CN106700076B - Cross-shaped siloxane polymer containing polymerizable functional group and hydrophilic group and preparation process thereof - Google Patents
Cross-shaped siloxane polymer containing polymerizable functional group and hydrophilic group and preparation process thereof Download PDFInfo
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Abstract
The invention provides a cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups and a preparation process thereof.
Description
Technical Field
The present invention relates to a siloxane polymer and a preparation process thereof, and more particularly to a cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups and a preparation process thereof.
Background
Since Silicone hydrogel (Silicone hydrogel) has good oxygen permeability, wettability and biocompatibility, it is commonly used in contact lens manufacture, and the silicon monomers used in contact lens manufacture today can be classified into linear siloxanes and cross siloxanes, such as taiwan patent publication No. TWI434865, which discloses a linear polysiloxane having hydrophilic side chains such as amide functional group or phosphorylcholine functional group, or US4463149, which discloses a small molecule cross siloxane structure.
Although the straight-chain siloxane can be modified to have better hydrophilicity, the straight-chain siloxane is a one-dimensional structure, and the oxygen permeability of the straight-chain siloxane is often lower than that of the cross-shaped siloxane with a two-dimensional structure, and the cross-shaped siloxane has better oxygen permeability, but the water content of the cross-shaped siloxane is also reduced due to the hydrophobic property of the cross-shaped siloxane.
Therefore, how to synthesize a polysiloxane compound with high oxygen permeability and high water content is the technical subject to be solved by the present invention.
Disclosure of Invention
In order to solve the problems described in the background art, the main object of the present invention is to provide a process for preparing a cross-shaped silicone polymer containing a polymerizable functional group and a hydrophilic group, wherein the process for preparing a cross-shaped silicone polymer containing a polymerizable functional group and a hydrophilic group comprises the following steps:
(a) providing a cross-type siloxane having hydrosilyl groups at the ends;
(b) subjecting the cross-shaped siloxane with hydrosilyl at the end to a first hydrosilation reaction to form a cross-shaped siloxane small molecule containing a polymerizable functional group;
(c) performing ring-opening polymerization to form a cross-shaped polysiloxane polymer containing silylhydride; and
(d) performing a second hydrosilation reaction to form a cross-shaped siloxane polymer containing a polymerizable functional group and a hydrophilic group.
In the step (a), the terminal silylhydride cross-shaped siloxane is represented by the formula (I),
in the formula (I), R0Is a chemical structure represented by the following formula,
at R0In (d), the value of d is between 0 and 20.
The cross-shaped siloxane with the terminal hydrosilyl group is tetra (dimethylsilyloxy) silane.
In the step (b), allyl methacrylate is added into the cross-shaped siloxane with the terminal hydrosilyl group, and the platinum-containing catalyst is used to catalyze the first hydrosilation reaction, so that the cross-shaped siloxane small molecule containing the polymerizable functional group represented by the formula (II) is formed,
in formula (II), the polymerizable functional group R has a chemical structure represented by the following formula,
in the step (b), the first hydrosilation reaction is carried out in nitrogen at a temperature of 85-90 ℃ for 23 hours.
In the step (c), a strong acid is added to the mixture of cyclosiloxane, cyclosiloxane and the cross-type siloxane micromolecule containing the polymerizable functional group to carry out the ring-opening polymerization reaction so as to form the cross-type polysiloxane macromolecule containing the hydrosilyl represented by the formula (III),
in the formula (III), R1Is a chemical structure represented by the following formula,
at R1In which m is between 5 and 1000 and n, representing the number of hydrosilyl groups, is between 1 and 150.
In the step (c), the ring-opening polymerization is performed under nitrogen at a temperature of 35 ℃ for 24 hours.
The mole number of the strong acid is 1-10% of the sum of the moles of the cyclosiloxane, the cyclosiloxane and the cross-shaped siloxane micromolecule containing the polymerizable functional group, and the strong acid comprises: trifluoromethanesulfonic acid or sulfuric acid.
The cyclosiloxane includes: at least one of octamethylcyclotetrasiloxane and hexamethylcyclotrisiloxane.
The cyclic hydrogen siloxane is 2,4,6, 8-tetramethylcyclotetrasiloxane.
In the step (d), a hydrophilic compound is added to the silylhydride-containing cross-shaped polysiloxane polymer, and the platinum-containing catalyst is used to catalyze the second hydrosilation reaction to form a cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups represented by the formula (IV),
in the formula (IV), R2Is a chemical structure represented by the following formula,
at R2Wherein m is 5-1000, n is 1-150, and the hydrophilic group R4Is a hydrophilic structure represented by the following formula,
at R4Wherein y is between 0 and 100, z is between 0 and 50, R3Comprises the following steps: any one of a hydroxyl group and a methyl group.
