CN105949422B - Polysiloxanes-urethane elastomers of the key containing Diels-Alder and preparation method thereof - Google Patents
Polysiloxanes-urethane elastomers of the key containing Diels-Alder and preparation method thereof 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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- 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
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- 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
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Abstract
The present invention relates to Material Fields; specially polysiloxanes-urethane elastomers and preparation method thereof of the key containing Diels-Alder; the polyester or polyethers, the dihydric alcohol of key containing Diels-Alder and catalyst dibutyltin dilaurylate of the dimethyl silicone polymer, isocyano sealing end that are blocked by crosslinking agent, isocyano are anhydrous 1; in six alkane of 4- dioxy, solidify gained after reacting under nitrogen protection.There is micro phase separation structure in the elastomer, many plastics microcells are formd inside elastomer, on the one hand these microcells play the role of improving tensile strength as physical crosslinking point.On the other hand, plastic deformation occurs for these plastics microcells itself in drawing process, plays the role of improving elongation at break.The raw material that this method uses is easy to get, and synthesis process is not necessarily to any specific condition or equipment, and synthesis technology is simple and easy to control, and yield is high.
Description
Technical field
The present invention relates to Material Field, specially polysiloxanes-urethane elastomers of the key containing Diels-Alder and
Preparation method.
Background technique
Polysiloxanes is a kind of to repeat Si-O key as main chain, be directly connected on silicon atom organic group it is half inorganic,
Half organic structure high-molecular compound, it is old with inorganic and organic polymer characteristic, such as high-low temperature resistant, weatherability
Change, electric insulation, resistance to ozone, hydrophobic, the good and nontoxic, biologically inert of gas-premeable etc..Be widely used in it is electric, build
It builds, automobile, weaving, the fields such as medical treatment.Polysiloxane molecule chain is submissive and intermolecular force is low, therefore usually with cross-linked elastomer
Form used, traditional silicone elastomer is faced with problem identical with all thermosetting materials: (1) material at
After there is breakage in type processing and use process, self-regeneration cannot achieve to extend the service life of material；(2) material is useless
It is difficult to recycle processing recycling after abandoning, causes greatly loss and the wasting of resources.
Currently, being had been reported about the selfreparing silicone elastomer that can be processed containing reversible dynamic key again.Harreld etc.
People discloses a kind of silicone elastomer based on hydrogen bond crosslinks in patent US 6783709B2.They introduce polypeptide poly-
Siloxane chain is prepared for cross linking polysiloxane elastomer using the characteristics of can forming hydrogen bond between polypeptide.The elastomer can
It selfreparing and processes again at room temperature, however, since 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 the material is crosslinked by boric acid ester bond is combined with the thermoplastic, polymeric materials such as pitch, PP, PE, SBS.But
The heavy processing temperature of material is higher (~200 DEG C), at the same can not judgement material self-healing properties superiority and inferiority.In addition to hydrogen bond and boric acid
Ester bond, Diels-Alder key are also a kind of effective reversible covalent bonds, the reaction have concurrently stereoselectivity, stereocpecificity and
Regioselectivity, and yield is high, and the irreversible temperature of reaction can be adjusted by changing the structure of close diene and diene, so as to
The processing temperature of controlled material, wherein furans-maleimide amine system due to its reaction condition it is most mild, thus study it is the widest
It is general.Xia Hesheng of Sichuan University et al. reports silicone elastomer (Zhao, the J. of a kind of Diels-Alder key crosslinking；
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.).They close first
At the siloxanes small molecule crosslinking agent that Maleimide-modified polysiloxane copolymer and furans block, the two passes through
Diels-Alder reacts the silicone elastomer to form the crosslinking of DA key.Material has excellent processing again and self-healing properties,
But the mechanical property of material is poor, and can not improve the mechanical property and self-healing properties of material simultaneously.
