CN109180943A - A kind of preparation method of polyhydroxy function POSS hybrid material - Google Patents
A kind of preparation method of polyhydroxy function POSS hybrid material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of polyhydroxy function POSS hybrid material, which is characterized in that following reactant is added in the reactor: the polyethyleneglycol derivative PEG (C=CH containing one end unsaturation carbon-carbon double bond2), alkenes organism (RHC=CH2), eight sulfydryl POSS and solvent radical initiator is added after reactant dissolution to be added is uniformly dispersed；Under nitrogen protection, 40min~4h is reacted under 30~80 DEG C or ultraviolet light conditions, obtains POSS hybrid material；It is removed remaining radical initiator and unreacted reactant, up to polyhydroxy function POSS hybrid material after drying.Operation of the present invention is simple, reaction material is easy to get, and is swift in response, reaction condition is mild；Polyhydroxy function POSS hybrid material prepared by the present invention has many advantages, such as good biocompatibility, controllable hydrophilicity and hydrophobicity, controllable condensed state form and polyfunctional reactant group.
Description
Technical field
The present invention relates to a kind of preparation methods of polyhydroxy function POSS hybrid material, and in particular to a kind of to contain more sulfydryls
Polyhedral oligomeric silsesquioxane (POSS-SH), olefinic organic, water-soluble PEG of the one end with unsaturated double-bond of functional group are derivative
Object, radical initiator and stirring solvent it is uniform after, click the preparation of polymerization reaction one-step method using sulfydryl-alkene and have specific polyhydroxy
The preparation method of the multi-functional POSS hybrid material of base sulfydryl, belongs to polymer synthesis method technical field.
Background technique
Hybrid inorganic-organic materials combine the advantages of organic and inorganic materials integral material on the whole, and certain
The shortcomings that the two is overcome in degree, therefore be concerned in recent years.Have many advantages, such as easily to shape and easily modify, institute in view of silicon skeleton
With focusing on the hybrid material for being mainly based upon silicon substrate.But based on the current method for preparing multi-functional silicon-based hybrid material
Process is comparatively laborious, and biocompatibility is also poor, therefore there is also very big deficiencies in preparation problem.
More special a kind of polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric in polysiloxanes
Silsesqu-ioxane is abbreviated as POSS), general molecular formula is (RSiO1.5) n, and n is generally 6,8,10,12 etc., can be in ladder
Shape, dendriform or cage type, wherein with the cage structure most typically of n=8.The three-dimensional dimension of POSS is generally 1-3nm, the surface POSS
Inertia group and partial polymer and monomer have good compatibility, it is mono- by copolymerization, grafting or mixed method, POSS
Body can be very easily in conjunction with polymer.After being added to polymer, novel organic and inorganic function hydridization material can get
Material.The reinforced phase for functioning as nanoscale of POSS molecule has extremely strong thermal deformation resistant ability；It is introduced on the surface POSS
One or more different functional groups can assign POSS nanoparticle functionality and high response, can be with other polymer
Various structure such as star, beading shape or network is formed, the good heat resistance of polymer material, chemical-resistant, insulating properties are assigned
And gas permeability etc., it is wide in fields such as liquid crystal material, dielectric material, luminescent material, heat-resisting and fire-retardant composite, bio-medical materials
General application.Currently, the quantity of the patent and publication in relation to POSS increases year by year, show a sharp upward trend, but research contents
It is confined to mechanical property and hot property of material etc. mostly, it is less to the research of material function.
In recent years, after click chemistry was proposed from 2001 by Sharpless, due to it is widely used, efficiently, reliably, it is high
The feature of selectivity rapidly becomes the new method of biological medicine and synthesis of polymer material.As what click chemistry was studied gos deep into,
Its reaction type is being increasing, and application range is also constantly expanding.Sulfydryl-alkene reaction that free radical or nucleopilic reagent cause is made
There are all features of click chemistry for a kind of novel click-reaction.Up to now, click chemistry application maturation the most is
Azide and end alkynes generate 1,2,3-triazoles compound, i.e. CuAAC under Cu (I) catalysis, however CuAAC reaction is due to making
Use Cu (I) as catalyst, so that heavy metal Cu can be remained in product；In addition it has been reported that depositing due to catalyst Cu (I)
In the degradation induction of virus or oligonucleotides, this will largely limit the reaction in biomaterial and pharmaceutical carrier
Etc. research.In the case, educational circles is attracted by the sulfydryl-alkene this kind click-reaction for not having to metal catalytic, sulfydryl-
Alkene becomes everybody focus of attention, by free radical reaction it is rapid, simple, it is controllable and insensitive to oxygen the advantages that,
Become a kind of efficient tool in curing reaction and polymer modification.
