CN112574418B - Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof - Google Patents
Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN112574418B CN112574418B CN202011428764.2A CN202011428764A CN112574418B CN 112574418 B CN112574418 B CN 112574418B CN 202011428764 A CN202011428764 A CN 202011428764A CN 112574418 B CN112574418 B CN 112574418B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- solution
- epoxy
- organic silicon
- preparation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to an organic silicon compound containing an epoxy group, a preparation method thereof, an epoxy resin composition and a preparation method thereof. The organic silicon compound contains-Si-O-C-bonds in molecules and has the characteristics of large bond angle, long bond length, low surface tension and the like. By utilizing the reactivity of an epoxy group in the organic silicon compound, an organic silicon molecule long chain is introduced into an epoxy resin crosslinking network and has synergistic effect with polyether amine and the like, the curing rate can be accelerated, the toughness of an epoxy resin cured product is greatly improved, the mechanical property is improved, meanwhile, the light/heat aging resistance of the cured product is also greatly improved, and the organic silicon compound can be widely applied to the fields of adhesives, wind power blades and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an organic silicon compound containing an epoxy group and a preparation method thereof, and a polyether amine and organic silicon synergistic toughening rapid curing epoxy resin composition prepared from the organic silicon compound and a preparation method thereof.
Background
The epoxy resin has the advantages of high storage stability, good processing technology performance, flexible and various formula design, low volume shrinkage rate in the curing process and the like, and the cured product of the epoxy resin has excellent mechanical performance, dimensional stability, chemical resistance, electrical performance, bonding performance and the like, and is widely applied to various fields of production and life, such as adhesives, composite materials, mechanical manufacturing, electronic and electrical products, aerospace, transportation, construction, military industry and the like. However, the toughness of the cured epoxy resin is generally low, so that the practical application of the cured epoxy resin is limited. For example, patent CN106281166A discloses an epoxy resin adhesive which has excellent adhesive performance, but the cured epoxy resin adhesive layer has high brittleness and risks of cracking and breaking. Therefore, toughening of epoxy resins has become a hot spot of industrial research.
Patent CN108250684A adopts a method of chemically modifying a curing agent to prepare a flexible curing agent, patent CN102604117A adopts a method of chemically modifying epoxy resin, patent CN101525519A adopts a curing agent with good toughness directly to improve the toughness of an epoxy cured material, and although the toughness of the cured material is improved, the curing agents of the types used in the three patents have the defects of high curing temperature and low curing speed. Patent CN110819283A also adopts a high-toughness curing agent to toughen epoxy cured materials, but the solution of toughening only with a high-toughness curing agent is too single, and the effect of improving toughness is very limited.
Xudi et al, in "dynamics of curing of mixed polyetheramine/epoxy resin for vacuum infusion", compared the curing speed difference between a mixed curing agent/epoxy resin system and a single curing agent system by using infrared spectroscopy, found that the curing speed of the epoxy resin system using a polyetheramine D-230 curing agent is extremely slow, and the curing degree in 4 hours is only 53%.
Therefore, the development of an epoxy resin curing system with high curing speed and good toughness has become a hot spot of industrial research
Disclosure of Invention
The invention aims to provide an organosilicon compound containing epoxy groups and a preparation method thereof, aiming at the problems of the prior epoxy resin composition, wherein the organosilicon compound contains-Si-O-C-bonds in molecules and has the characteristics of large bond angle, long bond length, low surface tension and the like.
The invention also provides a polyether amine and organic silicon synergistic toughening fast curing epoxy resin composition and a preparation method thereof. By utilizing the reactivity of epoxy groups in the organic silicon compound, an organic silicon molecular long chain is introduced into an epoxy resin crosslinking network and has synergistic effect with polyether amine and the like, so that the curing rate can be accelerated, the toughness of an epoxy resin cured product is greatly improved, the mechanical property is improved, the light/heat aging resistance of the cured product is greatly improved, and the organic silicon molecular long chain organic silicon epoxy resin cured product can be widely applied to the fields of adhesives, wind power blades and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the structure of the organic silicon compound containing the epoxy group is shown as the formula I
Wherein R is selected from chain links containing one or more of-Si-O-C-, -Si-O-Si-, -C-O-C-, ester groups and the like, and is preferably
m＝3～6，n＝5～10；
Preferably, the structure of the organosilicon compound containing epoxy group is shown as formula II or formula III:
wherein m is 3 to 6 and n is 5 to 10.
In the present invention, there is also provided a method for preparing an epoxy group-containing organosilicon compound having a structure represented by formula I, as exemplified by an epoxy group-containing organosilicon compound having a structure represented by formula ii or formula iii, comprising the steps of:
s1, dissolving the reactant 1, the chloroplatinic acid catalyst and the hydroquinone in toluene in an inert gas atmosphere, and heating and stirring to obtain a mixed solution;
in step S1, reactant 1 is 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane or glycidyl methacrylate;
s2, adding polymethylhydrosiloxane into the mixed liquid in the step S1, and heating for reaction to obtain the organic silicon compound containing the epoxy group and having the structure shown in the formula I.
In the preparation method, in step S1, the inert gas is one or two of nitrogen and argon.
In the preparation method of the invention, in step S1, when reactant 1 is 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane, the structure of the prepared organic silicon compound containing epoxy groups is shown as II; when the reactant 1 is glycidyl methacrylate, the structure of the prepared organic silicon compound containing the epoxy group is shown as III;
wherein, the structure of the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane is shown as formula IV:
the preparation method of the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane comprises the following steps:
1) dissolving m-chloroperoxybenzoic acid in dichloromethane to prepare a solution A with the mol/L of 0.6-0.8;
2) dissolving tetramethyl divinyl disiloxane in dichloromethane to prepare a solution B of 0.3-0.5 mol/L;
3) and adding the solution A into the solution B under an ice bath condition at 0-4 ℃, wherein the adding time is 0.5-1.5 h, preferably adopting a dropwise adding mode, heating to 45-55 ℃ after the adding is finished, and carrying out reflux reaction for 46-48 h to obtain the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane.
