CN117264171A - Polymer silica gel with siloxane-based polyurethane as matrix and preparation method thereof - Google Patents
Polymer silica gel with siloxane-based polyurethane as matrix and preparation method thereof Download PDFInfo
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- CN117264171A CN117264171A CN202311339910.8A CN202311339910A CN117264171A CN 117264171 A CN117264171 A CN 117264171A CN 202311339910 A CN202311339910 A CN 202311339910A CN 117264171 A CN117264171 A CN 117264171A
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- Prior art keywords
- polyethylene glycol
- silica gel
- polydimethylsiloxane
- polyhydroxy
- preparation
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000741 silica gel Substances 0.000 title claims abstract description 29
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 29
- 239000004814 polyurethane Substances 0.000 title claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011159 matrix material Substances 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 title claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 67
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 polydimethylsiloxane chain Polymers 0.000 claims abstract description 31
- 150000002334 glycols Chemical class 0.000 claims abstract description 30
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 230000008961 swelling Effects 0.000 abstract description 7
- 239000003431 cross linking reagent Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 7
- 239000000499 gel Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229920003225 polyurethane elastomer Polymers 0.000 description 5
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000013008 moisture curing Methods 0.000 description 4
- 230000002522 swelling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000037311 normal skin Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
- C08G18/40—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
- C08G18/28—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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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 provides a macromolecule silica gel taking siloxane polyurethane as a matrix and a preparation method thereof, wherein a part of polyethylene glycol is converted into polyethylene glycol derivatives containing a plurality of hydroxyl groups, the derivatives are taken as cross-linking agents, the increase of hydrophilic chain segments in a cross-linked network is ensured, and simultaneously, the constructed large cross-linked network endows the polydimethylsiloxane chain segments with larger degree of freedom, so that the swelling degree of the prepared silica gel is above 130%, and the water vapor permeability is 28g/m 2 The oxygen permeability coefficient is 140 multiplied by 10 < -11 > cm above/h 3 ·cm/(cm 2 s.mmHg) or more, and an effective balance of water absorption, water vapor permeability and oxygen permeability can be sufficiently ensured.
Description
Technical field:
the invention relates to the field of polymer gel, in particular to polymer silica gel with siloxane polyurethane as a matrix and a preparation method thereof.
The background technology is as follows:
the gel is a polymer compound with a reticular structure, and the silica gel is a polymer gel formed by adding a proper reinforcing agent, a vulcanizing machine and a catalyst into liquid silicone rubber, uniformly mixing and vulcanizing, and has the advantages of simple preparation process, colorless and transparent after molding, high elasticity and excellent long-term fitting capability with skin. The physical properties of the silica gel film are similar to those of normal skin, and the silica gel film has excellent permeability to gases such as oxygen, carbon dioxide and the like, so that the silica gel film is often applied to wound medical dressings.
The main chain segment of the silica gel is polydimethylsiloxane and has hydrophobicity, so the silica gel has basically no water absorption capacity and has water vapor permeability of about 4.5g/m 2 /h, only half of the skin (normal human skin is about 8.5g/m 2 And/h), therefore, is generally not used for wounds with greater exudation.
CN105399912a discloses an amphiphilic polyurethane elastomer based on polysiloxane-polyethylene glycol and a preparation method thereof, wherein polyisocyanate and polyethylene glycol are reacted to obtain polyurethane prepolymer with end group as isocyanate group; polysiloxane and chain extender are added to prepare the amphiphilic polyurethane elastomer based on polysiloxane-polyethylene glycol, and the prepared amphiphilic polyurethane elastomer has the moisture permeability of 6.2-16.1g/m 2 And/h, the moisture permeability of the skin is close to that of human body. The scheme has lower moisture permeability and still has the risk of causing infection when being applied to wound surfaces with more seepage.
