CN113248719B - Single-end-capped organic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method - Google Patents
Single-end-capped organic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method Download PDFInfo
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Abstract
The invention discloses a single-end-capped organic siloxane oligomer which is well mixed with various hydrophilic monomers under the condition of no solvent-assisted dissolution, overcomes the problem that the organic siloxane oligomer and the hydrophilic monomers are difficult to dissolve mutually, and can prepare a silicon hydrogel material with high oxygen permeability and high hydrophilicity. The invention also provides a silicon hydrogel which is formed by polymerizing the single-end-capped organic siloxane oligomer, hydrophilic monomers and the like, and a solvent is not added in the formula of the silicon hydrogel, so that the silicon hydrogel is beneficial to large-scale industrial production; and the addition proportion of the organic siloxane oligomer in the silicon hydrogel is large, so that the silicon hydrogel has high oxygen permeability, and simultaneously, the high hydrophilicity and flexibility of the gel are maintained. The invention also provides a corneal contact lens which is prepared from the silicon hydrogel material and has the advantages of high oxygen permeability, strong hydrophilicity, good light transmittance, less lipid deposition, good flexibility, comfortable wearing and the like.
Description
Technical Field
The invention relates to a single-end-capped organic siloxane oligomer, silicon hydrogel, a corneal contact lens and a preparation method thereof, belonging to the field of preparation of contact lens materials.
Background
Contact lenses, also known as contact lenses, are lenses that are worn directly on the eye of a person to correct vision. Compared with the common glasses, the contact lenses have the characteristics of convenience, attractiveness, comfort and the like. Contact lenses can be classified into hard contact lenses and soft contact lenses. Hard contact lenses have disadvantages such as being hard in material and poor in wettability, and therefore tend to cause discomfort to the eyeball when worn. The soft corneal contact lens has good chemical stability, light transmission, biocompatibility, ion permeability and mechanical property, and is more comfortable to wear.
In the development history of the soft contact lens industry, hydrogel materials prepared from acrylic acid were the first to appear, and in the 20 th 70 th century, hydrogels based on poly (2-hydroxyethyl methacrylate) (HEMA) and other hydrophilic polymers were introduced as materials to meet the requirements of gas transport and mechanical operability of contact lenses. However, these polymers are essentially impermeable to oxygen and only allow oxygen to be transferred through the water molecules swollen therein, resulting in low oxygen permeability.
The oxygen permeability of the material in the field of corneal contact lenses is high, if oxygen cannot be normally supplied in the wearing process of the contact lenses, the cornea is lack of oxygen, and the problems of corneal epithelium thinning, dry eyes and the like can be caused by insufficient oxygen supply for a long time. In order to solve the problem of oxygen supply, attempts have been made to improve the oxygen permeability of hydrogels by increasing the water content thereof in the early stage. But the components of the conventional hydrogel are not changed, the water content is simply improved, the oxygen permeability value can only reach 40 barrers to the maximum, and although the requirements of partial biomedicine fields can be met, the application of products such as corneal contact lenses which have higher requirements on oxygen permeability still has limitations.
With the progress of research, many materials with high oxygen permeability are discovered, wherein the silicon-containing polymer material has the advantages of extremely high oxygen permeability, good mechanical property and biocompatibility, safety, environmental protection and the like, but the surface of the material is hydrophobic, and can adhere to lipid and protein when being applied to biological tissues, so that the material has harm in long-term use. Since there is a complementation between the properties of this material and the hydrogel material, researchers have attempted to modify the composition of hydrogels and combine them with highly oxygen permeable materials to improve their oxygen permeability. Based on good air permeability and biocompatibility of the silicon-containing polymer, the silicon-containing polymer and the silicon-containing polymer are combined to form silicon hydrogel with good comprehensive performance, the oxygen permeability of the material is determined by the siloxane part of the silicon-containing hydrogel, and the abrasion between the material and tissues can be reduced by the hydrogel part, so that the comfort is improved. Based on the unique performance advantages of the silica hydrogel, the silica hydrogel has wide application prospect in the field of corneal contact lenses.
