CN106700076A - Cross siloxane macromolecule containing polymerizable functional group and hydrophilic group and preparation process thereof - Google Patents
Cross siloxane macromolecule containing polymerizable functional group and hydrophilic group and preparation process thereof Download PDFInfo
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- CN106700076A CN106700076A CN201510496151.5A CN201510496151A CN106700076A CN 106700076 A CN106700076 A CN 106700076A CN 201510496151 A CN201510496151 A CN 201510496151A CN 106700076 A CN106700076 A CN 106700076A
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Abstract
The invention provides a cross siloxane macromolecule containing a polymerizable functional group and hydrophilic group and a preparation process thereof. The preparation process includes: firstly providing cross siloxane with a silicon hydrogen group at the end, then carrying out first hydrosilation reaction to synthesize a cross siloxane micromolecule containing a polymerizable functional group, then carrying out ring-opening polymerization reaction to synthesize a cross polysiloxane macromolecule containing a silicon hydrogen group, and finally carrying out second hydrosilation reaction to synthesize the cross siloxane macromolecule containing the polymerizable functional group and hydrophilic group.
Description
Technical field
Present invention is directed to a kind of siloxanes macromolecule and its preparation technology, espespecially a kind of base containing polymerizable functionalities
With the cross siloxanes macromolecule and its preparation technology of hydrophilic group.
Background technology
Because organosilicon glue (Silicone hydrogel) has good oxygen permeability, wettability and bio-compatible
Property, therefore contact lenses making is widely used in, the silicon monomer for being made for contact lenses now can be divided into directly
Chain siloxanes and cross siloxanes, such as Taiwan Patent are announced in No. TWI434865, disclose a kind of straight
Chain and with the polysiloxanes of the hydrophilic side-chains such as amide functional base or phosphocholine functional group, or as the U.S. is special
In profit bulletin the US4463149th, a kind of cross siloxane structure of small molecule is disclosed.
Though straight chain type siloxanes can make it have preferable hydrophily via modification, straight chain type siloxanes is one
Dimension structure, its oxygen transmission rate is often below the cross siloxanes of two-dimensional structure, though and cross siloxanes have compared with
Good oxygen transmission rate, but due to its hydrophobic property, also result in the decline of its moisture content.
It is this case therefore how to synthesize one and there is high oxygen permeability and the polysiloxane compound of high-moisture percentage is had concurrently
The technical task to be solved.
The content of the invention
It is a kind of containing polymerizable official it is a primary object of the present invention to provide in order to solve the problems, such as described in background technology
Can base and hydrophilic group the high molecular preparation technology of cross siloxanes, it is characterised in that base containing polymerizable functionalities with
The high molecular preparation technology of cross siloxanes of hydrophilic group comprises the following steps:
A () provides the cross siloxanes that end has silicon hydrogen-based;
B () carries out the first silicon hydrogenation to the cross siloxanes of end tool silicon hydrogen-based, form it into and contain
The cross siloxanes small molecule of polymerizable functionalities base;
C () carries out ring-opening polymerization, form it into the cross polysiloxanes macromolecule of hydrosilyl group-containing;And
D () carries out the second silicon hydrogenation, form it into the cross silica of base containing polymerizable functionalities and hydrophilic group
Alkane macromolecule.
In the step (a), the cross siloxanes of the end tool silicon hydrogen-based represents it with formula (I),
In formula (I), R0It is the chemical constitution that following formula is represented,
In R0In, d values are between 0-20.
The cross siloxanes of the end tool silicon hydrogen-based is one or four (dimethylsilyl bis) silane.
In the step (b), addition allyl methacrylate has the cross silica of silicon hydrogen-based in the end
In alkane, and first silicon hydrogenation is catalyzed with platiniferous catalyst, forms it into and contain and can gather with what formula (II) was represented
The cross siloxanes small molecule of functional group is closed,
In formula (II), the chemical constitution that polymerizable functionalities base R tool following formulas are represented,
In the step (b), in nitrogen, with 85-90 DEG C of temperature and effect 23 hours under conditions of, carry out
First silicon hydrogenation.