Chinese patent " CN201410856419.7 " discloses a kind of mercaptan-alkene clicking chemistry method preparation poly- methyl of POSS/
The method of dimethylaminoethyl acrylate organic/inorganic hybridization material, obtained POSS/PDMAEMA hybrid material
Material has many advantages, such as the chemical bond and uniform particle diameter that size is small, stable, effectively improves POSS's with the click-reaction of PDMAEMA
Hydrophilicity, and POSS/PDMAEMA organic/inorganic hybridization material has good temperature sensitivity and pH quick in aqueous solution
Perception.Chinese patent " CN201510178683.4 " design has the organic/inorganic hybridization material POSS- of temperature and pH-sensitivity
The preparation method of PDMAEMA, by mercaptan-alkene clicking chemistry method by polymethylacrylic acid dimethylamine ethyl ester and octavinyl-POSS
Reaction generates a kind of organic/inorganic hybridization material POSS-PDMAEMA.POSS-PDMAEMA in aqueous solution can with temperature and
The variation of pH and self assembly occurs and forms micella.The patent is the organic/inorganic hybridization material for being prepared for simple function.
Summary of the invention
It is to be solved by this invention to be: a kind of preparation method with polyhydroxy POSS hybrid material is provided.
To solve the above-mentioned problems, the present invention provides following technical schemes: a kind of polyhydroxy function POSS hybrid material
Preparation method, which comprises the following steps:
Step 1): following reactant is added in the reactor first: the polyethylene glycol containing one end unsaturation carbon-carbon double bond
Derivative PEG (C=CH2), alkenes organism (RHC=CH2), eight sulfydryl POSS and solvent, reactant to be added dissolves dispersion
After uniformly, radical initiator is added；Polyethyleneglycol derivative PEG (C=CH2), alkenes organism (RHC=CH2), eight sulfydryls
The molar ratio of POSS is 2~6: 6~2: 1；
Step 2): the solution that step 1) is obtained under nitrogen protection, reacts 40min under 30~80 DEG C or ultraviolet light conditions
~4h obtains POSS hybrid material；
Step 3): the POSS hybrid material that step 2) is obtained removes remaining radical initiator and unreacted reaction
Object, up to polyhydroxy function POSS hybrid material after drying.
Preferably, the radical initiator in the step 1) is using azo-initiator, peroxidating class initiator, oxidation
Restore class initiator or free radical photo-initiation.
Preferably, the polyethyleneglycol derivative PEG (C=CH in the step 1) containing one end unsaturation carbon-carbon double bond2)
Synthetic method are as follows: first polyethyleneglycol derivative is reacted under the conditions of 0~5 DEG C with acryloyl chloride to get to one end with not
It is saturated the polyethyleneglycol derivative of carbon-carbon double bond.
It is highly preferred that the number-average molecular weight for the polyethylene glycol raw material that the polyethyleneglycol derivative uses for 400~
20000。
It is highly preferred that the molar ratio of the polyethyleneglycol derivative and acryloyl chloride is 1: 1.
Preferably, alkenes organism (RHC=CH in the step 1)2) in R be inertia alkane, aromatic hydrocarbons or heterocycle
Group, or be activity functional groups.
Preferably, the method that remaining radical initiator and unreacted reactant are removed in the step 3) is through saturating
Analyse bag dialysis 2-30h.
