CN1039590C - Medical stick-resistant silastic membrane and preparation thereof - Google Patents
Medical stick-resistant silastic membrane and preparation thereof Download PDFInfo
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- CN1039590C CN1039590C CN91100853A CN91100853A CN1039590C CN 1039590 C CN1039590 C CN 1039590C CN 91100853 A CN91100853 A CN 91100853A CN 91100853 A CN91100853 A CN 91100853A CN 1039590 C CN1039590 C CN 1039590C
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Abstract
The present invention relates to a medical anti-adhesion silastic membrane. The silastic membrane is prepared by the following steps: 100 portions by weight of raw rubber of methyl-ethenyl silicon, 45 to 55 portions by weight of gas-phase white carbon black and 3 to 8 portions by weight of hydroxyl silicon oil are orderly and uniformly mixed; the obtained mixture is pressed into a silastic membrane sheet with the thickness of 0.2 to 0.5 millimeter; radiation crosslinking is carried out with the irradiation dose of 50 to 100 kGy; then the treated silastic membrane sheet is immersed in a stem grafting liquid prepared from 20 portions by weight of HEMA, 60 to 80 portions by weight of ethanol and 0 to 20 portions by weight of water to make radiation grafting carried out with the irradiation dose of 3 to 5 kGy. The prepared silastic stem grafting membrane can be grafted into the repair part of a wound in surgical operation to prevent the adhesion of tissues.
Description
The present invention relates to radiation crosslinking, radiation graft process prepares the medical polymer film.
The silicon rubber physicochemical property is stable, has the physiology natural instincts, and is nontoxic, can stand harsh conditions for sterilization, easily makes tubing, sheet material, film or special-shaped component as required, is ideal medical macromolecular materials comparatively.Present medical grade silicon rubber adopts the chemical method sulfidization molding more.Because the chemical method sulfuration has the superoxide residue to exist, and makes silastic product be easy to wear out, and with easily causing foreign body reaction in vivo.Have both at home and abroad in recent years research to medical macromolecular materials such as silicon rubber with method of radiating grafting hydrophilic monomer to improve its biocompatibility.In 1987 the 2nd phase 37-41 of Shanghai Science and Technology Univ.'s journal page or leaf for example, U.S. ACS Polymer Preprints 13,729-735 (1972) and Polymer Sci.Tehol.SeriesNo7,159-171, (1975), introduced silicon rubber has been carried out radiation grafting hydrophilic monomer or hydrophilic, hydrophobicity mix monomer improving the research of its performance, and done a small amount of animal and bury test.But do not see as yet successfully prepare can be applicable to clinical, as the report of the silicone rubber membrane of surgical operation anti.
The purpose of this invention is to provide a kind of purity height, good with biocompatible, can be used for the preparation method of the silicone rubber membrane of surgical operation anti.
The present invention adopts that radiation method is crosslinked, the radiation method grafting, and adopts suitable composition of raw materials and processing condition to realize above-mentioned purpose.Specific practice is as follows:
(1) batching system film: raw material is pressed 100 parts of methyl ethylene silicon raw rubbers, gas-phase silica 45-55 part, the weight proportion of hydroxy silicon oil 3-8 part is mixing successively evenly, through thin-pass, park, back mixing, extrusion forming, making thickness is the silicon rubber diaphragm of 0.2-0.5 millimeter;
(2) radiation crosslinking: the above-mentioned diaphragm that makes is placed irradiation field, carry out radiation vulanization under certain irradiation temperature, irradiation dose is the 50-100 kilogray (kGy), makes gel fraction after crosslinked greater than 94%; Described irradiation temperature is a room temperature to 55 ℃;
(3) radiation grafting: place ethanol to soak more than 4 hours on the silicon rubber diaphragm behind the above-mentioned radiation crosslinking, soaking temperature is a room temperature to 60 ℃, after the taking-up, dry constant weight, then diaphragm is immersed in the grafting liquid, sealing, behind the letting nitrogen in and deoxidizing, place irradiation field, irradiation dose is the 3-5 kilogray (kGy); Grafting diaphragm behind the irradiation is put into distilled water digestion washing more than 4 hours repeatedly, again with the alcohol immersion washing,, dry then to remove surperficial homopolymer; The weight proportion of described grafting liquid is HEMA: ethanol: water=20: 60-80: 20-0.Obtaining percentage of grafting is 10-30%, the silicon rubber graft copolymer membrane of water-intake rate 〉=30%.
