CN105968242B - Macromolecule hydrogel and its micellar copolymerization preparation method using polysiloxanes based polyurethanes as crosslinking agent - Google Patents
Macromolecule hydrogel and its micellar copolymerization preparation method using polysiloxanes based polyurethanes as crosslinking agent Download PDFInfo
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- CN105968242B CN105968242B CN201610375891.8A CN201610375891A CN105968242B CN 105968242 B CN105968242 B CN 105968242B CN 201610375891 A CN201610375891 A CN 201610375891A CN 105968242 B CN105968242 B CN 105968242B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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Abstract
The invention discloses the macromolecule hydrogel and its micellar copolymerization preparation method using polysiloxanes based polyurethanes as crosslinking agent.During preparation, the polysiloxane group polyurethane macromers of first synthesis of acrylic ester monomer end-blocking, and with surfactant formulatory micellar aqueous solution；Then macromonomer is added in micellar aqueous solution, macromonomer is entered in micella, add acrylamide monomers and light trigger, and it is completely dissolved with ultrasound, obtain water solution system；The homopolymerization of monomer and copolymerization contained by this light-initiated system, the macromolecule hydrogel using polysiloxanes based polyurethanes as crosslinking agent is made.The preparation process of macromolecule hydrogel of the present invention is simple and easy, is substantially shorter preparation time, and without using any organic solvent；The elongation at break ＞ 600% of the hydrogel of gained, oxygen permeability coefficient >=45 × 10‑11cm3·cm/(cm2·s·mmHg)。
Description
Technical field
The present invention relates to a kind of macromolecule hydrogel, more particularly to a kind of using polysiloxanes based polyurethanes as crosslinking agent
Macromolecule hydrogel and its micellar copolymerization preparation method.
Background technology
High-molecular hydrogel dressing can absorb a large amount of sepages, promote the autologous debridement of the surface of a wound, maintain wound surface moderate
Humidity environment, accelerate wound healing.But the oxygen permeability of conventional hydrogels is generally poor, cover for a long time possible during wound
The surface of a wound can be made to have feeling of oppression and heat and burn feeling, increase the property of not relaxing of patient, be unfavorable for wound healing.
Organosilicon material is a kind of excellent bio-medical material, and its strand compares compliance, and larger containing volume
- Si (CH3)2O- groups, there is excellent permeability.Therefore, macromolecule hydrogel can be improved using organosilicon material
Oxygen permeability.At present, it is in silicone molecules chain silicone molecules chain to be incorporated into the main method of macromolecule hydrogel
Bonded reactable group (for example, epoxy radicals, sulfydryl, carbon-carbon double bond etc.), then it is passed through polymerisation shape with hydrophilic monomer
Into cross-linked network structure.Based on the structure and degree of functionality of reactable group in silicone molecules chain, silicone molecules chain can be with
The mode of side chain or crosslinking points is incorporated into macromolecule hydrogel strand.However, organosilicon is a kind of non-polar material,
Dissolubility extreme difference in water, thus the preparation process base for the macromolecule hydrogel on the strand containing organosilicon reported at present
This is carried out in organic solvent, then is replaced by solvent to obtain the macromolecule hydrogel of the strand containing organosilicon.This kind of preparation
Method has to use organic solvent, therefore operation is complex, and preparation process is not environmentally.Entitled
“Hemocompatibility and cytocompatibility of styrenesulfonate‐grafted PDMS‐
polyurethane‐HEMA hydrogel(Chien‐Hong Lin,Win‐Chun Jao,Yi‐Hsing Yeh,Wen‐Ching
Lin,Ming‐Chien Yang,Colloids and Surfaces B:Biointerfaces, 2009,70,132.) grinding "
Study carefully in paper, author first designs and be prepared for the polysiloxane group polyurethane macromers that end carries carbon-carbon double bond, then will
It is copolymerized the macromolecule hydrogel that the strand containing organosilicon is made with hydroxyethyl methacrylate.Although the system will effectively can have
Machine silicon strand is incorporated into macromolecule hydrogel, but copolymerization system needs with big after completion of polymerization using tetrahydrofuran as solvent
The water displacement tetrahydrofuran of amount, preparation spent time is longer, can produce the largely waste water containing organic matter, and the macromolecule water of gained
The elongation at break highest of gel only has 100% or so.
