CN114957923B - Vinyl organosilicon toughened and modified epoxy resin and preparation method thereof - Google Patents
Vinyl organosilicon toughened and modified epoxy resin and preparation method thereof Download PDFInfo
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- CN114957923B CN114957923B CN202111641338.1A CN202111641338A CN114957923B CN 114957923 B CN114957923 B CN 114957923B CN 202111641338 A CN202111641338 A CN 202111641338A CN 114957923 B CN114957923 B CN 114957923B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses vinyl organosilicon toughening modified epoxy resin and a preparation method thereof. The modified epoxy resin comprises the following components in percentage by mass: 60-75% of liquid epoxy resin, 2-20% of vinyl organic silicon resin, 10-30% of curing agent I and 2-20% of curing agent II. The invention uses low-viscosity organic silicon resin through limiting the viscosity of the organic silicon resin, has very good compatibility with epoxy resin, is simple to operate, and simultaneously obviously reduces the viscosity of an epoxy resin system, so that the application of the epoxy resin is wider, and the prepared modified epoxy resin has very good toughness and strength.
Description
Technical Field
The invention relates to the technical field of resin modification, in particular to vinyl organosilicon toughening modified epoxy resin and a preparation method thereof.
Background
Epoxy resins are one of the most widely used thermosetting resins because of their excellent mechanical properties, processability, and adhesion to other substrates, and they are widely used in the fields of aerospace, machinery, construction, electronics, and the like as composite materials, paints, adhesives, and the like. The fastest growing area of epoxy resin usage is composites. It is expected that the global annual growth rate (CAGR) of epoxy composites will reach 7.3% from 2015 to 2022. The epoxy resin can be subjected to curing reaction with various curing agents and accelerators to form a crosslinked network structure. The rigid structure such as benzene ring is contained in the molecular chain, and the defect of poor impact resistance and poor fracture toughness of the cured product is caused by high crosslinking density, so that the application of the epoxy resin in the field of composite materials is greatly limited. The high-performance resin becomes the key of the development of high and new composite materials, so that the improvement of the comprehensive performance of the epoxy resin becomes the key point and hot spot of research.
Various approaches have been taken by the former to improve the toughness of epoxy resins. The toughening with rubber particles in an epoxy matrix was proposed by McGarry in 1970 and was the first method to toughen epoxy resins. Since then, various toughening methods have been discovered and studied extensively. These methods can be divided into two main categories: soft phases (e.g., rubber); hard phases (e.g., nanoparticles). The toughening method comprises toughening of rubber, thermoplastic materials, rigid fillers, block copolymers and dendritic materials, and also comprises a method of compounding and toughening by adopting two or more materials. The epoxy resin modified by the hydroxyl-terminated or carboxyl-terminated liquid rubber becomes a common means for toughening and modifying the epoxy resin. In the liquid rubber modified epoxy resin, in addition to solving the compatibility of the liquid rubber and the epoxy resin, functional groups such as hydroxyl end groups, carboxyl end groups and the like need to participate in the reaction of the epoxy groups to form a crosslinked network structure so as to form a stable cured product. However, the reaction temperature is relatively high, which limits the application of the epoxy resin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides vinyl organosilicon toughening modified epoxy resin and a preparation method thereof. According to the molecular structure of the organic silicon, the invention uses the click reaction between sulfhydryl compounds to make the functional group of the alkenyl group pass through the curing condition of the epoxy resin, the organic silicon resin is bonded with the epoxy resin by chemical bonds to form a cross-linked network, and the low-temperature co-curing of the organic silicon resin and the epoxy resin is realized under the condition of no high temperature, so that the modified epoxy resin is prepared, the preparation process is simple, and the obtained modified epoxy resin has good toughness.
The technical scheme of the invention is as follows:
the vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: 60-75% of liquid epoxy resin, 2-20% of vinyl organic silicon resin, 10-30% of curing agent I and 2-20% of curing agent II.
Further, the liquid epoxy resin is E-51 or E44 epoxy resin.
Further, the vinyl silicone resin has a vinyl content of 0.2 to 10wt% and a viscosity of 100 to 500cp.
