CN1331870C - Epoxy-silsesquioxanes preparation method - Google Patents
Epoxy-silsesquioxanes preparation method Download PDFInfo
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- CN1331870C CN1331870C CNB2004100731978A CN200410073197A CN1331870C CN 1331870 C CN1331870 C CN 1331870C CN B2004100731978 A CNB2004100731978 A CN B2004100731978A CN 200410073197 A CN200410073197 A CN 200410073197A CN 1331870 C CN1331870 C CN 1331870C
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- epoxy
- methylimidazole
- hydrochloric acid
- concentrated hydrochloric
- water
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Abstract
The present invention relates to a preparation method for siloxane sesquisilicate with epoxy groups. A new catalyst system is adopted, which has the advantages of high combined efficiency, high purity and simple manufacturing process. The present invention has the technical characteristics that: 1. according to a molar ratio, mono-gamma-(2, 3-epoxy propoxy)propyl trimethoxysilane, water, concentrated hydrochloric acid as catalysts and 1-methylimidazole are orderly added to mix liquid of ice and water; 2. absolute methanol solvents also are added; 3. solution is stirred at medium speed until showing turbidity; 4. the solution is heated, and then, the heat is preserved for about 24 hours; 5. the solvents and impurities are removed, and transparent and viscous resin is obtained. A specific catalyst system is adopted, and the synthesis of the gamma-(2, 3-epoxy propoxy) propyl sesquisilicate siloxane overcomes the defects of the prior art. The present invention has the advantages of simple reaction step, short reaction time and convenient operation, and the product has the advantages of high productivity ratio and high purity.
Description
Technical field
The present invention relates to a kind of method for preparing band epoxy group(ing) silsesquioxane, present method has adopted a kind of new catalyst system, and combined coefficient height, purity height, technology are simple.
Background technology: multiaspect oligomeric silsesquioxanes (Polyhedral Oligosilsesquioxane, POSS) be a kind of three-dimensional structure of organic-inorganic intramolecularly nano hybridization, three-dimensional dimension has 1-8 reactive organic group about 1.5nm, structure is (RSiO
1.5)
8, inorganic components is between silicon-dioxide (SiO
2) and silicone resin (R
2SiO) between, its performance has concurrently organic and character mineral compound.Typical POSS monomer is single functional, comprises Si
8O
12Inorganic core, only contain 1 reactive group and 7 non-reacted organic groups on every side, wherein non-reacted group is used for increasing silsesquioxane and other dielectric compatibility, reactive group is used for participating in reaction and forms hybrid material.
The preparation method mainly contains trifunctional silane (siloxanes) XSiY
3Hydrolytie polycondensation, different cohydrolysis, the polycondensation of organic annular siloxane [XYSiO] m, the thermolysis of organopolysiloxane, the utilization (HSiO that forms with the organo-siloxane of structure
1.5) addition reaction of silicon with hydrogen of Si-H key among the n, typical reaction formula is:
Figure.2?The?formation?of?silsesquioxanes?from?the?condensation?of?silanes
Band oxygen groups silsesquioxane can be used as a kind of properties-correcting agent to be added in the Resins, epoxy, then by copolyreaction, forms the hybrid material on the molecular level, and this material has good thermal characteristics and mechanical property.Synthesis technique is so that γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (MAS) has following several for monomeric typical synthesis technique at present:
1: with HCOOH (0.1N) is catalyzer, and tetrahydrofuran (THF) (THF) is a solvent (consumption is 1.5g/mL), and keeping water and monomeric mol ratio is 3.Above each component is kept 50 ℃, 24 hours.
2: amount of monomer is 4.2 * 10
-2Mol, catalyzer are hydrochloric acid (cat/MAS=1.05 * 10
-1), H
2O/MAS=1.5, keeping temperature is 70 ℃, CH
3The OH consumption is 14ml, and the nitrogen atmosphere flow is 360ml/min.Reaction times is 3h.
3: amount of monomer is 4.2 * 10
-2Mol, catalyzer are ammoniacal liquor (cat/MAS=1.0 * 10
-1), H
2O/MAS=3.0, keeping temperature is 70 ℃, CH
3The OH consumption is 14ml, and the nitrogen atmosphere flow is 360ml/min.Reaction times is 3h.