The R is2In which at least 3 have a hydrophilic group R4。
In the step (d), the second hydrosilation reaction is carried out in nitrogen at a temperature of 85-90 ℃ for 24 hours.
The hydrophilic compound includes: at least one of 3-allyloxy-1, 2-propanediol, 2-allyloxyethanol, and trimethylol propane allyl ether.
Another object of the present invention is to provide a cross-type siloxane polymer containing a polymerizable functional group and a hydrophilic group, which is characterized by being produced by the above-mentioned production process.
The result of hydrogen nuclear magnetic resonance spectrum of the cross-shaped siloxane polymer containing the polymerizable functional group and the hydrophilic group is as follows:
1h NMR (CDCl3,400MHz) 6.1(s,4H),5.54(s,4H),4.10(t,8H),3.40-3.90(m,288H),1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m, Si-CH3), where the number 3.40-3.90(m,288H) represents the formation of hydrophilic structures in the polymer.
Another object of the present invention is to provide a silicone gum substrate, which is characterized by comprising the cross-shaped siloxane polymer containing a polymerizable functional group and a hydrophilic group.
Another object of the present invention is to provide a silicone hydrogel lens, which is characterized by comprising the cross-shaped silicone polymer containing a polymerizable functional group and a hydrophilic group.
The silica gel lens comprises at least one of tri- [ tri (trimethylsiloxy) ] propyl methacrylate silane, N-vinyl pyrrolidone and 2-hydroxyethyl methacrylate.
Drawings
FIG. 1 is a schematic flow chart showing the steps of synthesizing a cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups according to the present invention.
Description of the reference numerals
S11-S14
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Since the preparation process of the cross-shaped silicone polymer containing polymerizable functional groups and hydrophilic groups, in which Ring-opening polymerization (Ring opening polymerization) and Hydrosilation (Hydrosilation) are utilized, is well understood by those skilled in the art, the following description is not fully provided.
The invention provides a cross siloxane polymer containing polymerizable functional group and hydrophilic group and a preparation process thereof, wherein the preparation process comprises the following steps: a first hydrosilylation reaction, a ring-opening polymerization reaction, and a second hydrosilylation reaction.
Referring to fig. 1, first, a cross-shaped silicone with hydrosilyl groups at the ends is provided (step S11), and the cross-shaped silicone with hydrosilyl groups at the ends is represented by the following formula:
wherein R is0Comprises the following steps:
at R0In (d), the value of d is between 0 and 20.
The cross-type siloxane having a silylhydride group at the terminal is, for example, tetrakis (dimethylsiloxy) silane (tetramethylsilyl) orthosilicate in the case where d is 0.
The first hydrosilation reaction with tetrakis (dimethylsilyloxy) silane (step S12) is performed as shown in the following chemical reaction formula (a):
step S12, Allyl methacrylate (2) is added to tetrakis (dimethylsiloxy) silane, and a platinum-containing catalyst (Pt/C) is used to catalyze the first hydrosilation reaction at 85-90 ℃ to obtain a cross-shaped siloxane small molecule (3) containing a polymerizable functional group R, where the polymerizable functional group R is:
wherein the polymerizable functional group has the structural formula of Si-O-Si.
Subsequently, a ring-opening polymerization reaction is performed (step S13), as shown in the following chemical reaction formula (b):
step S13, adding strong acid (6) into a mixture of cyclosiloxane (4), cyclosiloxane (5) and cross siloxane micromolecule (3) containing polymerizable functional group R, wherein the mole number of the strong acid (6) is 1-10% of the total mole number of the mixture of cyclosiloxane (4), cyclosiloxane (5) and cross siloxane micromolecule (3) containing polymerizable functional group R. Performing ring-opening polymerization reaction at normal temperature (about 35 ℃) to form a silylhydride-containing cross-shaped polysiloxane macromolecule (7), wherein R of the silylhydride-containing cross-shaped polysiloxane macromolecule (7)1The chemical structure of (A) is as follows:
wherein m is 5-1000, and n is 1-150.
