CN105949422A - Polysiloxane-carbamate elastomer containing Diels-Alder bond and preparation method of polysiloxane-carbamate elastomer - Google Patents
Polysiloxane-carbamate elastomer containing Diels-Alder bond and preparation method of polysiloxane-carbamate elastomer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
- C08G18/3846—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring containing imide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
Abstract
The invention relates to the field of materials, in particular to a polysiloxane-carbamate elastomer containing a Diels-Alder bond and a preparation method of the polysiloxane-carbamate elastomer. The polysiloxane-carbamate elastomer is prepared from a cross-linking agent, isocyanato-terminated polydimethylsiloxane, isocyanato-terminated polyester or polyether, diol containing the Diels-Alder bond as well as a catalyst dibutyltin dilaurate through curing after a reaction in anhydrous 1,4-dioxane under the protection of nitrogen. The elastomer has a microphase separation structure, multiple plastic micro-areas are formed in the elastomer, and on one hand, the micro-areas are taken as physical crossing points to improve tensile strength; on the other hand, the plastic micro-areas generate plastic deformation in a stretching process to increase elongation at break. The method adopts easily available raw materials, a synthesis process requires no special conditions or equipment, a synthesis technology is simple and easy to control, and the yield is high.
Description
Technical field
The present invention relates to Material Field, be specially the polysiloxanes-urethane elastomers containing Diels-Alder key and system thereof
Preparation Method.
Background technology
Polysiloxanes is a class to repeat Si-O key as main chain, silicon atom is directly connected to organic group half inorganic, partly have
Machine structuring polymer compound, it is with inorganic and organic polymer characteristic, such as high-low temperature resistant, weather-resistant,
Electric insulation, resistance to ozone, hydrophobic, gas-premeable good and nontoxic, biologically inert etc..Be widely used in electric,
The fields such as building, automobile, weaving, medical treatment.Polysiloxane molecule chain is submissive and intermolecular force is low, therefore generally with crosslinking
The form of elastomer is used, and traditional silicone elastomer is faced with a difficult problem identical with all thermosets: (1)
After there is breakage during processing and forming and use in material, it is impossible to realize self-regeneration thus extend the service life of material；
(2) it is difficult to after material scrap reclaim processing recycling, causes loss and the wasting of resources greatly.
Have been reported currently, with respect to the selfreparing silicone elastomer can heavily processed containing reversible dynamic key.Harreld et al. exists
Patent US 6783709B2 discloses a kind of silicone elastomer based on hydrogen bond crosslinks.Polypeptide is introduced poly-silicon by them
Oxygen alkane side chain, utilizes the feature that can form hydrogen bond between polypeptide to be prepared for cross linking polysiloxane elastomer.This elastomer can be
Selfreparing and heavily processing under room temperature condition, but, owing to hydrogen bond action intensity is weak, the poor mechanical property of material.Odriozola
Ibon et al. discloses a kind of selfreparing silicone elastomer based on boric acid ester bond in patent WO 2013127989A1.
The polysiloxanes that this material is cross-linked by boric acid ester bond is composited with the thermoplastic, polymeric materials such as Colophonium, PP, PE, SBS.
But the heavy processing temperature of material higher (～200 DEG C), cannot judge the quality of material self-healing properties simultaneously.Except hydrogen bond
With boric acid ester bond, Diels-Alder key is also a kind of effective reversible covalent bonds, and this reaction has stereo selectivity, solid concurrently specially
One property and regioselectivity, and productivity is high, can be regulated the irreversible temperature of reaction by the structure changing parent's diene and diene,
Such that it is able to the processing temperature of controlled material, wherein furan-maleimide amine system due to its reaction condition the gentleest, thus grind
Study carefully the most extensive.Xia Hesheng of Sichuan University et al. reports the silicone elastomer of a kind of Diels-Alder key crosslinking
(Zhao,J.；Xu,R.；Luo,G.X.；Wu,J.；Xia,H.S.A self-healing,re-moldable and biocompatible
crosslinked polysiloxane elastomer.J.Mater.Chem.B,2016,4,982-989.).First they synthesized horse
Coming imide-modified polysiloxane copolymer and the siloxanes little molecule cross-linking agent of furan end-blocking, both pass through Diels-Alder
Reaction forms the silicone elastomer of DA key crosslinking.Material have excellence heavily processing and self-healing properties, but material
Mechanical property poor, and mechanical property and the self-healing properties of material cannot be improved simultaneously.
