CN108484824A - A kind of temperature sensing polymer and its preparation method and use - Google Patents
A kind of temperature sensing polymer and its preparation method and use Download PDFInfo
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Abstract
The invention discloses a kind of temperature sensing polymer and its preparation method and use, the structure of the temperature sensing polymer is shown in formula I, and synthetic method includes the following steps：Initiator, monomer and aglucon are added in solvent, deoxygenation, cuprous bromide is then added, reacted 0.5 5.0 hours, several times by product washing of precipitate, copolymer is obtained after dry；Copolymer is dissolved in N, in N dimethyl formamide solutions, imidazoles is added, reacts 24 48 hours, product precipitate and is washed several times, temperature sensing polymer is obtained after drying.The temperature sensing polymer of the present invention can make polymer show different temperature-sensing properties by adjusting copolymer composition, and can be made up of regulated in wider range polymer change its LCST either UCST cloud point temperatures can be applied to drug controlled release, catalyst discharge stage by stage, biochemistry, medicine or the food every field such as cell embedding.
Description
Technical field
The invention belongs to high molecular polymer fields, and in particular to a kind of temperature sensing polymer and its synthetic method and use
On the way, which has certain LCST (lower critical solution temperature) and UCST (high critical solution temperature) range.
Background technology
Thermosensitive polymer is very sensitive to temperature, is generally divided into lower critical solution temperature (LCST) type and high Critical Solution
Temperature (UCST) type, polymer does not dissolve in the solution when corresponding to respectively below and above critical-temperature.However, when referring to
Thermosensitive polymer, the generally referred to as polymer with LCST characteristics, because of the polymer number with UCST characteristics in water
It measures considerably less.However, relative to LCST type polymer, UCST types polymer has potential application at many aspects.Therefore, it opens
The polymer of sending out novel in aqueous solution with UCST characteristics and with LCST performance polymers, and have simultaneously LCST and
UCST performance polymers all become extremely important.
Phase transition temperature with LCST and UCST performance polymers is by polymer composition, molecular weight and its shadow of distribution
It rings.Therefore, polymer architecture control becomes the key factor for adjusting polymer phase transition temperature.Simple combined polymerization is a kind of non-
Often effective strategy.Under normal conditions, DMAEMA, NIPAAm and polyoxyethylene monomer can be copolymerized with other monomers to obtain
The polymer of different LCST phase transition temperatures, including the monomer of sulfobetaines and NAGAM monomers can be copolymerized with other monomers
Conjunction obtains UCST copolymers.Under normal circumstances, the cloud point temperature of LCST copolymers with it is hydrophilic polymerized close monomer increase and
Increase, is reduced with the increase of hydrophobicity copolymerization monomer, vice versa, is also such for UCST copolymers.
Although the above-mentioned heat-sensitive copolymer referred to has had many reports, most of this kind of polymer only individual
UCST or LCST characteristics.If same type of polymer can show LCST and UCST spies simultaneously according to its composition variation
Property, it will it is more conducive to its practical application, because copolymer preparation is very simple.
In fact, had similar report, such as the copolymer that NAGA and DAAM is formed, it can be by adjusting monomer ratio
Example obtains LCST or UCST characteristics.But this kind of polymer adjustable extent is relatively narrow, is only capable of adjusting in 20% and 10% range
LCST or UCST characteristics, the corresponding larger LCST or UCST cloud point temperatures change of smaller polymer composition floating will be unfavorable for essence
Really adjust.
Invention content
Shortcoming and deficiency existing in terms of in order to overcome above-mentioned temperature sensing polymer design preparation, primary and foremost purpose of the invention
It is to provide a kind of temperature sensing polymer, itself LCST and UCST characteristic can be adjusted by the variation that polymer forms.
Another object of the present invention is to provide the synthetic methods of above-mentioned temperature sensing polymer.
It is still another object of the present invention to provide the purposes of above-mentioned temperature sensing polymer.
The purpose of the invention is achieved by the following technical solution：
A kind of temperature sensing polymer, structure are shown in formula I：
Include glycidyl methacrylate (glycidyl methacrylate) monomer and 2- of imidazoles substitution in Formulas I
The copolymer of (2- methoxy ethoxies) ethylmethyl acrylate monomer composition；
In Formulas I, the range of x is 0~1；N is 10~500, preferably 30~200.