The present invention is that the quantity of system preparation control styrene monomer and PEG derivative is clicked by sulfydryl-alkene, by
It generates free radicals, is prepared with polyhydroxy and functional POSS hybrid material under radical initiator.It is prepared by the present invention
Polyhydroxy function POSS hybrid material overcomes the disadvantages of tradition prepares poor biocompatibility by transition metal click chemistry,
Have the characteristics that it is simple and convenient, prepare that yield is high, no pollution to the environment.
Sulfydryl-alkene clicks system and not only has the advantages of click chemistry, but also also overcomes conventional point and hit chemical method
(CuAAC) it is prepared for polyhydroxy function POSS hybrid material, i.e., it is catalytic media that initiator, which causes radical reaction, will sufficiently be drawn
The characteristics of the advantages of sending out agent elicitation procedure and traditional click-reaction, combines.Therefore, using made from sulfydryl-alkene click system
Polyhydroxy function POSS hybrid material not only has efficient controllability, but also it is raw to can be avoided excessive metalcatalyzing bring
Object toxicity.And the polyhydroxy function POSS hybrid material as made from sulfydryl-alkene click system has preferable controllable parent
Hydrophobicity and biocompatibility are conducive to hybrid material in life, environment and medical science functional material and novel polyamides
The potential application of amine, polyester, nano molecular hybrid material, multifunctional material, composite material etc..
Compared with the prior art, the present invention has the following beneficial effects:
1. the present invention clicks system preparation using sulfydryl-alkene there is polyhydroxy and functional POSS hybrid material to provide
A kind of feasible method, method is simple and easy, and reaction is efficiently quick, and reaction condition is milder；
2. the present invention utilizes the relationship of free radical efficiency of initiation and temperature and ultraviolet ray intensity, this relationship is carrying out it
Click process prepares polyhydroxy POSS function hybrid material has controllability over time and space, so that reasonable utilization causes
The different condition of agent goes to control the amount of required functional group, this is that traditional handicraft is difficult to realize；
3. sulfydryl prepared by the present invention-alkene, which clicks system preparation, has polyhydroxy and functional POSS hybrid material, fill
Divide the characteristics of combining click-reaction and unsaturated double-bond polymerization reaction.Make full use of sulfydryl and alkene without copper click-reaction system,
It is avoided that transition metal-catalyzed bring bio-toxicity, is polyhydroxy and functional POSS hybrid material in biological medicine, imitative
The application of green material and field of medicine release provides may；
4. sulfydryl prepared by the present invention-alkene, which clicks system preparation, has polyhydroxy and functional POSS hybrid material, tool
There are the excellent properties such as preferable cementability, high refractiveness, biological degradability and hydrolytic resistance, has in terms of functional polymer material
Have broad application prospects；
5. the method synthesis organic/inorganic hybridization material that the present invention is combined using enol-sulfydryl click chemistry, has and produces
The advantages that rate is high, the stereoselectivity of reaction is strong, reaction condition is simple, raw material and reaction reagent are easy to get；
6. prepared by the method POSS base hybrid material have the characteristics that it is amphiphatic, it is (poly- by regulation hydrophilic segment
Ethylene glycol) and hydrophobic chain (styrene) section realize the multifunctionality of hybrid material, while present invention introduces rhodamine derivatives
Preparation, in terms of probe with good application prospect；
7. preparation method of the present invention have it is easy to operate, prepare yield high, no pollution to the environment and application prospect light etc.
Advantage is high performance material product of new generation, can be used for organic novel polyamide, polyester, nano molecular hybrid material, multi-functional
The fields such as material, composite material and environment and biology.
