CN107163282A - Macroporous polymer resin of fast temperature response and preparation method thereof - Google Patents
Macroporous polymer resin of fast temperature response and preparation method thereof Download PDFInfo
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- CN107163282A CN107163282A CN201710591328.9A CN201710591328A CN107163282A CN 107163282 A CN107163282 A CN 107163282A CN 201710591328 A CN201710591328 A CN 201710591328A CN 107163282 A CN107163282 A CN 107163282A
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- temperature
- polymer resin
- hydrophily
- pioloform
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000004044 response Effects 0.000 title claims abstract description 24
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 17
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 17
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 230000010148 water-pollination Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical class CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 10
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical class CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 241000233803 Nypa Species 0.000 claims description 5
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical group [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- XKVZLRDEADGMFT-UHFFFAOYSA-N cerium perchloric acid Chemical compound [Ce].Cl(=O)(=O)(=O)O XKVZLRDEADGMFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 230000033116 oxidation-reduction process Effects 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- -1 vinyl acetal Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- UFGARSYRUQYBQX-UHFFFAOYSA-N cerium chloric acid Chemical compound [Ce].Cl(=O)(=O)O UFGARSYRUQYBQX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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
- C08J2433/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a kind of preparation method of the macroporous polymer resin of fast temperature response, comprises the following steps:Under acid condition, in the presence of initiator, the temperature sensitive monomer of hydrophily carries out graft reaction with Pioloform, polyvinyl acetal foam, obtains the macroporous polymer resin of fast temperature response;The temperature sensitive monomer of hydrophily is any one or more in N N-isopropylacrylamides, N ethyl acrylamides and N, N acrylamide.The present invention uses redox initiate polymerization, first the polymer segment with Thermo-sensitive is introduced in macroporous polyvinyl alcohol formal precursor, resulting materials maintain polyvinylalcohol formal foam specific interconnected pore space structure in itself, it ensure that resulting materials can only need to reach swelling equilibrium in several minutes at low temperature, and also only need to just reach swelling equilibrium several minutes at high temperature.
Description
Technical field
The present invention relates to technical field of macromolecules, more particularly to a kind of fast temperature response macroporous polymer resin and its
Preparation method.
Background technology
In recent years, the development of synthetic technology causes substantial amounts of intellectual material, such as:Shape-memory material, self-healing material with
And material is designed stimuli responsive (light, electricity, heat, magnetic) and report comes out.It is high due to structure design and the diversity of chemical composition
The intellectual material of molecule base is always study hotspot and causes the extensive concern of scientific research personnel.Wherein, especially prominent is to have
The high polymer material of temperature-responsive, may be used as insoluble drug release material, tissue engineering material, Gene releaser material etc..
Temperature-responsive high polymer material refers to that its solution state can be showed at a certain temperature in temperature changing process
Go out Volume-phase transition (Volume Phase Transition) behavior, wherein, as temperature reduction shows immiscible height
Molecule is referred to as high critical consolute temperature (UCST) macromolecule, and it is referred to as low to show immiscible macromolecule with temperature rise
Critical consolute temperature (LCST) macromolecule.Wherein, the temperature-sensitive macromolecular with low critical consolute temperature (LCST) is nearly more than ten
The system being widely studied over year.Many polymer, such as poly- (N-isopropylacrylamide) (PNIPAAm), polyvinyl acyl in oneself
Amine (PVCL) and poly- (N, N- acrylamide) (PDEAAM), all shows LCST phenomenons in aqueous.With
It is so far because it has and the close phase transition temperature (~33 DEG C) of Human Physiology temperature (~36.5 DEG C) exemplified by PNIPAAm
Untill study Thermo-sensitive material the most deep.It occurs the phenomenon of Volume-phase transition earliest by Tanaka et al. near 32 DEG C
Report, when ambient temperature is less than LCST, hydrophilic radical N-H and C=O and hydrone formation hydrogen bond, polymer in PNIPAAm
Solvation occurs for chain and completely soluble in water, when ambient temperature is increased to PNIPAAm more than LCST, hydrophilic N-H and C=
O bases formation intramolecular hydrogen bond, hydrophobic polymer chain shrinks in water, draining and aggregation, and is further settled from water.