The content of the invention
It is an object of the invention to prepare one kind without using organic solvent using micell polymerization method, there is good oxygen permeability
With the macromolecule hydrogel and its micellar copolymerization preparation method using polysiloxanes based polyurethanes as crosslinking agent of physical and mechanical properties.
A kind of preparation method using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent proposed by the present invention, first
The polysiloxane group polyurethane macromers of synthesis of acrylic ester monomer end-blocking, and it is water-soluble with surfactant formulatory micella
Liquid；Then, macromonomer is added in micellar aqueous solution and stirred, macromonomer is entered in micella, added
Acrylamide monomers and light trigger, and it is completely dissolved it with ultrasound, obtain containing acrylamide monomers, esters of acrylic acid
The micella of polysiloxane group polyurethane macromers and the water solution system of light trigger of monomer end-blocking；With it is light-initiated this
The free radical copolymerization between macromonomer in the homopolymerization of monomer contained by system and acrylamide monomers and micella,
The chain containing polysiloxane molecule, macromolecule hydrogel using polysiloxanes based polyurethanes as crosslinking agent is made.The micella of the present invention
Polymerization prepares simple, easy without using organic solvent, technique by the macromolecule hydrogel of crosslinking agent of polysiloxanes based polyurethanes
Capable, controllable, raw material is easy to get, the composition of material and being regulated and controled according to performance requirement for structure, prepared macromolecule water
Gel can have good oxygen permeability and physical and mechanical properties.
The object of the invention is achieved through the following technical solutions：
Micellar copolymerization preparation method using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel, including following step
Suddenly：
1) synthesis of the polysiloxane group polyurethane macromers of acrylic ester monomer end-blocking：Polysiloxanes is existed
Vacuum dehydration 2~3 hours at 100~120 DEG C, placement cool to less than 60 DEG C；Then, polyisocyanates is added under agitation,
70~90 DEG C are warming up to again, are reacted 3~5 hours；Acrylic ester monomer and catalyst is added dropwise, reacts 10~24 hours,
The polysiloxane group polyurethane macromers of acrylic ester monomer end-blocking are made, sealing refrigeration is stand-by after vacuum defoamation；Institute
The catalyst stated be dibutyl tin laurate, stannous octoate, dibutyltin diacetate and dimethyl cyclohexyl amine in one kind or
Two kinds；
2) preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：By surfactant and sodium chloride
It is added in deionized water, stirring adds the polysiloxanes that acrylic ester monomer blocks until the transparent micellar aqueous solution of acquisition
Based polyurethanes macromonomer, and stir, the polysiloxanes based polyurethanes for obtaining the end-blocking containing acrylic ester monomer divide greatly
The aqueous solution of sub- monomer micella；Then, acrylamide monomers and light trigger are added in obtained micellar aqueous solution,
And it is completely dissolved it with ultrasound, obtain the poly- ammonia of polysiloxane group containing acrylamide monomers, acrylic ester monomer end-blocking
The micella of macromonomer and the water solution system of light trigger；Homopolymerization and acrylamide monomers with light-initiated monomer
With the free radical copolymerization between the macromonomer in micella, the high score using polysiloxanes based polyurethanes as crosslinking agent is made
Sub- hydrogel；
Described light trigger is 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones, 2,4,6-
Trimethylbenzoy-dipheny phosphine oxide, benzophenone, 2- hydroxyls -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones and ɑ -one
One or more in glutaric acid；Described surfactant is neopelex, lauryl sodium sulfate, octadecane
One or more in base dimethyl benzyl ammonium chloride and cetyl trimethylammonium bromide.
Further to realize the object of the invention, it is preferable that in terms of mass fraction, raw material components composition is：
Preferably, described polyisocyanates is IPDI, 1,6- hexamethylene diisocyanates, first
Phenylene diisocyanate, diphenyl methane -4,4 '-diisocyanate, XDI, the isocyanide of methylcyclohexyl two
One or more in acid esters, tetramethylxylylene diisocyanate.
