CN105111470A - Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof - Google Patents
Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof Download PDFInfo
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Abstract
The invention discloses a reversible covalent crosslinking polysiloxane elastomer, a preparation method therefor and an application thereof. The reversible covalent crosslinking polysiloxane elastomer has the following structure: FORMULA as shown in the specification. The present invention further discloses a preparation method and an application for the reversible covalent crosslinking polysiloxane elastomer. The polysiloxane elastomer provided by the present invention has advantages of relatively low temperature of reprocessing, good reprocessing performance and high self-repairing efficiency. The reversible covalent crosslinking polysiloxane elastomer is simple in preparation process and relatively low in cost.
Description
Technical field
The present invention relates to a kind of preparation method and application of silicone elastomer, be specifically related to a kind of THERMALLY REVERSIBLE COVALENT polysiloxane and preparation method thereof and application.
Background technology
Polysiloxane is a class with the Si-O key repeated for main chain, the polymkeric substance of direct connection organic group on Siliciumatom.According to molecular size range or whether be cross-linked, silicone oil, silicon rubber and silicone resin three major types can be divided into.Wherein, silicon rubber is one of most important product in polysiloxane, is linear polysiloxanes before crosslinked, is cancellated elastomerics after crosslinked.Silicon rubber has the features such as excellent high-low temperature resistant, weather-proof, resistance to ozone, anti-electric-arc, electric insulating quality, some chemical reagent resistance to, highly air-permeable and physiological inertia, is widely used in the field such as electric, building, automobile, weaving, medical treatment.But silicon rubber exists a difficult problem identical with all thermosetting material: after (1) material in use occurs breakage, when without cannot teaching display stand reparation when additional renovation agent; (2) because its cross-linking set is irreversible, be difficult to after material damage reclaim processing recycling, cause damage and the wasting of resources greatly.
At present, can have been reported by the crosslinked polymeric materials heavily processed of selfreparing about containing reversible dynamic key.Such as, disclose a kind of silicone materials based on hydrogen bond crosslinks in prior art US6783709B2, this material can selfreparing and heavily processing at ambient temperature; But, because hydrogen bond action intensity is weak, the poor mechanical property of material.Disclose in WO2013127989A1 a kind of can the silicone elastomer of selfreparing, the polysiloxane that this material is cross-linked by boric acid ester bond and the thermoplastic, polymeric materials such as pitch, PP, PE are composited, but the heavy processing temperature of material is higher 150 ~ 200 DEG C, the quality of material self-healing properties cannot be judged simultaneously.
Except hydrogen bond and boric acid ester bond, Diels-Alder key is also a kind of effective reversible covalent bonds, its reaction has stereoselectivity, stereospecificity and regioselectivity concurrently, and productive rate is high, and the structure by changing close diene and diene regulates the irreversible temperature of reaction, thus can the processing temperature of controlled material.Such as, disclose a kind of polymer materials crosslinked based on Diels-Alder key in US6933361B2, the mechanical property of this material can match in excellence or beauty epoxy resin, and can realize selfreparing in a heated condition; But this polymkeric substance is prepared by small molecule monomer, and degree of crosslinking is too high, material deformation ability, and monomer synthesize process is comparatively complicated.Disclose a kind of epoxy resin containing furan group in CN200810198162, after this epoxy resin and anhydride-cured, define the reversible crosslink epoxy resin containing Diels-Alder key, but severe reaction conditions.
To sum up, although Diels-Alder key has been widely used in preparing in all kinds of THERMALLY REVERSIBLE COVALENT polymkeric substance, yet there are no the report be applied in the preparation of silicone elastomer.Therefore, explore a kind of silicone elastomer having reversibility Diels-Alder key and be cross-linked, the THERMALLY REVERSIBLE COVALENT silicone elastomer poor mechanical property solving existing hydrogen bonds or boric acid ester bond and the problem weighing processing temperature high are new research directions.
