CN106032400A - Network polymer, composition for producing biomedical apparatus, and biomedical apparatus - Google Patents
Network polymer, composition for producing biomedical apparatus, and biomedical apparatus Download PDFInfo
- Publication number
- CN106032400A CN106032400A CN201510116575.4A CN201510116575A CN106032400A CN 106032400 A CN106032400 A CN 106032400A CN 201510116575 A CN201510116575 A CN 201510116575A CN 106032400 A CN106032400 A CN 106032400A
- Authority
- CN
- China
- Prior art keywords
- polymer
- monomer
- methacrylate
- unsaturated group
- hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 C*(CCC1CN(*)C(*C=C)=[U])C1=O Chemical compound C*(CCC1CN(*)C(*C=C)=[U])C1=O 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a network polymer, wherein an isocyanate-terminated prepolymer and a reactant having at least a hydroxyl group and at least an unsaturated group are subjected to a reaction to prepare the network polymer, wherein the prepolymer is obtained by carrying out a polymerization reaction on a starting material in the presence of a catalyst, and the reactant is obtained by carrying out a reaction on a mixing material in the presence of a catalyst. The present invention further provides a composition for producing a biomedical apparatus, and the biomedical apparatus obtained by molding the composition. According to the present invention, the network polymer has the special structure design so as to easily form the composition, such that the subsequently produced biomedical apparatus can meet the practical application requirements.
Description
Technical field
The present invention relates to a kind of net high-polymer, the constituent containing this net high-polymer and profit
With raw doctor's device (biomedical device) obtained by this constituent, particularly relate to one and contain
There are the net high-polymer of siloxane monomer unit, the constituent containing this net high-polymer and profit
With the raw doctor's device obtained by this constituent.
Background technology
Siloxanes (silicone) have low heat conductivity, low chemical reactivity, high thermal stability,
High gas permeability, biocompatibility and be unfavorable for the character such as bacterial growth, thus extensively used
In various fields, such as fields such as photoelectricity, chemical industry and raw doctors.As a example by giving birth to doctor field, silica
Alkane can be employed prepares various raw doctor's device [such as fluid channel (microfluidics), sealing member
(seals), liner (gaskets)] etc.；Siloxanes [the namely siloxanes glue of colloidal form
(silicone hydrogel)] more can be employed for binder, dressing, implant (implants),
Support, Ophthalmoligic instrument are [such as intraocular lens, contact lens, corneal onlays (corneal
Onlay)] etc..
At least one region of siloxanes glue material surface is usually hydrophobicity, may be from eye
Eyeball adsorbs lipid or protein and adheres on eyes.Therefore, for preparing Ophthalmoligic instrument
Siloxanes glue, the siloxanes glue particularly applying to prepare contact lens typically requires again
Modified, could promote the character such as moisture retention and high oxygen permeability, and allow contact lens wear person
Feel comfortably cool.US 2013/0172504A1 discloses a kind of Photocrosslinkable prepolymer and siloxanes
Glue material.This Photocrosslinkable prepolymer comprises in its copolymer chain: (1) be derived from one or
Multiple vinyl monomer containing siloxanes and/or containing siloxanes giant molecule (macromer)
Siloxane unit, (2) be derived from one or more the first hydrophilic ethylene system's monomer and/or hydrophilic
The macromolecular hydrophilic units of property, (3) have UV and can prolong the chain of activatable free radical generation part
Long unit and (4) ethylene unsaturated group.It is preferred that the ethylene system that should contain siloxanes is single
Body and/or containing siloxanes giant molecule be single ethylene functionalization monomer of containing siloxanes or
Giant molecule, is shown below:
The X of above formula1Represent-COO-,-CONR18-,-OCOO-or-OCONR18-, R13
For hydrogen or C1-C7Alkyl.R11Represent C1-C25Stretch alkyl or C6-C30Stretch aralkyl
(arylalkylene)。R12Represent C1-C25Alkyl or C6-C30Aryl.R7～R10And R14～R17
Represent C1-C8Alkyl, through C1-C4Alkyl or C1-C4The substituted phenyl of alkoxyl, C1-C18
Fluoroalkyl, C1-C12Cyanoalkyl, C1-C6Hydroxyalkyl or C1-C6Amine alkyl.M and p is 5
Integer and m+p between 700 are 5 to 700.The monomer of above formula or follow-up of giant molecule
X can be passed through1The other double bond on carbon further with hydrophilic ethylene system monomer or giant molecule, chain
Extend agent and ethylene unsaturated compound reacts.
US 2013/0172574 A1 also discloses a kind of hydrophilic siloxane with formula
Giant molecule:
The R of above formula18Represent C1-C12Alkyl.R19Expression-(CH2)b-O-(CH2)cOr C3-C6
Alkyl, b and c is 2 to 4.R20Represent hydrogen or methyl.W represents
OrWherein R21For C1-C4Alkyl；R22
For C1-C2Alkyl；R23For C1-C3Alkyl；D and e is 2 to 4.L be-COO-,
-CONH-,-NHCOO-or-NHCONH-.Y is-(CH2)f-or-COO (CH2)g-；
F is 0 to 4；G is 2 to 4.
Siloxanes giant molecule in above-mentioned two U.S. Publication cases the most only has one can reaction double
Key, needs sequentially to react with hydrophilic ethylene system monomer or ethylene unsaturated compound,
Thus make reaction be restricted, and cannot quickly prepare glue via a step.Again because of silicon
Oxygen alkanes molecule is hydrophobicity, and conventional synthesis siloxanes giant molecule mode has with hydrophilic monomer
Consistency problem, easily produces and is separated.It follows that how to increase siloxanes giant molecule
Reactivity, improve the macromolecular consistency problem of siloxanes and so as to quickly preparing water simultaneously
Glue, becomes current industry and desires most ardently the project of exploitation.