In general, the hydrophobic interaction of its molecule interchain can be reduced comprising hydrophilic component in thermo-responsive hydro gel, causes phase
Transition temperature is raised, and the introducing of hydrophobic components can then cause the reduction of phase transition temperature.Such architectural characteristic causes temperature sensitive
Property hydrogel such as PINPAAm have a wide range of applications in terms of biological medicine in terms of such as insoluble drug release, artificial organs muscle
Prospect.
But, when ambient temperature is higher than LCST, traditional PNIPAAm gels can be in its outer surface during phase in version
Form the dense layer surface (Dense skin layer) that one layer of limitation gel internal water molecule outwards spreads;And when temperature is less than
During LCST, the dense skin layer formed can equally limit the entrance of external water molecule so that PNIPAAm is warm to external world
Degree change shows obvious response lag, meanwhile, vitrification phenomenon of the polymer chain in contraction process can also respond it
Speed is slack-off, and which greatly limits its application in real process.
The content of the invention
In view of this, the technical problem to be solved in the present invention is the macroporous polymer tree for providing a kind of fast temperature response
Fat and preparation method thereof, the macroporous polymer resin of preparation has fast temperature response characteristic.
The invention provides a kind of preparation method of the macroporous polymer resin of fast temperature response, comprise the following steps:
Under acid condition, in the presence of initiator, the temperature sensitive monomer of hydrophily is grafted with Pioloform, polyvinyl acetal foam
Reaction, obtains the macroporous polymer resin of fast temperature response;
The temperature sensitive monomer of hydrophily is NIPA, N- ethyl acrylamides and N, N- diethyl acryloyl
Any one or more in amine.
The present invention is using Pioloform, polyvinyl acetal foam as raw material, with NIPA, N- ethyl acrylamides and N,
Any one or more in N- acrylamides is temperature sensitive monomer, and the macroporous polymer resin prepared remains poly-
The distinctive open-celled structure of vinyl acetal foam so that material is in extraneous temperature changing process, and the hydrone in its network is easy
In diffusion, it is ensured that material has the characteristic of fast temperature response.
The preparation method that the present invention is provided, is carried out in acid condition, the acid condition be preferred to use aqueous sulfuric acid,
Any one in aqueous hydrochloric acid solution and phosphate aqueous solution, or a variety of mixed solutions.
It is preferred that, the acid concentration of the acid condition is 0.01~1M.
The initiator of the graft reaction is water-soluble organic and inorganic redox initiation system, wherein, oxidant is preferred
For any one or a few in manganese pyrophosphate, ammonium ceric nitrate, Cericammoniumsulfate and perchloric acid cerium, reducing agent is Pioloform, polyvinyl acetal
Foam itself.
The concentration of the oxidant is preferably 0.001~0.5M.
The temperature sensitive monomer of hydrophily is preferably NIPA, N- ethyl acrylamides and N, N- diethyl third
Any one or more in acrylamide.
The concentration of the temperature sensitive monomer of hydrophily is preferably 1~5M.
In the temperature sensitive monomer of hydrophily and Pioloform, polyvinyl acetal foam the mol ratio of graft site be preferably (2.5~
20):1.
The temperature of the graft reaction is preferably 0~70 DEG C, and the reaction time is preferably 6~72h.
In some embodiments of the invention, the raw material of the graft reaction also includes hydrophilic monomer, the parent
Aqueous monomers are preferably any one or more in acrylamide, Methacrylamide and N hydroxymethyl acrylamide.