With the increase of the polyethylene glycol dosage, the hydrophilic chain segment is increased, so that the swelling degree and the moisture permeability of the polyurethane elastomer are obviously improved; however, this also enhances the miscibility between the polar polyisocyanate and the polyethylene glycol, greatly enhances the hydrogen bonding of the urethane group, induces more segments to form a microcrystalline structure, and thus greatly reduces the solubility coefficient of the gas and lowers the oxygen permeability. Therefore, it is highly demanded to prepare a silica gel which can ensure both the moisture permeability and the oxygen permeability and improve the application effect on the wound medical dressing.
The invention comprises the following steps:
the invention aims to provide a high molecular silica gel taking siloxane-based polyurethane as a matrix and a preparation method thereof, and aims to obtain the silica gel which can ensure water absorption, moisture permeability and oxygen permeability.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a high-molecular silica gel using siloxane polyurethane as matrix is prepared from polyhydroxy polyethanediol derivative, polyethanediol, polyisocyanate, polydimethyl siloxane and chain extender.
The preparation method of the silica gel of the invention comprises the following steps: reacting polyhydroxy polyethylene glycol derivative with polyethylene glycol, polyisocyanate and the like to obtain a polyurethane elastomer; and adding polysiloxane and a chain extender to finally obtain the high molecular silica gel taking siloxane polyurethane as a matrix.
The preparation method of the polyhydroxy polyethylene glycol derivative comprises the following steps: the polyethylene glycol reacts with epoxy chloropropane to obtain epoxy group end capped polyethylene glycol glycidyl ether, and the polyethylene glycol is subjected to ring opening under the catalysis of acid to generate polyhydroxy polyethylene glycol derivatives.
According to the invention, a part of polyethylene glycol is converted into a polyethylene glycol derivative containing a plurality of hydroxyl groups, and the derivative is used as a cross-linking agent, so that the increase of hydrophilic polyethylene glycol chain segments in a cross-linked network is ensured, the water absorption and the water vapor transmittance are greatly improved, and the constructed large cross-linked network is endowed with a larger degree of freedom for the polydimethylsiloxane chain segments, so that the obtained silica gel can achieve excellent balance of water absorption, water vapor transmittance and oxygen transmittance. The invention has simple scheme, cheap raw materials and certain adjustability.
Specifically, the technical scheme of the invention comprises the following steps:
adding polyhydroxy polyethylene glycol derivative and polyethylene glycol, stirring, heating to 90-130 deg.C, vacuum dewatering, and cooling to 40-60 deg.C; then, dropwise adding polyisocyanate, adding an organotin catalyst after dropwise adding, reacting a reaction system at 70-90 ℃ for 2-4 hours, adding polydimethylsiloxane, a chain extender and a solvent, continuously stirring and reacting for 6-8 hours, then introducing into a polytetrafluoroethylene mould for paving, putting the mould into a vacuum dryer, vacuumizing and defoaming for 0.5-1 hour, and then solidifying at a constant temperature of 50-70 ℃ for 8-12 hours to obtain the high polymer silica gel taking siloxane polyurethane as a matrix.
The preparation method of the polyhydroxy polyethylene glycol derivative specifically comprises the following steps: under the action of quaternary ammonium salt catalyst and sodium hydroxide, polyethylene glycol and epoxy chloropropane react for 2-4 hr at 40-60 deg.c to obtain epoxy group end capped polyethylene glycol glycidyl ether, deionized water and concentrated sulfuric acid are added to regulate pH value to acidity, ring opening reaction is performed at room temperature for 2-4 hr, sodium carbonate is used to regulate to neutrality, vacuum distillation is performed, the distilled product is filtered to eliminate precipitate, and the product is dried at 110-130 deg.c for 2-4 hr to obtain polyhydroxy polyethylene glycol derivative.
Preferably, in the process of preparing the polyhydroxy polyethylene glycol derivative, the quaternary ammonium salt catalyst is one or more of benzyl triethyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bisulfate.