In the ring-opening polymerization (step S13), the cyclosiloxane (4) may be at least one of Octamethylcyclotetrasiloxane (octamethylcyclotetramisoxane) and Hexamethylcyclotrisiloxane (Hexamethylcyclotrisiloxane); the cyclic hydrogen siloxane (5) can be 2,4,6,8-Tetramethylcyclotetrasiloxane (2,4,6, 8-Tetramethylcyclotetrasiloxane); the strong acid (6) may be Sulfuric acid (Sulfuric acid) instead of trifluoromethanesulfonic acid (Trifluoromethane sulfonic acid) represented by the chemical formula (b).
Thereafter, a second hydrosilation reaction is performed (step S14), as shown in chemical reaction formula (c):
step S14, adding hydrophilic compound (8) to the silylhydride-containing cross-shaped polysiloxane polymer (7), and catalyzing the second hydrosilation reaction by platinum-containing catalyst (Pt/C) at 85-90 ℃ to obtain cross-shaped siloxane polymer (9) containing polymerizable functional group and hydrophilic group, R of the cross-shaped siloxane polymer (9) containing polymerizable functional group and hydrophilic group2The chemical structure of (A) is as follows:
wherein m is 5-1000, n is 1-150, and hydrophilic group R4Comprises the following steps:
in the above-mentioned hydrophilic compound (8) and the hydrophilic group R4Wherein y is between 0 and 100, z is between 0 and 50, R3Comprises the following steps: hydroxy (OH), methyl (CH)3) Any one of them. And the hydrophilic compound (8) may be 3-allyloxy-1, 2-propanediol (3-Allylox)y-1,2-propanediol), 2-Allyloxyethanol (2-Allyloxyethanol), and Trimethylolpropane allyl ether (trimethyleneallyl ether).
Four Rs of the cross-shaped siloxane polymer (9) containing the polymerizable functional group and the hydrophilic group2In the total, at least 3R2Having a hydrophilic radical R4。
Example 1
The first hydrosilation reaction is the synthesis of cross-shaped siloxane small molecules containing polymerizable functional groups.
Allyl methacrylate (10.52g,83.39mmol), stabilizer 4-Methoxyphenol (4-Methoxyphenol) (9mg) and platinum-containing catalyst (Pt/C) (5% on carbon,0.6g) were placed in a 250m L two-necked flask, a reflux tube and a serum stopper were placed on the 250m L two-necked flask, vacuum was applied and nitrogen was again introduced three times, then solvent anhydrous Toluene (Toluene) (60m L) was taken and solvent was injected into the 250m L two-necked flask with a glass syringe, then tetrakis (dimethylsiloxy) silane (6g,18.25mmol) was taken and injected into the 250m L two-necked flask with a syringe, the 250m L two-necked flask was placed in an oil bath, heated to 85-90 ℃ for reaction, after 23 hours, liquid (4-6 times) was collected by suction filtration, and the collected liquid was gravity filtered again.
The organic solvent was removed by concentration under reduced pressure, and then the above-mentioned product after concentration under reduced pressure was extracted with Ethyl acetate (100m L) and saturated brine (150m L) (extraction was repeated 5 times), the organic layer was collected, concentration under reduced pressure was performed using a reduced pressure concentration apparatus, the product collected from the organic layer was concentrated by heating in a water bath (about 50 ℃) and applying vacuum (about 3 hours) and the organic solvent was removed, and the small cross-type siloxane molecule containing a polymerizable functional group was collected by column chromatography (EA/Hexane 1/20) at a yield of about 37%.
The result of the hydrogen nuclear magnetic resonance spectrum of the cross-shaped siloxane micromolecule containing the polymerizable functional group is as follows:1HNMR (CDCl3,400MHz) 6.09(s,4H),5.54(s,4H),4.10(t,8H),1.93(m,12H),1.63-1.79(m,8H),0.55-0.64(m,8H),0.04-0.20(m,24H), wherein the values of 6.09(s,4H),5.54(s,4H),4.10(t,8H) and 1.93(m,12H) represent a cross-type siloxane containing polymerizable functional groupsAnd (3) forming small molecules.
Ring-opening polymerization: synthesis of a silylhydride-containing cross-shaped polysiloxane polymer (n is 8, and m is 43).