The synthetic method of above-mentioned temperature sensing polymer, includes the following steps：
(1) initiator, monomer and aglucon are added in solvent, lead to argon gas Gu steep 30 minutes it is above with deoxygenation, then add
Enter cuprous bromide, reacted 0.5-5.0 hours at 60~90 DEG C, if product crosses neutral alumina column and washing of precipitate after reaction
Dry time, it is then dried under vacuum to constant weight, obtains copolymer；
(2) copolymer made from step (1) is dissolved in n,N-Dimethylformamide solution, addition imidazoles, 60~80
React 24-48 hours at DEG C, product is precipitated and washed several times after reaction, is then dried in vacuo, is obtained Thermo-sensitive
Polymer；
The preferred 2- isobutyl bromides methyl esters of initiator, 2- isobutyl ethyl bromides, methoxyl group 2- isobutyl bromides described in step (1)
One kind in ethyl ester, benzyl chloride or trimethyl silicon substrate propinyl -2- isobutyl ethyl bromides；
Monomer described in step (1) includes glycidyl methacrylate and 2- (2- methoxy ethoxies) ethyl-methyl
The molar ratio of acrylate, the two is 0/100~100/0；
The molar ratio of monomer and initiator described in step (1) is 1000/1~10/1, preferably 200/1~20/1；
Aglucon preferably 2,2 '-bipyridyls, 4,4 '-dinonyl bipyridyls or pentamethyl-diethylenetriamine described in step (1)
In one kind；
The molar ratio of aglucon and initiator described in step (1) is 5/1~0.2/1.0, preferably 2/1~0.5/1.0；
Solvent described in step (1) is one or more of toluene, tetrahydrofuran, methyl phenyl ethers anisole, cyclohexanone or butanone；
The volume ratio of solvent and monomer described in step (1) is 10/1~0.5/1.0, preferably 2/1~0.5/1.0；
The solvent used in washing of precipitate described in step (1) be in n-hexane, hexamethylene, ether or petroleum ether it is a kind of with
On；
A concentration of 5~50g/L of the product of step (1) described in step (2) in n,N-Dimethylformamide solution, it is excellent
Select 10~20g/L；
The mass ratio of imidazoles and the product of step (1) described in step (2) is 10/1~1/1, preferably 7/1~4/1；
The solvent used in washing of precipitate described in step (2) can be one or more of n-hexane, ether or petroleum ether.
The principle of the present invention is：Using ATRP method synthesizing methyl glycidyl acrylates and 2- (2- methoxyl group ethoxies
Base) ethylmethyl acrylate copolymer, recycle imidazoles to glycidyl methacrylate carry out epoxy addition, in first
Imidazole group is introduced on base glycidyl acrylate and generates hydroxyl.Imidazole modified glycidyl methacrylate and 2-
The homopolymer of (2- methoxy ethoxies) ethylmethyl acrylate respectively has UCST and LCST characteristics, and both monomers
Itself has hydrophily.Therefore, copolymer can show UCST and LCST characteristics, and can be by controlling polymer composition
The Thermo-sensitive of copolymer is adjusted.
The present invention has the following advantages and effects with respect to the prior art：
(1) polymer designed by the present invention can also pass through conventional free radical by ATRP method controllable preparations
Prepared by polymer process, therefore preparation method is easy, easy to spread.
(2) temperature sensing polymer of the invention can make polymer show different temperature sensitive spies by adjusting copolymer composition
Property, and can be made up of regulated in wider range polymer and change itself LCST UCST cloud point temperature.
(3) temperature sensing polymer prepared by the present invention in water there is suitable LCST or UCST therefore can apply
It is discharged stage by stage in drug controlled release, catalyst, biochemistry, medicine or the food every field such as cell embedding.
Description of the drawings
Fig. 1 is 1 product of embodiment1H NMR results.
Fig. 2 is 2 product of embodiment1H NMR results.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of temperature sensing polymer, is prepared by following methods：
(1) 0.71g glycidyl methacrylate, 3.76g 2- (2- methoxyl groups are added in the round-bottomed flask of 100ml
Ethyoxyl) ethylmethyl acrylate, 0.051g trimethyl silicon substrate propinyl -2- isobutyl ethyl bromides, 0.150g 4,4 '-two
Reaction system stirring and dissolving is led to argon gas Gu and steeps deoxygenation in 30 minutes, 0.026g is then added by nonyl bipyridyl and 10ml methyl phenyl ethers anisoles
Cuprous bromide, polymerisation 2.5h is carried out at 80 DEG C, and reaction product crosses neutral alumina pillar, filtrate after being diluted with tetrahydrofuran
It concentrates and then is deposited in ether, product repeats washing of precipitate twice, is then dried in vacuo at ambient temperature for 24 hours to permanent
Weight, obtains 3.87g glycidyl methacrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, produces
Product yield is 86.5%.
Product1Shown in H NMR results such as Fig. 1 (a), interpretation of result shows that polymer polymerizing degree is 122, i.e. n=122.First
Molar content ratio is in the polymer for base glycidyl acrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate
1:4, i.e. x=0.2.Gel exclusion chromatography characterization result shows that the number-average molecular weight of polymer is 2.3 × 104G/mol, dispersibility
Index is 1.08.
(2) the above-mentioned copolymers of 1.05g and 1.52g imidazoles and 50mL DMF are added in 250mL round-bottomed flasks.Mixing
Object is stirred overnight in 75 DEG C of oil baths.Then reaction solution is added in 100mL ether and is precipitated, precipitated products ether weight
It is dried in vacuo at ambient temperature after washing twice again for 24 hours to constant weight, it is sweet to obtain the imidazole modified Glycidyl methacrylates of 1.02g
Grease and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, product yield 89.8%.
Product1Shown in H NMR results such as Fig. 1 (b), interpretation of result shows that polymer polymerizing degree is 121, i.e. n=121.First
Molar content ratio is in the polymer for base glycidyl acrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate
1:4, i.e. x=0.2.Gel exclusion chromatography characterization result shows that the number-average molecular weight of polymer is 2.6 × 104G/mol, dispersibility
Index is 1.12, measures polymer with lowest critical solution temperature (LCST) with ultraviolet-visible spectrophotometer, value is
41.5 DEG C (pH=6.5), 29 DEG C (pH=7.0) or 24.9 DEG C (pH=7.5).Structure is shown below：
Embodiment 2
A kind of temperature sensing polymer, is prepared by following methods：
(1) 2.84g glycidyl methacrylate, 0.94g 2- (2- methoxyl groups are added in the round-bottomed flask of 100ml
Ethyoxyl) ethylmethyl acrylate, 0.053g trimethyl silicon substrate propinyl -2- isobutyl ethyl bromides, 0.152g 4,4 '-two
Reaction system stirring and dissolving is led to argon gas Gu and steeps deoxygenation in 30 minutes, 0.025g is then added by nonyl bipyridyl and 10ml methyl phenyl ethers anisoles
Cuprous bromide, polymerisation 1.0h is carried out at 80 DEG C, and reaction product crosses neutral alumina pillar, filtrate after being diluted with tetrahydrofuran
It concentrates and then is deposited in ether, product repeats washing of precipitate twice, is then dried in vacuo at ambient temperature for 24 hours to permanent
Weight, obtains 3.49g glycidyl methacrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, produces
Product yield is 90.3%.
Product1Shown in H NMR results such as Fig. 2 (a), interpretation of result shows that polymer polymerizing degree is 123, i.e. n=123.First
Molar content ratio is in the polymer for base glycidyl acrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate
4:1, i.e. x=0.8.Gel exclusion chromatography characterization result shows that the number-average molecular weight of polymer is 1.9 × 104G/mol, dispersibility
Index is 1.11.
(2) the above-mentioned copolymers of 1.06g and 3.26g imidazoles and 50mL DMF are added in 250mL round-bottomed flasks.Mixing
Object is stirred overnight in 80 DEG C of oil baths.Then reaction solution is added in 100mL ether and is precipitated, precipitated products ether weight
It is dried in vacuo at ambient temperature after washing twice again for 24 hours to constant weight, it is sweet to obtain the imidazole modified Glycidyl methacrylates of 1.36g
Grease and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, product yield 95.1%.
