CN116622046B - Post-crosslinkable high molecular weight polyurethane and preparation method thereof - Google Patents
Post-crosslinkable high molecular weight polyurethane and preparation method thereof Download PDFInfo
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- CN116622046B CN116622046B CN202310885161.2A CN202310885161A CN116622046B CN 116622046 B CN116622046 B CN 116622046B CN 202310885161 A CN202310885161 A CN 202310885161A CN 116622046 B CN116622046 B CN 116622046B
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- chain extender
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- -1 polyethylene Polymers 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- OWJKJLOCIDNNGJ-UHFFFAOYSA-N 4-[[4-hydroxybutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-ol Chemical group OCCCC[Si](C)(C)O[Si](C)(C)CCCCO OWJKJLOCIDNNGJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- VFUGMTAIQWBRCM-UHFFFAOYSA-N dihydroxy-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(O)O VFUGMTAIQWBRCM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000004132 cross linking Methods 0.000 abstract description 13
- 239000012948 isocyanate Substances 0.000 abstract description 11
- 150000002513 isocyanates Chemical class 0.000 abstract description 11
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract description 9
- 150000003138 primary alcohols Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 5
- 239000007943 implant Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 18
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920006264 polyurethane film Polymers 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
Classifications
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses high molecular weight polyurethane capable of being post-crosslinked and a preparation method thereof, and belongs to the technical field of polyurethane materials. The invention designs a novel chain extender by utilizing the difference of the reaction rates of primary alcohol or secondary alcohol and secondary amine with isocyanate, so that the isocyanate preferentially reacts with the secondary amine, and the hydroxyl of the primary alcohol or secondary alcohol of a side chain is reserved, so that the linear high molecular weight polyurethane with the hydroxyl in the side chain is prepared. The polyurethane prepared by the preparation method has high molecular weight, can be subjected to post-crosslinking, has improved mechanical properties, and is a long-term implant material with excellent performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to high molecular weight polyurethane capable of being post-crosslinked and a preparation method thereof.
Background
The usual post-crosslinking modes of polyurethanes at present are generally: firstly, synthesizing a prepolymer with lower molecular weight, then adding a low molecular weight cross-linking agent such as an isocyanate group or a hydroxyl end-capped polyurethane prepolymer into the system, wherein a plurality of polyurethane prepolymers can be connected into a three-dimensional network structure through chemical reaction by using polyol or polyisocyanate as the cross-linking agent of the system. The tensile strength, modulus, solvent resistance, high temperature resistance and other properties of the polyurethane can be greatly improved after moderate crosslinking. However, the polyurethane prepared by the post-crosslinking mode lacks the possibility of further processing and forming, the molecular weight between crosslinking points is low, the mechanical property is limited, and the post-crosslinking mode needs higher temperature to excite the reaction, so that the application of the polyurethane is greatly limited.
The polyurethane material with good toughness and high strength can be obtained by preparing the polyurethane with high molecular weight and side chain containing hydroxyl groups and then carrying out secondary crosslinking. The most common preparation method is to protect hydroxyl groups by adopting protecting groups, and then deprotect the polyurethane after the preparation of the polyurethane is completed, so as to obtain the linear polyurethane with the hydroxyl groups on the side chains. However, the deprotection reaction inevitably uses strong acid, strong alkali or strong oxidation or strong reducing agents, which can damage polyurethane molecular chains, for example, strong acid and strong alkali can hydrolyze ester bonds in polyester polyurethane, so that the molecular weight of polyurethane is reduced. Meanwhile, the introduction of the deprotection step increases the process flow, improves the production cost, and is difficult to realize large-scale production due to the requirement of a large amount of solvent for dissolution. Therefore, the use of protecting group strategies to introduce hydroxyl groups in the polyurethane side chains is very limited.
Disclosure of Invention
Aiming at the prior art, the invention provides post-crosslinkable high molecular weight polyurethane and a preparation method thereof, so as to solve the technical problem of difficult preparation of post-crosslinked polyurethane.
