CN101638481B - Polyphenyl methoxylsilane and preparation method and application thereof - Google Patents
Polyphenyl methoxylsilane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyphenyl methoxylsilane, a preparation method thereof and the application thereof in modifying bisphenol A-type ethoxyline resin. The main chain of the polyphenyl methoxylsilane a silicon-oxygen chain section, the branched chains of the polyphenyl methoxylsilane are a phenyl chain section and a methoxyl chain section, the relative molecular mass of the polyphenyl methoxylsilane is 700-2000, and the content of active methoxyl is 10-20 percent by mass. The preparation method is as below: firstly, mixing and uniformly stirring phenyl trimethoxylsilane monomers and diphenyl dimethoxylsilane monomers; then adding a mixture consisting of deionized water and catalyst; sequentially carrying out reflux reaction and reduced pressure distillation so as to evaporate methanol and water generated during the reaction; and then reducing the temperature to the room temperature and filtering. When the polyphenyl methoxylsilane is used for modifying ethoxyline resin, the compatibility between organic silicone and the ethoxyline resin can be improved, and the heat resistibility of a modified ethoxyline resin system is remarkably improved.
Description
Technical field
The present invention relates to the epoxy resin field, particularly a kind of polyphenyl methoxylsilane and preparation method thereof is applied to the modification of epoxy resin with it.
Background technology
Epoxy resin has good mechanical property, electric property, chemical property, adhesiveproperties and easy-formation processing, advantage such as with low cost, is widely used in fields such as coating, tackiness agent, electric insulating material; But, because epoxy resin is the 3 D stereo reticulated structure, lacking slip between molecular chain, C-C, carbon-oxygen bond bond energy are less, and surface energy is higher, has some hydroxyls etc., makes that its internal stress is big, matter is crisp, high temperature is prone to degraded down, be subject to the water influence.Silicone resin has low temperature flexibility, low surface energy, heat-resisting, weather-proof, hydrophobic, dielectric strength advantages of higher; But it exists mechanical property, sticking power, wear resistance, organic solvent-resistant is relatively poor and shortcoming such as cost height.Modifying epoxy resin by organosilicon be development in recent years get up can reduce the effective way that the epoxy resin internal stress can increase epoxy resin toughness, performance such as heat-resisting again.Modifying epoxy resin by organosilicon forms tridimensional network, generates similar inorganic silicate structure, and that the bond energy of Si-O key is 372.16KJ/mol is more much bigger than the bond energy 242.18KJ/mol of C-C key, thereby the thermotolerance of modified epoxy is improved; Flexible organosilicon segmental has introduced epoxy resin toughness reinforcing; So modifying epoxy resin by organosilicon has good toughness, resistance toheat, pressing mold performance, adhesiveproperties and erosion-resisting characteristics.
The polysiloxane molecule chain is-the Si-O-chain, and side chain is the R base, and generally mostly is organic substituents such as methyl, ethyl, phenyl and allyl group, and the substituting group of different sorts and ratio is very big to synthetic ZGK 5 performance impact.Stability to aging that methyl content is high and low temperature kindliness are good, and poor stability; The resistance to elevated temperatures that phenyl content is high is good, stability in storage is good.
Modifying epoxy resin by organosilicon mainly contains two kinds of method of modifying of physics and chemistry: because the two content parameter differs bigger, the physically modified DeGrain; Chemical modification be utilize organosilicon with reactive group such as hydroxyl, amino and alkoxyl group etc. and epoxy resin in epoxy group(ing), hydroxyl reaction.[polymer such as Emel; 1998,39 (8-9), 1691-1695] the reactive YSR 3286 oligopolymer modified epoxy of employing; But the existence of a large amount of methyl causes the further variation of consistency of organosilicon and epoxy resin; And siloxanes has the low temperature kindliness, so the raising of the resistance toheat of its modified epoxy is limited, and second-order transition temperature (Tg) has obvious decline.[Journal of Polymer Science:Part A:Polymer Chemistry such as Lin S T; 1996; 34:869-884.] adopt YSR 3286 (PDMS) and PSI (PMPS) that bisphenol A type epoxy resin is carried out modification respectively; Though shock strength, the flame retardant resistance of modified resin improve a lot, the resistance toheat of system is not significantly improved, and especially second-order transition temperature (Tg) does not improve basically.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide a kind of and can improve the stable on heating polyphenyl methoxylsilane of epoxy resin.