Polyurethane elastomer (Polyurethane elastomer is called for short PU) is containing carbamate (-NH-COO-) in molecule
The general designation of the polymeric material of structure.Formed by oligomer polyol and polyisocyanate polyaddition.Its MOLECULE DESIGN ability
By force, according to raw material and the difference of formula, the polyurethane elastomer material of different performance can be obtained.All polyurethane all can be seen
Making rigid chain segment and block copolymer that soft segment is alternately formed by connecting, due to the incompatibility of two kinds of segments, polyurethane exists
In micro phase separation structure on microcosmic.The unique texture of this microphase-separated of polyurethane elastomer imparts material, and to have other a lot
Excellent combination property not available for commercialization rubber and plastics: high intensity and high elongation rate, good wearability；Great Rong
The load support of amount, strong damping impact resistance, oil resistant, solvent resistance etc..
Summary of the invention
For existing hydrogen bonds or boric acid ester bond THERMALLY REVERSIBLE COVALENT silicone elastomer poor mechanical property, heavily process temperature
Degree height, and Diels-Alder key cross linking polysiloxane mechanics of elastic bodies performance and self-healing properties cannot be the most improved
Problem, in conjunction with the feature that polyurethane molecular design is strong, the invention provides a kind of poly-silica based on furan-maleimide
Alkane-urethane elastomers and preparation method thereof.This mechanics of elastic bodies excellent performance, weight good processability, self-repair efficiency
Height, preparation technology is simple, is of relatively low cost.
Concrete technical scheme is:
Polysiloxanes-urethane elastomers containing Diels-Alder key, is made up according to parts by weight of following initiation material:
Cross-linking agent 20 parts, the polydimethylsiloxane 5 of isocyano end-blocking～20 parts, the polyester or poly-of isocyano end-blocking
Ether 0～15 parts, containing Diels-Alder key dihydroxylic alcohols 60 parts；
Preparation method comprises the following steps:
(1) preparation of the polydimethylsiloxane (NCO-PDMS-NCO) of isocyano end-blocking:
Polydimethylsiloxane, triethylamine and double (trichloromethyl) carbonic ester that aminopropyl blocks being dissolved in benzene, nitrogen is protected
Protect down and reaction 6 hour is stirred at room temperature；Reaction is filtered after terminating, and obtains brown liquid, and 60 DEG C of rotations are evaporated off solvent and obtain isocyanide
The polydimethylsiloxane (NCO-PDMS-NCO) of acid group end-blocking；
(2) isocyano end-blocking polyester or the preparation of polyethers:
The 80 DEG C of stirrings under nitrogen protection of polyester or polyether polyol and diisocyanate are reacted 2 hours, obtain isocyano
The polyester of end-blocking or polyethers, seal standby；
(3) preparation containing Diels-Alder key dihydroxylic alcohols:
The furan 1 waiting material amount is dissolved in excess Isosorbide-5-Nitrae-dioxane with maleic anhydride 2, stirring reaction 24h under room temperature,
The precipitate obtained is smashed to pieces, through sucking filtration, ether washing, dries, obtain product 3；Product 3 and hydramine Deng material amount
Being dissolved in methanol under condition of ice bath, at 75 DEG C, stirring reaction 24h, puts into refrigerator crystallisation by cooling, then by reaction mixture
Through sucking filtration, ether washing, dry, obtain product 4；Product 4 is joined in the toluene of excess, be stirred at reflux at 130 DEG C
Reaction 12h, then filters solution, and filtrate puts into refrigerator crystallisation by cooling, through sucking filtration, ether washing, dries, is produced
Thing 5；Stir in 80 DEG C of Toluenes with furfuryl alcohol to react 24h Deng the product 5 of material amount, the precipitate obtained is smashed to pieces, warp
The washing of sucking filtration, ether, drying, obtain product 6, be containing Diels-Alder key dihydroxylic alcohols；
(4) preparation of the polysiloxanes-urethane elastomers containing Diels-Alder key:
20 parts of cross-linking agent, the polydimethylsiloxane of 5～20 parts of isocyano end-blockings, polyester of 0～15 part of isocyano end-blocking
Or polyethers, 60 parts add anhydrous 1,4-containing Diels-Alder key dihydroxylic alcohols and catalyst dibutyltin dilaurylate (DBTL)
In dioxy six alkane, 80 DEG C of stirrings are reacted 12～24 hours under nitrogen protection, and in whipping process, each component is gradually dissolved in solvent
In；
Question response terminates, and 70 DEG C of rotations are evaporated off solvent, obtain flowable viscous prepolymer；
Finally prepolymer is poured into uncovered Teflon mould, is placed in 80 DEG C of baking ovens and allows prepolymer continue solidification
24～96 hours, obtain the polysiloxanes-urethane elastomers containing Diels-Alder key, be removed from the molds standby.