For the purposes of the present invention, it is preferred that the molar ratio of polyethylene glycol, polyisocyanate, polydimethylsiloxane, chain extender is 1: (3-5): (0.5-1.5): (0.2-1); the mass ratio of polyethylene glycol to polyhydroxy polyethylene glycol derivative is (5-25): 1, a step of; the mass ratio of polyisocyanate to organotin catalyst is 100: (0.5-2); the mass ratio of the polydimethylsiloxane to the solvent is 1: (1-3).
Preferably, in the process of preparing the polyhydroxy polyethylene glycol derivative, the molar ratio of polyethylene glycol, epichlorohydrin, sodium hydroxide and quaternary ammonium salt catalyst is 1: (1.5-3): (1.5-3): (0.005-0.05).
Preferably, the polyethylene glycol has a molecular weight of 400 to 3000g/mol, more preferably 1000 to 2000g/mol.
Preferably, the polydimethylsiloxane is one or more of hydroxyl-terminated polydimethylsiloxane and amino-terminated polydimethylsiloxane; the molecular weight is 1000-6000g/mol, wherein the molecular weight is more preferably 1000-3000g/mol.
Preferably, the polyisocyanate is one or more of isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI).
Preferably, the chain extender is one or more of 1, 4-butanediol, diethylene glycol, ethylene glycol, and 1, 4-cyclohexanediol.
Preferably, the solvent is one or more of tetrahydrofuran, acetone, toluene, dimethyl sulfoxide and chloroform.
Preferably, the organotin catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and stannous oleate.
Compared with the prior art, the invention has the following beneficial effects:
the invention converts partial polyethylene glycol into polyethylene glycol derivative containing polyhydroxy, and takes the derivative as a cross-linking agent, the swelling degree of the prepared silica gel is above 130%, and the water vapor permeability is 28g/m 2 The oxygen permeability coefficient is 140 multiplied by 10 < -11 > cm above/h 3 ·cm/(cm 2 s.mmHg) or more, and an effective balance of water absorption, water vapor permeability and oxygen permeability can be sufficiently ensured.
The specific embodiment is as follows:
in order to make the purposes, technical solutions and advantages of the implementation of the present invention more clear, the technical solutions of the present invention are further described below by means of specific embodiments. Those skilled in the art should appreciate that the examples are only for aiding in understanding the technical contents and effects of the present invention and should not be construed as limiting the present invention.
Production example 1
Mixing 0.2mol (400 g) of polyethylene glycol-2000 (PEG-2K) with 0.4mol (37 g) of epichlorohydrin, adding 0.005mol (1.1 g) of benzyl triethyl ammonium chloride and 0.4mol (16 g) of sodium hydroxide, reacting at 55 ℃ for 2 hours to obtain epoxy group-terminated polyethylene glycol glycidyl ether, adding deionized water and concentrated sulfuric acid, adjusting the pH value to 5, carrying out ring-opening reaction at room temperature for 3 hours, adjusting to neutrality by sodium carbonate, carrying out reduced pressure distillation at 90 ℃ and vacuum degree of 0.085MPa, carrying out suction filtration to remove sediment, and weighing to obtain 375.14g of polyhydroxy polyethylene glycol derivative. The molecular weight of the polyhydroxy polyethylene glycol derivative is about 2150g/mol according to the structure calculation, and about 0.174mol of the product is obtained.
Production example 2
Mixing 0.2mol (200 g) of polyethylene glycol-1000 (PEG-1K) with 0.6mol (55.5 g) of epichlorohydrin, adding 0.005mol (about 1.6 g) of tetrabutylammonium bromide and 0.5mol (20 g) of sodium hydroxide, reacting at 45 ℃ for 4 hours to obtain epoxy group-terminated polyethylene glycol glycidyl ether, adding deionized water and concentrated sulfuric acid, adjusting the pH value to 5.5, carrying out ring-opening reaction at room temperature for 4 hours, adjusting to be neutral by sodium carbonate, distilling at 90 ℃ under vacuum degree of 0.085MPa under reduced pressure, filtering out suction filtration to remove sediment, drying at 110 ℃ for 4 hours, and weighing to obtain 192.46g of polyhydroxy polyethylene glycol derivative. The molecular weight of the polyhydroxy polyethylene glycol derivative is about 1150g/mol according to the structure calculation of the obtained polyhydroxy polyethylene glycol derivative, and the product of about 0.167mol is obtained.