Another object of the present invention is to provide a kind of preparation method of above-mentioned polyphenyl methoxylsilane.
A purpose more of the present invention is to provide the method for above-mentioned polyphenyl methoxylsilane modified epoxy.
The object of the invention is realized through following technical proposals:
A kind of polyphenyl methoxylsilane (being called for short PPMS), main chain is the silica segment, and side chain is phenyl and methoxyl group segment, and relative molecular mass is 700～2000, active methoxyl group (W
OCH3) content is 10%～20% (quality), structural formula is suc as formula shown in 1:
Formula 1
In the formula 1, Ph is a phenyl, and m and n are natural number.
The preparation method of above-mentioned polyphenyl methoxylsilane (PPMS); Comprise the steps: at first phenyltrimethoxysila,e monomer and dimethoxydiphenylsilane monomer are mixed and stir; 0.4 add the mixed solution of deionized water and catalyzer in～0.6 hour, back flow reaction underpressure distillation after 1.3～1.7 hours, the first alcohol and water that reaction is generated steams; Reduce to room temperature, filtration again, make polyphenyl methoxylsilane.
The monomeric consumption of said phenyltrimethoxysila,e is 50～150 weight parts, is preferably 100 weight parts.The dimethoxydiphenylsilane monomer is 60 weight parts.
Said deionized water is a redistilled water, and consumption is 10～50 weight parts, is preferably 30～40 weight parts.
Said catalyzer comprises hydrochloric acid, sulfuric acid or sodium hydroxide, and consumption is 0.075～0.3 weight part, is preferably 0.15～0.2 weight part.
Said temperature of reaction is 40 ℃～70 ℃, is preferably 50 ℃～60 ℃.
Above-mentioned polyphenyl methoxylsilane can be applicable to modified bisphenol A type epoxy resin.
Polyphenyl methoxylsilane modified bisphenol A type epoxy resin; Specifically comprise the steps: at first the bisphenol A type epoxy resin of 50～100 weight parts is heated to 80～100 ℃, add the polyphenyl methoxylsilane of 10～50 weight parts and the catalyzer of 0.05～0.3 weight part after the fusion, stir; Be warming up to 100～150 ℃; React and obtain the sticky thing of water white transparency after 2～6 hours, be cooled to 80～90 ℃ after, add YLENE and cyclohexanone solvent wiring solution-forming again.
Said catalyzer is organosilicon titanium or organotin; The preferred titanium isopropylate of said organosilicon titanium catalyst (TIPT), the preferred dibutyl tin dilaurate of said organotin catalysts.The preferred titanium isopropylate of catalyzer, consumption is preferably 0.15～0.2 weight part.
Said bisphenol A type epoxy resin comprises E-20, E-12, E-44, E-51 epoxy resin; Be preferably E-20 epoxy resin, consumption is preferably 70～80 weight parts.
The consumption of said polyphenyl methoxylsilane is preferably 20～30 weight parts.
Said temperature of reaction is preferably 120 ℃～130 ℃.
The said reaction times is preferably 3～4 hours.
The present invention compared with prior art has following advantage and effect:
(1) there is not methyl in polyphenyl methoxylsilane of the present invention (PPMS) structure; Only contain phenyl and active methoxyl group; The existence of phenyl can improve organosilyl resistance toheat, and the existence of active methoxyl group simultaneously can make polyphenyl methoxylsilane (PPMS) be easy to other high molecular polymers of further modification.