Summary of the invention
The first object of the present invention be to provide a kind of easily prepared, have relatively low preparation cost,
Reactive good, there is no consistency problem and be applicable to the composition formed for making raw doctor's device
The net high-polymer of thing.
Net high-polymer of the present invention, be by the prepolymer that end is NCO with have
It is obtained that the reactant of at least one hydroxyl and at least one unsaturated group carries out reaction.This is pre-
Polymer is to be carried out polyreaction gained in the presence of catalyst by parent material, this initial material
Material includes polysiloxanes, multicomponent isocyanate and polyhydric alcohol containing C-terminal.This reaction
Thing is to be carried out reacting gained in the presence of catalyst by mixing material, and this mixing material includes hydroxyl
And the monomer of unsaturated group or oligomer, the biocompatibility macromolecule of hydroxyl and polynary different
Cyanate.
The second object of the present invention is to provide a kind of constituent for making raw doctor's device.
This constituent being used for making raw doctor's device comprises above-mentioned net high-polymer, containing extremely
Few monomer of a unsaturated group, initiator and cross-linking agent, should be unsaturated containing at least one
The monomer of base is hydrophilic monomer, hydrophobic monomer or a combination of both.
The third object of the present invention is to provide a kind of raw doctor's device.
This life doctor's device is to be obtained moulding such as above-mentioned constituent.
The beneficial effects of the present invention is: utilize have special construction design prepolymer and
Reactant reacts, and can without consider under consistency problem simple prepare this have to
The net high-polymer of a few unsaturated group.This net high-polymer can owing to having at least one
The unsaturated group of reaction and possess preferably reactive, be conducive to allowing containing this netted height simultaneously
The constituent of molecule carries out moulding and allow the final raw doctor's device prepared meet application demand.
Hereinafter will be described in detail with regard to present invention:
Before address " the raw doctor device " vocabulary used below and show that one is designed to suckling
Object in animal tissue or in mammalian body fluid, is preferably used on human tissue or people
Object in pseudo body fluid.This raw doctor's device such as but not limited to: conduit, implant, support,
And Ophthalmoligic instrument [ophthalmic device, as intraocular lens, contact lens, cornea cover
Cover material (corneal onlay), glaucoma shunts (glaucoma shunt) etc.] etc..It is preferred that
This life doctor's device refers to Ophthalmoligic instrument；More preferably, this life doctor device refer to intraocular lens or
Contact lens.
Aforementioned and " unsaturated group " used hereinafter vocabulary shows containing double bond or ginseng key
Etc. carrying out the group of photopolymerization reaction, this unsaturated group such as but not limited to: thiazolinyl is (such as second
Thiazolinyl etc.) or alkynyl.
" (methyl) acrylic acid " used hereinafter word comprises methacrylic acid and propylene
Acid.Similarly, " (methyl) acrylate " word comprises methacrylate and acrylic acid
Ester.
[net high-polymer]
The net high-polymer of the present invention be by the prepolymer that end is NCO with have
It is obtained that the reactant of at least one hydroxyl and at least one unsaturated group carries out reaction.
The consumption of this prepolymer and this reactant can be according to the follow-up netted height to be prepared
The property requirements of molecule is adjusted.It is preferred that be 100 weights with the consumption of this prepolymer
Amount part, the amount ranges of this reactant is 5 to 200 weight portions.It is preferred that this prepolymerization
Thing and this reactant are to carry out under nitrogen environment the temperature range of 60～90 DEG C.Below will
Respectively each composition is illustrated:
1. end is the prepolymer of NCO
This prepolymer is to be carried out polyreaction institute in the presence of a catalyst by a parent material
Prepare.This parent material include the polysiloxanes containing C-terminal, multicomponent isocyanate and
Polyhydric alcohol.It is preferred that the weight average molecular weight scope of this prepolymer is
2000～200000.
(1-1) polysiloxanes containing C-terminal
The poly-silicon with at least one C-terminal should be represented containing the polysiloxanes of C-terminal
Oxygen alkane.It is preferred that containing polysiloxanes of C-terminal lower formula (I) structure should have:
This R1、R2、R3Each represent alkyl, hydroxyl ,-(CH2)x1OH、
-(CH2)x2(OCH2CH2)x3OH、-(CH2)x4OCH2CH(OH)(CH2)x5CH3Or
-(CH2)x6OCH2CH(OH)CH2OH, x1, x2, x3, x4, x5 and x6 are 1 to 6
Integer；
This R4Represent hydrogen, alkyl ,-(CH2)y1OH、-(CH2)y2(OCH2CH2)y3OH、
-(CH2)y4OCH2CH(OH)(CH2)y5CH3Or-(CH2)y6OCH2CH(OH)CH2OH,
Y1, y2, y3, y4, y5 and y6 are the integer of 0 to 6；
N is the integer of 1 to 100；And
Its condition is to work as R4During for alkyl, R1、R2And R3At least one of which be necessary for hydroxyl,
-(CH2)x1OH、-(CH2)x2(OCH2CH2)x3OH、
-(CH2)x4OCH2CH(OH)(CH2)x5CH3Or-(CH2)x6OCH2CH(OH)CH2OH。
It is preferred that the weight average molecular weight scope of the polysiloxanes that should contain C-terminal is
300 to 6000.The commercial goods double ends (dual end as manufactured by Gui Liguang company of SHIN-ETSU HANTOTAI
Type) type reaction siloxanes fluids KF-6001 (it has two C-terminals), Gelest produce
Product DMS series of products produce with Dow Corning silicon alcohol-group liquid (Silanol Fluid) series
Product.