Preferably, described polysiloxanes is hydroxy-terminated polysiloxane, amino-terminated polysiloxanes and end hydroxy polyether
One or more in polysiloxanes.
Preferably, the molecular weight of described polysiloxanes is 1000~6000g/mol.
Preferably, described acrylic ester monomer is hydroxyethyl methacrylate, hydroxy-ethyl acrylate and polyethylene glycol
One or more in acrylate.
Preferably, described acrylamide monomers be acrylamide, Methacrylamide, NIPA,
One or more in N- isopropyl acrylamides and dimethylamino-propyl acrylamide.
Preferably, in step 2), the polysiloxane group polyurethane macromers of the end-blocking containing acrylic ester monomer are obtained
The condition of the aqueous solution of micella stirs 30~60 minutes at a temperature of being 25~40 DEG C.
Preferably, in step 2), the homopolymerization of light-initiated monomer and acrylamide monomers and the macromolecular list in micella
The duration of the free radical copolymerization of body is 30~120 minutes.
One kind is using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel, by above-mentioned micellar copolymerization preparation method system
, tensile strength >=90kPa of macromolecule hydrogel, elongation at break ＞ 600%, oxygen permeability coefficient >=45 × 10-11cm3·cm/
(cm2·s·mmHg)。
Relative to prior art, the present invention has advantages below：
1) the micell polymerization method preparation process of the macromolecule hydrogel of the strand of the present invention containing organosilicon need not appoint
What organic solvent, it is not necessary to handle substantial amounts of organic wastewater, there are no document report in the prior art and utilize micellar copolymerization legal system
The macromolecule hydrogel of the standby strand containing organosilicon；Prepared macromolecule hydrogel has good oxygen permeability and physical mechanical
Performance.
2) macromolecule hydrogel prepared by is the ammonia in polysiloxanes based polyurethanes in micella using micella as crosslinking points
Carbamate base can form hydrogen bond, when stress acts on, the dissociation and association of hydrogen bond can dispersive stress well, so as to favourable
In the physical and mechanical properties for improving hydrogel.
3) raw material used in the present invention is the industrial goods of commercialization, cheap and easy to get, and building-up process is without special condition
And equipment, synthesis technique is simple, easy, and easily regulation and control, and it is relatively low to prepare cost.
Brief description of the drawings
Fig. 1 is the red of the polysiloxane group polyurethane macromers that acrylic ester monomer made from embodiment 1 blocks
Outer spectrogram.
Fig. 2 is the core for the polysiloxane group polyurethane macromers that acrylic ester monomer made from embodiment 1 blocks
The spectrogram of magnetic resonance hydrogen spectrum.
Fig. 3 is the infrared spectrum of macromolecule hydrogel made from embodiment 1.
Fig. 4 is the load-deformation curve of macromolecule hydrogel made from embodiment 1.
Embodiment
To more fully understand the present invention, the invention will be further described with reference to embodiments, but the reality of the present invention
Apply mode not limited to this.In embodiment, hydrogel sample carries out tensile property test by standard GB/T/T 528-2009, presses
Standard GB/T/T2918 measures oxygen permeability coefficient.
Embodiment 1
The synthesis of the polysiloxane group polyurethane macromers of hydroxyethyl methacrylate end-blocking：In terms of mass fraction,
2.0 parts of hydroxy-terminated polysiloxanes are added in conical flask, 100 DEG C is heated to, vacuum dehydration 3 hours, places cooling
To 50 DEG C；Then, 0.50 part of IPDI is added, controls temperature to be reacted 2 hours at 90 DEG C after adding, by
0.30 part of hydroxyethyl methacrylate and 0.05 part of dibutyl tin laurate are added dropwise to, is reacted 10 hours, metering system is made
The polysiloxane group polyurethane macromers of sour hydroxyl ethyl ester end-blocking, sealing refrigeration is stand-by after vacuum defoamation.
Preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：In terms of mass fraction, by 3.0 part ten
Dialkyl sulfonates and 0.01 part of sodium chloride are added in 70 parts of deionized waters, are stirred up to obtaining transparent micellar aqueous solution,
The polysiloxane group polyurethane macromers of the hydroxyethyl methacrylate end-blocking of above-mentioned synthesis are added, are stirred at 25 DEG C
60 minutes, obtain the aqueous solution of the polysiloxane group polyurethane macromers micella of the end-blocking containing hydroxyethyl methacrylate；So
Afterwards, 8.0 parts of acrylamide monomers and 0.20 part of light trigger 2- hydroxy-2-methyl -1- phenylacetone are added, makes its complete with ultrasound
Fully dissolved, obtain the polysiloxane group polyurethane macromers containing acrylamide monomer, hydroxyethyl methacrylate end-blocking
The water solution system of micella and light trigger；With the homopolymerization of monomer and acrylamide monomer and micella in this light-initiated system
In macromonomer between free radical copolymerization, reaction continue 30 minutes, be made using polysiloxanes based polyurethanes for friendship
Join the macromolecule hydrogel of agent.
Fig. 1 is the polysiloxane group polyurethane macromers that hydroxyethyl methacrylate made from the present embodiment blocks
Infrared spectrum.It can be seen that in 1720cm-1There is the stretching vibration absworption peak of-C ═ O in carbamate in place, and
In 1538cm-1There is the absworption peak of the acid amides II in polyurethane, 3340cm in place-1For the N-H stretching vibrations in carbamate
Peak, 1261cm-1There is Si-C absworption peak, 1096cm in place-1For Si-O-Si stretching vibration absworption peak, 801cm-1For Si atoms
The flexural vibrations peak of upper methyl, 1637cm-1For C=C absworption peak.
Fig. 2 is the polysiloxane group polyurethane macromers that hydroxyethyl methacrylate made from the present embodiment blocks
The spectrogram of proton nmr spectra.As seen from the figure, chemical shift be 5.51ppm and 6.06ppm at be to belong to methacrylic acid
- C (CH in hydroxyl ethyl ester3)=CH2The characteristic peak of two hydrogen on upper carbon-carbon double bond, it is methacrylic acid at 1.88ppm that chemical shift, which is,
- C (CH in hydroxyl ethyl ester3)=CH2The proton peak of methyl on segment, 3.3~3.6ppm of chemical shift be hydroxyethyl methacrylate and
The proton peak of methylene on polysiloxanes, there is methyl in IPDI at 0.8~1.0ppm of chemical shift
Proton peak, chemical shift 0.0ppm are the proton peak of methyl on polysiloxanes.Show to synthesize institute really through infrared and nmr analysis
The polysiloxane group polyurethane macromers of the hydroxyethyl methacrylate end-blocking of design.
Fig. 3 is the infrared spectrum of macromolecule hydrogel made from the present embodiment.As seen from the figure, in 1096cm-1For Si-
O-Si stretching vibration absworption peak, 801cm-1For the flexural vibrations peak of methyl on Si atoms, show to have successfully synthesized with poly-
Siloxy group polyurethane is the macromolecule hydrogel of crosslinking agent.
Polysiloxane molecule chain has soft Si-O-Si segments, can assign hydrogel higher elongation at break.It incite somebody to action this
Hydrogel sample made from embodiment carries out tensile property test by standard GB/T/T 528-2009, obtain Fig. 4 stress-
Strain curve.It can be seen that the tensile strength of hydrogel sample is 90kPa, elongation at break is 700% (according to state
Family standard GB/T 528-2009 carry out extension test, and the data drawn have tensile strength, elongation at break, modulus of elasticity
Deng), good mechanical property is embodied, the elongation at break highest for overcoming the macromolecule hydrogel obtained by prior art only has
100% or so the defects of.
In order to compare, the polysiloxanes based polyurethanes of hydroxyethyl methacrylate end-blocking are replaced with octadecyl acrylate
Macromonomer, the macromolecule water-setting using octadecyl acrylate as crosslinking agent is prepared with identical constituent and method
Glue.
