CN109517107A - A kind of Thermo-sensitive poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof - Google Patents
A kind of Thermo-sensitive poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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Abstract
The present invention provides a kind of Thermo-sensitives poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof, and chemical structural formula is as shown in the formula (I), wherein x=0.10 ~ 0.28, y=0.72 ~ 0.90；Its minimum critical solution temperature is 22.6 ~ 39.2 DEG C；It is first to carry out ring-opening reaction using 2- phenyl -2- oxazoline, 2- ethyl -2- oxazoline and the acrylic acid of specific feed ratio as raw material, then carry out obtained after free radical copolymerization.Polymer of the invention not only has excellent temperature-sensing property, also with good biocompatibility, preparation method is simple, mild condition, and it is swift in response, it is easy to operate, it can be used for drug controlled release, bio-separation, immunoassay etc. to the higher application field of the biocompatibility requirement of Thermo-sensitive material, be worth with important research and development.
Description
Technical field
The present invention relates to a kind of polymer and preparation method thereof, concretely relate to a kind of poly- (propionamido of Thermo-sensitive
Ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof.
Background technique
Temperature sensing polymer refers to the macromolecular for having reversible response characteristic to extraneous variation of ambient temperature, is a kind of heavy
The intellectual material wanted has been widely used for the biomedicines such as drug controlled release, bio-separation, enzyme immobilization, immunoassay
Field.One most important physical parameter of temperature sensing polymer is exactly that lowest critical solution temperature (LCST) or highest are critical molten
It solves temperature (UCST), i.e. aqueous solutions of polymers varies with temperature temperature corresponding when reversibly occurring physically or chemically to change
Degree.
Polymer material have temperature-sensing property premise be on macromolecular chain should containing hydrophilic radical and hydrophobic grouping, and two
Person reaches relative equilibrium, and hydrogen bond action (hydrophily) can occur therewith with temperature change hydrone and constantly enhance or subtract
It is weak.Currently, common temperature sensing polymer is broadly divided into polyamide-based, polyethers, polyesters etc..
Polyacrylic acid is a kind of common water-soluble polymer, due to containing a large amount of carboxyls on its strand, with soda acid
Sensibility, but do not have temperature-sensing property.Currently, design, synthesis based on polyacrylic acid and have by modified or base group modification
The polymer material of temperature-responsive is still faced with certain challenge.
Summary of the invention
An object of the present invention is to provide a kind of poly- (propionamido ethyl propylene acid esters-co- benzamido of Thermo-sensitive
Ethyl propylene acid esters).
The second object of the present invention is to provide a kind of poly- (propionamido ethyl propylene acid esters-co- benzamido of Thermo-sensitive
Ethyl propylene acid esters) preparation method.
An object of the present invention is achieved in that
A kind of Thermo-sensitive is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters), chemical structural formula
It is as shown in the formula (I):
；
Wherein, x=0.10 ~ 0.28, y=0.72 ~ 0.90；Its minimum critical solution temperature (LCST) is 22.6 ~ 39.2 DEG C,
Close to room temperature and body temperature.
Preferably, the molecular weight of the polymer is 2.8 ~ 5.1 × 104G/mol, molecular weight distribution are 1.5 ~ 1.9；
It is highly preferred that the molecular weight of the polymer is 2.85 ~ 5.01 × 104G/mol, molecular weight distribution are 1.56 ~ 1.9.
The second object of the present invention is to what is be achieved:
A kind of preparation method of Thermo-sensitive poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters), packet
Include following steps:
(a) ring-opening reaction
Acrylic acid, 2- phenyl -2- oxazoline and 2- ethyl -2- oxazoline are subjected to ring-opening reaction, propionamido ethyl third is made
Olefin(e) acid ester, benzamido ethyl propylene acid esters；
Wherein, the molar ratio of 2- ethyl -2- oxazoline, 2- phenyl -2- oxazoline and acrylic acid is 0.80 ~ 0.95: 0.05 ~ 0.20
:1；
(b) after ring-opening reaction is complete, propionamido ethyl propylene acid esters and benzamido ethyl propylene acid esters are in initiator
Free radical copolymerization is carried out under the conditions of existing, and poly- (the propionamido ethyl propylene acid esters-co- benzoyl of Thermo-sensitive is made
Aminoethylacrylate).