Preferably, in the step 3), the molar ratio of the solution a to the solution B, calculated on the m-chloroperoxybenzoic acid and the tetramethyldivinyldisiloxane in the solution a to the solution B, is 2-3: 1, preferably 2.4-2.6: 1;
preferably, in the step 3), the reflux reaction is monitored by thin layer chromatography, and the eluent is a mixed solvent of n-hexane and ethyl acetate, preferably the mixing mass ratio is 5: 3;
preferably, in the step 3), after the reflux reaction is completed, conventional post-treatment processes such as acid washing, alkali washing, separation, drying, filtration, concentration and the like are further included, in some examples, 2-3 times of acid washing and 2-3 times of alkali washing are respectively performed, then separation, drying and filtration are performed, and finally the solvent is removed by reduced pressure distillation, wherein 5wt% of 2, 3-dihydroxysuccinic acid aqueous solution is preferably used for acid washing, and 5wt% of NaHCO is preferably used for alkali washing 3 Separating the oil phase and the water phase, drying, separating the oil phase and the water phase by using a separating funnel, and selecting MgSO 4 The alkali-washed organic layer was dried.
In the preparation method, in step S1, the chloroplatinic acid catalyst is an isopropanol solution of chloroplatinic acid, and the concentration of the solution is 0.008 to 0.018wt%, preferably 0.011 to 0.015 wt%;
furthermore, the dosage of the chloroplatinic acid catalyst is 0.008-0.018 wt% of the mass of the reactant 1, and preferably 0.011-0.015 wt%, calculated by isopropyl alcohol solution of the chloroplatinic acid. The amount of the catalyst used in the step S1 is strictly controlled within the above range, and if the amount of the catalyst is more than 0.018wt%, the reaction is severe and the heat generation is severe, and Pt 4+ Can be reduced into platinum black and loses catalytic activity; if the amount of the catalyst is less than 0.008 wt%, the catalytic action is not significant, and the degree of reaction is not high.
In step S1, the hydroquinone has a polymerization inhibiting effect, and the amount of the hydroquinone is 0.05 to 0.10wt%, preferably 0.07 to 0.08wt%, of the mass of the reactant 1.
The preparation method comprises the step S1 of heating and stirring, wherein the heating temperature in the operation process is 80-100 ℃, and preferably 85-95 ℃; the stirring time is 20-40 min, preferably 28-32 min; in the step S1, the pre-complexing process of the double bond in the reactant 1 and the chloroplatinic acid catalyst occurs by heating and stirring, and in the process, the moderate temperature rise is favorable for the complexing reaction of the double bond and the catalyst, but the polymerization reaction of the double bond is initiated when the temperature is higher than 100 ℃.
In the preparation method, in step S2, the mass fraction of active hydrogen in the polymethylhydrosiloxane is 0.5-1.5%, preferably 0.9-1.1%, such as 1.06%;
further, the molar ratio of Si-H in the polymethylhydrosiloxane to C ═ C in the reactant 1 added in step S1 is 1:0.8 to 1.4, preferably 1:1.0 to 1.2. When the ratio is more than 1:0.8, the dosage of the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane is low, the C is less, and the reaction degree is low; when the ratio is less than 1:1.4, C ═ C is too excessive, resulting in an increased burden on the post-treatment. When the molar ratio of Si — H to C ═ C is in the preferred range of 1:1.0 to 1.2, the degree of reaction between Si — H and C ═ C is high, the excess of reactant 1 is small, and it can be removed by distillation under reduced pressure.
Further, the polymethylhydrosiloxane is added into the mixed solution in the step S1, a continuous feeding mode can be adopted, a dripping mode is preferred, the dripping time is preferably controlled to be 0.8-1.2 h, if the dripping speed is too fast, the reaction speed is accelerated, the heat release is increased sharply, and the implosion of double bonds in the system is easily caused.
In the preparation method, in the step S2, the reaction is carried out at the temperature of 80-100 ℃, preferably 88-92 ℃; the reaction time is 3-7 h, preferably 4.5-5.5 h.
In step S2, the preparation method of the present invention further includes a post-treatment process of the obtained crude product after the reaction is finished, wherein the post-treatment process is preferably a vacuum distillation solvent removal process, which is a conventional treatment process in the art and is not specifically required in the present invention.
On the other hand, the invention provides a polyether amine and organic silicon synergistic toughening fast curing epoxy resin composition, which comprises a component A and a component B,
the component A comprises the following raw materials:
100 parts of epoxy resin;
10-20 parts of organic silicon, preferably 12-18 parts;
the component B comprises the following raw materials:
20-40 parts of polyether amine, preferably 27-33 parts;
5-10 parts of an accelerator, preferably 6-8 parts;
the parts are parts by mass;
the organosilicon is selected from the epoxy group-containing organosilicon compounds with the structure shown in the formula I, preferably one or two of the epoxy group-containing organosilicon compounds shown in the formula II or III, and more preferably the epoxy group-containing organosilicon compounds shown in the formula II.
Further, the epoxy resin composition of the present invention, wherein the molar ratio of active hydrogen in the polyetheramine to epoxy groups in the epoxy resin is 1: 0.7 to 1.3, preferably 1: 0.8-1.2 such as 1:1.
In the epoxy resin composition of the present invention, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, hydroxymethyl bisphenol a type epoxy resin, o-cresol formaldehyde type epoxy resin and resorcinol type epoxy resin, preferably bisphenol a type epoxy resin and/or bisphenol F type epoxy resin;
preferably, the epoxy resin is liquid at room temperature, and the viscosity of the epoxy resin is 7000-18000 mPa & s (25 ℃), preferably 7000-10000 mPa & s (25 ℃).
In the epoxy resin composition of the present invention, the polyether amine is selected from aliphatic polyether amines, preferably aliphatic amine-terminated polyether amines. The polyether amine can play a role of a curing agent, and compared with an aromatic or alicyclic amine curing agent, the aliphatic amino-terminated polyether long chain has flexibility and can effectively improve the toughness of an epoxy resin cured product;
preferably, the molecular weight of the polyether amine is 200-500, and the functionality is 2-6; when the molecular weight is too high, the viscosity of the polyether amine is increased, and the use is inconvenient;
more preferably, the polyetheramine is selected from
8100、
D-400、 
One or more of T-403.
