CN109384905A - A kind of over-expense SiClx skeleton bisphenol-a derivative epoxy acrylic resin and preparation method - Google Patents
A kind of over-expense SiClx skeleton bisphenol-a derivative epoxy acrylic resin and preparation method Download PDFInfo
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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Abstract
The present invention relates to it is a kind of overspend SiClx skeleton bisphenol-a derivative epoxy acrylic resin preparation method, including (1) with phenol be the first monomer, acetophenone is second comonomer, under the conditions of certain catalyst, temperature, prepares bisphenol-a derivative Ph-BPA；(2) phenyltrimethoxysila,e is hydrolyzed, three silanol of phenyl is obtained；(3) be the first monomer with bisphenol-a derivative Ph-BPA, phenyl silanetriol is second comonomer, and epoxychloropropane is Third monomer, in certain catalyst, at a temperature of synthesis of super branched silicon skeleton bisphenol-a derivative epoxy resin；(4) gained over-expense SiClx skeleton bisphenol-a derivative resin is the first monomer, and acrylic acid is second comonomer, under the conditions of certain catalyst and polymerization inhibitor temperature, synthesis of super branched silicon skeleton bisphenol-a derivative epoxy acrylate.Synthesized over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate good mechanical properties, adhesive force is strong, has extremely excellent heat resistance.
Description
Technical field
The present invention relates to a kind of over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate, in particular to preparation method,
Belong to coating, adhesive field.
Background technique
Epoxy resin makes it have good mechanical property, chemical corrosion resistance, electricity is absolutely due to its unique molecular structure
Edge, caking property.Solidify that after-contraction is small, and processing performance is good, cheap simultaneously.But after solidifying, poor toughness, impact resistance
It is insufficient.Epoxy resin is widely used in coating, adhesive, chemical preservation, machine-building, the multiple fields such as plastic pattern at present.
Aqueous epoxy resins refer to the decentralized medium being dispersed in epoxy resin in the form of particle, drop or colloid using water as continuous phase
In be made into stable dispersion.Meet environment friendly chemical requirements, does not contain volatile organic solvent (VOC).
Dissaving polymer is by the irregular macromolecular of highly branched but structure that branching primitive forms and three-dimensional dendron
Shaped polymer.The unique physics of dissaving polymer and chemical property, hydrodynamic performance, excellent viscosity behavior, in electronics
There is application well to fields such as coating, adhesives, dissaving polymer, can be significantly due to containing a large amount of active end group
Improve reactivity.
The method elder generation synthesis of super branched silicon skeleton bisphenol-a derivative epoxy resin of this patent A2+B3 polycondensation, then use propylene
Acid reacts synthesis of super branched silicon skeleton bisphenol-a derivative epoxy with the over-expense SiClx skeleton bisphenol-a derivative epoxy resin of synthesis
Acrylate.
Summary of the invention
It is of the invention crucial there is provided a kind of over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate preparation method,
The over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate being synthesized has low viscosity, excellent mechanical property, attachment
Power greatly improves the heat resistance of epoxy acrylic.