I.e. under acid condition, in the presence of initiator, the mixture of the temperature sensitive monomer of hydrophily and hydrophilic monomer is with gathering
Vinyl acetal foam carries out graft reaction, obtains the macroporous polymer resin of fast temperature response.
The presence of above-mentioned hydrophilic segment can be effectively improved gained sample hydrophily, while it can also be effectively improved low
Degree of swelling when LCST, realizes the larger temperature response characteristics of material.
The molal weight ratio of the hydrophilic monomer and graft site in polyvinyl formal foam is (2.5~20):
1, preferably 10:1.
In the present invention, the M represents mol/L.
The present invention is graft-polymerized by Redox Initiator, and temperature sensitive segment is introduced on Pioloform, polyvinyl acetal foam-based and is assigned
Material has the characteristic of temperature-responsive, while the open-celled structure of Pioloform, polyvinyl acetal foamed material is still protected after modification
Hold, the modified poly ethylene acetal foamed material finally prepared has the characteristic of fast temperature response, and preparation technology is simple.
Present invention also offers a kind of macroporous polymer resin of fast temperature response, according to the preparation of above-mentioned preparation method
Into.
Aperture and its distribution of the macroporous polymer resin of the fast temperature response are determined by mercury injection method, as a result table
Bright, its aperture is 2~200 μm, and integrated distribution is in 90 μm.At low temperature (20 DEG C), dry state sample can reach within 3 minutes
Absorb water saturation;At high temperature (48 DEG C), water saturated sample is inhaled under low temperature can reach dehydration balance within 1 minute.
Compared with prior art, the present invention provides a kind of preparation method of the macroporous polymer resin of fast temperature response,
Comprise the following steps:Under acid condition, in the presence of initiator, the temperature sensitive monomer of hydrophily is carried out with Pioloform, polyvinyl acetal foam
Graft reaction, obtains the macroporous polymer resin of fast temperature response;
The temperature sensitive monomer of hydrophily is NIPA, N- ethyl acrylamides and N, N- diethyl acryloyl
Any one or more in amine.
The present invention uses redox initiate polymerization, is introduced first in macroporous polyvinyl alcohol formal precursor with temperature
The polymer segment of quick property, resulting materials maintain polyvinylalcohol formal foam specific interconnected hole in itself
Hole structure, it is ensured that resulting materials can only need to reach swelling equilibrium in several minutes at low temperature, and also only need at high temperature
Swelling equilibrium can just be reached several minutes.Several hours are needed even to can be only achieved within several days relative to traditional temperature-sensitive hydrogel
Swelling equilibrium is swelled and goes, the material shows the speed of response being exceedingly fast;And with the use thing reported on current most of documents
Temperature-sensitive hydrogel prepared by reason and chemical method is compared, the block Pioloform, polyvinyl acetal base macropore temperature prepared by the present invention
The features such as sensitive materials have even aperture distribution and rate of water absorption faster, meanwhile, its preparation method has reaction condition temperature
With, the characteristics of method is simple, and short preparation period, thus it is easy to amplification preparation.
Embodiment
In order to further illustrate the present invention, the polymer of the fast temperature response provided with reference to embodiment the present invention
Macroreticular resin and preparation method thereof is described in detail.
Embodiment 1
The addition 1500mL 0.01M hydrochloric acid solutions in two mouthfuls of flasks of 2500mL, 50g Pioloform, polyvinyl acetal foamed materials,
0.2mol perchloric acid ceriums, add 7molN- N-isopropylacrylamides (NIPAAm), sealing, and 70h is reacted in 0 DEG C, and sample takes out
Neutrality is washed to distillation afterwards, is dried in vacuum drying oven to constant weight, the polyethylene of poly-N-isopropyl acrylamide grafting is obtained
Acetal foam.