The polyether amine and the organic silicon adopted by the invention have synergistic toughening effect, because the organic silicon molecule contains-Si-O-C-bond, the bond angle is large, the bond length is longer than-C-C-C-, the flexibility of the whole molecular chain is good, the flexible organic silicon molecular chain segment is introduced into the epoxy resin cross-linked network framework through the epoxy group, meanwhile, the flexible polyether chain segment is bonded into the epoxy resin crosslinking network framework through the curing agent, on one hand, the crosslinking network framework can be changed from 'rigid' to 'flexible', so that the toughness of the epoxy cured material is improved, on the other hand, due to the introduction of polyether and organosilicon chain segments, micro-phase separation can occur when the epoxy resin is cured, and the interior of a cured product is in a loose and compact structure, so that a classic 'sea-island' structure is formed. When external stress is applied, the 'sea island' structure distributed in the curing system can effectively absorb energy generated by the stress, so that the toughness of the cured material is further improved.
In the epoxy resin composition of the present invention, the accelerator is one or two of N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine, preferably
DMCHA、
One or two of PMDETA.
The polyether amine and the organic silicon have a synergistic toughening effect, but the polyether amine serving as an epoxy curing agent has the defect of low curing speed, because compared with a cyclic structure curing agent with poor molecular structure regularity, such as isophorone diamine or 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane, the polyether amine has a regular linear structure and obvious hydrogen bond action, so that a functional group is stable, and the activity is greatly reduced. The N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine have a plurality of tertiary amine structures and can react with C + Ions carry out nucleophilic attack to reduce the reaction activation energy of the curing agent, so that the reaction of the polyether amine curing epoxy resin can be effectively promoted, and the promotion effect is not only in shortening the curing time, but also in improving the curing degree. In addition, the N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine are used as the epoxy resin curing accelerator, compared with other amines, the accelerating effect of the epoxy resin curing accelerator is consistent, the epoxy resin is not easy to age and discolor after being cured, and the comprehensive performance is better.
The invention also provides a preparation method of the polyether amine and organic silicon synergistic toughening fast curing epoxy resin composition, which comprises the following steps:
(1) heating the epoxy resin at 60-80 ℃ for 12-18 min, and then uniformly mixing the epoxy resin with the organic silicon to prepare a component A;
(2) uniformly mixing polyether amine and an accelerant to prepare a component B;
(3) and (3) after the component A is cooled to room temperature, uniformly mixing the A, B components, placing the mixture in a vacuum oven to remove bubbles, and then curing.
According to the preparation method, in the step (1), the epoxy resin is preferably placed in an oven at a temperature of 68-72 ℃ for heating for 12-17 min, so that the viscosity is reduced to 800-1200.
According to the preparation method, in the step (3), the vacuum oven has the vacuum degree of-0.08 to-0.1 MPa, the temperature of 23 to 26 ℃ and the time of 10 to 20 min.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) according to the invention, through synthesizing the organic silicon compound containing the epoxy group, the organic silicon molecular chain with a large bond angle, a long bond length and good flexibility is introduced into the epoxy resin cross-linked network structure by means of the epoxy group, and the toughness of the cross-linked framework is improved together with the flexible polyether amine molecular long chain in the cross-linked network. Meanwhile, the two soft chain segments have good compatibility and are clustered to form a special sea-island structure, and the sea-island structure can absorb energy and buffer when the epoxy cured material is subjected to external force, so that a new toughening effect is synergistically generated, and the toughness of the cured material prepared by the method is greatly improved compared with that of a pure epoxy resin curing system. In addition, due to the synergistic effect of the polyether amine molecular chain and the organic silicon molecular chain with the structure, the light aging resistance and the heat aging resistance of the cured epoxy resin product are greatly improved, and the application of the epoxy resin product in the fields of outdoor anti-yellowing epoxy ornament glue and the like is expanded.
(2) The organic silicon molecule with the structure also has a defoaming effect, and due to the characteristic of low surface tension, bubbles wrapped in an epoxy resin system can be effectively reduced, so that the performances of tensile strength and the like of a cured product are improved.
(3) According to the invention, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine are matched with polyetheramine to serve as a reaction accelerator for accelerating the curing of the epoxy resin, and the reaction accelerator can keep a free state in the whole cross-linking and curing reaction process of the epoxy resin, so that the accelerating effect of the epoxy resin can be maintained all the time, excessive use of a curing agent is not required, the purpose of increasing the curing speed and the curing degree can be achieved, the residue of micromolecules of the curing agent is reduced, the volatilized smell and VOC pollution are reduced, and the heat resistance of the epoxy resin is further improved by increasing the curing degree. And because N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine promote the epoxy resin to react and have small steric hindrance, the epoxy resin is not easy to age and discolor after being cured, and the comprehensive performance is better.
(4) In addition, the synergistic effect of the polyether amine and the organic silicon also improves the hydrophobicity of the epoxy resin.
In conclusion, the epoxy group-containing organosilicon compound, the polyether amine and the organosilicon synergistic toughening rapid curing epoxy resin composition have simple preparation methods and convenient use, and can be widely applied to the fields of adhesives, wind power blades and the like.
Detailed Description
In order that the technical features and contents of the present invention may be better understood, preferred embodiments of the present invention will be described below in detail. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The main testing method used by the invention comprises the following steps:
1. gel time testing of epoxy resin compositions
According to the preparation method, the total amount of A, B components after mixing and defoaming is controlled to be 100 +/-2 g, and the gel time test is carried out at the curing temperature of 40 ℃ according to the national standard GB/T12007.7-1989 'method for measuring gel time of epoxy resin', and the result is the gel time of the epoxy resin composition.
2. Elongation at break test of cured epoxy resin
Preparation of cured product test samples: firstly, heating a polytetrafluoroethylene mold to 40 ℃, and preserving heat for 10-20 min. And mixing and defoaming the A, B components according to the curing process, pouring the mixture into a mold for natural leveling, and curing for 5 hours at the temperature of 40 ℃. And (5) naturally cooling the mold, and demolding.
The cured sample was processed to 50X 10X 4mm 3 The dumbbell specimens (see above) were subjected to elongation at break test using a universal material tester (Zwick/Roell Z020, Germany) in accordance with the national Standard GB/T2567 resin cast body Performance test method.