In the step (c), strong acid to cyclosiloxane, ring hydrogen siloxane and the base containing polymerizable functionalities is added
Cross siloxanes small molecule mixture in, carry out the ring-opening polymerization and form it into formula (III) table
The cross polysiloxanes macromolecule of the hydrosilyl group-containing for showing,
In formula (III), R1It is the chemical constitution that following formula is represented,
In R1In, m values represent the n values of silicon hydrogen-based number between 0-150 between 5-1000.
In the step (c), in lying in nitrogen, with 35 DEG C of temperature and effect 24 hours under conditions of, carry out institute
State ring-opening polymerization.
The mole number of the strong acid is the cyclosiloxane, the ring hydrogen siloxane and the base containing polymerizable functionalities
Cross siloxanes small molecule three mole number summation 1-10%, and the strong acid includes:TFMS,
Any one in sulfuric acid.
The cyclosiloxane includes:At least one in octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane.
The ring hydrogen siloxane is one 2,4,6,8 tetramethyl-ring tetrasiloxanes.
In the step (d), the cross polysiloxanes for adding hydrophilic compounds to the hydrosilyl group-containing is high
In molecule, and second silicon hydrogenation is catalyzed with platiniferous catalyst, forming it into containing of representing can with formula (IV)
Polymerization functional group and the cross siloxanes macromolecule of hydrophilic group,
In formula (IV), R2It is the chemical constitution that following formula is represented,
In R2In, between 5-1000, n values are between 0-150, hydrophilic group R for m values4Represented with following formula for one
Hydrophilic structure,
In R4In, between 0-100, z values are between 0-50, R for y values3For:Any one in hydroxyl, methyl.
The R2In, at least 3 tool hydrophilic group R4。
In the step (d), in lying in nitrogen, with 85-90 DEG C of temperature and effect 24 hours under conditions of, enter
Row second silicon hydrogenation.
The hydrophilic compounds include:3- allyloxy -1,2, propane diols, 2- allyloxyethanols, trimethyl
At least one in alcohol propane-allyl ether.
A kind of cross siloxanes another object of the present invention is to provide base containing polymerizable functionalities and hydrophilic group
Macromolecule, it is characterised in that it is to be obtained by foregoing preparation technology manufacture.
The hydrogen nuclear magnetic resonance spectrum knot of the cross siloxanes macromolecule of the base containing polymerizable functionalities and hydrophilic group
Fruit is as follows:
1H NMR(CDCl3,400MHz):δ6.1(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),
Wherein 3.40-3.90 (m, the 288H) numerical value represents the formation of hydrophilic structure in macromolecule.
A further object of the present invention is to provide a kind of silicon glue base material, it is characterised in that comprising foregoing containing polymerizable
Functional group and the cross siloxanes macromolecule of hydrophilic group.
Another mesh of the invention the is to provide a kind of silicon glue eyeglass, it is characterised in that comprising foregoing containing polymerizable
Functional group and the cross siloxanes macromolecule of hydrophilic group.
The silicon glue eyeglass is included:Three-[three (trimethylsiloxy group)] propyl methacrylate silane, N- vinyl
At least one in pyrrolidones, methacrylic acid -2- hydroxy methacrylates.
Brief description of the drawings
Fig. 1 is the cross siloxanes high score of synthesis base containing polymerizable functionalities provided by the present invention and hydrophilic group
The implementation steps schematic flow sheet of son.
Description of reference numerals
S11~S14 steps
Specific embodiment
Due to the high molecular system of cross siloxanes disclosed herein its base containing polymerizable functionalities and hydrophilic group
Standby technique, wherein the ring-opening polymerization (Ring opening polymerization) and silicon hydrogenation that are utilized
(Hydrosilation), for correlative technology field tool usually intellectual can be appreciated, therefore with saying hereinafter
It is bright, no longer make complete description.
