CN101831077A - Phenylo boric acid-silane-ethynyl polymer and preparation method thereof - Google Patents
Phenylo boric acid-silane-ethynyl polymer and preparation method thereof Download PDFInfo
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- CN101831077A CN101831077A CN 201010175000 CN201010175000A CN101831077A CN 101831077 A CN101831077 A CN 101831077A CN 201010175000 CN201010175000 CN 201010175000 CN 201010175000 A CN201010175000 A CN 201010175000A CN 101831077 A CN101831077 A CN 101831077A
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Abstract
The invention discloses phenylo boric acid-silane-ethynyl polymer and a preparation method thereof. The polymer is prepared by taking dihalo-silane, phenylo boric acid, trichloroethylene and organic lithium as raw materials in three-step reaction under the protection of inert gas. In the first step, the phenylo boric acid and the dihalo-silane react to form a polymer with a silane-phenylo boric acid-silane repetitive structure and halogen-sealed end. In the second step, the trichloroethylene and the organic lithium react to form an ethynyl dilithium. Finally, the ethynyl dilithium and the polymer formed in the first step generate coupling reaction to obtain the final product after hydrolyzation. The used raw materials are easy to obtain, the process flow is simple, and the operation process is feasible. The prepared polymer generates crosslinking reaction to form thermosets with good high temperature resistance and thermal oxidation resistance property under the thermal or chemical initiation, and is further heated to form a ceramic structure. The prepared polymer can be used as matrix resin, high temperature-resistance coating and ceramic precursor of the advanced composite material.
Description
Technical field
The present invention relates to a kind of high temperature resistant and thermal oxidation resistance polymkeric substance, particularly contain the hybrid inorganic-organic polymkeric substance of boron, silicon and ethynyl on the main chain, its main chain is made up of Si-O-B and C ≡ C.Curing cross-linking reaction takes place and forms tridimensional network in ethynyl under light, heat or initiator effect, further form ceramic structure under high temperature action.
Background technology
Silicone resin be a kind of be molecular backbone chain with the Si-O-Si key, connect the polymkeric substance of organic group on the Siliciumatom, both contained organic group in its structure, contain inorganic structure again.This special composition and molecular structure make it integrate organism characteristic and inorganics function, has unique physical and chemical performance, such as heat-resisting, cold-resistant, the electric insulation of excellence and performance such as weather-proof, be widely used in fields such as aerospace, national defence, electric, chemical industry, machinery.Yet the main chain of silicone resin is made of pure Si-O key, and " separating button " and " thermal rearrangement " degraded easily takes place, and can only be lower than life-time service under 250 ℃ of environment with low irradiation.Along with the further raising of application requiring, the heat-resisting and radiation resistance of silicone resin is had higher requirement.The present invention is by introducing inorganic boron and C ≡ C in the organosilicon main chain, improve the heat-resisting and thermal oxidation of silicone resin, can be used as matrix resin, ceramic forerunner and the fire-resistant oxidation resistant coating of advanced composite material, have broad application prospect in high-end fields such as national defence, aviation and space flight.
Summary of the invention
An object of the present invention is to provide a kind of novel phenylboronic acid-silane-ethynyl high-temperature polymer, described polymer architecture formula is as follows:
Wherein: (1) R
1, R
2Be hydrogen atom, alkyl, aryl; (2) m, n are 〉=1 integer.
The invention provides the brand-new polymkeric substance of a kind of structure, its repeating unit contains a silane-phenylo boric acid-silane structure at least, and contains ethynyl in the main chain.By regulating the mol ratio of phenylo boric acid, silane, and the add-on of trieline, molecular weight, cross-linking density and silicon that can controlling polymers, the percentage composition of boron, thus realize the controllability of polymer performance.
Novel fire resistant polymkeric substance of the present invention is an extremely thick resin of low viscosity, is soluble in various low boiling point organic solvents such as acetone, tetrahydrofuran (THF), ether, can be used as high temperature resistant composite resin matrix, ceramic forerunner and fire-resistant oxidation resistant coating.