3. Gel content test of cured epoxy resin
The gel content of the cured epoxy resin was measured by an extraction method. 0.25g of a cured product test sample was cut into several pieces of 1.5X 1mm 3 Pieces of (2), weighed as m 1 Extracting for 24h in a Soxhlet extractor by using dimethylbenzene as an extracting agent, taking out a sample, washing the sample with dimethylbenzene for three times, then placing the sample in a vacuum oven at 80 ℃ for drying for 24h, and weighing the sample as m 2 . Gel Content (GC) was calculated according to the following formula:
4. glass transition temperature (Tg) test of epoxy resin cured product
The Tg of the cured epoxy resin was measured by a differential scanning calorimeter (DSC, Perkin Elmer DSC-7). Firstly, high-purity indium is used for respectively correcting the baseline, the temperature and the enthalpy of an instrument, then 8-10mg of a cured object test sample is weighed and sealed in an aluminum DSC crucible, the protective gas is dynamic dry high-purity nitrogen (20mL/min), and the Tg of the cured epoxy resin is measured from 0 to 250 ℃ at the heating rate of 10 ℃/min.
5. Test of degree of reaction of 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane with polymethylhydrosiloxane
In the reaction process, Si-H on the polymethylhydrosiloxane molecules is continuously consumed, and the reaction degree of the Si-H can be calculated by measuring the content of the Si-H in a system before and after the reaction.
The method for measuring the Si-H content in the raw materials and the products comprises the following steps: 0.1000g of the starting material or product (refined to 0.0001) was weighed out and placed in a 250mL iodine vialIn, measure 20mL CCl 4 10mL of 0.2mol/L bromine-acetic acid solution and 0.5mL of deionized water were added to an iodine flask and mixed well, and reacted for 30 min. Then 25mL of 10wt% potassium iodide solution and a certain amount of 0.5 wt% starch solution (as an indicator, based on the change of the system to purple) are measured and added into an iodometric flask, 0.1mol/L sodium thiosulfate standard solution is used for titration, and meanwhile, a blank experiment is carried out, and at the end point of titration, the system is changed from purple to colorless. The Si-H content can be calculated according to the following formula:
wherein ω is the Si-H content of the product, wt.%; v 0 Is a blank sample consuming Na 2 S 2 O 3 Volume of (1), mL; v 1 Is the product consumes Na 2 S 2 O 3 Volume of (1), mL; m is the weight of the product, g.
The degree of Si-H reaction was calculated as follows:
wherein, is the reaction degree of Si-H,%; m is 0 The material amount of the polymethylhydrosiloxane is g; m is 1 Mass of product, g; omega is the Si-H content of the product, wt%.
6. Test of light aging Property of epoxy resin cured product
The cured epoxy resin is placed in an ultraviolet aging box (GT-7035-UB) and is subjected to light aging for 400h under the illumination power of 30W and the wavelength of 400nm plus 280, and a colorimeter (CR-10, Cho Kogyo instruments Co., Ltd. in Hangzhou province) is used for measuring the color difference (the color difference from standard white is represented by delta b, the larger the value is, the more serious the color change is), the color change degree of different samples is compared, the lighter the color change is, and the better the light aging resistance is.
7. Heat aging Property test of cured epoxy resin
The thermal aging performance of the cured epoxy resin is represented by a thermal weight loss analysis test. A sample of about 2mg of the cured product of the adhesive to be tested was taken and subjected to thermogravimetric analysis (Pyris 1TGA thermal analyzer, manufactured by PE in America) at a temperature rise rate of 20 ℃/min within a temperature range of 50 ℃ to 700 ℃ in a nitrogen atmosphere.
8. Test for hydrophobic Properties
The method is characterized in that a contact angle measuring instrument (JC 2000DM, digital technology equipment, Inc. of Shanghai, China) is adopted to measure the static contact angle of a water drop on the surface of a sample, a measuring instrument system is composed of a hardware device and a corresponding software program, the hardware device can shoot the wetting state of the water drop on the surface of the sample, and the software device is responsible for processing and analyzing the size of the static contact angle.
9. Infrared Spectrum analysis (FTIR)
And (3) characterizing the synthesis of the organosilicon compound containing the epoxy group by analyzing the change of the characteristic functional groups before and after the reaction by utilizing Fourier infrared spectroscopy. The product is evenly smeared on a potassium bromide salt sheet for scanning, and the scanning range is 4000- -1 。
Information of used main raw materials
Chloroplatinic acid (speier catalyst): shanghai Aladdin Biotechnology Ltd, chloroplatinic acid concentration is about 0.015 wt%;
hydroquinone: shanghai Aladdin Biotechnology GmbH;
polymethylhydrosiloxane: jiaxing Union chemical, Inc.;
m-chloroperoxybenzoic acid: shanghai Aladdin Biotechnology GmbH;
tetramethyldivinyldisiloxane: shanghai Aladdin Biotechnology GmbH;
bisphenol a type epoxy resin: WSR618 with viscosity of 7000-18000 mPa · s (25 ℃), Nantong Xincheng blue star synthetic materials GmbH;
polyether amine curing agent:
8100 aliphatic amine terminated polyether, average molecular weight 230 + -10, functionalityIs 4, wanhua chemistry;
alicyclic amine curing agent:
PACM, average molecular weight 210, functionality 4, Evonik;
pentamethyldiethylenetriamine:
PMDETA, wanhua chemistry;
n, N' -dimethylcyclohexylamine:
DMCHA, wanghua chemistry;
glycidyl methacrylate: shanghai Aladdin Biotechnology GmbH;
if not specifically stated, the rest are common raw materials purchased from the market.
Example 1
Preparing 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane by the following steps:
1) dissolving m-chloroperoxybenzoic acid in dichloromethane to prepare a solution A with the concentration of 0.696 mol/L;
2) dissolving tetramethyl divinyl disiloxane in dichloromethane to prepare a solution B of 0.4 mol/L;
3) dropwise adding the solution A into the solution B (the molar ratio of m-chloroperoxybenzoic acid to tetramethyl divinyl disiloxane is 2.5:1) at the temperature of 0-4 ℃ in an ice bath condition for 1h, heating to 50 ℃ after the addition is finished, and carrying out reflux reaction for 47 h; the progress of the reaction was monitored by thin layer chromatography (using a mixed solvent of hexane and ethyl acetate in a mass ratio of 5: 3). After the reaction is finished, the obtained crude product is respectively subjected to two times of acid washing (5 wt% of 2, 3-dihydroxysuccinic acid aqueous solution is adopted) and three times of alkali washing (5% of NaHCO aqueous solution is adopted) 3 Aqueous solution), then separating the oil phase from the water phase by using a separating funnel and MgSO 4 Drying, filtering, distilling under reduced pressure to remove solvent to obtain product 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy di-saccharide by infrared spectrum analysisSiloxane conversion rate 95% and yield 90%.