(1-2) multicomponent isocyanate
This multicomponent isocyanate is the polysiloxanes containing C-terminal for this and polyhydric alcohol enters
Row reaction.It is preferred that this multicomponent isocyanate is diisocyanate；More preferably, this is polynary
Isocyanates be selected from 2,4 toluene diisocyanate (2,4-toluene diisocyanate,
2,4-TDI), 2,6-toluene di-isocyanate(TDI) (2,6-toluene diisocyanate, 2,6-TDI),
Normal hexane-1,6-diisocyanate (n-hexane-diisocyanate, 1,6-HDI), diphenyl-methane
-4,4 '-diisocyanate (diphenyl methane-4,4 '-diisocyanate, MDI), hydrogenation
'-diphenylmethane diisocyanate (hydrogenated diphenyl
Methane-4,4 '-diisocyanate, H12-MDI), different Buddhist ketone diisocyanate
(isophorone diisocyanate, IPDI) or aforesaid combination.
(1-3) polyhydric alcohol
It is preferred that this polyhydric alcohol is poly-dihydric alcohol；More preferably, this polyhydric alcohol is that straight chain type gathers
Ethylene glycol or branched chain type Polyethylene Glycol.The weight average molecular weight model of this straight chain type Polyethylene Glycol
Enclose preferably 300 to 2000.This branched chain type Polyethylene Glycol preferably can have 3,4,6 or 8
Individual branch (branched), and weight average molecular weight scope is preferably 1000 to 10000.
In this parent material, contain the gross weight of polysiloxanes of C-terminal for 100 with this
Listed as parts by weight, the amount ranges of this multicomponent isocyanate is 10 to 100 weight portions, and should
The amount ranges of polyhydric alcohol is 10 to 100 weight portions.
This parent material is by this polysiloxanes containing C-terminal, this multicomponent isocyanate
And polyhydric alcohol is obtained by mixing, and this parent material is to be polymerized in the presence of a catalyst
Reaction.This catalyst can use polyhydric alcohol to be used when reacting with multicomponent isocyanate
Catalyst.It is preferred that this catalyst is selected from dibutyl tin laurate (dibutyltin
Diaurate, DBTDL), iron chloride (FeCl3), tin octoate (stannous octoate) or three
Ethamine (triethylamine).
It is preferred that this parent material contains solvent.This solvent such as but not limited to ketone (such as first
Ethyl ketone) or esters (such as ethyl acetate).With the gross weight of this polysiloxanes containing C-terminal it is
100 listed as parts by weight, the amount ranges of this solvent is 50 to 300 weight portions.
It is preferred that the polyreaction of this parent material is at the temperature range of 60～90 DEG C and nitrogen
Carry out under compression ring border.
2. there is the reactant of at least one hydroxyl and at least one unsaturated group
This reactant is to be carried out reacting gained, this mixing material in the presence of catalyst by mixing material
Including hydroxyl and the monomer of unsaturated group or oligomer, the biocompatibility high score of hydroxyl
Son and multicomponent isocyanate.Respectively each composition will be illustrated below:
(2-1) hydroxyl and the monomer of unsaturated group or oligomer
This hydroxyl and the monomer of unsaturated group or oligomer are mainly used for having isocyanide with this
The prepolymer of perester radical reacts.It is preferred that this hydroxyl and the monomer of unsaturated group
It is selected from hydroxyalkyl (methyl) acrylate, dihydroxyalkyl (methyl) acrylate or aforesaid
Combination.
This hydroxyalkyl (methyl) acrylate is such as but not limited to (2-hydroxyethyl) metering system
Acid esters [2-hydroxyethyl methacrylate, HEMA], (2-hydroxyethyl) acrylate
[2-hydroxyethyl acrylate], (4-hydroxybutyl) acrylate [4-hydroxybutyl
Acrylate], (3-hydroxypropyl) acrylate [3-hydroxypropyl acrylate] or aforementioned
Combination.
This dihydroxyalkyl (methyl) acrylate is such as but not limited to (2,3-dihydroxypropyl) first
Base acrylate [namely glyceryl methacrylate, glycerol methacrylate,
GMA]。
This oligomer contains hydroxyl and unsaturated group, such as PEG metering system equally
Acid esters [Poly (ethylene glycol) methacrylate], its weight average molecular weight is
360～1200.
(2-2) biocompatibility macromolecule of hydroxyl
Should " biocompatibility macromolecule of hydroxyl " refer to containing at least one hydroxyl and with
Mammalian tissues or mammal fluids have the macromolecule of the compatibility；It is preferably and the mankind
Tissue or body fluid have the hydroxyl macromolecule of the compatibility.
It is preferred that the biocompatibility macromolecule of this hydroxyl is selected from polyvinyl alcohol
(polyvinyl alcohol), poly-[(2-hydroxyethyl) methacrylate]
[poly (2-hydroxyethyl) methacrylate, PHEMA], poly-[(2,3-dihydroxypropyl)
Methacrylate] [poly (2,3-dihydroxypropyl) methacrylate], (2-hydroxyl second
Base) methacrylate and N-vinyl-2-Pyrrolizidine ketone (N-vinyl-2-pyrrolidone)
Copolymer [P (HEMA-co-NVP)], (2-hydroxyethyl) methacrylate are with acrylic acid
Copolymer [P (HEMA-co-MAA)], (2-hydroxyethyl) methacrylate and N-vinyl
-2-Pyrrolizidine ketone and acrylic acid copolymer [P (HEMA-co-NVP-co-MAA)] or aforementioned
Combination.
It is preferred that the weight average molecular weight scope of the biocompatibility macromolecule of this hydroxyl
It is 1000～100000.
(2-3) multicomponent isocyanate
Multicomponent isocyanate used in this multicomponent isocyanate and this parent material can be phase
Same or different.This multicomponent isocyanate in this mixing material refers to aforesaid explanation.
In this mixing material, with this hydroxyl and the monomer of unsaturated group or the gross weight of oligomer
Being 100 listed as parts by weight, the amount ranges of the biocompatibility macromolecule of this hydroxyl is 10
To 300 weight portions, and the amount ranges of this multicomponent isocyanate is 20 to 300 weight portions.