In order to achieve the above purpose, the technical scheme adopted by the invention is to provide a preparation method of high molecular weight polyurethane capable of post-crosslinking, which comprises the following steps:
s1: removing water from the propyl polyethylene glycol-terminated polydimethylsiloxane and the macromolecular dihydric alcohol, uniformly mixing the dehydrated propyl polyethylene glycol-terminated polydimethylsiloxane, the macromolecular dihydric alcohol, diisocyanate and the catalyst in an inert atmosphere, and reacting for 1-3 hours at 75-85 ℃ to obtain a polyurethane prepolymer system;
s2: adding a micromolecular dihydric alcohol chain extender into the polyurethane prepolymer system, and reacting for 1-3 hours at 75-85 ℃ to obtain a first chain extension system;
s3: dissolving the first chain extender system in a solvent, reducing the temperature of the solution to 5-15 ℃, adding a second chain extender into the solution, reacting for 30min in an ice bath, heating to 75-85 ℃, and continuing to react for 2-5 h to obtain the chain extender; the second chain extender is diamine with hydroxyl in the side chain.
Based on the technical scheme, the invention can also be improved as follows:
further, the macromolecular diol is polytetrahydrofuran ether glycol, polyethylene oxide ether glycol, polypropylene oxide ether glycol, polyhexamethylene ether glycol or poly (hexamethylene carbonate) glycol, and the molecular weight of the macromolecular diol is 500-2000; the macromolecule dihydric alcohol is dehydrated under vacuum, the dehydration temperature is 90-110 ℃, and the dehydration time is 1.5-2 h.
Further, the diisocyanate is at least one of isophorone diisocyanate, 4 '-methylenebis (phenyl isocyanate), 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and m-xylylene diisocyanate.
Further, the catalyst is an organotin catalyst or an organobismuth catalyst; the catalyst is used in an amount of 1% by weight based on the total weight of the substrate.
Further, the catalyst is dibutyl tin dilaurate.
Further, the small molecular diol chain extender is 1, 3-bis (4-hydroxybutyl) tetramethyl disiloxane or tetramethyl dihydroxy disiloxane.
Further, the structural general formula of the second chain extender is shown as formula I:
，
wherein R is 1 And R is 2 Are respectively and independently alkyl with 1-3 carbon atoms, R 3 Is alkyl with hydroxyl.
Further, the second chain extender is one of the following compounds,
、/>、/>。
further, the mass ratio of the macromolecular dihydric alcohol to the micromolecular dihydric alcohol chain extender is 2-9:1-8; the molar ratio of the small molecular diol chain extender to the second chain extender is 1:1.
The invention also discloses the high molecular weight polyurethane which can be post-crosslinked and is prepared by the preparation method.
The beneficial effects of the invention are as follows:
the steric effect in the chemical structure of the alcohol compound is greatly influenced by the steric effect in the chemical structure of the alcohol compound like other compounds, primary alcohol and isocyanate groups can react immediately at the temperature of 25-30 ℃, and under the same condition, the reaction rate of secondary alcohol is only 30% of that of primary alcohol, and the reaction rate of tertiary alcohol and isocyanate is slower and is only 0.5% of that of primary alcohol. In comparison, the reaction rate of the amino group and the isocyanate is much higher, and the reaction rate of the secondary amine and the isocyanate is tens to hundreds times that of the primary amine at the temperature of 25-30 ℃. Therefore, the invention designs a novel chain extender by utilizing the difference of the reaction rates of primary alcohol or secondary alcohol and secondary amine with isocyanate, so that the isocyanate preferentially reacts with the secondary amine, and the hydroxyl of the primary alcohol or secondary alcohol of a side chain is reserved, so that the linear high molecular weight polyurethane with the hydroxyl in the side chain is prepared. The secondary amine is selected instead of the primary amine because the primary amine group and the isocyanate react to form an allophanate bond which is easy to crosslink with the isocyanate, while the secondary amine and the isocyanate form a non-allophanate bond which is not easy to react with the isocyanate again, and the active hydrogen of the secondary amine is disappeared after the secondary amine and the isocyanate react, so that the crosslinking is not easy to occur.
Detailed Description
The following describes the present invention in detail with reference to examples.