Detailed description of the invention
Fig. 1 is the synthetic route chart of embodiment 1-5；
Fig. 2 is the synthetic route chart of embodiment 6-9；
Fig. 3 is the synthetic route chart of embodiment 10.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
POSS-PEG- styrene ratio is the synthesis of (1: 2: 6): 0.3g (0.3mmol) dry sulfydryl POSS is added to
In the three-necked flask of 100mL, the PEG-400 and 0.188g of the one end (0.6mmol) 0.271g connection acryloyl chloride is added
(1.8mmol) styrene, and 2, the 2- dimethoxy -2- phenyl acetophenone (DMPA) of 0.0060g (0.024mmol) is added, make
For the photoinitiator of system.30mL anhydrous tetrahydro furan is added, quickly stirring makes sufficiently to dissolve.Bottleneck is sealed with rubber stopper, and
Mixed solution 20min is brushed with nitrogen.Under room temperature, it is placed under ultraviolet lamp (15W) and irradiates 1h.By obtained mixed solution into
Row filters remove insoluble matter after, rotary evaporation removes solvent, obtain faint yellow viscous liquid, as with PEG group and
The target product of benzene radicals.Yield: 90.6%.Synthetic route and molecular formula are shown in synthetic route 1.M.P=-7.9 DEG C.FTIR
(KBr): v=3415cm-1(- OH), 2924cm-1(-CH2), 2552cm-1(- SH), 1736cm-1(C=O), 1628,1449cm-1
(-C6H5), 1110cm-1(Si-O-Si)。1HNMR (600MHz, CDCl3, 298K, δ/ppm): δ 7.63 (d, 30H), 4.27 (s,
2H), 3.75-3.45 (m, 70H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H).13CNMR (600MHz, CDCl3,
298K, δ/ppm): δ 172.01,140.67,134.47,128.27,126.35,103.92,72.55,66.34,61.33,
53.57 36.21,32.33,23.44.
Embodiment 2
The present embodiment difference from example 1 is that:
POSS-PEG- styrene ratio is the synthesis of (1: 3: 5): in step 1), one end connection acryloyl chloride is added
The amount of PEG-400 is 0.407g (0.9mmol) and the amount of styrene is 0.158g (1.5mmol), and 2,2- dimethoxy -2- is added
The amount (DMPA) of phenyl acetophenone is 0.0038g (0.024mmol), the photoinitiator as system.It is substantially dissolved in it
In 20mL anhydrous tetrahydrofuran solution.Remaining is just the same with embodiment 1.Yield: 93.9%.Synthetic route and molecular formula are shown in conjunction
At route 1.M.P=-7.1 DEG C.FTIR (KBr): V=3415cm-1(- OH), 2924cm-1(-CH2)2552cm-1(-SH)
1736cm-1(C=O) 1628,1449cm-1(-C6H5)1110cm-1(Si-O-Si)。1HNMR (600MHz, CDCl3, 298K, δ/
Ppm): δ 7.63 (d, 25H), 4.27 (s, 2H), 3.75-3.45 (m, 105H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s,
2H)。13CNMR (600MHz, CDCl3, 298K, δ/ppm): δ 172.01,140.67,134.47,128.27,126.35,
103.92,72.55,66.34,61.33,53.57,36.21,32.33,23.44.
Embodiment 3
The present embodiment difference from example 1 is that:
POSS-PEG- styrene ratio is the synthesis of (1: 4: 4): in step 1), one end connection acryloyl chloride is added
The amount of PEG-400 is 0.542g (1.2mmol) and the amount of styrene is 0.125g (1.2mmol), and 2,2- dimethoxy -2- is added
The amount of phenyl acetophenone is 0.0062g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL anhydrous
In tetrahydrofuran solution.Remaining is just the same with embodiment 1.Yield: 93.5%.Synthetic route and molecular formula are shown in synthetic route 1.
M.P=-6.7 DEG C.FTIR (KBr): v=3415cm-1(- OH), 2924cm-1(-CH2), 2552cm-1(- SH), 1736cm-1(C=
O), 1628,1449cm-1(-C6H5), 1110cm-1(Si-O-Si)。1HNMR (600MHz, CDCl3, 298K, δ/ppm): δ 7.63
(d, 20H), 4.27 (s, 2H), 3.75-3.45 (m, 140H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H).13CNMR
(150MHz, CDCl3, 298K, δ/ppm): δ 172.01,140.67,134.47,128.27,126.35,103.92,72.55,
66.34,61.33,53.57,36.21,32.33,23.44.
Embodiment 4
The present embodiment difference from example 1 is that:
1) POSS-PEG- styrene ratio is the synthesis of (1: 5: 3): in step 1), one end connection acryloyl chloride is added
The amount of PEG-400 is 0.678g (1.5mmol) and the amount of styrene is 0.094g (0.9mmol), and 2,2- dimethoxy -2- is added
The amount of phenyl acetophenone is 0.0062g (0.048mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL anhydrous
In tetrahydrofuran solution.Remaining is just the same with embodiment 1.Yield: 95.7%.Synthetic route and molecular formula are shown in synthetic route 1.