This mixing material is by this hydroxyl and the monomer of unsaturated group or oligomer, this hydroxyl
Biocompatibility macromolecule and this multicomponent isocyanate mix and obtain.This mixing material
It is to react in the presence of a catalyst.This catalyst and the catalyst being previously mentioned are identical.
This catalyst in this mixing material refers to aforesaid explanation.
It is preferred that this mixing material contains solvent.This solvent such as but not limited to ketone (such as first and second
Ketone) or esters (such as ethyl acetate).With this hydroxyl and the monomer of unsaturated group or oligomer
Gross weight is 100 listed as parts by weight, and the amount ranges of this solvent is 50 to 1500 weight portions.
It is preferred that the reaction of this mixing material is at the temperature range of 60～90 DEG C and nitrogen environment
Under carry out.
The unsaturated group quantity of the net high-polymer of the present invention can be used for generating instead by adjustment
The consumption answering the hydroxyl in the mixing material of thing and the monomer of unsaturated group or oligomer becomes
Change, so as to higher reactivity can be represented, the most more can meet subsequent applications demand.
[for making the constituent of raw doctor's device]
This constituent being used for making raw doctor's device comprises net high-polymer as above, contains
There are the monomer of at least one unsaturated group, initiator and cross-linking agent.The constituent of the present invention is
By by net high-polymer, monomer, initiator and crosslinking containing at least one unsaturated group
Agent mixes and obtains, and the monomer that should contain at least one unsaturated group can be with this netted height
The unsaturated group of molecule reacts.Respectively each composition will be illustrated below:
[containing the monomer of at least one unsaturated group]
Hydrophilic monomer, hydrophobicity should be selected from containing the monomer of at least one unsaturated group
Monomer or a combination of both.
1. should the monomer containing at least one unsaturated group be hydrophilic monomer:
It is preferred that this hydrophilic monomer is selected from (2-hydroxyethyl) methacrylate, (2-
Hydroxyethyl) acrylate, (4-hydroxybutyl) acrylate, (3-hydroxypropyl) acrylic acid
Ester, (2,3-dihydroxypropyl) methacrylate, 3-(1,1,2,2-tetrafluoro ethyoxyl)-2-hydroxyl
Propyl methacrylate [3-(1,1,2,2-tetrafluoroethoxy)-2-hydroxypropyl
Meth-acrylate], methacrylic acid, acrylic acid, itaconic acid (itaconic acid), two
Methylamino ethylmethyl acrylate (dimethylaminoethyl methacrylate), diethyl
Amido ethylmethyl acrylate (diethylaminoethyl methacrylate), acrylamide
(acrylamide), Methacrylamide (methacrylamide), N, N '-dimethyl acryloyl
Amine (N, N'-dimethylacrylamide), N, N '-acrylamide
(N, N'-diethylacrylamide) or N-vinyl-2-Pyrrolizidine ketone
(N-vinyl-2-pyrrolidone, NVP).
It is preferred that be 100 weight portions with this net high-polymer gross weight, this hydrophilic monomer
Amount ranges is 5 to 200 weight portions.
2. should the monomer containing at least one unsaturated group be hydrophobic monomer:
It is preferred that this hydrophobic monomer is that [such as acrylic acid methyl ester., acrylic acid is different for acrylate
Propyl ester (isopropyl acrylate), Isobutyl 2-propenoate (isobutyl acrylate), acrylic acid
Stearyl (octadecyl acrylate) etc.], methacrylate [such as methacrylic acid
Methyl ester, ethyl methacrylate (ethyl methacrylate), butyl methacrylate (butyl
Methacrylate), isobutyl methacrylate (isobutyl methacrylate), metering system
The own ester of acid (hexylmethacrylate), isodecyl methacrylate
(isodecylmethacrylate), lauryl methacrylate (lauryl methacrylate), first
Base phenyl acrylate (phenyl methacrylate) etc.], or a combination of both.It is preferred that with
This net high-polymer gross weight is 100 weight portions, the amount ranges of this hydrophobic monomer be 5 to
300 weight portions.
[initiator]
This initiator can use any contribute to allowing there is radical reaction between unsaturated group
Initiator.It is preferred that this initiator is selected from bis oxide (2,4,6-trimethylbenzoyl)
Phenylphosphine [bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, commercially available business
Product IRGACURE 819, benzoin ethyl ether (benzoin ethyl as manufactured by BASF AG
Ether), base dimethyl ketal (benzyl dimethyl ketal), α, α-diethoxybenzene second
Ketone (α, α-diethoxyacetophenone), 2-hydroxy-2-methyl propiophenone
(2-hydroxy-2-methylpropiophenone, commercial goods is as manufactured by Ciba company
Darocure 1173), or aforesaid combination.
[cross-linking agent]
This cross-linking agent can use any cross-linking agent for preparing contact lens, and can foundation
The monomer or the prepolymer that are used select.It is preferred that this cross-linking agent is selected from second
Diol dimethacrylate (ethylene glycol dimethacrylate, EGDMA), two
Ethylene glycol dimethacrylate (diethylene glycol dimethacrylate), TEG
Dimethylacrylate (tetraethylene glycol dimethacrylate), Polyethylene Glycol diformazan
Base acrylate (polyethylene glycol dimethacrylate), trimethylolpropane tris first
Base acrylate (trimethylolpropane trimethacrylate, TMPTMA), Ji Wusi
Alcohol tetramethyl acrylate (penterythritol tetramethacrylate), bisphenol-A dimethyl
Acrylate (bisphenol A dimethacrylate), vinyl methacrylate (vinyl
Or aforesaid combination methacrylate).
In the constituent of the present invention, this net high-polymer, should be unsaturated containing at least one
The consumption of the monomer of base, this initiator and this cross-linking agent can be according to the follow-up raw doctor to be prepared
Device is adjusted.It is preferred that be 100 weight portions with the gross weight of this net high-polymer, should
Amount ranges containing at least one unsaturated group is 5 to 300 weight portions, this initiator
Amount ranges is 0.01 to 5 weight portion, and the amount ranges of this cross-linking agent is 0.01 to 3
Weight portion.