Silicone hydrogel lenses are generally made by copolymerizing silicone monomers and hydrophilic monomers, and usually contain one or more than two small molecular weight silicone monomers or silicone oligomers of greater molecular weight. Small molecule organosilicon monomers such as methacryloxypropyltris (trimethylsiloxy) silane (TRIS), 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane (SIGMA) and the like have good hydrophilicity and good compatibility with hydrophilic monomers, but have a limited effect of improving the oxygen permeability of the material. The organic silicon oligomer with larger molecular weight is generally obtained by grafting a reactive functional group on Polydimethylsiloxane (PDMS) and is copolymerized with a hydrophilic monomer, so that the oxygen permeability of the material can be effectively improved. However, since PDMS has high hydrophobicity, poor compatibility with hydrophilic monomers and limited addition amount, the improvement of the oxygen permeability of the material is limited; and the obtained silicon hydrogel has stronger surface hydrophobicity, which influences the wearing comfort of the lens.
In addition, since PDMS has a low surface energy and is hydrophobic, silicon-containing groups are easily migrated to the surface of the silicon hydrogel after polymerization of the silicone monomer and the hydrophilic monomer, resulting in higher lipid adsorption. The lens with high lipid adsorption easily causes blurred vision, reduces wearing comfort, and also causes inflammation after long-term wearing.
Therefore, it is one of the technical problems to be solved by those skilled in the art to develop an effective organosiloxane oligomer for preparing a silicone hydrogel lens with high oxygen permeability, high hydrophilicity and anti-lipid precipitation property.
Disclosure of Invention
The invention aims to provide a single-end-capped organic siloxane oligomer which is well mutually soluble with a plurality of hydrophilic monomers under the condition of no solvent-assisted dissolution and can be used for preparing a silicon hydrogel lens with high oxygen permeability, high hydrophilicity and low lipid adsorption rate; meanwhile, the silicon hydrogel material and the corneal contact lens have good oxygen permeability, light transmittance and lipid precipitation resistance, and are strong in hydrophilicity, good in flexibility and comfortable to wear.
The invention provides a single-end-capped organic siloxane oligomer which has a structure shown as a formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1).
The invention also provides a preparation method of the single-end-capped organic siloxane oligomer, which comprises the following steps: under the action of a catalyst, in the temperature range of 20-90 ℃, the monohydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer shown in the formula (I).
The single-end-capped organic siloxane oligomer is used for preparing silicon hydrogel and a corneal contact lens.
On the other hand, the invention also provides a silicon hydrogel which comprises the single-end-capped organic siloxane oligomer and the following components in parts by mass and is prepared through polymerization reaction:
5 to 55 portions of single-end-capping organic siloxane oligomer of the formula (I),
0 to 30 parts of micromolecular silicon monomer,
15 to 70 parts of hydrophilic monomer,
an initiator and a crosslinking agent;
wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecular silicon monomer and the weight of the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
According to a particular but non-limiting embodiment of the invention, the mass fraction of the mono-end-capped organosiloxane oligomer of formula (I) is between 30 and 55 parts.
According to a specific but non-limiting embodiment of the present invention, the small molecule silicon monomer is one or any combination of methacryloxymethyltris (trimethylsiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, gamma-aminopropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane.
According to a specific but non-limiting embodiment of the invention, the hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, vinyl cyclohexane amide, polyether methacrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-dimethylacrylamide, N-vinyl acetamide and N-vinyl methyl acetamide.
According to a particular but non-limiting embodiment of the invention, the initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone and 2,4,6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide;
the cross-linking agent is at least one of triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinyl polyethylene glycol ether and trimethylolpropane trimethacrylate.
The invention also provides a corneal contact lens which is prepared from the silicon hydrogel.