Overspend SiClx skeleton bisphenol-a derivative epoxy acrylate specific the preparation method is as follows:
(a) by the certain acetic acid aqueous solution of mass fraction, be slowly added dropwise, in a certain amount of phenyltrimethoxysila,e, acetic acid water
Mixture is cooled to certain temperature for 1.8-2.5:1. and stirred by solution and phenyltrimethoxysila,e mass ratio, then, white
Crystal is slowly precipitated out, and liquid phase becomes homogeneously, and mixture is cooled to -20 DEG C of holding half an hour, is then filtered, by what is waited until
White crystal distilled water, dry overnight at room temperature, obtains three silanol of product phenyl in a vacuum drying oven；
Reaction temperature: 5-10 degree；
Acetic acid aqueous solution mass fraction is 0.5%；
Reaction time: 4-8 hours；
(b) with phenol for the first monomer, sulfuric acid and thioglycolic acid are catalyst.Second comonomer acetophenone is added, first is single
Body and second comonomer molar ratio are 4-3:1, and sulfuric acid and second comonomer molar ratio are 6:1, thioglycolic acid 100-250mg.Slowly
Slowly it instills dropwise.Reaction is overnight.Rufous thick solid is obtained, is successively constantly filtered, is obtained with boiling water and methylene chloride respectively
To white solid powder, synthesis of bisphenol A derivative Ph-BPA；
Reaction temperature: 55 degree；
(c) with three silanol of phenyl (Phenylsilanetriol) for the first monomer, bisphenol-a derivative Ph-BPA is second single
Body, epoxychloropropane is Third monomer, the first monomer and second comonomer and Third monomer molar ratio in 1:5-10:35-50, in nitrogen
Gas shielded reaction condition under catalyst, generates over-expense SiClx skeleton bisphenol-a derivative epoxy resin；
Reaction temperature: 110 degree；
Reaction time: 4-6 hours；
Catalyst: 5mol/l sodium hydrate aqueous solution；
(d) to overspend SiClx skeleton bisphenol-a derivative epoxy resin for the first monomer, acrylic acid is second comonomer, the first monomer
Epoxy group and second comonomer carboxyl molar ratio be 2:1.Under conditions of certain catalyst and polymerization inhibitor is added, Mei Geban
Hour measurement reaction acid value, until reaction acid value drops to 0 KOH/g.Stop reaction.It is down to room temperature, is extracted with chloroform and a large amount of water
It takes, separates organic phase, be spin-dried for, obtain over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate；
Catalyst: tetrabutylammonium bromide, n,N-Dimethylaniline.Catalyst amount 1%-3%；
Polymerization inhibitor: hydroquinone, p methoxy phenol.Polymerization inhibitor dosage 0.1%-1%；
Reaction dissolvent: DMF；
Reaction temperature: 90-100 degree.
Detailed description of the invention
Fig. 1 is the schematic arrangement for overspending SiClx skeleton bisphenol-a derivative epoxy resin.
Fig. 2 is the schematic arrangement for overspending SiClx skeleton bisphenol-a derivative epoxy acrylate.
The 1H-NMR spectrogram of Ph-BPA synthesized by Fig. 3 embodiment 1.
The 13C-NMR spectrogram of Ph-BPA synthesized by Fig. 4 embodiment 1.
The infrared spectroscopy of the over-expense of sample prepared by Fig. 5 embodiment 1 SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA
Figure.
Sample prepared by Fig. 6 embodiment 1 overspends the 1H-NMR spectrum of SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA
Figure.
Sample prepared by Fig. 7 embodiment 1 overspends the 13C-NMR spectrum of SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA
Figure.
The infrared spectrogram of the over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate of sample prepared by Fig. 8 embodiment 1.
The 1H-NMR spectrogram of the over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate of sample prepared by Fig. 9 embodiment 1.
Sample prepared by Figure 10 embodiment 1 overspends the 13C-NMR spectrum of SiClx skeleton bisphenol-a derivative epoxy acrylate
Figure.
Figure 11 synthetic example 1-5 resin coating film mechanical property.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these implementation columns are merely to illustrate this hair
It is bright rather than limit the scope of the invention.
Embodiment 1
(1) 0.3mol phenol, 46ml the synthesis of bisphenol-a derivative Ph-BPA: are added in 250ml three neck round bottom flask
The sulfuric acid solution of 1.3mol/L and the thioglycolic acid of 220mg.In thermostat water bath, 40 degree of lower stirring half an hour, keep phenol complete
Fully dissolved.Temperature is adjusted to 55 DEG C, and the acetophenone of 0.1mol is added in constant pressure funnel, slowly instills dropwise.Reaction is overnight.
