CN104673179A - Epoxy-acryloyloxy primer for silicon rubber heat insulating layers and preparation method thereof - Google Patents
Epoxy-acryloyloxy primer for silicon rubber heat insulating layers and preparation method thereof Download PDFInfo
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- CN104673179A CN104673179A CN201310638471.0A CN201310638471A CN104673179A CN 104673179 A CN104673179 A CN 104673179A CN 201310638471 A CN201310638471 A CN 201310638471A CN 104673179 A CN104673179 A CN 104673179A
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- coupling agent
- silicon rubber
- silane coupling
- epoxy
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Abstract
The invention relates to an epoxy-acryloyloxy primer for silicon rubber heat insulating layers and a preparation method thereof. The novel epoxy-acryloyloxy primer comprises a coupling agent, a crosslinking agent, a tackifier, a diluter and a curing catalyst, wherein the coupling agent is an epoxy silane coupling agent and/or an acryloyloxy silane coupling agent; the crosslinking agent is an organosilicon external crosslinking agent; the tackifier is a metal organic salt; the diluter is a siloxane capable of performing the dissolution and dilution functions of the solvent, and can be used for wiping and cleaning the silicon rubber surface; and the curing catalyst is a metal salt. The primer for solid propulsor silicon rubber heat insulating layer surface modification treatment can enhance the bonding performance of the interface between the butyl hydroxy lining layer and the silicon rubber heat insulating layer.
Description
Technical field
The present invention relates to epoxy-acryloxy silane coupling agent, particularly a kind of solid propellant rocket silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent and preparation method thereof.More particularly, the present invention relates to a kind of with epoxy radicals silicone hydride and acryloxy silane for film forming coupling agent, positive silicic acid four butyl ester is linking agent, and tetra-n-butyl titanate is tackifier, the novel silane coupling agent that triphenyl bismuth (TPB) is curing catalysts.
Background technology
Along with the requirement of missile weapon system to solid propellant rocket over-all properties is more and more higher, silicon rubber thermal insulation layer is the advantage such as safety performance is good, low signature, resistance to ablation, antiscour because having, and be expected to become solid propellant rocket thermal insulation layer material of new generation, be subject to extensive concern at home and abroad.But due to itself and fourth hydroxyl, polyurethane class high molecular material adhesive poor-performing, hinder its range of application, bonding interface problems demand solves, correspondingly, silicon rubber thermal insulation layer needs the silane coupling agent adapted with fourth hydroxyl lining.
Silane coupling agent is the modifying interface agent enabling solid propellant rocket silicon rubber thermal insulation layer and lining strong bond, the good bonding integrity ensured between propelling agent interface, and then play the advantage of silicon rubber thermal insulation layer to greatest extent, thus improve solid propellant rocket performance.
About silane coupling agent application between silicon rubber and organic interface research and report that more is that membrane-forming agent itself contains active group, as unsaturated link(age), epoxide group etc., the adhesiveproperties at interface is improved, as the vinyl terminated polysiloxane silane coupling agent etc. that US Patent No. 20030104224 is reported by the chemical reaction between component.
Yasuyoshi Kuroda etc. in order to improve silicon rubber and polymer interface (as, polyphenylene sulfide, polyimide etc.) adhesiveproperties, application vinyl terminated polysiloxane is matrix, be furnished with a small amount of organic hydride polysiloxane, Ethynylcyclohexane, be polymerized under the effect of platinum catalyst, addition reaction, wherein-CH
2=CH
2-significantly can not consume with the Procuring of silane coupling agent and solidification, increase silastic surface active group quantity, be conducive to, between itself and unsaturated organic polymer, addition reaction occurs, increase the chemical bonding between silicon rubber/organic polymer interface, improve interfacial adhesion.But contained unsaturated link(age) is less in fourth hydroxyl lining, be not easy to produce chemical bonding, bonding strength increase rate is not obvious.