The present invention is a kind of base containing polymerizable functionalities of offer and the cross siloxanes macromolecule and its system of hydrophilic group
Standby technique, this manufacturing process includes:First silicon hydrogenation, ring-opening polymerization and the second silicon hydrogenation.
Fig. 1 is referred to, first, there is provided end has the cross siloxanes (step S11) of silicon hydrogen-based, end tool
The cross siloxanes of silicon hydrogen-based is represented with following formula:
Wherein, R0For:
In R0In, d values are between 0-20.
The end has the cross siloxanes of silicon hydrogen-based, such as be four (dimethyl-silicons in the case of d=0
Epoxide) silane (Tetrakis (dimethylsilyl) orthosilicate).
The first silicon hydrogenation (step S12) is carried out with four (dimethylsilyl bis) silane, such as following chemical reaction
Shown in formula (a):
Step S12 adds allyl methacrylate (Allyl methacrylate) (2) in four (dimethylsilyl bis)
In silane, in the environment of 85-90 DEG C of temperature, the first silicon hydrogenation is catalyzed with platiniferous catalyst (Pt/C), and obtained
The cross siloxanes small molecule (3) of polymerizable functionalities base R must be contained, polymerizable functionalities base R is:
Wherein, polymerizable functionalities base has the structural formula of Si-O-Si.
Then, ring-opening polymerization (step S13) is carried out, such as shown in following chemical equation (b):
Step S13 is in the cross silica of cyclosiloxane (4), ring hydrogen siloxane (5) and the R of base containing polymerizable functionalities
Strong acid (6) is added in the mixture of alkane small molecule (3) three, wherein, the mole number of strong acid (6) is cyclosiloxane (4),
The total mole number of cross siloxanes small molecule (3) mixture of ring hydrogen siloxane (5) and the R of base containing polymerizable functionalities
1-10%.In the environment of normal temperature (about 35 DEG C), ring-opening polymerization is carried out, to form the cross of hydrosilyl group-containing
Type polysiloxanes macromolecule (7), the R of the cross polysiloxanes macromolecule (7) of the hydrosilyl group-containing1Chemistry knot
Structure is:
Wherein, m values represent the n values of silicon hydrogen-based (Si-H) number between 0-150 between 5-1000.
In ring-opening polymerization (step S13), cyclosiloxane (4) can be octamethylcy-clotetrasiloxane
(Octamethylcyclotetrasiloxane), in hexamethyl cyclotrisiloxane (Hexamethylcyclotrisiloxane)
At least one;Ring hydrogen siloxane (5) can be 2,4,6,8 tetramethyl-ring tetrasiloxanes
(2,4,6,8-Tetramethylcyclotetrasiloxane);Strong acid (6) is except the fluoroform sulphur shown in chemical equation (b)
Sour (Trifluoromethane sulfonic acid) can be used sulfuric acid (Sulfuric acid) to replace outward, also.
Thereafter, the second silicon hydrogenation (step S14) is carried out, such as shown in chemical equation (c):
It is high to the cross polysiloxanes of the hydrosilyl group-containing of hydrosilyl group-containing that step S14 adds hydrophilic compounds (8)
In molecule (7), in the environment of 85-90 DEG C of temperature, the second silicon hydrogenation is catalyzed with platiniferous catalyst (Pt/C),
And obtain the cross siloxanes macromolecule (9) of base containing polymerizable functionalities and hydrophilic group, base containing polymerizable functionalities and
The R of the cross siloxanes macromolecule (9) of hydrophilic group2Chemical constitution be:
Wherein, between 5-1000, n values are between 0-150, hydrophilic group R for m values4For:
In above-mentioned hydrophilic compounds (8) and hydrophilic group R4In, between 0-100, z values are between 0-50, R for y values3
For:Hydroxyl (OH), methyl (CH3) in any one.And hydrophilic compounds (8) can be 3- allyloxy -1,2,
Propane diols (3-Allyloxy-1,2-propanediol), 2- allyloxyethanols (2-Allyloxyethanol), trimethyl
At least one in alcohol propane-allyl ether (Trimethylolpropane allyl ether).