In step (1) aminopropyl end-blocking polydimethylsiloxane be molecular weight be 900,1000,3000 or 5000
Any one in aminopropyl end-blocking polydimethylsiloxane.
In step (1), reaction system concentration is 0.03～0.06g/ml.
Polydimethylsiloxane, triethylamine and double (trichloromethyl) carbonic acid that in step (1), in reaction system, aminopropyl blocks
The ratio of the amount of the material of ester is 1:4.5:1.5.
In step (2), diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two
Any one in isocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate.
In step (2), PEPA is 10PE27, polyadipate ethylene glycol propylene glycol ester, polyadipate
Any one in ethylene glycol butanediol ester, poly-epsilon-caprolactone glycol.
In step (2), polyether polyol is the equal polyether polyol of poly(propylene oxide), the equal polyether polyol of poly(ethylene oxide), tetrahydrochysene furan
Mutter any one in equal polyether polyol.
Ratio-the NCO/-OH=2/1 of the amount of material in step (2).
In step (3), hydramine is carbinolamine, ethanolamine, normal propyl alcohol amine, isopropanolamine, 4-amino n-butyl alcohol, 6-amino
In hexanol and diglycolamine any one.
In step (4), cross-linking agent is hexamethylene diisocyanate trimer, toluene diisocyanate trimer, diphenyl
Any one in methane diisocyanate trimer.
In step (4), the concentration of reaction system is 0.1～0.3g/mL.
Polysiloxanes-the urethane elastomers containing Diels-Alder key prepared has selfreparing and the performance heavily processed.
Polysiloxanes-the urethane elastomers containing Diels-Alder key prepared can be applicable to 3D printing, organizational project
With fields such as artificial skins.
Present invention have the advantage that
(1) owing to the polysiloxanes-urethane elastomers containing Diels-Alder key having micro phase separation structure, bullet
Gonosome has been internally formed many plastics microcells, and on the one hand these microcells are as physical crosslinking point, play the work improving hot strength
With.On the other hand, in drawing process there is plastic deformation in these plastics microcells itself, plays the effect improving elongation at break.
(2) Diels-Alder key is a kind of thermal reversion chemical bond, at high temperature can rupture, and reduces temperature and can regenerate again,
This characteristic makes the prepared polysiloxanes-urethane elastomers containing Diels-Alder key both have the property heavily processed
Can, selfreparing can be realized in the case of without any additional renovation agent or catalyst again.
(3) polysiloxanes-urethane elastomers containing Diels-Alder key has hot-working character, can be applicable to 3D
Print.The biocompatibility of material matrix is preferable, and polysiloxanes has water proofing property and the breathability of excellence, can be applicable to group
Weaver's journey and artificial skin field.
(4) raw material that the method uses is easy to get, and building-up process is without any specific condition or equipment, and synthesis technique is the easiest
Control, productivity is high.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the polydimethylsiloxane of the isocyano end-blocking of embodiment 1 preparation；
Fig. 2 is the nucleus magnetic hydrogen spectrum containing Diels-Alder key glycol of embodiment 3 preparation；
Fig. 3 is the heavy processing characteristics of the polysiloxanes-urethane elastomers containing Diels-Alder key of embodiment 4 preparation
Photo display；
Fig. 4 is the original sample of the polysiloxanes-urethane elastomers containing Diels-Alder key of embodiment 4 preparation and repaiies
The load-deformation curve of duplicate sample.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to this is pointed out that the present embodiment is served only for this again
What invention was carried out further illustrates, it is impossible to being interpreted as limiting the scope of the invention, person skilled in art can root
Some nonessential improvement and adjustment are made according to the content of foregoing invention.Amount part of material it is without the following number of specified otherwise
Number.
