CN100494282C - Composition of organosilicon, and controlled release rubberized tube for medication prepared from the composition - Google Patents
Composition of organosilicon, and controlled release rubberized tube for medication prepared from the composition Download PDFInfo
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- CN100494282C CN100494282C CNB2004100531401A CN200410053140A CN100494282C CN 100494282 C CN100494282 C CN 100494282C CN B2004100531401 A CNB2004100531401 A CN B2004100531401A CN 200410053140 A CN200410053140 A CN 200410053140A CN 100494282 C CN100494282 C CN 100494282C
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Abstract
An organosilicon composition is prepared from the additive silicon rubber, methylbutynol as inhibitor and the catalyst generated by the reaction between chloroplatinic acid and tetramethyl divinyl bisilicoether. A rubber tube for controlling the release of medicine, especially the durable contraceptive, is prepared from said composition through extruding and sulfurizing in hot air channel.
Description
Technical field
The present invention relates to a kind of based on organosilicon material constituent and the thin-walled sebific duct of making by this constituent, relate in particular to a kind of based on addition-type silicon rubber the sulfurized extruded organosilicon constituent and by the controlled release sebific duct that is used for medicament slow release preparation of this constituent manufacturing.
Background technology
Usually the silicon rubber sebific duct is extruded continuously, continues with the sulfuration of warm air drying tunnel, essential hot sulfurization (HTV) the type silicon rubber that adopts, and adopt 2,4-dichlorobenzoperoxide, but the residue after the peroxide breakdown as vulcanizing agent, harmful, therefore can not be used for the manufacturing of medical product.For this reason, be used at present that medical product produces, especially the silastic product that will implant for a long time, generally all adopt the addition-type silicon rubber manufacturing, its crosslinked mechanism and common hot-vulcanized silicone rubber are completely different, if, hot-vulcanized silicone rubber is to generate free radical by the superoxide decomposes, cause the organic radical dehydrogenation on the silicon rubber molecular backbone chain, and then cause crosslinked words, addition-type silicon rubber then is that linking agent by siliceous hydrogen base and the vinyl on the silicon rubber molecular backbone chain addition reaction takes place under the effect of platinum catalyst are realized crosslinked and chainpropagation so, the former unavoidably has the peroxide breakdown residue to produce, and the latter then can avoid this disadvantage.Shanghai Rubber Products Insitute development country's " the Seventh Five-Year Plan " brainstorm project---the long-acting contraception implants comprises the silicon rubber rod of two match wood sizes, every silicon rubber rod is made up of the silicon rubber medicine core that contains contraceptive bian (LNG) the thin-walled silicone rubber tube outer with being wrapped in the medicine core, it is subcutaneous that it is implanted the women of child-bearing age, medicine in the medicine core can be by the thin-walled sebific duct (release-controlled film) of outsourcing, evenly and slowly discharge, thereby guarantee effectively contraception 5 years, the medical thin-walled silicone rubber tube that this implants is used must adopt the addition-type silicon rubber manufacturing certainly.Yet, problem is that addition-type silicon rubber is to have adopted active very high platinum to cause silicon-hydrogen addition (crosslinked) reaction as catalyzer, and this reaction at room temperature just can be carried out, and moulds if it is placed to extrude in the forcing machine, sizing material will soon slaking, and " stuck " is in machine barrel.For this reason, in the laboratory study stage, the method of determining is to use injection molding---adopt six punch dies, before each injection molding two kinds of sizing materials of first, second (separate be added in these two kinds of sizing materials as the containing hydrogen silicone oil and the catalyzer platinum of linking agent) are mixed on rubber mixing machine, place immediately in the injecting glue cylinder, add at press and to depress, allow sizing material flow into die cavity, heating and pressurizing is finished sulfuration then, though the product dimensional precision height that this method obtains, but shortcoming is obvious: after 1. two kinds of sizing materials of first, second mix, must use up in short-term, otherwise sizing material will bin cure; 2. inefficiency, each injecting glue, mould must cool off, and is very time-consuming; Very easily broken or torn during the 3. rectangular thin-walled sebific duct demoulding, so qualification rate is low; Owing to will use soap class releasing agent, cause the product appearance scabbing serious; 4. the most also be that the most serious problem is the scale production that this technology can't continuous tissueization.