Meanwhile, the invention also provides a preparation method of the corneal contact lens, which comprises the following steps: uniformly mixing 5-55 parts of single-end-capped organic siloxane oligomer shown in the formula (I), 0-30 parts of micromolecule silicon monomer, 15-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mould, carrying out polymerization and curing under photo-initiation or thermal initiation, and hydrating to obtain the corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecular silicon monomer and the weight of the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
The invention has the following beneficial effects:
1. the single-end-capped organic siloxane oligomer has excellent hydrophilicity, is well dissolved with the hydrophilic monomer, effectively solves the problem that the organic siloxane oligomer and the hydrophilic monomer are difficult to dissolve with each other, can be added into the silicone hydrogel in a large proportion under the condition of not needing a dissolving assisting solvent, greatly improves the addition amount of the organic siloxane oligomer, and obviously improves the oxygen permeability of the silicone hydrogel, so that the prepared silicone hydrogel material has high hydrophilicity, high oxygen permeability and good light transmittance.
2. The silicon hydrogel disclosed by the invention is free of solvent in the formula, is beneficial to large-scale industrial production, not only reduces the production cost and reduces the environmental pollution, but also more importantly, avoids the volatilization of a large amount of solvent in the process of preparing the lens by polymerizing the mixed monomer, and reduces the health hazard to operators and the risks of serious accidents such as explosion and combustion.
3. The silicon hydrogel material prepared by the invention has good oxygen permeability and light transmittance, maintains the high hydrophilicity and flexibility of the gel, and has good lipid precipitation resistance.
4. The cornea contact lens prepared by the invention has the advantages of high oxygen permeability, high water content, good lipid precipitation resistance and the like, is comfortable to wear, has good flexibility, can reduce the incidence of ophthalmic diseases caused by oxygen deficiency due to high oxygen permeability, and is beneficial to eye health.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a single end-capped organosiloxane oligomer prepared in example 1.
Detailed Description
The following specific embodiments are provided to further illustrate the present invention, but the present invention is not limited to only the following embodiments.
The inventor of the application finds through experiments that when the polyether chain segment is connected with the polysiloxane long chain, the synthesized organic siloxane oligomer has better hydrophilicity and good intersolubility with hydrophilic monomers, and can be added into the silicone hydrogel in a large proportion, so that the addition of the organic siloxane oligomer is greatly improved, and the oxygen permeability of the silicone hydrogel material is remarkably improved. Usually, the organic siloxane oligomer can be well dissolved with hydrophilic monomers under the participation of a cosolvent, however, the single-end-capped organic siloxane oligomer synthesized by the invention has excellent hydrophilic performance and can be well mixed with various hydrophilic monomers without solvent dissolution assistance, so that no solvent is added in the formula of the silicon hydrogel, and the use of the solvent is avoided, thereby being beneficial to large-scale industrial production, and the beneficial effect of the invention is very obvious. The single-end-capped organic siloxane oligomer structure provided by the invention and the silicon hydrogel prepared from the single-end-capped organic siloxane oligomer structure are not reported in documents at present.
The invention provides a single-end-capped organic siloxane oligomer which has a structure shown as a formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1). Preferably, m is an integer ranging from 8 to 15, and n is an integer ranging from 20 to 60.
The above-described mono-end-capped organosiloxane oligomers of formula (I) are block copolymers in which the long polysiloxane chains (1) give the material good oxygen permeability and the polyether segments (2) and the end-grafted amide and methacrylate groups (3) provide good hydrophilicity. Experiments show that when the polyether chain segment (2) is connected with the polysiloxane long chain (1), the synthesized polymer has better hydrophilicity and good mutual solubility with hydrophilic monomers, the problem that organic siloxane oligomers and hydrophilic monomers are difficult to mutually dissolve is solved, the organic siloxane oligomers can be added into the silicone hydrogel in a large proportion under the condition of no need of a dissolving assisting solvent, the addition amount of the organic siloxane oligomers is greatly increased, and the oxygen permeability and the light transmittance of the silicone hydrogel material are remarkably improved. Moreover, the polyether chain segment (2) is connected with the polysiloxane long chain (1) so as to be beneficial to improving the anti-lipid precipitation performance of the silicon hydrogel material, and experiments show that the prepared silicon hydrogel lens has lower lipid adsorption when the polyether chain segment and the polysiloxane long chain are connected.
