CN101693766B - Hyper-branched silicon-contained aryne polymer and preparation method thereof - Google Patents
Hyper-branched silicon-contained aryne polymer and preparation method thereof Download PDFInfo
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- CN101693766B CN101693766B CN2009101974715A CN200910197471A CN101693766B CN 101693766 B CN101693766 B CN 101693766B CN 2009101974715 A CN2009101974715 A CN 2009101974715A CN 200910197471 A CN200910197471 A CN 200910197471A CN 101693766 B CN101693766 B CN 101693766B
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Abstract
The invention discloses a hyper-branched silicon-contained aryne polymer and a preparation method thereof. The polymer is structurally characterized in that the polymer is a hyper-branched structure containing silicone atoms and aryne group. The preparation method of the polymer comprises the following steps: taking diethynyl-benzene, trichlorosilane or tetrachlorosilane, halohydrocarbon and magnesium powders as raw materials, and synthesizing the hyper-branched silicon-contained aryne polymer by the following three steps under the protection of inert gas: the halohydrocarbon and the magnesium powders react to generate the alkyl magnesium halide Grignard reagent firstly; the alkyl magnesium halide Grignard reagent and the diethynyl-benzene react to generate the diphenylacetylene magnesium halide Grignard reagent subsequently, and the diphenylacetylene magnesium halide Grignard reagent and the trichlorosilane or tetrachlorosilane react to generate the hyper-branched silicon-contained aryne polymer. In the invention, the process is simple, the operation is convenient, the reaction time is short, the process condition is easy to be controlled, and the post processing is simple. The prepared hyper-branched polymer is brown viscous liquid or primrose yellow powdered solid, is stable at room temperature and is easy for storage, and the condensate thereof has excellent thermal stability.
Description
Technical field
The present invention relates to a kind of hyper-branched silicon-contained aryne polymer of novelty, also relate to the preparation method of this hyper-branched silicon-contained aryne polymer.
Background technology
Hyperbranched polymer is a kind of highly branched three-dimensional near-spherical polymkeric substance, and at the molecular structure surface aggregation a large amount of functional end-groups is arranged, and is compared to line polymer, and hyperbranched polymer has low viscosity and good solubility.Organosilicon polymer is the speciality polymer material, has unique physical and chemical performance, has extremely widely at high-technology fields such as aerospace electronic information and uses.In recent years, in polymer molecular chain, introduce element silicon simultaneously and carbon carbon triple-linked organosilicon polymer causes people's very big interest.This base polymer has good processing properties, at the addition reaction crosslinking curing that passes through under the effect of high temperature or catalyzer between carbon carbon triple bond, thereby obtain having the material of excellent heat-resisting and ablation resistance, therefore become the research focus of high-performance polymer material.Usually in the building-up process of hyperbranched polymer, unsaturated link(age)s such as carbon-carbon double bond or carbon carbon triple bond are commonly used to participate in reaction as active group, and in the present invention, carbon carbon triple bond is to be retained in the structure as functional groups.
Hyper-branched silicon-contained aryne polymer of the present invention is a kind of hyperbranched polymer that contains Si-≡-Ar structure of novelty, does not have document that the report of related fields is arranged as yet.The present invention synthesizes described hyperbranched polymer with the Grignard reagent method.The Grignard reagent method is simple to operate, easily-controlled reaction conditions, productive rate height.
Summary of the invention
The purpose of this invention is to provide a kind of novel hyper-branched silicon-contained aryne polymer and preparation method thereof.In order to reach this purpose, the technical scheme that the present invention takes is:
A kind of hyper-branched silicon-contained aryne polymer, described polymkeric substance has following structure:
Wherein: R is hydrogen base, alkyl, alkoxyl group, vinyl, allyl group or aryl.
Described alkyl is methyl, ethyl or cyclopentyl; Described alkoxyl group is a methoxyl group; Described aryl is a phenyl.