Described irradiation field can be a cobalt 60, also can be linear accelerator.
Described percentage of grafting and water-intake rate are measured as follows:
With before the grafting through pre-treatment, dry to constant weight W
0Diaphragm, behind the irradiation grafting, remove homopolymer, wash, dry to constant weight Wg, put into distilled water and soaked 24 hours, take out, blot water stainly with filter paper, be weighed as Wh, be calculated as follows:
Described gel fraction is measured as follows: take by weighing certainweight W
1Diaphragm behind the gram cross-linking radiation is cut into about 0.3 * 0.3 millimeter
2The fragment of size after the copper wire gauze wrapping, is put into fatty extractor, is weighed as W with the benzene extracting after 48 hours
2Gram is calculated as follows:
The effect of product of the present invention buries simultaneous test by animal and on probation acquisition of surgical operation confirms.
It is as follows that animal buries the simultaneous test situation:
To be respectively 4% by the percentage of grafting of radiation method sulfuration of the present invention, the preparation of radiation method grafting method, 8% and 15% silicon rubber graft copolymer membrane test piece and the test piece of chemical method sulfurized silicone rubber membrane, with 75% alcohol-pickled 24 hours, after the sterile saline immersion was disinfected in 24 hours, implant 1.0 * 3.0 centimetres respectively under the deep fascia everywhere all around again in healthy rabbits the small of the back ridge both sides
2One of the differing materials test piece of size makes it entirely contact skin suture with tissue.After burying certain hour, the sampling pathologic finding.The result is shown in Table I and Table II: table 1 test piece number buried time capillary vessel fiber knot is formed the huge C of inflammatory cell foreign matter
(hour) hyperplastic tissue reaction A chemical method sulfuration 84 ++++ +++beta radiation method sulfuration 84 +++++-C percentage of grafting 4% 84 +++++-E percentage of grafting 15% 84+++-
Table 11 test piece number rabbit numbering buried time capillary vessel fiber knot is formed the huge C of inflammatory cell foreign matter
(my god) hyperplastic tissue reaction A chemical method vulcanize 1 3.5 +++++ ++-beta radiation method vulcanizes 2 3.5 +++++-C percent grafting 8% 3 3.5 +++++-E percent grafting 15% 4 3.5+++-the A chemical method vulcanize 5 15-+++ the beta radiation method vulcanizes 6 15++-+C percent grafting 4% 7 15-+++-E percent grafting 15% 8 15++--the A chemical method vulcanize 9 30--+-B radiation methods vulcanize 10 30--+-D percent graftings 8% 12 30+---E percent grafting 15% 13 30----A chemical methods vulcanize 14 45 +++++the beta radiation method vulcanize 15 45-+++ C percent grafting 8% 16 45-+--E percent graftings 15% 17 45-+--
By animal experiment as can be known, radiation method is crosslinked, the test piece of radiation method grafted silicon rubber diaphragm, and postoperative takes out to be observed, and its color and luster, smooth situation do not become, and do not have aging or distortion, and the inflammatory cell of Chan Shenging, blood capillary proliferation and foreign-body giant cell are fewer on every side.Test piece and surrounding tissue do not have adhesion, bury January above person and can form the fiber sheathing around it, and the sheath inner face is smooth, the reaction of local organization NIP, and these characteristics can be used as some surgery, particularly orthopaedics, and prevention tissue adhesion uses in the operation.
According to animal test results, it is the processing condition of 10-30% as irradiation grafting that the present invention selects percentage of grafting.Percentage of grafting is too low, and diaphragm-operated physiologically acceptable property improvement is not obvious; Percentage of grafting is too high, and membrane tension is bigger, and operation is used inconvenient.
