CN103709374A - Preparation method of flame-retardant silane coupling agent - Google Patents
Preparation method of flame-retardant silane coupling agent Download PDFInfo
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- CN103709374A CN103709374A CN201310730563.1A CN201310730563A CN103709374A CN 103709374 A CN103709374 A CN 103709374A CN 201310730563 A CN201310730563 A CN 201310730563A CN 103709374 A CN103709374 A CN 103709374A
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Abstract
The invention relates to a preparation method of a flame-retardant silane coupling agent, which comprises the following steps: by using acetone as a solvent and an amino silane coupling agent as a reaction base, adding a flame-retardant epoxy resin, and stirring at room temperature in a nitrogen protective atmosphere for 1-2 hours to remove the solvent, thereby obtaining a viscous liquid product which is the flame-retardant modified silane coupling agent. The flame-retardant epoxy resin is a brominated epoxy resin of which the chemical structure is R1Br4Om, wherein R1 is phenolic alkane, the epoxide equivalent is 300-500, and the bromine content is higher than 50%. The silane coupling agent is an amino silane coupling agent containing active reaction group NH2yRSiX3, wherein R represents an alkylidene group, X represents a hydrolyzable group, and y represents one or more reactive amino groups. The method has the characteristics of simple technique and low cost, enhances the flame retardancy of glass fibers on the premise of enhancing the surface compatibility between the glass fibers and resin, and widens the application range of the silane coupling agent in the field of glass fibers.
Description
Technical field
The present invention relates to a kind of preparation method of flame-proof silicone hydride coupling agent.
Background technology
Silane coupling agent is a kind of auxiliary agent that can promote cement properties between inorganic substance and organic substance, contains two kinds of groups of different nature in its molecule, and one is the group of close inorganics, easily and the surperficial react with of inorganic materials; Another is close organic group, can with organic polymer generation physics or chemical reaction, so coupling agent is often known as " molecular bridge ", in order to improve the interface interaction between inorganics and organism, thereby greatly improves the various performances of matrix material.Silane coupling agent is not only an of paramount importance class coupling agent in coupling agent, also be that glass fibre reinforced composion industry is the most important, the class coupling agent being most widely used, silane coupling agent is in fiberglass surfacing is processed, after hydrolysable group hydrolysis due to silane coupling agent, can carry out dehydration condensation with the hydroxyl of fiberglass surfacing, generate stable siloxane bond, and its organic group can with resin formation hydrogen bond or chemical bond, therefore the glass fibre of processing through silane coupling agent can be used as the strongthener of most of thermosetting resins and thermoplastic resin, and can improve significantly the performance of matrix material each side.But the functionalization for silane coupling agent, even especially the research of flame retardant properties aspect is in initial stage: Chinese patent application publication number CN101613370A has announced a kind of flame retardant modified silane coupler that contains nitrogen phosphorus and preparation method thereof, the phosphorus compound that its utilization contains active reactive group reacts the silane coupling agent of the flame retardant resistance modification that preparation contains nitrogen phosphorus with silane coupling agent.This kind of method is owing to having introduced phosphoric in molecule, make this type of silane coupling agent there is fine flame retardant effect, but due to this kind of method complex process, and the silane coupling agent poorly water-soluble of preparing, price is relatively high, its application of manufacturing field at glass fibre is restricted, so need the method for the flame-retardant modified silane coupling agent of a kind of easy preparation, make to adopt the silane coupling agent that this method is made can improve the flame retardant properties of glass fibre when improving glass fibre and resin surface consistency.
Summary of the invention
The technical problem that the present invention solves is the above-mentioned defect that overcomes prior art, and provide the preparation method of the flame-proof silicone hydride coupling agent that a kind of technique is simple and easy, cost is low, utilize flame-retardant modified silane coupling agent prepared by this method to process for fiberglass surfacing, when improving glass fibre and resin surface consistency, improve the flame retardant properties of glass fibre, further expand it in the range of application in glass fibre field.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of flame-proof silicone hydride coupling agent; it is characterized in that take that acetone is as solvent; using and contain amino silane coupling agent as reactive matrix; add fire-retardant epoxy resin; under nitrogen protection condition, stirring at room is except desolventizing after 1～2 hour, and the product liquid of resulting thickness is and contains flame-retardant modified silane coupling agent.
It is a kind of brominated epoxy resin that fire-retardant epoxy resin of the present invention is selected, and its chemical structure is R1Br
4om, R1 can be phenolic group alkanes, and m can be one or more Sauerstoffatom, and epoxy equivalent (weight) scope is 300～500, and the content of bromo element is more than 50%.
Silane coupling agent of the present invention adopts the common amino silane coupling agent NH2yRSiX3 that contains active reactive group, in formula, R represents that alkylidene group, X represent that group, the y that can be hydrolyzed represent one or more active amino group, as γ-aminopropyl trimethoxysilane, N-β (aminoethyl)-3-aminopropyl trimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane etc.