Polysiloxane molecule chain contains the larger-Si of volume (CH3)2O- groups, it can effectively improve the gas permeability of polysiloxanes
Energy.The obtained macromolecule hydrogel using polysiloxanes based polyurethanes as crosslinking agent of embodiment is measured by standard GB/T/T2918
Oxygen permeability coefficient be 45 × 10-11cm3·cm/(cm2SmmHg), the macromolecule using octadecyl acrylate as crosslinking agent
The oxygen permeability coefficient of hydrogel is 20 × 10-11cm3·cm/(cm2·s·mmHg).It can be seen that using polysiloxanes based polyurethanes as crosslinking
The macromolecule hydrogel of agent has obvious more preferable oxygen permeability.In addition, according to standard GB/T/T 528-2009 to obtained
Using octadecyl acrylate as crosslinking agent macromolecule hydrogel carry out extension test, obtained tensile strength is 14kPa,
Elongation at break is 3700%.It can be seen that the macromolecule hydrogel using polysiloxanes based polyurethanes as crosslinking agent has higher drawing
Stretch intensity.
The micell polymerization method preparation process of the macromolecule hydrogel for the strand containing organosilicon that the present embodiment is related to need not appoint
What organic solvent, it is not necessary to handle substantial amounts of organic wastewater, overcome prior art using tetrahydrofuran as solvent, completed in polymerization
After need to replace tetrahydrofuran with substantial amounts of water, it is longer to prepare spent time, the problem of producing largely waste water containing organic matter.
Embodiment 2
The synthesis of the polysiloxane group polyurethane macromers of hydroxyethyl methacrylate end-blocking：In terms of mass fraction,
5 parts of hydroxy-terminated polysiloxanes are added in conical flask, are heated to 120 DEG C, vacuum dehydration 2 hours, placement cools to
50℃；Then, 2 parts of IPDI is added, controls temperature to be reacted at 70 DEG C after adding 5 hours, adds dropwise
Enter 2 parts of hydroxyethyl methacrylates and 0.1 part of dibutyl tin laurate, react 24 hours, hydroxyethyl methacrylate is made
The polysiloxane group polyurethane macromers of end-blocking, sealing refrigeration is stand-by after vacuum defoamation.
Preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：In terms of mass fraction, by 5.0 part ten
Dialkyl sulfonates and 0.10 part of sodium chloride are added in 70 parts of deionized waters, are stirred up to obtaining transparent micellar aqueous solution,
The polysiloxane group polyurethane macromers of the hydroxyethyl methacrylate end-blocking of above-mentioned synthesis are added, are stirred at 40 DEG C
30 minutes, obtain the aqueous solution of the polysiloxane group polyurethane macromers micella of the end-blocking containing hydroxyethyl methacrylate；So
Afterwards, 8.0 parts of acrylamide monomers and 0.30 part of light trigger 2- hydroxy-2-methyl -1- phenylacetone are added, makes its complete with ultrasound
Fully dissolved, obtain the polysiloxane group polyurethane macromers containing acrylamide monomer, hydroxyethyl methacrylate end-blocking
The water solution system of micella and light trigger；With the homopolymerization of monomer and acrylamide monomer and micella in this light-initiated system
In macromonomer between free radical copolymerization, reaction continue 120 minutes, be made using polysiloxanes based polyurethanes for friendship
Join the macromolecule hydrogel of agent.
After tested, the obtained tensile strength using polysiloxanes based polyurethanes as the macromolecule hydrogel sample of crosslinking agent
For 100kPa, elongation at break 650%, oxygen permeability coefficient is 50 × 10-11cm3·cm/(cm2·s·mmHg).With embodiment 1
Compared to knowable to, the oxygen permeability coefficient of macromolecule hydrogel increases obtained hydrogel as polysiloxane group polyurethane content increases
Add.The macromolecule of the oxygen permeability with requirements at the higher level can be prepared by regulating and controlling polysiloxane group polyurethane content in hydrogel
Hydrogel.
