CN107129577A - It is grafted polysiloxane block copolymers and preparation method and the application of cysteine - Google Patents
It is grafted polysiloxane block copolymers and preparation method and the application of cysteine Download PDFInfo
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- CN107129577A CN107129577A CN201710242673.1A CN201710242673A CN107129577A CN 107129577 A CN107129577 A CN 107129577A CN 201710242673 A CN201710242673 A CN 201710242673A CN 107129577 A CN107129577 A CN 107129577A
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Abstract
The invention discloses a kind of polysiloxane block copolymers for being grafted cysteine and preparation method and application.The present invention triggers the cyclic monomer ring-opening polymerisations such as hexamethyl cyclotrisiloxane and trimethyl trivinyl cyclotrisiloxane with n-BuLi, obtains PDMS b PVMS by active anion ring-opening polymerisation；Then by the Radical Addition of sulfydryl vinyl, N mucolyticum acid groups is introduced to the block containing vinyl, PDMS b (PDMS g Acys) are obtained；Finally acetyl group is hydrolyzed in acid condition, PDMS b (PDMS g Cys) are obtained.Solid material is soaked in PDMS b (PDMS g Cys) aqueous solution, the adsorption layer of the block copolymer can be formed in material surface, the effect for reducing protein in adsorption is reached.
Description
Technical field
The invention belongs to the preparation field of functional high-polymer block copolymer, more particularly to a kind of grafting cysteine
Polysiloxane block copolymers and preparation method and application.
Background technology
Protein is in the prerequisite that the absorption of material surface is often material surface biodeterioration, anti-protein adsorbent
Study hotspot thus as numerous areas such as medical material, marine anti-pollution, UF membranes.Amphoteric ion polymer is inhaled in anti-albumen
Excellent performance is shown by forming " hydrated sheath " with iris action in attached research, but it is good to be in order at itself
Good water solubility, in aqueous amphoteric ion polymer be often difficult to be formed easily by the hydrophobic surface of protein contamination being assembled
Effective stable adsorption layer, thus needing many application scenarios of anti-protein adsorption to be restricted.
Obtain one kind and can in aqueous stablize being adsorbed onto surface and so as to play anti-protein adsorption making therefore, it is necessary to study
Amphoteric ion polymer.
The content of the invention
The primary and foremost purpose of the present invention is to overcome the shortcoming and deficiency of prior art to be grafted the poly- of cysteine there is provided a kind of
The preparation method of silicone block copolymer.
Another object of the present invention is to provide the polysiloxanes of the grafting cysteine obtained by above-mentioned preparation method
Block copolymer.
It is still another object of the present invention to provide the application of the polysiloxane block copolymers of above-mentioned grafting cysteine.
The purpose of the present invention is achieved through the following technical solutions：A kind of polysiloxane block copolymers for being grafted cysteine
Preparation method, comprise the following steps：
(1) synthesis of dimethyl silicone polymer-Polymethyl methacrylate block copolymer：Add in organic solvent A
Enter hexamethyl cyclotrisiloxane (D3), in inert gas atmosphere, first time polymerisation is triggered with n-BuLi, solution is obtained
E；By D3With 1,3,5- trivinyl -1,3,5- trimethyl cyclotrisiloxane (D3 V) be dissolved in organic solvent A, solution F is obtained,
Solution F and solution E are mixed, second of polymerisation is carried out；It is eventually adding trim,ethylchlorosilane and terminates polymerisation；To reaction
Obtained product purification, obtains transparent oily liquid product, i.e. dimethyl silicone polymer-b- Polymethyl methacrylates block
Copolymer (PDMS-b-PVMS)；
(2) synthesis of dimethyl silicone polymer-polysiloxane-grafted N-acetylcystein block copolymer：Will be organic molten
Agent B, organic solvent C, PDMS-b-PVMS, N-acetylcystein and dimethoxybenzoin mixing, the solution clarified, are used
Ultraviolet light-initiated Radical Addition, the product purification obtained to reaction, obtains dimethyl silicone polymer-b- polysiloxanes and connects
Branch N-acetylcystein block copolymer【PDMS-b-(PDMS-g-Acys)】；
(3) synthesis of the polysiloxane block copolymers of grafting cysteine：PDMS-b- is added in organic solvent D
(PDMS-g-Acys) and hydrochloric acid, it is heated at reflux reaction；The product purification obtained to reaction, obtains being grafted the poly- silicon of cysteine
Oxygen alkane block copolymer【PDMS-b-(PDMS-g-Cys)】.