Infrared spectroscopic analysis shows that the reaction time is 1635cm after the reaction compared with that before the reaction -1 The absorption peak at C ═ C decreased while the peak was first at 910cm -1 An epoxy group absorption peak appears, and the prepared product is 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane.
Example 2
Preparing 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane by the following steps:
1) dissolving m-chloroperoxybenzoic acid in dichloromethane to prepare a solution A with the concentration of 0.6 mol/L;
2) dissolving tetramethyl divinyl disiloxane in dichloromethane to prepare a solution B of 0.3 mol/L;
3) dropwise adding the solution A into the solution B (the molar ratio of m-chloroperoxybenzoic acid to tetramethyl divinyl disiloxane is 2:1) at the temperature of 0-4 ℃ in an ice bath condition for 1h, heating to 55 ℃ after the addition is finished, and carrying out reflux reaction for 46 h; the progress of the reaction was monitored by thin layer chromatography (using a mixed solvent of hexane and ethyl acetate in a mass ratio of 5: 3). After the reaction is finished, the obtained crude product is respectively subjected to two times of acid washing (5 wt% of 2, 3-dihydroxysuccinic acid aqueous solution is adopted) and three times of alkali washing (5% of NaHCO aqueous solution is adopted) 3 Aqueous solution), then separating the oil phase from the water phase by using a separating funnel and MgSO 4 Drying, filtering, and distilling under reduced pressure to remove the solvent to obtain 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane with the yield of 87%.
Example 3
Preparing 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane by the following steps:
1) dissolving m-chloroperoxybenzoic acid in dichloromethane to prepare a solution A with the concentration of 0.8 mol/L;
2) dissolving tetramethyl divinyl disiloxane in dichloromethane to prepare a solution B with the concentration of 0.5 mol/L;
3) dropwise adding the solution A into the solution B (the molar ratio of m-chloroperoxybenzoic acid to tetramethyl divinyl disiloxane is 3:1) at the temperature of 0-4 ℃ in an ice bath condition for a period of time1h, heating to 45 ℃ after the feeding is finished, and carrying out reflux reaction for 48 h; the progress of the reaction was monitored by thin layer chromatography (using a mixed solvent of hexane and ethyl acetate in a mass ratio of 5: 3). After the reaction is finished, the obtained crude product is respectively subjected to two times of acid washing (5 wt% of 2, 3-dihydroxysuccinic acid aqueous solution is adopted) and three times of alkali washing (5% of NaHCO aqueous solution is adopted) 3 Aqueous solution), then separating the oil phase from the water phase by using a separating funnel and MgSO 4 Drying, filtering, and distilling under reduced pressure to remove the solvent to obtain the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane with the yield of 90 percent.
Example 4
The preparation of the organosilicon compound containing epoxy group shown in formula II comprises the following steps:
s1, dissolving 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane prepared in example 1, chloroplatinic acid catalyst and hydroquinone in a mass ratio of 100:0.013:0.08 in toluene under nitrogen atmosphere, heating and stirring at 90 ℃ for 30 min;
s2, dropping the polymethylhydrosiloxane (active hydrogen content is 1%) into the mixture obtained in the step S1 by using a dropping funnel according to the molar ratio of Si-H in the polymethylhydrosiloxane (active hydrogen content is 1%) to C in the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane is 1:1.1, and reacting for 5 hours at 90 ℃. After the reaction is finished, the solvent toluene in the product is removed by a rotary evaporator at 70 ℃ and 0.1MPa, and the organic silicon compound containing epoxy group with the structure of formula II (m is 6, n is 5) is prepared into light yellow transparent liquid.
By infrared spectroscopic analysis, it was found that 2165cm was used before the reaction -1 The absorption peak of Si-H is greatly reduced after the reaction, which shows that most of Si-H on the polymethylhydrosiloxane reacts with C ═ C on 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane, and 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxy disiloxane is successfully grafted to the polymethylhydrosiloxane molecular chain, namely the product is an organosilicon compound containing an epoxy group shown in a formula II, and the reaction degree is 75%.
Example 5
An epoxy-containing organosilicon compound of the formula III is prepared by reference to the procedure of example 1, except that: by replacing 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane in step S1 with glycidyl methacrylate, it was found by infrared spectroscopic analysis that glycidyl methacrylate was successfully grafted onto the polymethylhydrosiloxane molecular chain, i.e., the epoxy group-containing organic silicon compound represented by formula iii (m ═ 6, n ═ 5) was successfully obtained, with a reaction degree of 76%.
Examples 6 to 13
An epoxy-containing organosilicon compound of the formula II is prepared by reference to the procedure of example 1, except that: changing the amount of chloroplatinic acid catalyst used in step S1 (mass ratio to 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane), the molar ratio of Si-H to C ═ C in S2; and reaction temperature and time in S2.
The reaction degree of 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane with polymethylhydrosiloxane was measured according to the above test method, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, the epoxy group-containing organosilicon compounds of formula ii can be prepared by varying the amount of chloroplatinic acid catalyst used in step S1 and the molar ratio of Si — H to C ═ C in S2. Meanwhile, the reaction degree gradually increases with the increase of the catalyst dosage; when the amount of the catalyst exceeds 0.015wt%, the reaction degree reaches 75%, and then the amount of the catalyst is continuously increased, so that the reaction degree is not changed greatly. From the viewpoint of resource saving, the amount of the catalyst can be controlled within 0.015 wt%. The reaction degree is gradually increased along with the increase of the molar ratio of C to Si-H; when the ratio exceeds 1.2, the degree of reaction reaches 74%, and then the amount of C ═ C is increased continuously, and the degree of reaction does not vary greatly. Therefore, the molar ratio of C ═ C to Si — H is preferably less than 1.5.
Example 14
The preparation process of the epoxy resin composition toughened by the cooperation of the polyether amine and the organic silicon comprises the following steps:
placing bisphenol A epoxy resin WSR618 in an oven at 70 ℃ for heating for 15min, reducing the viscosity to 1000mPa ≤, taking out 100g, and mechanically stirring and mixing with 15g of the epoxy group-containing organosilicon compound of formula II prepared in example 3 to obtain component A;
29g of polyetheramine curing agent
8100. And 7g of accelerant pentamethyldiethylenetriamine is fully and uniformly mixed to obtain the component B.
After the component A is cooled to room temperature, A, B components are mixed uniformly, placed in a vacuum oven at 25 ℃ for 15min to remove bubbles, the vacuum degree is-0.09 MPa, and then cured for 1h at room temperature. The results of the gel time and gel content test performed during the curing reaction according to the above test methods are shown in Table 2.
The cured product was subjected to the test methods as described above for elongation at break, light aging resistance, heat aging resistance (Tg) and water repellency, and the results are shown in Table 2.
Comparative example 1
The only difference from example 14 is that: the component A is an organosilicon compound without epoxy groups, and the component B is a polyether amine curing agent replaced by an alicyclic amine curing agent.
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from table 2, compared with comparative example 1 containing only an alicyclic amine curing agent, the elongation at break of example 14 in which polyetheramine and an organic silicon compound containing an epoxy group are added is greatly improved, which is 2.5 times of the elongation at break of comparative example 1, which shows that the organic silicon compound containing an epoxy group prepared by the invention and polyetheramine have a remarkable synergistic toughening effect, so that the toughness of an epoxy resin cured product is greatly improved; compared with comparative example 1 only containing an alicyclic amine curing agent, Tg of example 14 is obviously improved, which shows that the organosilicon compound containing an epoxy group prepared by the invention can effectively improve the heat resistance of an epoxy cured product, Delta b is reduced compared with comparative example 1, which shows that the photo-aging discoloration of example 14 is reduced after the organosilicon compound is added, so that the photo-aging resistance of the epoxy cured product is improved, and the contact angle of example 14 is larger than that of comparative example 1, which shows that the organosilicon compound containing an epoxy group prepared by the invention can effectively improve the hydrophobic property of the epoxy cured product.
Comparative example 2
The only difference from example 14 is that: the component B does not contain accelerator pentamethyldiethylenetriamine.
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from Table 2, the gel time of example 14 is reduced by 51% compared with comparative example 2 without pentamethyldiethylenetriamine, which indicates that the curing process of the epoxy resin composition can be effectively accelerated by adding pentamethyldiethylenetriamine as an accelerator; the gel content is improved by 13 percent, which shows that the curing degree of the epoxy resin composition can be improved by adding pentamethyldiethylenetriamine; compared with comparative example 2, the increase of Tg in example 14 shows that the difficulty of the molecular chain of the cured product from freezing to segmental motion is increased, which is caused by the increase of the crosslinking degree, and the fact that the curing crosslinking degree of the epoxy resin composition can be improved by pentamethyldiethylenetriamine is proved from another angle.
Comparative examples 3 to 5
The only difference from example 14 is that: the component B promoter does not adopt N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine, and is sequentially replaced by 2, 4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and dimethylaniline.
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from table 2, when N, N '-dimethylcyclohexylamine and pentamethyldiethylenetriamine are used as the epoxy resin curing accelerator (example 13), compared with the use of accelerators such as 2, 4, 6-tris (dimethylaminomethyl) phenol and triethanolamine (comparative examples 3 to 5), the gel time is greatly shortened, the gel content is increased, and it is demonstrated that N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine are used as the epoxy resin curing accelerator, the curing speed and the curing degree can be effectively increased, and since the molecules do not contain reactive groups such as hydroxyl groups, the whole epoxy resin crosslinking curing reaction process can be kept in a free state, so that the accelerating effect can be maintained throughout the whole process; compared with an accelerant (comparative examples 5-1-5-3) which uses dimethylaniline, 2, 4, 6-tri (dimethylaminomethyl) phenol and the like and contains benzene rings with larger volume and conjugate effect (which easily causes the cured epoxy resin to change color and yellow), N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine are used as the accelerant, the epoxy resin is not easy to age and change color (less delta b) after being cured, and the comprehensive performance is better.
Example 15
The preparation of an epoxy resin composition synergistically toughened with polyetheramine and silicone, with reference to the procedure of example 14, differs only in that: the epoxy-containing organosilicon compound used in the formulation was replaced by 14g of an epoxy-containing organosilicon compound of the formula iii (m ═ 6, n ═ 5).
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from Table 2, the epoxy group-containing organosilicon compounds of the formula III prepared according to the invention also achieve the properties of example 14.
Examples 16 to 18 and comparative example 6
The preparation of an epoxy resin composition synergistically toughened with polyetheramine and silicone, with reference to the procedure of example 14, differs only in that: the dosage of the organosilicon compound containing epoxy group in the formula II is changed.
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from Table 2, when the amount of the organosilicon compound containing epoxy groups is 20 parts, the elongation at break is greatly improved, and the toughness of the cured epoxy resin is better; when the amount of the epoxy group-containing organosilicon compound is increased to more than 20 parts, the toughness is substantially unchanged. This is probably because the degree of participation of the organosilicon compound containing epoxy group in the epoxy resin cross-linked network structure is limited, and the organosilicon compound containing epoxy group cannot participate in the curing cross-linking process even if the amount of the organosilicon compound is excessive, so that the toughness is not greatly improved.
Example 19
The preparation process of the epoxy resin composition synergistically toughened with polyether amine and organosilicon, with reference to the procedure of example 13, differs only in that: the kind of the accelerator used in the formula system is changed, namely N, N' -dimethylcyclohexylamine is selected as the accelerator.
The curing reaction process test results and the cured product test results are shown in table 2.
As can be seen from Table 2, the properties of example 13 are also achieved by using N, N' -dimethylcyclohexylamine as the accelerator.
Comparative example 7
The preparation process of the epoxy resin composition synergistically toughened with polyether amine and organosilicon, with reference to the procedure of example 13, differs only in that: the organic silicon compound containing epoxy group in the formula II is replaced by polymethylhydrosiloxane.
The curing reaction process test results and the cured product test results are shown in table 2.