Polyurethane elastomer (Polyurethane elastomer abbreviation PU) is to contain carbamate (- NH- in molecule
COO-) the general designation of the polymer material of structure.It is formed by oligomer polyol and polyisocyanate polyaddition.Its MOLECULE DESIGN
Ability is strong, according to the difference of raw material and formula, the polyurethane elastomer material of available different performance.All polyurethane
Regard the block copolymer that rigid chain segment and soft segment are alternately formed by connecting as, due to the incompatibility of two kinds of segments, polyurethane
Microcosmic upper in micro phase separation structure.The unique texture of this microphase-separated of polyurethane elastomer, which imparts material, has other very
Excellent comprehensive performance not available for more commercialization rubber and plastics: high-intensitive 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 the THERMALLY REVERSIBLE COVALENT silicone elastomer poor mechanical property of existing hydrogen bonds or boric acid ester bond, again process
Temperature height and Diels-Alder key cross linking polysiloxane mechanics of elastic bodies performance and self-healing properties can not be changed simultaneously
Kind problem, in conjunction with the strong feature of polyurethane molecular design, it is poly- based on furans-maleimide that the present invention provides a kind of
Siloxanes-urethane elastomers and preparation method thereof.The mechanics of elastic bodies is had excellent performance, and weight processing performance is good, selfreparing
High-efficient, preparation process is simple, is of relatively low cost.
Specific technical solution are as follows:
Polysiloxanes-urethane elastomers of the key containing Diels-Alder, according to parts by weight by following starting material
It is made:
20 parts of crosslinking agent, 5~20 parts of dimethyl silicone polymer of isocyano sealing end, the polyester of isocyano sealing end or poly-
0~15 part of ether, 60 parts of the dihydric alcohol of key containing Diels-Alder；
Preparation method the following steps are included:
(1) preparation of the dimethyl silicone polymer (NCO-PDMS-NCO) of isocyano sealing end:
Dimethyl silicone polymer, triethylamine and bis- (trichloromethyl) carbonic esters that aminopropyl blocks are dissolved in benzene, nitrogen
Reaction 6 hours is stirred at room temperature under gas shielded；It filters after reaction, obtains brown liquid, 60 DEG C of revolvings removing solvents obtain different
The dimethyl silicone polymer (NCO-PDMS-NCO) of cyanate radical sealing end；
(2) preparation of the polyester or polyethers of isocyano sealing end:
Polyester or the pure and mild diisocyanate of polyether polyols are stirred to react 2 hours for 80 DEG C under nitrogen protection, obtain isocyanic acid
The polyester or polyethers of root sealing end, seal spare；
(3) preparation of the dihydric alcohol of key containing Diels-Alder:
By etc. amount of substance furans 1 and maleic anhydride 2 be dissolved in excessive Isosorbide-5-Nitrae-dioxane, be stirred to react at room temperature
For 24 hours, obtained sediment is smashed to pieces, is filtered, ether washing, drying, obtains product 3；Etc. amount of substance product 3 and hydramine exist
It is dissolved in methanol, is stirred to react at 75 DEG C for 24 hours under condition of ice bath, reaction mixture is put into refrigerator crystallisation by cooling, then through taking out
Filter, ether washing, drying, obtain product 4；Product 4 is added in excessive toluene, reaction 12h is stirred at reflux at 130 DEG C,
Then solution is filtered, filtrate is put into refrigerator crystallisation by cooling, is filtered, ether washing, drying, obtains product 5；Etc. amount of substance
Product 5 and furfuryl alcohol are stirred to react for 24 hours in 80 DEG C of Toluenes, and obtained sediment is smashed to pieces, are filtered, ether washing, drying,
Obtain product 6, the as dihydric alcohol of key containing Diels-Alder；
(4) polysiloxanes-urethane elastomers preparation of the key containing Diels-Alder:
20 parts of crosslinking agents, the dimethyl silicone polymer of 5~20 parts of isocyanos sealing end, 0~15 part of isocyano sealing end
Polyester or polyethers, 60 parts of dihydric alcohols of key containing Diels-Alder and catalyst dibutyltin dilaurylate (DBTL) are added anhydrous
In six alkane of Isosorbide-5-Nitrae-dioxy, it is stirred to react 12~24 hours for 80 DEG C under nitrogen protection, each component is gradually dissolved in whipping process
In solvent；
To the end of reacting, 70 DEG C of revolvings remove solvent, obtain flowable viscous prepolymer；
Prepolymer is finally poured into open Teflon mould, is placed in 80 DEG C of baking ovens and prepolymer is allowed to continue to solidify
24~96 hours, polysiloxanes-urethane elastomers of the key containing Diels-Alder are obtained, are removed from the molds spare.
The dimethyl silicone polymer that aminopropyl blocks in step (1) is the ammonia that molecular weight is 900,1000,3000 or 5000
Propyl blocks any one of dimethyl silicone polymer.
Reaction system concentration is 0.03~0.06g/mL in step (1).