Example 1
Uniformly stirring 40g of polyhydroxy polyethylene glycol derivative prepared in preparation example 1 and 0.4mol (800 g) of polyethylene glycol (PEG-2K), heating to 110 ℃, dehydrating in vacuum, and reducing the temperature to 50 ℃; then, 1.6mol (278.4 g) of toluene diisocyanate was added dropwise, after the completion of the dropwise addition, 2.5g of dibutyltin dilaurate was added, the reaction system was allowed to react at 70℃for 4 hours, then 0.3mol (300 g) of an amino-terminated polydimethylsiloxane (molecular weight: 1000), 0.3mol (18.6 g) of ethylene glycol, and 900g of acetone were added, the reaction was continued for 6 hours with stirring, and then the mixture was introduced into a polytetrafluoroethylene mold and laid flat, the mold was placed in a vacuum drier, and after the vacuum degassing treatment for 1 hour, the mixture was cured at a constant temperature of 60℃for 10 hours, to obtain a polymer silicone gel having a silicone-based polyurethane as a matrix.
Example 2
Uniformly stirring 20g of polyhydroxy polyethylene glycol derivative prepared in preparation example 2 and 0.2mol (100 g) of polyethylene glycol (PEG-1K), heating to 130 ℃, dehydrating in vacuum, and reducing the temperature to 60 ℃; then, 0.6mol (133.2 g) isophorone diisocyanate was added dropwise, 1.5g dibutyltin dilaurate was added after the completion of the dropwise addition, the reaction system was allowed to react at 90℃for 2 hours, then 0.2mol (400 g) hydroxyl-terminated polydimethylsiloxane (molecular weight: 2000), 0.05mol (4.5 g) 1, 4-butanediol, 600g tetrahydrofuran were added, the reaction was continued for 8 hours with stirring, and then the mixture was introduced into a polytetrafluoroethylene mold and laid flat, the mold was placed in a vacuum dryer, and after the evacuation and deaeration treatment for 0.5 hour, the mixture was cured at a constant temperature of 70℃for 8 hours, to obtain a polymer silicone gel based on a silicone-based polyurethane.
Example 3
Based on example 1, 0.4mol (800 g) of polyethylene glycol (PEG-2K) was replaced with 0.4mol (320 g) of polyethylene glycol-800 (PEG-800), the remaining conditions being unchanged.
Example 4
Based on example 2, 0.2mol (400 g) of hydroxy-terminated polydimethylsiloxane (molecular weight 2000) was replaced by 0.2mol (600 g) of hydroxy-terminated polydimethylsiloxane (molecular weight 3000), with the remaining conditions unchanged.
Comparative example 1
Based on example 1, no polyhydric polyethylene glycol derivative was added, the remaining conditions being unchanged.
Comparative example 2
Based on example 1, the curing conditions in the mold were changed to: moisture curing in air at room temperature for 24 hours, then moving to an oven, and continuously curing at 60 ℃ for 24 hours to obtain high polymer silica gel taking siloxane-based polyurethane as a matrix; the remaining conditions were unchanged.
Comparative example 3
Based on example 2, the amount of the polyhydric polyethylene glycol derivative was adjusted to 35g, and the remaining conditions were unchanged.
Comparative example 4
Based on example 2, the polyhydric polyethylene glycol derivative was replaced by 0.017mol (2.3 g) of pentaerythritol, the remaining conditions being unchanged.