Cross-linking and curing reaction can take place in the ethynyl in the new polymers of the present invention under heat, light or chemical initiation, form tridimensional network, and can further add the thermosetting ceramic structure in air or rare gas element.
Another object of the present invention provides a kind of method for preparing described phenylboronic acid-silane-ethynyl high-temperature polymer.This method is as follows:
The first step: phenylo boric acid and electrophilic reagent two halosilanes are reacted, and forming two ends is halogen end capped poly-(phenyl-boron dihydroxide-silane):
X represents a kind of of F, Cl, Br or I, R
1, R
2Be hydrogen atom, alkyl or aryl.Wherein n is 〉=1 integer.
The invention is characterized in: the mol ratio of two halosilanes and phenylo boric acid is (1.1～1.9): 1; The temperature of reaction of two halosilanes and phenylo boric acid is 60 ℃～190 ℃, and the reaction times is 15～50 hours.
Second step: trieline and organolithium RLi reaction obtain the two lithiums of ethynyl:
R is an alkyl or aryl, and R preferentially is chosen as butyl.
The invention is characterized in: the mol ratio of trieline and organolithium is 1: (3～4); Trieline and organolithium temperature of reaction are-30 ℃～20 ℃, and the reaction times is 1～6 hour.
The 3rd step: the ethynyl two-lithium compound and the first step that second step generated are reacted the polymkeric substance generation linked reaction that forms, thereby the resulting polymers hydrolysis obtains final required product.
Wherein, X represents a kind of of F, Cl, Br or I, R
1, R
2Be hydrogen atom, alkyl or aryl.M, n are 〉=1 integer.
The invention is characterized in: the mol ratio of halogen is (1.1～1.9) in the reaction of the lithium and the first step generates in the ethynyl two-lithium compound poly-(phenyl-boron dihydroxide-silane): 1; The temperature of three-step reaction is-5 ℃～25 ℃, 10～24 hours reaction times.
Preparation method of the present invention has adopted brand-new synthetic route, and synthesis technique is simple, and is easy to operate; Required starting material source is abundant, and product at room temperature has satisfactory stability, and is high temperature resistant and antioxidant property is excellent, has industrial applicibility.
Specifically describe institute's synthetic polymkeric substance and synthesis route below for example.
Specific embodiments
Embodiment 1: the first step reaction: at rare gas element N
2Protection under, 10mmol phenylo boric acid and 140ml butylacetate are added in the 250ml there-necked flask, slowly drip the 19mmol dimethyldichlorosilane(DMCS) in there-necked flask by constant pressure funnel then, dropping process 10～20 minutes.Slowly heat up from room temperature, keep butylacetate to be in reflux state, reacted 20 hours.Second step reaction: at rare gas element N
2Protection adds the 15mmol trieline down in another 250ml there-necked flask, 50ml tetrahydrofuran (THF), ice bath make system be in-20 ℃, slowly drip the 45mmol butyllithium by constant pressure funnel, dropwises the back and reacts 4 hours under-20 ℃ temperature.The product of second step reaction is joined in the first step reaction system, 15 ℃ of reactions 24 hours.Reaction adds saturated NH after finishing
4Cl solution fully stirs, and separatory is got upper oil phase, repeats 3～5 times, is neutral until solution.The oil phase underpressure distillation except that desolvating, is obtained subject polymer.
Embodiment 2: the first step reaction: at rare gas element N
2Protection under, 20mmol phenylo boric acid and 180ml glycol dimethyl ether are added in the 250ml there-necked flask, slowly drip the 30mmol methyl hydrogen dichlorosilane in there-necked flask by constant pressure funnel then, dropping process 10～20 minutes.Slowly heating up makes glycol dimethyl ether be in reflux state, reacts 30 hours.Second step reaction: at rare gas element N
2Protection adds the 15mmol trieline down in another 250ml there-necked flask, 50ml tetrahydrofuran (THF), ice bath make system be in-10 ℃, slowly drip the 60mmol butyllithium by constant pressure funnel, dropwises the back and reacts 4 hours under-20 ℃ temperature.The product of second step reaction is joined in the first step reaction system, 10 ℃ of reactions 20 hours.Reaction adds saturated NH after finishing
4Cl solution fully stirs, and separatory is got upper oil phase, repeats 3～5 times, is neutral until solution.The oil phase underpressure distillation except that desolvating, is obtained subject polymer.