The temperature-responsives of resulting materials is characterized by the difference of its water absorbent rate at low temperatures and high temperatures, is detected
Method is as follows:
Low temperature water absorbent rate:A certain amount of foamed material obtained above (A) is accurately weighed, is respectively put into (20 DEG C) of low temperature
Distilled water immersion 3min, takes out the water for being placed on 30s eliminations surface on filter screen, and weighs (B), under the liquid absorbency rate of foamed material is used
The formula in face is calculated:Liquid absorbency rate=(B-A)/A.In triplicate, the average value of measurement is used as water absorbent rate to the process.
High temperature water absorbent rate:Sample after above-mentioned test is put into the distilled water of higher temperature (60 DEG C) and soaked 3 minutes,
Its water absorbent rate at high temperature is determined according to the method described above.
The PVA-based large pore material for being grafted PNIPAM of the above-mentioned preparations of 0.1g is taken, respectively according to upper
Method described in text determines its absorptivity at low temperatures and high temperatures to distilled water.At low temperature, its reach saturated absorption when
Between and liquid absorbency rate be respectively 3min and 45g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively
2.5min and 20g/g.
Embodiment 2
In two mouthfuls of flasks of 2500mL, 0.02M hydrochloric acid solutions are added, 50g Pioloform, polyvinyl acetal foamed materials, 0.3mol is high
60h is reacted in chloric acid cerium, 1molN- N-isopropylacrylamides and 6mol acrylamides, sealing in 10 DEG C, and sample uses distillation after taking out
Neutrality is washed to, is dried in vacuum drying oven to constant weight, obtains poly-N-isopropyl acrylamide and Polyacrylamide Grafted copolymerization
Pioloform, polyvinyl acetal foam.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
4min and 52g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively 3min and 35g/g.
Embodiment 3
In two mouthfuls of flasks of 2500mL, addition 1500mL 0.2M sulfuric acid solutions, 50g Pioloform, polyvinyl acetal foamed materials,
0.08mol Cericammoniumsulfates, 5molN- N-isopropylacrylamides and 1.8mol Methacrylamides, sealing react 55h in 20 DEG C,
Sample is washed to neutrality after taking out with distillation, is dried in vacuum drying oven to constant weight, obtains poly-N-isopropyl acrylamide and poly-
The Pioloform, polyvinyl acetal foam of Methacrylamide graft copolymerization.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
3min and 100g/g;At high temperature, it reaches the time for shrinking balance and liquid absorbency rate is 3.5min and 35g/g.
Embodiment 4
In two mouthfuls of flasks of 2500mL, addition 1500mL0.4M sulfuric acid solutions, 50g Pioloform, polyvinyl acetal foamed materials,
0.04mol Cericammoniumsulfates, 2.25molN- ethyl acrylamides and 2.25molN- NMAs, sealing are anti-in 30 DEG C
Answer 48h, sample to be washed to neutrality with distillation after taking out, dried in vacuum drying oven to constant weight, obtain poly- N- ethyl acrylamides
With the Pioloform, polyvinyl acetal foam of poly- NMA graft copolymerization.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
5min and 50g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively 3min and 24g/g.
Embodiment 5
In two mouthfuls of flasks of 2500mL, addition 1500mL 0.6M sulfuric acid solutions, 50g Pioloform, polyvinyl acetal foamed materials,
0.004mol ammonium ceric nitrates, 5molN- ethyl acrylamides and 1molN- N-isopropylacrylamides, sealing react 36h in 40 DEG C,
Sample is washed to neutrality after taking out with distillation, is dried in vacuum drying oven to constant weight, obtain the grafting of poly- N- ethyl acrylamides and
The Pioloform, polyvinyl acetal foam of PNIPAM graft copolymerization.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
2.5min and 43g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively 3min and 15g/g.