The problem that above-mentioned preparation method exists is: synthetic yield lower (being usually less than 10%), and the reactions steps more complicated, the processing technology of gained resin is also bad.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of method for preparing band epoxy group(ing) silsesquioxane, introduced the catalyst system of concentrated hydrochloric acid/1-Methylimidazole first, made γ-(2,3-epoxy third oxygen) propyl group silsesquioxane of present method preparation can overcome above-mentioned shortcoming.
Technical scheme
Technical characterictic of the present invention is:
A, in the frozen water mixed solution according to 1: 1.5: (0.02-0.03): mol ratio (0.01-0.02) adds monomer γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, water, catalyzer concentrated hydrochloric acid and 1-Methylimidazole and solvent anhydrous methanol one by one;
C, middling speed are stirred to the solution shape that becomes turbid;
D, be warming up to 55-60 ℃, be incubated 24 hours;
E, desolventize and impurity, obtain transparent heavy-gravity resin.
Described catalyzer is the mixed solution of concentrated hydrochloric acid and 1-Methylimidazole, and wherein the concentration of concentrated hydrochloric acid is 36-38%, and the purity of 1-Methylimidazole is 98%.
The principle of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane hydrolytie polycondensation is as follows:
The hydrolysis condensation reaction of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is divided into two processes:
(1) hydrolysis reaction (the hydrolysis reaction)
(OR
2)
4-xRX
1Si+H
2O→RX
1Si(OH)(OR
2)
4-x-1+R
2OH
(2) polycondensation (the condensation reactions)
1) polycondensation dealcoholysis (Alcohol Condensation)
2) polycondensation dehydration (Water Condensation)
(R wherein
1Be γ-(2,3-epoxy third oxygen) propyl group, R
2Be methoxyl group)
The katalysis of acid is mainly reflected in the oxygen attack among the ≡ Si-OH
In the Si atom, generate the Si-O-Si key at last, be shown below.
Because Si-OCH
3Speed of reaction in water is very fast, must introduce the feasible reaction of a kind of solvent control easily.Methyl alcohol can participate in reaction as the solvent of reaction, so more effective inhibited reaction speed, and can make organic phase with inorganic mutually can thorough mixing.
Beneficial effect
The invention has the beneficial effects as follows: adopt a kind of special catalyst system, make synthetic γ-(2,3-epoxy third oxygen) propyl group silsesquioxane overcome the shortcoming of prior art, make reactions steps simple, shortened the reaction times, easy to operate, productivity ratio is higher, and the purity of product also improves greatly.
Description of drawings
Fig. 1: preparation method's schema
Embodiment
Now in conjunction with the accompanying drawings the present invention is further described:
Embodiment 1: there-necked flask places the frozen water mixed solution, and γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, distilled water, concentrated hydrochloric acid, 1-Methylimidazole were according to 1: 1.5: 0.02: 0.01 mol ratio adds wherein one by one.Middling speed is stirred to the solution shape that becomes turbid, and the beginning warming-in-water is incubated about 24 hours to 55-60 ℃.Desolventize then and impurity, obtain transparent heavy-gravity resin.
Embodiment 2: there-necked flask places the frozen water mixed solution, and γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, distilled water, concentrated hydrochloric acid, 1-Methylimidazole were according to 1: 1.5: 0.02: 0.015 mol ratio adds wherein one by one.Middling speed is stirred to the solution shape that becomes turbid, and the beginning warming-in-water is incubated about 24 hours to 55-60 ℃.Desolventize then and impurity, obtain transparent heavy-gravity resin.
Embodiment 3: there-necked flask places the frozen water mixed solution, and γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, distilled water, concentrated hydrochloric acid, 1-Methylimidazole were according to 1: 1.5: 0.02: 0.02 mol ratio adds wherein one by one.Middling speed is stirred to the solution shape that becomes turbid, and the beginning warming-in-water is incubated about 24 hours to 55-60 ℃.Desolventize then and impurity, obtain transparent heavy-gravity resin.