In above-mentioned base containing polymerizable functionalities and four R of the cross siloxanes macromolecule (9) of hydrophilic group2In, extremely
Rare 3 R2Tool hydrophilic group R4。
Embodiment 1
First silicon hydrogenation:The synthesis of the cross siloxanes small molecule containing polymerizable functionalities base.
By allyl methacrylate (10.52g, 83.39mmol), stabilizer:4- metoxyphenols
(4-Methoxyphenol) (9mg) is placed in the double necks of 250mL with platiniferous catalyst (Pt/C) (5%on carbon, 0.6g)
In bottle;Pour into nitrogen again in device return duct on 250mL two-neck bottles and serum plug, after being vacuumized three times,
Then take solvent:Solvent is simultaneously injected 250mL two-neck bottles by dry toluene (Toluene) (60mL) with glass syringe
In.Then four (dimethylsilyl bis) silane (6g, 18.25mmol) are taken again and with the syringe injection double necks of 250mL
In bottle.250mL two-neck bottles are placed in oil bath pan, 85-90 DEG C are heated to and are reacted, by 23 hours
Afterwards, to be evacuated filtering in the way of collect liquid (4-6 times), collected liquid is carried out into gravity filtration again.
Organic solvent is gone in mode concentrated under reduced pressure, thereafter, using ethyl acetate (Ethyl acetate) (100mL) and
Saturated aqueous common salt (150mL) extracts above-mentioned product (repeating extraction 5 times) after being concentrated under reduced pressure, collected organic layer.
It is concentrated under reduced pressure using instrument concentrated under reduced pressure, the product that will be collected from organic layer is with heating water bath (about 50 DEG C)
And vacuumize the mode of (about 3 hours) and concentrated and except organic solvent.With flow tube column chromatography
(EA/Hexane=1/20) mode collects the cross siloxanes small molecule containing polymerizable functionalities base, and yield is about
37%.
The hydrogen nuclear magnetic resonance spectral results of the cross siloxanes small molecule containing polymerizable functionalities base are as follows:1H
NMR(CDCl3,400MHz):δ6.09(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 6.09 (s, 4H), 5.54 (s,
4H), 4.10 (t, 8H) and 1.93 (m, 12H) these numerical value cross siloxanes of the representative containing polymerizable functionalities base are small
The formation of molecule.
Ring-opening polymerization:The high molecular synthesis of the cross polysiloxanes (n=8, m=43) of hydrosilyl group-containing.
By octamethylcy-clotetrasiloxane (15g, 50.57mmol), 2,4,6,8 tetramethyl-ring tetrasiloxanes (3g, 12.47
Mmol), the first silicon hydrogenation produce containing polymerizable functionalities base cross siloxanes small molecule (2.4g,
2.88mmol) and solvent:Chloroform (Chloroform) (14mL) is placed in 250mL two-neck bottles;In 250
Device serum plug and check valve, nitrogen is passed through from check-valve port on mL two-neck bottles, takes TFMS (0.1mL)
And with syringe injection 250mL two-neck bottles in, under nitrogen environment and room temperature (about 35 DEG C) react 24 hours, with
Device for opening adds saturated aqueous sodium carbonate (0.5mL) in the serum plug on 250mL two-neck bottles afterwards, with
Terminate ring-opening polymerization.
Organic solvent is removed using spin concentration instrument, extraction step is carried out afterwards, using ethyl acetate (200mL)
The product after above-mentioned spin concentration (repeating extraction 5 times) is extracted with saturated aqueous common salt (150mL), collecting top has
Machine layer.Recycle machine concentrated under reduced pressure to be concentrated under reduced pressure and removed organic solvent.With acetone (Acetone) (6mL)
Dissolving it is above-mentioned it is concentrated under reduced pressure after product, and to instill and carry out reprecipitation in methyl alcohol (Methanol) (27mL);Afterwards,
Gravity filtration is carried out with filter paper again, with the dope on methyl alcohol (250mL) cleaning filter paper upper strata.Collect upper strata sticky
Thing simultaneously removes organic solvent with spin concentration instrument;Repeat secondary foregoing reprecipitation step.Collect filter paper upper strata
Dope, you can (yield is about to obtain the cross polysiloxanes macromolecule of the colourless sticky hydrosilyl group-containings of 10.9g
53%).