Example 1
A post-crosslinkable high molecular weight polyurethane prepared by the steps of:
(1) Polyether polyurethane prepolymer with silicon-containing synthetic main chain
20g of propylpolyethylene glycol-terminated polydimethylsiloxane (PDMS, mn=1000) and 5g of polyhexamethylene ether glycol (PHMO, mn=700) were weighed, put into a three-necked flask, and dried for 2 hours under a vacuum environment at 105 ℃ to remove water in the system; the reaction system was then cooled to 60℃and N was bubbled in 2 Then, 14.66g of 4,4' -dicyclohexylmethane diisocyanate (isomer mixture) (HMDI) was added, 50. Mu.L of dibutyltin dilaurate (DBTDL, 1 wt.%) was added as a catalyst, and after the addition was completed, the temperature of the system was raised to 80℃and the reaction was continued for 2 hours to obtain a polyurethane prepolymer.
(2) First step chain extension reaction
3.93g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane (BHTD) was added to the flask after the reaction, and the reaction was continued at 80℃for 2 hours to complete the first chain extension; 290mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) was then added to dissolve the first chain-extended prepolymer into a homogeneous clear solution, and an ice bath was performed to reduce the temperature.
(3) Second step chain extension reaction
Dissolving a second chain extender (1.86 g) in 12mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) and slowly dropping the second chain extender into a flask by using a dropping funnel when the system is lowered to 10 ℃, reacting for 30min under ice bath, and then heating to 80 ℃ to continue to react for 3h to finish the second chain extension, thereby obtaining the high molecular weight polyurethane capable of being post-crosslinked; placing the mixture in a glass bottle for preservation. Wherein the second chain extender (mn= 132.21) has the following structural formula:
(4) Post-crosslinking (film formation): HMDI accounting for 3 percent of the mass of polyurethane is added into the high molecular weight polyurethane solution capable of being post-crosslinked, and then the mixture is poured into a polytetrafluoroethylene disc, and is put into an oven at 80 ℃ for drying for 24 hours, and then is put into a vacuum oven at 80 ℃ for drying for 24 hours, so that the post-crosslinked high molecular weight polyurethane film is obtained.
Example 2
A post-crosslinkable high molecular weight polyurethane prepared by the steps of:
(1) Polyether polyurethane prepolymer with silicon-containing synthetic main chain
20g of propyl polyethylene glycol-terminated polydimethylsiloxane (PDMS, mn=1000) and 5g of polytetrahydrofuran ether glycol (PTMG, mn=700) were weighed, put into a three-necked flask, and dried for 2 hours under a vacuum environment at 105 ℃ to remove water in the system; the reaction system was then cooled to 60℃and N was bubbled in 2 Then, 14.25g of melted and completely transparent liquid 4,4' -methylenebis (phenyl isocyanate) (MDI) was added, 50. Mu.L of dibutyltin dilaurate (DBTDL, 1 wt.%) was added as a catalyst, and after the addition, the temperature of the system was raised to 80℃and the reaction was carried out for 2 hours with heat preservation, to obtain a polyurethane prepolymer.
(2) First step chain extension reaction
4.07g of 1, 3-bis (4-hydroxybutyl) tetramethyl disiloxane (BHTD) was added to the flask after the reaction, and the reaction was continued at 80℃for 2 hours to complete the first chain extension; 287mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) was then added to dissolve the first chain-extended prepolymer into a homogeneous clear solution, and an ice bath was performed to reduce the temperature.
(3) Second step chain extension reaction
Dissolving a second chain extender (2.14 g) in 14mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) and slowly dropping the second chain extender into a flask by using a dropping funnel when the system is lowered to 10 ℃, reacting for 30min under ice bath, and then heating to 80 ℃ to continue to react for 3h to finish the second chain extension, thereby obtaining the high molecular weight polyurethane capable of being post-crosslinked; placing the mixture in a glass bottle for preservation. Wherein the second chain extender (mn= 146.23) has the following structural formula:
(4) Post-crosslinking (film formation): adding MDI accounting for 3 percent of the mass of polyurethane into the high molecular weight polyurethane solution capable of being post-crosslinked, pouring the polyurethane into a polytetrafluoroethylene disc, drying the polyurethane in an oven at 80 ℃ for 24 hours, and then drying the polyurethane in a vacuum oven at 80 ℃ for 24 hours to obtain the post-crosslinked high molecular weight polyurethane film.