Embodiment 1
The synthesis of the polydimethylsiloxane of isocyano end-blocking: the polydimethylsiloxane DMS-A12 of 10g aminopropyl end-blocking
(10mmol), 4.5g triethylamine (45mmol) and 4.45g triphosgene (15mmol) be dissolved in 300mL benzene,
Reaction 6 hour is stirred at room temperature under nitrogen protection.Reaction is filtered after terminating, and obtains brown liquid, and 60 DEG C of rotations are evaporated off solvent and obtain
Arrive～9.9g viscous brown thing.Its infrared spectrum is as shown in Figure 1.
Embodiment 2
The synthesis of the poly-epsilon-caprolactone of isocyano end-blocking: weigh poly-epsilon-caprolactone with the ratio-OH/-NCO=2/1 of the amount of material
Dihydroxylic alcohols and methyl diphenylene diisocyanate, the lower 80 DEG C of stirring reactions of nitrogen protection 2 hours, obtain white solid Carbimide.
The poly-epsilon-caprolactone of root end-blocking, seals standby.
Embodiment 3
Synthesis containing Diels-Alder key dihydroxylic alcohols: the furan 1 waiting material amount is dissolved in excess 1,4-bis-with maleic anhydride 2
In oxygen six ring, under room temperature, stirring reaction 24h, smashs to pieces the precipitate obtained, and through sucking filtration, ether washing, dries, obtains
Product 3；It is dissolved in methanol under condition of ice bath with ethanolamine Deng the product 3 of material amount, stirring reaction 24h at 75 DEG C, will
Reaction mixture puts into refrigerator crystallisation by cooling, then through sucking filtration, ether washing, drying, obtains product 4；Product 4 is added
Entering in the toluene of excess, be stirred at reflux reaction 12h, then filtered by solution at 130 DEG C, filtrate puts into refrigerator cooling
Crystallization, through sucking filtration, ether washing, dries, obtains product 5；Deng the product 5 of material amount with furfuryl alcohol in 80 DEG C of Toluenes
Stirring reaction 24h, smashs to pieces the precipitate obtained, and through sucking filtration, ether washing, dries, obtains product 6, be and contain
Diels-Alder key dihydroxylic alcohols.Its nucleus magnetic hydrogen spectrum is as shown in Figure 2.
Embodiment 4
The preparation of the polysiloxanes-urethane elastomers containing Diels-Alder key: weigh 1.07g hexa-methylene two isocyanide
The Diels-Alder key dihydroxylic alcohols of synthesis, the poly dimethyl of 3g isocyano end-blocking in acid esters trimer, 1.52g embodiment 3
The poly-epsilon-caprolactone of siloxanes and 0.62g isocyano end-blocking, in 50mL round-bottomed flask, adds the anhydrous Isosorbide-5-Nitrae-two of 25mL
Oxygen six alkane and two catalyst dibutyltin dilaurylate (DBTL), 80 DEG C of stirrings are reacted 24 hours under nitrogen protection,
In whipping process, each component is gradually dissolved in solvent.Question response terminates, and 70 DEG C of rotations are evaporated off major part solvent, obtain flowing
Dynamic viscous prepolymer.Finally prepolymer is poured into uncovered Teflon mould, is placed in 80 DEG C of baking ovens and allows prepolymer
Continue solidification 96 hours, obtain the polysiloxanes-urethane elastomers containing Diels-Alder key, be removed from the molds standby
With.
Embodiment 5
The heavy processing characteristics of the polysiloxanes-urethane elastomers containing Diels-Alder key is shown.Embodiment 4 will be made
Standby elastomer rectangular specimens shreds into fritter, then these is shredded into fritter compression molding, condition of molding: 140 DEG C,
Keep 30min under the conditions of 20MPa, then place 24h at 80 DEG C.Fig. 3 attaches most importance to the photo display of processing characteristics.