The flame-retardant modified silane coupling agent that method of the present invention makes, its feature molecular formula is R1Br4OmNH2 (y-1) RSiX3, wherein R1 can be that phenolic group alkanes, m can be one or more Sauerstoffatoms, and R represents that alkylidene group, X represent the group that can be hydrolyzed, the amino group that y represents one or more in addition.This kind of method is owing to having introduced bromo element in molecule; make this type of silane coupling agent there is fine flame retardant effect; utilize flame retardant resistance silane coupling agent prepared by this method to process for fiberglass surfacing; when improving glass fibre and resin surface consistency; fiberglass surfacing is played to fire-resisting protection effect, reach excellent flame retardant effect.
Figure of description
Fig. 1 is the fire-retardant epoxy resin of the embodiment of the present invention and the principle schematic that contains amino silane coupling agent building-up reactions generation flame-proof silicone hydride coupling agent.
Embodiment
The preparation method of flame-proof silicone hydride coupling agent of the present invention be take acetone as solvent; using and contain amino silane coupling agent as reactive matrix; the epoxy resin that adds fire-retardant (property); under nitrogen protection condition, stirring at room is except desolventizing after 1～2 hour, and the product liquid of resulting thickness is and contains flame-retardant modified silane coupling agent.
As a kind of special case, described fire-retardant epoxy resin is selected brominated epoxy resin, and its chemical structure is R1Br4Om, and R1 can be that phenolic group alkanes, m can be one or more Sauerstoffatoms, and epoxy equivalent (weight) scope is 300～500, and the content of bromo element is more than 50%.
The present invention utilizes acetone for solvent, for dissolving brominated epoxy resin.
Silane coupling agent of the present invention is the common amino silane coupling agent NH2yRSiX3 that contains active reactive group, R represents that alkylidene group, X represent that group, the y that can be hydrolyzed represent one or more active amino group, as γ-aminopropyl trimethoxysilane (such as A1100), N-β (aminoethyl)-3-aminopropyl trimethoxysilane (such as A1120), N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane etc.
The flame-retardant modified silane coupling agent that method of the present invention makes, its feature molecular formula is R1Br4OmNH2 (y-1) RSiX3, wherein R1 can be that phenolic group alkanes, m can be one or more Sauerstoffatoms, and R represents that alkylidene group, X represent the group that can be hydrolyzed, the amino group that y represents one or more in addition.This kind of method is owing to having introduced bromo element in molecule; make this type of silane coupling agent there is fine flame retardant effect; utilize flame retardant resistance silane coupling agent prepared by this method to process for fiberglass surfacing; when improving glass fibre and resin surface consistency; fiberglass surfacing is played to fire-resisting protection effect, reach excellent flame retardant effect.
By the following examples the present invention is specifically described, but content of the present invention is not subject to any restriction of following examples.
embodiment 1:
By a certain amount of brominated resins A(epoxy equivalent (weight) 400) be dissolved in the there-necked flask that a certain amount of acetone soln inflated with nitrogen is housed, be stirred to mixing and stirring, drip a certain amount of A1100 coupling agent, dropwise rear maintenance room temperature reaction 1 hour, except desolventizing.The liquid of the thickness of gained is final product after completion of the reaction.In experiment, the reaction ratio of brominated resins and A1100 is in Table 1, and reaction process and product are shown in Fig. 1.
Thermogravimetic analysis (TGA) test: with TAQ100 type hot weightless instrument, sample is carried out to thermal weight loss test, test result is in Table 2.
embodiment 2:
According to the method for embodiment 1, change a certain amount of brominated resins A into brominated resins B(epoxy equivalent (weight) 430) be dissolved in the there-necked flask that a certain amount of acetone solvent inflated with nitrogen is housed, be stirred to mixing and stirring, drip a certain amount of A1100 coupling agent, dropwise rear maintenance room temperature reaction 1 hour, except desolventizing.The liquid of the thickness of gained is final product after completion of the reaction.Experiment proportioning is also carried out thermal weight loss test according to the method for implementing 1 in Table the obtained product of 1, embodiment 2, and test result is in Table 2.
embodiment 3:
According to the method for embodiment 1, change a certain amount of brominated resins A into brominated resins C(epoxy equivalent (weight) 415) be dissolved in the there-necked flask that a certain amount of acetone solvent inflated with nitrogen is housed, be stirred to mixing and stirring, drip a certain amount of A1100 coupling agent, dropwise rear maintenance room temperature reaction 1 hour, except desolventizing.The liquid of the thickness of gained is final product after completion of the reaction.Experiment proportioning is also carried out thermal weight loss test according to the method for implementing 1 in Table the obtained product of 1, embodiment 3, and test result is in Table 2.