In step (a), ring-opening reaction solvent for use can dissolve reaction raw materials (acrylic acid, 2- phenyl -2- oxazoline simultaneously
With 2- ethyl -2- oxazoline), ring-opening reaction product (propionamido ethyl propylene acid esters and benzamido ethyl propylene acid esters)
And initiator；Preferably, solvent can be dehydrated alcohol, anhydrous methanol, ethyl acetate, acetone etc..
Preferably, in step (a), acrylic monomers is first dissolved in solvent, it is to be mixed uniformly after, then 2- second is added thereto
Base -2- oxazoline and 2- phenyl -2- oxazoline carry out ring-opening reaction.
Preferably, in step (a), the reaction temperature of ring-opening reaction is room temperature, and the reaction time is 5 ~ 10 h, is preferably being stirred
Under the conditions of carry out ring-opening reaction.
Preferably, in step (a), using thin-layer chromatography (TLC) method, using anhydrous ether as solvent, observation oxazoline with
Whether acrylic monomers ring-opening reaction carries out completely.
In step (b), the initiator of free radical copolymerization is initiator well known by persons skilled in the art, preferably
Ground, the initiator are azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO) or azobisisoheptonitrile etc..
Preferably, the initiator be azodiisobutyronitrile (AIBN), mole dosage be acrylic monomers 0.5% ~
2%。
Preferably, in step (b), when carrying out free radical copolymerization under an inert atmosphere；Optionally, to reaction vessel
After middle addition initiator, extracts the air in container reaction vessel out and be filled with dry high purity nitrogen, be repeated 5 times, to eliminate air
Middle oxygen, prevents inhibition.
Preferably, in step (b), the reaction temperature of free radical copolymerization is 55 ~ 80 DEG C, and the reaction time is 12 ~ 18
h。
Preferably, in step (b), gained reaction mixture after free radical copolymerization is poured into bag filter with distillation
Water 24 h of dialysis, and be freeze-dried, obtain poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive
Acid esters).
A kind of poly- the potential of (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) of Thermo-sensitive is answered
With, can be used for its drug controlled release, bio-separation, in terms of, the especially biology to Thermo-sensitive material
The more demanding application field of compatibility, biological degradability.
With the novel high polymer material of temperature-sensing property, i.e., poly- (propionamido ethyl propylene acid esters-co- benzene in the present invention
Carboxamidoethyl acrylate) (PEO-PO), it is to be disliked using 2- ethyl -2- oxazoline, the 2- phenyl -2- of specific feed ratio
As Material synthesis novel monomeric, gained monomer passes through free radical copolymerization again and target polymerization is made for oxazoline and acrylic acid
Object.Preparation method of the present invention is simple, mild condition, and is swift in response, easy to operate, can the rapid synthesis polymer, and
Can Effective Regulation polymer material hydrophily and hydrophobicity, promote polymer macromolecule chain to reach the relatively flat of its hydrophilic-hydrophobic
Weighing apparatus, and then can assign polymer material good temperature-sensing property, more Thermo-sensitive polymerizations can be provided for field of biomedicine
Object material.
Poly- (the propionamido ethyl propylene acid esters-co- benzamido ethylacrylic acid of novel high polymer material of the invention
Ester) the minimum critical solution temperature (LCST) of (PEO-PO) is 22.6 ~ 39.2 DEG C, close to room temperature and body temperature, there is good temperature
Quick characteristic, and without apparent cytotoxicity, the bio-compatible of material is good, establishes for it in the practical application of field of biomedicine
Basis is determined.