Takanori Kawashima etc. selects the silane coupling agent containing epoxide group to be membrane-forming agent, is issuing biochemical reaction containing amino silane coupling agent effect.Epoxide group carries out ring-opening reaction thus generates active group-OH, then reacts with the isocyano-NCO in fourth hydroxyl lining, thus produces chemical bonding, improves adhesiveproperties between interface.Edwin R Evans selects epoxy silane coupling equally, and titanic acid ester not only as the catalyzer of esterification, condensation reaction, can also can use as the tensio-active agent of silicon rubber, thus improves the adhesiveproperties between interface.But, when application epoxy group(ing) is as silane coupling agent, applies improper meeting and make silane coupling agent, after Procuring, crack performance occur, thus affect bonding interface.In addition, other compositional selectings are improper, can make fourth hydroxyl lining catalyzer that " poisoning " phenomenon occurs, and cause interface solidification incomplete, thus are unfavorable for the further raising of interfacial adhesion strength.
In sum, lack the silane coupling agent that adapt bonding with silicon rubber/fourth hydroxyl lining, silicon rubber thermal insulation material is a kind of novel solid propelling agent thermal insulation layer, and the research about silicon rubber/fourth hydroxyl lining interface adhesiveproperties and epoxy coupling agents and the composite silane coupling agent of acryloxy coupling agent is not also reported.
Summary of the invention
The present invention deals with problems and is to provide a kind of solid propellant rocket silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent and preparation method thereof, to improve the adhesiveproperties at interface between lining and silicon rubber thermal insulation layer, epoxy provided by the present invention-acryloxy silane coupling agent is applicable to the bonding of silicon rubber thermal insulation layer and fourth hydroxyl lining interface.
Epoxy of the present invention-acryloxy silane coupling agent can be painted on silicon rubber thermal insulation layer surface in solid propellant rocket, plays the effect of bonding fourth hydroxyl lining, with the reliability of the integrity and work that ensure fourth hydroxyl lining.
Another object of the present invention is to provide a kind of preparation method of above-mentioned epoxy-acryloxy silane coupling agent.
Silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent of the present invention, composed of the following components according to weight proportion:
(1) coupling agent 20-35 part;
(2) linking agent 20-30 part;
(3) tackifier 15-30 part;
(4) thinner 30-50 part;
(5) curing catalysts 0.5-1 part;
Described epoxy coupling agents and acryloxy coupling agent are the matrixes of epoxy-acryloxy silane coupling agent, coupling agent is γ-glycidyl ether propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane, the bonding energy of epoxy, acryloxy coupling agent is adopted to form stable chemical covalent bonds, the bonding persistence of very big raising and stability, the moisture of fourth hydroxyl lining and bonding interface can also be absorbed simultaneously, thus improve processing performance, improve bonding strength and ageing-resistant performance.
Described linking agent is linking agent is positive silicic acid four butyl ester, forms nanogel phase, prepares the epoxy systems with gel property, also can be used as the linking agent of silicon rubber, wherein butyl ester group (-OC in epoxy coupling agents system
4h
9) generation hydroxyl (-OH) can be hydrolyzed, thus it is active to improve silastic surface, forms hydrogen bond with substrate surface, improves the adhesiveproperties at interface.
Described tackifier are tetra-n-butyl titanates, not only can be used as the catalyzer of esterification, transesterify, condensation reaction, provide Quick cross-linking to react, and also contribute to the activity improving silastic surface, improve the binding property of fourth hydroxyl lining.
Described thinner is the one in hexamethyldisiloxane, tetramethyl disiloxane, hexanaphthene, plays dilution, solvency action, and be uniformly dispersed to coupling agent, linking agent and catalyzer; Be heated and volatilize rapidly, contribute to the film forming of silane coupling agent.
Described curing catalysts is triphenyl bismuth (TPB), and the curing catalysts as interface uses, can curing reaction speed effectively between adjustment interface, avoids unsticking phenomenon.
, under tackifier, curing catalysts effect, there is open loop, hydrolysis, condensation, esterification in described epoxy, acryloxy coupling agent, positive silicic acid four butyl ester.
The method of the epoxy-acryloxy silane coupling agent of preparation and invention is made up of following steps:
First, at ambient temperature, by weight ratio epoxy coupling agents, acryloxy coupling agent, thinner are joined in mixing vessel successively, stir after feeding in raw material at every turn.
Then, add tackifier, curing catalysts, stir, be i.e. obtained novel epoxy-acryloxy silane coupling agent, and it is interior with precaution of hydrolysis to be placed on moisture eliminator, follows the principle of " instant standby ".