Dimethyl silicone polymer, triethylamine and bis- (trichloromethyl) carbon that aminopropyl blocks in reaction system in step (1)
The ratio between amount of substance of acid esters is 1:4.5:1.5.
Diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two in step (2)
Any one of isocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate.
Polyester polyol is polyethylene glycol adipate, polyadipate ethylene glycol propylene glycol ester, polyadipate in step (2)
Any one of ethylene glycol butanediol ester, poly-epsilon-caprolactone glycol.
Polyether polyol is the equal polyether polyol of polypropylene oxide, the equal polyether polyol of polyethylene oxide, tetrahydro furan in step (2)
It mutters any one of equal polyether polyol.
The ratio between amount of substance-NCO/-OH=2/1 in step (2).
In step (3) hydramine be carbinolamine, ethanol amine, n-propanolamine, isopropanolamine, 4- amino n-butanol, 6- amino just
It is any in hexanol and diglycolamine.
Crosslinking agent is hexamethylene diisocyanate trimer, toluene diisocyanate trimer, diphenyl in step (4)
Any one of methane diisocyanate tripolymer.
The concentration of reaction system is 0.1~0.3g/mL in step (4).
Polysiloxanes-urethane elastomers of the key obtained containing Diels-Alder have selfreparing and process again
Performance.
Polysiloxanes-urethane elastomers of the key obtained containing Diels-Alder can be applied to 3D printing, group weaver
The fields such as journey and artificial skin.
The present invention has the advantage that
(1) due to having micro phase separation structure in polysiloxanes-urethane elastomers of the key containing Diels-Alder,
Many plastics microcells are formd inside elastomer, on the one hand these microcells play as physical crosslinking point and improve tensile strength
Effect.On the other hand, plastic deformation occurs for these plastics microcells itself in drawing process, plays the work for improving elongation at break
With.
(2) Diels-Alder key is a kind of thermal reversion chemical bond, can be broken at high temperature, and reducing temperature can give birth to again again
At, this characteristic polysiloxanes-urethane elastomers of the prepared key containing Diels-Alder are both had to process again
Performance, and can be realizing selfreparing without any outer plus renovation agent or catalyst in the case where.
(3) polysiloxanes-urethane elastomers of the key containing Diels-Alder have hot-working character, can be applied to
3D printing.The biocompatibility of material matrix is preferable, and polysiloxanes has excellent waterproofness and gas permeability, can be applied to group
Weaver's journey and artificial skin field.
(4) raw material that this method uses is easy to get, and synthesis process is not necessarily to any specific condition or equipment, and synthesis technology is simply easy
Control, yield are high.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the dimethyl silicone polymer of isocyano sealing end prepared by embodiment 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum of the glycol of key containing Diels-Alder prepared by embodiment 3；
Fig. 3 is polysiloxanes-urethane elastomers processing again of the key containing Diels-Alder prepared by embodiment 4
Performance photo display；
Fig. 4 is the original sample of polysiloxanes-urethane elastomers of the key containing Diels-Alder prepared by embodiment 4
With the load-deformation curve for repairing sample.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which this is pointed out that the present embodiment is served only for again
To the further explanation that the present invention carries out, it should not be understood as limiting the scope of the invention, person skilled in art can
Some nonessential modifications and adaptations are made with the content according to foregoing invention.It is substance without the following number of specified otherwise
Measure number.
Embodiment 1
The synthesis of the dimethyl silicone polymer of isocyano sealing end: the dimethyl silicone polymer DMS- of 10g aminopropyl sealing end
A12 (10mmol), 4.5g triethylamine (45mmol) and 4.45g triphosgene (15mmol) are dissolved in 300mL benzene, under nitrogen protection
Reaction 6 hours is stirred at room temperature.It filters after reaction, obtains brown liquid, 60 DEG C of revolvings remove solvent and obtain~9.9g brown
Dope.Its infrared spectrum is as shown in Figure 1.
Embodiment 2
Isocyano sealing end poly-epsilon-caprolactone synthesis: with the ratio between the amount of substance-OH/-NCO=2/1 weigh poly- ε-oneself
Lactone dihydric alcohol and methyl diphenylene diisocyanate, lower 80 DEG C of nitrogen protection are stirred to react 2 hours, obtain white solid isocyanide
The poly-epsilon-caprolactone of acid group sealing end, seals spare.
