wt% or less, an acid value of 192mgKOH/g or more, and a fatty acid content of 96wt% or more;
the viscosity is tested according to the method described in GB/T22314-2008, and the epoxy equivalent is tested according to the method described in GB/T4612-2008.
Example 1
30g of tall oil fatty acid and 550g of liquid epoxy resin E51 (epoxy equivalent is 186.6g/eq, viscosity is 12000cp.s.) are added into a 1000mL four-mouth bottle, mixed and heated, when the temperature is raised to 90 ℃ by stirring, 29.3g of bisphenol A is added, after the temperature is maintained for 15min, 0.09g of triphenylphosphine is added, the temperature is raised to 140 ℃ within 60min, and the TOFA modified epoxy resin is obtained, wherein the test viscosity is 536cp.s, and the epoxy equivalent is 184.2g/eq.
Example 2
Adding 25g of tall oil fatty acid and 475g of liquid epoxy resin E54 (epoxy equivalent is 188.3g/eq, viscosity is 11200cp.s) into a 1000mL four-mouth bottle, mixing and heating, stirring and heating to 102 ℃, adding 43g of bisphenol A, keeping the temperature for 25min, adding 0.13g of brominated butyl triphenylphosphine, heating to 145 ℃ within 80min to obtain the TOFA modified epoxy resin, wherein the test viscosity is 683cp.s, and the epoxy equivalent is 190.5g/eq.
Example 3
15g of tall oil fatty acid and 286g of liquid epoxy resin E54 (epoxy equivalent is 184.2g/eq, viscosity is 12500cp.s.) are added into a 500mL four-mouth bottle to be mixed and heated, when the temperature is raised to 115 ℃ by stirring, 23.5g of bisphenol A is added, after the temperature is kept for 30min, 0.05g of ethyl triphenyl phosphine chloride is added, and the temperature is raised to 152 ℃ within 100min to obtain the TOFA modified epoxy resin, wherein the test viscosity is 742cp.s, and the epoxy equivalent is 180.7g/eq.
Example 4
Adding 18g of tall oil fatty acid and 342g of liquid epoxy resin E51 (epoxy equivalent is 182.3g/eq, viscosity is 10500cp.s) into a 500mL four-mouth bottle, mixing and heating, stirring and heating to 118 ℃, adding 14.6g of bisphenol A, keeping the temperature for 22min, adding 0.03g of ethyl triphenyl phosphonium bromide, heating to 160 ℃ within 115min to obtain the TOFA modified epoxy resin, wherein the test viscosity is 496cp.s, and the epoxy equivalent is 177.8g/eq.
Example 5
Adding 40g of tall oil fatty acid and 380g of liquid epoxy resin E54 (epoxy equivalent is 187.2g/eq, viscosity is 13000cp.s) into a 1000mL four-mouth bottle, mixing and heating, stirring and heating to 93 ℃, adding 40g of bisphenol A, keeping the temperature for 17min, adding 0.05g of ethyl triphenyl phosphine iodide, heating to 147 ℃ within 75min to obtain the TOFA modified epoxy resin, wherein the test viscosity is 856cp.s, and the epoxy equivalent is 182.6g/eq.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of low-viscosity TOFA modified epoxy resin comprises the following steps:
mixing liquid epoxy resin, tall oil fatty acid, bisphenol A and a catalyst, and modifying to obtain the low-viscosity TOFA modified epoxy resin.
2. The method of claim 1, wherein the mixing of the liquid epoxy resin, tall oil fatty acid, bisphenol a, and catalyst comprises: mixing tall oil fatty acid and liquid epoxy resin, heating to 90-120 ℃, adding bisphenol A, preserving heat for 15-30 min, and adding a catalyst.
3. The production method according to claim 1 or 2, characterized in that the catalyst comprises triphenylphosphine or a triphenylphosphine derivative.
4. The production method according to claim 3, wherein the triphenylphosphine derivative comprises butyltriphenylphosphine bromide, ethyltriphenylphosphine chloride, ethyltriphenylphosphine bromide, or ethyltriphenylphosphine iodide.
5. The production method according to claim 1 or 4, wherein the mass of the catalyst is 0.1 to 0.3% of the mass of the bisphenol A.
6. The production method according to claim 1, wherein the liquid epoxy resin includes a liquid epoxy resin E51 or a liquid epoxy resin E54; the epoxy equivalent of the liquid epoxy resin is 180-190 g/eq.
7. The method according to claim 1 or 6, wherein the mass ratio of the tall oil fatty acid to the liquid epoxy resin is (5-10) to (90-100).
8. The method according to claim 1, wherein the bisphenol A is 5 to 10% by mass based on the total mass of the tall oil fatty acid and the liquid epoxy resin.
9. The method according to claim 1, wherein the temperature of the modification is 140 to 160 ℃ and the time for raising the temperature to the modification is 1 to 2 hours.
10. The low viscosity TOFA modified epoxy resin prepared by the preparation method of any one of claims 1-9, wherein the viscosity of the low viscosity TOFA modified epoxy resin is 496-856 cp.s.
CN202211620921.9A 2022-12-16 2022-12-16 Low-viscosity TOFA modified epoxy resin and preparation method thereof Pending CN115894862A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211620921.9A CN115894862A (en) 2022-12-16 2022-12-16 Low-viscosity TOFA modified epoxy resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211620921.9A CN115894862A (en) 2022-12-16 2022-12-16 Low-viscosity TOFA modified epoxy resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115894862A true CN115894862A (en) 2023-04-04

