CN106750008A - The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel - Google Patents
The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel Download PDFInfo
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- CN106750008A CN106750008A CN201611126795.6A CN201611126795A CN106750008A CN 106750008 A CN106750008 A CN 106750008A CN 201611126795 A CN201611126795 A CN 201611126795A CN 106750008 A CN106750008 A CN 106750008A
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- C—CHEMISTRY; METALLURGY
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- 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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Abstract
The present invention relates to a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The method is to make comonomer with MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methacrylic acid oxygen ethyl trimellitic anhydride ester, crotonic acid, PEGDMA-400 makees crosslinking agent, and potassium peroxydisulfate sodium hydrogensulfite makees initiator and carry out copolymerization in deionized water to obtain organic amphiprotic copolymerized macromolecule first network gel；The first network gel is swelling in the aqueous solution that abscisic acid, mannitol, methacrylic acid oxygen propyl group trimellitic anhydride ester, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester and deionized water are prepared, monomer, crosslinking agent in the aqueous solution are copolymerized conjunction, esterification through the effect of potassium peroxydisulfate, pyridoxine hydrochloride, finally obtain organic amphiprotic copolymerized macromolecule interpenetrating networks gel.
Description
Technical field
The present invention relates to a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel.
Background technology
Gel is a kind of special dispersion, and high-polymer molecular or colloidal solid interconnect, and to form three dimensions netted
Structure, can absorb substantial amounts of water-swellable and water insoluble, and definite shape can be kept in water, have solid and liquid duality concurrently
Matter.Macroscopically see, high-molecular gel has certain shape, applying certain external force can deform, can recover original after removal external force
Shape, the viscoplasticity with solid；Seen on microcosmic, high-molecular gel has three-dimensional net structure water insoluble, three-dimensional network point
Son can stretch in water, with liquid property.With soft, water content it is high and have the viscoelastic gel of rubber environmental protection, weaving,
All many-sides such as building materials, petrochemical industry, food, agricultural gardening, daily cosmetics have and are widely applied.
Organism including humans is all high-molecular gel composition, mostly with electrical, such as protein, amino acid.
Copolymerization Amphiphatic high polymer interpenetrating networks gel can obtain Protean specific performance, particularly height and contains with the change of copolymerization component
The similitude of the electrical and organization of human body in water and molecule, good biocompatibility, environmental stimulus response is cured in biology
The fields such as medicine controlled releasing, bio-sensing, the organizational project in medicine field have obtained some applications.
The problem that the preparation method of current organic amphiprotic copolymerized macromolecule interpenetrating networks gel is primarily present is monomer propylene
The toxic articles of acid amides category " carcinogenic, aberration inducing, mutagenesis ", crosslinking agent N, N methylene diacrylamine toxicity is larger, and gel is deposited
In unfavorable toxic effect；The interpenetrating networks gel stability that single crosslinking agent is formed is relatively low.Exploitation uses nontoxic or low toxicity
Monomer, crosslinking agent carry out combined polymerization to reduce gel toxicity, forming multiple interpenetrating networks using compounding crosslinking agent improves gel
The preparation method of the organic amphiprotic copolymerized macromolecule interpenetrating networks gel of stability has larger practical value.