Octamethylcyclotetrasiloxane (15g,50.57mmol), 2,4,6,8-tetramethylcyclotetrasiloxane (3g,12.47mmol), the cross-shaped siloxane small molecule containing polymerizable functional groups (2.4g,2.88mmol) produced by the first hydrosilation reaction, and a solvent, trichloromethane (Chloroform) (14m L), were placed in a 250m L two-necked flask, a serum stopper and a one-way valve were mounted on the 250m L two-necked flask, nitrogen was introduced from the one-way valve port, trifluoromethanesulfonic acid (0.1m L) was taken and injected into the 250m L two-necked flask by a syringe, and reacted for 24 hours under nitrogen atmosphere at room temperature (about 35 ℃), and then the serum stopper mounted on the 250m L two-necked flask was opened, and a saturated aqueous solution of sodium carbonate (0.5m L) was added to terminate the ring-opening polymerization reaction.
The organic solvent was removed by a spin concentrator, and then an extraction step was performed, in which the above-mentioned spin-concentrated product was extracted with ethyl acetate (200m L) and saturated saline (150m L) (extraction was repeated 5 times), and the upper organic layer was collected, and then the organic solvent was removed by vacuum concentration using a vacuum concentrator, the above-mentioned vacuum-concentrated product was dissolved with Acetone (Acetone) (6m L), and the solution was dropped into Methanol (Methanol) (27m L) to reprecipitate, and then gravity filtration was performed with filter paper, and the viscous substance on the upper layer of the filter paper was washed with Methanol (250m L), the viscous substance on the upper layer was collected and the organic solvent was removed by a spin concentrator, and the above-mentioned reprecipitation step was repeated twice, and the viscous substance on the upper layer was collected with filter paper, whereby 10.9g of colorless viscous silicone base-containing cross polymer was obtained (yield about 53%).
The result of hydrogen nuclear magnetic resonance spectrum of the cross-type polysiloxane polymer containing hydrosilyl is that 1HNMR (CDCl3,400MHz) is 6.1(s,4H),5.56(s,4H),4.70(m,32H),4.10(t,8H),1.95(s,12H),1.65-1.75(m,8H),0.50-0.65(m,8H),0.04-0.20(m, Si-CH3), wherein the value of 4.70(m,32H) represents the formation of hydrosilyl.
And (2) a second hydrosilation reaction, namely synthesizing a cross-shaped siloxane polymer containing a polymerizable functional group and a hydrophilic group (n is 8, and m is 50).
3-allyloxy-1, 2-propanediol (4.69g,35.49mmol) and platinum-containing catalyst (Pt/C) (5% oncarbon,0.95g) were placed in a 250m L two-necked flask, then a reflux tube and a dropping tube were installed on the 250m L two-necked flask, vacuum-pumping and nitrogen gas-filling were conducted three times, the solvent, anhydrous toluene (35m L), was injected into the above 250m L two-necked flask by syringe, and the 250m L two-necked flask was placed in an oil bath and heated to 85-90 ℃.
The silylhydride-containing cross-shaped polysiloxane macromolecules (n 8, m 43, molecular weight estimated by NMR of approximately 15500) (10g,0.645mmol) obtained by the ring-opening polymerization reaction were placed in another 100m L two-necked flask, a serum stopper and a one-way valve were mounted on the 100m L two-necked flask, followed by vacuum pumping and nitrogen filling three times, the silylhydride-containing cross-shaped polysiloxane macromolecules dissolved in the silylhydride-containing solution with a stabilizer, 4-methoxyphenol (6mg/20m L1 in toluene,4m L) were taken out from the 100m L two-necked flask by means of a syringe and were poured into the 100m L two-necked flask, the silylhydride-containing cross-shaped polysiloxane macromolecules dissolved in the silylhydride-containing solution with the silylhydride-free toluene were taken out from the 100m L two-necked flask by means of a syringe, the taken out of the syringe and the syringe was poured into a 250m L two-necked flask (anhydrous time is not more than 4 minutes), and if the residue remained in the 100m L, the syringe is washed, and the residue in the 100m L, the syringe, the residue was poured into the 100m L.
After 24 hours of reaction, the reaction mixture was collected by suction filtration (4 to 6 times), then was gravity-filtered (2 times), the organic solvent was removed by a rotary concentrator, the product after the rotary concentration was dissolved in acetone (15m L), the product dissolved in acetone was added to pure water (76m L) to reprecipitate, gravity-filtered using filter paper, the product on the upper layer of the filter paper was washed with pure water (about 250m L), the upper layer was collected and the organic solvent was removed by a rotary concentrator, and the above reprecipitation step was repeated twice.8.12 g of yellow and clear viscous cross-shaped silicone polymer containing polymerizable functional groups and hydrophilic groups (8.12g, 63% yield) was obtained by collecting the viscous substance on the upper layer of the filter paper.