M.P=-6.1 DEG C.FTIR (KBr): v=3415cm-1(-OH)2924cm-1(-CH2), 2552cm-1(- SH), 1736cm-1(C=
O), 1628,1449cm-1(-C6H5), 1110cm-1(Si-O-Si)。1H NMR (600MHz, CDCl3, 298K, δ/ppm): δ 7.63
(d, 15H), 4.27 (s, 2H), 3.75-3.45 (m, 175H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H)13CNMR
(150MHz, CDCl3, 298K, δ/ppm): δ 172.01,140.67,134.47,128.27,126.35,103.92,72.55,
66.34,61.33,53.57,36.21,32.33,23.44.
Embodiment 5
The present embodiment and embodiment 4 the difference is that:
POSS-PEG- styrene ratio is the synthesis of (1: 6: 2): in step 1), one end connection acryloyl chloride is added
The amount of PEG-400 is 0.815g (1.8mmol) and the amount of styrene is 0.063g (0.6mmol), and 2,2- dimethoxy -2- is added
The amount of phenyl acetophenone is 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL anhydrous
In tetrahydrofuran solution.Remaining is just the same with embodiment 4.Yield: 92.9%.Synthetic route and molecular formula are shown in synthetic route 1.
M.P=-4.7 DEG C.FTIR (KBr): v=3415cm-1(-OH)2924cm-1(-CH2), 2552cm-1(- SH), 1736cm-1(C=
O), 1628,1449cm-1(-C6H5), 1110cm-1(Si-O-Si)。1H NMR (600MHz, CDCl3, 298K, δ/ppm): δ 7.63
(d, 10H), 4.27 (s, 2H), 3.75-3.45 (m, 210H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H)13CNMR
(150MHz, CDCl3, 298K, δ/ppm): δ 172.01,140.67,134.47,128.27,126.35,103.92,72.55,
66.34,61.33,53.57,36.21,32.33,23.44.
Embodiment 6
The present embodiment difference from example 1 is that:
POSS-PEG ratio is the synthesis of (1: 1): in step 1), the amount of the PEG-400 of one end connection acryloyl chloride is added
Amount for 0.815g (1.8mmol) and POSS-HS is 1.83g (1.8mmol), and 2,2- dimethoxy -2- phenyl acetophenone is added
Amount be 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL water tetrahydrofuran solution
In.Remaining is just the same with embodiment 5.M.p=-6.2 DEG C.FTIR (KBr, cm-1): v=3349cm-1(OH)；2922,
2861cm-1(-CH2), 2555cm-1(S-H), 1734cm-1(C=O), 1250cm-1(Si-C), 1114.7cm-1and
1033.8cm-1(Si-O-Si), 693cm-1(Si-C)。1H NMR(CDCl3, 600MHz, 298K, δ/ppm): δ 0.69 (d, Si-
CH2), 1.37 (- SH), 1.64 (s ,-CH2), 2.50 (s ,-CH2- S), 3.56 (s, CH2- OH), 4.18 (s, OH).13C NMR
(CDCl3, 150MHz, 298K, δ/ppm): δ 11.38,25.23,27.43,34.98,50.11,61.84,63.81,67.96,
69.06,70.27,70.58,77.64,171.85.