The above organic solvent A, B, C, D are to be used to dissolve reactive material, and itself does not participate in reaction.Organic solvent
A, B, C, D can be identical material or different materials.
The above inert atmosphere is preferably nitrogen atmosphere.
The condition of first time polymerisation described in step (1) is preferably 0~5 DEG C of polymerization 12h.
The condition of second of polymerisation described in step (1) is preferably 0~5 DEG C of polymerization 12h.
Organic solvent A described in step (1) is preferably one or both of tetrahydrofuran and ether.
The volumetric usage of organic solvent A is preferably equivalent to hexamethyl cyclotrisiloxane in solution E described in step (1)
2~4 times of (mL of monomer mass：g).
N-BuLi described in step (1) is preferably to be first dissolved in n-hexane, is then added in reaction system；Positive fourth
The consumption of base lithium is suitable with the mole of final product.
D in first time polymerisation described in step (1)3Consumption be preferably by n-BuLi mole：D3Rub
You measure=1：4.5~9 proportionings.
D in second of polymerisation described in step (1)3And D3 VConsumption be preferably press and n-BuLi mol ratio：
D3Mole：D3 VMole=1:18~22.5：18~22.5 proportionings.
The volumetric usage of organic solvent A is preferably equivalent to hexamethyl cyclotrisiloxane in solution F described in step (1)
Gross mass (the mL of monomer, 1,3,5- trivinyl -1,3,5- trimethyl cyclotrisiloxane monomers：g).
The step of purifying described in step (1) is preferably：Solvent is removed and unpolymerized small point by vacuum distillation
Sub- raw material, is then filtered to remove side product chlorinated lithium powder, obtains PDMS-b-PVMS after purification.
The proportioning of PDMS-b-PVMS, N-acetylcystein and dimethoxybenzoin described in step (2) is preferably
According to the mole of PDMS-b-PVMS medium vinyls：The mole of N-acetylcystein：The mole of dimethoxybenzoin=
1:(1.2~1.5):0.3 proportioning.
Ultraviolet light described in step (2) is preferably the ultraviolet light that wavelength is 350-365nm；More preferably 360nm purple
Outer light.
The condition of Radical Addition described in step (2) preferably reacts 30~60min at room temperature.Described room
Temperature is 15~30 DEG C；More preferably 25 DEG C.
Organic solvent B described in step (2) is preferably one in tetrahydrofuran, ether, chloroform and dichloromethane
Kind or at least two.
Organic solvent C described in step (2) is preferably one kind or at least two in methanol, ethanol and isopropanol.
The quality consumption of organic solvent B described in step (2) is preferably 5 of the gross mass equivalent to PDMS-b-PVMS
~6 times.
The quality consumption of organic solvent C described in step (2) is preferably the quality consumption equivalent to organic solvent B.
The step of purifying described in step (2), is preferably as follows：Solvent is removed by vacuum distillation, by gained thick liquid
Dissolved with chloroform, with water washing is distilled three to five times, then vacuum distillation removes chloroform, obtains after purification
PDMS-b-(PDMS-g-Acys)。
PDMS-b- (PDMS-g-Acys) and hydrochloric acid proportioning described in step (3) are preferably according to PDMS-b- (PDMS-
G-Acys the mole of acetyl group in)：Mole=1 of hydrogen chloride in hydrochloric acid：4 proportionings.
The condition for being heated at reflux reaction described in step (3) is preferably in 75~90 DEG C of stirring reaction 5h；More preferably
In 90 DEG C of stirring reaction 5h.
Organic solvent D described in step (3) is preferably one kind or at least two in methanol, ethanol and isopropanol.
The quality consumption of organic solvent D described in step (3) is preferably equivalent to 2.4~2.5 times of hydrochloric acid quality.
The step of purifying described in step (3), is preferably as follows：Vacuum distillation removes solvent and hydrogen chloride, thick by what is obtained
Product is dissolved in the water, and dialysis removes small molecular weight impurity in distilled water, obtains PDMS-b- (PDMS-g-Cys) after purification.
The condition of dialysis described in step (3) is preferably in distilled water using the bag filter that molecular cut off is 2000Da
Middle dialysis 3 days.
Pass through D in rate-determining steps (1)3、D3 VRate of charge, the polymerization reaction time of monomer, can prepare PDMS blocks
Adjustable with PVMS block lengths, the PVMS block medium vinyl adjustable PDMS-b-PVMS of chain link ratio are then obtained by subsequent reactions
To different block lengths than the PDMS-b- (PDMS-g-Cys) from different cysteine graft ratios.
A kind of polysiloxane block copolymers for being grafted cysteine, are obtained by above-mentioned preparation method.
The polysiloxane block copolymers of described grafting cysteine are preferably the Guang ammonia of grafting half with following feature
The polysiloxane block copolymers of acid：Block length ratio is PDMS：PDMS-g-Cys=2~4：8, PDMS block length 1~
The long 4kDa of 2kDa, PDMS-g-Cys block.
The polysiloxane block copolymers of described grafting cysteine prepare the anti-egg of solid material surface in aqueous
Application in white adsorption layer.
Described application comprises the following steps：The polysiloxane block that solid material is placed in into above-mentioned grafting cysteine is total to
Soaked in the polymers aqueous solution, you can obtaining surface has the solid material of anti-protein adsorption layer.
Described solid material includes metal material, high polymer material.
The time of described immersion is preferably 30min.
The present invention has the following advantages and effect relative to prior art：
The polysiloxane block copolymers for the grafting cysteine that the present invention is provided are containing zwitterionic amphipathic embedding
Section copolymer, due to introducing hydrophobicity interactive construction in amphoteric ion polymer, is conducive to amphoteric ion polymer water-soluble
Adsorb to form stable amphion adsorption layer to solid-liquid interface in liquid, play anti-protein adsorption effect.
Brief description of the drawings
Fig. 1 is the chemical reaction route map of embodiment 1.
Fig. 2 is PDMS-b-PVMS GPC elution curve figures；Wherein, figure (A) is PDMS-b-PVMS- prepared by embodiment 1
1, figure (B) is PDMS-b-PVMS-2 prepared by embodiment 2, and figure (C) is PDMS-b-PVMS-3 prepared by embodiment 3.
Fig. 3 is PDMS-b-PVMS hydrogen nuclear magnetic resonance spectrogram；Wherein, figure (A) is PDMS-b- prepared by embodiment 1
PVMS-1, figure (B) is PDMS-b-PVMS-2 prepared by embodiment 2, and figure (C) is PDMS-b-PVMS-3 prepared by embodiment 3.
Fig. 4 is the PDMS-b- (PDMS-g-Cys) -1 of embodiment 1 IR Characterization spectrogram.
Fig. 5 shows for the chemical shift of the PDMS-b- (PDMS-g-Cys) of embodiment 1 proton nmr spectra and corresponding proton
It is intended to.
Fig. 6 is the bovine serum albumin adsorbance inspection after the different PDMS-b- (PDMS-g-Cys) in gold plaque adsorption
Survey result figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Reagent used in the present invention is commercially available.