Rufous thick solid is obtained, is successively constantly filtered with boiling water and methylene chloride respectively, obtains white solid powder.Ph-BPA
Nuclear magnetic spectrogram see Fig. 3,4.1H-NMR (400 MHz,DMSO-d6,σ/ppm): 1.985Hd (s, 3H, Ha),9.273
(s, 2H, Ha),6.614(d, 1H, He), 6.797(d, 1H, Hf), 6.997(d, 1H, Hg),7.152(t, 4H,
Hc), 7.237 (t, 4H, Hb). 13C-NMR (400 MHz,DMSO-d6, d, ppm): 30.77 (C2), 51.10
(C1), 114.93 (C9),126.06 (C6), 128.17(C5), 128.69 (C4), 129.67 (C8),139.96
(C3), 150.34 (C7), 155.65 (C10)；
(2) synthesis of Phenylsilanetriol: in two mouthfuls of round-bottomed flasks be added phenyltrimethoxysila,e (20g,
0.1mol), then 10.9g acetic acid aqueous solution (0.5wt%) is slowly added dropwise in reaction flask, and mixture is cooled to 10 DEG C
Stirring 4 hours, then, white crystal is slowly precipitated out, and liquid phase becomes homogeneously, and it is small that mixture is cooled to -20 DEG C of holdings 0.5
When, it then filters, the white crystal distilled water that will be waited until, dry overnight at room temperature, obtains product phenyl in a vacuum drying oven
Silantriol；
(3) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy resin: adding under protection of argon gas into three neck round bottom flask
Enter three silanol of 0.5g phenyl, 5g bisphenol-a derivative Ph-BPA, 11.60g epoxychloropropane, is under stiring slowly increased to temperature
110℃.The sodium hydroxide solution that 12.5ml specification is 5mol/L is slowly dropped by constant pressure funnel, continues to stir anti-after 4h
It should stop.At 100 ~ 200 DEG C, 2kPa ~ 50kPa, vacuum distillation removes excessive epoxychloropropane.Then reactant is poured into
In separatory funnel, water-yielding stratum is separated, organic layer is left, is then washed 2-3 times with 15% sodium chloride solution, finally, hyperbranched organic
Epoxy silicone is dry under 80 DEG C of vacuum conditions to obtain over-expense SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA for 24 hours,
Epoxide number 0.247mol/100g is measured according to GB hydrochloric acid acetone method.Its infrared spectrogram such as Fig. 5,2918 ~ 2979cm-1,
3059cm-1 is aliphatic and the telescope features peak of aromatic series-C-H respectively；3440cm-1 is the stretching vibration peak of-OH,
1605cm-1,1503cm-1,1453cm-1 are phenyl ring carbon skeleton characteristic absorption peak, and 1238cm-1 is aromatic series ehter bond characteristic absorption
Peak, 1121cm-1,1184cm-1 are the characteristic absorption peak of Si-O key, and 1034cm-1 is the characteristic absorption peak of aliphatic ehter bond.
919cm-1,830cm-1 is the characteristic absorption peak of epoxy group.Nuclear magnetic spectrogram such as Fig. 6,7；
(4) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy acrylate: in three neck round bottom flask, the super of 6g is added
The p methoxy phenol of branch SiClx skeleton bisphenol-a derivative epoxy resin and 60mg, 50mlDMF work as reaction dissolvent.In temperature to 70
Under degree, after stirring half an hour, 95 degree is warming up to, the tetrabutylammonium bromide of 100mg is added, 1.067ml acrylic acid is slowly added dropwise, often
And a half hours measurement reaction acid value, until reaction acid value drop to 0 KOH/g.Stop reaction.It is down to room temperature, with chloroform and largely
Water extraction, separates organic phase, is spin-dried for, and obtains over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.Its infrared spectroscopy Fig. 8.
Strong at 3432cm-1, broad peak is hydroxyl characteristic absorption peak, and 1723cm-1,1242cm-1 and 1030cm-1 are ester band feature peak,
3028cm-1And 1635cm-1Place proves there is carbon-carbon double bond, and is conjugated with ester.It is derivative that proof synthesizes over-expense SiClx skeleton bisphenol-A
Object epoxy acrylate.Nuclear magnetic spectrogram such as Fig. 9,10.