Embodiment 7
The present embodiment difference from example 1 is that:
POSS-PEG ratio is the synthesis of (1: 2): in step 1), the amount of the PEG-400 of one end connection acryloyl chloride is added
Amount for 1.631g (3.6mmol) and POSS-HS is 1.83g (1.8mmol), and 2,2- dimethoxy -2- phenyl acetophenone is added
Amount be 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL water tetrahydrofuran solution
In.Remaining is just the same with embodiment 6.M.p=-6.5 DEG C.FTIR (KBr, cm-1): v=3394cm-1(OH)；2912,
2861cm-1(-CH2), 2555cm-1(S-H), 1734cm-1(C=O), 1249cm-1(Si-C), 1114.7cm-1and
1033.8cm-1(Si-O-Si), 693cm-1(Si-C).1H NMR(CDCl3, 600MHz, ppm): δ 0.69 (d, Si-CH2),
1.37 (- SH), 1.64 (s ,-CH2), 2.50 (s ,-CH2- S), 3.75-3.45 (s, 70H), 2.51 (s, 2H), 1.65 (s, 2H),
0.74 (s, 2H).13C NMR(CDCl3, 150MHz, ppm): δ 11.38,25.23,27.43,34.98,50.11,61.84,
63.81,67.96,69.06,70.27,70.58,77.64,171.85.
Embodiment 8
The present embodiment difference from example 1 is that:
POSS-PEG ratio is the synthesis of (1: 4): in step 1), the amount of the PEG-400 of one end connection acryloyl chloride is added
Amount for 3.262g (7.2mmol) and POSS-HS is 1.83g (1.8mmol), and 2,2- dimethoxy -2- phenyl acetophenone is added
Amount be 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL water tetrahydrofuran solution
In.Remaining is just the same with embodiment 7.M.p=-7.1 DEG C.FTIR (KBr, cm-1): v=3419cm-1(OH)；2912,
2876cm-1(-CH2), 2612cm-1(S-H), 1720cm-1(C=O), 1248cm-1(Si-C), 1110.7cm-1 and
1033.8cm-1(Si-O-Si), 697cm-1(Si-C).1H NMR(CDCl3, 600MHz, ppm): δ 0.69 (d, Si-CH2),
1.37 (- SH), 1.64 (s ,-CH2), 2.50 (s ,-CH2- S), 3.56 (s, CH2- OH), 4.18 (s, OH)1H NMR(CDCl3,
600MHz, ppm): δ 0.69 (d, Si-CH2), 1.37 (- SH), 1.64 (s ,-CH2), 2.50 (s ,-CH2- S), 3.75-3.45
(m, 140H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H).13C NMR(CDCl3, 150MHz, ppm): δ 11.38,
25.23,27.43,34.98,50.11,61.84,63.81,67.96,69.06,70.27,70.58,77.64,171.85.
Embodiment 9
The present embodiment difference from example 1 is that:
POSS-PEG ratio is the synthesis of (1: 8): in step 1), the amount of the PEG-400 of one end connection acryloyl chloride is added
Amount for 6.523g (14.4mmol) and POSS-HS is 1.83g (1.8mmol), and 2,2- dimethoxy -2- phenyl acetophenone is added
Amount be 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL water tetrahydrofuran solution
In.Remaining is just the same with embodiment 8.M.p=-7.9 DEG C.FTIR (KBr, cm-1): v=3429cm-1(OH)；2921,
2861cm-1(-CH2), 1798cm-1(C=O), 1260cm-1(Si-C), 1118.7cm-1and 1033.8cm-1(Si-O-Si),
712cm-1(Si-C).1H NMR(CDCl3, 400MHz, ppm): δ 0.69 (d, Si-CH2), 1.37 (- SH), 1.64 (s ,-
CH2), 2.50 (s ,-CH2- S), 3.56 (s, CH2- OH), 4.18 (s, OH)1H NMR(CDCl3, 600MHz, 298K, δ/ppm):
δ 0.69 (d, Si-CH2), 1.37 (- SH), 1.64 (s ,-CH2), 2.50 (s ,-CH2- S), 3.75-3.45 (m, 280H), 2.51
(s, 2H), 1.65 (s, 2H), 0.74 (s, 2H).13C NMR(CDCl3, 150MHz, 298K, δ/ppm): δ 11.38,25.23,
27.43,34.98,50.11,61.84,63.81,67.96,69.06,70.27,70.58,77.64,171.85.
