CN105384912B - A kind of itaconic acid basic ring shape silicon skeletal epoxy resin, preparation method and its application of coating is prepared as matrix resin - Google Patents
A kind of itaconic acid basic ring shape silicon skeletal epoxy resin, preparation method and its application of coating is prepared as matrix resin Download PDFInfo
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Abstract
The application of coating is prepared the invention discloses a kind of itaconic acid basic ring shape silicon skeletal epoxy resin, preparation method and its as matrix resin, the epoxy resin is itaconic acid methylene (functional group of formula 2) monosubstituted or polysubstituted polynary cyclosiloxane;It is the addition compound product of itaconic acid diglycidyl ester, cyclosiloxane under platinum catalyst catalysis.The epoxy resin that the present invention is provided has excellent pliability;And will not be greatly lowered or even can keep the rigidity of material.The itaconic acid diglycidyl ester for using is bio-renewables, and product property can be regulated and controled by charge ratio.The epoxy resin provided using the present invention can prepare the coating of function admirable as substrate resin.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of itaconic acid basic ring shape silicon skeletal epoxy resin, preparation
Method and its application of coating is prepared as matrix resin.
Background technology
Epoxy resin has excellent mechanical performance, resistance to elevated temperatures, corrosion resistance, cementability and electrical insulating property, extensively
Automobile is applied to, is built, electronics, the field such as aviation.But form highly cross-linked three in the curing process due to epoxy resin
Dimension space network, molecule interchain lacks slip;Bond energy along with C-C keys, C-O keys is smaller, and surface can be higher;Cause
Solidified resin internal stress is larger, property is crisp, be also easy to produce crackle, so as to limit its application in some technical fields.In order to improve
The toughness and combination property of epoxy resin, further expand its application field, and domestic and foreign scholars have carried out numerous studies work.
Recent study it is more be polysiloxane toughening epoxy resin.Polysiloxanes has flexible and thermally-stabilised well
Property, numerous studies prove, polysiloxanes can with epoxy resin toughened, but not be really fine due to compatibility, and toughening effect is not
It is very notable.In order to improve the compatibility of polysiloxanes and epoxy resin, substantial amounts of research has been done both at home and abroad, including:Draw
Enter silane coupler, polysiloxane chain termination on polar group (such as:Hydroxyl, amino, epoxy radicals, carboxyl, isocyano etc.),
The segment of close epoxy resin is introduced in polysiloxane chain, and polysiloxanes is connected in epoxy resin by being chemically bonded.
The Chinese patent literature of Publication No. CN101787132A discloses a kind of preparation of organic-silicon hybridization epoxy resin
Method, is obtained by the silicone oil and epoxyalkylsilane coupling agent hydrolysis-condensation reaction of silicone-containing structure, is comprised the steps of:Will
The silicone oil of 100 mass parts silicone-containing structures, 50~500 mass parts epoxyalkylsilane coupling agents, 50~600 mass parts are organic
Solvent, 5~120 mass parts deionized waters and 0.5~6 mass parts of catalyst are well mixed, and then react 2~8 in 50~100 DEG C
Hour, except the organic solvent and deionized water of dereaction, obtain organic-silicon hybridization epoxy resin.The method preparation process is answered
It is miscellaneous, substantial amounts of silane coupler, and the hybrid meeting residual hydroxyl that hydrolytie polycondensation is obtained are make use of, easily it is cross-linked with each other.
It is solid altogether that the Chinese patent literature of Publication No. CN102977554A discloses a kind of LED encapsulation epoxy/organosilicon
Change composite and preparation method thereof, including following components by weight:The hydrogeneous cyclosiloxane 50~500 of epoxy radicals
Part, 0~10 part of antioxidant, 0~10 part of ultra-violet absorber, 0~15 part of light scattering agent, 100 parts of phenyl vinyl polysiloxane, ring
0.01~1.0 part of 0.5~15.0 part of oxygen curing agent and Si―H addition reaction curing catalysts.
