CN1228447A - Medical cross-linked polyacrylamide gel and its preparing method - Google Patents
Medical cross-linked polyacrylamide gel and its preparing method Download PDFInfo
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- CN1228447A CN1228447A CN 99116009 CN99116009A CN1228447A CN 1228447 A CN1228447 A CN 1228447A CN 99116009 CN99116009 CN 99116009 CN 99116009 A CN99116009 A CN 99116009A CN 1228447 A CN1228447 A CN 1228447A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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Abstract
The preparation method of medical polyacrylamide hydrogel includes the following steps: using crosslinked acrylamide as substrate, dispersing a proper quantity of acrylamide, crosslinking agent, catalyst, accelerator and promotor in sterile secondary distilled water medium to make them produce polymerization reaction to prepare, then making the obtained gel undergo the processes of washing, soaking and extraction after-treatments, and making it into the medical hydrogel with different crosslinking density and concentration. The chemical stability of said hydrogel is good, and its thermal stability is good, residual free monomer content is low, pH value is stable and heavy metal content is low.
Description
The present invention relates to the medicochemistry goods, be specifically related to a kind of medical cross-linked polyacrylamide gel and preparation method thereof.
In the last hundred years, cosmetic plastic surgery doctor and the brainstrust of being engaged in the development medical material are all being sought a kind of surrogate of human body soft tissue.As far back as the 19th-century end, Gersuny ' s at first reports with whiteruss and replaces testis as weighting agent.Also there are human beeswax organic oil or inorganic wet goods this phase; The sixties in 20th century, people begin to adopt liquid-state silicon gel, tetrafluoroethylene paste and particle etc., but all because of existing problem in various degree to be eliminated.Over past ten years, people begin to adopt bovine collagen, autologous fat, gelatin substrate etc., but these material great majority just are absorbed behind some months, use to be restricted and the possibility of bringing out immunological rejection arranged.Therefore, more preferably based on the biocompatible hydrogel material of synthetic polymer.Disclose a kind of biocompatible hydrogel as Chinese invention patent application 94195147, comprise polymkeric substance based on polyacrylamide, by using the biocompatibility linking agent, preparing as using the catalyzer of radical polymerization effect in the apirogen water of dispersion medium.This kind material has good elasticity, conformality and stability, is fit to the requirement of treatment and lift face.But what above-mentioned patent application was adopted is the oxidation system of single catalyst, and reaction conditions does not have clearly restriction, after finishing, polyreaction do not carry out aftertreatment, thereby there is the quality instability in the hydrogel that obtains, reaction not exclusively, defective such as the content of free monomer is higher.
The objective of the invention is in order to overcome above-mentioned the deficiencies in the prior art part, and provide a kind of residual monomer content less, medical hydrogel of polyacrylamide of excellent property and preparation method thereof.This method adopts redox system, has increased accelerator, makes response intensity more steady, and polymerization technology is controlled easily.Selected the polyreaction top condition simultaneously, under nitrogen protection, temperature, time have all been done clearly restriction, and reaction is carried out fully.Simultaneously, the preparation process of this hydrogel has also adopted technologies such as polyreaction, aftertreatment, gel preparation.Make the hydrogel product steady quality, the qualification rate height.
The objective of the invention is to reach: construct a kind of medical hydrogel of polyacrylamide by following measure, with the crosslink propylene acid amides is matrix, carry out polyreaction in the aseptic second distillation water medium and prepare by an amount of acrylamide, linking agent, catalyzer, accelerator and promotor are distributed to, it is characterized in that, aftertreatments such as the gel that polyreaction is obtained washs, soaks, extraction are mixed with the medical aquogel of different degree of crosslinking and concentration then.
Because the present invention has increased aftertreatment technology in the process of preparation medical hydrogel of polyacrylamide, thereby greatly reduces the content of goods free monomers.With reference to the analytical procedure of GB12005.5-89, utilizing the measured value of gas chromatograph (GC, model SP-3700) residual monomer content is 0.0000016%, thereby greatly reduces the toxicity of hydrogel articles, has satisfied the needs of field of orthopedic surgery well.