(2) polyphenyl methoxylsilane of the present invention (PPMS) is applied to modified epoxy; Owing to contain a large amount of phenyl in the polyphenyl methoxylsilane (PPMS); Significantly improved the consistency of organosilicon and epoxy resin, and the resistance toheat of the epoxy-resin systems after the modification is significantly increased.
Description of drawings
Fig. 1: thermogravimetric curve (TGA) figure of the modified epoxy resin condensate of PSI (DC-3074), polyphenyl methoxylsilane (PPMS).
The infrared spectrogram of the polyphenyl methoxylsilane of Fig. 2: embodiment 1 preparation.
The GPC spectrogram of the polyphenyl methoxylsilane of Fig. 3: embodiment 1 preparation.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiment of the present invention is not limited thereto.
Embodiment 1
A. the preparation of polyphenyl methoxylsilane (PPMS)
In the four-hole boiling flask that whisking appliance, reflux condensate device, tap funnel, TM are housed, add 100g phenyltrimethoxysila,e and 60g dimethoxydiphenylsilane; Back intensification degree to 60 ℃ stirs; 0.5h the interior mixture that dropwise adds an amount of 30g deionized water and 0.15g concentrated hydrochloric acid; Underpressure distillation behind the back flow reaction 1.5h steams the small molecules such as first alcohol and water that generate, and reduces to the room temperature filtration and can obtain polyphenyl methoxylsilane (PPMS).The infrared spectrogram of PPMS and GPC spectrogram are seen Fig. 2, Fig. 3.
B. the preparation of polyphenyl methoxylsilane (PPMS) modified epoxy
In the four-hole round-bottomed flask of mechanical stirring, TM, feed hopper, reflux condensing tube is housed; Be warmed up to 90 ℃; Behind the heating and melting 70g E-20 epoxy resin (oxirane value is 0.20mol/100g); Add 30g polyphenyl methoxylsilane (PPMS) and 0.15g TIPT, be warming up to 120 ℃ of reaction 4h, obtain the translucent sticky thing of oyster white.After being cooled to 90 ℃, add the YLENE and the pimelinketone equal solvent of an amount of proportioning, obtain the certain modifying epoxy resin by organosilicon solution of mass fraction of solids.
C. solidify
Make solidifying agent with alicyclic modified amine then and be cured, self-vulcanizing laggard line correlation resistance toheat test in 7 days.
Embodiment 2
A. the preparation of polyphenyl methoxylsilane (PPMS)
In the four-hole boiling flask that whisking appliance, reflux condensate device, tap funnel, TM are housed, add 50g phenyltrimethoxysila,e and 60g dimethoxydiphenylsilane; Back intensification degree to 40 ℃ stirs; 0.5h the interior mixture that dropwise adds an amount of 10g deionized water and 0.075g concentrated hydrochloric acid; Underpressure distillation behind the back flow reaction 1h steams the methyl alcohol and the portion water that generate, reduces to the room temperature filtration and can obtain polyphenyl methoxylsilane (PPMS).
B. the preparation of polyphenyl methoxylsilane (PPMS) modified epoxy
In the four-hole round-bottomed flask of mechanical stirring, TM, feed hopper, reflux condensing tube is housed; Be warmed up to 90 ℃; Behind the heating and melting 90g E-20 epoxy resin (oxirane value is 0.20mol/100g); Add 10g polyphenyl methoxylsilane and 0.05g TIPT, be warming up to 100 ℃ of reaction 2h, obtain the translucent sticky thing of oyster white.After being cooled to 90 ℃, add the YLENE and the pimelinketone equal solvent of an amount of proportioning, obtain the modifying epoxy resin by organosilicon solution that mass fraction of solids does not wait.
C. solidify
Make solidifying agent with alicyclic modified amine then and be cured, self-vulcanizing laggard line correlation resistance toheat test in 7 days.