Example 3
A post-crosslinkable high molecular weight polyurethane prepared by the steps of:
(1) Polyether polyurethane prepolymer with silicon-containing synthetic main chain
20g of propylpolyethylene glycol-terminated polydimethylsiloxane (PDMS, mn=2000) and 5g of polyhexamethylene ether glycol (PHMO, mn=1000) were weighed into a three-necked flask, and dried under a vacuum environment at 105 ℃ for 2 hours to remove water in the system; the reaction system was then cooled to 60℃and N was bubbled in 2 Then 11.48g isophorone diisocyanate (IPDI) was added, 50. Mu.L dibutyltin dilaurate (DBTDL, 1 wt.%) was added as a catalyst, and after the addition, the system temperature was raised to 80℃and the reaction was continued for 2 hours to obtain a polyurethane prepolymer.
(2) First step chain extension reaction
5.03g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane (BHTD) was added to the flask after the reaction, and the reaction was continued at 80℃for 2 hours to complete the first chain extension; 277mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) was then added to dissolve the first chain-extended prepolymer into a homogeneous clear solution, and an ice bath was performed to reduce the temperature.
(3) Second step chain extension reaction
Dissolving a second chain extender (3.94 g) in 26mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) and slowly dropping the second chain extender into a flask by using a dropping funnel when the system is lowered to 10 ℃, reacting for 30min under ice bath, and then heating to 80 ℃ to continue the reaction for 3h to finish the second chain extension, thereby obtaining the high molecular weight polyurethane capable of being post-crosslinked; placing the mixture in a glass bottle for preservation. Wherein the second chain extender (mn= 218.34) has the following structural formula:
(4) Post-crosslinking (film formation): and adding IPDI accounting for 5% of the mass of polyurethane into the high molecular weight polyurethane solution capable of being post-crosslinked, pouring the solution into a polytetrafluoroethylene disc, drying the solution in an oven at 80 ℃ for 24 hours, and then drying the solution in a vacuum oven at 80 ℃ for 24 hours to obtain the post-crosslinked high molecular weight polyurethane film.
Comparative example 1
A polyurethane prepared by the steps of:
(1) Polyether polyurethane prepolymer with silicon-containing synthetic main chain
20g of propyl polyethylene glycol-terminated polydimethylsiloxane (PDMS, mn=1000) and 5g of polyhexamethylene ether glycol (PHMO, mn=700) are weighed, put into a three-necked flask, dried for 2 hours under the vacuum environment of 105 ℃ and the moisture in the system is removed; the reaction was then reduced to 60℃and N was bubbled in 2 15.28g of 4,4' -dicyclohexylmethane diisocyanate (isomer mixture) (HMDI) and 50 mu L of dibutyltin dilaurate (DBTDL, 1 wt.%) were added as a catalyst, and after the addition, the temperature of the system was raised to 80℃and the reaction was continued for 2 hours to obtain a polyurethane prepolymer.
(2) First step chain extension reaction
4.25g of 1, 3-bis (4-hydroxybutyl) tetramethyl disiloxane (BHTD) was added to the flask, and the reaction was continued at 80℃for 2 hours to complete the first step of chain extension; then 295mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) is added to dissolve the prepolymer after the first chain extension into a uniform and clear solution, and ice bath is carried out to reduce the temperature;
(3) Second step chain extension reaction
Ethylenediamine (0.92 g) was dissolved in 6mL of anhydrous N, N-dimethylacetamide (DMAc, 15 wt%) and when the system was lowered to 10 ℃, it was slowly dropped into the flask using a dropping funnel, reacted under ice bath for 30min, then heated to 80 ℃ for further reaction for 3h, the second chain extension was completed to obtain polyurethane, which was put in a glass bottle for preservation.
(4) Film formation (uncrosslinked): pouring the product into a polytetrafluoroethylene disc, putting the polytetrafluoroethylene disc into an oven at 80 ℃ for drying for 24 hours, and then putting the polytetrafluoroethylene disc into a vacuum oven at 80 ℃ for drying for 24 hours to obtain the polyurethane film.