The mono-end-blocked organosiloxane oligomers of the formula (I) can be prepared by the following process:
under the action of a catalyst, in a temperature range of 20-90 ℃, monohydroxy terminated polyether modified polydimethylsiloxane (HO-PDMS) firstly reacts with isophorone diisocyanate (IPDI) to generate an IPDI terminated intermediate product, and then hydroxyethyl methacrylate (HEMA) is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer. Wherein the catalyst is dibutyltin dilaurate. HO-PDMS reacts with IPDI and HEMA in equal proportion.
Wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1).
Further, the invention provides a silicon hydrogel which comprises the following components in parts by mass and is prepared through polymerization reaction:
5 to 55 portions of single-end-capping organic siloxane oligomer of the formula (I),
0 to 30 parts of micromolecular silicon monomer,
15 to 70 parts of hydrophilic monomer,
an initiator and a crosslinking agent;
wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecular silicon monomer and the weight of the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
Preferably, the mass portion of the single-end-capped organic siloxane oligomer in the formula (I) is 30-55 parts, and the mass portion range of other components is unchanged.
In particular, the mono-end-capped organosiloxane oligomers of formula (I) are as described above.
The small molecular silicon monomer can be one or any combination of methacryloxymethyl tri (trimethylsiloxy) silane (MTTS), methacryloxypropyl tri (trimethylsiloxyalkyl) silane (TRIS), gamma-aminopropyltriethoxysilane (KH-550), 3- (methacryloxy) propyltrimethoxysilane (KH-570) and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane (SIGMA). The micromolecular silicon monomer is used as a solubilizing monomer in the silicon hydrogel, so that the intermiscibility of the siloxane macromonomer and the hydrophilic monomer can be increased, and meanwhile, the micromolecular silicon monomer has a certain effect on improving the oxygen permeability.
The hydrophilic monomer can be one or more of N-vinyl pyrrolidone (NVP), vinyl cyclohexane amide (NVCA), polyether methacrylate, methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-Dimethylacrylamide (DMA), N-vinyl acetamide (NVA) and N-vinyl methylacetamide. The performance characteristics of each hydrophilic monomer are different, and the excellent performance of each monomer can be fully exerted by using a plurality of monomers in a composite way.
The initiator is a photoinitiator or a thermal initiator. The photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone (D1173) and 2,4,6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile and Benzoyl Peroxide (BPO).
The cross-linking agent may be at least one of triallyl isocyanurate (TAIC), ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate, polyethylene glycol diacrylate (PEGDA), tetraethylene glycol dimethacrylate, divinylpolyglycol ether, and trimethylolpropane trimethacrylate.
In actual production, other functional monomers can be added to the silicone hydrogel material according to needs, such as monomers containing colored monomers, color-changing monomers or monomers for blocking ultraviolet light, blue light and near infrared light.
Because the single-end-capped organic siloxane oligomer in the formula (I) has excellent hydrophilicity, has good intermiscibility with hydrophilic monomers, and does not need a solvent for assisting dissolution, no solvent is added in the silicon hydrogel formula, which is a great advantage for large-scale industrial production. Since the addition of organic solvent is a very serious limiting factor in large-scale industrial production, the addition of organic solvent not only increases the production and recovery costs, but also causes environmental pollution. More importantly, in the process of preparing the lens by polymerizing the mixed monomers, the solvent can be greatly volatilized into the air no matter thermal polymerization or photopolymerization, and when the concentration of the solvent in the air exceeds a certain value, the health of operators can be influenced, and risks such as explosion, combustion and the like can be caused.