The high molecular hydrogen nuclear magnetic resonance spectral results of cross polysiloxanes of hydrosilyl group-containing are as follows:1H
NMR(CDCl3,400MHz):δ6.1(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), wherein 0.04-0.20 (m, Si-CH3), numerical value 4.70 (m,
32H) represent the formation of silicon hydrogen-based.
Second silicon hydrogenation:The high molecular synthesis of cross siloxanes of base containing polymerizable functionalities and hydrophilic group
(n=8, m=50).
By 3- allyloxy -1,2, propane diols (4.69g, 35.49mmol) and platiniferous catalyst (Pt/C) (5%on carbon,
0.95g) it is placed in 250mL two-neck bottles;Then, managed with dropwise addition in device return duct on 250mL two-neck bottles,
Vacuumized and poured into nitrogen three times;Take solvent:Dry toluene (35mL) simultaneously injects above-mentioned 250mL with syringe
In two-neck bottle, 250mL two-neck bottles are inserted into oil bath pan and 85-90 DEG C is heated to.
By the cross polysiloxanes macromolecule of the hydrosilyl group-containing obtained by ring-opening polymerization (n=8, m=43, by
NMR calculates that molecular weight is about 15500) (10g, 0.645mmol) and is placed in another 100mL two-neck bottle, in
Device serum plug and check valve on 100mL two-neck bottles, are then vacuumized and are poured into nitrogen three times, take nothing
Water-toluene (25mL) and stabilizer:4- mequinols (6mg/20mL in toluene, 4mL) simultaneously inject 100mL
In two-neck bottle, then the cross for extracting the hydrosilyl group-containing dissolved with dry toluene out from 100mL two-neck bottles with syringe
Type polysiloxanes Polymer Solution;Then, the solution injection device that will be extracted out is in the drop on 250mL two-neck bottles
Plus pipe, and by (time for adding is no more than 4 minutes) in dropwise addition pipe instillation 250mL two-neck bottles.If 100mL is double
Still there is residue in neck bottle, the remnants that dry toluene (15mL) is cleaned in 100mL two-neck bottles can be taken with syringe
Thing, and the residue injection that will be washed out is added dropwise in pipe, then instill 250mL two-neck bottles.
The 250mL two-neck bottles continuous heating that is placed in oil bath pan is simultaneously held in 85-90 DEG C, makes it in nitrogen ring
The second silicon hydrogenation is carried out under border;After reagentia 24 hours, to be evacuated filtering in the way of collect liquid (4-6
It is secondary), then gravity filtration (2 times) is carried out, organic solvent is removed using spin concentration instrument, then with acetone (15mL)
Product after dissolving spin concentration, will be dissolved in during pure water (76mL) is put in the addition of the product of acetone carries out reprecipitation,
Gravity filtration is carried out using filter paper, with the product on pure water (about 250mL) cleaning filter paper upper strata, upper strata product is collected
And organic solvent is removed with spin concentration instrument, repeat secondary above-mentioned reprecipitation step.Collect filter paper upper strata
Dope is that can obtain about 8.12g yellow and to clarify sticky base containing polymerizable functionalities cross with hydrophilic group
Siloxanes macromolecule (8.12g, yield 63%).
The high molecular hydrogen nuclear magnetic resonance spectral results of cross siloxanes of base containing polymerizable functionalities and hydrophilic group are such as
Under:
1H NMR(CDCl3,400MHz):δ6.1(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),
Wherein numerical value 3.40-3.90 (m, 288H) represents the formation of hydrophilic structure in macromolecule.