Embodiment 2
(1) 0.6mol phenol, 82ml the synthesis of bisphenol-a derivative Ph-BPA: are added in 250ml three neck round bottom flask
The sulfuric acid solution of 1.3mol/L and the thioglycolic acid of 400mg.In thermostat water bath, 40 degree of lower stirring half an hour, keep phenol complete
Fully dissolved.Temperature is adjusted to 55 DEG C, and the acetophenone of 0.2mol is added in constant pressure funnel, slowly instills dropwise.Reaction is overnight.
Rufous thick solid is obtained, is successively constantly filtered with boiling water and methylene chloride respectively, obtains white solid powder；
(2) synthesis of Phenylsilanetriol: in two mouthfuls of round-bottomed flasks be added phenyltrimethoxysila,e (40g,
0.2mol), then 35g acetic acid aqueous solution (0.5wt%) is slowly added dropwise in reaction flask, and mixture is cooled to 6 DEG C of stirrings
4 hours, then, white crystal was slowly precipitated out, and liquid phase becomes homogeneously, mixture being cooled to -20 DEG C and is kept for 0.5 hour,
Then it filters, the white crystal distilled water that will be waited until, dry overnight at room temperature, obtains product phenyl silane in a vacuum drying oven
Triol；
(3) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy resin: adding under protection of argon gas into three neck round bottom flask
Enter three silanol of 1.0g phenyl, 5g bisphenol-a derivative Ph-BPA, 11.60g epoxychloropropane, is under stiring slowly increased to temperature
110℃.The sodium hydroxide solution that 12.5ml specification is 5mol/L is slowly dropped by constant pressure funnel, continues to stir anti-after 5h
It should stop.Vacuum distillation removes excessive epoxychloropropane.Then reactant is poured into separatory funnel, separates water-yielding stratum,
Organic layer is left, is then washed 2-3 times with 15% sodium chloride solution, finally, hyperbranched silicone epoxy resin is in 80 DEG C of vacuum items
It is dry under part to obtain over-expense SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA for 24 hours, ring is measured according to GB hydrochloric acid acetone method
Oxygen value 0.343mol/100g；
(4) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy acrylate: in three neck round bottom flask, being added 10g's
Overspend the p methoxy phenol of SiClx skeleton bisphenol-a derivative epoxy resin and 100mg, 50mlDMF works as reaction dissolvent.In temperature
To under 70 degree, after stirring half an hour, 100 degree is warming up to, the tetrabutylammonium bromide of 120mg is added, 1.23g propylene is slowly added dropwise
Acid value is reacted in acid, measurement in every and a half hours, until reaction acid value drops to 0 KOH/g.Stop reaction.Be down to room temperature, with chloroform and
A large amount of water extraction, separates organic phase, is spin-dried for, and obtains over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.
Embodiment 3
(1) 1.2mol phenol, 184ml the synthesis of bisphenol-a derivative Ph-BPA: are added in 1000ml three neck round bottom flask
The sulfuric acid solution of 1.3mol/L and the thioglycolic acid of 500mg.In thermostat water bath, 40 degree of lower stirring half an hour, keep phenol complete
Fully dissolved.Temperature is adjusted to 55 DEG C, and the acetophenone of 0.4mol is added in constant pressure funnel, slowly instills dropwise.Reaction is overnight.