The preparation method of described hyper-branched silicon-contained aryne polymer comprises the steps:
(1) under inert gas protection, halohydrocarbon is added drop-wise to reaction generation alkyl Grignard reagent in the mixture of magnesium powder and solvent;
(2) in the product of step (1), add diacetylene-benzene and react generation sweet-smelling alkynyl Grignard reagent;
(3) adding trichlorosilane or tetrachloro silicane react in the product of step (2), generate hyper-branched silicon-contained aryne polymer;
The mol ratio of described halohydrocarbon and magnesium powder is 1: 1.05～1.20; The mol ratio of described diacetylene-benzene and described alkyl Grignard reagent is 1: 2.00～2.20; The mol ratio of described sweet-smelling alkynyl Grignard reagent and described trichlorosilane or tetrachloro silicane is 2～4: 1; Described solvent is one or more the mixture in tetrahydrofuran (THF), toluene, ether and the dioxane.
Described trichlorosilane has the R substituting group, R=hydrogen base, alkyl, alkoxyl group, vinyl, allyl group or aryl.
Described alkyl is methyl, ethyl or cyclopentyl; Described alkoxyl group is a methoxyl group; Described aryl is a phenyl.
Described halohydrocarbon is C2～C12 alkyl or aryl halides.
END CAPPED GROUP when described hyperbranched reaction finishes is phenylacetylene base or acetylenylbenzene ethynyl.
The temperature of reaction of described step (1) is 0～60 ℃, and the reaction times is 0.5～5 hour.
The temperature of reaction of described step (2) is 0～70 ℃, and the reaction times is 2～6 hours.
The temperature of reaction of described step (3) is 0～70 ℃, and the reaction times is 2～6 hours.
The present invention is with diacetylene-benzene, trichlorosilane or tetrachloro silicane, and halohydrocarbon and MAGNESIUM METAL are raw material, with the siliceous aryne polymkeric substance of Grignard reagent method synthesis of super branched structure, reaction process following (is example with EtBr):
The reaction of (1) step generates alkyl magnesium halide Grignard reagent:
The mol ratio of halohydrocarbon and MAGNESIUM METAL is 1: 1.05～1.20, best 1: 1.05～1.15, and temperature of reaction is 0～60 ℃, best 10～50 ℃, the reaction times is 0.5～5 hour, is preferably in 1～3 hour.
The reaction of (2) step generates diacetylene phenyl Grignard reagent (phenylacetylene base Grignard reagent):
The mol ratio of diacetylene-benzene and alkyl Grignard reagent is 1: 2.00～2.20, best 1: 2.05～2.20, and temperature of reaction is 0～70 ℃, best 20～70 ℃, the reaction times is 2～6 hours.
The reaction of (3) step generates the synthetic hyperbranched polymer of wanting:
The mol ratio of diacetylene-benzene Grignard reagent and chlorosilane is 2～4: 1, and temperature of reaction is 0～70 ℃, and best 20～70 ℃, the reaction times is 2～6 hours.
Technical scheme of the present invention is: magnesium powder and solvent are placed in the four-hole boiling flask that is filled with nitrogen, with the cooling bath cooling, and to wherein dripping halohydrocarbon, 15～40 minutes dropping time, dropwise post-heating and continue reaction 0.5～5 hour.In cooled system, drip diacetylene-benzene then, 15～90 minutes dropping time, dropwise post-heating and continue reaction 2～6 hours.With the system cool to room temperature, and, reacted 15～90 minutes, and heating continues reaction 2～6 hours to wherein adding trichlorosilane fast.Reaction finishes the back and add acid (for example, acetate or dilute hydrochloric acid) in system, fully stir, with toluene extraction, phase-splitting, washing, be neutral until pH value, revolve steam desolventize target product and use methanol extraction, through suction filtration, washing, vacuum-drying, get target product.
Institute of the present invention synthetic polymkeric substance is a kind of hyper-branched silicon-contained aryne polymer with three-dimensional space three-dimensional arrangement, and products therefrom normal temperature is stable down, easily preserves, can be by the thermopolymerization crosslinking curing, and the cured article excellent heat stability.
Description of drawings
Fig. 1 is the infrared spectra of the hyper-branched silicon-contained aryne polymer of embodiment 1;
Fig. 2 be hyper-branched silicon-contained aryne polymer proton nmr spectra (
1H NMR);
Fig. 3 be hyper-branched silicon-contained aryne polymer carbon-13 nmr spectra (
13C NMR);
Fig. 4 be hyper-branched silicon-contained aryne polymer nucleus magnetic resonance silicon spectrum (
29Si NMR).
Embodiment
By the following examples hyper-branched silicon-contained aryne polymer of the present invention and preparation method thereof is specifically described, but does not limit interest field of the present invention.