The result of hydrogen nuclear magnetic resonance spectrum of the cross-shaped siloxane polymer containing the polymerizable functional group and the hydrophilic group is as follows:
1h NMR (CDCl3,400MHz) 6.1(s,4H),5.54(s,4H),4.10(t,8H),3.40-3.90(m,288H),1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m, Si-CH3), where the numbers 3.40-3.90(m,288H) represent the formation of hydrophilic structures in the polymer.
Example 2
The silicone hydrogel lenses were prepared from the synthesized cross-shaped siloxane polymer (n 8, m 50) containing polymerizable functional groups and hydrophilic groups, straight-chain siloxane (n 32, m 200) and the small-molecule cross-shaped siloxane disclosed in U.S. Pat. No. US4463149, and the formulations thereof are shown in the following table:
TRIS TRIS- [ TRIS (trimethylsiloxy) ] propylmethacrylate silane (3- [ Tris (trimethylsiloxy) silyll ] propylmethacrylate)
NVP N-vinylpyrrolidone (N-Vinyl-2-pyrrolidone)
HEMA 2-Hydroxyethyl Methacrylate (Hydroxyethyl Methacrylate)
The three silicon hydrogel lenses prepared by different silicon monomer formulas are respectively tested for oxygen permeability and water content, and the test results are shown in the following table:
as can be seen from the above table, the oxygen permeability of the silicone rubber lens containing the synthesized cross-shaped siloxane polymer of the present invention is higher than that of the silicone rubber lens containing straight-chain siloxane under the condition that n and m have the same value. The silica hydrogel lens containing the small molecular cross-shaped siloxane has lower oxygen permeability and water content than the small molecular polymer and the hydrophilic structure (O ═ C-O).
In addition, the cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups synthesized by the method can be used as a silica hydrogel lens, can also be used for manufacturing a silica hydrogel substrate, and can be applied to other medical or health-care products containing the silica hydrogel material.
In summary, the cross-shaped siloxane polymer containing polymerizable functional groups and hydrophilic groups provided by the present invention has the characteristics of high oxygen permeability and high water content; therefore, the present invention has great industrial value.
Claims (18)
1. A preparation process of a cross-shaped siloxane polymer containing a polymerizable functional group and a hydrophilic group is characterized in that the preparation process of the cross-shaped siloxane polymer containing the polymerizable functional group and the hydrophilic group comprises the following steps:
(a) providing a cross-shaped siloxane with hydrosilyl at the end, wherein the chemical structural formula of the cross-shaped siloxane is shown as the formula (I):
in the formula (I), R0Comprises the following steps:
wherein d is between 0 and 20;
(b) subjecting the terminal cross-shaped siloxane with hydrosilyl groups to a first hydrosilation reaction with allyl methacrylate to form a cross-shaped siloxane small molecule containing polymerizable functional groups, wherein the chemical structural formula of the cross-shaped siloxane small molecule containing polymerizable functional groups is shown as formula (II):
in the formula (II), the polymerizable functional group-containing group R is:
(c) carrying out ring-opening polymerization reaction on the cross-shaped siloxane micromolecule containing the polymerizable functional group, cyclosiloxane and cyclosiloxane to form a hydrosilyl-containing cross-shaped polysiloxane macromolecule, wherein the chemical structural formula of the hydrosilyl-containing cross-shaped polysiloxane macromolecule is shown as the formula (III):
in the formula (III), R1Comprises the following steps:
wherein, the value of m is between 5 and 1000, and the value of n representing the number of hydrosilyl is between 1 and 150; and
(d) and carrying out a second hydrosilation reaction on the silylhydride-containing cross polysiloxane polymer shown in the formula (III) and a hydrophilic compound to form a cross siloxane polymer containing a polymerizable functional group and a hydrophilic group, wherein the chemical structural formula of the cross siloxane polymer is shown in the formula (IV):
in the formula (IV), R2Comprises the following steps:
wherein m is between 5 and 1000, n is between 1 and 150,
R4is a hydrophilic structure, and the chemical structural formula is as follows:
wherein y is between 0 and 100, z is between 0 and 50,
R3comprises the following steps: any one of a hydroxyl group and a methyl group.
2. The process for preparing a cross-shaped siloxane macromolecule containing polymerizable functional groups and hydrophilic groups according to claim 1, wherein the cross-shaped siloxane with hydrosilyl at the terminal is tetrakis (dimethylsilyloxy) silane.
3. The process according to claim 1, wherein in step (b), the first hydrosilation reaction is catalyzed by a platinum-containing catalyst to form the polymerizable functional group-containing cross-shaped siloxane macromolecule.