Experimental example 1: characterization of molecular weight
The post-crosslinkable high molecular weight polyurethanes prepared in the examples and the polyurethanes prepared in the comparative examples were characterized by molecular weight using gel chromatography (GPC) with a mobile phase of N, N-dimethylacetamide (DMAc) and 0.05mol/L lithium bromide, the stationary phase consisting of four μ -styrene gel HT columns (HT 2, HT3, HT4 and HT 5), the mobile phase having a flow rate of 1.0 mL/min, and the experiment being carried out at 80 ℃. The results are shown in Table 1.
TABLE 1 evaluation of polyurethane molecular weight
As can be seen from GPC results, the post-crosslinkable polyurethanes prepared according to the invention have a number average molecular weight in the range of more than one hundred thousand, while the polydispersity is smaller and is not very different from the non-post-crosslinkable polyurethanes (comparative example 1).
Experimental example 2: characterization of mechanical Properties
The tensile properties of the materials were tested using a universal tester. The polyurethane film after film formation was cut into 4 x 50 standard dumbbell shapes with a draw rate of 200mm/min and the results are shown in table 2.
TABLE 2 evaluation of mechanical Properties of postcrosslinked high molecular weight polyurethanes
As can be seen from Table 2, compared with polyurethane (comparative example 1) in which no post-crosslinkable hydroxyl groups are introduced into the side chains, the products of examples 1 to 3 of the present invention undergo post-crosslinking during the film formation process, and the obtained polyurethane has good mechanical properties.
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (7)
1. A process for the preparation of a postcrosslinkable high molecular weight polyurethane comprising the steps of:
s1: removing water from the propyl polyethylene glycol-terminated polydimethylsiloxane and the macromolecular dihydric alcohol, uniformly mixing the dehydrated propyl polyethylene glycol-terminated polydimethylsiloxane, the macromolecular dihydric alcohol, diisocyanate and the catalyst in an inert atmosphere, and reacting for 1-3 hours at 75-85 ℃ to obtain a polyurethane prepolymer system; the macromolecular dihydric alcohol is polytetrahydrofuran ether glycol, polyethylene oxide ether glycol, polypropylene oxide ether glycol, polyhexamethylene ether glycol or poly (hexamethylene carbonate) glycol, and the molecular weight of the macromolecular dihydric alcohol is 500-2000; the macromolecule dihydric alcohol is dehydrated under vacuum, the dehydration temperature is 90-110 ℃, and the dehydration time is 1.5-2 hours;
s2: adding a micromolecular dihydric alcohol chain extender into the polyurethane prepolymer system, and reacting for 1-3 hours at 75-85 ℃ to obtain a first chain extension system;
s3: dissolving the first chain extender system in a solvent, reducing the temperature of the solution to 5-15 ℃, adding a second chain extender into the solution, reacting for 30min in an ice bath, heating to 75-85 ℃, and continuing to react for 2-5 h to obtain the chain extender; the second chain extender is diamine with a side chain containing hydroxyl; the second chain extender is one of the following compounds,
、/>、/>。
2. the method of manufacturing according to claim 1, characterized in that: the diisocyanate is at least one of isophorone diisocyanate, 4 '-methylenebis (phenyl isocyanate), 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and m-xylylene diisocyanate.
3. The method of manufacturing according to claim 1, characterized in that: the catalyst is an organotin catalyst or an organobismuth catalyst; the catalyst is used in an amount of 1% by weight based on the total weight of the substrate.
4. A method of preparation according to claim 3, characterized in that: the catalyst is dibutyl tin dilaurate.
5. The method of manufacturing according to claim 1, characterized in that: the small molecular dihydric alcohol chain extender is 1, 3-bis (4-hydroxybutyl) tetramethyl disiloxane or tetramethyl dihydroxy disiloxane.
6. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the macromolecular dihydric alcohol to the micromolecular dihydric alcohol chain extender is 2-9:1-8; the mole ratio of the small molecular dihydric alcohol chain extender to the second chain extender is 1:1.
7. A post-crosslinkable high molecular weight polyurethane produced by the production process according to any one of claims 1 to 6.
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