Summary of the invention
Technical problem to be solved by this invention is, provide and a kind ofly based on furans and maleimide reaction, there is crosslinked silicone elastomer of reversibility Diels-Alder key and preparation method thereof and application, it is lower that this silicone elastomer has heavy processing temperature, heavy good processability, self-repair efficiency is high; Preparation technology is simple, and cost is low.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of THERMALLY REVERSIBLE COVALENT silicone elastomer, has following structure:
The technical scheme that the present invention solves the employing of its technical problem is further that a kind of preparation method of THERMALLY REVERSIBLE COVALENT silicone elastomer, comprises the following steps:
(1) synthesis of the polysiloxane of side base band dienophile: be heated to 120 ~ 150 DEG C of stirring reactions 7 ~ 12 hours containing amino silicone copolymers (preferred aminopropyltriethoxy siloxane-dimethylsiloxane multipolymer, aminoethylaminopropyl methylsiloxane-dimethylsiloxane copolymer or aminoethyl ammonia butyl methyl siloxane-dimethylsiloxane multipolymer) and MALEIC ANHYDRIDE in glacial acetic acid, revolve and steam removing glacial acetic acid, obtain light brown viscous liquid; Then by light brown viscous liquid dissolves in methylene dichloride, wash 2 ~ 4 times with deionized water, collected organic layer, siccative (preferred anhydrous magnesium sulfate) is dry, and underpressure distillation removing methylene dichloride, obtains the polysiloxane of side base band maleimide.
(2) synthesis of the polysiloxane cross-linking agent of diene body end-blocking: by hydroxyl or amino-terminated polysiloxane (preferably hydroxy-end capped polydimethylsiloxane, hydroxy-end capped diphenyl siloxane-dimethylsiloxane copolymer, hydroxy-end capped diphenyl siloxane, hydroxy-end capped poly-trifluoro propyl methyl polysiloxane, the polydimethylsiloxane of aminopropyl end-blocking or the polydimethylsiloxane of hydroxyl alkylene oxide group end-blocking), DMAP and triethylamine are dissolved in anhydrous methylene chloride, then under ice bath environment, slowly drip the anhydrous methylene chloride solution of 2 furoyl chloride, dropping limit, limit is stirred, stirring reaction is continued at ambient temperature 22 ~ 26 hours after dropping terminates, filter the white precipitate generated, then alkaline aqueous solution (preferred saturated sodium bicarbonate) is used to wash 2 ~ 4 times, collected organic layer, siccative (preferred anhydrous magnesium sulfate) is dry, underpressure distillation removing methylene dichloride, obtain the polysiloxane cross-linking agent of furans end-blocking.
(3) containing the preparation of THERMALLY REVERSIBLE COVALENT point silicone elastomer: at room temperature, by polysiloxane (the preferred maleimide propylmethylsiloxane-dimethylsiloxane copolymer of the side base band maleimide of preparation, Mailed Ethyl aminopropyltriethoxy siloxane-dimethylsiloxane multipolymer, at least one in Mailed Ethyl ammonia butyl methyl siloxane-dimethylsiloxane multipolymer) and the polysiloxane cross-linking agent (polydimethylsiloxane of preferred furans end-blocking of furans end-blocking, diphenyl siloxane-the dimethylsiloxane copolymer of furans end-blocking, the diphenyl siloxane of furans end-blocking, furans end-blocking gathers trifluoro propyl methyl polysiloxane, the polydimethylsiloxane of furans propyl group end-blocking, at least one in the polydimethylsiloxane of furans alkylene oxide group end-blocking) be dissolved in organic solvent (preferred acetone, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, methylene dichloride, trichloromethane, Skellysolve A, normal hexane, normal heptane, octane, one or more mixture in toluene and dimethylbenzene) in, abundant stirring, standing and defoaming until completely dissolved, then solution is poured in Teflon mould, solvent flashing, then at 80 ~ 100 DEG C, carry out crosslinking reaction 4 ~ 5 days, the silicone elastomer of THERMALLY REVERSIBLE COVALENT can be obtained.
Further, in step (1), reaction system concentration is 0.05 ~ 0.5g/ml, and silicone copolymers amino in reaction system is 1:2 ~ 1:10 with the ratio of the amount of substance of MALEIC ANHYDRIDE.
Further, in step (2), reaction system concentration is 0.05 ~ 0.5g/ml, in reaction system, hydroxyl or amino-terminated polysiloxane are 1:4 ~ 1:10 with the ratio of the amount of substance of 2 furoyl chloride, the ratio of the amount of substance of triethylamine and hydroxyl or amino-terminated polysiloxane is 2:1 ~ 4:1, and the ratio of the amount of substance of DMAP and hydroxyl or amino-terminated polysiloxane is 1:25 ~ 1:100.