Embodiment 10
The present embodiment and embodiment 8 the difference is that:
POSS-PEG-Rha ratio is the synthesis of (1: 4: 1): in step 1), the PEG- of one end connection acryloyl chloride is added
The amount that 400 amount is 3.262g (7.2mmol) and POSS-HS is 1.83g (1.8mmol), and 2,2- dimethoxy -2- phenyl is added
The amount of acetophenone is 0.0063g (0.024mmol), the photoinitiator as system.It is set to be substantially dissolved in 20mL water tetrahydro furan
It mutters in solution.Remaining is just the same with embodiment 8.M.P=-4.3 DEG C.FTIR (KBr pellet, cm-1): 3447 (NH),
2937,2970 (CH3, CH2), 2553 (- SH), 1730 (C=O), 1686and 1515 (Ar-H), 1615 (C=C or C=N),
1119 (C-O-C), 1250cm-1(Si-C), 1114.7cm-1and 1033.8cm-1(Si-O-Si), 693cm-1(Si-C)。1H
NMR (600MHz, CDCl3), δ (ppm): 7.98 (d, 1H, ArH), 7.63-7.53 (m, 1H, ArH), 7.53-7.42 (m, 1H,
ArH), 7.12 (d, 1H, ArH), 6.86 (s, 1H, NH), 6.67 (d, 2H, ArH), 6.36 (d, 2H, ArH), 6.29 (s, 2H,
ArH), 3.33 (q, 8H, CH2), 1.15 (t, 12H, CH3), 0.69 (d, Si-CH2-), 1.37 (- SH), 1.64 (s ,-CH2),
2.50 (s ,-CH2- S), 3.75-3.45 (m, 140H), 2.51 (s, 2H), 1.65 (s, 2H), 0.74 (s, 2H).13C NMR
(150MHz, CDCl3), δ (ppm): 11.38,12.84,25.23,27.43,34.98,44.59,50.11,61.84,63.81,
66.11,67.96,69.06,70.27,70.58,77.64,98.21,104.83,123.18,124.04,128.31,130.26,
132.70,149.09,151.78,154.07,166.32,170.15,171.85.
Claims (7)
1. a kind of preparation method of polyhydroxy function POSS hybrid material, which comprises the following steps:
Step 1): following reactant is added in the reactor first: the polyethylene glycol containing one end unsaturation carbon-carbon double bond is derivative
Object PEG (C=CH2), alkenes organism (RHC=CH2), eight sulfydryl POSS and solvent, reactant dissolution to be added is uniformly dispersed
Afterwards, radical initiator is added；Polyethyleneglycol derivative PEG (C=CH2), alkenes organism (RHC=CH2), eight sulfydryl POSS
Molar ratio be 2~6: 6~2: 1；
Step 2): the solution that step 1) is obtained react under nitrogen protection, under 30~80 DEG C or ultraviolet light conditions 40min~
4h obtains POSS hybrid material；
Step 3): the POSS hybrid material that step 2) is obtained removes remaining radical initiator and unreacted reactant,
Up to polyhydroxy function POSS hybrid material after drying.
2. the preparation method of polyhydroxy function POSS hybrid material as claimed in claim 1, which is characterized in that in the step 1)
Radical initiator uses azo-initiator, peroxidating class initiator, redox type initiators or free radical photo-initiation.
3. the preparation method of polyhydroxy function POSS hybrid material as described in claim 1, which is characterized in that the step 1)
In the polyethyleneglycol derivative PEG (C=CH containing one end unsaturation carbon-carbon double bond2) synthetic method are as follows: first by polyethylene glycol
The polyethylene glycol that derivative is reacted with acryloyl chloride under the conditions of 0~5 DEG C to get unsaturated carbon-carbon double bond is had to one end is derivative
Object.
4. the preparation method of polyhydroxy function POSS hybrid material as claimed in claim 3, which is characterized in that the poly- second two
The number-average molecular weight for the polyethylene glycol raw material that 01 derivatives use is 400~20000.
5. the preparation method of polyhydroxy function POSS hybrid material as claimed in claim 3, which is characterized in that the poly- second two
The molar ratio of 01 derivatives and acryloyl chloride is 1: 1.
6. the preparation method of polyhydroxy function POSS hybrid material as described in claim 1, which is characterized in that the step 1)
Middle alkenes organism (RHC=CH2) in R be inertia alkane, aromatic hydrocarbons or heterocyclic group, or be activity functional groups.