The Chinese patent literature of Publication No. CN104356361A discloses a kind of abundant clothing health of utilization bio-based source
The bio-based epoxies such as sour 2-glycidyl ester, maleic acid 2-glycidyl ester, fumaroyl 2-glycidyl ester with
End hydrogen siloxane hydrosilylation, the bio-based silicon skeletal epoxy resin for obtaining.The process employs the chain end poly- silica of hydrogen
Resin, cost is very high, and prepare modified epoxy the toughness particularly length to chain such as heat resistance, intensity, hardness
It is short very sensitive.
The existing most synthetic method of modified epoxy resin is complicated, and the raw material of use is unable to sustainable development.And using existing
The intensity and toughness aspect for having the coating of modified epoxy preparation are difficult while reaching preferable effect.
The content of the invention
The invention provides a kind of polyfunctionality ring-type silicon skeletal epoxy resin based on itaconic acid, its middle ring silicon skeleton knot
Structure can assign the polyfunctionality of the excellent toughness of epoxy resin cured product and modified epoxy;So that epoxy resin is solid
Compound has excellent heat resistance.
A kind of itaconic acid basic ring shape silicon skeletal epoxy resin, is one or more of the structural compounds of formula 1:
R is-H or the functional group of formula 2;
N is the integer of 3-8;In wherein n R, at least one is the functional group of formula 2.
The present invention is monosubstituted using itaconic acid methylene (functional group of formula 2) or hydrogen of Si-H of polysubstituted cyclosiloxane, from
And ring-type silicon skeleton is embedded in epoxy molecule.Can introduce more epoxy functionalized in the epoxy molecule structure
Group;And there is Si-O-Si flexible chains in molecule, when by external impacts, the energy that will can be absorbed is turned by molecular motion
Change heat energy into;Help to increase the toughness of the epoxy resin.The silicon skeleton structure of the epoxy resin is cyclic structure, is not only had
There is the excellent flexibility of general organosilicon, simultaneously because cyclic molecules volume ratio is larger, whole molecule segment is moved and is had
There is certain inhibition, it is possible to resolve existing epoxy resin may be greatly lowered that epoxy resin is rigid to ask in toughing ways
Topic.
By formula 1, the epoxy resin (the itaconic acid basic ring shape silicon skeletal epoxy resin of present invention offer is provided)
Ring-type silicon skeleton for it is hexa-atomic, eight yuan, ten yuan, ten binary, ten quaternarys or sixteen-ring siloxane structure.In cyclosiloxane structure,
Each silicon atom contains a methyl;And at least one silicon atom is replaced by the functional group of formula 2, other silicon atoms by hydrogen or
The functional group of formula 2 replaces.
Preferably, the ring-type silicon skeleton of the epoxy resin is hexa-atomic or octatomic ring siloxane structure.
Hexa-atomic or octatomic ring shape silicon skeletal epoxy resin structure size is moderate, the space bit of the functional group of intermolecular formula 2
Resistance is little, and the functional group of formula 2 substitution number Modulatory character is good, and the range of application of the based epoxy resin is wider.
Further preferably, described itaconic acid basic ring shape silicon skeletal epoxy resin is one kind or several of the structural compounds of formula 3
Kind:
R1、R2、R3、R4It is-H or the functional group of formula 2;Wherein, R1、R2、R3、R4At least one is the functional group of formula 2.
The epoxy resin structural stabilization of the octatomic ring siloxane structure, preparing raw material is simple and easy to get, can be with molecular structure
The functional groups of 2-8 Ge Shi 2 are loaded, the epoxy resin has excellent performance in flexibility.
Still more preferably, in the structural compounds of formula 3, R1、R2、R3、R4It is the functional group of formula 2.
The epoxy functionalities of the epoxy resin are more, excellent self toughening performance not only shown after solidification, while having
Excellent heat, mechanical property.