Claims (9)
1. high temperature-resisting phenylboronic acid-silane-ethynyl linear polymer, it has following structural formula:
Wherein, (1) R
1, R
2Be hydrogen atom, alkyl, aryl;
(2) m, n are 〉=1 integer.
2. prepare the method for the polymkeric substance of claim 1, it is characterized in that: described method divided for three steps carried out, and key step is:
(1) the first step reaction: phenylo boric acid and electrophilic reagent two halosilanes are reacted, and forming two ends is halogen end capped poly-(phenyl-boron dihydroxide-silane);
(2) second steps reaction: under protection of inert gas, organolithium reagent and trieline reaction are formed the ethynyl two-lithium compound;
(3) three-step reactions: the ethynyl two-lithium compound and the first step that the reaction of second step generates are reacted the polymkeric substance generation linked reaction that forms, and the resulting polymers hydrolysis obtains final product.
3. according to the technology of claim 2, it is characterized in that: the mol ratio of two halosilanes and phenylo boric acid is (1.1～1.9): 1.
4. according to the technology of claim 2, it is characterized in that the temperature of reaction of two halosilanes and phenylo boric acid is 60 ℃～190 ℃, the reaction times is 15～50 hours.
5. according to the technology of claim 2, it is characterized in that: the mol ratio of trieline and organolithium is 1: (3～4).
6. according to the technology of claim 2, it is characterized in that: trieline and organolithium temperature of reaction are-30 ℃～20 ℃, and the reaction times is 1～6 hour.
7. according to the technology of claim 2, it is characterized in that: organolithium reagent is an alkyl or aryl, preferentially is chosen as butyllithium.
8. according to the technology of claim 2, it is characterized in that: the mol ratio of halogen is (1.1～1.9) in the reaction of the lithium and the first step generates in the ethynyl two-lithium compound poly-(phenyl-boron dihydroxide-silane): 1.
9. according to the technology of claim 2, it is characterized in that: the temperature of three-step reaction is-5 ℃～25 ℃, 10～24 hours reaction times.
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| CN102585239A (en) * | 2012-01-06 | 2012-07-18 | 华东理工大学 | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof |
| CN110078927A (en) * | 2019-05-24 | 2019-08-02 | 合肥工业大学 | A kind of heat-resisting boracic containing hydrogen silicone oil and preparation method |
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| CN101235113A (en) * | 2008-01-04 | 2008-08-06 | 华东理工大学 | Aryne resin containing polysilicone and preparation method thereof |
| CN101544765A (en) * | 2009-05-07 | 2009-09-30 | 华东理工大学 | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof |
| JP2009269989A (en) * | 2008-05-07 | 2009-11-19 | Jsr Corp | Silicon-containing polymer, preparation method thereof and optical material |
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Patent Citations (4)
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| US20020143132A1 (en) * | 2001-03-27 | 2002-10-03 | National Institute Of Advanced Industrial Science And Technology | Silsesquioxane polymer molding and method of preparing same |
| CN101235113A (en) * | 2008-01-04 | 2008-08-06 | 华东理工大学 | Aryne resin containing polysilicone and preparation method thereof |
| JP2009269989A (en) * | 2008-05-07 | 2009-11-19 | Jsr Corp | Silicon-containing polymer, preparation method thereof and optical material |
| CN101544765A (en) * | 2009-05-07 | 2009-09-30 | 华东理工大学 | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102585239A (en) * | 2012-01-06 | 2012-07-18 | 华东理工大学 | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof |
| CN110078927A (en) * | 2019-05-24 | 2019-08-02 | 合肥工业大学 | A kind of heat-resisting boracic containing hydrogen silicone oil and preparation method |
| CN110078927B (en) * | 2019-05-24 | 2021-04-20 | 合肥工业大学 | Heat-resistant boron-containing hydrogen-containing silicone oil and preparation method thereof |
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