Embodiment 3
The synthesis of the dihydric alcohol of key containing Diels-Alder: by etc. amount of substance furans 1 and maleic anhydride 2 be dissolved in excessive 1,
It in 4- dioxane, is stirred to react at room temperature for 24 hours, obtained sediment is smashed to pieces, filtered, ether washing, drying, produced
Object 3；Etc. amount of substance product 3 and ethanol amine be dissolved in methanol under condition of ice bath, be stirred to react at 75 DEG C for 24 hours, reaction is mixed
It closes liquid and is put into refrigerator crystallisation by cooling, then filtered, ether washing, drying, obtain product 4；Product 4 is added to excessive first
In benzene, it is stirred at reflux reaction 12h at 130 DEG C, then filters solution, filtrate is put into refrigerator crystallisation by cooling, is filtered, ether
Washing, drying, obtain product 5；Etc. amount of substance product 5 and furfuryl alcohol be stirred to react in 80 DEG C of Toluenes for 24 hours, it is heavy by what is obtained
Starch is smashed to pieces, is filtered, ether washing, drying, obtains product 6, the as dihydric alcohol of key containing Diels-Alder.Its nucleus magnetic hydrogen spectrum
As shown in Figure 2.
Embodiment 4
Polysiloxanes-urethane elastomers preparation of the key containing Diels-Alder: 1.07g hexa-methylene two is weighed
The poly- diformazan of the Diels-Alder key dihydric alcohol, 3g isocyano sealing end that are synthesized in isocyanate trimer, 1.52g embodiment 3
Anhydrous Isosorbide-5-Nitrae-the dioxy of 25mL is added in 50mL round-bottomed flask in the poly-epsilon-caprolactone of radical siloxane and 0.62g isocyano sealing end
Six alkane and two drops catalyst dibutyltin dilaurylate (DBTL), are stirred to react 24 hours for 80 DEG C under nitrogen protection, stirred
Each component is gradually dissolved in solvent in journey.To the end of reacting, 70 DEG C of revolvings remove most of solvent, obtain flowable sticky
Prepolymer.Prepolymer is finally poured into open Teflon mould, is placed in 80 DEG C of baking ovens and prepolymer is allowed to continue to solidify
96 hours, polysiloxanes-urethane elastomers of the key containing Diels-Alder are obtained, are removed from the molds spare.
Embodiment 5
The heavy processing performance of polysiloxanes-urethane elastomers of the key containing Diels-Alder is shown.By embodiment 4
The elastomer rectangular specimens of middle preparation shred into fritter, these are then shredded into fritter and is pressed and molded, condition of molding: 140
DEG C, keep 30min under the conditions of 20MPa, then place for 24 hours at 80 DEG C.Fig. 3 attaches most importance to the photo display of processing performance.
Embodiment 6
Polysiloxanes-urethane elastomers self-healing properties of the key containing Diels-Alder are shown.By embodiment 4
In prepare elastomer rectangular specimens and cut off with blade, then both ends of the surface are fit together rapidly and are placed in 140 DEG C of baking ovens
30min is then placed in 80 DEG C of baking ovens for 24 hours.Fig. 4 is original sample and the load-deformation curve for repairing sample.
Claims (8)
1. polysiloxanes-urethane elastomers preparation method of the key containing Diels-Alder, described contains Diels-
Polysiloxanes-urethane elastomers of Alder key, are made according to parts by weight of following starting material:
20 parts of crosslinking agent, 5~20 parts of dimethyl silicone polymer of isocyano sealing end, the polyester or polyethers 0 of isocyano sealing end
~15 parts, 60 parts of the dihydric alcohol of key containing Diels-Alder；
Characterized by comprising the following steps:
(1) preparation of the dimethyl silicone polymer of isocyano sealing end:
Dimethyl silicone polymer, triethylamine and bis- (trichloromethyl) carbonic esters that aminopropyl blocks are dissolved in benzene, nitrogen is protected
Reaction 6 hours is stirred at room temperature under shield；It filters after reaction, obtains brown liquid, 60 DEG C of revolvings remove solvent and obtain isocyanic acid
The dimethyl silicone polymer of root sealing end；
(2) preparation of the polyester or polyethers of isocyano sealing end:
Polyester or the pure and mild diisocyanate of polyether polyols are stirred to react 2 hours for 80 DEG C under nitrogen protection, obtain isocyano envelope
The polyester or polyethers at end seal spare；
(3) preparation of the dihydric alcohol of key containing Diels-Alder:
By etc. amount of substance furans 1 and maleic anhydride 2 be dissolved in excessive Isosorbide-5-Nitrae-dioxane, be stirred to react at room temperature for 24 hours, will