Utilize the performance characterization of band epoxy group(ing) silsesquioxane of present method preparation as follows:
1. product is transparent heavy-gravity resin, and oxirane value is 0.46-0.48, and productive rate is 60-75%.Thermogravimetric analysis shows that product residual volume in the time of 1000 ℃ is 40%, and thermal characteristics is fine.
2. with 4,4 '-diaminodiphenylsulfone(DDS) (DDS) makes solidifying agent and POSS solidifies, and when POSS and DDS equivalent proportioning, adopts certain curing process to be cured, and the residual volume during 900 ℃ of cured articles has reached 64%.Show that cured article has good thermal characteristics.
3. with synthetic epoxy group(ing) silsesquioxane industrial Resins, epoxy E51 resin is carried out modification, E51/POSS co-mixing system and DDS solidify, the result shows, adopt certain proportioning and curing process, the POSS/E51/DDS curing system is 45% at 1000 ℃ of following residual volumes, has improved 35% than the residual volume of E51/DDS under the same terms, meanwhile, the heat-drawn wire of system has improved 51 ℃ than the E51/DDS curing system, has reached 220 ℃.Through mechanical test, the adding of POSS makes the bending of cured article and shock strength reach 79.42MPa and 16.01KJ/m respectively
2, when the adding that shows POSS significantly improves the thermal characteristics of former system, do not reduce the mechanical property of material.
Claims (2)
1. one kind prepares the method for being with the epoxy group(ing) silsesquioxane, it is characterized in that:
A, in the frozen water mixed solution according to 1: 1.5: (0.02-0.03): mol ratio (0.01-0.02) adds monomer γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, water, catalyzer concentrated hydrochloric acid and 1-Methylimidazole and solvent anhydrous methanol one by one;
B, middling speed are stirred to the solution shape that becomes turbid;
C, be warming up to 55-60 ℃, be incubated 24 hours;
D, desolventize and impurity, obtain transparent heavy-gravity resin.
2. the method for preparing band epoxy group(ing) silsesquioxane according to claim 1 is characterized in that: described catalyzer is the mixed solution of concentrated hydrochloric acid and 1-Methylimidazole, and wherein the concentration of concentrated hydrochloric acid is 36-38%, and the purity of 1-Methylimidazole is 98%.
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|---|---|---|---|
| CNB2004100731978A CN1331870C (en) | 2004-10-27 | 2004-10-27 | Epoxy-silsesquioxanes preparation method |
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|---|---|---|---|
| CNB2004100731978A CN1331870C (en) | 2004-10-27 | 2004-10-27 | Epoxy-silsesquioxanes preparation method |
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|---|---|
| CN1765903A CN1765903A (en) | 2006-05-03 |
| CN1331870C true CN1331870C (en) | 2007-08-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508698B (en) * | 2009-04-01 | 2011-06-22 | 北京化工大学 | Tetra-epoxy cage type sesquialter siloxane and preparation thereof |
| CN102443099B (en) * | 2011-09-16 | 2013-11-27 | 陕西科技大学 | Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion |
| CN104745132B (en) * | 2015-03-17 | 2017-07-28 | 深圳市九晟光电通讯科技有限公司 | A kind of outdoor paster lamp bead epoxide-resin glue and preparation method thereof |
| CN110746606A (en) * | 2019-11-14 | 2020-02-04 | 北京林业大学 | Preparation method of cage-like silsesquioxane cross-linking agent containing epoxy group |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1008104B (en) * | 1985-08-20 | 1990-05-23 | 信越化学工业株式会社 | Method for preparation of aqueous emulsion of polysilsesquioxane |
| CN1513858A (en) * | 2003-08-20 | 2004-07-21 | 胡立江 | Preparation method of multihydroxy sesqui siloxane |
-
2004
- 2004-10-27 CN CNB2004100731978A patent/CN1331870C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1008104B (en) * | 1985-08-20 | 1990-05-23 | 信越化学工业株式会社 | Method for preparation of aqueous emulsion of polysilsesquioxane |
| CN1513858A (en) * | 2003-08-20 | 2004-07-21 | 胡立江 | Preparation method of multihydroxy sesqui siloxane |
Non-Patent Citations (1)
| Title |
|---|
| 含倍半硅氧烷的杂化聚合物 卢婷利等，高分子通报，第2期 2004 * |
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