The content of the invention
For the problem that the preparation method of current organic amphiprotic copolymerized macromolecule interpenetrating networks gel is present, mesh of the invention
Be to provide it is a kind of use nontoxic or low-toxicity monomer, the crosslinking agent to carry out combined polymerization to reduce gel toxicity, use and compound crosslinking agent
The preparation method that multiple interpenetrating networks improve the organic amphiprotic copolymerized macromolecule interpenetrating networks gel of gel stability is formed, it is special
It is that in closed reactor component A and deionized water stirring can added to prepare the aqueous solution to levy, and the weight concentration for controlling component A is
28%~62%；After the completion of prepared by solution, relative degree of vacuum is evacuated to for -0.02MPa~-0.08MPa, be passed through nitrogen and recover anti-
After answering device to normal pressure, add the aqueous solution prepared by B component and deionized water under agitation, the weight concentration of B component for 20%~
40%；After the aqueous solution charging of B component terminates, 35 DEG C~50 DEG C are warming up to, add matched somebody with somebody by component C and deionized water under agitation
The aqueous solution of system, the weight concentration of component C is 5%~15%；Control ph is 4~10, in 35 DEG C~50 DEG C constant temperature, continues to stir
Reaction 2h~3.5h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, in the case where nitrogen is passed through, will
The aqueous solution that first network gel input is prepared equipped with D components and deionized water can be swelling in closed reactor, D components
Weight concentration is 1.8%~11%, by weight, first network gel:Weight ratio=1 of D component deionized water solutions:（95~
155）, swelling 2h~6h；Add the aqueous solution prepared by component E and deionized water and continue swelling, the weight concentration of component E is
10%~20%, swelling 16 h~24 h；After the completion of swelling, 75 DEG C~95 DEG C are warming up to, control ph is 3~7,75 DEG C~95
DEG C constant temperature, reacts 4h~6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The component A is by methacryloxypropyl
Ethyl-trimethyl salmiac, methacrylic acid oxygen ethyl trimellitic anhydride ester, crotonic acid composition, by the gauge of material, methyl-prop
Alkene acyloxyethyl trimethyl ammonium chloride:Methacrylic acid oxygen ethyl trimellitic anhydride ester:The ratio between amount of material of crotonic acid=
（0.5~1.2）:（0.3~1.6）:（0.4~1.1）；B component is PEGDMA-400, and number-average molecular weight is
2000~20000, its gross weight that feeds intake is the 2.5%~11% of component A gross weight；Component C is by potassium peroxydisulfate-sodium hydrogensulfite group
Into its gross weight that feeds intake is the 0.3%~1.8% of component A gross weight, by weight, potassium peroxydisulfate:The weight of sodium hydrogensulfite it
Than=1:（0.2~1.1）；D components are by abscisic acid, mannitol, methacrylic acid oxygen propyl group trimellitic anhydride ester and trimethacrylate
Triethylenetetraminehexaacetic acid alkanolamine ester is constituted, by the gauge of material, abscisic acid:Mannitol:The thing of methacrylic acid oxygen propyl group trimellitic anhydride ester
The ratio between amount of matter=（0.5~2.0）:（0.08~0.32）:（0.4~1.1）, by weight, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester
Charged material weight be abscisic acid, mannitol, three kinds the 1.8% of total monomer weight of methacrylic acid oxygen propyl group trimellitic anhydride ester~
5.5%；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, potassium peroxydisulfate charged material weight be D component weights 0.1%~
1.2%, pyridoxine hydrochloride charged material weight is the 0.8%~5.6% of D component weights.
What technical method of the invention was realized in：Methylacryoyloxyethyl front three can be being prepared in closed reactor
Ammonium chloride CH2=C(CH3)COO(CH2)2N(CH3)3Cl, methacrylic acid oxygen ethyl trimellitic anhydride ester CH2=C(CH3)COO
(CH2)2OOCC6H3C2O3, crotonic acid CH3The aqueous solution of CH=CHCOOH comonomers；After vacuumizing deoxidation, nitrogen protection is passed through,
Add the aqueous solution of crosslinking agent PEGDMA-400；After intensification, add redox initiator potassium peroxydisulfate-
Sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, the poly- second of crosslinking agent dimethacrylate
Diol ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network structure, through chain termination reaction,
Obtain organic amphiprotic copolymerized macromolecule first network gel.Logical nitrogen protection, organic amphiprotic copolymerized macromolecule first network gel
In abscisic acid (C9H13O2)-CH=CHC(CH3)=CHCOOH, mannitol HOCH2(CHOH)4CH2OH, methacrylic acid oxygen propyl group are inclined
Benzenetricarboxylic anhydride ester CH2=C(CH3)COO(CH2)3OOCC6H3C2O3, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester (CH2=C(CH3)
COOC2H4) 3It is swelling under the aqueous solution effect of N, add initiator potassium persulfate K2S2O8, catalyst pyridoxine hydrochloride (CH3)
(HOCH2)2(HO)C5Continue swelling in the presence of the HNHCl aqueous solution, in swelling process, monomer, crosslinking agent in the aqueous solution,
Initiator, catalyst enter into organic amphiprotic copolymerized macromolecule first network gel inside and are uniformly distributed；Through initiation, combined polymerization
Chain propagation reaction forms line style copolymerization macromolecular, and crosslinking agent trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester participates in copolyreaction and line style is common
Poly- macromolecular crosslinks reaction, forms cross-linked network structure, pyridoxine hydrochloride molecule of the catalysis with carboxylic group and band hydroxyl
There is esterification in the molecule of base group, because mannitol will form crosslinking with six OH groups with the molecule with carboxylic group
Network structure；Further reaction, finally due to the chain termination and the completion of esterification of radical copolymerization macromolecular, is formed with
Machine both sexes copolymerized macromolecule interpenetrating networks gel.