Embodiment 3
A. the preparation of polyphenyl methoxylsilane (PPMS)
In the four-hole boiling flask that whisking appliance, reflux condensate device, tap funnel, TM are housed, add 150g phenyltrimethoxysila,e and 60g dimethoxydiphenylsilane; Back intensification degree to 70 ℃ stirs; 0.5h the interior mixed solution that dropwise adds an amount of 50g deionized water and 0.3g concentrated hydrochloric acid; Underpressure distillation behind the back flow reaction 3.5h steams the methyl alcohol and the portion water that generate, reduces to the room temperature filtration and can obtain polyphenyl methoxylsilane (PPMS).
B. the preparation of polyphenyl methoxylsilane (PPMS) modified epoxy
In the four-hole round-bottomed flask of mechanical stirring, TM, feed hopper, reflux condensing tube is housed; Be warmed up to 90 ℃; Behind the heating and melting 50g E-20 epoxy resin (oxirane value is 0.20mol/100g); Add 50g polyphenyl methoxylsilane and 0.3g dibutyl tin dilaurate, be warming up to 150 ℃ of reaction 6h, obtain the translucent sticky thing of oyster white.After being cooled to 90 ℃, add the YLENE and the pimelinketone equal solvent of an amount of proportioning, obtain the modifying epoxy resin by organosilicon solution that mass fraction of solids does not wait.
C. solidify
Make solidifying agent with alicyclic modified amine then and be cured, self-vulcanizing laggard line correlation resistance toheat test in 7 days.
Comparative Examples 1
The properties-correcting agent that this Comparative Examples adopts be the polyphenylmethyl methoxylsilane (DC-3074, DowCorning, Ph/CH3=1), W
OCH3=14%～18%, Mw=1000～2000, structural formula is suc as formula shown in 2:
Formula 2
In the formula 2, Me is a methyl, and m and n are natural number.
(1) preparation of polyphenylmethyl methoxylsilane (DC-3074) modified epoxy
In the four-hole round-bottomed flask of mechanical stirring, TM, feed hopper, reflux condensing tube is housed; Be warmed up to 90 ℃; Behind the heating and melting 70g E-20 epoxy resin (oxirane value is 0.20mol/100g); Add 30g DC-3074 and 0.15g TIPT, be warming up to 120 ℃ of reaction 4h, obtain the translucent sticky thing of oyster white.After being cooled to 90 ℃, add the YLENE and the pimelinketone equal solvent of an amount of proportioning, admittedly contained the modifying epoxy resin by organosilicon solution that does not wait.
(2) solidify
Make solidifying agent with alicyclic modified amine then and be cured, self-vulcanizing laggard line correlation resistance toheat test in 7 days.
Test case 1
Table 1, table 2 and Fig. 1 are respectively the prepared EPMS-30 of embodiment 1 and Comparative Examples 1, the second-order transition temperature (Tg) and the thermal weight loss decomposition curve of ED-30 modified epoxy resin condensate.Wherein, E-20 is unmodified epoxy resin; ED-30 is the epoxy resin cured product of Comparative Examples 1DC-3074 modification; EPMS-30 is the epoxy resin cured product of embodiment 1PPMS modification.
The Tg of the different DC-3074 of table 1, PPMS content modified resin cured article
The thermal weight loss data of the different DC-3074 of table 2, PPMS modified epoxy curing system
Can know by table 1; The second-order transition temperature (Tg) of embodiment 1 polyphenyl methoxylsilane (PPMS) modified epoxy curing system (EPMS-30) has improved 9.0 ℃ than unmodified E-20, and the second-order transition temperature (Tg) of Comparative Examples 1DC-3074 modified epoxy curing system (ED-30) has only improved 1.5 ℃.