Embodiment 1
The preparation of dimethyl silicone polymer-polysiloxane-grafted cysteine block copolymer：Block length ratio is
PDMS：PDMS-g-Cys=1：The long 1kDa of 4, PDMS blocks, the long 4kDa of PDMS-g-Cys blocks.In PDMS-g-Cys blocks, its
It is 1/2 to be grafted total chain number ratio (graft ratio) shared by the chain link of cysteine residues.Preparation process is as shown in figure 1, specific step
It is rapid as follows：
(1) in the reaction bulb equipped with magnetic stir bar, 2.5g D are added3, then sealed with silica gel plug, will take out true in bottle
High pure nitrogen is passed through after sky, repeats three times to ensure to be full of nitrogen in bottle.10mL dry tetrahydrofurans are injected with syringe
Dissolve D3Obtain after settled solution, inject the hexane solution 1.0mL of the n-BuLi containing 2.5mol/L at room temperature, trigger it is cloudy from
Sub- ring-opening polymerisation.It is kept stirring at 0~5 DEG C after about 12h, takes a small amount of reaction solution to terminate active chain end with methanol, is surveyed for GPC
The first block (PDMS) molecular weight is tried, its result is as shown in the dotted line in Fig. 2 (A).After sampling, D containing 5.3g is injected3 VWith 4.7g
D3Dry tetrahydrofuran solution 20mL, at 0~5 DEG C continue react about 12h formation contain vinyl methyl siloxane chain link
The second block PVMS.Take 0.4mL trim,ethylchlorosilanes to be injected into reaction bulb, continue stir about 30min and gathered with complete terminate
Close.Reaction solution rotary evaporation is removed after solvent and small molecule monomer, there are a large amount of lithium chloride byproduct powder to separate out, is filtrated to get
The thick liquid product PDMS-b-PVMS-1 of water white transparency；
The molecular weight of two blocks can be obtained by GPC (gel permeation chromatography) tests in PDMS-b-PVMS-1, GPC tests
Condition is：Using chloroform as mobile phase, setting flow velocity is 1.0mL/min, and it is 35 DEG C, chromatogram post separation to set Composition distribution temperature
Temperature is 40 DEG C.So that narrow rnonodisperse polystyrene is as standard sample bioassay standard curve and calculates molecular weight analyte and molecular weight point
Cloth.Shown in its result such as Fig. 2 (A), wherein dotted line is the first block (PDMS) elution curve, and solid line is diblock strand
PDMS-b-PVMS-1 elution curve.The cysteine residues graft ratio of final product is containing vinyl in PVMS blocks
Chain link accounts for the ratio of total chain number, the integral area calculating of relevant peaks can be obtained in proton nmr spectra, its result such as Fig. 3
(A) shown in.Proton nmr spectra test condition is：With deuterochloroform sample dissolution, tested at 25 DEG C.
(2) in the suprasil flask equipped with magnetic stir bar, 1.0g PDMS-b-PVMS-1,1.05g N- second are added
Acyl cysteine, 0.38g dimethoxybenzoins；Add 5.0g tetrahydrofurans and 5.0g methanol fully dissolves above-mentioned raw materials formation nothing
Color clear solution.Under the ultraviolet light of 360nm wavelength, it is kept stirring for reacting 30min.Terminate after reaction, decompression steams molten
Agent, obtains thick liquid crude product, is dissolved in chloroform, to distill water washing three times.Last vacuum distillation removes three
Chloromethanes, obtains sticky product liquid PDMS-b- (PDMS-g-Acys) -1；
(3) in the glass flask equipped with magnetic stir bar, 1.0g PDMS-b- (PDMS-g-Acys) -1 are added, are used
2.63g ethanol dissolves, and adds the hydrochloric acid that 1.05g mass concentrations are 36%, flow back 5h at 90 DEG C.Terminate after reaction, decompression is steamed
Go out ethanol, water and hydrogen chloride, crude product is dissolved in the water, the bag filter using molecular cut off as 2000Da is saturating in distilled water
Analysis 3 days.Finally take liquid pressure-reducing distilled in bag filter to remove moisture, obtain final product PDMS-b- (PDMS-g-Cys) -1.
The IR Characterization result of final product is as shown in Figure 4：Wherein, 3415cm-1It is-NH3 +Stretching vibration absworption peak,
1733cm-1It is-COO-Stretching vibration absworption peak, 1000-1100cm-1It is the characteristic absorption peak of Si-O-Si linear polysiloxanes,
Show the isostructural presence of siloxane chain in product, cysteine.
The nuclear-magnetism characterization result of final product is as shown in Figure 5：Product heavy water dissolves, and carries out proton nmr spectra test,
As a result and corresponding chemical displacement schematic diagram as shown in the figure.