Polymer of the invention not only has excellent temperature-sensing property, also with good biocompatibility, in medicine
Object control release, bio-separation, immunoassay etc. have potential application, especially the biology to Thermo-sensitive material
The higher application field of compatibility requirements is worth with important research and development.
Detailed description of the invention
Fig. 1 is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) prepared by embodiment 1
(PEO-PO) infrared spectrogram.
Fig. 2 is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) prepared by embodiment 1
(PEO-PO) hydrogen nuclear magnetic spectrogram.
Fig. 3 is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) prepared by embodiment 1
(PEO-PO) ultraviolet-visible spectrogram, i.e., it is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters)
(PEO-PO) aqueous solution light transmittance varies with temperature curve.
Fig. 4 is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) prepared by embodiment 1
(PEO-PO) to the toxicity assessment result of HeLa cell.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any
Mode limits the scope of the invention.
The process and method being not described in detail in the following embodiments are conventional method well known in the art, institute in embodiment
It is to analyze pure or chemical pure and commercially available or prepared by method well known within the skill of those ordinarily skilled with reagent.Under
Stating embodiment realizes the purpose of the present invention.
Embodiment 1
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL dehydrated alcohols of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.The 2- of the 2- ethyl -2- oxazoline and 0.147 g of 0.891 g of precise
Phenyl -2- oxazoline, adds it in flask, stirs 8 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin-layer chromatography
(TLC) method, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.026g azodiisobutyronitrile (AIBN) and is added in reaction flask, take out
The air in flask and it is filled with dry high purity nitrogen out, is repeated 5 times, to eliminate oxygen in air, prevents inhibition.It will
Flask is placed on heating magnetic stirring apparatus, and 18 h are reacted at 65 DEG C.Reaction mixture is poured into saturating with distilled water in bag filter
24 h are analysed, obtain poly- (propionamido ethyl propylene acid esters-by freeze-dryingcoBenzamido ethyl propylene acid esters)
(PEO-PO), yield 57.9%.
The reaction equation of the reaction is as follows:
。
Using infrared spectroscopy (FTIR), NMR spectrum (1H-NMR), ultraviolet-visible spectrum (UV) is to what is be prepared
Poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) (PEO-PO) carries out structure and performance characterization,
Gained infrared spectroscopy as shown in Figure 1, hydrogen nuclear magnetic spectrogram as shown in Fig. 2, ultraviolet-visible spectrogram, that is, poly- (propionamido ethyl propylene
Acid esters-co- benzamido ethyl propylene acid esters) to vary with temperature curve as shown in Figure 3 for (PEO-PO) aqueous solution light transmittance.Separately
Outside, the molecular weight of PEO-PO is 3.64 × 104 G/mol, molecular weight distributing index 1.86, calculates through nuclear magnetic data, PEO-
X/y=15 on PO strand: 85, lowest critical solution temperature (LCST) is 31.5 DEG C.
Embodiment 2
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL anhydrous methanols of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.The 2- of the 2- ethyl -2- oxazoline and 0.074 g of 0.951 g of precise
Phenyl -2- oxazoline, adds it in flask, stirs 10 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin-layer chromatography
(TLC) method, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.034g azodiisobutyronitrile (AIBN) and is added in reaction flask, take out
The air in flask and it is filled with dry high purity nitrogen out, is repeated 5 times, to eliminate oxygen in air, prevents inhibition.It will
Flask is placed on heating magnetic stirring apparatus, and 12 h are reacted at 60 DEG C.Reaction mixture is poured into saturating with distilled water in bag filter
24 h are analysed, obtain poly- (propionamido ethyl propylene acid esters-by freeze-dryingcoBenzamido ethyl propylene acid esters)
(PEO-PO), yield 65.3%.The molecular weight of PEO-PO is 2.85 × 104G/mol, molecular weight distributing index 1.71,
X/y=10 on PEO-PO strand: 90, lowest critical solution temperature (LCST) is 39.2 DEG C.
Embodiment 3
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL anhydrous acetic acid second of precise is added
Ester stirs 6 min, is uniformly mixed acrylic acid and ethyl alcohol.2- ethyl -2- the oxazoline of 0.916 g of precise and 0.110 g
2- phenyl -2- oxazoline, add it in flask, stir 6 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin layer color
(TLC) method of composing, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.020 g azodiisobutyronitrile and is added in reaction flask, extract flask out
In air and be filled with dry high purity nitrogen, be repeated 5 times, to eliminate oxygen in air, prevent inhibition.Flask is set
In on heating magnetic stirring apparatus, 15 h are reacted at 70 DEG C.By reaction mixture pour into bag filter with distilled water dialyse 24 h,
Poly- (propionamido ethyl propylene acid esters-is obtained by freeze-dryingcoBenzamido ethyl propylene acid esters) (PEO-PO), it produces
Rate is 68.4%.The molecular weight of PEO-PO is 3.08 × 104G/mol, molecular weight distributing index 1.90, on PEO-PO strand
X/y=12: 88, lowest critical solution temperature (LCST) is 35.9 DEG C.
Embodiment 4
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL anhydrous propanones of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.The 2- of the 2- ethyl -2- oxazoline and 0.221 g of 0.842 g of precise
Phenyl -2- oxazoline, adds it in flask, stirs 5 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin-layer chromatography
(TLC) method, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.025 g azodiisobutyronitrile (AIBN) and is added in reaction flask, take out
The air in flask and it is filled with dry high purity nitrogen out, is repeated 5 times, to eliminate oxygen in air, prevents inhibition.It will
Flask is placed on heating magnetic stirring apparatus, and 18 h are reacted at 55 DEG C.Reaction mixture is poured into saturating with distilled water in bag filter
24 h are analysed, obtain poly- (propionamido ethyl propylene acid esters-by freeze-dryingcoBenzamido ethyl propylene acid esters)
(PEO-PO), yield 75.1%.The molecular weight of PEO-PO is 5.01 × 104G/mol, molecular weight distributing index 1.69,
X/y=23 on PEO-PO strand: 77, lowest critical solution temperature (LCST) is 25.9 DEG C.
Embodiment 5
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL dehydrated alcohols of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.The 2- of the 2- ethyl -2- oxazoline and 0.294 g of 0.792 g of precise
Phenyl -2- oxazoline, adds it in flask, stirs 6 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin-layer chromatography
(TLC) method, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.0289g azobisisoheptonitrile and is added in reaction flask, extract flask out
In air and be filled with dry high purity nitrogen, be repeated 5 times, to eliminate oxygen in air, prevent inhibition.Flask is set
In on heating magnetic stirring apparatus, 12 h are reacted at 80 DEG C.By reaction mixture pour into bag filter with distilled water dialyse 24 h,
Poly- (propionamido ethyl propylene acid esters-is obtained by freeze-dryingcoBenzamido ethyl propylene acid esters) (PEO-PO), it produces
Rate is 73.2%.The molecular weight of PEO-PO is 3.56 × 104G/mol, molecular weight distributing index 1.54, PEO-PO strand
Upper x/y=28: 72, lowest critical solution temperature (LCST) is 22.6 DEG C.
Comparative example 1
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL dehydrated alcohols of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.2- ethyl -2- the oxazoline of 0.990 g of precise, adds it to burning
In bottle, 8h is stirred at room temperature, it is ensured that ring-opening reaction is complete.
After acrylic monomers fully reacting, accurately weighs 0.026g azodiisobutyronitrile (AIBN) and be added to reaction flask
In, it extracts the air in flask out and is filled with dry high purity nitrogen, be repeated 5 times, to eliminate oxygen in air, prevent polymerization inhibitor and make
With.Flask is placed on heating magnetic stirring apparatus, 18 h are reacted at 65 DEG C.Reaction mixture is poured into bag filter with distillation
Water 24 h of dialysis, obtain poly- propionamido ethyl propylene acid esters (PEO), yield 83.7% by freeze-drying.