Further, in step (3), system concentration is 0.5 ~ 1g/ml, and the ratio of the amount of substance of the polysiloxane of described side base band maleimide and the polysiloxane cross-linking agent of furans end-blocking is 10:1 ~ 1:1.
The technical scheme that the present invention solves the employing of its technical problem is further, the application of a kind of THERMALLY REVERSIBLE COVALENT silicone elastomer in 3D printing and artificial skin material.
Compared with prior art, the present invention has following useful technique effect:
(1) on the side base of polysiloxane molecule chain, introduce the polysiloxane cross-linking agent of dienophile and diene body end-blocking, react at 60 ~ 100 DEG C, form the cross linking polysiloxane elastomerics that there is reversibility Diels-Alder key and be connected.Because Diels-Alder key is a kind of thermal reversion chemical bond, at high temperature can rupture, reduce temperature can regenerate again, this characteristic makes prepared silicone elastomer both have the performance of heavily processing, when without any additional renovation agent or catalyzer, selfreparing can be realized at mild conditions again.Again because Diels-Alder key is a kind of covalent linkage, this characteristic makes the mechanical property of prepared silicone elastomer than the excellence of the silicone elastomer be cross-linked to form by non covalent bond, and by regulating cross-linking density, in a big way, change material property.
(2) silicone elastomer of the present invention has hot workability, can be applicable to 3D and prints; Material matrix is polysiloxane, has excellent water-repellancy and ventilation property, can be applicable to artificial skin.
(3) the present invention all adopts single stage method to prepare the polysiloxane of side base band dienophile and diene body end-blocking, and raw material is easy to get, and building-up process is without the need to any special conditions or equipment, and synthesis technique is simple and easy to control, and productive rate is high, and relative cost is lower.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polysiloxane of side base band maleimide prepared by the present invention.
Fig. 2 is the infrared spectrum of the polysiloxane cross-linking agent of furans end-blocking prepared by the present invention.
Fig. 3 is the weighed processing characteristics photo display containing THERMALLY REVERSIBLE COVALENT point silicone elastomer prepared by the present invention.
Fig. 4 is the original sample containing THERMALLY REVERSIBLE COVALENT point silicone elastomer prepared by the present invention and the stress-strain curve repairing sample.
Embodiment
Below in conjunction with embodiment, the present invention is illustrated further.
Raw material: polysiloxane is all buied from Gelest company, other reagent all commercially.
Reaction formula:
Embodiment 1: the preparation of THERMALLY REVERSIBLE COVALENT silicone elastomer
(1) synthesis of the polysiloxane of side base band dienophile: the aminopropyltriethoxy siloxane-dimethylsiloxane multipolymer (trade mark: AMS-191, aminopropyltriethoxy content of siloxane 9 ~ 11%, molecular-weight average 3000) 10g, MALEIC ANHYDRIDE 6.52g and 100ml glacial acetic acid add in the 250ml single port flask with prolong, are heated to 140 DEG C of stirring reactions 12 hours in oil bath pan.At temperature 60 C after reaction terminates, vacuum tightness 0.08 ~ 0.1MPa backspin steams, removing glacial acetic acid, obtain light brown viscous liquid, then by light brown viscous liquid dissolves in 100ml methylene dichloride, three times are washed with deionized water, collected organic layer, after anhydrous magnesium sulfate drying, revolve and steam removing methylene dichloride, obtain the polysiloxane of side base band maleimide, as shown in Figure 1,696.1 is C-H out-of-plane bending stretching vibration absorption peak in maleimide ring double bond, illustrates that dienophile has been successfully introduced in polysiloxane.