Embodiment 2
The preparation of dimethyl silicone polymer-polysiloxane-grafted cysteine block copolymer：Block length ratio is
PDMS：PDMS-g-Cys=3：The long 1.5kDa of 8, PDMS blocks, the long 4kDa of PDMS-g-Cys blocks.In PDMS-g-Cys blocks,
It is 1/2 that it, which is grafted total chain number ratio (graft ratio) shared by the chain link of cysteine residues,.
(1) in the reaction bulb equipped with magnetic stir bar, 3.75g D are added3, then sealed, will be taken out in bottle with silica gel plug
High pure nitrogen is passed through after vacuum, repeats three times to ensure to be full of nitrogen in bottle.Tetrahydrochysene furan is dried with syringe injection 10mL
Mutter dissolving D3Obtain after settled solution, the hexane solution 1.0mL of the n-BuLi containing 2.5mol/L is injected at room temperature, trigger
Anionic ring-opening polymerization.It is kept stirring at 0~5 DEG C after about 12h, takes a small amount of reaction solution to terminate active chain end with methanol, be used for
GPC tests the first block (PDMS) molecular weight, and its result is as shown in Fig. 2 (B) dotted line.After sampling, D containing 5.3g is injected3 VWith
4.7g D3Dry tetrahydrofuran solution 20mL, at 0~5 DEG C continue react about 12h formation contains vinyl methyl siloxane
Second block PVMS of chain link.Take 0.4mL trim,ethylchlorosilanes to be injected into reaction bulb, continue stir about 30min with completely eventually
Only it polymerize.Reaction solution rotary evaporation is removed after solvent and small molecule monomer, there are a large amount of lithium chloride byproduct powder to separate out, filtering
Obtain the thick liquid product PDMS-b-PVMS-2 of water white transparency；
The molecular weight of two blocks can be obtained by GPC tests in PDMS-b-PVMS-2, GPC test conditions and embodiment 1 one
Cause.Shown in its result such as Fig. 2 (B), wherein dotted line is the first block (PDMS) elution curve, and solid line is diblock strand
PDMS-b-PVMS-2 elution curve.The cysteine residues graft ratio of final product is containing vinyl in PVMS blocks
Chain link accounts for the ratio of total chain number, the integral area calculating of relevant peaks can be obtained in proton nmr spectra, proton nmr spectra
Test condition is consistent with embodiment 1, shown in its result such as Fig. 3 (B).
(2) in the suprasil flask equipped with magnetic stir bar, 1.1g PDMS-b-PVMS-2,1.05g N- second are added
Acyl cysteine, 0.38g dimethoxybenzoins；Add 6.0g tetrahydrofurans and 6.0g methanol fully dissolves above-mentioned raw materials formation nothing
Color clear solution.Under the ultraviolet light of 360nm wavelength, it is kept stirring for reacting 30min.Terminate after reaction, decompression steams molten
Agent, obtains thick liquid crude product, is dissolved in chloroform, to distill water washing three times.Last vacuum distillation removes three
Chloromethanes, obtains sticky product liquid PDMS-b- (PDMS-g-Acys) -2；
(3) in the glass flask equipped with magnetic stir bar, 1.0g PDMS-b- (PDMS-g-Acys) -2 are added, are used
2.53g ethanol dissolves, and adds the hydrochloric acid that 1.02g mass concentrations are 36%, flow back 5h at 90 DEG C.Terminate after reaction, decompression is steamed
Go out ethanol, water and hydrogen chloride, crude product is dissolved in the water, the bag filter using molecular cut off as 2000Da is saturating in distilled water
Analysis 3 days.Finally take liquid pressure-reducing distilled in bag filter to remove moisture, obtain final product PDMS-b- (PDMS-g-Cys) -2.
Embodiment 3
The preparation of dimethyl silicone polymer-polysiloxane-grafted cysteine block copolymer：Block length ratio is
PDMS：PDMS-g-Cys=1：The long 2kDa of 2, PDMS blocks, the long 4kDa of PDMS-g-Cys blocks.In PDMS-g-Cys blocks, its
It is 1/2 to be grafted total chain number ratio (graft ratio) shared by the chain link of cysteine residues.