Embodiment 6
The self-healing properties of the polysiloxanes-urethane elastomers containing Diels-Alder key is shown.Embodiment 4 will be made
Standby elastomer rectangular specimens blade cuts off, and then both ends of the surface is fit together rapidly and is placed in 140 DEG C of baking ovens 30
Min, is then placed within 24h in 80 DEG C of baking ovens.Fig. 4 is original sample and the load-deformation curve repairing sample.
Claims (9)
1. polysiloxanes-the urethane elastomers containing Diels-Alder key, it is characterised in that pressed by following initiation material
Make according to parts by weight:
Cross-linking agent 20 parts, the polydimethylsiloxane 5 of isocyano end-blocking～20 parts, the polyester or poly-of isocyano end-blocking
Ether 0～15 parts, containing Diels-Alder key dihydroxylic alcohols 60 parts.
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 1,
It is characterized in that, comprise the following steps:
(1) preparation of the polydimethylsiloxane of isocyano end-blocking:
Polydimethylsiloxane, triethylamine and double (trichloromethyl) carbonic ester that aminopropyl blocks being dissolved in benzene, nitrogen is protected
Protect down and reaction 6 hour is stirred at room temperature；Reaction is filtered after terminating, and obtains brown liquid, and 60 DEG C of rotations are evaporated off solvent and obtain isocyanide
The polydimethylsiloxane of acid group end-blocking；
(2) isocyano end-blocking polyester or the preparation of polyethers:
The 80 DEG C of stirrings under nitrogen protection of polyester or polyether polyol and diisocyanate are reacted 2 hours, obtain isocyano
The polyester of end-blocking or polyethers, seal standby；
(3) preparation containing Diels-Alder key dihydroxylic alcohols:
The furan 1 waiting material amount is dissolved in excess Isosorbide-5-Nitrae-dioxane with maleic anhydride 2, stirring reaction 24h under room temperature,
The precipitate obtained is smashed to pieces, through sucking filtration, ether washing, dries, obtain product 3；Product 3 and hydramine Deng material amount
Being dissolved in methanol under condition of ice bath, at 75 DEG C, stirring reaction 24h, puts into refrigerator crystallisation by cooling, then by reaction mixture
Through sucking filtration, ether washing, dry, obtain product 4；Product 4 is joined in the toluene of excess, be stirred at reflux at 130 DEG C
Reaction 12h, then filters solution, and filtrate puts into refrigerator crystallisation by cooling, through sucking filtration, ether washing, dries, is produced
Thing 5；Stir in 80 DEG C of Toluenes with furfuryl alcohol to react 24h Deng the product 5 of material amount, the precipitate obtained is smashed to pieces, warp
The washing of sucking filtration, ether, drying, obtain product 6, be containing Diels-Alder key dihydroxylic alcohols；
(4) preparation of the polysiloxanes-urethane elastomers containing Diels-Alder key:
20 parts of cross-linking agent, the polydimethylsiloxane of 5～20 parts of isocyano end-blockings, polyester of 0～15 part of isocyano end-blocking
Or polyethers, 60 parts add anhydrous 1,4-containing Diels-Alder key dihydroxylic alcohols and catalyst dibutyltin dilaurylate (DBTL)
In dioxy six alkane, 80 DEG C of stirrings are reacted 12～24 hours under nitrogen protection, and in whipping process, each component is gradually dissolved in solvent
In；
Question response terminates, and 70 DEG C of rotations are evaporated off solvent, obtain flowable viscous prepolymer；
Finally prepolymer is poured into uncovered Teflon mould, is placed in 80 DEG C of baking ovens and allows prepolymer continue solidification
24～96 hours, obtain the polysiloxanes-urethane elastomers containing Diels-Alder key, be removed from the molds standby.
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 2,
It is characterized in that, in described step (1) aminopropyl end-blocking polydimethylsiloxane be molecular weight be 900,1000,3000
Or the aminopropyl of 5000 blocks any one in polydimethylsiloxane.
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 2,
It is characterized in that, polydimethylsiloxane, triethylamine and double (three that in described step (1), in reaction system, aminopropyl blocks
Chloromethyl) ratio of amount of material of carbonic ester is 1:4.5:1.5；Reaction system concentration is 0.03～0.06g/ml.