The structure of polymkeric substance characterizes (is solvent with the deuterochloroform) with infrared spectra and nuclear magnetic resonance spectrum, and molecular weight is measured (is solvent with tetrahydrofuran (THF) (THF)) with gel chromatography (GPC) method.
Embodiment 1
Under nitrogen protection; magnesium powder 3.3g (138mmol)/THF (80ml) is placed four-hole boiling flask; cool off with cooling bath; and to wherein adding monobromethane (EtBr) 13.6g (126mmol)/THF (30ml); 50 ℃ of reactions are after 2 hours then; in cooled system, drip diacetylene-benzene 7.56g (60mmol)/THF (30ml), and reacted 2 hours down at 70 ℃.With the system cool to room temperature, and to wherein adding METHYL TRICHLORO SILANE (CH
3SiCl
3) 3.0g (20mmol), and under 70 ℃, be incubated 5 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, must the brown viscous liquid through underpressure distillation except that after desolvating.Its infrared spectra such as Fig. 1, nuclear magnetic resonance spectrum hydrogen spectrum (
1H NMR) as Fig. 2, nuclear magnetic resonance spectrum carbon spectrum (
13C NMR) as Fig. 3, nuclear magnetic resonance spectrum silicon spectrum (
29Si NMR) as Fig. 4.Molecular weight is 771, and PDI is 3.64.
Embodiment 2
Under nitrogen protection; magnesium powder 2.5g (103mmol) is placed four-hole boiling flask; toluene and ether are mixed solvent; cool off with cooling bath; and to wherein adding EtBr10.2g (94mmol); 40 ℃ of reactions dripped diacetylene-benzene 5.67g (45mmol) after 3 hours in cooled system then, and 50 ℃ were reacted 5 hours.With the system cool to room temperature, and to wherein adding METHYL TRICHLORO SILANE (CH
3SiCl
3) 3.0g (20mmol), and 60 ℃ the insulation 4 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, must the brown viscous liquid through underpressure distillation except that after desolvating.Molecular weight is 1130, and PDI is 3.25.
Embodiment 3
Under nitrogen protection; magnesium powder 2.5g (103mmol)/THF (60ml) is placed four-hole boiling flask; cool off with cooling bath; and to wherein adding bromo pentane silane 14.2g (94mmol)/THF (20ml); 50 ℃ of reactions are after 3 hours then; in cooled system, drip diacetylene-benzene 5.67g (45mmol)/THF (20ml), and 40 ℃ were reacted 5 hours.With the system cool to room temperature, and to wherein adding METHYL TRICHLORO SILANE (CH
3SiCl
3) 3.29g (22mmol), and 70 ℃ the insulation 3 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, use methanol extraction, suction filtration, washing, vacuum-drying get the faint yellow solid powder.Molecular weight is 7380, and PDI is 2.92.
Embodiment 4
Under nitrogen protection; magnesium powder 2.5g (103mmol)/THF (70ml) is placed the four-hole round-bottomed flask; cool off with cooling bath; and to wherein adding EtBr10.2g (94mmol)/THF (20ml); 50 ℃ of reactions are after 1.5 hours then; in cooled system, drip diacetylene-benzene 5.67g (45mmol)/THF (30ml), and 70 ℃ were reacted 2 hours.With the system cool to room temperature, and to wherein adding METHYL TRICHLORO SILANE (CH
3SiCl
3) 3.29g (22mmol), and 30 ℃ the insulation 6 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, use methanol extraction, suction filtration, washing, vacuum-drying get the faint yellow solid powder.Molecular weight is 7837, and PDI is 2.76.
Embodiment 5
Under nitrogen protection; magnesium powder 3.3g (138mmol) is placed the four-hole round-bottomed flask; toluene and ether are mixed solvent; cool off with cooling bath; and to wherein adding Bian Ji chlorine 15.9g (126mmol); 30 ℃ of reactions dripped diacetylene-benzene 7.56g (60mmol) after 3 hours in cooled system then, and 70 ℃ were reacted 2 hours.With the system cool to room temperature, and to wherein adding METHYL TRICHLORO SILANE (CH
3SiCl
3) 11.96g (80mmol), and 50 ℃ the insulation 4 hours.In cooled system, add the phenylacetylene Grignard reagent 120mmol that has prepared, and 70 ℃ are incubated 3 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, must the brown viscous liquid through underpressure distillation except that after desolvating.Molecular weight is 1260, and PDI is 2.60.
Embodiment 6
Under nitrogen protection; magnesium powder 2.5g (103mmol)/THF (60ml) is placed the four-hole round-bottomed flask; cool off with cooling bath; and to wherein adding bromo pentane silane 14.2g (94mmol)/THF (20ml); 50 ℃ of reactions are after 2 hours then; in cooled system, drip diacetylene-benzene 5.67g (45mmol)/THF (20ml), and 70 ℃ were reacted 3 hours.With the system cool to room temperature, and to wherein adding vinyl trichloro silane (CH
2=CHSiCl
3) 3.23g (20mmol), and 70 ℃ the insulation 3 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, use methanol extraction, suction filtration, washing, vacuum-drying get the faint yellow solid powder.Molecular weight is 6027, and PDI is 1.72.
Embodiment 7
Under nitrogen protection; magnesium powder 2.5g (103mmol)/THF (70ml) is placed four-hole boiling flask; cool off with cooling bath; and to wherein adding EtBr10.2g (94mmol)/THF (20ml); 40 ℃ of reactions are after 3 hours then; in cooled system, drip diacetylene-benzene 5.67g (45mmol)/THF (20ml), and 60 ℃ were reacted 4 hours.With the system cool to room temperature, and to wherein adding phenyl-trichloro-silicane (PhSiCl
3) 4.23g (20mmol), and 70 ℃ the insulation 3 hours.With sour termination reaction and with the toluene extraction, get organic phase after the washing, use methanol extraction, suction filtration, washing, vacuum-drying get the faint yellow solid powder.Molecular weight is 3773, and PDI is 1.86.
Claims (10)
1. a hyper-branched silicon-contained aryne polymer is characterized in that, described polymkeric substance has following structure:
Wherein: R is hydrogen base, alkyl, alkoxyl group, vinyl, allyl group or aryl.
2. hyper-branched silicon-contained aryne polymer according to claim 1 is characterized in that, described alkyl is methyl, ethyl or cyclopentyl; Described alkoxyl group is a methoxyl group; Described aryl is a phenyl.
3. the preparation method of claim 1 or 2 arbitrary described hyper-branched silicon-contained aryne polymers is characterized in that, comprises the steps:
(1) under inert gas protection, halohydrocarbon is added drop-wise to reaction generation alkyl Grignard reagent in the mixture of magnesium powder and solvent;
(2) in the product of step (1), add diacetylene-benzene and react generation sweet-smelling alkynyl Grignard reagent;
(3) adding trichlorosilane or tetrachloro silicane react in the product of step (2), generate hyper-branched silicon-contained aryne polymer;
The mol ratio of described halohydrocarbon and magnesium powder is 1: 1.05～1.20; The mol ratio of described diacetylene-benzene and described alkyl Grignard reagent is 1: 2.00～2.20; The mol ratio of described sweet-smelling alkynyl Grignard reagent and described trichlorosilane or tetrachloro silicane is 2～4: 1;
Described solvent is one or more the mixture in tetrahydrofuran (THF), toluene, ether and the dioxane.
4. preparation method according to claim 3 is characterized in that described trichlorosilane has the R substituting group, R=hydrogen base, alkyl, alkoxyl group, vinyl, allyl group or aryl.
5. preparation method according to claim 4 is characterized in that, described alkyl is methyl, ethyl or cyclopentyl; Described alkoxyl group is a methoxyl group; Described aryl is a phenyl.
6. preparation method according to claim 3 is characterized in that, described halohydrocarbon is C2～C12 alkyl or aryl halides.
7. preparation method according to claim 3 is characterized in that, the END CAPPED GROUP when described hyperbranched reaction finishes is phenylacetylene base or acetylenylbenzene ethynyl.
8. preparation method according to claim 3 is characterized in that, the temperature of reaction of described step (1) is 0～60 ℃, and the reaction times is 0.5～5 hour.
9. preparation method according to claim 3 is characterized in that, the temperature of reaction of described step (2) is 0～70 ℃, and the reaction times is 2～6 hours.
10. according to the preparation method of claim 3, it is characterized in that the temperature of reaction of described step (3) is 0～70 ℃, the reaction times is 2～6 hours.
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| CN101293959A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Hyperbranched conjugated polymer sensing material, preparation method and application thereof |
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