Family

ID=86487952

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211620921.9A Pending CN115894862A (en) 2022-12-16 2022-12-16 Low-viscosity TOFA modified epoxy resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115894862A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722981A (en) * 1986-02-14 1988-02-02 The Dow Chemical Company Epoxy resins of controlled conversion and a process for their preparation
US6071991A (en) * 1997-01-21 2000-06-06 Shell Oil Company Modified epoxy resin modified epoxy resin composition and a process for the preparation of the modified epoxy resin
JP2000248047A (en) * 1999-03-04 2000-09-12 Yuka Shell Epoxy Kk Modified epoxy resin and composition for coating material
CN102030886A (en) * 2009-09-30 2011-04-27 关西涂料株式会社 Epoxy resin combination and coating combination containing the same
KR20120122127A (en) * 2011-04-28 2012-11-07 코오롱인더스트리 주식회사 Fatty acid-modified epoxy resin for paint, method of producing the same and paint composition comprising the same
CN105061728A (en) * 2015-08-04 2015-11-18 江苏扬农锦湖化工有限公司 Modifying method of solid epoxy resin
CN109627427A (en) * 2018-11-19 2019-04-16 天津翔盛新材料有限公司 A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints
CN114516949A (en) * 2020-11-20 2022-05-20 南通星辰合成材料有限公司 Anti-crystallization modified epoxy resin for crack sealer and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4722981A (en) * 1986-02-14 1988-02-02 The Dow Chemical Company Epoxy resins of controlled conversion and a process for their preparation
US6071991A (en) * 1997-01-21 2000-06-06 Shell Oil Company Modified epoxy resin modified epoxy resin composition and a process for the preparation of the modified epoxy resin
JP2000248047A (en) * 1999-03-04 2000-09-12 Yuka Shell Epoxy Kk Modified epoxy resin and composition for coating material
CN102030886A (en) * 2009-09-30 2011-04-27 关西涂料株式会社 Epoxy resin combination and coating combination containing the same
KR20120122127A (en) * 2011-04-28 2012-11-07 코오롱인더스트리 주식회사 Fatty acid-modified epoxy resin for paint, method of producing the same and paint composition comprising the same
CN105061728A (en) * 2015-08-04 2015-11-18 江苏扬农锦湖化工有限公司 Modifying method of solid epoxy resin
CN109627427A (en) * 2018-11-19 2019-04-16 天津翔盛新材料有限公司 A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints
CN114516949A (en) * 2020-11-20 2022-05-20 南通星辰合成材料有限公司 Anti-crystallization modified epoxy resin for crack sealer and preparation method and application thereof

Similar Documents

Publication Publication Date Title
KR102393692B1 (en) Thermosetting resin composition
CN109651595B (en) Halogen-free flame-retardant bio-based epoxy resin precursor and preparation method and application thereof
JPH09272786A (en) Thermosetting resin composition and its cured item
CN110577799B (en) Epoxy compound modified rosin resin and preparation method and application thereof
EP2751160B1 (en) Epoxy resins with high thermal stability and toughness
CN113061416A (en) High-strength high-toughness epoxy binder and preparation method thereof
CN104892858A (en) High biomass content epoxy resin composition, and curing method and applications thereof
CN108659203A (en) A kind of Maleic anhydride fimctionalized liquid polybutadiene modified epoxy and its preparation method and application
CN105482713A (en) Highly-disproportionated rosin glycidyl methacrylate and preparation method thereof
CN112210222A (en) Epoxy asphalt material for roads and bridges and preparation method thereof
CN115651165A (en) Recyclable epoxy resin and preparation method and recycling method thereof
CN109134825B (en) Modified epoxy resin and preparation and application thereof
KR101693605B1 (en) A epoxy adhesive composition comprising poly-thiolhardner and manufacturetingmthetod of it
CN115894862A (en) Low-viscosity TOFA modified epoxy resin and preparation method thereof
JP2697883B2 (en) Method for producing high molecular weight epoxy dimer acid ester resin
CN112574706A (en) Epoxy resin adhesive for solvent-resistant permeable membrane and preparation and application methods thereof
CN112608450A (en) Tung oil-based flexible anhydride curing agent and preparation method thereof
US4529537A (en) Liquid epoxy resin hardeners and processes for their preparation
CN116041785A (en) Modified liquid nitrile rubber and preparation method and application thereof
KR900008718B1 (en) Process for manufacturing of epoxy resin compositions
US3075932A (en) Process for curing polyepoxides with polyamino polyamide compounds and resulting products
CN113512269A (en) Preparation method and use method of modified epoxy resin
CN114075366A (en) Bio-based epoxy resin composition, full bio-based flame-retardant composite material and preparation method thereof
CN110951252A (en) Novel cyanate/epoxy modified resin matrix composition
CN116023565B (en) Vegetable oil-based recyclable epoxy resin and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination