CN113004524B - Epoxy-organic silicon resin and preparation method and application thereof - Google Patents
Epoxy-organic silicon resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of epoxy resin modification, and particularly relates to an epoxy-organic silicon resin and a preparation method and application thereof, wherein the preparation method of the epoxy-organic silicon resin comprises the following steps: i. taking MT resin containing vinyl and siloxane ring body as raw materials, and carrying out a balance reaction under the action of an acid catalyst to prepare MDT resin containing vinyl; ii. And contacting the obtained MDT resin containing vinyl with peroxide to carry out oxidation reaction to obtain the MDT organic silicon resin with the end group containing epoxy group. The preparation method of the epoxy-organic silicon resin is simple, can flexibly and reasonably adjust the structure of the epoxy-organic silicon resin, has good compatibility with the epoxy resin, and can prepare transparent organic silicon modified epoxy resin; the epoxy-organic silicon resin can maintain good temperature resistance and weather resistance of the cured epoxy resin, and can effectively improve the mechanical properties (such as bending strength and toughness) of the cured epoxy resin.
Description
Technical Field
The invention belongs to the technical field of epoxy resin modification, and particularly relates to an epoxy-organic silicon resin and a preparation method and application thereof.
Background
Epoxy resins are polymers with good adhesion and mechanical strength, and thus are widely used in the fields of automobiles, electronics, and electrical appliances. However, the epoxy resin itself may also have some performance deficiencies. In order to improve the properties of epoxy resin such as flame retardancy, toughness and weather resistance, the application of silicone resin modified epoxy resin has been reported.
The application of the silicone resin modified epoxy resin reported in the literature at present mainly comprises two types of silicone resins: silicone resins that do not contain epoxy functional groups and silicone resins that contain epoxy functional groups. For example, patent document CN 101307132A provides a method for modifying an epoxy resin with a silanol-containing hydroxyl-or alkoxy-terminated silicone resin, and a silicone-modified epoxy resin is obtained by a reaction between a silanol hydroxyl group or alkoxy group and an epoxy group, and the water resistance of the product is improved, but the mechanical properties are not mentioned. Patent document US20080255321 provides a method for modifying epoxy resin by using silicone resin, wherein epoxy groups are introduced on the silicone resin by using hydrosilylation reaction, and then the epoxy resin is modified by using the silicone resin containing the epoxy groups, so that the heat resistance and the bonding performance of the epoxy resin are effectively improved. However, the patent document does not mention improvement of mechanical properties and the preparation process is complicated. Patent document US5952439 provides a method for modifying epoxy resin with silicone resin containing epoxy group, which effectively improves the heat resistance such as glass transition temperature of epoxy resin, wherein the silicone resin containing epoxy group is obtained by hydrosilylation reaction of silicone resin containing silicon hydride and epoxy monomer containing allyl, but the raw material price is high and the preparation method is relatively complex. Further, no mention is made of the problem of transparency of the cured epoxy resin.
Therefore, how to obtain a silicone resin containing epoxy functional groups, which can effectively improve the mechanical properties of epoxy resins, by a convenient and efficient method is an important subject to be researched.
Disclosure of Invention
The invention aims to provide epoxy-organic silicon resin and a preparation method and application thereof aiming at the defects in the application of the prior organic silicon resin modified epoxy resin, the preparation method of the epoxy-organic silicon resin is simple, the structure of the epoxy-organic silicon resin can be flexibly and reasonably adjusted, the compatibility with the epoxy resin is good, and the transparent organic silicon modified epoxy resin can be prepared; the epoxy-organic silicon resin can maintain good temperature resistance and weather resistance of the cured epoxy resin, and can effectively improve the mechanical properties (such as bending strength and toughness) of the cured epoxy resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, an epoxy-silicone resin is provided having a chemical structure according to formula (I):
in the formula (I), the compound is shown in the specification,
R 1 is composed of
R 2 、R 3 、R 4 、R 5 、R 6 The same or different, each is independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
a. c and d are positive numbers, and b is 0 or a positive number.
According to the epoxy-silicone resin provided by the present invention, in some examples, in formula (I),
a has a value of 2-50 (e.g., 4, 8, 10, 15, 18, 25, 30, 35, 40, 45), preferably 5-20;
b is from 0 to 200 (e.g., 1, 5, 15, 30, 50, 70, 90, 100, 120, 150, 180), preferably from 10 to 80;
c has a value of 20-200 (e.g., 25, 30, 35, 45, 50, 60, 80, 100, 120, 150, 180), preferably 40-160;
d has a value of 10-1000 (e.g., 20, 50, 100, 200, 500, 800), preferably 50-500.
The epoxy-organic silicon resin has good compatibility with epoxy resin, and an epoxy resin condensate obtained by modifying the epoxy resin with the epoxy-organic silicon resin is transparent.
The epoxy-organic silicon resin can change the modification effect on the epoxy resin by adjusting the values of a and d.
In some examples, R 2 、R 3 、R 4 、R 5 、R 6 The same or different, each is independently selected from C1-C6 saturated alkyl, C2-C5 unsaturated alkyl, trifluoropropyl or C6-C12 aryl.
In some preferred embodiments, R 2 、R 3 、R 4 、R 6 Identical or different, each being independently selected from methyl, ethyl, phenyl or trifluoropropyl, more preferably methyl.
In some preferred embodiments, R 5 Selected from methyl, ethyl, phenyl or vinyl, more preferably phenyl.
According to the epoxy-silicone resin provided by the present invention, in some examples, the epoxy value of the epoxy-silicone resin is 0.01 to 1.0 (e.g., 0.02, 0.04, 0.08, 0.12, 0.2, 0.4, 0.7, 0.9), preferably 0.01 to 0.50.
In some examples, the weight average molecular weight of the epoxy-silicone resin is 10000 to 100000 (e.g., 20000, 40000, 60000, 80000), preferably 10000 to 50000.
In another aspect, there is provided a method of preparing the epoxy-silicone resin as described above, comprising the steps of:
i. taking MT resin containing vinyl and siloxane ring body as raw materials, and carrying out a balance reaction under the action of an acid catalyst to prepare MDT resin containing vinyl;
ii. And (e) contacting the MDT resin containing the vinyl group obtained in the step i with peroxide to perform oxidation reaction to obtain the MDT organic silicon resin with the end group containing an epoxy group, namely the epoxy-organic silicon resin.
According to the preparation method provided by the present invention, in some examples, in the step i, the MT resin containing vinyl groups has a chemical structural formula shown in formula (II):
in the formula (I), the compound is shown in the specification,
R 1 ' is a vinyl group;
R 2 、R 3 、R 4 、R 5 the same or different, each is independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
a. c is a positive number, b is 0 or a positive number; the value of a is preferably 2-50, more preferably 5-20; the value of b is preferably 0-200, more preferably 10-80; the value of c is preferably 20 to 200, more preferably 40 to 160.
In the formula (II), values of a, b and c can be the same as those of the formula (I), and a, b and c can represent the molar contents of the respective corresponding repeating units; r 2 、R 3 、R 4 、R 5 May also be the same as in formula (I). In the formula (II), the value of a defines the molar content of the vinyl in the MT resin containing the vinyl.
According to the preparation method provided by the present invention, in some examples, the siloxane ring body is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltris (trifluoropropyl) cyclotrisiloxane, tetramethyltetrakis (trifluoropropyl) cyclotrisiloxane, and siloxane mixed ring body; preferably selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or mixed siloxane rings. In some examples, the siloxane ring is a siloxane mixed ring, i.e., a mixture of two or more siloxane rings.
In some examples, the acidic catalyst is selected from one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and an acidic cationic resin, preferably from trifluoromethanesulfonic acid and/or an acidic cationic resin. The acidic cationic resin is preferably a polystyrene sulfonic acid resin.
In some examples, the peroxide is selected from one or more of hydrogen peroxide, peroxybenzoic acid, peroxyacetic acid, and peroxyformic acid, preferably from one or more of peroxybenzoic acid, peroxyacetic acid, and peroxyformic acid.
According to the preparation method provided by the invention, in some examples, the vinyl group-containing MDT resin prepared in step i has a chemical structural formula shown in formula (III):
in the formula (I), the compound is shown in the specification,
R 1 "is vinyl;
R 2 、R 3 、R 4 、R 5 、R 6 the same or different, each independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
a. c and d are positive numbers, and b is 0 or a positive number; the value of a is preferably 2-50, more preferably 5-20; the value of b is preferably 0-200, more preferably 10-80; the value of c is preferably 20-200, more preferably 40-160; the value of d is preferably 10 to 1000, more preferably 50 to 500.
In the formula (III), values of a, b, c and d can be the same as those of the formula (I), and a, b, c and d can represent the molar contents of the respective corresponding repeating units; r 2 、R 3 、R 4 、R 5 、R 6 May also be the same as in formula (I). In the formula (III), the value of d depends on the mass ratio of the MT resin containing vinyl groups to the siloxane ring body. The higher the mass ratio of the vinyl-containing MT resin to the siloxane ring body, the smaller the value of d.
In some examples, R of formula (II) 2 、R 3 、R 4 、R 5 The same or different, each is independently selected from C1-C6 saturated alkyl, C2-C5 unsaturated alkyl, trifluoropropyl or C6-C12 aryl. R of the formula (III) 2 、R 3 、R 4 、R 5 、R 6 Identical or different, each independently selected from C1-C6 saturated hydrocarbon radicalsC2-C5 unsaturated alkyl, trifluoropropyl or C6-C12 aryl.
In the formulae (I) to (III) of the present invention, the C1-C6 saturated hydrocarbon group may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or pentyl; the C2-C6 unsaturated hydrocarbon group can be selected from vinyl or propenyl; the C6-C12 aryl group may be selected from phenyl or tolyl.
In some preferred embodiments, R is as described for formula (I) 2 、R 3 、R 4 、R 6 And is selected from methyl, ethyl, phenyl or trifluoropropyl, more preferably methyl.
In some preferred embodiments, R is as described in formula (I) 5 Selected from methyl, ethyl, phenyl or vinyl, more preferably phenyl.
In some preferred embodiments, R is as described in formula (II) 2 、R 3 、R 4 Identical or different, each independently selected from methyl, ethyl, phenyl or trifluoropropyl, more preferably methyl.
In some preferred embodiments, R is as described in formula (II) 5 Selected from methyl, ethyl, phenyl or vinyl, more preferably phenyl.
In some preferred embodiments, R is as described in formula (III) 2 、R 3 、R 4 、R 6 Identical or different, from methyl, ethyl, phenyl or trifluoropropyl, more preferably methyl.
In some preferred embodiments, R is described in formula (III) 5 Selected from methyl, ethyl, phenyl or vinyl, more preferably phenyl.
According to the production method provided by the present invention, in some examples, in step i, the mass ratio of the vinyl group-containing MT resin to the siloxane ring body is 1; in some examples, the acidic catalyst is used in an amount of 0.01wt% to 5wt% (e.g., 0.015wt%, 0.03wt%, 0.08wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 4 wt%), preferably 0.02wt% to 2wt%, of the sum of the mass of the vinyl-containing MT resin and the mass of the silicone ring.
In some examples, the process conditions of the equilibrium reaction of step i include: the reaction temperature is 50-90 deg.C (e.g., 60 deg.C, 70 deg.C, 80 deg.C, 85 deg.C), and the reaction time is 4-48h (e.g., 8h, 12h, 15h, 20h, 30h, 40 h), preferably 4-24h.
In some examples, after the equilibration reaction in step i is completed, an alkaline substance such as sodium carbonate may be added to the reaction system. The reaction system is added with alkaline matter which is used for neutralizing the acid catalyst in the equilibrium reaction, and the dosage of the alkaline matter can be 5 to 20 times of the mass of the acid catalyst.
In some examples, the reaction solution obtained in step i may be subjected to a filtration treatment to remove low volatiles in the reaction solution. Such filtration processes are well known to those skilled in the art and will not be described in detail herein.
According to the preparation method provided by the present invention, preferably, in step ii, the molar ratio of the peroxide to the vinyl group in the vinyl group-containing MDT resin is 1.1 to 10 (for example, 1.3.
The process conditions of the oxidation reaction in step ii comprise: the reaction temperature is-10 to 20 ℃ (for example, -8 ℃, -4 ℃, -1 ℃,2 ℃,5 ℃, 12 ℃,18 ℃), preferably 0 to 10 ℃; the reaction time is 12 to 48 hours (e.g., 15 hours, 20 hours, 28 hours, 35 hours, 40 hours), preferably 24 to 48 hours.
In some examples, the reaction may be carried out by dissolving the MDT resin containing vinyl groups obtained in step i in an organic solvent and then contacting the solution with a peroxide. The organic solvent can be selected from toluene and xylene. The organic solvent may be used in an amount of 20 to 500wt%, preferably 30 to 300wt%, based on the mass of the MDT resin containing a vinyl group.
In some examples, the crude product obtained after the oxidation reaction in step ii may be filtered and washed to neutrality so that the volatiles may be removed. The post-treatment steps of filtration and washing to neutrality are well known to those skilled in the art and will not be described in detail herein.
In a further aspect, there is provided a use of the epoxy-silicone resin as described above or the epoxy-silicone resin prepared by the preparation method as described above in the modification of an epoxy resin.
The epoxy value of the epoxy-organic silicon resin is related to the compatibility of the epoxy-organic silicon resin and the epoxy resin and the crosslinking density of a cured epoxy resin, and further influences the mechanical strength, such as bending strength, of the epoxy resin.
In the chemical structural formula of the epoxy-organic silicon resin, if the value of a is less than 2, the epoxy-organic silicon resin cannot enter a cross-linked network of an epoxy resin cured material; if a is greater than 50, the crosslinking density is too high, which results in an increase in the brittleness of the epoxy resin.
The d size in the epoxy-organic silicon resin is related to the influence on the mechanical property and the toughness of the cured epoxy resin. In the chemical structural formula of the epoxy-organic silicon resin, if the value of d is too small, the toughness of the cured epoxy resin cannot be improved; if d is too large, the softening point of the epoxy resin is lowered.
Therefore, the modification effect on the epoxy resin can be changed by adjusting the values of a and d in the epoxy-organic silicon resin or in the preparation process of the epoxy-organic silicon resin.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the epoxy-silicone resin prepared by the invention can be used for improving the mechanical strength (such as bending strength) and toughness (such as impact strength) of an epoxy resin cured product, and can maintain good temperature resistance and weather resistance of the epoxy resin cured product.
In addition, the epoxy-organic silicon resin has the advantage of adjustable structure, and can flexibly adjust the relation between the strength and the toughness of the epoxy resin with improved performance, thereby meeting different use requirements. By modifying the epoxy-organic silicon resin, a transparent epoxy resin condensate can be obtained, and the epoxy-organic silicon resin can meet the field with higher requirement on transparency.
The preparation method of the epoxy-organic silicon resin is flexible, convenient and fast, has simple operation process and can realize large-scale application.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. 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.
1. Information on main raw materials in examples and comparative examples
Siloxane ring body I: octamethylcyclotetrasiloxane, purchased from alatin reagent, inc;
siloxane ring body II: decamethylcyclopentasiloxane, purchased from alatin reagent, inc;
siloxane ring body III: siloxane mixed ring bodies, purchased from Aladdin reagents, inc.;
triflic acid, purchased from alatin reagent ltd;
concentrated sulfuric acid, 98% in concentration, purchased from alatin reagent limited;
MT resin A containing vinyl groups is purchased from Chenguang Boda technologies, inc., the number average molecular weight of the resin A is 10600, the vinyl group content of the resin A is 0.47mmol/g, and the chemical structural formula of the resin A is shown as a formula (IV):
the MT resin B containing vinyl is purchased from Chenguang Boda technology limited, the number average molecular weight of the resin B is 11000, the vinyl content is 1.82mmol/g, and the chemical structural formula is shown as a formula (V):
MT resin C containing vinyl groups, purchased from Chenguang Boda technologies, inc., having a number average molecular weight of 12000 and a vinyl group content of 0.17mmol/g, has the chemical formula shown in formula (VI):
MT resin D containing vinyl groups, purchased from Chenguang Boda technologies, inc., having a number average molecular weight of 14000 and a vinyl group content of 3.57mmol/g, has the chemical formula shown in formula (VII):
MT resin E containing vinyl groups, purchased from Chenguang Boda technologies, inc., having a number average molecular weight of 15000, a vinyl group content of 3.97mmol/g, and a chemical formula as shown in formula (VIII):
peracetic acid, purchased from alatin reagent, inc;
perbenzoic acid, purchased from alatin reagent, inc;
3,3' -Diamino Diphenyl Sulfone (DDS), purchased from Aladdin reagents, inc.
2. Test methods used in examples and comparative examples
Epoxy value test method: referring to GB/T1677-2008 epoxy value determination-hydrochloric acid acetone method;
method for testing weight average molecular weight: performing High Performance Liquid Chromatography (HPLC) with toluene as mobile phase;
the bending strength test method comprises the following steps: the test of the bending property of the plastic refers to GB/T9341-2008;
the notch impact strength test method comprises the following steps: reference is made to the test for impact strength of GB/T1843-2008 plastic cantilevers.
Preparation of epoxy-silicone resin the following examples and comparative examples, in which the reaction raw materials in the steps are all used in parts by weight.
Example 1
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body I and 100 parts of MT resin A containing vinyl and having a chemical structure shown as a formula (IV) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (I) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (I) resin containing vinyl obtained in the step I and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 4 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 0 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (I) resin containing epoxy groups, namely epoxy-organic silicon resin; the epoxy value was 0.029 and the weight average molecular weight was 22500.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 2
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 200 parts of siloxane ring body II and 100 parts of MT resin A containing vinyl and having a chemical structure shown as a formula (IV) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid for equilibrium reaction, and reacting for 6h; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction solution, and removing low-volatility substances to obtain the MDT-Vi (II) resin containing vinyl.
ii. Adding 100 parts of MDT-Vi (II) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene and mixing the materials in a reaction kettle; cooling the reaction kettle to 0 ℃, and adding 5 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 0 ℃ for reaction for 20h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (II) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.020 and its weight average molecular weight was 32000.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 3
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body II and 100 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction, and reacting for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (III) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (III) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 20 parts of peroxyacetic acid to carry out oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (III) resin containing epoxy groups, namely epoxy-organic silicon resin; the epoxy value was 0.11 and the weight average molecular weight was 23000.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 4
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 200 parts of siloxane ring body I and 100 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 70 ℃, adding 1 part of trifluoromethanesulfonic acid for equilibrium reaction, and reacting for 6h; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (IV) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (IV) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 30 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 0 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (IV) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.080 and its weight-average molecular weight was 32600.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 5
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body II and 100 parts of MT resin C containing vinyl and having a chemical structure shown as a formula (VI) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction, and reacting for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (V) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (V) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 5 parts of peroxyacetic acid to carry out oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (V) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.011 and its weight average molecular weight was 2450.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 6
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 500 parts of siloxane ring body II and 100 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction, and reacting for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low volatile matters to obtain the MDT-Vi (VI) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (VI) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 10 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (VI) resin containing epoxy groups, namely epoxy-organic silicon resin; the epoxy value was 0.045 and the weight average molecular weight was 57600.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 7
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 500 parts of siloxane ring body II and 50 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (VII) resin containing vinyl.
ii. Adding 100 parts of MDT-Vi (VII) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle; cooling the reaction kettle to 0 ℃, and adding 15 parts of peroxyacetic acid; keeping the mixture at 5 ℃ for reaction for 24h, filtering and washing the mixture to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (VII) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.026, and its weight average molecular weight was 89000.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 8
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body II and 100 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 10 parts of concentrated sulfuric acid to carry out equilibrium reaction for 12 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (VIII) resin containing vinyl.
ii. Adding 100 parts of MDT-Vi (VIII) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene and mixing in a reaction kettle; cooling the reaction kettle to 0 ℃, and adding 20 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (VIII) resin containing epoxy groups, namely epoxy-organic silicon resin; the epoxy value was 0.11 and the weight average molecular weight was 22800.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 9
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body II and 100 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 10 parts of concentrated sulfuric acid to carry out equilibrium reaction, and reacting for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid to remove low-volatility substances to obtain the MDT-Vi (IX) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (IX) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene to a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 30 parts of peroxybenzoic acid for oxidation reaction; keeping the temperature at 0 ℃ for reacting for 36h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (IX) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.11 and its weight average molecular weight was 23200.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
example 10
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 20 parts of siloxane ring body III and 200 parts of vinyl MT resin D shown as a structural formula (VII) into a reaction kettle, heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid, and reacting for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (X) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (X) resin containing vinyl obtained in the step i and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 80 parts of peroxybenzoic acid to carry out oxidation reaction; keeping the temperature at 0 ℃ for reacting for 36h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (X) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.34 and its weight average molecular weight was 19200.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
comparative example 1
The preparation method of the epoxy-organic silicon resin comprises the following steps:
adding 100 parts of MT (V) resin B containing vinyl and having a chemical structure shown as a formula (V) and 200 parts of dimethylbenzene into a reaction kettle and mixing; cooling the reaction kettle to 0 ℃, and adding 32 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MT-EP (XI) resin containing epoxy groups, namely epoxy-organic silicon resin; the epoxy value was 0.18 and the weight average molecular weight was 14300.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
comparative example 2
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 100 parts of siloxane ring body II and 100 parts of MT resin E containing vinyl and having a chemical structure shown as a formula (VIII) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 1 part of trifluoromethanesulfonic acid to carry out equilibrium reaction for 5 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; and filtering the obtained reaction liquid, and removing low-volatility substances to obtain the MDT-Vi (XII) resin containing vinyl.
ii. Adding 100 parts of the MDT-Vi (XII) resin containing vinyl groups obtained in step i and 200 parts of dimethylbenzene and mixing; cooling the reaction kettle to 0 ℃, and adding 50 parts of peroxyacetic acid for oxidation reaction; keeping the temperature at 5 ℃ for reaction for 24h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (XII) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.26 and its weight average molecular weight was 30200.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
comparative example 3
The preparation method of the epoxy-organic silicon resin comprises the following steps:
i. adding 200 parts of siloxane ring body II and 10 parts of MT resin B containing vinyl and having a chemical structure shown as a formula (V) into a reaction kettle; heating the reaction kettle to 75 ℃, adding 10 parts of concentrated sulfuric acid to carry out equilibrium reaction, and reacting for 12 hours; adding 10 parts of sodium carbonate into the reaction kettle, and continuously stirring for 1 hour; the reaction solution was filtered to remove low volatiles, and an MDT-Vi (XIII) resin containing vinyl groups was obtained.
ii. Adding 100 parts of the MDT-Vi (XIII) resin containing vinyl groups obtained in step i and 200 parts of dimethylbenzene and mixing; cooling the reaction kettle to 0 ℃, and adding 10 parts of peroxybenzoic acid to carry out oxidation reaction; keeping the temperature at 0 ℃ for reacting for 36h, filtering and washing the obtained product to be neutral after the reaction is finished, and removing volatile matters to obtain MDT-EP (XIII) resin containing epoxy groups, namely epoxy-organic silicon resin; its epoxy value was 0.013, and its weight average molecular weight was 192000.
The structural formula of the obtained product epoxy-organic silicon resin is as follows:
in the process of preparing epoxy-silicone resin in each example and comparative example, part of the raw material ratios are shown in table 1.
TABLE 1 partial raw material ratios for preparing epoxy-silicone resins
Application example
An amount of E51 epoxy resin (epoxy value 0.51), the epoxy-silicone resins prepared in the above examples and comparative examples, and 3,3' -diaminodiphenyl sulfone (DDS) were mixed uniformly at 100 ℃ to obtain a mixture. Wherein, the components and the dosage thereof are shown in Table 2. Then the mixture is injected into a PTFE mold, put into an oven and cured according to the conditions of 140 ℃/2h and 180 ℃/2 h. Finally obtaining the cured epoxy resin.
In addition, a blank example was also set as an application comparative example 4, i.e., E51 epoxy resin (epoxy value 0.51) and 3,3' -diaminodiphenyl sulfone (DDS) were uniformly mixed at 100 ℃ without adding epoxy-silicone resin to obtain a mixture. Then the mixture is injected into a PTFE mold, put into an oven and cured according to the conditions of 140 ℃/2h and 180 ℃/2 h. Finally obtaining the cured epoxy resin.
TABLE 2 Components and their amounts (parts by weight) in the preparation of cured epoxy resins
The results of the bending strength and notched impact strength tests on the cured epoxy resins obtained by curing the above-described examples and comparative examples are shown in Table 3.
TABLE 3 results of performance test of cured epoxy resins
The performance test results of the epoxy resin condensate obtained by each application example show that the prepared organosilicon-epoxy resin can effectively enhance the toughness and the bending strength of the epoxy resin at the same time, and particularly obviously improve the toughness.
In each embodiment, the change of the value a directly causes the change of the epoxy value of the organosilicon-epoxy resin, and further can influence the mechanical property of the cured epoxy resin, and in a reasonable range, the larger the value a is, the higher the epoxy value is, the higher the bending strength of the cured epoxy resin is, and the toughness is slightly reduced, and vice versa. The change of the value of d comes from the change of the dosage ratio between the MT resin containing vinyl and the siloxane ring body, the larger the mass ratio of the MT resin containing vinyl is, the smaller the value of d is, the smaller the weight average molecular weight of the organosilicon-epoxy resin is, the higher the bending strength of the cured epoxy resin is, and the toughness is slightly reduced, and vice versa. Therefore, the toughness and the bending strength of the obtained cured epoxy resin are comprehensively influenced by the values of a and d.
Compared with application example 3, the epoxy-silicone resin cured product obtained by applying the epoxy-silicone resin of comparative example 1 has poor flexural strength and toughness because no siloxane ring body is added in the preparation process.
In the preparation process of the epoxy-silicone resin of comparative example 2, if the value of a of the MT resin containing vinyl is greater than 50, the brittleness of the cured epoxy resin is increased due to too high crosslinking density.
In the preparation process of the epoxy-silicone resin in the comparative example 3, the dosage ratio between the MT resin containing vinyl and the siloxane ring body is too small, so that the value of d is too large, the softening point of the cured epoxy resin is reduced, and the bending strength is poor.
Application comparative example 4 the toughness of the cured epoxy resin was poor because no epoxy-silicone resin was used for the modification.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (16)
1. An epoxy-silicone resin characterized by having a chemical structural formula as shown in formula (I):
in the formula (I), the compound is shown in the specification,
R 1 is composed of
R 2 、R 3 、R 4 、R 5 、R 6 The same or different, each independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
the value of a is 4-50,
the value of b is 0 to 200,
the value of c is 20-200,
the value of d is 10-1000.
2. The epoxy-silicone resin according to claim 1, characterized in that, in formula (I),
the value of a is 5-20;
the value of b is 10-80;
c is 40-160;
d has a value of 50-500.
3. The epoxy-silicone resin according to claim 1, wherein the epoxy value of the epoxy-silicone resin is from 0.01 to 1.0;
the weight average molecular weight of the epoxy-organic silicon resin is 10000-100000.
4. The epoxy-silicone resin according to claim 3, wherein the epoxy value of the epoxy-silicone resin is 0.01 to 0.50;
the weight average molecular weight of the epoxy-organic silicon resin is 10000-50000.
5. A method of preparing the epoxy-silicone resin of any of claims 1-4, comprising the steps of:
i. taking MT resin containing vinyl and siloxane ring body as raw materials, and carrying out a balance reaction under the action of an acid catalyst to prepare MDT resin containing vinyl;
ii. And (e) contacting the MDT resin containing the vinyl group obtained in the step i with peroxide to carry out oxidation reaction to obtain the MDT organic silicon resin with the terminal group containing an epoxy group, namely the epoxy-organic silicon resin.
6. The method according to claim 5, wherein in step i, the vinyl-containing MT resin has a chemical formula shown in formula (II):
in the formula (I), the compound is shown in the specification,
R 1 ' is vinyl;
R 2 、R 3 、R 4 、R 5 the same or different, each independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
the value of a is 4-50;
the value of b is 0-200;
the value of c is 20-200.
7. The process according to claim 6, wherein in the formula (II),
the value of a is 5-20;
the value of b is 10-80;
the value of c is 40-160.
8. The method of claim 5, wherein the siloxane ring body is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltris (trifluoropropyl) cyclotrisiloxane, tetramethyltetrakis (trifluoropropyl) cyclotrisiloxane, and siloxane mixture ring body; and/or
The acidic catalyst is selected from one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid and acidic cationic resin; and/or
The peroxide is selected from one or more of hydrogen peroxide, peroxybenzoic acid, peroxyacetic acid and peroxyformic acid.
9. The method of claim 8, wherein the siloxane ring is selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, or a siloxane mixture ring; and/or
The acidic catalyst is selected from trifluoromethanesulfonic acid and/or acidic cationic resin; the acidic cation resin is polystyrene sulfonic acid resin; and/or
The peroxide is selected from one or more of peroxybenzoic acid, peroxyacetic acid and peroxyformic acid.
10. The method of claim 5, wherein the vinyl group-containing MDT resin has a chemical structure represented by formula (III):
in the formula (I), the compound is shown in the specification,
R 1 "is vinyl;
R 2 、R 3 、R 4 、R 5 、R 6 the same or different, each is independently selected from C1-C6 saturated alkyl, C2-C6 unsaturated alkyl, trifluoropropyl or C6-C12 aryl;
the value of a is 4-50;
the value of b is 0-200;
the value of c is 20-200;
the value of d is 10-1000.
11. The process according to claim 10, wherein, in the formula (III),
the value of a is 5-20;
the value of b is 10-80;
c is 40-160;
d has a value of 50-500.
12. The production method according to any one of claims 5 to 11, wherein in step i, the mass ratio of the vinyl-containing MT resin to the siloxane ring body is from 1; the dosage of the acidic catalyst is 0.01-5 wt% of the sum of the mass of the MT resin containing vinyl and the mass of the siloxane ring body;
the process conditions of the equilibrium reaction in the step i comprise: the reaction temperature is 50-90 ℃ and the reaction time is 4-48h.
13. The method according to claim 12, wherein in step i, the mass ratio of the vinyl-containing MT resin to the siloxane ring body is 1; the dosage of the acidic catalyst is 0.02 to 2 weight percent of the sum of the mass of the MT resin containing vinyl and the mass of the siloxane ring body;
the process conditions of the equilibrium reaction in the step i comprise: the reaction temperature is 50-90 ℃, and the reaction time is 4-24h.
14. The process according to any one of claims 5 to 11, wherein in step ii, the molar ratio of the peroxide to the vinyl groups in the vinyl group-containing MDT resin is from 1.1 to 10;
the process conditions of the oxidation reaction in the step ii comprise: the reaction temperature is-10 to 20 ℃; the reaction time is 12-48h.
15. The method according to claim 14, wherein in step ii, the molar ratio of the peroxide to the vinyl group in the vinyl group-containing MDT resin is 1.1 to 4;
the process conditions of the oxidation reaction in the step ii comprise: the reaction temperature is 0-10 ℃; the reaction time is 24-48h.
16. Use of the epoxy-silicone resin according to any one of claims 1 to 4 or the epoxy-silicone resin produced by the production process according to any one of claims 5 to 15 for the modification of epoxy resins.
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