Comparative example 2
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL dehydrated alcohols of precise is added, stirs
5 min are mixed, acrylic acid and ethyl alcohol are uniformly mixed.The 2- of the 2- ethyl -2- oxazoline and 0.368 g of 0.743 g of precise
Phenyl -2- oxazoline, adds it in flask, stirs 10 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin-layer chromatography
(TLC) method, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.030 g azodiisobutyronitrile (AIBN) and is added in reaction flask, take out
The air in flask and it is filled with dry high purity nitrogen out, is repeated 5 times, to eliminate oxygen in air, prevents inhibition.It will
Flask is placed on heating magnetic stirring apparatus, and 12 h are reacted at 65 DEG C.Reaction mixture is poured into saturating with distilled water in bag filter
24 h are analysed, obtain poly- (propionamido ethyl propylene acid esters-by freeze-dryingcoBenzamido ethyl propylene acid esters)
(PEO-PO), yield 71.2%.
Comparative example 3
(a) typical small molecule ring-opening reaction
In the 25 mL flasks equipped with magneton, the 0.720 g acrylic monomers and 6 mL anhydrous acetic acid second of precise is added
Ester stirs 5min, is uniformly mixed acrylic acid and ethyl alcohol.2- ethyl -2- the oxazoline of 0.594 g of precise and 0.588 g
2- phenyl -2- oxazoline, add it in flask, stir 5 h at room temperature, it is ensured that ring-opening reaction is complete.Using thin layer color
(TLC) method of composing, using anhydrous ether as solvent, whether observation oxazoline and acrylic monomers ring-opening reaction are carried out completely.
(b) free radical copolymerization
It after acrylic monomers fully reacting, accurately weighs 0.025 g azodiisobutyronitrile (AIBN) and is added in reaction flask, take out
The air in flask and it is filled with dry high purity nitrogen out, is repeated 5 times, to eliminate oxygen in air, prevents inhibition.It will
Flask is placed on heating magnetic stirring apparatus, and 15 h are reacted at 70 DEG C.Reaction mixture is poured into saturating with distilled water in bag filter
24 h are analysed, obtain poly- (propionamido ethyl propylene acid esters-by freeze-dryingcoBenzamido ethyl propylene acid esters)
(PEO-PO), yield 65.5%.
Embodiment 6
Temperature-sensing property test, test result the following table 1 institute are carried out to polymer material prepared by embodiment 1 ~ 5 and comparative example 1 ~ 3
Show.
Table 1
Note: EO, PO, AA respectively represent 2- ethyl -2- oxazoline, 2- phenyl -2- oxazoline and acrylic monomers.
Embodiment 7
Using 3- (4,5- dimethylthiazole -2) -2,5- diphenyltetrazolium bromide bromide (thiazolyl blue) method (MTT) to embodiment 1
The PEO-PO of preparation carries out Cytotoxic evaluation.HeLa cell (is reached in Dulbecco ' s modified Eagle ' s medium
Er Baike modified Eagle medium) in, maintain 37 DEG C of 5% CO2Under air conditions, 10% cow's serum is added.In laboratory
In, 6 orifice plates concentration is 1.5 × 104It is cultivated under the conditions of cells/mL one day, the polymer solution of various concentration is then added
(0.2,1,5,25 and 125 μ g/mL).After culture in 1 ~ 3 day, is washed twice using FBS and measure extinction at 570nm
Degree, and then calculate the survival rate of HeLa.
PEO-PO prepared by embodiment 1 is as shown in Figure 4 to the toxicity assessment result of HeLa cell.It can be seen from the figure that
After HeLa cell is cultivated 1 ~ 3 day in the PEO-PO solution that concentration is respectively 0.2,1,5,25 and 125 μ g/mL, HeLa cell
Survival rate be above 93%.That is, PEO-PO to the growth of HeLa cell without obvious inhibiting effect, i.e., without apparent
Cytotoxicity.Therefore, this novel temperature sensing polymer material can be in drug controlled release, bio-separation, immunoassay
Etc. have certain application value, it is especially more demanding to biocompatibility, the biological degradability of Thermo-sensitive material
Application field.