(2) synthesis of the polysiloxane cross-linking agent of diene body end-blocking: claim the polydimethylsiloxane (1 putting aminopropyl end-blocking in 250ml single port flask, two (the 3-aminopropyl)-1 of 3-, 1, 3, 3-tetramethyl disiloxane, molecular-weight average 248) 11.5g, DMAP 0.11g and triethylamine 9.37g, then dissolve with 100ml anhydrous methylene chloride, stir under ice bath environment, 2 furoyl chloride 12.14g is dissolved in 50ml anhydrous methylene chloride, dropping limit, limit is stirred, and be slowly added drop-wise in flask, stir at ambient temperature after dropping terminates and continue to mix reaction 24 hours, the white precipitate of generation is filtered out after reaction terminates, then three times are washed with saturated sodium bicarbonate aqueous solution, collected organic layer, after anhydrous magnesium sulfate drying, temperature 40 DEG C, vacuum tightness 0.08 ~ 0.1MPa backspin steams, removing methylene dichloride, obtain the polysiloxane cross-linking agent of furans end-blocking, as shown in Figure 2, diene body dienophile has been successfully introduced in polysiloxane.
(3) containing the preparation of THERMALLY REVERSIBLE COVALENT point silicone elastomer: at room temperature, the polysiloxane 8.61g of side base band maleimide of preparation and the polysiloxane cross-linking agent 1.74g of furans end-blocking is dissolved in 20ml methylene dichloride, abundant stirring, leave standstill 15min deaeration until completely dissolved, then solution is poured in Teflon mould, at room temperature solvent flashing, then reacts 3 days, can obtain the silicone elastomer of THERMALLY REVERSIBLE COVALENT at 80 DEG C.
Embodiment 2: the weighed processing characteristics of THERMALLY REVERSIBLE COVALENT point silicone elastomer
Preparation shredded into fritter containing THERMALLY REVERSIBLE COVALENT point silicone elastomer rectangular specimens, then these is shredded into fritter compression molding, condition of molding: 140 DEG C, keep 3h under 20MPa condition, then place 24h at 80 DEG C, as shown in Figure 3.
As shown in Figure 3, when without any additional renovation agent or catalyzer, ganoid full sheet can be obtained in a mild condition, there is good elasticity, can selfreparing be realized.Embodiment 3: the self-healing properties of THERMALLY REVERSIBLE COVALENT point silicone elastomer
Cutting off preparation containing THERMALLY REVERSIBLE COVALENT point silicone elastomer rectangular specimens blade, then rapid both ends of the surface being fit together is placed on 3h in 140 DEG C of baking ovens, is then placed on 3h in 80 DEG C of baking ovens, as shown in Figure 4.
As shown in Figure 4, the cross linking polysiloxane elastomerics of preparation is when being heated to 120 ~ 140 DEG C, and THERMALLY REVERSIBLE COVALENT point can rupture, and when temperature is down to 60 ~ 100 DEG C, THERMALLY REVERSIBLE COVALENT point can be formed again again, realizes the reversibility of crosslink material network structure.
Claims (9)
1. a THERMALLY REVERSIBLE COVALENT silicone elastomer, is characterized in that, it has following structure:
2. a preparation method for THERMALLY REVERSIBLE COVALENT silicone elastomer as claimed in claim 1, is characterized in that, comprise the following steps:
(1) synthesis of the polysiloxane of side base band dienophile: be heated to 120 ~ 150 DEG C of stirring reactions 7 ~ 12 hours containing amino silicone copolymers and MALEIC ANHYDRIDE in glacial acetic acid, revolves and steams removing glacial acetic acid, obtain light brown viscous liquid; Then by light brown viscous liquid dissolves in methylene dichloride, wash 2 ~ 4 times with deionized water, collected organic layer, desiccant dryness, underpressure distillation removing methylene dichloride, obtain the polysiloxane of side base band maleimide.
(2) synthesis of the polysiloxane cross-linking agent of diene body end-blocking: by hydroxyl or amino-terminated polysiloxane, DMAP and triethylamine are dissolved in anhydrous methylene chloride, then under ice bath environment, slowly drip the anhydrous methylene chloride solution of 2 furoyl chloride, dropping limit, limit is stirred, stirring reaction is continued at ambient temperature 22 ~ 26 hours after dropping terminates, filter the white precipitate generated, then 2 ~ 4 times are washed with alkaline aqueous solution, collected organic layer, desiccant dryness, underpressure distillation removing methylene dichloride, obtain the polysiloxane cross-linking agent of furans end-blocking.