It is present invention additionally comprises a kind of preparation method of above-mentioned itaconic acid Quito degree of functionality silicon skeletal epoxy resin including following
Step:
By the itaconic acid diglycidyl ester of 100 mass parts, the organic solvent of 20~500 mass parts, 25~100 mass parts
Cyclosiloxane and relative to itaconic acid diglycidyl ester and the platinum catalyst of the gross mass of cyclosiloxane, 60~140 DEG C plus
The lower reaction of heat 0.5~50 hour, the itaconic acid basic ring shape silicon skeletal epoxy resin is obtained after removing solvent through revolving.
It is anti-that itaconic acid diglycidyl ester carries out addition under the catalysis of the platinum catalyst with the Si -- H bond of cyclosiloxane
Should, due to the effect of steric hindrance, the addition compound product of generation is mainly the mixture of the structural compounds of formula 1.In the present invention, can be with
Regulate and control polyfunctional group (functional group of formula 2) by regulating and controlling itaconic acid diglycidyl ester relative to the ingredient proportion of cyclosiloxane to take
The product assay in generation, such as increases ingredient proportion of the itaconic acid diglycidyl ester relative to cyclosiloxane, prepared asphalt mixtures modified by epoxy resin
The content of the epoxy resin of the polyfunctional group substitution of fat can be higher.Therefore, it can control product by regulating and controlling the proportioning of material
Performance, so as to meet the preparation demand of the epoxy resin of industrial different demands.
In the present invention, cyclosiloxane provides multiple reaction sites, increased the diversity of product.
In addition reaction, the mass fraction of catalyst is the total matter relative to itaconic acid diglycidyl ester and cyclosiloxane
For amount.
Under the reaction temperature, the high catalytic efficiency of the catalyst of the inventory, reaction can be complete within a short period of time
Into.Under the reaction system, by extending the reaction time, the ratio of polyfunctional group substitution product can be increased, the ring for thus preparing
The toughness of oxygen tree fat can be preferable, thus, also can be in the performance of regulation product lower to a certain degree by regulating and controlling the reaction time.
Preferably, described platinum catalyst is chloroplatinic acid or 1,3- divinyl -1,1,3,3- tetramethyl disiloxane
Platinum (0).
Preferably, described cyclosiloxane is the structural compounds of formula 4,
Wherein, m is the integer of 3-8.
Described cyclosiloxane for it is hexa-atomic, eight yuan, ten yuan, ten binary, ten quaternarys or sixteen-ring siloxanes, and each silicon
A methyl and a hydrogen are all connected with atom respectively.Wherein, Si-H is carried out under catalyst with itaconic acid diglycidyl ester
Addition reaction.
Further preferably, described cyclosiloxane is the hydrogen cyclotrisiloxane of 1,3,5- trimethyl three or 1,3,5,7- tetramethyls
Tetrahydrochysene cyclotetrasiloxane.
Still more preferably, described cyclosiloxane is 1,3,5,7- tetramethyl tetrahydrochysene cyclotetrasiloxanes.
The itaconic acid diglycidyl ester structural formula such as formula 5:
, using reproducible itaconic acid diglycidyl ester as epoxy donor, the epoxy donor is in the solvent for the present invention
Lower and cyclosiloxane has compatibility higher, the high conversion rate of raw material.During addition reaction, in the space bit of cyclosiloxane
The product (anti-Markonikov's rule product) of the structure of formula 1 is mainly generated under resistance effect, this kind of product imparts the good rotation of Si-C keys
Performance, effectively reduces the steric hindrance between the functional group of adjacent formula 2 of prepared product.In the synthesis of the epoxy resin
During, the introducing quantity (being equal to the introducing quantity of epoxy radicals) of the functional group of formula 2 will not be limited because of steric hindrance
System, such that it is able to the performance of manual control product, contributes to the industrial applicability of the epoxy resin prepared by expanding.
Described organic solvent is tetrahydrofuran, dioxane, butyl acetate, toluene, benzene, dimethylbenzene, N, N '-dimethyl
One or more in formamide, dimethyl sulfoxide (DMSO).
Organic solvent plays a part of dissolving and diluting reaction thing, and above-mentioned non-protonic solvent contributes to entering for addition reaction
OK, and moderate boiling point, the solvent recovery of post processing is conducive to apply mechanically.