Product silicon rubber graft copolymer membrane clinic trial of the present invention is in operation back tissue adhesions such as prevention osteoarticular injury and illness, tendon injuries, before using silicon rubber grafting diaphragm carried out disinfection with conventional high pressure steam process or be immersed in 75% spirituous solution more than 24 hours, be immersed in the sterile saline standby then.
According to wound site and scope, cut aquagel membrane by required size, implant the position that easily produces adhesion.Be placed on joint cavity until the suprapatellar bursa place as knee joint; Elbow joint is placed on upper arm joint space and the dark face of the triceps muscle of arm is close to key place.Tendon injury person is placed on the depth two sides of depth tendon, does not make the shell type method and covers.Put the end of planting Antiadhesive film and dark muscle tissue apposition 1-2 pin, and the end of a thread that stays about 1.5cm to grow, the mark when getting film later on.The time of placing film is generally 4-8 week.Can be from former otch when getting film one section enters, and can take out film smoothly by mark, and checks the integrity of film.
From 50 routine case trial state follow-up observations, result of treatment is as follows:
The wound group: 35 examples, postoperative 32 examples are followed up a case by regular visits to, and are the longest 5 years, the shortest 1 year.Knee joint 10 examples wherein, excellent 7 examples, good 2 examples can 1 example; Elbow joint 11 examples, excellent 8 examples, good 2 examples can 2 examples, and wrist joint 4 examples can 1 example; Hip joint 1 example, excellent 1 example; Ankle joint 1 example, excellent 1 example.5 examples are repaired in the extensor tendon fracture, and excellent 4 examples differ from 1 example, heel string 1 example, excellent 1 example.Good rate is 86%.
The rheumatoid arthritis group: in 7 examples, there is 8 knee joints of 6 examples (bilateral 2 examples) postoperative to follow up a case by regular visits to, the longest 4 years, the shortest 2 years zero January.Excellent 5 knees in 8 knees, good 2 knees can 1 knee.Good rate 80%.
This is organized also has congenital abnormality 2 examples in 50 examples, second metatarsal bone head bland necrosis 3 examples (making semiarthrosis uses), month osteonecrosis 1 example, benign bone tumour 2 examples, totally 8 examples.Postoperative was followed up a case by regular visits to more than 2 years, excellent 7 examples, good 1 example.
Above-mentioned curative effect evaluation criteria excellent, good, that can, differ from is as follows:
Wound group (comprising tendon injury): press injury and adjacent segment functional rehabilitation and formulate, the functional rehabilitation of fresh damage postoperative is compared with natural joint, and the functional rehabilitation of outmoded injury postoperative is compared with function of joint before the art.
Excellent: function of joint recovers normal fully.
Very: joint function recovery more normally is less than 20 ° or than increasing before the art greater than 40 °.
Can: joint function recovery more normally is less than more than 20 °, or is less than 40 ° than increasing before the art.
Difference: function of joint does not have improvement.
The rheumatoid arthritis group is pressed postoperative arthralgia relief, detumescence and function improvement situation and is formulated.
Excellent: no pain, no swelling, range of motion increases greater than 40 °.
Very: pain and swelling have slightly and alleviate, and range of motion is increased between 20 °-40 °.
Can: pain and arsine expand to have slightly and alleviate, and range of motion increases less than 20 °.
Difference: arthralgia and swelling, function does not have improvement.
In the clinic trial of product of the present invention, the situation of difference does not take place, total good rate is more than 85%.
The surgical operation anti is done in product application of the present invention,, recovered the movable function of patient's wound site alleviating patient's misery, recover patient's work capacity, effect is remarkable, and important booster action is played in the success that cooperates operative treatment, has good social benefit and economic benefit.
Because the inventive method adopts radiation method crosslinked, guaranteed the high purity of silastic material before the grafting, avoid the crosslinked shortcoming that impurity such as superoxide residue are arranged of chemical method, and can also play disinfection to material irradiation the time; Because the inventive method adopts radiation method grafting hydrophilic monomer, does not introduce impurity such as catalyzer, thereby has guaranteed the high purity of the finished product; Graft copolymer suction back forms stable hydrogel, can reduce the interfacial energy that material contacts with body fluid, helps micromolecular infiltration, diffusion and migration, has increased the biocompatibility and the anticoagulation function of material, thereby can be suitable for medical needs.
The present invention adds an amount of strengthening agent white carbon black and constitution controller hydroxy silicon oil in raw material, and has selected suitable irradiation technique condition, thereby has guaranteed that product has good mechanical mechanics property.Through using the omnipotent puller system of Instron-1122 electric power, at 24 ℃, pulling rate 20 cm per minute, refer under 5 centimetres of/hour conditions of speed, product wet type of the present invention test piece to 0.5 millimeter of wide 10 mm thick is measured, record breaking tenacity 〉=4MPa, tearing toughness 〉=8KN/m, specific elongation rate 〉=100%.
Following examples specify the process that the present invention prepares medical anti-adhesive silicon rubber graft copolymer membrane:
Embodiment 1:
(1) mixing ingredient moulding:
The methyl ethylene silicon raw rubber of 100 parts of contents of ethylene about 4% by bag roller refining glue, is added 50 parts of No. 2 gas-phase silicas then and carries out mixingly, add 5 parts of hydroxy silicon oils again, thin-pass 15 times, following sheet was parked 48 hours.After appropriate back mixing, get the sizing material of certainweight, be placed between the polyester film of each cleaning up and down, together be put in tabletting machine with these two polyester films sizing material, under the condition of room temperature, pressure 2MPa, be pressed into 0.3 millimeter diaphragm, remove sheet together with polyester film one up and down then.
(2) radiation crosslinking:
Above-mentioned diaphragm is vertically placed 60,000 Curie's cobalt 60 irradiation fields, is that 28 ℃, dose rate are that 16.7 kilogray (kGy)s/hour following irradiation was promptly finished crosslinked in 5 hours in temperature.
Peel the diaphragm after crosslinked off two layers polyester film up and down, the sample that on middle layered material diaphragm, takes a morsel, drying, W weighs
1=0.3573 gram is cut into 0.3 * 0.3 millimeter
2The fragment of size after the copper wire gauze wrapping, is put into extractor, uses the benzene extracting after 48 hours, drying, and W weighs
2=0.3368 gram calculates its cohesion mark according to weighting method, to determine whether gel fraction reaches 〉=94% requirement.The calculated for gel mark:
(3) radiation grafting:
Layered material diaphragm in the middle of above-mentioned is immersed in the ethanol, under 60 ℃ of temperature, soaked 4 hours, put into vacuum drying oven then, 8.66 * 10
3Be dried to constant weight W under Pa pressure and 60 ℃ of temperature
0
This dried diaphragm is placed the grafting bottle, be placed with the grafting liquid of forming by HEMA20%, ethanol 80% for preparing in advance in the grafting bottle, diaphragm is immersed in the grafting liquid, seal after filling the nitrogen deoxygenation, place cobalt 60 irradiation fields, in temperature is that 28 ℃, dose rate are 5 kilogray (kGy)s/hour following irradiation 50 minutes, takes out diaphragm, uses earlier distilled water wash; Be placed in the distilled water repeatedly digestion washing 8 hours to remove homopolymer, then with alcohol immersion washing 4 hours to clean, put into vacuum drying oven and dry to constant weight, standby with the clean-keeping paper parcel.
Embodiment 2, and batching is 100 parts of methyl ethylene rubbers, 45 parts of gas-phase silicas, 4 parts of hydroxy silicon oils; Employing dose rate 25 kilogray (kGy)s during cross-linking radiation/hour, 12 ℃ of irradiation temperatures, irradiation 2 hours; It is HEMA20% that irradiation grafting adopts weight proportion, ethanol 60%, the grafting liquid of water 20%, radiation dose rate adopt 3 kilogray (kGy)s/hour, 12 ℃ of irradiation temperatures, irradiation 1.5 hours.All the other steps are with embodiment 1.
Claims (2)
1. the preparation method of a medical stick-resistant silastic membrane is characterized in that via following process steps:
(1) batching system film: raw material is pressed 100 parts of methyl ethylene silicon raw rubbers, gas-phase silica 45-55 part, the weight proportion of hydroxy silicon oil 3-8 part is mixing successively evenly, through thin-pass, park, back mixing, extrusion forming, making thickness is the silicon rubber diaphragm of 0.2-0.5 millimeter;
(2) radiation crosslinking: the above-mentioned diaphragm that makes is placed irradiation field, carry out radiation vulanization under certain irradiation temperature, irradiation dose is the 50-100 kilogray (kGy), makes gel fraction after crosslinked greater than 94%; Described irradiation temperature is a room temperature to 55 ℃;
(3) radiation grafting: place ethanol to soak more than 4 hours on the silicon rubber diaphragm behind the above-mentioned radiation crosslinking, soaking temperature is a room temperature to 60 ℃, take out the washing back, dry to constant weight, then diaphragm is immersed in the grafting liquid, sealing is behind the letting nitrogen in and deoxidizing, place irradiation field, irradiation dose is the 3-5 kilogray (kGy); Grafting diaphragm behind the irradiation is put into distilled water digestion washing more than 4 hours repeatedly, again with after the alcohol immersion, drying; The weight proportion of described grafting liquid is HEMA: ethanol: water=20: 60-80: 20-0.
2. the preparation method of silicone rubber membrane according to claim 1 is characterized in that described irradiation field can be a cobalt 60, also can be linear accelerator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91100853A CN1039590C (en) | 1991-02-08 | 1991-02-08 | Medical stick-resistant silastic membrane and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91100853A CN1039590C (en) | 1991-02-08 | 1991-02-08 | Medical stick-resistant silastic membrane and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1063877A CN1063877A (en) | 1992-08-26 |
| CN1039590C true CN1039590C (en) | 1998-08-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN91100853A Expired - Fee Related CN1039590C (en) | 1991-02-08 | 1991-02-08 | Medical stick-resistant silastic membrane and preparation thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363429C (en) * | 2004-11-04 | 2008-01-23 | 上海橡胶制品研究所 | Silicon rubber membrane and its production method |
| CN104623753B (en) * | 2013-05-25 | 2017-02-01 | 芜湖道润药业有限责任公司 | Anti-adhesion material of pair PVC (polyvinyl chloride) medical soup storage bag and operation process |
| CN104623752B (en) * | 2013-05-25 | 2017-02-01 | 芜湖道润药业有限责任公司 | Anti-adhesion material of pair PVC (polyvinyl chloride) medical soup storage bag and operation process |
| CN112239558A (en) * | 2020-09-02 | 2021-01-19 | 南京航空航天大学 | Hydrophilic swellable silicone rubber and radiation chemical preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256166A (en) * | 1961-06-27 | 1966-06-14 | Grace W R & Co | Photo-initiated graft polymerization of cellulosic compositions |
| US3826678A (en) * | 1972-06-06 | 1974-07-30 | Atomic Energy Commission | Method for preparation of biocompatible and biofunctional materials and product thereof |
| US5080924A (en) * | 1989-04-24 | 1992-01-14 | Drexel University | Method of making biocompatible, surface modified materials |
-
1991
- 1991-02-08 CN CN91100853A patent/CN1039590C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3256166A (en) * | 1961-06-27 | 1966-06-14 | Grace W R & Co | Photo-initiated graft polymerization of cellulosic compositions |
| US3826678A (en) * | 1972-06-06 | 1974-07-30 | Atomic Energy Commission | Method for preparation of biocompatible and biofunctional materials and product thereof |
| US5080924A (en) * | 1989-04-24 | 1992-01-14 | Drexel University | Method of making biocompatible, surface modified materials |
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| CN1063877A (en) | 1992-08-26 |
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