(1) in the reaction bulb equipped with magnetic stir bar, 5.0g D are added3, then sealed with silica gel plug, will take out true in bottle
High pure nitrogen is passed through after sky, repeats three times to ensure to be full of nitrogen in bottle.10mL dry tetrahydrofurans are injected with syringe
Dissolve D3Obtain after settled solution, the hexane solution 1.0mL of the n-BuLi containing 2.5mol/L is injected at room temperature, trigger cloudy
Cationic ring opening polymerization.It is kept stirring at 0~5 DEG C after about 12h, takes a small amount of reaction solution to terminate active chain end with methanol, for GPC
The first block (PDMS) molecular weight is tested, its result is as shown in Fig. 2 (C) dotted line.After sampling, D containing 5.3g is injected3 VWith 4.7g
D3Dry tetrahydrofuran solution 20mL, at 0~5 DEG C continue react about 12h formation contain vinyl methyl siloxane chain link
The second block PVMS.Take 0.4mL trim,ethylchlorosilanes to be injected into reaction bulb, continue stir about 30min and gathered with complete terminate
Close.Reaction solution rotary evaporation is removed after solvent and small molecule monomer, there are a large amount of lithium chloride byproduct powder to separate out, is filtrated to get
The thick liquid product PDMS-b-PVMS-3 of water white transparency；
The molecular weight of two blocks can be obtained by GPC tests in PDMS-b-PVMS-3, GPC test conditions and embodiment 1 one
Cause.Shown in its result such as Fig. 2 (C), wherein dotted line is the first block (PDMS) elution curve, and solid line is diblock strand
PDMS-b-PVMS-3 elution curve.The cysteine residues graft ratio of final product is containing vinyl in PVMS blocks
Chain link accounts for the ratio of total chain number, the integral area calculating of relevant peaks can be obtained in proton nmr spectra, proton nmr spectra
Test condition is consistent with embodiment 1, shown in its result such as Fig. 3 (C).
(2) in the suprasil flask equipped with magnetic stir bar, 1.2g PDMS-b-PVMS-3,1.05g N- second are added
Acyl cysteine, 0.38g dimethoxybenzoins；Add 6.0g tetrahydrofurans and 6.0g methanol fully dissolves above-mentioned raw materials formation nothing
Color clear solution.Under the ultraviolet light of 360nm wavelength, it is kept stirring for reacting 30min.Terminate after reaction, decompression steams molten
Agent, obtains thick liquid crude product, is dissolved in chloroform, to distill water washing three times.Last vacuum distillation removes three
Chloromethanes, obtains sticky product liquid PDMS-b- (PDMS-g-Acys) -3；
(3) in the glass flask equipped with magnetic stir bar, 1.0g PDMS-b- (PDMS-g-Acys) -3 are added, are used
2.43g ethanol dissolves, and adds the hydrochloric acid that 1.00g mass concentrations are 36%, flow back 5h at 90 DEG C.Terminate after reaction, decompression is steamed
Go out ethanol, water and hydrogen chloride, crude product is dissolved in the water, the bag filter using molecular cut off as 2000Da is saturating in distilled water
Analysis 3 days.Finally take liquid pressure-reducing distilled in bag filter to remove moisture, obtain final product PDMS-b- (PDMS-g-Cys) -3.
Application Example
Anti- protein adsorption performance monitoring：Setting protein model is bovine serum albumin；Control group is blank gold plaque；Experimental group
Gold plaque in the preparation-obtained PDMS-b- of the 1-3 of embodiment containing 3.0mg/mL respectively (PDMS-g-Cys) -1, PDMS-b-
(PDMS-g-Cys) -2, in PDMS-b- (PDMS-g-Cys) -3 pure water solution immersion 30min to form correspondence block on surface
The adsorption layer of copolymer, then rinses surface with pure water, PBS successively；Control group is identical with the gold plaque size of experimental group.