(3) containing the preparation of THERMALLY REVERSIBLE COVALENT point silicone elastomer: at room temperature, the polysiloxane cross-linking agent of the polysiloxane of the side base band maleimide of preparation and furans end-blocking is dissolved in organic solvent, abundant stirring, standing and defoaming until completely dissolved, then solution is poured in Teflon mould, solvent flashing, then carries out crosslinking reaction 4 ~ 5 days, can obtain the silicone elastomer of THERMALLY REVERSIBLE COVALENT at 80 ~ 100 DEG C.
3. the preparation method of THERMALLY REVERSIBLE COVALENT silicone elastomer according to claim 2, it is characterized in that, in step (1), reaction system concentration is 0.05 ~ 0.5g/ml, and silicone copolymers amino in reaction system is 1:2 ~ 1:10 with the ratio of the amount of substance of MALEIC ANHYDRIDE.
4. the preparation method of the THERMALLY REVERSIBLE COVALENT silicone elastomer according to Claims 2 or 3, it is characterized in that, in step (1), described is aminopropyltriethoxy siloxane-dimethylsiloxane multipolymer, aminoethylaminopropyl methylsiloxane-dimethylsiloxane copolymer or aminoethyl ammonia butyl methyl siloxane-dimethylsiloxane multipolymer containing amino silicone copolymers; Described siccative is anhydrous magnesium sulfate.
5. according to the preparation method of the THERMALLY REVERSIBLE COVALENT silicone elastomer one of claim 2 ~ 4 Suo Shu, it is characterized in that, in step (2), reaction system concentration is 0.05 ~ 0.5g/ml, in reaction system, hydroxyl or amino-terminated polysiloxane are 1:4 ~ 1:10 with the ratio of the amount of substance of 2 furoyl chloride, the ratio of the amount of substance of triethylamine and hydroxyl or amino-terminated polysiloxane is 2:1 ~ 4:1, and the ratio of the amount of substance of DMAP and hydroxyl or amino-terminated polysiloxane is 1:25 ~ 1:100.
6. according to the preparation method of the THERMALLY REVERSIBLE COVALENT silicone elastomer one of claim 2 ~ 5 Suo Shu, it is characterized in that, in step (2), described hydroxyl or amino-terminated polysiloxane are hydroxy-end capped polydimethylsiloxane, hydroxy-end capped diphenyl siloxane-dimethylsiloxane copolymer, hydroxy-end capped diphenyl siloxane, hydroxy-end capped poly-trifluoro propyl methyl polysiloxane, the polydimethylsiloxane of aminopropyl end-blocking or the polydimethylsiloxane of hydroxyl alkylene oxide group end-blocking; Described alkaline aqueous solution is saturated sodium bicarbonate; Described siccative is anhydrous magnesium sulfate.
7. according to the preparation method of the THERMALLY REVERSIBLE COVALENT silicone elastomer one of claim 2 ~ 6 Suo Shu, it is characterized in that, in step (3), system concentration is 0.5 ~ 1g/ml, and the ratio of the amount of substance of the polysiloxane of described side base band maleimide and the polysiloxane cross-linking agent of furans end-blocking is 10:1 ~ 1:1.
8. according to the preparation method of the THERMALLY REVERSIBLE COVALENT silicone elastomer one of claim 2 ~ 7 Suo Shu, it is characterized in that, in step (3), the polysiloxane of described side base band maleimide is at least one in maleimide propylmethylsiloxane-dimethylsiloxane copolymer, Mailed Ethyl aminopropyltriethoxy siloxane-dimethylsiloxane multipolymer, Mailed Ethyl ammonia butyl methyl siloxane-dimethylsiloxane multipolymer; The polysiloxane cross-linking agent of described furans end-blocking is the polydimethylsiloxane of furans end-blocking, the diphenyl siloxane-dimethylsiloxane copolymer of furans end-blocking, the diphenyl siloxane of furans end-blocking, furans end-blocking gather trifluoro propyl methyl polysiloxane, at least one in the polydimethylsiloxane of the polydimethylsiloxane of furans propyl group end-blocking, furans alkylene oxide group end-blocking; Described organic solvent is one or more the mixture in acetone, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, methylene dichloride, trichloromethane, Skellysolve A, normal hexane, normal heptane, octane, toluene and dimethylbenzene.
9. the application of THERMALLY REVERSIBLE COVALENT silicone elastomer according to claim 1 in 3D printing and artificial skin material.
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