Obtained sediment is smashed to pieces, is filtered, ether washing, drying, obtains product 3；Etc. amount of substance product 3 and hydramine in ice bath item
It is dissolved in methanol, is stirred to react at 75 DEG C for 24 hours under part, reaction mixture is put into refrigerator crystallisation by cooling, then filtered, ether
Washing, drying, obtain product 4；Product 4 is added in excessive toluene, reaction 12h is stirred at reflux at 130 DEG C, it then will be molten
Liquid filtering, filtrate are put into refrigerator crystallisation by cooling, are filtered, ether washing, drying, obtain product 5；Etc. the product 5 of amount of substance with
Furfuryl alcohol is stirred to react for 24 hours in 80 DEG C of Toluenes, and obtained sediment is smashed to pieces, is filtered, ether washing, drying, is produced
Object 6, as key containing Diels-Alder dihydric alcohol；
(4) polysiloxanes-urethane elastomers preparation of the key containing Diels-Alder:
The polyester that dimethyl silicone polymer, 0~15 part of isocyano that 20 parts of crosslinking agents, 5~20 parts of isocyanos block block
Or anhydrous 1,4- is added in polyethers, 60 parts of dihydric alcohols of key containing Diels-Alder and catalyst dibutyltin dilaurylate (DBTL)
In six alkane of dioxy, it is stirred to react 12~24 hours for 80 DEG C under nitrogen protection, each component is gradually dissolved in solvent in whipping process
In；
To the end of reacting, 70 DEG C of revolvings remove solvent, obtain flowable viscous prepolymer；
Prepolymer is finally poured into open Teflon mould, be placed in 80 DEG C of baking ovens allow prepolymer continue solidification 24~
96 hours, polysiloxanes-urethane elastomers of the key containing Diels-Alder are obtained, are removed from the molds spare.
2. polysiloxanes-urethane elastomers preparation side of the key according to claim 1 containing Diels-Alder
Method, which is characterized in that the dimethyl silicone polymer that aminopropyl blocks in the step (1) be molecular weight be 900,1000,
Any one of 3000 or 5000 aminopropyl sealing end dimethyl silicone polymer.
3. polysiloxanes-urethane elastomers preparation side of the key according to claim 1 containing Diels-Alder
Method, which is characterized in that aminopropyl blocks in reaction system in the step (1) dimethyl silicone polymer, triethylamine and double
The ratio between amount of substance of (trichloromethyl) carbonic ester is 1:4.5:1.5；Reaction system concentration is 0.03~0.06g/mL.
4. polysiloxanes-urethane elastomers preparation side of the key according to claim 1 containing Diels-Alder
Method, which is characterized in that in the step (2) diisocyanate be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
Any one of benzene dimethylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate；
Polyester polyol is polyethylene glycol adipate, polyadipate ethylene glycol propylene glycol ester, polyadipate second two in step (2)
Any one of alcohol butanediol ester, poly-epsilon-caprolactone glycol；
Polyether polyol is that the equal polyether polyol of polypropylene oxide, the equal polyether polyol of polyethylene oxide, tetrahydrofuran are equal in step (2)
Any one of polyether polyol.
5. polysiloxanes-urethane elastomers preparation of the key according to claim 1 or 4 containing Diels-Alder
Method, which is characterized in that the ratio between amount of substance-NCO/-OH=2/1 in the step (2).
6. polysiloxanes-urethane elastomers preparation side of the key according to claim 1 containing Diels-Alder
Method, which is characterized in that hydramine is carbinolamine, ethanol amine, n-propanolamine, isopropanolamine, the positive fourth of 4- amino in the step (3)
It is any in alcohol, 6- amino n-hexyl alcohol and diglycolamine.
7. polysiloxanes-urethane elastomers preparation side of the key according to claim 1 containing Diels-Alder
Method, which is characterized in that crosslinking agent is hexamethylene diisocyanate trimer, toluene di-isocyanate(TDI) in the step (4)
Any one of tripolymer, methyl diphenylene diisocyanate tripolymer.
8. polysiloxanes-urethane elastomers preparation of the key according to claim 1 or claim 7 containing Diels-Alder
Method, which is characterized in that the concentration of reaction system is 0.1~0.3g/mL in the step (4).
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| Application Number | Priority Date | Filing Date | Title |
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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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