After blank gold plaque and experimental group gold plaque are weighed respectively, then the concentration of same volume is separately immersed in for the ox blood containing 1.0mg/mL
30min in albumin/PBS solution, makes protein adsorption.Surface is rinsed with PBS after absorption.It is micro- with quartz crystal
Balance is measured to detect the protein adsorption quantity on gold plaque surface.As a result it is as shown in Figure 5.It can be seen that the poly- diformazan that embodiment 1~3 is prepared
Radical siloxane-polysiloxane-grafted cysteine block copolymer can be adsorbed onto solid material surface in aqueous, be formed
Stable adsorption layer, and significantly reduce protein adsorption quantity.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
The change made under limitation, other any Spirit Essences and principle without departing from the present invention, modification,
Substitute, combine, simplify, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method for the polysiloxane block copolymers for being grafted cysteine, it is characterised in that comprise the following steps：
(1) PDMS-b-PVMS synthesis：Hexamethyl cyclotrisiloxane is added in organic solvent A, in inert gas atmosphere,
First time polymerisation is triggered with n-BuLi, solution E is obtained；By hexamethyl cyclotrisiloxane and 1,3,5- trivinyl -1,
3,5- trimethyl cyclotrisiloxane are dissolved in organic solvent A, obtain solution F, and solution F and solution E are mixed, and are carried out second
Polymerisation；It is eventually adding trim,ethylchlorosilane and terminates polymerisation；The product purification obtained to reaction, obtains clear oil liquid
Body product, is PDMS-b-PVMS；
(2) PDMS-b- (PDMS-g-Acys) synthesis：By organic solvent B, organic solvent C, PDMS-b-PVMS, N- acetyl half
Cystine and dimethoxybenzoin mixing, the solution clarified, with ultraviolet light-initiated Radical Addition, are obtained to reaction
Product purification, obtain PDMS-b- (PDMS-g-Acys)；
(3) PDMS-b- (PDMS-g-Cys) synthesis：PDMS-b- (PDMS-g-Acys) and hydrochloric acid are added in organic solvent D,
It is heated at reflux reaction；The product purification obtained to reaction, obtains PDMS-b- (PDMS-g-Cys).
2. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：
The consumption of hexamethyl cyclotrisiloxane is mole by n-BuLi in first time polymerisation described in step (1)
Amount：Mole=1 of hexamethyl cyclotrisiloxane：4.5~9 proportionings；
Hexamethyl cyclotrisiloxane and 1,3,5- trivinyls -1,3,5- three in second of polymerisation described in step (1)
The consumption of methyl cyclotrisiloxane be by with n-BuLi mol ratio：The mole of hexamethyl cyclotrisiloxane：The second of 1,3,5- tri-
Mole=1 of alkenyl -1,3,5- trimethyl cyclotrisiloxane:18~22.5：18~22.5 proportionings；
PDMS-b-PVMS, N-acetylcystein and dimethoxybenzoin described in step (2) is according to PDMS-b-PVMS
The mole of medium vinyl：The mole of N-acetylcystein：Mole=1 of dimethoxybenzoin:(1.2-1.5):0.3
Proportioning；
PDMS-b- (PDMS-g-Acys) described in step (3) presses acetyl group in PDMS-b- (PDMS-g-Acys) with hydrochloric acid
Mole：Mole=1 of hydrogen chloride in hydrochloric acid：4 proportionings.
3. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：
The condition of first time polymerisation described in step (1) is 0~5 DEG C of polymerization 12h；
The condition of second of polymerisation described in step (1) is 0~5 DEG C of polymerization 12h；
The condition of Radical Addition described in step (2) is to react 30~60min in 15~30 DEG C；
The condition for being heated at reflux reaction described in step (3) is in 75~90 DEG C of stirring reaction 5h.
4. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：Ultraviolet light described in step (2) is ultraviolet light that wavelength is 350-365nm.
5. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：
Organic solvent A described in step (1) is one or both of tetrahydrofuran and ether；
Organic solvent B described in step (2) is one kind in tetrahydrofuran, ether, chloroform and dichloromethane or at least
Two kinds；
Organic solvent C described in step (2) is one kind or at least two in methanol, ethanol and isopropanol；
Organic solvent D described in step (3) is one kind or at least two in methanol, ethanol and isopropanol.
6. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：
The volumetric usage of organic solvent A is equivalent to hexamethyl cyclotrisiloxane monomer mass in solution E described in step (1)
2~4 times；
In solution F described in step (1) volumetric usage of organic solvent A be equivalent to hexamethyl cyclotrisiloxane monomer and 1,
The gross mass of 3,5- trivinyl -1,3,5- trimethyl cyclotrisiloxane monomers；
5~6 times of gross mass of the quality consumption equivalent to PDMS-b-PVMS of organic solvent B described in step (2)；
The quality consumption of organic solvent C described in step (2) is identical with the quality consumption of organic solvent B；
2.4~2.5 times of the quality consumption of organic solvent D described in step (3) equivalent to hydrochloric acid quality.
7. the preparation method of the polysiloxane block copolymers of grafting cysteine according to claim 1, its feature exists
In：
The step of purifying described in step (1) is：Solvent and unpolymerized small-molecule starting material are removed by vacuum distillation, so
After be filtered to remove side product chlorinated lithium powder, obtain PDMS-b-PVMS after purification；
The step of purifying described in step (2), is preferably as follows：Solvent is removed by vacuum distillation, gained thick liquid is used three
Chloromethanes dissolves, with water washing is distilled three to five times, and then vacuum distillation removes chloroform, obtains PDMS-b- after purification
(PDMS-g-Acys)；
The step of purifying described in step (3), is preferably as follows：Vacuum distillation removes solvent and hydrogen chloride, by obtained crude product
It is dissolved in the water, dialysis removes small molecular weight impurity in distilled water, obtains PDMS-b- (PDMS-g-Cys) after purification.
8. a kind of polysiloxane block copolymers for being grafted cysteine, it is characterised in that：Pass through any one of claim 1~7
Described preparation method is obtained.
9. the polysiloxane block copolymers of the grafting cysteine described in claim 8 prepare solid material table in aqueous
Application in the anti-protein adsorption layer in face.
10. application according to claim 9, it is characterised in that comprise the following steps：Solid material is placed in claim 8
Soaked in the polysiloxane block copolymers aqueous solution of described grafting cysteine, obtaining surface has anti-protein adsorption layer
Solid material.
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| CN112592478A (en) * | 2020-11-24 | 2021-04-02 | 华南农业大学 | Non-permeable random copolymer containing polysiloxane, preparation method and application thereof |
| CN113577313A (en) * | 2021-07-19 | 2021-11-02 | 西北工业大学 | Targeted recognition type hyperbranched polysiloxane fluorescent material, and preparation method and use method thereof |
| CN117468239A (en) * | 2023-10-26 | 2024-01-30 | 清远市宏图助剂有限公司 | Amino acid modified polysiloxane fabric color fixing agent, preparation method and application thereof |
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| CN101948570A (en) * | 2010-08-19 | 2011-01-19 | 邬元娟 | Method for preparing organic silicon-modified collagen material |
| CN104031267A (en) * | 2014-04-25 | 2014-09-10 | 西北工业大学 | Preparation method of polysiloxane with specific content of vinyl groups |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112592478A (en) * | 2020-11-24 | 2021-04-02 | 华南农业大学 | Non-permeable random copolymer containing polysiloxane, preparation method and application thereof |
| CN112592478B (en) * | 2020-11-24 | 2022-03-25 | 华南农业大学 | Non-permeable random copolymer containing polysiloxane, preparation method and application thereof |
| CN113577313A (en) * | 2021-07-19 | 2021-11-02 | 西北工业大学 | Targeted recognition type hyperbranched polysiloxane fluorescent material, and preparation method and use method thereof |
| CN113577313B (en) * | 2021-07-19 | 2023-05-23 | 西北工业大学 | Targeting recognition type hyperbranched polysiloxane fluorescent material, preparation method and use method |
| CN117468239A (en) * | 2023-10-26 | 2024-01-30 | 清远市宏图助剂有限公司 | Amino acid modified polysiloxane fabric color fixing agent, preparation method and application thereof |
| CN117468239B (en) * | 2023-10-26 | 2024-04-16 | 清远市宏图助剂有限公司 | Amino acid modified polysiloxane fabric color fixing agent, preparation method and application thereof |
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