Relative to art methods, outstanding advantages of the present invention are monomer methacryloxypropyl second used in technology of preparing
Base trimethyl ammonium chloride, methacrylic acid oxygen ethyl trimellitic anhydride ester, crotonic acid, methacrylic acid oxygen propyl group trimellitic anhydride
Ester and crosslinking agent trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester low toxicity, monomer abscisic acid and crosslinking agent dimethyl allene acid polyethylene glycol
Ester, mannitol are nontoxic, reduce gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network knot
Structure, improves the stability of interpenetrating networks gel；Preparation method is simple, reaction condition is gentle, be suitable for production, with good ring
Border benefit and economic benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the 110.5g methacrylic acid inclined benzene of oxygen ethyl
Three acid anhydride esters, 43g crotonic acids and 648.8ml deionized waters are added to volume and can stir mixing in closed reactor for 2L
Even, the weight concentration of the aqueous solution is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor
To normal pressure, the number-average molecular weight for adding 8.3g is that 4000 PEGDMA-400 and 31.4ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 21%；37 DEG C are then heated to, 1.07g potassium peroxydisulfates, 0.32g sulfurous acid is added
The aqueous solution that hydrogen sodium and 23.9ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%, in 37 DEG C of constant temperature, control ph
It is 4.5, continues stirring reaction 2.3h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through
Under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 164.2g input volumes can be swelling in closed reactor for 20L's,
In the reactor equipped with 158.6g abscisic acids, 18.2g mannitol, 145.1g methacrylic acid oxygen propyl group trimellitic anhydrides ester,
The aqueous solution that 6.4g trimethacrylate triethylenetetraminehexaacetic acid alkanolamine esters and 16090.8ml deionized waters are prepared, the weight concentration of the aqueous solution
It is 2%, the weight of first network gel（164.2g）:The weight of the aqueous solution（16419.1g）=1:100, swelling 3h；Add
The aqueous solution that 0.66g potassium peroxydisulfates, 3.28g pyridoxine hydrochlorides and 33.6ml deionized waters are prepared continues swelling, the aqueous solution
Weight concentration be 10.5%, swelling 17h；77 DEG C are warming up to after the completion of swelling, control ph is 3.4, in 77 DEG C of isothermal reactions
4.3h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling
Rate（ESR）=5267%（Deionized water）, gel swelling rate（ESR）=5198%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the 414.4g methacrylic acid inclined benzene of oxygen ethyl
Three acid anhydride esters, 86.1g crotonic acids and 485.8ml deionized waters are added to volume for 1L can stir mixing in closed reactor
Even, the weight concentration of the aqueous solution is 60%；Relative degree of vacuum -0.07MPa is evacuated to, nitrogen is then passed to and is recovered reactor
To normal pressure, the number-average molecular weight for adding 72.9g is that 19000 PEGDMA-400 and 114ml deionized waters are matched somebody with somebody
The aqueous solution of system, the weight concentration of the aqueous solution is 39%；48 DEG C are then heated to, 5.47g potassium peroxydisulfates, 5.47g sulfurous is added
The aqueous solution that sour hydrogen sodium and 64.5ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, in 48 DEG C of constant temperature, control
PH value is 9.5, continues stirring reaction 3.2h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down,
It is passed through under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 57.5g inputs 10L can be swelling in closed reactor, reaction
475.8g abscisic acids, 54.7g mannitol, 290.3g methacrylic acid oxygen propyl group trimellitic anhydrides ester, 41g trimethyls are housed in device
The aqueous solution that acrylic acid triethanolamine ester and 7755.6ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, the first net
The weight of network gel（57.5g）:The weight of the aqueous solution（8617.3g）=1:150, swelling 5.5h；Add 1.72g persulfuric acid
The aqueous solution that potassium, 8.62g pyridoxine hydrochlorides and 42.7ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
19.5%, swelling 23h；93 DEG C are warming up to after the completion of swelling, control ph is 6.5, in 93 DEG C of isothermal reaction 5.6h, obtain organic
Both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=4275%
（Deionized water）, gel swelling rate（ESR）=4167%（The NaCl aqueous solution of weight concentration 1%）.