Present invention additionally comprises a kind of using described itaconic acid Quito degree of functionality silicon skeletal epoxy resin as matrix resin system
The application of standby coating.
The preparation field of coating is applied the invention to, helps to prepare painting the features such as with high intensity, high tenacity
Material.
The itaconic acid basic ring shape silicon skeletal epoxy resin of above-mentioned synthesis is heating and curing with the curing agent of commercialization and is formed.
Preferably, the coating includes that weight ratio is 1:The itaconic acid basic ring shape silicon skeleton asphalt mixtures modified by epoxy resin of 0.1-0.4
Fat and curing agent.
Above-mentioned curing agent is existing commercial Common curing agents, preferably, described curing agent is IPDA, DDM, polyethers
Amine, polyamide.
In the present invention, the itaconic acid basic ring shape silicon skeletal epoxy resin of the structure of formula 1 can be used to prepare thermosetting resin;Ring-type
The presence of silicon skeleton so that thermosetting resin possesses self toughening characteristic, being also used as flexibilizer additive increases other asphalt mixtures modified by epoxy resin
The toughness of fat.At least contain 2 epoxide groups in the epoxy resin structural for being provided in the present invention, at most up to 16, together
When due to the big molecular volume of ring-type silicon skeleton, can to a certain extent hinder the motion of molecule segment, therefore after solidification being made
Solidfied material (prepared coating) is heat-resist, and being added in other epoxy-resin systems as toughener will not equally reduce body
The heat resistance of system.
The epoxy resin that the present invention is provided has excellent pliability;And will not be greatly lowered or even material can be kept
Rigidity.The itaconic acid diglycidyl ester for using is bio-renewables, and product property can be regulated and controled by charge ratio.
The epoxy resin provided using the present invention can prepare the coating of function admirable as substrate resin.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of itaconic acid basic ring shape silicon skeletal epoxy resin prepared by embodiment 1.
Specific embodiment
Following examples press the implementation of aforesaid operations method:
Embodiment 1
By itaconic acid diglycidyl ester 10g, dioxane 2g, 1,3,5,7- tetramethyl tetrahydrochysene cyclotetrasiloxane 2.5g and
1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.0001g, in 100 DEG C of conventional heatings
Reaction 20 hours, itaconic acid basic ring shape silicon skeletal epoxy resin is obtained after removing solvent through vacuum distillation.According to the itaconic acid base
Polyfunctionality silicon skeletal epoxy resin1H NMR spectras as shown in figure 1,1There is 2.5-3.18ppm in H NMR spectras and represent ring
The peak of oxygen groups, 1.25ppm or so represent Si―H addition reaction is formed and Si-CH2- on hydrogen, add other peaks and itaconic acid base
The H proton displacements of polyfunctionality silicon skeletal epoxy resin are consistent, while it is 0.66 to measure epoxide number using hydrochloric acid-acetone method.Can
The material that proof is obtained is the itaconic acid basic ring shape silicon skeletal epoxy resin shown in Formulas I.
By the epoxy resin 10g of above-mentioned synthesis, and 4,4 '-diaminodiphenyl-methane 3.3g is well mixed, first at 80 DEG C
Solidification 3 hours, then solidifies 2 hours at 150 DEG C, and last 180 DEG C solidify 2 hours, obtain epoxy resin cured product, solidfied material
Impact strength is 64kJ/m2, glass transition temperature is 181 DEG C, and tensile strength is 97MPa.Relative to existing publication
The epoxy resin (epoxide number is 0.68) of bio-based straight chain silicon skeleton prepared by (A of CN 104356361) embodiment 5, identical
Curing agent and condition of cure under the solidfied material for preparing, performance is more excellent.
Embodiment 2
By itaconic acid diglycidyl ester 10g, tetrahydrofuran 6g, 1,3,5,7- tetramethyl tetrahydrochysene cyclotetrasiloxane 5g and 1,
3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.001g, in 60 DEG C of conventional heating reactions
50 hours, itaconic acid basic ring shape silicon skeletal epoxy resin is obtained after removing solvent through vacuum distillation.Measured using hydrochloric acid-acetone method
Epoxide number is 0.55.
By the epoxy resin 10g of above-mentioned synthesis, and 4,4 '-diaminodiphenyl-methane 2.7g is well mixed, first at 80 DEG C
Solidification 3 hours, then solidifies 2 hours at 150 DEG C, and last 180 DEG C solidify 2 hours, obtain epoxy resin cured product, solidfied material
Impact strength is 70kJ/m2, glass transition temperature is 175 DEG C, and tensile strength is 90MPa.
Embodiment 3
By itaconic acid diglycidyl ester 10g, dimethyl sulfoxide (DMSO) 20g, dimethylbenzene 30g, 1,3,5,7- tetramethyl tetrahydrochysene ring
Tetrasiloxane 10g and chloroplatinic acid 0.01g, reacts 0.5 hour in 140 DEG C of conventional heatings, is obtained after removing solvent through vacuum distillation
Itaconic acid basic ring shape silicon skeletal epoxy resin.It is 0.41 to measure epoxide number using hydrochloric acid-acetone method.
By the epoxy resin 10g of above-mentioned synthesis, and 4,4 '-diaminodiphenyl-methane 2g is well mixed, first solid at 80 DEG C
Change 3 hours, then solidify 2 hours at 150 DEG C, last 180 DEG C solidify 2 hours, obtain epoxy resin cured product, solidfied material it is anti-
Impact strength is 76kJ/m2, glass transition temperature is 166 DEG C, and tensile strength is 85MPa.
Embodiment 4
By itaconic acid diglycidyl ester 10g, ethyl acetate 6g, the silica of benzene 6g, 1,3,5,7,9- pentamethyl pentahydro- ring five
Alkane 4g and chloroplatinic acid 0.003g, is reacted 40 hours in 80 DEG C of conventional heatings, and itaconic acid base is obtained after removing solvent through vacuum distillation
Ring-type silicon skeletal epoxy resin.It is 0.58 to measure epoxide number using hydrochloric acid-acetone method.
By the epoxy resin 10g of above-mentioned synthesis, and 4,4 '-diaminodiphenyl-methane 2.9g is well mixed, first at 80 DEG C
Solidification 3 hours, then solidifies 2 hours at 150 DEG C, and last 180 DEG C solidify 2 hours, obtain epoxy resin cured product, solidfied material
Impact strength is 72kJ/m2, glass transition temperature is 177 DEG C, and tensile strength is 92MPa.
Embodiment 5
By itaconic acid diglycidyl ester 10g, 10g toluene, 20g N,N-dimethylformamides, the hydrogen of 1,3,5- trimethyls three
Cyclotrisiloxane 7.5g and 1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.006g,
Reacted 10 hours in 120 DEG C of conventional heatings, itaconic acid basic ring shape silicon skeletal epoxy resin is obtained after removing solvent through vacuum distillation.
It is 0.48 to measure epoxide number using hydrochloric acid-acetone method.
By the epoxy resin 10g of above-mentioned synthesis, and 4,4 '-diaminodiphenyl-methane 2g is well mixed, first solid at 80 DEG C
Change 3 hours, then solidify 2 hours at 150 DEG C, last 180 DEG C solidify 2 hours, obtain epoxy resin cured product, solidfied material it is anti-
Impact strength is 72kJ/m2, glass transition temperature is 169 DEG C, and tensile strength is 88MPa.