Reaction product is carried out to thermogravimetic analysis (TGA) test, find that the sample thermostability of the silane coupling agent of the modification through making in the present embodiment improves greatly: temperature during thermal weight loss 5% is: T embodiment 1 product=T embodiment 2 products=T embodiment 3 product > TA1100; Temperature during thermal weight loss 50% is: T embodiment 3 product >T embodiment 2 product > T embodiment 1 product > TA1100.Can find the silane coupling agent through brominated resins modification simultaneously, residual volume obviously increases, and different brominated resins are different on the impact of the flame retardant effect of silane coupling agent, these thermostabilitys that flame-retardant modified silane coupling agent synthesizing has all been described increase, combustibility declines greatly, through the flame-retardant modified silane coupling agent sample making in the present embodiment, has fire retardation.
Table 1 embodiment 1, embodiment 2 and the building-up reactions proportioning of implementing 3
Table 2 embodiment 1, embodiment 2, embodiment 3, and the thermal weight loss Data Comparison of A1100
The equivalent transformation of every technical solution of the present invention and technical characterictic or combination, all should think and fall into protection scope of the present invention.
Claims (3)
1. the preparation method of a flame-proof silicone hydride coupling agent; it is characterized in that: take acetone as solvent; using and contain amino silane coupling agent as reactive matrix; add fire-retardant epoxy resin; under nitrogen protection condition, stirring at room is except desolventizing after 1～2 hour, and the product liquid of resulting thickness is and contains flame-retardant modified silane coupling agent.
2. the preparation method of flame-proof silicone hydride coupling agent according to claim 1, is characterized in that: described fire-retardant epoxy resin is selected brominated epoxy resin, and its chemical structure is R1Br
4om, R1 is phenolic group alkanes, and epoxy equivalent (weight) scope is 300～500, and the content of bromo element is more than 50%.
3. the preparation method of flame-proof silicone hydride coupling agent according to claim 1 and 2, it is characterized in that: described silane coupling agent adopts the amino silane coupling agent NH2yRSiX3 that contains active reactive group, in formula, R represents that alkylidene group, X represent that group, the y that can be hydrolyzed represent one or more active amino group.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880763A (en) * | 2017-10-12 | 2018-04-06 | 费全中 | Water-proof environmental protection coating and preparation method thereof |
| CN108456393A (en) * | 2018-02-05 | 2018-08-28 | 合肥市大卓电力有限责任公司 | A kind of power distribution cabinet special panel material and preparation method |
| CN111073348A (en) * | 2019-12-11 | 2020-04-28 | 江苏联瑞新材料股份有限公司 | Preparation method of flame-retardant modified silica micropowder for halogen-free copper-clad plate |
| CN113461907A (en) * | 2021-06-28 | 2021-10-01 | 中车青岛四方机车车辆股份有限公司 | Flame-retardant epoxy resin and preparation method and application thereof |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
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| CN101613370A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | Flame retardant modified silane coupler of a kind of phosphorous nitrogen and preparation method thereof |
| CN101787132A (en) * | 2010-03-29 | 2010-07-28 | 中科院广州化学有限公司 | Organic-silicon hybridization epoxy resin as well as preparation method and application thereof |
| CN103468095A (en) * | 2013-07-23 | 2013-12-25 | 江苏博特新材料有限公司 | Silane coupling agent-modified epoxy resin, and preparation method and application thereof |
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2013
- 2013-12-26 CN CN201310730563.1A patent/CN103709374B/en active Active
Patent Citations (3)
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| CN101613370A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | Flame retardant modified silane coupler of a kind of phosphorous nitrogen and preparation method thereof |
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| TAKESHI YAMAUCHI ET AL.: "Immobilization of Flame Retardant onto Silica Nanoparticle Surface and Properties of Epoxy Resin Filled with the Flame Retardant-Immobilized Silica", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880763A (en) * | 2017-10-12 | 2018-04-06 | 费全中 | Water-proof environmental protection coating and preparation method thereof |
| CN107880763B (en) * | 2017-10-12 | 2020-12-11 | 江苏振华造漆有限公司 | Waterproof environment-friendly coating and preparation method thereof |
| CN108456393A (en) * | 2018-02-05 | 2018-08-28 | 合肥市大卓电力有限责任公司 | A kind of power distribution cabinet special panel material and preparation method |
| CN111073348A (en) * | 2019-12-11 | 2020-04-28 | 江苏联瑞新材料股份有限公司 | Preparation method of flame-retardant modified silica micropowder for halogen-free copper-clad plate |
| CN113461907A (en) * | 2021-06-28 | 2021-10-01 | 中车青岛四方机车车辆股份有限公司 | Flame-retardant epoxy resin and preparation method and application thereof |
| CN113461907B (en) * | 2021-06-28 | 2023-11-21 | 中车青岛四方机车车辆股份有限公司 | Flame-retardant epoxy resin and preparation method and application thereof |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
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