Product1Shown in H NMR results such as Fig. 2 (b), interpretation of result shows that polymer polymerizing degree is 121, i.e. n=121.First
Molar content ratio is in the polymer for base glycidyl acrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate
4:1, i.e. x=0.8.Gel exclusion chromatography characterization result shows that the number-average molecular weight of polymer is 2.7 × 104G/mol, dispersibility
Index is 1.14, measures polymer with lowest critical solution temperature (UCST) with ultraviolet-visible spectrophotometer, value is
28.9 DEG C (pH=6.5) or 61.8 DEG C (pH=7.0).Structure is shown below：
Embodiment 3
A kind of temperature sensing polymer, is prepared by following methods：
(1) 2.12g glycidyl methacrylate, 2.83g 2- (2- methoxyl groups are added in the round-bottomed flask of 50ml
Ethyoxyl) ethylmethyl acrylate, 0.061g trimethyl silicon substrate propinyl -2- isobutyl ethyl bromides, 0.183g 4,4 '-two
Reaction system stirring and dissolving is led to argon gas Gu and steeps deoxygenation in 30 minutes, 0.032g is then added by nonyl bipyridyl and 10ml methyl phenyl ethers anisoles
Cuprous bromide, polymerisation 1.5h is carried out at 80 DEG C, and reaction product crosses neutral alumina pillar, filtrate after being diluted with tetrahydrofuran
It concentrates and then is deposited in ether, product repeats washing of precipitate twice, is then dried in vacuo at ambient temperature for 24 hours to permanent
Weight, obtains 4.36g glycidyl methacrylate and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, produces
Product yield is 88.1%.
Product1H NMR interpretations of result show that polymer polymerizing degree is 119, i.e. n=119.Glycidyl methacrylate
Molar content ratio is 1 in the polymer with 2- (2- methoxy ethoxies) ethylmethyl acrylate:1, i.e. x=0.5.Gel is arranged
Chromatography characterization is hindered the result shows that the number-average molecular weight of polymer is 2.1 × 104G/mol, monodispersity index 1.10.
(2) the above-mentioned copolymers of 1.023g and 2.11g imidazoles and 50mL DMF are added in 100mL round-bottomed flasks.Mixing
Object is stirred overnight in 65 DEG C of oil baths.Then reaction solution is added in 100mL ether and is precipitated, precipitated products ether weight
It is dried in vacuo at ambient temperature after washing twice again for 24 hours to constant weight, obtains the imidazole modified Glycidyl methacrylates of 1.212g
Glyceride and 2- (2- methoxy ethoxies) ethylmethyl acrylate copolymer, product yield 98.2%.
Product1H NMR interpretations of result show that polymer polymerizing degree is 120, i.e. n=120.Glycidyl methacrylate
Molar content ratio is 1 in the polymer with 2- (2- methoxy ethoxies) ethylmethyl acrylate:1, i.e. x=0.5.Gel is arranged
Chromatography characterization is hindered the result shows that the number-average molecular weight of polymer is 2.5 × 104G/mol, monodispersity index 1.13, with it is ultraviolet-
Visible spectrophotometer measure polymer have lowest critical solution temperature (LCST), value be 37.5 DEG C (pH=7.0) or
21.3 DEG C (pH=7.5).
Embodiment 4
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 1, except 4.71g 2- (2- methoxy ethoxies) ethylmethyl acrylate is added, final products are purple
It is 27 DEG C (pH=6.5) that outside-visible spectrophotometer, which measures polymer to have lowest critical solution temperature (LCST), value,
27.2 DEG C (pH=7.0) or 27.1 DEG C (pH=7.5).
Embodiment 5
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 3, except addition 1.42g glycidyl methacrylate, 3.71g 2- (2- methoxy ethoxies) second
Methyl acrylate, final products measure polymer with ultraviolet-visible spectrophotometer has lowest critical solution temperature
(LCST), value is 56.5 DEG C (pH=6.5), 32.5 DEG C (pH=7.0) or 24.1 DEG C (pH=7.5).
Embodiment 6
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 3, except addition 0.51g glycidyl methacrylate, 4.03g 2- (2- methoxy ethoxies) second
Methyl acrylate, final products measure polymer with ultraviolet-visible spectrophotometer has lowest critical solution temperature
(LCST), value is 36.9 DEG C (pH=6.5), 28.5 DEG C (pH=7.0) or 25.2 DEG C (pH=7.5).
Embodiment 7
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 3, except addition 0.43g glycidyl methacrylate, 5.08g 2- (2- methoxy ethoxies) second
Methyl acrylate, final products measure polymer with ultraviolet-visible spectrophotometer has lowest critical solution temperature
(LCST), value is 31 DEG C (pH=6.5), 27.5 DEG C (pH=7.0) or 27.5 DEG C (pH=7.5).
Embodiment 8
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 2, except addition 3.07g glycidyl methacrylate, 0.66g 2- (2- methoxy ethoxies) second
Methyl acrylate, final products measure polymer with ultraviolet-visible spectrophotometer has highest critical solution temperature
(UCST), value is 44.8 DEG C (pH=6.5) or 70.3 DEG C (pH=7.0).
Embodiment 9
A kind of temperature sensing polymer, is prepared by following methods：
With embodiment 2, except addition 3.23g glycidyl methacrylate, 0.43g 2- (2- methoxy ethoxies) second
Methyl acrylate, final products measure polymer with ultraviolet-visible spectrophotometer has highest critical solution temperature
(UCST), value is 61.3 DEG C (pH=6.5) or 93.6 DEG C (pH=7.0).
Polymer obtained by embodiment has apparent temperature-sensing property, and has minimum accordingly face according to its composition
Boundary's solution temperature (LCST) or highest critical solution temperature (UCST).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of temperature sensing polymer, it is characterised in that structure is shown in formula I：
In Formulas I, the range of x is 0~1.
2. the synthetic method of temperature sensing polymer described in claim 1, it is characterised in that include the following steps：
(1) initiator, monomer and aglucon are added in solvent, lead to argon gas Gu and steep 30 minutes or more with deoxygenation, bromine is then added
Change cuprous, reacts 0.5-5.0 hours at 60~90 DEG C, product crosses neutral alumina column after reaction and washing of precipitate is several
It is secondary, it is then dried under vacuum to constant weight, obtains copolymer；
(2) copolymer made from step (1) is dissolved in n,N-Dimethylformamide solution, addition imidazoles, at 60~80 DEG C
Reaction 24-48 hour, after reaction product precipitated and washed several times, be then dried in vacuo, obtain Thermo-sensitive polymerize
Object；
Monomer described in step (1) includes glycidyl methacrylate and 2- (2- methoxy ethoxies) ethyl-methyl propylene
The molar ratio of acid esters, the two is 0/100~100/0.
3. synthetic method according to claim 2, it is characterised in that：Initiator described in step (1) is 2- isobutyl bromides
Methyl esters, 2- isobutyl ethyl bromides, methoxyl group 2- isobutyl ethyl bromides, benzyl chloride or trimethyl silicon substrate propinyl -2- isobutyl bromide second
One kind in ester.
4. synthetic method according to claim 2, it is characterised in that：Mole of monomer and initiator described in step (1)
Than being 1000/1~10/1.
5. synthetic method according to claim 2, it is characterised in that：Aglucon described in step (1) be 2,2 '-bipyridyls,
One kind in 4,4 '-dinonyl bipyridyls or pentamethyl-diethylenetriamine.
6. synthetic method according to claim 2, it is characterised in that：Mole of aglucon and initiator described in step (1)
Than for 5/1~0.2/1.0.
7. synthetic method according to claim 2, it is characterised in that：The volume ratio of solvent and monomer described in step (1)
For 10/1~0.5/1.0.
8. synthetic method according to claim 2, it is characterised in that：The product of step (1) described in step (2) is in N, N-
A concentration of 5~50g/L in dimethyl formamide solution.
9. synthetic method according to claim 2, it is characterised in that：The product of imidazoles and step (1) described in step (2)
Mass ratio be 10/1~1/1.
10. temperature sensing polymer described in claim 1 drug controlled release, catalyst discharge stage by stage or cell embedding in
Application.
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| CN109517107A (en) * | 2018-11-28 | 2019-03-26 | 河北大学 | A kind of Thermo-sensitive poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof |
| CN111466367A (en) * | 2020-02-17 | 2020-07-31 | 天津大学 | Composition for preserving cells |
| CN113512153A (en) * | 2021-04-15 | 2021-10-19 | 陕西科技大学 | Method for preparing novel UCST type temperature-sensitive polymer immobilized enzyme |
| CN115594551A (en) * | 2022-09-28 | 2023-01-13 | 山东农业大学（Cn） | Accurate controlled-release film filled with temperature-sensitive polymer nanoparticles and application thereof |
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| CN109517107A (en) * | 2018-11-28 | 2019-03-26 | 河北大学 | A kind of Thermo-sensitive poly- (propionamido ethyl propylene acid esters-co- benzamido ethyl propylene acid esters) and preparation method thereof |
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| CN113512153A (en) * | 2021-04-15 | 2021-10-19 | 陕西科技大学 | Method for preparing novel UCST type temperature-sensitive polymer immobilized enzyme |
| CN113512153B (en) * | 2021-04-15 | 2022-06-10 | 陕西科技大学 | Method for immobilizing UCST type temperature-sensitive polymer |
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