Rufous thick solid is obtained, is successively constantly filtered with boiling water and methylene chloride respectively, obtains white solid powder；
(2) synthesis of Phenylsilanetriol: in two mouthfuls of round-bottomed flasks be added phenyltrimethoxysila,e (40g,
0.2mol), then 22g acetic acid aqueous solution (0.5wt%) is slowly added dropwise in reaction flask, and mixture is cooled to 6 DEG C of stirrings
8 hours, then, white crystal was slowly precipitated out, and liquid phase becomes homogeneously, mixture being cooled to -20 DEG C and is kept for 0.5 hour,
Then it filters, the white crystal distilled water that will be waited until, dry overnight at room temperature, obtains product phenyl silane in a vacuum drying oven
Triol；
(3) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy resin: adding under protection of argon gas into three neck round bottom flask
Enter three silanol of 1.5g phenyl, 5g bisphenol-a derivative Ph-BPA, 11.60g epoxychloropropane, is under stiring slowly increased to temperature
110℃.The sodium hydroxide solution that 12.5ml specification is 5mol/L is slowly dropped by constant pressure funnel, continues to stir anti-after 6h
It should stop.Vacuum distillation removes excessive epoxychloropropane.Then reactant is poured into separatory funnel, separates water-yielding stratum,
Organic layer is left, is then washed 2-3 times with 15% sodium chloride solution, finally, hyperbranched silicone epoxy resin is in 80 DEG C of vacuum items
It is dry under part to obtain over-expense SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA for 24 hours, ring is measured according to GB hydrochloric acid acetone method
Oxygen value 0.363mol/100g；
(4) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy acrylate: in three neck round bottom flask, being added 10g's
Overspend the p methoxy phenol of SiClx skeleton bisphenol-a derivative epoxy resin and 100mg, 50mlDMF works as reaction dissolvent.In temperature
To under 70 degree, after stirring half an hour, 90 degree is warming up to, the tetrabutylammonium bromide of 120mg is added, 1.3g acrylic acid is slowly added dropwise,
Acid value is reacted in measurement in every and a half hours, until reaction acid value drops to 0 KOH/g.Stop reaction.It is down to room temperature, with chloroform and largely
Water extraction, separate organic phase, be spin-dried for, obtain over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.
Embodiment 4
(1) 0.9mol phenol, 138ml the synthesis of bisphenol-a derivative Ph-BPA: are added in 250ml three neck round bottom flask
The sulfuric acid solution of 1.3mol/L and the thioglycolic acid of 450mg.In thermostatical oil bath, 40 degree of lower stirring half an hour, keep phenol complete
Fully dissolved.Temperature is adjusted to 55 DEG C, and the acetophenone of 0.3mol is added in constant pressure funnel, slowly instills dropwise.Reaction is overnight.
Rufous thick solid is obtained, is successively constantly filtered with boiling water and methylene chloride respectively, obtains white solid powder；
(2) synthesis of Phenylsilanetriol: in two mouthfuls of round-bottomed flasks be added phenyltrimethoxysila,e (40g,
0.2mol), then 22g acetic acid aqueous solution (0.5wt%) is slowly added dropwise in reaction flask, and mixture is cooled to 6 DEG C of stirrings
6 hours, then, white crystal was slowly precipitated out, and liquid phase becomes homogeneously, mixture being cooled to -20 DEG C and is kept for 0.5 hour,
Then it filters, the white crystal distilled water that will be waited until, dry overnight at room temperature, obtains product phenyl silane in a vacuum drying oven
Triol；
(3) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy resin: adding under protection of argon gas into three neck round bottom flask
Enter three silanol of 1.5g phenyl, 10g bisphenol-a derivative Ph-BPA, 20g epoxychloropropane, temperature is slowly increased to 110 under stiring
℃.The sodium hydroxide solution that 15ml specification is 5mol/L is slowly dropped by constant pressure funnel, continues to react and stop after stirring 6h
Only.Vacuum distillation removes excessive epoxychloropropane.Then reactant is poured into separatory funnel, separates water-yielding stratum, leaves
Organic layer is then washed 2-3 times with 15% sodium chloride solution, finally, hyperbranched silicone epoxy resin is under 80 DEG C of vacuum conditions
It is dry to obtain over-expense SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA for 24 hours, epoxide number is measured according to GB hydrochloric acid acetone method
0.353mol/100g；
(4) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy acrylate: in three neck round bottom flask, being added 10g's
Overspend the p methoxy phenol of SiClx skeleton bisphenol-a derivative epoxy resin and 100mg, 50mlDMF works as reaction dissolvent.In temperature
To under 70 degree, after stirring half an hour, 95 degree is warming up to, the tetrabutylammonium bromide of 120mg is added, 1.25g acrylic acid is slowly added dropwise,
Acid value is reacted in measurement in every and a half hours, until reaction acid value drops to 0 KOH/g.Stop reaction.It is down to room temperature, with chloroform and largely
Water extraction, separate organic phase, be spin-dried for, obtain over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.