Summary of the invention
The present invention is intended to overcome above-mentioned shortcoming, provide a kind of can meeting to make the medical product requirement and can adopt the sulfurized the extruded organosilicon constituent of extruding sulfuration plastotype technology again based on addition-type silicon rubber, and with the medicine controlled releasing usefulness thin-walled silicon rubber sebific duct of this constituent manufacturing.
The present invention is achieved in that at first it is a kind of sulfurized extruded organosilicon constituent based on addition-type silicon rubber, it is characterized in that the component of forming this constituent comprises:
A) contents of ethylene is 0.10～0.50mol%, and relative molecular mass is 100000～600000 methylvinyl-polysiloxane 100 mass parts;
B) Si-H base content is 0.8～1.6mol%, and viscosity (25 ℃) is 20～100mm
2Polysiloxane 0.3～2.0 mass parts of/s;
C) contain an alkynyl (≡ C-) and hydroxyl (-OH) hydrocarbon polymer 0.03～2.0 mass parts in the molecular structure at least;
D) platinum complex 0.000002～0.00005 mass parts;
E) based on strengthening agent 20～50 mass parts of gas-phase silica.
Component A wherein belongs to usually alleged methyl vinyl silicon kautschuk, and it should contain an amount of vinyl, for the linking agent generation addition reaction that contains Si-H base, form crosslinked (being vulcanization reaction).In general, the content of vinyl is with 0.10～0.50mol%, and relative molecular mass 100000～600000 is advisable, the content of vinyl is low excessively, causes the cross-linking density deficiency, the too high levels of vinyl, cause cross-linking density excessive, all be difficult to make excellent property and get cross-linked rubber.Relative molecular mass is low excessively, the cross-linked rubber undercapacity that obtains, and relative molecular mass is excessive, is unfavorable for processing operation.Certainly, in order in crosslinking reaction, transfer reaction to take place,, preferably adopt silicon rubber with ethenyl blocking with the good cross-linked rubber of obtained performance.
Component B belongs to the linking agent of addition-type silicon rubber, be also referred to as and be containing hydrogen silicone oil, it is the polysiloxane that contains an amount of Si-H base in a kind of molecular structure, same its Si-H base content is preferably 0.8～1.6mol%, this too high levels or mistake are low can to cause cross-linking density too high or too low, unfavorable to the cured properties that obtains, for ease of blending dispersion, its viscosity (25 ℃) is preferably 20～100mm
2/ s, same, use with Si-H end-blocking containing hydrogen silicone oil and mix comparatively ideal of use by a certain percentage with above-mentioned containing hydrogen silicone oil.In component A is 100 mass parts, and the consumption of component B is preferably 0.3～2.0 mass parts, can obtain suitable cross-linking density.
Component C is the key component of this constituent, in order to use extrusion apparatus processing addition-type silicon rubber material, primary key is to locate a kind of suitable inhibitor, the activity that can prevent catalyzer platinum, (for example make it in certain temperature, below 110 ℃) under do not have an effect, two kinds of sizing materials of above-mentioned like this first, the second that mixes with regard to not can because of slaking " stuck " too early in machine barrel, in addition, because product application is in pharmaceutical preparation, this inhibitor also must be accomplished and can not produce detrimentally affect to the biology performance of addition-type silicon rubber.The compound that can be used as the addition-type silicon rubber vulcanization inhibitor is a lot, nitrogenous compound, heterogeneous ring compound, alkylamide and alkynol compounds are arranged, consider from medical angle, at least contain in the molecular structure alkynyl (≡ C-) and hydroxyl (-OH) alkynol hydrocarbon is the safest because this compounds has following characteristic: (1) this as a kind of pharmaceutical intermediate; (2) boiling point is lower, is easy to remove; (3) have surfactivity, alkynol-C ≡ CH and-OH makes it have stronger polarity and wetting ability, the alkyl of alkynol makes it have hydrophobicity, so alkynol is the nonionogenic tenside of excellent property; (4) excellent wetting capacity: the branched group in the alkyl is methyl basically, and two polar groups are arranged again in the structure, and these characteristics are given alkynol with good wettability; (5) low bubble property and defoaming: the hydrocarbon side chain in the alkynol has weakened the magnetism between adjacent molecule, forms compressible, easy gas-pervious expanded film at liquid-gas interface, thereby itself is difficult for forming foam, has certain froth breaking ability, can prevent the extrusion profile entrained air bubbles; (5) good dispersity: the molecular weight of alkynol is low, more easily diffusion, good dispersity; (6) with addition-type silicon rubber and usefulness, can react, and addition-type silicon rubber is played the sulfurized effect that suppresses with its vulcanization system.Can be selected from a kind of in methylbutynol, butynediol, the propiolic alcohol as component C, wherein be best especially with the methylbutynol, because its stable in properties, meet heat and autohemagglutination can not take place, can be decomposed into gas release in the time of 130 ℃ comes out, noresidue does not influence the biology performance of complete processing, working (machining) efficiency and the finished product.Test shows: under the condition of inhibiting not, when barrel zone temperature during at 100 ℃, sizing material is promptly basic sulfuration behind 10min, at this moment must take out vulcanized rubber immediately, cleans machine barrel; But adding under the condition of inhibitor, when barrel zone temperature during at 100 ℃, sizing material can use a few hours in machine barrel continuously, and the silicone rubber tube of extruding is not seen micelle, has both guaranteed the effective rate of utilization of sizing material, can obtain the high silicone rubber tube of qualification rate again.The consumption of inhibitor is 100 mass parts in component A, is preferably 0.03～2.0 mass parts; Consumption is very few, and restraining effect is not obvious, and consumption does not too much produce further restraining effect, causes waste.The effect of inhibitor is as shown in the table:
| Inhibitor consumption (mass parts) | 0 | 0.1 | 0.3 | 2.0 |
| T 1，℃ | 40 | 97 | 99.5 | 104 |
| T 2，℃ | 96 | 100 | 108 | 109 |
| Δ＝T 2—T 1，min | 6 | 5 | 3 | 4 |
Annotate: T in the table
1And T
2Be respectively the reacting initial temperature and the reaction end temp that on the DSC curve, record.
Test shows, just can bring up to 106 ℃ to temperature of reaction as long as add the above-mentioned inhibitor of 0.3 mass parts, that is to say, and the whole course of processing, as long as temperature is controlled at below 106 ℃, operation safety.
Component D is the platinum catalyst that is used to impel methyl vinyl silicone rubber and linking agent containing hydrogen silicone oil generation addition reaction, because platinum is a kind of precious metal, so generally its consumption only is ppm (several ppm) of silicon rubber amount, add that platinum is as catalyzer, very easily poisoned, cause its effect to descend, for this reason by some impurity, according to the present invention, platinum is made complex compound with organosilicon material in advance.So both can avoid platinum catalyst to be poisoned, also help the abundant dispersion of platinum catalyst.Described platinum complex is the reaction product of Platinic chloride and MMVT, is promptly formed through back flow reaction under the condition of logical nitrogen protection and progressively intensification by Platinic chloride and MMVT.Consumption is that 100 mass parts are preferably 0.000002～0.00005 mass parts in component A.
As everyone knows, raw-silastic continuously is the semi-fluid shape, intensity is very low, make each based article, the an amount of strengthening agent, particularly thermal silica of essential interpolation comprises through silazane or chlorosilane surface-treated and not surface treated, component E in Here it is the constituent of the present invention, its consumption is that 100 mass parts are preferably 20～50 mass parts in component A.Consumption is low excessively, and reinforcing effect is not obvious, and consumption is excessive, the sizing material processing difficulties.
Use constituent provided by the invention, make the medicine controlled releasing sebific duct that the even constant release of control medicine is used with the forcing machine extrusion moulding, for guaranteeing that drug release reaches essential value, promptly the 7th day release in vitro degree is 80～120 μ g/ days, and the wall thickness of this sebific duct should be 0.14～0.20mm; For being complementary with the medicine core that is wrapped in it, internal diameter should be 2 ± 0.2mm, the thin-walled sebific duct pipe of extruding is sent into the warm air drying tunnel with certain temperature and length and is vulcanized, can realize the serialization operation, the sebific duct that makes meets fully after tested and is used for the requirement that the long-acting contraception implants is wrapped in the outer thin-walled silicone rubber tube of medicine core, and the test result of its release effect is as follows:
| The test fate | Subdermal implants A (the not silicone rubber tube of inhibiting) | Subdermal implants B (silicone rubber tube of inhibiting) |
| 1 | 109 | 110 |
| 2 | 93 | 95 |
| 3 | 95 | 94 |
| 4 | 96 | 90 |
| 5 | 94 | 92 |
| 6 | 91 | 98 |
| 7 | 91 | 92 |
| 8 | 93 | 91 |
| 9 | 93 | 90 |
| 10 | 90 | 88 |
Release in vitro degree according to this product requires (the 7th day release in vitro degree is 80～120 μ g/ days), no matter whether add inhibitor, the 7th day external release of implants product is all in allowed band.Therefore, if adopt inhibitor in the course of processing, the silicone rubber tube that makes thus has same effectively control sustained drug release effect.
Therefore, employing the present invention can realize extruding sulfuration based on the serialization of the sizing material of addition-type silicon rubber, the medical thin-walled sebific duct that makes, appearance transparent, section rounding, wall thickness are evenly and wall thickness 0.14～0.20mm only, meet and be used for the requirement that the long-acting contraception implants is wrapped in the outer thin-walled silicone rubber tube of medicine core, the more former injection molding method of yield rate is much improved, and former method is about 60%, now reaches more than 90%.
Description of drawings
Fig. 1 is to use constituent of the present invention, extrudes continuously with forcing machine and moulds the process flow diagram of medicine controlled releasing with the thin-walled sebific duct.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention never is confined to these embodiment.
Platinum complex preparation: in the 500ml there-necked flask that is equipped with agitator, thermometer, logical nitrogen pipe, add Platinic chloride 10g and MMVT 250g; under the condition of logical nitrogen protection; with the oil bath heating, progressively be warmed up to 115～120 ℃, back flow reaction 1h under this temperature.Be cooled to room temperature then, the elimination black precipitate obtains lurid filtrate, is washed with distilled water to neutrality again, adds an amount of calcium chloride drying, promptly obtains light yellow aqueous platinum complex of the present invention after the filtration.Be kept in the Brown Glass Brown glass bottles and jars only stand-by.
Embodiment 1
The prescription of constituent:
Contents of ethylene is 0.30mol%, methyl vinyl silicone rubber 100 mass parts of relative molecular mass about 100000
Si-H base content is 1.0mol%, and 25 ℃ of following viscosity are 50mm
2The polysiloxane of/s
0.9 mass parts
Platinum complex 0.00001 mass parts
Methylbutynol 0.1 mass parts
Gas-phase silica 25 mass parts
By above-mentioned prescription, at first on rubber mixing machine that silicon rubber and white carbon black is mixing evenly, the rubber unvulcanizate that obtains is divided into sizing material first and sizing material second, in these two kinds of sizing materials, add polysiloxane (linking agent) and the platinum complex (catalyzer) that contains Si-H base respectively, by technical process shown in Figure 1, the medicine controlled releasing sebific duct that is used for the long-acting contraception implants with the mode manufacturing of serialization, used forcing machine is the silicon rubber single screw extrusion machine of Φ 65nm, sizing material is extruded by forcing machine, drying tunnel temperature was controlled to be 300 ℃ when the thin-walled sebific duct pipe of extruding was sent into the drying tunnel sulfuration, pipe is 2min by the time of drying tunnel, from the sebific duct complete cure that drying tunnel comes out, sebific duct appearance transparent, surfacing is smooth, wall thickness is even, reaches 0.17mm, and the tensile strength of single pipe is 4.8N.
Embodiment 2
The prescription of constituent:
Contents of ethylene is 0.40mol%, methyl vinyl silicone rubber 100 mass parts of relative molecular mass about 130000
Si-H base content is 1.2mol%, and 25 ℃ of following viscosity are 80mm
2The polysiloxane of/s
1.1 mass parts
Platinum complex 0.000005 mass parts
Methylbutynol 0.3 mass parts
Gas-phase silica 35 mass parts through the silazane processing
Make medicine controlled releasing thin-walled sebific duct by embodiment 1 identical working method and processing condition, pipe changes 3min into by the time of drying tunnel, the sebific duct complete cure that comes out from drying tunnel, the sebific duct appearance transparent, surfacing is smooth, wall thickness is even, reaches 0.18mm, and the tensile strength of single pipe is 6.6N.
Embodiment 3
The prescription of constituent:
Contents of ethylene is 0.40mol%, methyl vinyl silicone rubber 100 mass parts of relative molecular mass about 600000
Si-H base content is 1.2mol%, and 25 ℃ of following viscosity are 80mm
2The polysiloxane of/s
1.5 mass parts
Platinum complex 0.00001 mass parts
Methylbutynol 0.7 mass parts
Gas-phase silica 35 mass parts through the silazane processing
Make medicine controlled releasing thin-walled sebific duct by embodiment 1 identical working method and processing condition, pipe changes 4min into by the time of drying tunnel, the sebific duct complete cure that comes out from drying tunnel, the sebific duct appearance transparent, surfacing is smooth, wall thickness is even, reaches 0.18mm, and the tensile strength of single pipe is 8.5N.
Embodiment 4
The prescription of constituent:
Contents of ethylene is 0.30mol%, the ethylene methacrylic of relative molecular mass about 100000
Base silicon rubber 100 mass parts
Si-H base content is 1.0mol%, and 25 ℃ of following viscosity are 50mm
2The polysiloxane of/s
1.5 mass parts
Platinum complex 0.00001 mass parts
Methylbutynol 1.2 mass parts
Gas-phase silica 25 mass parts
Make medicine controlled releasing thin-walled sebific duct by embodiment 1 identical working method and processing condition, pipe changes 5.5min into by the time of drying tunnel, the sebific duct complete cure that comes out from drying tunnel, the sebific duct appearance transparent, surfacing is smooth, wall thickness is even, reaches 0.16mm, and the tensile strength of single pipe is 5.6N.
Claims (2)
1, a kind ofly can it is characterized in that the component of forming this constituent comprises by extruding the organosilicon constituent that medicine controlled releasing thin-walled sebific duct is made in sulfuration based on addition-type silicon rubber:
A) contents of ethylene is 0.10～0.50mol%, and relative molecular mass is 100000～600000 methylvinyl-polysiloxane 100 mass parts;
B) Si-H base content is 0.8～1.6mol%, and the viscosity that records under 25 ℃ is 20～100mm
2Polysiloxane 0.3～2.0 mass parts of/s;
C) contain an alkynyl (≡ C-) and hydroxyl (-OH) hydrocarbon polymer 0.03～2.0 mass parts in the molecular structure at least;
D) platinum complex 0.000002～0.00005 mass parts;
E) based on strengthening agent 20～50 mass parts of gas-phase silica;
Wherein, (-OH) hydrocarbon polymer is a methylbutynol component C) to contain an alkynyl (≡ C-) and hydroxyl in the molecular structure at least; Component D) platinum complex is the reaction product of Platinic chloride and MMVT.
2, can make the application of the organosilicon constituent of medicine controlled releasing thin-walled sebific duct by extruding sulfuration by claim 1 is described, it is characterized in that, described constituent is made the medicine controlled releasing thin-walled sebific duct that is used for the long-acting contraception implants by the sulfuration of warm air drying tunnel, and described sebific duct wall thickness is 0.14～0.20mm; Internal diameter---2 ± 0.2mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100531401A CN100494282C (en) | 2004-07-26 | 2004-07-26 | Composition of organosilicon, and controlled release rubberized tube for medication prepared from the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100531401A CN100494282C (en) | 2004-07-26 | 2004-07-26 | Composition of organosilicon, and controlled release rubberized tube for medication prepared from the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1727409A CN1727409A (en) | 2006-02-01 |
| CN100494282C true CN100494282C (en) | 2009-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100531401A Ceased CN100494282C (en) | 2004-07-26 | 2004-07-26 | Composition of organosilicon, and controlled release rubberized tube for medication prepared from the composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494282C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009027486A1 (en) * | 2009-07-06 | 2011-01-13 | Wacker Chemie Ag | Process for the preparation of silicone coatings and silicone moldings from light-crosslinkable silicone mixtures |
| CN113413358B (en) * | 2021-06-11 | 2022-11-15 | 上海达华药业有限公司 | Preparation method of contraceptive implant drug core |
| WO2023174450A2 (en) * | 2022-03-18 | 2023-09-21 | 沈阳星华医药科技有限公司 | Silicone material, silicone tube, implant, pharmaceutical composition, and test method for amount of drug released |
-
2004
- 2004-07-26 CN CNB2004100531401A patent/CN100494282C/en not_active Ceased
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