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 2,
It is characterized in that, in described step (2) diisocyanate be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
Any one in XDI, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate；
In step (2), PEPA is 10PE27, polyadipate ethylene glycol propylene glycol ester, polyadipate
Any one in ethylene glycol butanediol ester, poly-epsilon-caprolactone glycol；
In step (2), polyether polyol is the equal polyether polyol of poly(propylene oxide), the equal polyether polyol of poly(ethylene oxide), tetrahydrochysene furan
Mutter any one in equal polyether polyol.
6. according to the preparation of the polysiloxanes-urethane elastomers containing Diels-Alder key described in claim 2 or 5
Method, it is characterised in that the ratio-NCO/-OH=2/1 of the amount of material in described step (2).
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 2,
It is characterized in that, in described step (3) hydramine be carbinolamine, ethanolamine, normal propyl alcohol amine, isopropanolamine, 4-amino just
In butanol, 6-amino hexanol and diglycolamine any one.
The preparation method of the polysiloxanes-urethane elastomers containing Diels-Alder key the most according to claim 2,
It is characterized in that, in described step (4), cross-linking agent is hexamethylene diisocyanate trimer, toluene di-isocyanate(TDI)
Any one in trimer, methyl diphenylene diisocyanate trimer.
9. according to the preparation of the polysiloxanes-urethane elastomers containing Diels-Alder key described in claim 2 or 8
Method, it is characterised in that in described step (4), the concentration of reaction system is 0.1～0.3g/mL.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610305872.8A CN105949422B (en) | 2016-05-10 | 2016-05-10 | Polysiloxanes-urethane elastomers of the key containing Diels-Alder and preparation method thereof |
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| CN201610305872.8A CN105949422B (en) | 2016-05-10 | 2016-05-10 | Polysiloxanes-urethane elastomers of the key containing Diels-Alder and preparation method thereof |
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| CN106893305A (en) * | 2017-01-18 | 2017-06-27 | 福建师范大学泉港石化研究院 | A kind of heat cured polyurethane 3D printing material and preparation method thereof |
| CN107216643A (en) * | 2017-08-03 | 2017-09-29 | 四川大学 | A kind of selfreparing polyurethane nano composite material and its production and use |
| CN107814937A (en) * | 2017-11-17 | 2018-03-20 | 四川大学 | The silicone elastomer and preparation method and application of a kind of repeatable processing of selfreparing |
| CN107936532A (en) * | 2017-12-05 | 2018-04-20 | 四川大学 | A kind of silicon rubber powder for SLS and its preparation method and application |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
| CN108035173A (en) * | 2017-12-12 | 2018-05-15 | 江苏新瑞贝科技股份有限公司 | It is a kind of to be used to improve textile auxiliary of color fastness and preparation method thereof |
| CN108440735A (en) * | 2018-04-24 | 2018-08-24 | 四川大学 | Selfreparing flame resistance polyurethane elastomer of key containing Diels-Alder and preparation method thereof |
| CN108610466A (en) * | 2018-05-17 | 2018-10-02 | 山东大学 | A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes |
| CN109384928A (en) * | 2017-08-08 | 2019-02-26 | 天津大学 | Silicone elastomer and preparation method thereof based on aromatic radical cystine linkage and imine linkage |
| CN109575233A (en) * | 2018-12-10 | 2019-04-05 | 山东大学 | A kind of silicone polyether type polyurethane elastomer of strong mechanical performance and preparation method thereof |
| CN109749049A (en) * | 2017-11-03 | 2019-05-14 | 北京化工大学 | A kind of method that reversible chain extender prepares with it and prepares cross-linked polyurethane using it |
| CN110092912A (en) * | 2018-01-31 | 2019-08-06 | 天津大学 | Silicone elastomer material based on Diels-Alder reaction is can application in remodelable material |
| CN110092911A (en) * | 2018-01-31 | 2019-08-06 | 天津大学 | Application of the silicone elastomer material based on Diels-Alder reaction in self-repair material |