The raw-material specification of the preparation of medical cross-linked polyacrylamide gel of the present invention sees Table 1, its weight percentage composition is: the acrylamide of 2.5-8%, the linking agent of 0.001-3.0%, the catalyzer of 0.001-4.00%, the accelerator of 0.001-2.00%, the aseptic redistilled water of the promotor of 0.001-2.00% and surplus.
In the preparation of medical cross-linked polyacrylamide gel of the present invention, preferred cross-linking agents is N, N '-ethylene bisacrylamide and homologue or N, N ' diallyl tartrate diamide.Adopt the molecular structure of chemistry of the prepared polymkeric substance of these preferred cross-linking agents good, elastic space is big, is fit to very much the needs of field of orthopedic surgery.
Described catalyzer can be Ammonium Persulfate 98.5 or Potassium Persulphate.
Preferred accelerator can be sodium bisulfite or sodium metabisulphite, and these accelerators play reductive agent in polyreaction, thereby reaction is carried out thoroughly, and residual free monomer content is few.
Preferred promotor comprises trolamine or triethylamine and contains substituent N, N ' ethylenediamines, and these promotor have the effect of stable pH value.
The present invention also provides the preparation method of described medical cross-linked polyacrylamide gel, may further comprise the steps:
An amount of acrylamide, linking agent, catalyzer, accelerator and promotor are distributed in the aseptic second distillation water medium, and thorough mixing feeds the rare gas element deoxygenation, carries out polyreaction under 20 ℃-35 ℃ condition;
Aftertreatments such as the gel that polyreaction is obtained washs, soaks, extraction;
Solid cross-linked polyacrylamide powder and redistilled water after handling are mixed with medical aquogel, and wherein, the content of cross-linked polyacrylamide is 2.5-8.0wt%.
Before carrying out polyreaction, raw material propylene acid amides that polyreaction is used and linking agent carry out recrystallization to be handled to purify and makes starting material reach subordinate list 1 defined technical indicator.
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Fig. 1 is in the preparation process of medical cross-linked polyacrylamide gel of the present invention, the synoptic diagram of polyreaction;
Fig. 2 is preparation technology's schema of medical cross-linked polyacrylamide gel of the present invention.
Embodiment 1:
With 25 gram acrylamides, 18 milliliter 1% N, the N '-ethylene bisacrylamide aqueous solution, 8 milliliter 1% the trolamine aqueous solution, in one liter of reaction flask, mix, impurity screening adds 10 milliliter 0.5% the Ammonium Persulfate 98.5 aqueous solution and 8 milliliter 0.4% aqueous solution of sodium bisulfite then, adds water and makes cumulative volume reach 982 milliliters, removed deoxidation in logical nitrogen 10-20 minute, under 25-30 ℃, insulation reaction 20-24 hour, just obtain containing the gel of 2.5% cross-linked polyacrylamide.With the gel stripping and slicing that forms, thorough washing, immersion, solvent extraction are filtered, and white polypropylene acrylamide gel solid is dried under 40-50 ℃ of vacuum, pulverize, and are mixed with 2.5% cross-linked polyacrylamide gel with redistilled water.Embodiment 2:
With 35 gram acrylamides, 35 milliliter 1% N, the N '-ethylene bisacrylamide aqueous solution, 15 milliliter 1% the trolamine aqueous solution, 35 milliliter 0.5% persulfate aqueous solution, 10 milliliter 0.4% aqueous solution of sodium bisulfite, in one liter of reaction flask, mix, adding water is 875 milliliters to cumulative volume, impurity screening, logical nitrogen deoxygenation, 25 ℃ of standing and reacting, after treating gel formation,, form the gel that contains 4% cross-linked polyacrylamide in 25-30 ℃ of insulation reaction 30 hours.Post-treating method is with example 1.Embodiment 3:
With 30 gram acrylamides, 45 milliliter 1% N, the N '-ethylene bisacrylamide aqueous solution, 4 milliliter 1% the trolamine aqueous solution, 70 milliliter 0.5% the Ammonium Persulfate 98.5 aqueous solution mixes in 500 milliliters of reaction flasks, and adding water is 375 milliliters to cumulative volume, after stirring fully, impurity screening, logical nitrogen deoxygenation formed gel in 30 minutes 20 ℃ of standing and reacting, be warmed up to 25 ℃ of sustained reactions 24 hours, form the hydrogel that contains 8% cross-linked polyacrylamide.Post-treating method is with example 1.
The physicochemical property test result of medical cross-linked polyacrylamide gel of the present invention is as follows: (1) outward appearance: transparent, colourless gel, no tramp material.(2)PH： 7-7.5。(3) heavy metal (Pb) content: 0.04PPM.(4) refractive index: 1.3375-1.3385.(5) chemical structure is identified: cross-linked polyacrylamide (IR).(6) remaining acrylamide monomer content range: 0.0000016%-0.000002%.(7) thermostability:＞300 ℃.(DSC differential thermal analysis).(8) chemical stability: after boiling water boiled, IR identified that chemical structure does not change.(9) oxidation capacity: maximum 0.2mg/ rises O
2(10) bromination ability: maximum 0.1mg/ rises Br
2
Above-mentioned data show, medical cross-linked polyacrylamide gel chemical stability of the present invention is good, Heat stability is good, residual free monomer content is few, pH value is stable, heavy metal content is low, meets the international standard (ISO10993-1:1992) that the biomaterial for medical purpose biological safe is estimated fully, also meets the relevant regulations that China Ministry of Health in 1997 and State Pharmaceutical Administration issue.
Table 1 preparation hydrophilic polyacrylamide gel is used specifications of raw materials
Claims (12)
1. medical hydrogel of polyacrylamide, it is characterized in that, with the crosslink propylene acid amides is matrix, carry out polyreaction in the aseptic second distillation water medium and prepare by an amount of acrylamide, linking agent, catalyzer, accelerator and promotor are distributed to, aftertreatments such as the gel that polyreaction is obtained washs, soaks, extraction are mixed with the medical aquogel of different degree of crosslinking and concentration then.
2. medical cross-linked polyacrylamide gel according to claim 1, it is characterized in that: preparing raw-material weight percentage composition is: the acrylamide of 2.5-8%, the linking agent of 0.001-3.0%, the catalyzer of 0.001-4.00%, the accelerator of 0.001-2.00%, the aseptic redistilled water of the promotor of 0.001-2.00% and surplus.
3. medical cross-linked polyacrylamide gel according to claim 1 and 2 is characterized in that: in the medical aquogel that is mixed with, the content of described cross-linked polyacrylamide is 2.5-8.0wt%.
4. medical cross-linked polyacrylamide gel according to claim 1 is characterized in that: join described linking agent and comprise N, N '-ethylene bisacrylamide and homologue or N, N ' diallyl tartrate diamide.
5. medical cross-linked polyacrylamide gel according to claim 1 and 2 is characterized in that: described accelerator comprises sodium bisulfite or sodium metabisulphite.
6. medical cross-linked polyacrylamide gel according to claim 1 and 2 is characterized in that: described promotor comprises trolamine or triethylamine and contains substituent N, N ' ethylenediamines.
7. the preparation method of claim 1 or 2 medical cross-linked polyacrylamide gel, may further comprise the steps: an amount of acrylamide, linking agent, catalyzer, accelerator and promotor are distributed in the aseptic second distillation water medium, thorough mixing, carry out polyreaction, it is characterized in that:
Aftertreatments such as the hydrogel that polyreaction is obtained washs, soaks, extraction;
Cross-linked polyacrylamide and redistilled water after handling are mixed with medical aquogel.
8. the preparation method of medical cross-linked polyacrylamide gel according to claim 7, it is characterized in that: preparing raw-material weight percentage composition is: the acrylamide of 2.5-8%, the linking agent of 0.001-3.0%, the catalyzer of 0.001-4.00%, the accelerator of 0.001-2.00%, the aseptic redistilled water of the promotor of 0.001-2.00% and surplus.
9. the preparation method of medical cross-linked polyacrylamide gel according to claim 7 is characterized in that: before carrying out described polyreaction, raw material propylene acid amides that polyreaction is used and linking agent carry out recrystallization to be handled and purifies.
10. the preparation method of medical cross-linked polyacrylamide gel according to claim 7, it is characterized in that: will carry out in the formulated medical aquogel through the solid cross-linked polyacrylamide and the redistilled water of aftertreatment, the content of cross-linked polyacrylamide is 2.5-8.0wt%.
11. the preparation method of medical cross-linked polyacrylamide gel according to claim 7 is characterized in that: before described polyreaction is carried out, in mixing solutions, feed the rare gas element deoxygenation.
12. the preparation method of medical cross-linked polyacrylamide gel according to claim 7 is characterized in that: described polyreaction is to carry out under 20-35 ℃ condition, and the carrying out time of polyreaction is 10-25 hour.
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| CN99116009A CN1068612C (en) | 1999-01-15 | 1999-01-15 | Medical cross-linked polyacrylamide gel and its preparing method |
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| CN99116009A CN1068612C (en) | 1999-01-15 | 1999-01-15 | Medical cross-linked polyacrylamide gel and its preparing method |
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| CN1068612C CN1068612C (en) | 2001-07-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116321C (en) * | 2000-04-21 | 2003-07-30 | 郑永碧 | Process for preparing, purifying and testing medical hydrogel of polyacrylamide |
| US7186419B2 (en) | 2000-08-25 | 2007-03-06 | Contura Sa | Polyacrylamide hydrogel for arthritis |
| US7678146B2 (en) | 2000-08-25 | 2010-03-16 | Contura A/S | Polyacrylamide hydrogel and its use as an endoprosthesis |
| CN110818832A (en) * | 2019-10-29 | 2020-02-21 | 江西科技师范大学 | Acrylamide granular hydrogel fire extinguishing agent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030176602A1 (en) * | 2001-08-25 | 2003-09-18 | Richard Schmidt | Temperature-controlled process for preparation of homogeneous polymers |
| CN1300221C (en) * | 2005-01-25 | 2007-02-14 | 天津大学 | Process for preparing rapidly responsive pH sensitive hydrogel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4746551A (en) * | 1985-11-20 | 1988-05-24 | Micro-Map, Inc. | Rehydratable polyacrylamide gels |
| UA10911C2 (en) * | 1994-08-10 | 1996-12-25 | Мале Впроваджувальне Підприємство "Іhтерфалл" | Biocompatible hydrogel |
-
1999
- 1999-01-15 CN CN99116009A patent/CN1068612C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116321C (en) * | 2000-04-21 | 2003-07-30 | 郑永碧 | Process for preparing, purifying and testing medical hydrogel of polyacrylamide |
| US7186419B2 (en) | 2000-08-25 | 2007-03-06 | Contura Sa | Polyacrylamide hydrogel for arthritis |
| US7678146B2 (en) | 2000-08-25 | 2010-03-16 | Contura A/S | Polyacrylamide hydrogel and its use as an endoprosthesis |
| US7780958B2 (en) | 2000-08-25 | 2010-08-24 | Contura Sa | Polyacrylamide hydrogel for the treatment of incontinence and vesicouretal reflux |
| US7790194B2 (en) | 2000-08-25 | 2010-09-07 | Contura A/S | Polyacrylamide hydrogel as a soft tissue filler endoprosthesis |
| US7935361B2 (en) | 2000-08-25 | 2011-05-03 | Contura A/S | Polyacrylamide hydrogel as a soft tissue filler endoprosthesis |
| US8216561B2 (en) | 2000-08-25 | 2012-07-10 | Contura A/S | Polyacrylamide hydrogel for the treatment of incontinence and vesicouretal reflex |
| CN110818832A (en) * | 2019-10-29 | 2020-02-21 | 江西科技师范大学 | Acrylamide granular hydrogel fire extinguishing agent |
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| CN1068612C (en) | 2001-07-18 |
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Address after: 130042 No. 8, Yueyang street, Changchun, Jilin Applicant after: Jilin Fuhua Medical High Moleuclar Material Co., Ltd. Address before: 518001 No. 2202 North Renmin Road, Shenzhen, Guangdong, Luohu District Applicant before: Cao Mengjun |
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Effective date of registration: 20060818 Address after: 518003 Shenzhen city Luohu District Huang Bei Road No. 1004 Shenzhen Fuhua Medical Esthetic Hospital Patentee after: Cao Mengjun Address before: 130042 No. 8, Yueyang street, Changchun, Jilin Patentee before: Jilin Fuhua Medical High Moleuclar Material Co., Ltd. |
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