Meanwhile, the single-end-capped organic siloxane oligomer in the formula (I) and the hydrophilic monomer are well dissolved mutually, and can be added into the silicon hydrogel in a large proportion, so that the addition of the organic siloxane oligomer is greatly increased, and the oxygen permeability of the silicon hydrogel is remarkably improved. The addition amount of the single-end-capped organic siloxane oligomer in the silicon hydrogel is 5-55%, and the organic siloxane oligomer almost accounts for 5-55% of the total weight of the silicon hydrogel, namely, the addition amount of the organic siloxane oligomer can reach more than 40%, while the commercially available single-end-capped organic siloxane oligomer can be added by about 20% and is far lower than the addition level of the single-end-capped organic siloxane oligomer.
The invention effectively solves the problem that organic siloxane oligomer and hydrophilic monomer are difficult to dissolve in each other, and greatly improves the oxygen permeability of the silicon hydrogel on the premise of keeping high water content, thereby realizing the aim that the silicon hydrogel material has high oxygen permeability and high water content, and greatly improving the performance of the silicon hydrogel material. Experiments show that the water content of the silicon hydrogel prepared by the invention is 30-60%, the oxygen permeability reaches more than 150barrer, even more than 180barrer, and the silicon hydrogel is obviously higher than that of a commercially available silicon hydrogel contact lens; moreover, the lipid adsorption is very low and is lower than 0.0030 mg/tablet, which shows that the lens prepared by the invention has excellent lipid adsorption resistance; meanwhile, the elongation at break reaches over 160 percent, which shows that the corneal contact lens prepared by the invention has good flexibility.
The invention also provides a corneal contact lens made of the silicon hydrogel material. The corneal contact lens is prepared by the following method:
uniformly mixing 5-55 parts of single-end-capped organic siloxane oligomer shown in the formula (I), 0-30 parts of micromolecule silicon monomer, 15-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mould, carrying out polymerization and solidification under photo-initiation or thermal initiation, and hydrating to obtain a silicon hydrogel corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecular silicon monomer and the weight of the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
The cornea contact lens is made of the silicon hydrogel material, and the silicon hydrogel material has good oxygen permeability and light transmittance, keeps high hydrophilicity and flexibility of gel, and has good lipid precipitation resistance. The corneal contact lens prepared by the silicon hydrogel is comfortable to wear, good in flexibility and high in oxygen permeability, can reduce the incidence of ophthalmic diseases caused by oxygen deficiency, and is beneficial to eye health; the good light transmission performance ensures the visual effect and comfort of wearing.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The experimental procedures used above and in the examples below are conventional unless otherwise specified. The materials, reagents and the like used above and in the following examples are commercially available unless otherwise specified.
Example 1
Preparation of mono-end-capped organosiloxane oligomers
Taking 50g of monohydroxy terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight is about 1500, structural formula is shown above, wherein m is about 8,n is about 15, purchased from Nanjing Fugu chemical Co., ltd.), dropwise adding 0.3g of dibutyltin dilaurate, stirring uniformly, gradually adding 7.41g of IPDI, simultaneously opening a constant temperature water bath heating device, adjusting the temperature to 70 ℃, starting timing after the dropwise adding is completed, and reacting for 4h. And (3) cooling to 50 ℃, dropwise adding 4.34g of HEMA monomer, stirring for 24h to obtain a product, marking as M1 (the structural formula is shown as the formula (I), wherein M is about 8,n is about 15), and sealing for storage. FIG. 1 is a nuclear magnetic spectrum of a single end-capped organosiloxane oligomer prepared in example 1.
Example 2
Preparation of single-end-capped organosiloxane oligomer
50g of monohydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight of about 3000, structural formula shown above, wherein m is about 10, n is about 35, and purchased from Nanjing Fugu chemical Co., ltd.) is taken, 0.2g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 3.71g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to be 70 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding 2.17g HEMA monomer dropwise, stirring for 24h to obtain product M2 (formula is shown as formula (I), wherein M is about 10, n is about 35), and sealing for storage.
Example 3
Preparation of mono-end-capped organosiloxane oligomers
50g of monohydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight of about 4000, structural formula shown above, wherein m is about 12, n is about 45 and purchased from Nanjing Fugu chemical Co., ltd.) is taken, 0.2g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 2.78g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to be 70 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding 1.63g HEMA monomer dropwise, stirring for 24h to obtain product M3 (formula is shown as formula (I), wherein M is about 12, n is about 45), and sealing for storage.
Example 4
Preparation of mono-end-capped organosiloxane oligomers
50g of monohydroxy-terminated polyether modified polydimethylsiloxane (HO-PDMS, number average molecular weight of about 6000, structural formula shown above, wherein m is about 15, n is about 70, and purchased from Nanjing Fugu chemical Co., ltd.) is taken, 0.15g of dibutyltin dilaurate is added dropwise, the mixture is stirred uniformly, 1.85g of IPDI is gradually added, a constant temperature water bath heating device is opened at the same time, the temperature is adjusted to be 70 ℃, timing is started after the dropwise addition is completed, and the reaction is carried out for 4 hours. Cooling to 50 deg.C, adding 1.08g HEMA monomer dropwise, stirring for 24 hr to obtain product M4 (formula is shown as formula (I), wherein M is about 15, n is about 70), and sealing for storage.
Examples 5 to 8
A silicone hydrogel prepared by polymerization of:
in examples 5-8, single end-capped organosiloxane oligomers were prepared from examples 1-4, respectively, with the other components and parts unchanged.
Examples 9 to 16
Preparation of corneal contact lenses
Uniformly mixing the single-end-capped organic siloxane oligomer, the micromolecule silicon monomer, the hydrophilic monomer, the initiator and the cross-linking agent, injecting into a corneal contact lens mould, thermally initiating polymerization, demoulding and hydrating to obtain the silicon hydrogel corneal contact lens. The contact lens is made to have an anterior surface and a posterior surface.
Wherein the single end-capped organosiloxane oligomers were prepared from examples 1-4, respectively; the micromolecular silicon monomer adopts methacryloxypropyltri (trimethylsiloxy alkyl) silane (TRIS); the hydrophilic monomer adopts N-vinyl pyrrolidone (NVP), vinyl cyclohexane amide (NVCA), hydroxypropyl methacrylate (HPMA); the initiator adopts Azobisisobutyronitrile (AIBN); the cross-linking agent is Ethylene Glycol Dimethacrylate (EGDMA). The contact lenses of examples 9-16 were prepared according to the above procedure, and their respective reaction components and formulation relationships (in parts by mass) are shown in table 1.
Comparative examples 1 to 2
Corneal contact lenses were prepared as described in examples 9-16, using commercially available mono-terminated macromer (7-9% methacryloxypropyl-methylsiloxane) -dimethylsiloxane copolymer (RMS-083) in place of the mono-terminated organosiloxane oligomer of the present invention, and the reaction components and ratios used are shown in Table 1, with other reaction conditions being unchanged.
TABLE 1 reaction Components and compounding ratios (in parts by mass) of examples 9 to 16 and comparative examples 1 to 2
Example 17
The corneal contact lenses prepared in examples 9 to 16 were each tested for elongation using an electronic tensile tester XLW (PC). The tensile elongation at break of the corneal contact lens samples was measured by holding each sample with a separate clamp plate, and the results are shown in Table 2.
The oxygen permeability of the contact lenses prepared in examples 9-16 were measured by the national standard (GBT 11417.3-2012) coulometry method, and the results are shown in Table 2.
The water content and the weight of the glass slide Q1 and the weight of the lens and the glass slide Q2 of the contact lenses prepared in examples 9 to 16 were measured by a weighing method, respectively, and after drying in an oven at 50 ℃ to a constant weight, the gross weight G3 and the water content = (Q2-G3)/(Q2-Q1) were obtained, and the test results are shown in table 2.
The lipid adsorption of examples 9-16 was detected by the ferric alum chromogenic in the presence of lipid, and then the amount of lipid adsorption was detected by an evalution type 220 spectrophotometer.
Comparative examples 1-2 were tested in combination with examples 9-16 for various properties, and the results are shown in Table 2.
Table 2 results of performance testing
As can be seen from Table 2, the oxygen permeability of the corneal contact lenses of the invention is above 150barrer, and some examples are even as high as above 180barrer, which is significantly higher than that of the comparative examples; the water content of the corneal contact lens is obviously higher than that of the comparative example; the corneal contact lens has very low lipid adsorption, is lower than a comparative example to a greater extent, and is reduced by more than 40% compared with the comparative example; this shows that the cornea contact lens prepared by the single-end-capped organic siloxane oligomer has the excellent performances of high oxygen permeability, high water content, lipid adsorption resistance and the like. Meanwhile, the corneal contact lens has high elongation at break, which shows that the corneal contact lens prepared by the invention has good flexibility, is durable and is not easy to break.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to further illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A mono-end-capped organosiloxane oligomer having the structure of formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl group of (1).
2. A method of preparing the mono-end-capped organosiloxane oligomer of claim 1 comprising: under the action of a catalyst, in the temperature range of 20-90 ℃, the monohydroxy terminated polyether modified polydimethylsiloxane firstly reacts with isophorone diisocyanate, and then hydroxyethyl methacrylate is added for continuous reaction to obtain the mono-terminated organic siloxane oligomer shown in the formula (I).
3. The use of the mono-end-capped organosiloxane oligomer of claim 1 in the preparation of silicone hydrogels and corneal contact lenses.
4. The silicone hydrogel is characterized by comprising the following components in parts by mass and prepared through polymerization reaction:
5 to 55 portions of single-end-capped organic siloxane oligomer,
0 to 30 parts of micromolecular silicon monomer,
15 to 70 parts of hydrophilic monomer,
an initiator and a crosslinking agent;
wherein the single-end-capped organic siloxane oligomer has a structure shown in a formula (I):
wherein m is an integer ranging from 4 to 20, n is an integer ranging from 5 to 100, and R is C 1 -C 10 Alkyl groups of (a);
the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capping organosiloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
5. The silicone hydrogel of claim 4, wherein the mass fraction of the mono-end-capped organosiloxane oligomer of formula (I) is from 30 to 55 parts.
6. The silicone hydrogel of claim 4 or 5, wherein the small molecule silicon monomer is one or any combination of methacryloxymethyltris (trimethylsiloxy) silane, methacryloxypropyltri (trimethylsiloxy) silane, γ -aminopropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, and 3- (3-methacryloxy-2-hydroxypropyl) propylbis (trimethylsiloxane) methylsilane.
7. The silicone hydrogel of claim 4 or 5, wherein said hydrophilic monomer is one or a combination of N-vinyl pyrrolidone, vinyl cyclohexanamide, polyether methacrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycerol methacrylate, glycidyl methacrylate, N-dimethylacrylamide, N-vinylacetamide and N-vinylmethylacetamide.
8. The silicone hydrogel of claim 4 or 5, wherein said initiator is a photoinitiator or a thermal initiator; the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone and 2,4,6-trimethylbenzyl diphenyl phosphine oxide, and the thermal initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide;
the cross-linking agent is at least one of triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinyl polyethylene glycol ether and trimethylolpropane trimethacrylate.
9. A corneal contact lens made from the silicone hydrogel of any one of claims 4 to 8.
10. A method of making a corneal contact lens as in claim 9, comprising: uniformly mixing 5-55 parts of single-end-capped organic siloxane oligomer shown in the formula (I), 0-30 parts of micromolecule silicon monomer, 15-70 parts of hydrophilic monomer, initiator and cross-linking agent, injecting into a corneal contact lens mould, carrying out polymerization and curing under photo-initiation or thermal initiation, and hydrating to obtain the corneal contact lens; wherein the sum of the mass parts of the single-end-capped organic siloxane oligomer, the micromolecular silicon monomer and the hydrophilic monomer is 100 parts; the initiator accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capped organic siloxane oligomer, the small molecular silicon monomer and the hydrophilic monomer; the cross-linking agent accounts for 0.5 to 3 percent of the sum of the weight of the single-end-capping organosiloxane oligomer, the weight of the micromolecule silicon monomer and the weight of the hydrophilic monomer.
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