Application examples 1
Itaconic acid Quito degree of functionality silicon skeletal epoxy resin (epoxide number 0.66) prepared by 3g embodiments 1 and 0.84g are different
Isophoronediamine is well mixed, and it is applied on clean black sheet iron with spreader, first solidifies 3 hours, then 130 at 80 DEG C
DEG C solidification 2 hours, finally 180 DEG C solidify 3 hours, 30 μm or so of the coating thickness for obtaining is measured instead according to ASTM D 2794
Face impact strength is more than 172, measures pencil hardness 5H, ASTM D 4366 according to ASTM D 3363 and measuresPendulum-rocker hardness
210s。
Comparative example 1
The bio-based straight chain silicon skeleton asphalt mixtures modified by epoxy resin that 3g is prepared by existing publication (A of CN 104356361) embodiment 5
Fat (epoxide number is 0.68), and 0.86g IPDs are well mixed, first solidify at 80 DEG C 3 hours, then 130 DEG C of solidifications 2
Hour, finally solidify 3 hours at 180 DEG C, 30 μm or so of the coating thickness for obtaining, reverse side impact is measured according to ASTM D 2794
Intensity 160, measures pencil hardness 4H, ASTM D 4366 and measures according to ASTM D 3363Pendulum-rocker hardness 185s.
Claims (10)
1. a kind of itaconic acid basic ring shape silicon skeletal epoxy resin, it is characterised in that for the structural compounds of formula 1 one or more:
R is-H or the functional group of formula 2;
N is the integer of 3-8;In wherein n R, at least one is the functional group of formula 2.
2. itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 1, it is characterised in that be the structure chemical combination of formula 3
One or more of thing:
R1、R2、R3、R4It is-H or the functional group of formula 2;Wherein, R1、R2、R3、R4At least one is the functional group of formula 2.
3. itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 2, it is characterised in that the structural compounds of formula 3
In, R1、R2、R3、R4It is the functional group of formula 2.
4. the preparation method of the itaconic acid basic ring shape silicon skeletal epoxy resin according to claim any one of 1-3, its feature
It is to comprise the following steps:
By the itaconic acid diglycidyl ester of 100 mass parts, the organic solvent of 20~500 mass parts, 25~100 mass parts ring
The platinum catalyst of siloxanes and 0.001~0.1 mass parts, reaction 0.5~50 hour, removes through revolving under 60~140 DEG C of heating
The itaconic acid basic ring shape silicon skeletal epoxy resin is obtained after solvent.
5. the preparation method of itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 4, it is characterised in that described
Platinum catalyst be chloroplatinic acid or 1,3- divinyl -1,1,3,3- tetramethyl disiloxanes platinum (0).
6. the preparation method of itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 4, it is characterised in that described
Organic solvent be tetrahydrofuran, dioxane, butyl acetate, toluene, benzene, dimethylbenzene, N,N-dimethylformamide, dimethyl
One or more in sulfoxide.
7. the preparation method of itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 4, it is characterised in that described
Cyclosiloxane be the structural compounds of formula 4,
Wherein, m is the integer of 3-8.
8. the preparation method of itaconic acid basic ring shape silicon skeletal epoxy resin according to claim 7, it is characterised in that described
Cyclosiloxane be 1,3,5,7- tetramethyl tetrahydrochysene cyclotetrasiloxanes.
9. the itaconic acid basic ring shape silicon skeletal epoxy resin described in any one according to claim 1-3 is prepared as matrix resin
The application of coating.
10. application according to claim 9, it is characterised in that comprise the following steps:The coating includes that weight ratio is 1:
The itaconic acid basic ring shape silicon skeletal epoxy resin and curing agent of 0.1-0.4.
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CN101223181A (en) * | 2006-03-02 | 2008-07-16 | 设计分子有限公司 | Adhesive composition containing cyclosiloxane |
CN103781814A (en) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | Photocurable resin composition and novel siloxane compound |
CN104356361A (en) * | 2014-10-15 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Bio-based multifunctional silicon-framework epoxy resin as well as preparing method and application thereof |
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CN101223181A (en) * | 2006-03-02 | 2008-07-16 | 设计分子有限公司 | Adhesive composition containing cyclosiloxane |
CN103781814A (en) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | Photocurable resin composition and novel siloxane compound |
CN104356361A (en) * | 2014-10-15 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Bio-based multifunctional silicon-framework epoxy resin as well as preparing method and application thereof |
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