Comparative example 8
The preparation process of the epoxy resin composition synergistically toughened with polyether amine and organosilicon, with reference to the procedure of example 13, differs only in that: used in a formulation system
8100 by alicyclic amine (
PACM). The curing reaction process test results and the cured product test results are shown in table 2.
As shown in Table 2, when the organosilicon compound without epoxy group, namely polymethylhydrosiloxane, is selected in the comparative example 7, the synergistic toughening effect is basically absent compared with that of polyether amine, in contrast, the toughness of the example 13 is greatly improved, and the organosilicon compound containing epoxy group prepared by the invention is used together with polyether amine, so that the synergistic toughening performance is excellent.
TABLE 2
Claims (20)
1. An organic silicon compound containing epoxy group, the structure of which is shown as formula II:
wherein m = 3-6 and n = 5-10.
2. A method for producing the organosilicon compound according to claim 1, comprising the steps of:
s1, dissolving the reactant 1, the chloroplatinic acid catalyst and the hydroquinone in toluene in an inert gas atmosphere, and heating and stirring to obtain a mixed solution;
in step S1, reactant 1 is 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane;
s2, adding polymethylhydrosiloxane into the mixed liquid in the step S1, and heating for reaction to obtain the organic silicon compound containing the epoxy group and having the structure shown in the formula II.
3. The method according to claim 2, wherein in step S1, the inert gas is one or both of nitrogen and argon; and/or
The chloroplatinic acid catalyst is an isopropanol solution of chloroplatinic acid, and the concentration of the solution is 0.008-0.018 wt%; and/or
The dosage of the chloroplatinic acid catalyst is 0.008-0.018 wt% of the mass of the reactant 1 by taking the isopropyl alcohol solution of the chloroplatinic acid as a reference; and/or
The dosage of the hydroquinone is 0.05-0.10 wt% of the mass of the reactant 1; and/or
And heating and stirring at the temperature of 80-100 ℃ for 20-40 min.
4. The preparation method according to claim 3, wherein the chloroplatinic acid catalyst is an isopropanol solution of chloroplatinic acid, and the concentration of the solution is 0.011-0.015 wt%; and/or
The dosage of the chloroplatinic acid catalyst is 0.011-0.015 wt% of the mass of the reactant 1, calculated by isopropyl alcohol solution of the chloroplatinic acid; and/or
The dosage of the hydroquinone is 0.07-0.08 wt% of the mass of the reactant 1; and/or
And heating and stirring at the temperature of 85-95 ℃ for 28-32 min.
5. The method according to claim 2, wherein the step S1 is a method for preparing 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane, which comprises the steps of:
1) dissolving m-chloroperoxybenzoic acid in dichloromethane to prepare a solution A with the concentration of 0.6-0.8 mol/L;
2) dissolving tetramethyl divinyl disiloxane in dichloromethane to prepare a solution B of 0.3-0.5 mol/L;
3) and adding the solution A into the solution B under an ice bath condition at 0-4 ℃, wherein the adding time is 0.5-1.5 h, heating to 45-55 ℃ after the adding is finished, and carrying out reflux reaction for 46-48 h to obtain the 1, 1, 3, 3-tetramethyl-1-vinyl-3-epoxydisiloxane.
6. The preparation method of claim 5, wherein in the step 3), the molar ratio of the solution A to the solution B is 2-3: 1 based on m-chloroperoxybenzoic acid and tetramethyl divinyl disiloxane in the solution A and the solution B respectively; and/or
The reflux reaction is monitored by adopting thin-layer chromatography, and the eluent is a mixed solvent of n-hexane and ethyl acetate.
7. The preparation method of claim 6, wherein the molar ratio of the solution A to the solution B is 2.4-2.6: 1; and/or
The mixed solvent of the n-hexane and the ethyl acetate is mixed in a mass ratio of 5: 3.
8. The preparation method according to claim 2, wherein in step S2, the mass fraction of active hydrogen in the polymethylhydrosiloxane is 0.5-1.5%; and/or
The molar ratio of Si-H in the polymethylhydrosiloxane to C = C in the reactant 1 added in the step S1 is 1: 0.8-1.4; and/or
Adding the polymethylhydrosiloxane into the mixed solution obtained in the step S1, and adopting a continuous feeding mode, wherein the feeding time is 0.8-1.2 hours; and/or
The reaction is carried out at the temperature of 80-100 ℃ for 3-7 h.
9. The preparation method according to claim 8, characterized in that the mass fraction of active hydrogen in the polymethylhydrosiloxane is 0.9-1.1%; and/or
The molar ratio of Si-H in the polymethylhydrosiloxane to C = C in the reactant 1 added in the step S1 is 1: 1.0-1.2; and/or
The reaction is carried out at the temperature of 88-92 ℃ for 4.5-5.5 h.
10. A polyether amine and organosilicon synergistic toughening fast curing epoxy resin composition is characterized by comprising a component A and a component B,
the component A comprises the following raw materials:
100 parts of epoxy resin;
10-20 parts of organic silicon;
the component B comprises the following raw materials:
20-40 parts of polyether amine;
5-10 parts of an accelerator;
the parts are parts by mass;
the organosilicon is selected from an epoxy group-containing organosilicon compound of the structure of formula ii as defined in claim 1, or an epoxy group-containing organosilicon compound of the structure of formula ii prepared by a process as defined in any one of claims 2 to 9.
11. The epoxy resin composition of claim 10, wherein the a component comprises the following raw materials:
100 parts of epoxy resin;
12-18 parts of organic silicon;
the component B comprises the following raw materials:
27-33 parts of polyether amine;
6-8 parts of an accelerator;
the parts are parts by mass.
12. The epoxy resin composition of claim 10, wherein the molar ratio of active hydrogen in the polyether amine to epoxy groups in the epoxy resin is 1: 0.7 to 1.3; and/or
The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydroxymethyl bisphenol A epoxy resin, o-cresol formaldehyde epoxy resin and resorcinol epoxy resin;
and/or
The polyether amine is selected from aliphatic polyether amine; and/or
The accelerant is one or two of N, N' -dimethylcyclohexylamine and pentamethyldiethylenetriamine.