Claims (1)
1. a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel, it is characterized in that can in closed reactor plus
Enter component A and deionized water stirring prepares the aqueous solution, it is 28%~62% to control the weight concentration of component A, after the completion of prepared by solution,
Relative degree of vacuum is evacuated to for -0.02MPa~-0.08MPa, after being passed through nitrogen recovery reactor to normal pressure, is added under agitation
Enter the aqueous solution prepared by B component and deionized water, the weight concentration of B component is 20%~40%, the aqueous solution charging knot of B component
Shu Hou, is warming up to 35 DEG C~50 DEG C, and the aqueous solution prepared by component C and deionized water is added under agitation, and the weight of component C is dense
It is 5%~15% to spend, and control ph is 4~10, in 35 DEG C~50 DEG C constant temperature, continues stirring reaction 2h~3.5h, obtains organic two
Property copolymerized macromolecule first network gel, then cooled down, in the case where nitrogen is passed through, by the first network gel input be equipped with D
The aqueous solution that component and deionized water are prepared can be swelling in closed reactor, the weight concentration of D components is 1.8%~11%, is pressed
Weight meter, first network gel:Weight ratio=1 of D component deionized water solutions:（95~155）, swelling time is 2h~6h, then
The aqueous solution prepared by component E and deionized water is added to continue swelling, the weight concentration of component E is 10%~20%, swelling time
Be 16 h~24 h, it is swelling after the completion of, be warming up to 75 DEG C~95 DEG C, control ph is 3~7, in 75 DEG C~95 DEG C constant temperature, reaction
4h~6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel；The component A is by methylacryoyloxyethyl trimethyl chlorine
Change ammonium, methacrylic acid oxygen ethyl trimellitic anhydride ester, crotonic acid composition, by the gauge of material, methylacryoyloxyethyl three
Ammonio methacrylate:Methacrylic acid oxygen ethyl trimellitic anhydride:The ratio between amount of material of crotonic acid=（0.5~1.2）:（0.3~
1.6）:（0.4~1.1）, B component is PEGDMA-400, and number-average molecular weight is 2000~20000, and it feeds intake
Gross weight is the 2.5%~11% of component A gross weight, and component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is A
The 0.3%~1.8% of component weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D
Component is made up of abscisic acid, mannitol, methacrylic acid oxygen propyl group trimellitic anhydride ester and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester,
By the gauge of material, abscisic acid:Mannitol:The ratio between amount of material of methacrylic acid oxygen propyl group trimellitic anhydride ester=（0.5~
2.0）:（0.08~0.32）:（0.4~1.1）, by weight, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester charged material weight be abscisic acid,
Mannitol, three kinds the 1.8%~5.5% of total monomer weight of methacrylic acid oxygen propyl group trimellitic anhydride ester, component E is by persulfuric acid
Potassium, pyridoxine hydrochloride composition, potassium peroxydisulfate charged material weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride is thrown
Material weight is the 0.8%~5.6% of D component weights.
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| CN105289316A (en) * | 2015-09-28 | 2016-02-03 | 浙江大学 | Preparation method of composite separating film filled by interpenetrating polymer network hydrogel |
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Application publication date: 20170531 |