Embodiment 5
(1) 0.3mol phenol, 46ml the synthesis of bisphenol-a derivative Ph-BPA: are added in 250ml three neck round bottom flask
The sulfuric acid solution of 1.3mol/L and the thioglycolic acid of 200mg.In thermostatical oil bath, 40 degree of lower stirring half an hour, keep phenol complete
Fully dissolved.Temperature is adjusted to 55 DEG C, and the acetophenone of 0.1mol is added in constant pressure funnel, slowly instills dropwise.Reaction is overnight.
Rufous thick solid is obtained, is successively constantly filtered with boiling water and methylene chloride respectively, obtains white solid powder；
(2) synthesis of Phenylsilanetriol: in two mouthfuls of round-bottomed flasks be added phenyltrimethoxysila,e (10g,
0.05mol), then 6g acetic acid aqueous solution (0.5wt%) is slowly added dropwise in reaction flask, and mixture is cooled to 6 DEG C of stirrings
6 hours, then, white crystal was slowly precipitated out, and liquid phase becomes homogeneously, mixture being cooled to -20 DEG C and is kept for 0.5 hour,
Then it filters, the white crystal distilled water that will be waited until, dry overnight at room temperature, obtains product phenyl silane in a vacuum drying oven
Triol；
(3) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy resin: adding under protection of argon gas into three neck round bottom flask
Enter three silanol of 0.5g phenyl, 10g bisphenol-a derivative Ph-BPA, 20g epoxychloropropane, temperature is slowly increased to 110 under stiring
℃.The sodium hydroxide solution that 15ml specification is 5mol/L is slowly dropped by constant pressure funnel, continues to react and stop after stirring 6h
Only.Vacuum distillation removes excessive epoxychloropropane.Then reactant is poured into separatory funnel, separates water-yielding stratum, leaves
Organic layer is then washed 2-3 times with 15% sodium chloride solution, finally, hyperbranched silicone epoxy resin is under 80 DEG C of vacuum conditions
It is dry to obtain over-expense SiClx skeleton bisphenol-a derivative epoxy resin HPh-BPA for 24 hours, epoxide number is measured according to GB hydrochloric acid acetone method
0.180mol/100g；
(4) overspend the synthesis of SiClx skeleton bisphenol-a derivative epoxy acrylate: in three neck round bottom flask, the super of 8g is added
The p methoxy phenol of branch SiClx skeleton bisphenol-a derivative epoxy resin and 60mg, 50mlDMF work as reaction dissolvent.In temperature to 70
Under degree, after stirring half an hour, 95 degree is warming up to, the tetrabutylammonium bromide of 100mg is added, 0.65g acrylic acid is slowly added dropwise, each
Half an hour measurement reaction acid value, until reaction acid value drops to 0 KOH/g.Stop reaction.It is down to room temperature, with chloroform and a large amount of water
Extraction separates organic phase, is spin-dried for, and obtains over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.By present embodiment
It is low according to standard GB1727-92,95% with the over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate that example 1-5 is obtained
Polymers, 5% photoinitiator, reactive diluent.Non-activated thinner chloroform is selected in the preparation of film.By resin oligomers and chlorine
It is imitative to be made into concentration 0.5g/ml solution.Photoinitiator is radical photoinitiator 1173, and cationic photoinitiator 6976 mixes
Liquid, the uniform coating on tinplate (120mm*50mm*0.2mm), solidifies, radiation length under 400w UV cure lamp
15cm records curing time.24 hours after photocuring, according to its pencil hardness of GB/T 6739-2006 standard testing, according to
Its adhesive force grade of GB/T 9286-1998 standard testing, cured film do the experiment of TGA thermal weight loss, and data preparation is in Figure 11.