[other compositions]
It is preferred that this constituent being used for making raw doctor's device also comprises UV absorbent.
This UV absorbent is such as but not limited to benzophenone, 2-(2-hydroxy-5-methyl base acryloyl-oxy
Base ethylphenyl)-2H-benzotriazole
[2-(2-hydroxy-5-methacryloxyethylphenyl)-2H-benzo-triazole], benzo
Triazole (Benzotriazole, BTA), 2-dihydroxy benaophenonel
(2-hydroxy-benzophenone), 2-(4-benzoyl-3-hydroxyphenoxy) acrylic acid second
Ester [2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate], 4-methacryloxypropyl
Base-2-dihydroxy benaophenonel (4-methacryloxy-2-hydroxybenzophenone) etc..Relatively
Goodly, it is 100 weight portions with this net high-polymer gross weight, the consumption of this UV absorbent
Scope is 0.01 to 5 weight portion.
It is preferred that this constituent being used for making raw doctor's device also comprises dyestuff or pigment.Should
Dyestuff or pigment are required to be the pigment (or dyestuff) that Food and Drug Administration checks and approves, pigment example
Such as, but not limited to: carbazole violet (Carbazole violet), phthalocyanine green (Phthalocyanine
Green), titanium dioxide (Titanium oxide), chromium oxide cobalt aluminum
(Chromium-cobalt-aluminum oxide), chrome oxide green (Chromium oxide
Green), ferrum oxide (Iron oxide), phthalocyanine copper (Phthalocyaninato (II) copper),
C.I. pigment Violet 23, C.I. alizarol saphirol 36 etc..Dyestuff is such as but not limited to C.I. response type Fructus Citri tangerinae
78, C.I. response type Huang 86, C.I. response type Huang 15, C.I. response type be red 11, C.I. reaction
Type is red 180, C.I. solvent blue 19 01 (C.I.solvent blue 101；Entitled Isosorbide-5-Nitrae-the Bis [(2 of chemistry
Methylphenyl) amino]-9,10-anthracenedione), C.I. response type indigo plant 246,
C.I. response type indigo plant 19, C.I. reduction Fructus Citri tangerinae 1 (C.I.vat orange 1), C.I. Vat brown 1 (C.I.
Vat brown 1), C.I. vat yellow 3 (C.I.vat yellow 3), C.I. reductive blue 6 (C.I.vat
Blue 6), C.I. vat green 1 (C.I.vat green 1), C.I. solvent yellow 18, C.I. reduce Fructus Citri tangerinae
5 (C.I.vat orange 5) etc., aforesaid pigment or dyestuff can be used alone or mix and make
With.It is preferred that be 100 weight portions with this net high-polymer gross weight, this pigment and dyestuff
Total amount ranges is 0.01 to 2 weight portion.
It is preferred that this constituent being used for making raw doctor's device also comprises solvent.This solvent example
Such as, but not limited to, alcohols (such as ethanol) or esters (such as ethyl acetate).It is preferred that with this netted height
Molecule gross weight is 100 weight portions, and the amount ranges of this solvent is 5 to 200 weight portions.
[raw doctor's device]
It is preferred that this life doctor's device is Ophthalmoligic instrument；More preferably, this raw doctor's device is stealthy
Glasses or intraocular lens.
This life doctor's device be the above-mentioned constituent for making raw doctor's device is moulded and
?.It is preferred that this life doctor's device is by being positioned in mould by this constituent, the most again
It is polymerized under ultraviolet light irradiates, and removes this mould and prepare.
When this life doctor's device is contact lens, this constituent comprises this net high-polymer, is somebody's turn to do
Hydrophilic monomer, this initiator and this cross-linking agent, the most also comprise ultra-violet absorption
Agent and pigment or dyestuff etc..
When this life doctor device be intraocular lens time, this constituent comprise this net high-polymer,
This hydrophobic monomer, this initiator and this cross-linking agent, the most also comprise ultraviolet and inhale
Receive agent and pigment or dyestuff etc..
Accompanying drawing explanation
Nothing
Detailed description of the invention
The present invention will be described further with regard to following example, however, it should be noted that this enforcement
Example is only the purposes illustrated, and is not necessarily to be construed as the restriction that the present invention implements.
The preparation of [embodiment 1] net high-polymer A
1. the preparation of parent material: by the polysiloxanes (letter containing C-terminal of 100 weight portions
Manufactured by Yue Guiliguang company, model is KF-6001, and weight average molecular weight is
1810), different Buddhist ketone diisocyanate (multicomponent isocyanate) of 24.6 weight portions, 21.2
The Polyethylene Glycol (PEG-1000, weight average molecular weight is 1000) of weight portion and 100.7
The butanone (solvent) of weight portion is stirred mixing and prepares parent material.
2. the preparation of prepolymer: add the tin dilaurate of 0.08 weight portion in this parent material
Dibutyl tin, then carries out polyreaction 2 little at 85 DEG C of temperature and nitrogen environment
Shi Hou, and prepare prepolymer.
3. mix the preparation of material: (weight is put down by the polyethylene glycol methacrylate-styrene polymer of 100 weight portions
Average molecular weight is 360, namely hydroxyl and the oligomer of unsaturated group), 51 weight
Different Buddhist ketone diisocyanate (multicomponent isocyanate) of part, the poly-[(2-of 39.7 weight portions
Hydroxyethyl) methacrylate] (weight average molecular weight is 15000, namely contains
The biocompatibility macromolecule of hydroxyl) and the butanone (solvent) of 228.3 weight portions carry out
Stirring mixes and obtains this mixing material.
4. the preparation of reactant: the dibutyl tin laurate of 0.37 weight portion is added this mixing
In material, after then carrying out polyreaction 2 hours at 85 DEG C of temperature and nitrogen environment,
Prepare reactant.