Further, the curing agent I is an organic amine curing agent.
Further, the organic amine curing agent comprises one or more of aliphatic amine, alicyclic amine, amide and tertiary amine; the fatty amine comprises at least one of dimethylamine and ethylenediamine; the alicyclic amines include, but are not limited to, isophorone diamine.
Further, the curing agent II is a sulfhydryl compound, and the curing agent II is a sulfhydryl compound containing more than two sulfhydryl groups.
Further, the curing agent II is 2,2' - (1, 2-ethylenedioxy) diethyl mercaptan, trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate).
The preparation method of the modified epoxy resin comprises the following steps in percentage by mass:
(1) Mixing and stirring 2-20% of vinyl organic silicon resin and 60-75% of epoxy resin to obtain an epoxy resin mixture;
(2) Adding 10-30% of curing agent I, stirring, adding 2-20% of curing agent II, mixing and stirring to obtain a resin mixture;
(3) And (3) placing the resin mixture obtained in the step (2) into a temperature test box, and curing to obtain the vinyl organosilicon toughening modified epoxy resin.
Further, in the steps (1) and (2), the stirring speed is 50-500 r/min, and the stirring time is 10-60 min.
Further, in the step (3), the specific curing process is as follows: firstly, reacting for 1-3 h at 50-60 ℃, then heating to 70-80 ℃ for reacting for 1-3 h.
According to the molecular structure of the organic silicon, the vinyl functional group is subjected to click reaction between sulfhydryl compounds based on the curing condition of the epoxy resin, the organic silicon resin is bonded through chemical bonds to form a crosslinked network with the epoxy resin, and the low-temperature co-curing of the organic silicon resin and the epoxy resin is realized under the condition of no high temperature, so that the modified epoxy resin is prepared. The cross-linked structure formed by co-curing greatly improves the toughness and impact property of the resin under the condition of almost not losing the rigidity of the epoxy resin. In the invention, the viscosity of the vinyl organic silicon resin is lower, the compatibility with the epoxy resin is very good, the operation is simple, and the viscosity of the epoxy resin system can be obviously reduced, so that the application of the epoxy resin is wider.
The beneficial technical effects of the invention are as follows:
(1) The invention uses the sulfhydryl curing agent and the amine curing agent to share, the vinyl functional group is bonded with the epoxy resin through chemical bonding by click reaction between sulfhydryl compounds, and the invention realizes the low-temperature co-curing of the organosilicon resin and the epoxy resin without high temperature.
(2) The invention uses low-viscosity organic silicon resin by limiting the viscosity of the organic silicon resin, has good compatibility with epoxy resin, is simple to operate, can obviously reduce the viscosity of an epoxy resin system, and ensures that the application of the epoxy resin is wider.
(3) According to the invention, the toughness of the epoxy resin is obviously improved on the basis of not sacrificing other performances of the epoxy resin by low-temperature co-curing of the organic silicon resin and the epoxy resin.
Detailed Description
The present invention will be specifically described with reference to examples.
Example 1
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: 66.2% of liquid epoxy resin E44, 7.4% of vinyl silicone resin, 0.5% by weight of vinyl content in the vinyl silicone resin, 150cp of viscosity and 22% of curing agent I, wherein the curing agent I is isophorone diamine and the curing agent II is 4.4% of curing agent II, and the curing agent II is trimethylolpropane tri (3-mercaptopropionate).
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
20g (7.4%) of vinyl silicone resin was weighed and added to 180g (66.2%) of E44 epoxy resin and stirred at 50r/min for 60min to obtain a well mixed epoxy resin.
60g (22%) of isophorone diamine is added, stirring is carried out for 60min at 50r/min, 12g (4.4%) of trimethylolpropane tri (3-mercaptopropionate) is added, after uniform mixing, the resin system is put into a temperature test box, the temperature test box reacts for 2 hours at 60 ℃, and the temperature is raised according to a curing process curve of 2 hours at 80 ℃ to prepare the vinyl organosilicon toughening modified epoxy resin.