4. The process according to claim 3, wherein the first hydrosilation is carried out in step (b) at 85-90 ℃ for 23 hours under nitrogen.
5. The process according to claim 1, wherein in step (c), a strong acid is added to the mixture of cyclosiloxane, cyclosiloxane and the cross siloxane micromolecule containing polymerizable functional group to perform the ring-opening polymerization reaction to form the hydrosilyl-containing cross polysiloxane macromolecule.
6. The process for preparing a cross-shaped silicone polymer having polymerizable functional groups and hydrophilic groups according to claim 5, wherein in step (c), the ring-opening polymerization is carried out at a temperature of 35 ℃ for 24 hours in a nitrogen atmosphere.
7. The process according to claim 5, wherein the molar amount of the strong acid is 1-10% of the sum of the molar amounts of the cyclosiloxane, the cyclosiloxane and the cross siloxane polymer containing the polymerizable functional group, and the strong acid comprises: trifluoromethanesulfonic acid or sulfuric acid.
8. The process for preparing a cross-shaped silicone macromolecule containing polymerizable functional groups and hydrophilic groups as claimed in claim 5, wherein the cyclosiloxane comprises: at least one of octamethylcyclotetrasiloxane and hexamethylcyclotrisiloxane.
9. The process for preparing a cross-shaped siloxane polymer having polymerizable functional groups and hydrophilic groups according to claim 5, wherein the cyclic hydrogen siloxane is 2,4,6, 8-tetramethylcyclotetrasiloxane.
10. The process according to claim 1, wherein in step (d), the hydrophilic compound is added to the silylhydride-containing cross-shaped polysiloxane polymer, and the platinum-containing catalyst is used to catalyze the second hydrosilation reaction to form the polymerizable functional group-and hydrophilic group-containing cross-shaped siloxane polymer.
11. The process for preparing a cross-shaped silicone macromolecule containing polymerizable functional groups and hydrophilic groups as in claim 10, wherein R is2At least three R2 having hydrophilic groups R4。
12. The process according to claim 10, wherein the second hydrosilation step (d) is carried out at a temperature of 85-90 ℃ for 24 hours under nitrogen.
13. The process for preparing a cross-shaped silicone macromolecule containing polymerizable functional groups and hydrophilic groups as in claim 10, wherein the hydrophilic compounds comprise: at least one of 3-allyloxy-1, 2-propanediol, 2-allyloxyethanol, and trimethylol propane allyl ether.
14. A cross-type siloxane polymer containing a polymerizable functional group and a hydrophilic group, which is produced by the production process according to any one of claims 1 to 13.
15. The cross-shaped silicone polymer with polymerizable functional groups and hydrophilic groups according to claim 14, wherein the cross-shaped silicone polymer with polymerizable functional groups and hydrophilic groups has the following hydrogen nuclear magnetic resonance spectroscopy results:
1h NMR (CDCl3,400MHz) 6.1(s,4H),5.54(s,4H),4.10(t,8H),3.40-3.90(m,288H),1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m, Si-CH3), where the number 3.40-3.90(m,288H) represents the formation of hydrophilic structures in the polymer.
16. A silicone base material comprising the cross-shaped silicone polymer having a polymerizable functional group and a hydrophilic group according to claim 14.
17. A silicone hydrogel lens comprising the cross-shaped siloxane polymer having a polymerizable functional group and a hydrophilic group according to claim 14.
18. The silicone hydrogel lens of claim 17, wherein the silicone hydrogel lens comprises at least one of tris- [ tris (trimethylsiloxy) ] propylmethacrylate silane, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate.
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| EP1300434A2 (en) * | 2001-10-03 | 2003-04-09 | Michigan Molecular Institute | Hyperbranched polymers with latent functionality and methods of making same |
| WO2007079240A2 (en) * | 2005-12-29 | 2007-07-12 | The University Of Akron | Photocurable polymers for ophthalmic applications |
| CN101659671A (en) * | 2008-08-27 | 2010-03-03 | 赢创戈尔德施米特有限公司 | Method for manufacturing branched sih-functional polysiloxanes and their use |
| CN103183803A (en) * | 2011-12-29 | 2013-07-03 | 晶硕光学股份有限公司 | Preparation method for hydrophilic silicone prepolymer |
| CN103183830A (en) * | 2011-12-29 | 2013-07-03 | 晶硕光学股份有限公司 | Preparation method for hydrophilic silicone macromer |
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