Embodiment 3
Preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：In terms of mass fraction, by 5.0 part ten
Dialkyl sulfonates and 0.10 part of sodium chloride are added in 85 parts of deionized waters, are stirred up to obtaining transparent micellar aqueous solution,
The polysiloxane group polyurethane macromers of the hydroxyethyl methacrylate end-blocking synthesized by embodiment 2 are added, at 40 DEG C
It is lower stirring 30 minutes, obtain containing hydroxyethyl methacrylate end-blocking polysiloxane group polyurethane macromers micella it is water-soluble
Liquid；Then, 10.0 parts of acrylamide monomers and 0.30 part of light trigger 2- hydroxy-2-methyl -1- phenylacetone are added, with ultrasound
It is completely dissolved, obtains the polysiloxane group polyurethane macromolecular containing acrylamide monomer, hydroxyethyl methacrylate end-blocking
The micella of monomer and the water solution system of light trigger；With the homopolymerization of monomer and acrylamide monomer in this light-initiated system
With the free radical copolymerization between the macromonomer in micella, reaction continues 120 minutes, is made with the poly- ammonia of polysiloxane group
Ester is the macromolecule hydrogel of crosslinking agent.
After tested, the obtained tensile strength using polysiloxanes based polyurethanes as the macromolecule hydrogel sample of crosslinking agent
For 95kPa, elongation at break 680%, oxygen permeability coefficient is 49 × 10-11cm3·cm/(cm2·s·mmHg).With the institute of embodiment 2
The oxygen permeability of hydrogel is made compared to knowable to, when the polysiloxane group polyurethane macromolecular list of hydroxyethyl methacrylate end-blocking
The content of body crosslinking agent is the same, and increases the content of acrylamide monomer, and the oxygen permeability coefficient of macromolecule hydrogel is suitable.The implementation
The oxygen permeability of obtained hydrogel, illustrates oxygen flow of the polysiloxanes based polyurethanes to hydrogel in example result and embodiment 1
Performance has large effect.
Embodiment 4
Preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：In terms of mass fraction, by 5.0 part ten
Eight zephirans and 0.10 part of sodium chloride are added in 70 parts of deionized waters, and stirring is until obtain transparent glue
The beam aqueous solution, add embodiment it is 2-in-1 into hydroxyethyl methacrylate end-blocking polysiloxane group polyurethane macromers,
Stirred 30 minutes at 40 DEG C, obtain the polysiloxane group polyurethane macromers micella of the end-blocking containing hydroxyethyl methacrylate
The aqueous solution；Then, 8.0 parts of NIPA monomers and 0.30 part of light trigger ɑ -one glutaric acid are added, with ultrasound
It is completely dissolved, obtains monomer containing NIPA, the poly- ammonia of polysiloxane group of hydroxyethyl methacrylate end-blocking
The micella of macromonomer and the water solution system of light trigger；It is different with the homopolymerization of monomer and N- in this light-initiated system
The free radicals copolymerization reaction between macromonomer in propylacrylamide monomer and micella, reaction continue 120 minutes, be made with
Polysiloxanes based polyurethanes are the macromolecule hydrogel of crosslinking agent.
The mechanical property using polysiloxanes based polyurethanes as the macromolecule hydrogel sample of crosslinking agent obtained by the present embodiment
Energy, oxygen permeability coefficient are suitable with the hydrogel obtained by embodiment 2.