Under the reaction conditions in comparative example 1, a crosslinked network was not completely formed, and therefore, there was no silica gel product having a certain mechanical strength, which was not subjected to the test of swelling property and the like, and only the swelling property, oxygen permeability and moisture permeability of the silica gel in examples 1 to 4 and comparative examples 2 to 4 were respectively tested.
Specific test methods are shown below.
The swelling performance was tested by cutting the silica gel into 3 cylinders of 5mm diameter and 10mm length, immersing them in phosphate buffer solution of ph=7.4 at room temperature until their mass was unchanged, namely, their mass was mw, and then placing the water-absorbed samples in a vacuum oven at 50 ℃ to constant weight, namely, their mass was md. The swelling properties were calculated by the following formula and averaged:
SR(％)＝(mw–md)/md×100％
the oxygen permeability was measured by differential pressure method, and a sample having a diameter of 50mm and a thickness of 1mm was placed in an atmosphere having a temperature of 25℃and a relative humidity of 50% for 12 hours as prescribed in GB/T2918 before the measurement. The test conditions were: the temperature was 25℃and the relative humidity was 50%, the external pressure was atmospheric pressure, and the test time was 8 hours.
The moisture permeability is tested by a moisture permeability tester, and a sample with the diameter of 50mm and the thickness of 1mm is placed in an environment with the temperature of 25 ℃ and the relative humidity of 50% for 12 hours according to the specification in GB/T2918 before the test. Test conditions: the temperature is 37 ℃, the relative humidity is 90+/-2 percent, the pressure is atmospheric, and the test time is 4 hours.
The results of the test are shown in table 1.
TABLE 1 results of tensile Properties, swelling Properties, oxygen permeability Properties and moisture permeability Properties of examples and comparative examples
From the test results of examples 1 to 4, the swelling degree of the polymer silica gel prepared by the invention and taking the siloxane-based polyurethane as a matrix is above 130%, and the water vapor permeability is 28g/m 2 The oxygen permeability coefficient is 140 multiplied by 10 above/h - 11 cm 3 ·cm/(cm 2 s.mmHg) or more, and an effective balance of water absorption, water vapor permeability and oxygen permeability can be sufficiently ensured.
From the comparison between example 1 and comparative example 2, the crosslinking mode in comparative example 2 is moisture curing, NCO groups react with moisture in the air, a cured network formed by moisture curing is smaller than a cured network using polyhydroxy polyethylene glycol derivatives as a crosslinking agent, crystallization is easy to form, polyethylene glycol segments are absent from the cured segments, hydrophilic network is reduced, insufficient network construction deep and inside the gel is caused by moisture curing, and finally, the swelling degree and water vapor permeability are low as a whole. In addition, the cured network becomes smaller, so that the degree of freedom of the polydimethylsiloxane in the space becomes smaller, and the gas passing is adversely affected. The curing network is large, polyethylene glycol in the curing chain segment is more, and the degree of freedom of the polydimethylsiloxane is higher, so that the effective balance of water absorption, water vapor transmittance and oxygen permeability coefficient can be fully ensured.
From example 2 and comparative example 3, as the amount of the polyhydroxy polyethylene glycol derivative increases, the degree of crosslinking becomes higher, excessive concentration of the crosslinked network will not be favorable for permeation of water vapor, and also for free rotation of the polydimethylsiloxane segment, which will result in a decrease in water vapor permeability and oxygen permeability coefficient; in addition, too dense a crosslinked network also leads to a decrease in the water swelling rate.
From example 2 and comparative example 4, the addition of pentaerythritol having a similar hydroxyl number as a crosslinking agent to replace the polyhydric polyethylene glycol derivative causes problems of too small a cured network and a reduced hydrophilic segment, resulting in a decrease in water absorption, water vapor permeability and oxygen permeability coefficient.