The present invention has following beneficial effect:
(1) silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent of the present invention, epoxy coupling agents is adopted to mix composite mode with acryloxy coupling agent, make to react at interface zone between silane coupling agent and fourth hydroxyl lining to form chemical bonding, the binding property of silicon rubber thermal insulation layer and fourth hydroxyl lining interface can be improved, meet the requirement of silicon rubber thermal insulation layer to powder charge interfacial adhesion.
(2) silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent of the present invention, adopt tetra-n-butyl titanate as tackifier, not only contribute to improving esterification, transesterify, condensation reaction, but also can use, to improve interfacial adhesion strength as silastic surface promoting agent.
(3) silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent of the present invention, select small molecules silane (hexamethyldisiloxane) as thinner, volatilization rapidly of being heated, little on silastic surface impact, and contribute to coupling agent film forming, be a kind of safe, stable thinner.
Embodiment
The present invention is further illustrated below by embodiment.
The concrete epoxy of table 1-acryloxy silane coupling agent composition
embodiment 1
At room temperature, polishing pre-treatment is carried out to the adiabatic film (thickness: 2mm) of silicon rubber; Film is put into the mould that 4mm is dark, pour 75g fourth hydroxyl glue lining into, uniform spreading is on silicon rubber film; Degassed; Finally its level is put into 65 DEG C of water-bath baking ovens, solidify 7 days, make the bonding test specimen of silicon rubber/lining and test, the results are shown in table 2.
embodiment 2
At room temperature, respectively 30g epoxy group(ing) coupling agent, 30g linking agent, 10g tackifier are joined in the beaker containing 50g thinner respectively, stir after feeding in raw material at every turn.Add 0.5g curing catalysts again to stir, namely can be made into epoxy priming coating agent.Silane coupling agent is evenly painted on silicon rubber thermal insulation layer surface, puts into 65 DEG C of water-bath baking ovens, Procuring 1 hour.Make silicon rubber/bonding test specimen of silane coupling agent/lining to test, the results are shown in table 2.
embodiment 3
Repeat the method for EXPERIMENTAL EXAMPLE 2 according to each component concentration formulated in table 1, but tackifier consumption is 20g.Test result lists in table 2.
embodiment 4
Repeat the method for EXPERIMENTAL EXAMPLE 2 according to each component concentration formulated in table 1, but dosage of crosslinking agent is 20g, tackifier consumption is 20g, and test result lists in table 2.
embodiment 5
Repeat the method for EXPERIMENTAL EXAMPLE 4 according to each component concentration formulated in table 1, but add acryloxy coupling agent 2g, test result lists in table 2.
embodiment 6
Repeat the method for EXPERIMENTAL EXAMPLE 5 according to each component concentration formulated in table 1, but tackifier consumption is 30g, test result lists in table 2.
embodiment 7
Repeat the method for EXPERIMENTAL EXAMPLE 5 according to each component concentration formulated in table 1, but dosage of crosslinking agent is 30g, test result lists in table 2.
The each embodiment the performance test results of table 2
As can be seen from the test-results of table 2, epoxy of the present invention-acryloxy silane coupling agent, apply it to modify silastic surface, process, make, between silicon rubber thermal insulation layer and fourth hydroxyl lining, there is excellent adhesiveproperties, the requirement of motor charge to interfacial adhesion can be met.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all belong to the protection domain of technical solution of the present invention.
Claims (8)
1. silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent, is characterized in that, comprising: coupling agent, and described coupling agent is epoxy silane coupling agent and/or acryloxy silane coupling agent; Linking agent, described linking agent is silicone based outside cross-linking agent; Tackifier, described tackifier are metal organic salt; Thinner, described thinner is siloxanes; Curing catalysts, described curing catalysts is metallic salt catalyzer.
2. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, it is characterized in that, the weight proportion of each component is:
Coupling agent, 20-35 part;
Linking agent, 20-30 part;
Tackifier, 15-30 part;
Thinner, 30-50 part;
Curing catalysts, 0.5-1 part.
3. the silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to right 1, is characterized in that, the material of described coupling agent is γ-glycidyl ether propyl trimethoxy silicane and/or γ-methacryloxypropyl trimethoxy silane.
4. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, is characterized in that, described linking agent is positive silicic acid four butyl ester.
5. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, it is characterized in that, tackifier are tetra-n-butyl titanate.
6. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, is characterized in that, thinner is one or more in hexamethyldisiloxane, tetramethyl disiloxane, hexanaphthene.
7. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, is characterized in that, the starting material of curing catalysts are triphenyl bismuth, and triphenyl bismuth dioctyl sebacate dissolves, and degree is 0.2%.
8. a kind of silicon rubber thermal insulation layer epoxy-acryloxy silane coupling agent according to claim 1, is characterized in that, comprise following processing step:
First, add in mixing vessel according to weight proportion by coupling agent, linking agent, thinner successively, each feeding in raw material stirs;
Then, add tackifier, curing catalysts, stir, be i.e. obtained novel epoxy-acryloxy silane coupling agent, and it is interior with precaution of hydrolysis to be placed on moisture eliminator, follows the principle of " instant standby ".
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| CN201310638471.0A CN104673179A (en) | 2013-12-03 | 2013-12-03 | Epoxy-acryloyloxy primer for silicon rubber heat insulating layers and preparation method thereof |
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| CN201310638471.0A CN104673179A (en) | 2013-12-03 | 2013-12-03 | Epoxy-acryloyloxy primer for silicon rubber heat insulating layers and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892945A (en) * | 2015-06-06 | 2015-09-09 | 深圳市富达瑞有机硅材料有限公司 | Organic silicon rubber composite tackifier and preparation method thereof |
| CN109852332A (en) * | 2018-12-05 | 2019-06-07 | 湖北航天化学技术研究所 | A kind of surface treating agent and its preparation method and application |
| CN112126396A (en) * | 2020-09-23 | 2020-12-25 | 湖北航泰科技有限公司 | Adhesive for improving adhesive property of heat insulating layer and lining and preparation and use methods thereof |
| CN113717633A (en) * | 2021-05-08 | 2021-11-30 | 杭州师范大学 | Primer for bonding silicon resin thermal protection coating and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1156088A2 (en) * | 2000-05-17 | 2001-11-21 | Kaneka Corporation | Primer composition and bonding method |
| US20030225189A1 (en) * | 2002-05-09 | 2003-12-04 | Fuller Robert Earl | Composition for improving adhesion of base-resistant fluoroelastomers to metal, ceramic or glass substrates |
| CN101872832A (en) * | 2010-06-13 | 2010-10-27 | 汕头市骏码凯撒有限公司 | Packaging material applied to light-emitting diode (LED) and preparation method and using method thereof |
| CN103102865A (en) * | 2012-12-30 | 2013-05-15 | 浙江工业大学 | Silane coupling agent for bonding addition type silicon rubber and leather material |
-
2013
- 2013-12-03 CN CN201310638471.0A patent/CN104673179A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1156088A2 (en) * | 2000-05-17 | 2001-11-21 | Kaneka Corporation | Primer composition and bonding method |
| US20030225189A1 (en) * | 2002-05-09 | 2003-12-04 | Fuller Robert Earl | Composition for improving adhesion of base-resistant fluoroelastomers to metal, ceramic or glass substrates |
| CN101872832A (en) * | 2010-06-13 | 2010-10-27 | 汕头市骏码凯撒有限公司 | Packaging material applied to light-emitting diode (LED) and preparation method and using method thereof |
| CN103102865A (en) * | 2012-12-30 | 2013-05-15 | 浙江工业大学 | Silane coupling agent for bonding addition type silicon rubber and leather material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892945A (en) * | 2015-06-06 | 2015-09-09 | 深圳市富达瑞有机硅材料有限公司 | Organic silicon rubber composite tackifier and preparation method thereof |
| CN109852332A (en) * | 2018-12-05 | 2019-06-07 | 湖北航天化学技术研究所 | A kind of surface treating agent and its preparation method and application |
| CN112126396A (en) * | 2020-09-23 | 2020-12-25 | 湖北航泰科技有限公司 | Adhesive for improving adhesive property of heat insulating layer and lining and preparation and use methods thereof |
| CN113717633A (en) * | 2021-05-08 | 2021-11-30 | 杭州师范大学 | Primer for bonding silicon resin thermal protection coating and preparation method and application thereof |
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