Embodiment 6
In two mouthfuls of flasks of 2500mL, addition 1500mL 0.8M salpeter solutions, 50g Pioloform, polyvinyl acetal foamed materials,
0.15mol ammonium ceric nitrates, 1.2molN- ethyl acrylamides and 1mol acrylamides, sealing react 24h in 50 DEG C, and sample takes
Neutrality is washed to distillation after going out, is dried in vacuum drying oven to constant weight, obtains poly- N- ethyl acrylamides and polyacrylamide
The Pioloform, polyvinyl acetal foam of graft copolymerization.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
2.5min and 30g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively 2min and 14g/g.
Embodiment 7
In two mouthfuls of flasks of 2500mL, addition 1500mL 1M salpeter solutions, 50g Pioloform, polyvinyl acetal foamed materials,
0.15mol perchloric acid cerium ammoniums, 0.7molN- N-isopropylacrylamides and 0.3mol Methacrylamides, sealing, in 70 DEG C of reactions
24h, sample is washed to neutrality after taking out with distillation, is dried in vacuum drying oven to constant weight, obtains poly-N-isopropyl acrylamide
With the Pioloform, polyvinyl acetal foam of polymethacrylamide graft copolymerization.
The PVA-based Thermo-sensitive large pore material that 0.1g is obtained is taken, method as described above determines it low respectively
To the absorbency of distilled water under gentle high temperature.At low temperature, it reaches that the time of saturated absorption and liquid absorbency rate are respectively
2.5min and 50g/g;At high temperature, it reaches that the time for shrinking balance and liquid absorbency rate are respectively 2min and 35g/g.
The temperature sensing material prepared from above-described embodiment, the present invention, with very quick temperature response characteristics.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. the preparation method of the macroporous polymer resin of a kind of fast temperature response, it is characterised in that comprise the following steps:
Under acid condition, in the presence of initiator, the temperature sensitive monomer of hydrophily carries out graft reaction with Pioloform, polyvinyl acetal foam,
Obtain the macroporous polymer resin of fast temperature response;
The temperature sensitive monomer of hydrophily is in NIPA, N- ethyl acrylamides and N, N- acrylamide
Any one or more.
2. preparation method according to claim 1, it is characterised in that the initiator is water-soluble organic and inorganic oxidation
Reduction initiating system.
3. preparation method according to claim 2, it is characterised in that in the initiator, oxidant is manganese pyrophosphate, nitre
Any one or a few in sour cerium ammonium, Cericammoniumsulfate and perchloric acid cerium, reducing agent is Pioloform, polyvinyl acetal foam itself.
4. preparation method according to claim 1, it is characterised in that the raw material of the graft reaction also includes hydrophily list
Body, the hydrophilic monomer is any one or more in acrylamide, Methacrylamide and N hydroxymethyl acrylamide.
5. preparation method according to claim 1, it is characterised in that the graft reaction is in aqueous sulfuric acid, hydrochloric acid water
Carried out in the mixed solution of any one or more in solution and phosphate aqueous solution.
6. preparation method according to claim 1, it is characterised in that the acid concentration of the acid condition is 0.01~1M.
7. preparation method according to claim 1, it is characterised in that the temperature of the graft reaction is 0~70 DEG C, reaction
Time is 6~72h.
8. preparation method according to claim 1, it is characterised in that the temperature sensitive monomer of hydrophily and Pioloform, polyvinyl acetal
The mol ratio of graft site is (2.5~20) in foam:1.
9. the macroporous polymer resin of fast temperature response prepared by the preparation method described in any one of claim 1~8.
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CN108219333A (en) * | 2018-01-31 | 2018-06-29 | 张秀群 | A kind of antibacterial thermo-sensitive phase material and preparation method thereof |
CN108219333B (en) * | 2018-01-31 | 2020-12-25 | 爹地宝贝股份有限公司 | Antibacterial temperature-sensitive resin material and preparation method thereof |
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CN110734574A (en) * | 2019-10-25 | 2020-01-31 | 中国科学院长春应用化学研究所 | polymer macroporous hydrogel with rapid temperature and pH dual sensitivity and preparation method thereof |
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