Claims (9)
1. using polysiloxanes based polyurethanes as the micellar copolymerization preparation method of crosslinking agent macromolecule hydrogel, it is characterised in that including
Following steps：
1) synthesis of the polysiloxane group polyurethane macromers of acrylic ester monomer end-blocking：By polysiloxanes 100~
Vacuum dehydration 2~3 hours at 120 DEG C, placement cool to less than 60 DEG C；Then, polyisocyanates is added under agitation, then is heated up
To 70~90 DEG C, react 3~5 hours；Acrylic ester monomer and catalyst is added dropwise, reacts 10~24 hours, is made third
The polysiloxane group polyurethane macromers of olefin(e) acid esters monomer end-blocking, sealing refrigeration is stand-by after vacuum defoamation；Described urges
Agent is one or both of dibutyl tin laurate, stannous octoate, dibutyltin diacetate and dimethyl cyclohexyl amine；
2) preparation using polysiloxanes based polyurethanes as the macromolecule hydrogel of crosslinking agent：Surfactant and sodium chloride are added to
In deionized water, until obtaining transparent micellar aqueous solution, the polysiloxane group for adding acrylic ester monomer end-blocking gathers for stirring
Urethane macromonomer, and stir, obtain the polysiloxane group polyurethane macromolecular list of the end-blocking containing acrylic ester monomer
The aqueous solution of body micella；Then, acrylamide monomers and light trigger are added in obtained micellar aqueous solution, are used in combination
Ultrasound is completely dissolved it, and it is big to obtain the polysiloxanes based polyurethanes containing acrylamide monomers, acrylic ester monomer end-blocking
The micella of molecule monomer and the water solution system of light trigger；With the homopolymerization of light-initiated monomer and acrylamide monomers and glue
The free radical copolymerization between macromonomer in beam, the macromolecule water using polysiloxanes based polyurethanes as crosslinking agent is made
Gel；
Described light trigger is 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones, 2,4,6- front threes
Base benzoyl-diphenyl phosphine oxide, benzophenone, 2- hydroxyls -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones and ɑ -one penta 2
One or more in acid；Described surfactant is neopelex, lauryl sodium sulfate, octadecyl two
One or more in methyl-benzyl ammonium chloride and cetyl trimethylammonium bromide；
In terms of mass fraction, raw material components composition is：
2. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that described polyisocyanates be IPDI, 1,6- hexamethylene diisocyanates,
Toluene di-isocyanate(TDI), diphenyl methane -4,4 '-diisocyanate, XDI, methylcyclohexyl two are different
One or more in cyanate, tetramethylxylylene diisocyanate.
3. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that described polysiloxanes is hydroxy-terminated polysiloxane, amino-terminated polysiloxanes and end hydroxy polyether
One or more in polysiloxanes.
4. prepared by the micellar copolymerization according to claim 3 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that the molecular weight of described polysiloxanes is 1000~6000g/mol.
5. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that described acrylic ester monomer is hydroxyethyl methacrylate, hydroxy-ethyl acrylate and polyethylene glycol
One or more in acrylate.
6. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that described acrylamide monomers be acrylamide, Methacrylamide, NIPA,
One or more in N- isopropyl acrylamides and dimethylamino-propyl acrylamide.
7. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that in step 2), obtain the polysiloxane group polyurethane macromers of the end-blocking containing acrylic ester monomer
The condition of the aqueous solution of micella stirs 30~60 minutes at a temperature of being 25~40 DEG C.
8. prepared by the micellar copolymerization according to claim 1 using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel
Method, it is characterised in that in step 2), the homopolymerization of light-initiated monomer and acrylamide monomers and the macromolecular list in micella
The duration of the free radical copolymerization of body is 30~120 minutes.
9. one kind is using polysiloxanes based polyurethanes as crosslinking agent macromolecule hydrogel, it is characterised in that it is appointed by claim 1-8
One micellar copolymerization preparation method is made, tensile strength >=90kPa of macromolecule hydrogel, elongation at break ＞ 600%,
Oxygen permeability coefficient >=45 × 10-11cm3·cm/(cm2·s·mmHg)。
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| CN110409194A (en) * | 2019-07-19 | 2019-11-05 | 温多利遮阳材料（德州）股份有限公司 | A kind of Fire-retarded carpet and its preparation process based on expansion type coating tailing |
| CN110540659B (en) * | 2019-08-29 | 2022-03-22 | 广州大学 | High-stretchability self-repairing hydrogel and preparation method thereof |
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| CN113248719B (en) * | 2021-04-19 | 2022-10-21 | 江苏海伦隐形眼镜有限公司 | Single-end-capped organic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method |
| CN115124920B (en) * | 2022-08-05 | 2023-05-26 | 之江实验室 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
| CN117264171B (en) * | 2023-10-17 | 2024-03-19 | 山东辰星医疗科技有限公司 | Polymer silica gel with siloxane-based polyurethane as matrix and preparation method thereof |
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