7. the preparation method of polyhydroxy function POSS hybrid material as described in claim 1, which is characterized in that the step 3)
The middle remaining radical initiator and the method for unreacted reactant of removing is the 2-30h that dialyses through bag filter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156998A (en) * | 2019-05-28 | 2019-08-23 | 洛阳理工学院 | Cage modle polysilsesquioxane-polyethylene glycol polymer solid electrolyte material and preparation method thereof |
| CN114561019A (en) * | 2022-03-21 | 2022-05-31 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer taking cage-shaped silsesquioxane as core and modified LMHs |
| CN116333317A (en) * | 2023-02-22 | 2023-06-27 | 安徽中烟工业有限责任公司 | POSS-based hydrophobic material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203378A (en) * | 2005-01-27 | 2008-06-18 | 杂混复合塑料公司 | Surface modification with polyhedral oligomeric silsesquioxanes silanols |
| CN101397308A (en) * | 2008-11-04 | 2009-04-01 | 东华大学 | POSS hybrid hole-transporting material and preparation method thereof |
| CN101580711A (en) * | 2009-06-05 | 2009-11-18 | 东华大学 | Star-structure organic inorganic hybridization green light material and preparation and application thereof |
| CN103172870A (en) * | 2011-12-26 | 2013-06-26 | 北京化工大学 | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof |
| CN103755901A (en) * | 2014-01-21 | 2014-04-30 | 上海交通大学 | Preparation method of octasulfydryl polyhedral oligomeric silsesquioxane modified elastomer material |
| KR20170018571A (en) * | 2015-08-10 | 2017-02-20 | (주)움프켐 | POSS/semifluorinated polymer having water and oil repellent and preparation method thereof and method of surface processing using POSS/semifluorinated polymer |
-
2018
- 2018-07-26 CN CN201810840411.XA patent/CN109180943A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203378A (en) * | 2005-01-27 | 2008-06-18 | 杂混复合塑料公司 | Surface modification with polyhedral oligomeric silsesquioxanes silanols |
| CN101397308A (en) * | 2008-11-04 | 2009-04-01 | 东华大学 | POSS hybrid hole-transporting material and preparation method thereof |
| CN101580711A (en) * | 2009-06-05 | 2009-11-18 | 东华大学 | Star-structure organic inorganic hybridization green light material and preparation and application thereof |
| CN103172870A (en) * | 2011-12-26 | 2013-06-26 | 北京化工大学 | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof |
| CN103755901A (en) * | 2014-01-21 | 2014-04-30 | 上海交通大学 | Preparation method of octasulfydryl polyhedral oligomeric silsesquioxane modified elastomer material |
| KR20170018571A (en) * | 2015-08-10 | 2017-02-20 | (주)움프켐 | POSS/semifluorinated polymer having water and oil repellent and preparation method thereof and method of surface processing using POSS/semifluorinated polymer |
Non-Patent Citations (3)
| Title |
|---|
| XU Y. ET AL.: "Versatile Functionalization of the Micropatterned Hydrogel of Hyperbranched Poly(ether amine) Based on "Thiol-yne" Chemistry", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 夏勇: "基于巯—烯点击化学有机硅功能材料的合成及性能研究", 《中国博士学位论文全文数据库-工程科技I辑》 * |
| 张进等: "聚乙二醇的端羟基改性研究进展", 《化学推进剂与高分子材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156998A (en) * | 2019-05-28 | 2019-08-23 | 洛阳理工学院 | Cage modle polysilsesquioxane-polyethylene glycol polymer solid electrolyte material and preparation method thereof |
| CN110156998B (en) * | 2019-05-28 | 2021-06-29 | 洛阳理工学院 | Cage type polysilsesquioxane-polyethylene glycol polymer solid electrolyte material and preparation method thereof |
| CN114561019A (en) * | 2022-03-21 | 2022-05-31 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer taking cage-shaped silsesquioxane as core and modified LMHs |
| CN116333317A (en) * | 2023-02-22 | 2023-06-27 | 安徽中烟工业有限责任公司 | POSS-based hydrophobic material and preparation method thereof |
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