| CN110563915A (en) * | 2019-09-11 | 2019-12-13 | 中国科学院宁波材料技术与工程研究所 | novel polyurethane film, block copolymer nanoparticles and preparation method thereof |
| CN110684220A (en) * | 2018-06-22 | 2020-01-14 | 苏州大学 | Transparent foldable polysiloxane membrane that curls |
| CN111040119A (en) * | 2018-10-12 | 2020-04-21 | 泉州三欣新材料科技有限公司 | Self-repairing type organic silicon modified polyurethane and preparation method thereof |
| CN111388355A (en) * | 2020-04-06 | 2020-07-10 | 华中科技大学同济医学院附属协和医院 | Skin protective agent for preventing pathogen contact and preparation method thereof |
| CN112521684A (en) * | 2020-11-16 | 2021-03-19 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
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| CN106893305B (en) * | 2017-01-18 | 2019-09-10 | 福建师范大学泉港石化研究院 | A kind of heat cured polyurethane 3D printing material and preparation method thereof |
| CN106893305A (en) * | 2017-01-18 | 2017-06-27 | 福建师范大学泉港石化研究院 | A kind of heat cured polyurethane 3D printing material and preparation method thereof |
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| CN108035173A (en) * | 2017-12-12 | 2018-05-15 | 江苏新瑞贝科技股份有限公司 | It is a kind of to be used to improve textile auxiliary of color fastness and preparation method thereof |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
| CN110092911B (en) * | 2018-01-31 | 2021-01-19 | 天津大学 | Application of polysiloxane elastomer material based on Diels-Alder reaction in self-repairing material |
| CN110092912A (en) * | 2018-01-31 | 2019-08-06 | 天津大学 | Silicone elastomer material based on Diels-Alder reaction is can application in remodelable material |
| CN110092911A (en) * | 2018-01-31 | 2019-08-06 | 天津大学 | Application of the silicone elastomer material based on Diels-Alder reaction in self-repair material |
| CN110092912B (en) * | 2018-01-31 | 2021-01-19 | 天津大学 | Application of polysiloxane elastomer material based on Diels-Alder reaction in remodelable material |
| CN108440735A (en) * | 2018-04-24 | 2018-08-24 | 四川大学 | Selfreparing flame resistance polyurethane elastomer of key containing Diels-Alder and preparation method thereof |
| CN108440735B (en) * | 2018-04-24 | 2020-08-14 | 四川大学 | Self-repairing flame-retardant polyurethane elastomer containing Diels-Alder bond and preparation method thereof |
| CN108610466A (en) * | 2018-05-17 | 2018-10-02 | 山东大学 | A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes |
| CN108610466B (en) * | 2018-05-17 | 2021-04-06 | 山东大学 | Polyurea elastomer with polysiloxane completely replacing polyether and preparation method thereof |
| CN110684220A (en) * | 2018-06-22 | 2020-01-14 | 苏州大学 | Transparent foldable polysiloxane membrane that curls |
| CN110684220B (en) * | 2018-06-22 | 2022-04-15 | 苏州大学 | Transparent foldable polysiloxane membrane that curls |
| CN111040119A (en) * | 2018-10-12 | 2020-04-21 | 泉州三欣新材料科技有限公司 | Self-repairing type organic silicon modified polyurethane and preparation method thereof |
| CN109575233A (en) * | 2018-12-10 | 2019-04-05 | 山东大学 | A kind of silicone polyether type polyurethane elastomer of strong mechanical performance and preparation method thereof |
| CN110563915A (en) * | 2019-09-11 | 2019-12-13 | 中国科学院宁波材料技术与工程研究所 | novel polyurethane film, block copolymer nanoparticles and preparation method thereof |
| CN110563915B (en) * | 2019-09-11 | 2022-04-05 | 中国科学院宁波材料技术与工程研究所 | Polyurethane film, segmented copolymer nanoparticles and preparation method thereof |
| CN111388355A (en) * | 2020-04-06 | 2020-07-10 | 华中科技大学同济医学院附属协和医院 | Skin protective agent for preventing pathogen contact and preparation method thereof |
| CN112521684A (en) * | 2020-11-16 | 2021-03-19 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
| CN112521684B (en) * | 2020-11-16 | 2023-01-03 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
| CN113980663A (en) * | 2021-11-10 | 2022-01-28 | 四川大学 | High-temperature-resistant self-foaming expansion silicone rubber plugging material and preparation method thereof |
| CN113980663B (en) * | 2021-11-10 | 2022-08-16 | 四川大学 | High-temperature-resistant self-foaming expansion silicone rubber plugging material and preparation method thereof |
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