Can know that by table 2 and Fig. 1 the heat decomposition temperature of PPMS modified resin cured article is 150 ℃, apparently higher than the heat decomposition temperature (110 ℃) of DC-3074 modified resin cured article; The thermal weight loss rate of two kinds of modified resin cured articles all remains unchanged between 200 ℃～320 ℃, but the thermal weight loss rate of PPMS modified resin cured article is merely 11.4%, is starkly lower than the thermal weight loss rate (16%) of DC-3074 modified resin cured article.
Claims (10)
1. polyphenyl methoxylsilane, main chain is the silica segment, and side chain is phenyl and methoxyl group segment, and relative molecular mass is 700～2000, and active methoxy content is 10%～20% quality, structural formula is:
Wherein, Ph is a phenyl, and m and n are natural number.
2. the preparation method of the described polyphenyl methoxylsilane of claim 1; It is characterized in that comprising the steps: at first phenyltrimethoxysila,e monomer and dimethoxydiphenylsilane monomer are mixed and stir; 0.4 add the mixed solution of deionized water and catalyzer in～0.6 hour, back flow reaction underpressure distillation after 1.3～1.7 hours, the first alcohol and water that reaction is generated steams; Reduce to room temperature, filtration again, make polyphenyl methoxylsilane.
3. the preparation method of polyphenyl methoxylsilane according to claim 2, it is characterized in that: the monomeric consumption of said phenyltrimethoxysila,e is 50～150 weight parts, the dimethoxydiphenylsilane monomer is 60 weight parts.
4. the preparation method of polyphenyl methoxylsilane according to claim 2, it is characterized in that: said deionized water is a redistilled water, consumption is 10～50 weight parts.
5. the preparation method of polyphenyl methoxylsilane according to claim 2, it is characterized in that: said catalyzer comprises hydrochloric acid, sulfuric acid or sodium hydroxide, consumption is 0.075～0.3 weight part.
6. the described polyphenyl methoxylsilane of claim 1 is applied to modified bisphenol A type epoxy resin.
7. polyphenyl methoxylsilane according to claim 6 is applied to modified bisphenol A type epoxy resin; It is characterized in that comprising the steps: at first the bisphenol A type epoxy resin of 50～100 weight parts is heated to 80～100 ℃; Add the polyphenyl methoxylsilane of 10～50 weight parts and the catalyzer of 0.05～0.3 weight part after the fusion; Stir, be warming up to 100～150 ℃, react and obtain the sticky thing of water white transparency after 2～6 hours; After being cooled to 80～90 ℃, add YLENE and cyclohexanone solvent wiring solution-forming again.
8. polyphenyl methoxylsilane according to claim 7 is applied to modified epoxy, it is characterized in that: said catalyzer is organosilicon titanium or organotin.
9. polyphenyl methoxylsilane according to claim 7 is applied to modified epoxy, it is characterized in that: said bisphenol A type epoxy resin comprises E-20, E-12, E-44, E-51 epoxy resin.
10. polyphenyl methoxylsilane according to claim 7 is applied to modified epoxy, it is characterized in that: the consumption of said polyphenyl methoxylsilane is 20～30 weight parts.
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| CN103044919B (en) * | 2012-12-20 | 2014-09-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| CN106349460A (en) * | 2016-09-05 | 2017-01-25 | 华南理工大学 | High-temperature-resistant organic silicon-modified epoxy resin and method for preparing same |
| CN106750309A (en) * | 2016-12-14 | 2017-05-31 | 东至绿洲环保化工有限公司 | A kind of technique for preparing dimethyl-silicon oil formulation |
| CN108794984B (en) * | 2018-05-31 | 2021-07-09 | 四川大学 | Impact-resistant high-heat-residual-weight modified epoxy resin and preparation method and application thereof |
| CN114196020A (en) * | 2021-11-12 | 2022-03-18 | 安徽沸点新材料有限公司 | Phenyl methoxy silane polymer and preparation method thereof |
| CN115505239B (en) * | 2022-09-27 | 2024-06-25 | 山东大学 | Preparation method of polysiloxane modified epoxy resin material |
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