Example 2
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: 66.2% of liquid epoxy resin E51.2%, 7.4% of vinyl silicone resin, 0.5% by weight of vinyl content in the vinyl silicone resin, 150cp of viscosity and 22% of curing agent I, wherein the curing agent I is isophorone diamine and the curing agent II is 4.4%, and the curing agent II is trimethylolpropane tri (3-mercaptopropionate).
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
20g (7.4%) of vinyl silicone resin (viscosity 150 cp) was weighed and added to 180g (66.2%) of E51 epoxy resin, and stirred at 500r/min for 10min to obtain a uniformly mixed epoxy resin.
60g (22%) of isophorone diamine is added, stirring is carried out for 10min at 500r/min, then 12g (4.4%) of trimethylolpropane tri (3-mercaptopropionate) is added, after uniform mixing, the resin system is put into a temperature test box, the temperature test box reacts for 3 hours at 50 ℃, and the temperature is raised according to a curing process curve of reacting for 3 hours at 70 ℃, so that the vinyl organosilicon toughening modified epoxy resin is prepared.
Example 3
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: 66.2% of liquid epoxy resin E44, 7.4% of vinyl organic silicon resin, 0.9% by weight of vinyl content in the vinyl organic silicon resin, 500cp of viscosity and 22% of curing agent I, wherein the curing agent I is isophorone diamine and the curing agent II is 4.4% of tetra (3-mercaptopropionic acid) pentaerythritol ester.
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
20g (7.4%) of vinyl silicone resin (viscosity 150 cp) was weighed and added to 180g (66.2%) of epoxy resin, and stirred at 500r/min for 10min to obtain a uniformly mixed epoxy resin.
60g (22%) of isophorone diamine is added, stirring is carried out for 10min at 500r/min, then 12g (4.4%) of pentaerythritol tetra (3-mercaptopropionic acid) ester is added, after uniform mixing, the mixture is put into a temperature test box, the temperature test box reacts for 1 hour at 55 ℃, the temperature of the mixture is raised according to a curing process curve of reaction for 1 hour at 750 ℃, and the vinyl organosilicon toughening modified epoxy resin is prepared.
Example 4
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: the epoxy resin comprises liquid epoxy resin E44 75%, vinyl silicone resin 2%, vinyl content in the vinyl silicone resin is 0.9wt%, viscosity is 500cp, and curing agent I is 10%, wherein the curing agent I is isophorone diamine and curing agent II is 13%, and the curing agent II is pentaerythritol tetra (3-mercaptopropionic acid).
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
6g (2%) of vinyl silicone resin (viscosity 150 cp) was weighed and added to 225g (75%) of epoxy resin, and stirred at 500r/min for 10min to obtain a uniformly mixed epoxy resin.
Adding 30g (10%) of isophorone diamine, stirring at 500r/min for 10min, adding 39g (13%) of pentaerythritol tetra (3-mercaptopropionate), mixing uniformly, placing into a temperature test box, reacting at 55 ℃ for 2 hours, and heating at 75 ℃ for 2 hours according to a curing process curve to obtain the vinyl organosilicon toughening modified epoxy resin.
Example 5
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: the epoxy resin comprises liquid epoxy resin E44 60%, vinyl silicone resin 10%, vinyl content in the vinyl silicone resin is 1.3wt%, viscosity is 500cp, and curing agent I is 10%, wherein the curing agent I is isophorone diamine and curing agent II is 20%, and the curing agent II is trimethylolpropane tri (3-mercaptopropyl ester).
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
30g (10%) of vinyl silicone resin (viscosity 150 cp) was weighed and added to 180g (60%) of epoxy resin, and stirred at 500r/min for 10min to obtain a uniformly mixed epoxy resin.
Adding 30g (10%) of isophorone diamine, stirring for 60min at 50r/min, adding 60g (20%) of trimethylolpropane tri (3-mercaptopropionate), mixing uniformly, placing into a temperature test box, reacting for 3 hours at 50 ℃ and heating according to a curing process curve of reacting for 3 hours at 70 ℃ to obtain the vinyl organosilicon toughening modified epoxy resin.