Claims (9)
1. a kind of Thermo-sensitive is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters), feature exists
In chemical structural formula is as shown in the formula (I):
；
Wherein, x=0.10 ~ 0.28, y=0.72 ~ 0.90；Its minimum critical solution temperature is 22.6 ~ 39.2 DEG C.
2. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 1
Acid esters), which is characterized in that its molecular weight is 2.8 ~ 5.1 × 104G/mol, molecular weight distribution are 1.5 ~ 1.9.
3. Thermo-sensitive described in claim 1 is poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters)
Preparation method, which comprises the steps of:
(a) ring-opening reaction
Acrylic acid, 2- phenyl -2- oxazoline and 2- ethyl -2- oxazoline are subjected to ring-opening reaction, propionamido ethyl third is made
Olefin(e) acid ester, benzamido ethyl propylene acid esters；
Wherein, the molar ratio of 2- ethyl -2- oxazoline, 2- phenyl -2- oxazoline and acrylic acid is 0.80 ~ 0.95: 0.05 ~ 0.20
:1；
(b) free radical copolymerization
After ring-opening reaction is complete, propionamido ethyl propylene acid esters and benzamido ethyl propylene acid esters exist in initiator
Under conditions of carry out free radical copolymerization, be made poly- (the propionamido ethyl propylene acid esters-co- benzamido of Thermo-sensitive
Ethyl propylene acid esters).
4. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (a), ring-opening reaction solvent for use be dehydrated alcohol, anhydrous methanol, acetic acid
Ethyl ester or acetone.
5. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (a), the reaction temperature of ring-opening reaction is room temperature, and the reaction time is 5 ~ 10
h。
6. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (a), acrylic monomers is first dissolved in solvent, it is to be mixed uniformly after, then to
2- ethyl -2- oxazoline and 2- phenyl -2- oxazoline is wherein added, carries out ring-opening reaction.
7. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (b), the initiator of free radical copolymerization be azodiisobutyronitrile,
Benzoyl peroxide or azobisisoheptonitrile, mole dosage are 0.5 ~ 2 % of acrylic monomers.
8. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (b), carry out free radical copolymerization under an inert atmosphere, reaction temperature
Degree is 60 ~ 80 DEG C, and the reaction time is 12 ~ 18 h.
9. poly- (the propionamido ethyl propylene acid esters-co- benzamido ethyl propylene of Thermo-sensitive according to claim 3
Acid esters) preparation method, which is characterized in that in step (b), by after free radical copolymerization gained reaction mixture pour into
It analyses in bag and is dialysed 24 h with distilled water, and be freeze-dried, obtain poly- (the propionamido ethyl propylene acid esters-co- benzoyl of Thermo-sensitive
Aminoethylacrylate).
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| CN103113595A (en) * | 2012-12-31 | 2013-05-22 | 中科院广州化学有限公司 | Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof |
| CN103881040A (en) * | 2014-03-10 | 2014-06-25 | 同济大学 | Preparation method of temperature and CO2 double-responsive block copolymer nano micelle |
| RU2560726C1 (en) * | 2014-07-30 | 2015-08-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" | Method of obtaining tetrazole-containing paired polymers |
| CN108484824A (en) * | 2018-04-18 | 2018-09-04 | 苏州科技大学 | A kind of temperature sensing polymer and its preparation method and use |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113595A (en) * | 2012-12-31 | 2013-05-22 | 中科院广州化学有限公司 | Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof |
| CN103881040A (en) * | 2014-03-10 | 2014-06-25 | 同济大学 | Preparation method of temperature and CO2 double-responsive block copolymer nano micelle |
| RU2560726C1 (en) * | 2014-07-30 | 2015-08-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" | Method of obtaining tetrazole-containing paired polymers |
| CN108484824A (en) * | 2018-04-18 | 2018-09-04 | 苏州科技大学 | A kind of temperature sensing polymer and its preparation method and use |
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