5. the preparation of net high-polymer A: by prepolymer and 25 weight portions of 100 weight portions
Reactant mixes, and then carries out reacting 2 at 85 DEG C of temperature and nitrogen environment
After hour, then solvent is removed, prepared net high-polymer A.
The preparation of [embodiment 2] net high-polymer B
1. the preparation of parent material: by the polysiloxanes (letter containing C-terminal of 100 weight portions
Manufactured by Yue Guiliguang company, model is KF-6001, and weight average molecular weight is
1810), different Buddhist ketone diisocyanate (multicomponent isocyanate) of 24.6 weight portions, 21.2
The Polyethylene Glycol (PEG-1000, weight average molecular weight is 1000) of weight portion and 100.7
The butanone (solvent) of weight portion is stirred mixing and prepares parent material.
2. the preparation of prepolymer: add the tin dilaurate of 0.08 weight portion in this parent material
Dibutyl tin, then carries out polyreaction 2 little at 85 DEG C of temperature and nitrogen environment
Shi Hou, prepares prepolymer.
3. mix the preparation of material: methacrylate is (also by (the 2-hydroxyethyl) of 100 weight portions
Be exactly hydroxyl and the monomer of unsaturated group or oligomer), the different Buddhist of 162.3 weight portions
Ketone diisocyanate (multicomponent isocyanate), poly-[(the 2-hydroxyethyl) of 126.1 weight portions
Methacrylate] (weight average molecular weight is 15000, namely the biology of hydroxyl
Compatible polymer) and the butanone (solvent) of 724.6 weight portions be stirred mixing and
Obtain this mixing material.
4. the preparation of reactant: the dibutyl tin laurate of 1.16 weight portions is added this mixing
In material, after then carrying out polyreaction 2 hours at 85 DEG C of temperature and nitrogen environment,
Prepare reactant.
5. the preparation of net high-polymer B: by prepolymer and 10 weight portions of 100 weight portions
Reactant mixes, and then carries out reacting 2 at 85 DEG C of temperature and nitrogen environment
After hour, then solvent is removed, prepared net high-polymer B.
[application examples 1] constituent and the preparation of contact lens
1. the preparation of constituent: by the net high-polymer obtained by the embodiment 1 of 100 weight portions
A, 81.8 weight portions hydrophilic monomer [by the N of 50.9 weight portions, N '-dimethyl
Acrylamide, the N-vinyl-2-Pyrrolizidine ketone of 21.8 weight portions and 9.1 weight portions
(2-hydroxyethyl) methacrylate is formed], the solvent (ethanol) of 18.2 weight portions,
The cross-linking agent (ethylene glycol dimethacrylate) of 0.91 weight portion, 1.09 weight portions
Initiator is (by Darocure 1173 and 0.18 weight portion of 0.91 weight portion
IRGACURE 819 is formed), the UV absorbent of 1.81 weight portions is [by 0.45
2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate of weight portion and 1.36 weight
4-methacryloxy-2-the dihydroxy benaophenonel of part is formed] and 0.02 weight portion
Dyestuff (C.I. response type indigo plant 19) be stirred mixing, it is thus achieved that constituent.
2. the preparation of contact lens: above-mentioned constituent is put into for forming contact lens
In mould (material is polypropylene, the combination of concave-convex mold), then at the purple of wavelength 380nm
(exposure rate is 3mW/cm to the irradiation of outer light2, irradiation time is about 20 minutes) under enter
Row curing molding, and on mould, form contact lens.Finally contact lens is taken out,
Then carry out extracting and purification with the alcohol water blend of concentration 70wt%, then insert physiology
Saline solution preserves.
[comparing application examples 1] constituent and the preparation of contact lens
1. the preparation of constituent: except this net high-polymer A is replaced into commercially available siliceous giant molecule
(the siloxanes giant molecule manufactured by Gui Liguang company of SHIN-ETSU HANTOTAI, model is X-22-164A),
Remaining composition, ratio and preparation process are all prepared identical with the constituent of application examples 1,
Step also according to application examples 1 carries out the preparation of constituent.
2. the preparation of contact lens: according to the contact lens preparation process of application examples 1, the most also
Prepared contact lens is inserted in normal saline solution and preserve.
[test]
Respectively by application examples 1 and compare the contact lens of application examples 1 and carry out following test:
1. moisture content (%) test: contact lens is taken out, removes the normal saline solution of lens surface
And carry out weighing and obtain weight in wet base.Then put into contact lens in 60 DEG C of baking ovens
Row is dried 24 hours, then carries out weighing and obtain dry weight.Last according to following formula meter
Calculate moisture content.The moisture content of general silicon glue contact lens is about 30～50%.
2. oxygen permeating amount [equivalent (barrer)] test: with reference to polarographic technique.Typically
The oxygen permeating amount of silicon glue contact lens is about 60～180 equivalents.
3. contact angle (spending) test: contact lens takes out and wipes the normal saline solution on dry surface,
Obtain the contact lens of a dry tack free.Then, the contact lens of dry tack free is put
It is placed in CA-XP 150 type contact angle instrument and tests.
Result obtained by above-mentioned every test arranges in table 1 below.
Table 1
| Moisture content (%) | Oxygen permeating amount (equivalent) | Contact angle (is spent) | |
| Application examples 1 | 45±2 | 82 | 35 |
| Relatively application examples 1 | 33±2 | 145 | 79 |
[result]
Can find from table 1, application examples 1 has higher moisture content and less contact angle,
Display is compared to comparing application examples 1, and the contact lens of application examples 1 has preferably hydrophilic.
Application examples 1 with in the oxygen permeating amount comparing application examples 1 the most in the industry cycle tolerance interval.
Provable by the above results: the constituent that this case contains net high-polymer can prepare to be had
Preferably hydrophilic nmature and the contact lens of moisture content.