In summary, according to the invention, by converting part of polyethylene glycol into the polyethylene glycol derivative containing a plurality of hydroxyl groups and using the derivative as the cross-linking agent, the increase of hydrophilic polyethylene glycol chain segments in a cross-linked network is ensured, so that the water absorption and the water vapor transmittance are greatly improved, and the constructed large cross-linked network ensures the greater degree of freedom of the polydimethylsiloxane chain segments, so that the obtained silica gel can achieve excellent balance of water absorption, water vapor transmittance and oxygen transmittance.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (9)
1. The preparation method of the polymer silica gel with the siloxane-based polyurethane as the matrix is characterized by comprising the following steps:
adding polyhydroxy polyethylene glycol derivative and polyethylene glycol, stirring, heating to 90-130 deg.C, vacuum dewatering, and cooling to 40-60 deg.C; then, dropwise adding polyisocyanate, adding an organotin catalyst after dropwise adding, reacting a reaction system at 70-90 ℃ for 2-4 hours, adding polydimethylsiloxane, a chain extender and a solvent, continuously stirring and reacting for 6-8 hours, then introducing into a polytetrafluoroethylene mould for paving, putting the mould into a vacuum dryer, vacuumizing and defoaming for 0.5-1 hour, and then solidifying at a constant temperature of 50-70 ℃ for 8-12 hours to obtain the high polymer silica gel taking siloxane polyurethane as a matrix.
2. The method according to claim 1, wherein the preparation method of the polyhydroxy polyethylene glycol derivative is specifically as follows: under the action of quaternary ammonium salt catalyst and sodium hydroxide, polyethylene glycol and epoxy chloropropane react for 2-4 hr at 40-60 deg.c to obtain epoxy group end capped polyethylene glycol glycidyl ether, deionized water and concentrated sulfuric acid are added to regulate pH value to acidity, ring opening reaction is performed at room temperature for 2-4 hr, sodium carbonate is used to regulate to neutrality, vacuum distillation is performed, the distilled product is filtered to eliminate precipitate, and the product is dried at 110-130 deg.c for 2-4 hr.
3. The method according to claim 2, wherein in the process of preparing the polyhydroxy polyethylene glycol derivative, the molar ratio of polyethylene glycol, epichlorohydrin, sodium hydroxide and quaternary ammonium salt catalyst is 1: (1.5-3): (1.5-3): (0.005-0.05); the quaternary ammonium salt catalyst is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride and tetrabutyl ammonium bisulfate.
4. The method according to claim 1, wherein the molar ratio of polyethylene glycol, polyisocyanate, polydimethylsiloxane, chain extender is 1: (3-5): (0.5-1.5): (0.2-1); the mass ratio of polyethylene glycol to polyhydroxy polyethylene glycol derivative is (5-25): 1, a step of; the mass ratio of polyisocyanate to organotin catalyst is 100: (0.5-2); the mass ratio of the polydimethylsiloxane to the solvent is 1: (1-3).
5. The method of claim 1, wherein the polyethylene glycol has a molecular weight of 400-3000g/mol, and the polydimethylsiloxane is one or more of a hydroxyl-terminated polydimethylsiloxane, an amino-terminated polydimethylsiloxane; the molecular weight is 1000-6000g/mol.
6. The method according to claim 5, wherein the polyethylene glycol has a molecular weight of 1000 to 2000g/mol and the polydimethylsiloxane has a molecular weight of 1000 to 3000g/mol.
7. The process of claim 1 wherein the polyisocyanate is one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate.
8. The method according to claim 1, wherein the chain extender is one or more of 1, 4-butanediol, diethylene glycol, ethylene glycol and 1, 4-cyclohexanediol, the solvent is one or more of tetrahydrofuran, acetone, toluene, dimethyl sulfoxide and chloroform, and the organotin catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and stannous oleate.
9. A polymeric silica gel based on a siloxane-based polyurethane, characterized in that it is obtainable by the preparation process according to any one of claims 1 to 8.
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