Claims (5)
1. a kind of over-expense SiClx skeleton bisphenol-a derivative epoxy resin, structural formula such as figure one.
2. the preparation method of over-expense SiClx skeleton bisphenol-a derivative epoxy resin according to claim 1, it is characterised in that
Following methods are taken to synthesize:
(a) by the certain acetic acid aqueous solution of mass fraction, be slowly added dropwise, in a certain amount of phenyltrimethoxysila,e, acetic acid water
Mixture is cooled to certain temperature for 1.8-2.5:1. and stirred by solution and phenyltrimethoxysila,e mass ratio, then, white
Crystal is slowly precipitated out, and liquid phase becomes homogeneously, and mixture is cooled to -20 DEG C of holding half an hour, is then filtered, by what is waited until
White crystal distilled water, dry overnight at room temperature, obtains three silanol of product phenyl in a vacuum drying oven.
Reaction temperature: 5-10 degree
Reaction time: 4-8 hours
Acetic acid aqueous solution mass fraction is 0.5%
(b) with phenol for the first monomer, sulfuric acid and thioglycolic acid are catalyst.Second comonomer acetophenone is added, first is single
Body and second comonomer molar ratio are 4-3:1, and sulfuric acid and second comonomer molar ratio are 6:1, thioglycolic acid 100-250mg.Slowly
Slowly it instills dropwise.Reaction is overnight.Rufous thick solid is obtained, is successively constantly filtered, is obtained with boiling water and methylene chloride respectively
To white solid powder, synthesis of bisphenol A derivative.
Reaction temperature: 55 degree
(c) with three silanol of phenyl (Phenylsilanetriol) for the first monomer, bisphenol-a derivative Ph-BPA is second comonomer,
Epoxychloropropane is Third monomer, the first monomer and second comonomer and Third monomer molar ratio in 1:5-10:35-50, in nitrogen
Reaction condition is protected, under catalyst, generates over-expense SiClx skeleton bisphenol-a derivative epoxy resin.
Reaction temperature: 110 degree
Reaction time: 4-6 hours
Catalyst: sodium hydrate aqueous solution.
3. preparation method according to claim 2, it is characterised in that: acetic acid aqueous solution mass fraction is 0.5wt%.Sulfuric acid solution
Concentration be 13mol/L.The concentration of sodium hydrate aqueous solution is 5mol/L.Sodium hydroxide concentration 12-15ml.
4. over-expense SiClx skeleton bisphenol-a derivative epoxy resin according to claim 1, is modified its end group, obtains
To a kind of over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate, structural formula such as Fig. 2.
5. overspending the preparation method of SiClx skeleton bisphenol-a derivative epoxy acrylate according to claim 4, feature exists
In using following methods to prepare: to overspend SiClx skeleton bisphenol-a derivative epoxy resin for the first monomer, acrylic acid is second single
Body, the epoxy group of the first monomer and the carboxyl molar ratio of second comonomer are 2:1.In the item that certain catalyst and polymerization inhibitor is added
Under part, acid value is reacted in measurement in every and a half hours, until reaction acid value drops to 0 KOH/g.Stop reaction.It is down to room temperature, uses chloroform
It is extracted with a large amount of water, separates organic phase, be spin-dried for, obtain over-expense SiClx skeleton bisphenol-a derivative epoxy acrylate.
Catalyst: tetrabutylammonium bromide, n,N-Dimethylaniline.Catalyst amount 1%-3%.
Polymerization inhibitor: hydroquinone, p methoxy phenol.Polymerization inhibitor dosage 0.1%-1%.
Reaction dissolvent: DMF
Reaction temperature: 90-100 degree.
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