Embodiment 2
Respectively with the cross siloxanes macromolecule of base containing polymerizable functionalities and the hydrophilic group of present invention synthesis (n=8,
M=50), the small molecule that straight chain type siloxanes (n=32, m=200) and U.S. Patent Bulletin US4463149 are disclosed
Cross siloxanes makes silicon glue eyeglass, and its formula is as shown in the table:
TRIS:Three-[three (trimethylsiloxy group)] propyl methacrylate silane
(3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)
NVP:NVP (N-Vinyl-2-pyrrolidone)
HEMA:Methacrylic acid -2- hydroxy methacrylates (Hydroxyethyl Methacrylate)
Above-mentioned three kinds its oxygen transmission rate of silicon glue eyeglass and moisture content being made with different silicon monomer formulas are tested respectively,
Test result is as shown in the table:
As seen from the above table, in the case of n and m value identicals, the cross siloxanes containing present invention synthesis is high
Its oxygen transmission rate of the silicon glue eyeglass of molecule is higher than the silicon glue eyeglass containing straight chain type siloxanes.And contain small molecule cross
The silicon glue eyeglass of type siloxanes, because it is molecular weight polymers, and wherein more hydrophilic structure is
(O=C-O), thus its oxygen permeability and moisture content are low compared with both.
Additionally, the cross siloxanes macromolecule of the base containing polymerizable functionalities of synthesis and hydrophilic group in the process of the present invention
In addition to it can be used as silicon glue eyeglass, also can be used to make silicon glue base material, and can be applied to other and include silicon glue
In the medical treatment of material or health product.
In sum, the cross siloxanes macromolecule of base containing polymerizable functionalities provided by the present invention and hydrophilic group
It has the characteristic of oxygen flow high and high-moisture percentage simultaneously;Therefore, the present invention closes actually great industrial value.
Claims (19)
1. the high molecular preparation technology of cross siloxanes of a kind of base containing polymerizable functionalities and hydrophilic group, its spy
Levy and be, under the base containing polymerizable functionalities includes with the high molecular preparation technology of cross siloxanes of hydrophilic group
Row step:
A () provides the cross siloxanes that end has silicon hydrogen-based;
B () carries out the first silicon hydrogenation to the cross siloxanes of end tool silicon hydrogen-based, being contained with formation can
The cross siloxanes small molecule of polymerization functional group;
C () carries out ring-opening polymerization, to form the cross polysiloxanes macromolecule of hydrosilyl group-containing;And
D () carries out the second silicon hydrogenation, to form the cross siloxanes of base containing polymerizable functionalities and hydrophilic group
Macromolecule.
2. base containing polymerizable functionalities as claimed in claim 1 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that in the step (a), the cross siloxanes of the end tool silicon hydrogen-based
Chemical structural formula is:
In formula (I), R0For:
Wherein, d values are between 0-20.
3. base containing polymerizable functionalities as claimed in claim 2 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that the cross siloxanes of the end tool silicon hydrogen-based is one or four (dimethyl silicas
Base) silane.
4. the cross siloxanes macromolecule of the base containing polymerizable functionalities as described in claim 1 and hydrophilic group
Preparation technology, it is characterised in that in the step (b), addition allyl methacrylate in the end
In the cross siloxanes of end tool silicon hydrogen-based, and first silicon hydrogenation is catalyzed with platiniferous catalyst, to be formed
The cross siloxanes small molecule containing polymerizable functionalities base, the cross silicon containing polymerizable functionalities base
The chemical structural formula of oxygen alkane small molecule is:
In formula (II), the R of base containing polymerizable functionalities is:
5. base containing polymerizable functionalities as claimed in claim 4 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that in the step (b), in nitrogen, with 85-90 DEG C of temperature and effect 23
Under conditions of hour, first silicon hydrogenation is carried out.
6. base containing polymerizable functionalities as claimed in claim 1 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that in the step (c), addition strong acid to cyclosiloxane, ring hydrogen siloxane and
In the mixture of the cross siloxanes small molecule containing polymerizable functionalities base, the ring-opening polymerization is carried out
To form the cross polysiloxanes macromolecule of the hydrosilyl group-containing, the cross polysiloxanes of the hydrosilyl group-containing
High molecular chemical structural formula is:
In formula (III), R1For:
Wherein, m values represent the n values of silicon hydrogen-based number between 0-150 between 5-1000.
7. base containing polymerizable functionalities as claimed in claim 6 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that in the step (c) is small with 35 DEG C of temperature and effect 24 in nitrogen
When under conditions of, carry out the ring-opening polymerization.
8. base containing polymerizable functionalities as claimed in claim 6 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that the mole number of the strong acid be the cyclosiloxane, the ring hydrogen siloxane and
The 1-10% of the cross siloxanes small molecule three mole number summation containing polymerizable functionalities base, and it is described strong
Acid includes:Any one in TFMS, sulfuric acid.
9. base containing polymerizable functionalities as claimed in claim 6 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that the cyclosiloxane includes:Octamethylcy-clotetrasiloxane, the silicon of pregnancy basic ring three
At least one in oxygen alkane.
10. base containing polymerizable functionalities as claimed in claim 6 is high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that the ring hydrogen siloxane is one 2,4,6,8 tetramethyl-ring tetrasiloxanes.
11. bases containing polymerizable functionalities as claimed in claim 1 are high molecular with the cross siloxanes of hydrophilic group
Preparation technology, it is characterised in that in the step (d), addition hydrophilic compounds to the hydrosilyl group-containing
Cross polysiloxanes macromolecule in, and second silicon hydrogenation is catalyzed with platiniferous catalyst, to be formed
State the cross siloxanes macromolecule of base containing polymerizable functionalities and hydrophilic group, the base containing polymerizable functionalities with it is hydrophilic
The high molecular chemical structural formula of cross siloxanes of base is:
In formula (IV), R2For:
Wherein m values between 5-1000, n values between 0-150,
R4It is hydrophilic structure, its chemical structural formula is:
Wherein y values between 0-100, z values between 0-50,
R3For:Any one in hydroxyl, methyl.
The cross siloxanes macromolecule of 12. bases containing polymerizable functionalities as claimed in claim 11 and hydrophilic group
Preparation technology, it is characterised in that in the R2, at least three R2 tool hydrophilic groups R4。
The cross siloxanes macromolecule of 13. bases containing polymerizable functionalities as claimed in claim 11 and hydrophilic group
Preparation technology, it is characterised in that in the step (d), in nitrogen, with 85-90 DEG C of temperature and effect
Under conditions of 24 hours, second silicon hydrogenation is carried out.
The cross siloxanes macromolecule of 14. bases containing polymerizable functionalities as claimed in claim 11 and hydrophilic group
Preparation technology, it is characterised in that the hydrophilic compounds include:3- allyloxy -1,2, propane diols, 2-
At least one in allyloxyethanol, trimethyl alcohol propane-allyl ether.
The cross siloxanes macromolecule of a kind of 15. bases containing polymerizable functionalities and hydrophilic group, it is characterised in that by
Preparation technology described in any one of claim 1 to 14 is manufactured and obtained.
The cross siloxanes macromolecule of 16. bases containing polymerizable functionalities as claimed in claim 15 and hydrophilic group,
Characterized in that, the high molecular hydrogen nuclear magnetic resonance of cross siloxanes of the base containing polymerizable functionalities and hydrophilic group
Spectral results are as follows:
1H NMR(CDCl3,400MHz):δ6.1(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),
Wherein 3.40-3.90 (m, the 288H) numerical value represents the formation of hydrophilic structure in macromolecule.
A kind of 17. silicon glue base materials, it is characterised in that comprising base containing polymerizable functionalities described in claim 15 with
The cross siloxanes macromolecule of hydrophilic group.
A kind of 18. silicon glue eyeglasses, it is characterised in that comprising base containing polymerizable functionalities described in claim 15 with
The cross siloxanes macromolecule of hydrophilic group.
19. silicon glue eyeglasses as claimed in claim 18, it is characterised in that the silicon glue eyeglass is included:
Three-[three (trimethylsiloxy group)] propyl methacrylate silane, NVP, methacrylic acid -2-
At least one in hydroxy methacrylate.
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