[application examples 2] constituent and the preparation of intraocular lens
1. the preparation of constituent: by 100 weight portions by the netted high score obtained by embodiment 2
Sub-B, 100 weight portions hydrophobic monomer (by 50 weight portions acrylic acid methyl ester. and
The methyl methacrylate of 50 weight portions is formed), the cross-linking agent (second two of 2 weight portions
Alcohol dimethylacrylate), the initiator of 1.8 weight portions is (by 1.4 weight portions
The IRGACURE 819 of Darocure 1173 and 0.4 weight portion is formed), 2.0 weights
The UV absorbent of amount part is (by the 2-(4-benzoyl-3-hydroxy benzenes of 0.5 weight portion
Epoxide) ethyl acrylate and the 4-methacryloxy-2-hydroxyl two of 1.5 weight portions
Benzophenone is formed) and the dyestuff (C.I. response type Huang 15) of 0.02 weight portion be stirred
Mixing, it is thus achieved that constituent.
2. the preparation of intraocular lens: first preparation one is made up of upper mould piece and lower module
Plastic mould, then pours in the lower module of this plastic mould by above-mentioned constituent,
Again upper mould piece is covered on this lower module and wavelength 380nm ultraviolet light irradiate
(exposure rate is 3mW/cm2, irradiation time is about 30 minutes) under carry out revolve mould become
Type.Upper mould piece is removed, takes out intraocular lens blank, then by this intraocular lens
Blank carries out the extraction of 6 hours with isopropanol, then enters with the pure water of temperature 90 DEG C
The row extraction of 24 hours, and intraocular lens (a diameter of 8.6mm, center can be prepared
Thickness is 1.05mm, and the curvature of acute angle is 0.06mm).
[test]
In addition to carrying out water cut test according to aforementioned 1st, separately utilize refractive index measurement instrument
Carry out refraction index test.Test result such as table 2 below:
Table 2
| Moisture content (%) | Refractive index | |
| Application examples 2 | ＜ 3 | 1.512 |
By in table 2, it was demonstrated that this case constituent can successfully prepare the people meeting industry demand really
Work crystalline lens.
In sum, the present invention utilizes prepolymer that special construction designs and reactant to carry out
Reaction, and prepare and there is the most reactive and the preferably compatibility net high-polymer, have simultaneously
It is beneficial to allow the constituent containing this net high-polymer be moulded and to obtain and meets subsequent applications need
The raw doctor's device asked, therefore really can reach the purpose of the present invention.
Claims (12)
1. a net high-polymer, it is characterised in that: it is to be the pre-of NCO by end
Polymer and the reactant with at least one hydroxyl and at least one unsaturated group are carried out
Reaction is obtained；
This prepolymer is to be carried out polyreaction in the presence of catalyst by parent material
Gained, this parent material includes the polysiloxanes containing C-terminal, polynary Carbimide.
Ester and polyhydric alcohol；And
This reactant is to be carried out reacting gained in the presence of catalyst by mixing material, and this mixes
Close material and include hydroxyl and the monomer of unsaturated group or oligomer, the biofacies of hydroxyl
Capacitive macromolecule and multicomponent isocyanate.
Net high-polymer the most according to claim 1, it is characterised in that: this prepolymer
Weight average molecular weight scope be 2000～200000.
Net high-polymer the most according to claim 1, it is characterised in that: should be containing hydroxyl
The consumption of the polysiloxanes of end is 100 weight portions, the consumption of this multicomponent isocyanate
Scope is 10 to 100 weight portions, and the amount ranges of this polyhydric alcohol is 10 to 100
Weight portion.
Net high-polymer the most according to claim 1, it is characterised in that: this hydroxyl and
The monomer of unsaturated group is selected from hydroxyalkyl (methyl) acrylate, dihydroxyalkyl (first
Base) acrylate or aforesaid combination.
Net high-polymer the most according to claim 1, it is characterised in that: this hydroxyl and
The oligomer of unsaturated group is PEG methacrylate.
Net high-polymer the most according to claim 1, it is characterised in that: this hydroxyl
Biocompatibility macromolecule is selected from polyvinyl alcohol, poly-[(2-hydroxyethyl) methyl-prop
Olefin(e) acid ester], poly-[(2,3-dihydroxypropyl) methacrylate], (2-hydroxyethyl)
Methacrylate and the copolymer of N-vinyl-2-Pyrrolizidine ketone, (2-hydroxyethyl)
Methacrylate and acrylic acid copolymer, (2-hydroxyethyl) methacrylate and
N-vinyl-2-Pyrrolizidine ketone and acrylic acid copolymer or aforesaid combination.
Net high-polymer the most according to claim 1, it is characterised in that: this hydroxyl
The weight average molecular weight scope of biocompatibility macromolecule is 1000 to 100000.
8. the constituent curing device for making life, it is characterised in that: it comprises according to power
Profit require the net high-polymer described in 1, monomer containing at least one unsaturated group,
Initiator and cross-linking agent, should the monomer containing at least one unsaturated group be hydrophilic list
Body, hydrophobic monomer or a combination of both.
Constituent for making raw doctor's device the most according to claim 8, its feature exists
In: should the monomer containing at least one unsaturated group be hydrophilic monomer, this hydrophilic
Monomer is selected from (2-hydroxyethyl) methacrylate, (2-hydroxyethyl) acrylic acid
Ester, (4-hydroxybutyl) acrylate, (3-hydroxypropyl) acrylate, (2,3-dihydroxy
Base propyl group) methacrylate, 3-(1,1,2,2-tetrafluoro ethyoxyl)-2-hydroxypropylmethyl
Acrylate, methacrylic acid, acrylic acid, itaconic acid, dimethylamino ethyl methyl
Acrylate, diethylin ethylmethyl acrylate, acrylamide, metering system
Amide, N, N '-dimethyl acrylamide, N, N '-acrylamide or N-ethylene
Base-2-Pyrrolizidine ketone.
Constituent for making raw doctor's device the most according to claim 8, its feature exists
In: should the monomer containing at least one unsaturated group be hydrophobic monomer, this hydrophobicity
Monomer is selected from acrylate, methacrylate or a combination of both.
11. constituents for making raw doctor's device according to claim 8, its feature exists
In: it is 100 listed as parts by weight with the gross weight of this net high-polymer, should be containing at least one
The amount ranges of the monomer of individual unsaturated group is 5 to 300 weight portions.
12. 1 kinds of raw doctor's devices, it is characterised in that: it is by use according to claim 8
Moulded in the constituent making raw doctor's device and obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510116575.4A CN106032400A (en) | 2015-03-17 | 2015-03-17 | Network polymer, composition for producing biomedical apparatus, and biomedical apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510116575.4A CN106032400A (en) | 2015-03-17 | 2015-03-17 | Network polymer, composition for producing biomedical apparatus, and biomedical apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106032400A true CN106032400A (en) | 2016-10-19 |
Family
ID=57150782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510116575.4A Pending CN106032400A (en) | 2015-03-17 | 2015-03-17 | Network polymer, composition for producing biomedical apparatus, and biomedical apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106032400A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032174A (en) * | 1987-09-25 | 1989-04-05 | 山东大学 | The preparation of polyurethane-polysiloxane line-type block polymer and application |
| CN1186550A (en) * | 1995-05-19 | 1998-07-01 | 诺瓦提斯公司 | Polysiloxane polyhydric alcohol large molecule monomer, its manufacture and use |
| US6313254B1 (en) * | 1996-09-23 | 2001-11-06 | Cardiac Crc Nominees Pty Ltd | Polysiloxane-containing polyurethane elastomeric compositions |
| TW479149B (en) * | 1998-08-12 | 2002-03-11 | Innova Vision Inc | Method for coloring lens of contact lens and lens thereof |
| CN101065157A (en) * | 2004-09-30 | 2007-10-31 | 庄臣及庄臣视力保护公司 | Biomedical devices containing amphiphilic block copolymers |
| CN101137691A (en) * | 2004-12-29 | 2008-03-05 | 博士伦公司 | Hydrogel copolymers for biomedical devices |
| CN102499696A (en) * | 2011-09-23 | 2012-06-20 | 长沙三诺生物传感技术股份有限公司 | Biological enzyme sensor capable of being implanted into human body and production method thereof |
-
2015
- 2015-03-17 CN CN201510116575.4A patent/CN106032400A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032174A (en) * | 1987-09-25 | 1989-04-05 | 山东大学 | The preparation of polyurethane-polysiloxane line-type block polymer and application |
| CN1186550A (en) * | 1995-05-19 | 1998-07-01 | 诺瓦提斯公司 | Polysiloxane polyhydric alcohol large molecule monomer, its manufacture and use |
| US6313254B1 (en) * | 1996-09-23 | 2001-11-06 | Cardiac Crc Nominees Pty Ltd | Polysiloxane-containing polyurethane elastomeric compositions |
| TW479149B (en) * | 1998-08-12 | 2002-03-11 | Innova Vision Inc | Method for coloring lens of contact lens and lens thereof |
| CN101065157A (en) * | 2004-09-30 | 2007-10-31 | 庄臣及庄臣视力保护公司 | Biomedical devices containing amphiphilic block copolymers |
| CN101137691A (en) * | 2004-12-29 | 2008-03-05 | 博士伦公司 | Hydrogel copolymers for biomedical devices |
| CN102499696A (en) * | 2011-09-23 | 2012-06-20 | 长沙三诺生物传感技术股份有限公司 | Biological enzyme sensor capable of being implanted into human body and production method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2017252590B2 (en) | Silicone elastomer-hydrogel hybrid contact lenses | |
| CN101765494B (en) | Method for producing plastic lens | |
| CN103168067B (en) | Can the silicone-containing prepolymer and uses thereof of water treatment | |
| CN101641615B (en) | Silicone-containing prepolymers with dangling hydrophilic polymeric chains | |
| CN103969706B (en) | Lens forming composition suitable for manufacturing silicone hydrogel contact lens | |
| EP0907668B1 (en) | Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom | |
| US20050113549A1 (en) | Crosslinkable polyurea prepolymers | |
| EP1817362B1 (en) | Crosslinkable poly(oxyalkylene)-containing polyamide prepolymers | |
| CN102498431A (en) | Prepolymers suitable for making ultra-violet absorbing contact lenses | |
| JPH02502676A (en) | Hydrophilic tinted contact lenses | |
| JP2008503368A (en) | Silicone crosslinking | |
| CN103597378A (en) | Silicone hydrogel lenses with nano-textured surfaces | |
| CN104125969B (en) | Polysiloxanes group block copolymer | |
| JP6351385B2 (en) | Contact lens manufacturing method | |
| CN110494519A (en) | Organosilicon, composition through ion modification and the medical equipment formed by it | |
| TWI694122B (en) | A colorant composition for colored silicone hydrogel contact lens, a colored silicone hydrogel contact lens comprising the same and a method of modifying a colorant for a colored silicone hydrogel contact lens | |
| CN106033150B (en) | Composite contact lens | |
| TWI521020B (en) | Mesh polymer, used in the production of medical equipment and medical equipment | |
| CN106032400A (en) | Network polymer, composition for producing biomedical apparatus, and biomedical apparatus | |
| KR20210009257A (en) | Contact lenses for blocking blue light and methods of manufacturing the same | |
| TW201831924A (en) | Eye lens, intraocular lens and method for manufacturing eye lens | |
| TWI571670B (en) | Composite contact lenses | |
| CN102690419B (en) | Silicon-containing prepolymer and silicone hydrogel biomaterial containing same | |
| TWI786836B (en) | Anti-blue light contact lens and material and method for manufacturing the same | |
| JP6351384B2 (en) | Contact lens and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161019 |
|
| WD01 | Invention patent application deemed withdrawn after publication |