Example 6
The vinyl organosilicon toughening modified epoxy resin comprises the following components in percentage by mass: the epoxy resin comprises liquid epoxy resin E44 60%, vinyl silicone resin 20%, vinyl content in the vinyl silicone resin is 1.3wt%, viscosity is 500cp, and curing agent I is 18%, wherein the curing agent I is isophorone diamine and curing agent II is 2%, and the curing agent II is trimethylolpropane tri (3-mercaptopropyl).
The preparation method of the vinyl organosilicon toughening modified epoxy resin comprises the following steps:
60g (10%) of vinyl silicone resin (viscosity 150 cp) was weighed and added to 180g (60%) of epoxy resin, and stirred at 500r/min for 10min to obtain a uniformly mixed epoxy resin.
Adding 30g (10%) of isophorone diamine, stirring at 200r/min for 30min, adding 3g (2%) of trimethylolpropane tri (3-mercaptopropionate), mixing uniformly, placing into a temperature test box, reacting at 55 ℃ for 1 hour, and heating at 80 ℃ for 1 hour according to a curing process curve to obtain the vinyl organosilicon toughening modified epoxy resin.
Comparative example:
the same as in example 1, except that no curing agent II was added.
Test example:
the modified epoxy resins prepared in examples 1-3 were tested on a 30 x 30 plate, and the resins were excellent in leveling property, free of shrinkage cavities, excellent in adhesion, and the results of the mechanical properties of the resins were shown in table 1.
TABLE 1
As can be seen from table 1: the embodiment of the invention has better tensile strength, the maximum elongation can reach 18.2 percent, and the bending strength and the yield strength are better. Therefore, the invention realizes the co-curing of the vinyl organic silicon resin and the epoxy resin by sharing the sulfhydryl curing agent and the amine curing agent, and the curing temperature of the obtained modified resin is lower when the modified resin is used for preparing the composite material.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the principles of the invention, and these modifications and variations should also be considered as being within the scope of the invention.
Claims (7)
1. The vinyl organosilicon toughened modified epoxy resin is characterized by comprising the following components in percentage by mass: 60-75% of liquid epoxy resin, 2-20% of vinyl silicone resin, 10-30% of curing agent I and 2-20% of curing agent II;
the vinyl content of the vinyl organic silicon resin is 0.2-5wt% and the viscosity is 100-500 cp;
the curing agent I is an organic amine curing agent;
the curing agent II is a sulfhydryl compound, and the sulfhydryl compound is a sulfhydryl compound containing more than two sulfhydryl groups; the curing agent II is 2,2' - (1, 2-ethylenedioxy) diethyl mercaptan, trimethylolpropane tri (3-mercaptopropionate) or tetra (3-mercaptopropionic acid) pentaerythritol ester.
2. The modified epoxy resin of claim 1, wherein the liquid epoxy resin is an E-51 or E44 epoxy resin.
3. The modified epoxy resin of claim 1, wherein the organic amine curing agent is one or more of aliphatic amine, alicyclic amine, amide, tertiary amine; the fatty amine comprises at least one of dimethylamine and ethylenediamine; the alicyclic amine includes isophorone diamine.
4. The modified epoxy resin of claim 1, wherein the curing agent II is 2,2' - (1, 2-ethanediyl dioxo) diethyl mercaptan, trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate).
5. A method for preparing the modified epoxy resin as claimed in any one of claims 1 to 4, comprising the following steps in mass percent:
(1) Mixing and stirring 2-20% of vinyl organic silicon resin and 60-75% of epoxy resin to obtain an epoxy resin mixture;
(2) Adding 10-30% of a curing agent I, stirring, adding 2-20% of a curing agent II, mixing and stirring to obtain a resin mixture;
(3) And (3) placing the resin mixture obtained in the step (2) into a temperature test box, and curing to obtain the vinyl organosilicon toughening modified epoxy resin.
6. The method according to claim 5, wherein in the steps (1) and (2), the stirring speed is 50-500 r/min, and the stirring time is 10-60 min.
7. The method according to claim 5, wherein in the step (3), the specific process of curing is: firstly, reacting for 1-3 hours at 50-60 ℃, and then heating to 70-80 ℃ for reacting for 1-3 hours.
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