13. The epoxy resin composition of claim 12, wherein the molar ratio of active hydrogen in the polyetheramine to epoxy groups in the epoxy resin is 1:0.8 to 1.2; and/or
The epoxy resin is selected from bisphenol A type epoxy resin and/or bisphenol F type epoxy resin; and/or
The polyether amine is selected from aliphatic amine-terminated polyether amine; and/or
The promoter is WANAMINE ® DMCHA、WANAMINE ® One or two of PMDETA.
14. The epoxy resin composition according to claim 13, wherein the epoxy resin is liquid at room temperature and has a viscosity of 7000 to 18000 mPa-s at 25 ℃.
15. The epoxy resin composition according to claim 14, wherein the viscosity of the epoxy resin at 25 ℃ is 7000 to 10000 mPas.
16. The epoxy resin composition of claim 13, wherein the polyetheramine has a molecular weight of 200 to 500 and a functionality of 2 to 6.
17. The epoxy resin composition of claim 16, wherein the polyetheramine is selected from the group consisting of WANAMINE ® 8100、JEFFAMINE ® D-400、JEFFAMINE ® One or more of T-403.
18. A method for preparing the epoxy resin composition according to any one of claims 10 to 17, comprising the steps of:
(1) heating the epoxy resin at 60-80 ℃ for 12-18 min, and then uniformly mixing the epoxy resin with the organic silicon to prepare a component A;
(2) uniformly mixing polyether amine and an accelerant to prepare a component B;
(3) and (3) after the component A is cooled to room temperature, uniformly mixing the A, B components, placing the mixture in a vacuum oven to remove bubbles, and then curing.
19. The method according to claim 18, wherein the step (1) comprises heating the epoxy resin in an oven at 68-72 ℃ for 12-17 min to reduce the viscosity to 800-1200 mPas.
20. The preparation method of claim 18, wherein in the step (3), the vacuum oven has a vacuum degree of-0.08 to-0.1 MPa, a temperature of 23 to 26 ℃ and a time of 10 to 20 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011428764.2A CN112574418B (en) | 2020-12-07 | 2020-12-07 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011428764.2A CN112574418B (en) | 2020-12-07 | 2020-12-07 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112574418A CN112574418A (en) | 2021-03-30 |
| CN112574418B true CN112574418B (en) | 2022-08-05 |
Family
ID=75130349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011428764.2A Active CN112574418B (en) | 2020-12-07 | 2020-12-07 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112574418B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354924B (en) * | 2021-06-24 | 2023-05-23 | 哈尔滨工业大学无锡新材料研究院 | Glass fiber composite material with low surface tension and preparation method thereof |
| CN116693810B (en) * | 2023-07-04 | 2024-08-16 | 嘉兴南洋万事兴化工有限公司 | High heat-resistant epoxy curing agent for LED packaging, preparation method and epoxy pouring sealant prepared by using high heat-resistant epoxy curing agent |
| CN117487497B (en) * | 2023-11-17 | 2024-09-20 | 江苏科麦特科技发展有限公司 | High-temperature-resistant epoxy resin composition for PCB |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265704B (en) * | 2013-05-28 | 2015-12-23 | 卢儒 | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof |
| CN105153645A (en) * | 2015-07-24 | 2015-12-16 | 常州大学 | Method for toughened epoxy resin by synergistic effect of epoxidized soybean oil and polyether amine |
| CN106947213A (en) * | 2016-01-07 | 2017-07-14 | 湖南师范大学 | A kind of epoxy resin of polyetheramides toughness reinforcing |
| CN109983077A (en) * | 2016-09-06 | 2019-07-05 | 明尼苏达大学董事会 | Pass through the coordination plasticizing of graphene and block copolymer-modified epoxy |
| CN112029463A (en) * | 2020-08-21 | 2020-12-04 | 深圳市优宝新材料科技有限公司 | Epoxy modified phenyl hydrogen-containing silicone oil, composite epoxy adhesive and preparation method thereof |
-
2020
- 2020-12-07 CN CN202011428764.2A patent/CN112574418B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112574418A (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112574418B (en) | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof | |
| CN105969301B (en) | A kind of organic silica gel for high-power LED encapsulation and preparation method thereof and application method | |
| CN110423334A (en) | A kind of preparation method of full biology base vitrimer | |
| CN111139021B (en) | Low-temperature-curable high-adhesion heat-resistant cyanate ester adhesive and preparation method thereof | |
| CN111363103B (en) | Preparation method of tackifier for addition type organic silicon adhesive | |
| CN111303200B (en) | Siloxane additive and preparation method and application thereof | |
| CN111849105A (en) | Polyphosphazene-boron nitride modified acrylic resin flame retardant material and preparation method thereof | |
| CN113185689B (en) | Low-water-absorption copolymerized nylon resin and preparation method thereof | |
| CN103923322B (en) | A kind of epoxy/polyurethane/organosilicon HB-LED encapsulating material preparation method | |
| CN112745528B (en) | Rubber antioxidant, composition containing rubber antioxidant, and preparation and application of rubber antioxidant | |
| CN109705799B (en) | YASI epoxy organic imide silica gel and preparation method thereof | |
| CN114835901A (en) | Epoxy modified vinyl silicone rubber and preparation method and application thereof | |
| CN112898516B (en) | Phenolic aldehyde modified amine and preparation method thereof | |
| CN114196024A (en) | Organic silicon modified phenolic resin and preparation method and application thereof | |
| CN107142060B (en) | High-temperature-resistant organic silicon adhesive and preparation method thereof | |
| CN115850714B (en) | POSS modified nitrile rubber compound and preparation method and application thereof | |
| CN111500248B (en) | Low-curing-temperature heat-resistant cyanate ester adhesive and preparation method thereof | |
| CN117384485A (en) | Vinyl MQ silicon resin reinforced protective material and preparation method thereof | |
| CN116144027A (en) | Long-chain epoxy organic silicon resin and preparation method and application thereof | |
| CN114213661B (en) | Photo-curing perfluoropolyether/alkenyl silicone resin, preparation method and application | |
| CN111087564B (en) | Organic silicon epoxy monomer modified phenolic resin and preparation method thereof | |
| CN109735295B (en) | Imide organic silica gel and preparation method thereof | |
| CN113150246A (en) | Fluorine-containing epoxy resin curing agent and preparation method thereof | |
| CN109880418B (en) | Modified water-based polyacrylate emulsion and preparation method and application thereof | |
| CN114940761A (en) | Furfural silane 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |