CN1377726A - Process for preparing phenolic resin hollow fibre film for auxiliary respirator - Google Patents
Process for preparing phenolic resin hollow fibre film for auxiliary respirator Download PDFInfo
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- CN1377726A CN1377726A CN 02100265 CN02100265A CN1377726A CN 1377726 A CN1377726 A CN 1377726A CN 02100265 CN02100265 CN 02100265 CN 02100265 A CN02100265 A CN 02100265A CN 1377726 A CN1377726 A CN 1377726A
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- doughnut
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Abstract
The present invention belongs to the field of bioengineering material technology. PVB material and phenolic resin in the weight ratio of 1 to 1-10 are mixed and dissolved in methanol to prepare 8-28 % concentration solution; the solution is produced into spinning dope through reduced pressure distillation, filtering and debubbling; and the spinning dope is further produced into hollow phenolic resin fiber film through stretching, carbonation, strengthening, toughening, anticoagulation and other specific steps. The material is non-toxic, has no toxic side effect, and may be used clinically; and it may be used in auxiliary respirator for extraneous and intracorporal use.
Description
Technical field
The present invention relates to a kind of doughnut preparation methods, relate in particular to a kind of doughnut preparation method of film material that is used for respiratory auxiliary system, belong to the biological engineering material technical field.
Background technology
Respiratory auxiliary system is a kind of supplemental treatment to the respiratory failure patient.Traditional treatment is the main mechanical ventilation method of using except that oxygen uptake, internal medicine support, anti-inflammatory method, and the method often causes further injury of lungs with wind-contusion.Desirable treatment is as early as possible, effectively to correct hypoxemia and hypercapnia, and body is not caused additional damage.Various respiratory auxiliary systems have been produced thus.The respiratory auxiliary system that uses has bubble type, blood membrane type, three types of membrane types (Liu Qingjun, artificial organs, 1984:P46～48) at present.Wherein blood forms thin film on the surface of metal or plastic plate in bubble type and blood membrane type respiratory auxiliary system, and blows oxygen and make blood oxidation.Because blood directly contacts with oxygen, easily produces bubble and haemolysis, is eliminated gradually.And the membrane type respiratory auxiliary system before this with thick be the function of the silicon rubber of 10-30 μ m or poly tetrafluoroethylene imitation body lung because film breaks easily, must strengthen with the polyester fiber network, make the capillary type artificial lung with silicon rubber, polypropylene afterwards.Thousands of capillaries are formed a branch of, linked to each other in the cylinder that is full of oxygen of packing into or with oxygen cylinder, blood is by in the capillary or outer process, and the carbon dioxide in the blood just exchanges between capillary wall with the oxygen in the cylinder.But because distribution of pores inequality on the capillary wall, reasons such as the easy infiltration of blood plasma and hydrone, existing respiratory auxiliary system can only provide 30% of adult's oxygen demand, (the Cox CS that has only 2～8 hours service life, Zwischenberger JB, Traber LD, et al.Use of an intravascular oxygenator IVOX inan ovine smoke inhalation injury model.ASAIO Trans, 1991,37:M411-M413) used membrane material is at biocompatibility, water, infiltration of plasma, aspect of performances such as the selectivity exchange of oxygen and carbon dioxide all can not meet clinical needs, and its scope of application has been subjected to very big restriction.Develop a kind of nontoxic, have no side effect, long service life and gas exchange rate height, the membrane material that is used for respiratory auxiliary system are the problems that presses for solution.
Summary of the invention
The present invention is intended to propose a kind of preparation method of phenolic resins hollow-fibre membrane of respiratory auxiliary system, make it at biocompatibility, water, infiltration of plasma, aspect of performances such as the selectivity exchange of oxygen and carbon dioxide can meet clinical needs, with service life of improving respiratory auxiliary system and enough oxygen demands are provided.
The present invention is achieved through the following technical solutions: a kind of preparation method of phenolic resins hollow-fibre membrane of respiratory auxiliary system, and this method may further comprise the steps successively:
(1) with pore-foaming agent polyvinyl butyral (PVB) with after refining phenolic resins mixes by 1: 1～10 (W/W), be dissolved in and make 8～28% solution in the methyl alcohol, decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) adopt fusion method that above-mentioned spinning solution is prepared into the nascent doughnut of linear phenolic aldehyde on spinning-drawing machine, through biaxial tension, washing, be placed on crosslinked in formaldehyde (or five dialdehyde) and the aqueous solution of hydrochloric acid, curing then, making internal diameter is 8～100 μ m, and external diameter is the netted phenolic resins doughnut of 18-150 μ m;
(3) netted phenolic resins doughnut is placed slowly intensification in the stove, make it carry out charing and handle, make the doughnut that the cinclides average pore size is 16～40 ;
(4) doughnut after the charing is flooded in former spinning solution, (3) carry out the charing processing more set by step;
(5) will soak in quaternary amine and medical polymer material respectively through enhancing, toughness reinforcing doughnut, airing is standby then;
(6) with epoxy resin many doughnuts are encapsulated, solidify, promptly get the phenolic resins hollow-fibre membrane.
Described step (4) also can adopt the doughnut after the charing is at room temperature put into closed reactor, and feeding pressure is the fluorine of 1～1.5 crust, strengthens, toughness reinforcing.
Quaternary amine described in the above-mentioned steps (5) adopts benzyl alkyl ammonium chloride or cetyl trimethyl ammonium chloride, and described medical polymer material is any in liquaemin, taxol or the carboxylated Sulfation shitosan.
Because the present invention is by the microcellular structure of control doughnut, improve technology and prepare ultra-fine doughnut, oxidation and charing improve its biocompatibility under specific temperature conditions, and by compound or fluoridize enhancing, toughness reinforcing, adsorb liver sodium etc., prepare the respiratory auxiliary system of gas exchange rate height, long service life.
Experiment shows, the phenolic resins doughnut of the present invention's preparation is at biocompatibility, water, infiltration of plasma, aspect of performances such as the selectivity exchange of oxygen and carbon dioxide can both meet clinical needs preferably, respiratory auxiliary system with its preparation, at least do not cause blood coagulation in 3 months, gas exchange rate is more than 80%, can be used as in the body or external respiration auxiliary system uses for a long time.
The specific embodiment:
(1) preparation spinning solution
Pore-foaming agent polyvinyl butyral (PVB) with after refining phenolic resins mixes by 1: 1～10 (W/W), is dissolved in and makes 8～28% solution in the methyl alcohol, and decompression distillation is except that desolvating, and spinning solution is made in filtration, deaeration;
(2) preparation doughnut
Adopt fusion method under 150～190 ℃ of temperature, above-mentioned spinning solution to be prepared into the nascent doughnut of linear phenolic aldehyde on spinning-drawing machine, through biaxial tension, washing, be placed on then contain crosslinked in 0.1～0.5M formaldehyde (or five dialdehyde) and the 0.1～0.2M aqueous solution of hydrochloric acid, solidified 0.5～1 hour, making internal diameter is 8～100 μ m, and external diameter is the netted phenolic resins doughnut of 18～150 μ m;
(3) carry out oxidation, charing processing
Netted phenolic resins doughnut placed slowly be warming up to 900 ℃ (programming rates: 2 ℃/minute) in the stove, at N
2Under the protection, constant temperature 0.5 hour makes it carry out charing and handles, and makes the doughnut that the cinclides average pore size is 16～40 ;
(4) enhancing of doughnut, toughness reinforcing doughnut after the charing was flooded in former spinning solution 30～60 minutes, (3) are carried out charing and are handled again set by step;
(5) surface treatment
To soak 2～6 hours in 0.2～1M quaternary amine and 0.1～0.2M medical polymer material respectively through enhancing, toughness reinforcing doughnut, airing can make the phenolic resins doughnut.
(6) assembling
With epoxy resin 600～1000 doughnuts are encapsulated, solidify, promptly get the phenolic resins hollow-fibre membrane.
Above-mentioned steps (4) also can adopt the doughnut after the charing is at room temperature put into closed reactor, and the fluorine reaction that feeds pressure and be 1～1.5 crust strengthened in 6 hours to 72 hours, toughness reinforcing.
Quaternary amine described in the above-mentioned steps (5) adopts benzyl alkyl ammonium chloride or cetyl trimethyl ammonium chloride, and described medical polymer material is any in liquaemin, taxol or the carboxylated Sulfation shitosan.
Raw material phenolic aldehyde used in the present invention is the commercial goods, and methyl alcohol, formaldehyde, five dialdehyde, nitrogen, hydrogen, quaternary amine, liquaemin, shitosan, taxol, carboxylated Sulfation shitosan etc. are chemically pure reagent, is bought by Beijing, chemical reagent shop, Shanghai.The mensuration employing M500～10AX stretching testing machine of mechanical strength (Testometric UniversalTester, England), test speed is 1mm/min, test specification is 10mm.ASAP2010 nitrogen adsorption instrument (American), N are adopted in the aperture test
2The molecule cross section is 0.162nm
2, mark product bore is 9.530mm.
Embodiment 1:
(1) preparation spinning solution
Be 300 polyvinyl butyral (PVB) with weight average molecular weight with after refining phenolic resins mixes by 1: 1 (W/W), be dissolved in and make 8% solution in the methyl alcohol that decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) preparation doughnut
Adopt fusion method under 150 ℃ temperature, above-mentioned spinning solution prepare the linear phenolic aldehyde doughnut of coming into being on spinning-drawing machine, through biaxial tension, washing, be placed on then crosslinked in the formaldehyde that contains 0.1M and the 0.1M aqueous solution of hydrochloric acid, solidify, solidified 0.5 hour, the internal diameter that makes doughnut is 10～50 μ m, and external diameter is the netted phenolic resins doughnuts of 20～70 μ m;
(3) carry out oxidation, charing processing
Above-mentioned netted doughnut placed slowly be warming up to 900 ℃ (2 ℃/minute) in the stove; constant temperature is 1 hour then; constant temperature is 0.5 hour under nitrogen protection; making the cinclides average pore size is the doughnut charcoal of 40 ; its tensile strength is 0.5 ± 0.01GPa; elastic modelling quantity is 60 ± 1GPa, extension at break 0.5 ± 0.01%.
(4) enhancing of doughnut, toughness reinforcing
Doughnut after the charing was flooded 30 minutes in former spinning solution, reoxidize and the charing processing, the tensile strength of doughnut improves 20%, and Young's modulus improves 10%.
(5) surface treatment
Will through enhancing, toughness reinforcing doughnut, in the aqueous solution of the liquaemin that contains 0.2M benzyl alkyl ammonium chloride and 0.1M, soaked 2 hours respectively, airing can make the phenolic resins doughnut that the anticoagulation time reaches 3 months.
(6) assembling
With epoxy resin 600 doughnuts are encapsulated, solidify, sterilization; Use silicon rubber tubule connection oxygen cylinder and the negative pressure pump handled through anticoagulation (0.015MPa), can make respiratory auxiliary system again.
Embodiment 2:
(1) preparation spinning solution
Be 300 polyvinyl butyral (PVB) with weight average molecular weight with after refining phenolic resins mixes by 1: 3 (W/W), be dissolved in and make 10% solution in the methyl alcohol that decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) preparation doughnut
Adopt fusion method under 160 ℃ temperature, above-mentioned spinning solution prepare the linear phenolic aldehyde doughnut of coming into being on spinning-drawing machine, through suitably biaxial tension, washing, be placed on then crosslinked in the formaldehyde that contains 0.2M and the 0.1M aqueous solution of hydrochloric acid, solidified 0.5 hour, getting the doughnut internal diameter is 8～100 μ m, and external diameter is the netted phenolic resins doughnut of 18～150 μ m;
(3) carry out oxidation, charing processing
Above-mentioned netted doughnut placed slowly be warming up to 900 ℃ (2 ℃/minute) in the stove, constant temperature is 1 hour then, at N
2Constant temperature is 0.5 hour under the protection, and making the cinclides average pore size is the doughnut charcoal of 30 , and its tensile strength is 1 ± 0.01GPa, and elastic modelling quantity is 100 ± 1GPa, extension at break 0.5 ± 0.01%.
(4) enhancing of doughnut, toughness reinforcing
The doughnut of charing was flooded 60 minutes in former spinning solution, reoxidize or the charing processing, the tensile strength of doughnut improves 30%, and Young's modulus improves 25%.
(5) surface treatment
Will through enhancing, toughness reinforcing doughnut, in the liquaemin of 1.0M benzyl alkyl ammonium chloride and 0.2M, soaked 4 hours airing respectively.
(6) assembling
With epoxy resin 800 doughnuts are encapsulated, solidify, sterilization uses the silicon rubber tubule of handling through anticoagulation to be communicated with oxygen cylinder again and negative pressure pump (0.020MPa), can make respiratory auxiliary system.
Embodiment 3:
(1) preparation of spinning solution
Be 300 polyvinyl butyral (PVB) with weight average molecular weight with after refining phenolic resins mixes by 1: 6 (W/W), be dissolved in and make 15% solution in the methyl alcohol that decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) preparation of doughnut
Adopt fusion method under 180 ℃ temperature, above-mentioned spinning solution prepare the linear phenolic aldehyde doughnut of coming into being on spinning-drawing machine, through suitably biaxial tension, washing, be placed on then crosslinked in five dialdehyde that contain 0.1M and the 0.2M aqueous solution of hydrochloric acid, solidified 1 hour, the internal diameter that gets doughnut is 8-100 μ m, and external diameter is the netted phenolic resins doughnut of 18-150 μ m;
(3) carrying out oxidation and charing handles
Above-mentioned netted doughnut placed slowly be warming up to 900 ℃ (2 ℃/minute) in the stove, at N
2Constant temperature is 0.5 hour under the protection, makes the hollow fiber carbon membrane that the cinclides average pore size is 20 , and its tensile strength is 4 ± 0.01GPa, and elastic modelling quantity is 100 ± 0.5GPa, extension at break 0.5 ± 0.01%.
(4) enhancing of doughnut, toughness reinforcing
The doughnut of charing is put into airtight nickel reactant device, feed the F of 1 crust
2, reacted 6 hours.The tensile strength of doughnut improves 30%, and Young's modulus carries 15%.
(5) surface treatment
Will through enhancing, toughness reinforcing doughnut, in the taxol of 0.2M cetyl trimethyl ammonium chloride and 0.1M, soaked 4 hours airing respectively.
(6) assembling
With epoxy resin 1000 doughnuts are encapsulated, solidify, sterilize, use the silicon rubber tubule of handling through anticoagulation to be communicated with oxygen cylinder and negative pressure pump again, can make respiratory auxiliary system.
Embodiment 4:
(1) preparation spinning solution
Be 300 polyvinyl butyral (PVB) with weight average molecular weight with after refining phenolic resins mixes by 1: 10 (W/W), be dissolved in and make 28% solution in the methyl alcohol that decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) preparation doughnut
Adopt fusion method under 190 ℃ temperature, above-mentioned spinning solution prepare the linear phenolic aldehyde doughnut of coming into being on spinning-drawing machine, through suitably biaxial tension, washing, be placed on then crosslinked in five or the two pure and mild 0.2M aqueous solution of hydrochloric acid that contain 0.5M, solidified 1 hour, making internal diameter is 8-100 μ m, and external diameter is the netted phenolic resins doughnut of 18-150 μ m;
(3) carry out oxidation, charing processing
Above-mentioned netted doughnut placed slowly be warming up to 900 ℃ (2 ℃/minute) in the stove, at N
2Constant temperature is 0.5 hour under the protection, makes the hollow fiber carbon membrane that the cinclides average pore size is 16 , and its tensile strength is 3 ± 0.05GPa, and elastic modelling quantity is 120 ± 0.5GPa, extension at break 1.5 ± 0.02%
(4) enhancing of doughnut, toughness reinforcing
The doughnut of charing is put into airtight nickel reactant device, feed the F of 1.5 crust
2, to react 72 hours, the tensile strength of doughnut improves 35%, and Young's modulus carries 20%.
(5) surface treatment
Will through enhancing, toughness reinforcing doughnut, in the carboxylated Sulfation shitosan of 1.0M cetyl trimethyl ammonium chloride and 0.2M, soaked 4 hours respectively, airing, standby.
(6) assembling
With epoxy resin 1000 doughnuts are encapsulated, solidify, sterilization uses the silicon rubber tubule of handling through anticoagulation to be communicated with oxygen cylinder and negative pressure pump again, can make respiratory auxiliary system.
Claims (3)
1. the preparation method of a respiratory auxiliary system phenolic resins hollow-fibre membrane, this method may further comprise the steps successively:
(1) with pore-foaming agent polyvinyl butyral (PVB) with after refining phenolic resins mixes by 1: 1～10 (W/W), be dissolved in and make 8～28% solution in the methyl alcohol, decompression distillation is except that desolvating, spinning solution is made in filtration, deaeration;
(2) adopt fusion method that above-mentioned spinning solution is prepared into the nascent doughnut of linear phenolic aldehyde on spinning-drawing machine, through biaxial tension, washing, be placed on crosslinked in formaldehyde (or five dialdehyde) and the aqueous solution of hydrochloric acid, curing then, making internal diameter is 8～100 μ m, and external diameter is the netted phenolic resins doughnut of 18-150 μ m;
(3) netted phenolic resins doughnut is placed slowly intensification in the stove, make it carry out charing and handle, make the doughnut that the cinclides average pore size is 16～40 ;
(4) doughnut after the charing is flooded in former spinning solution, (3) carry out the charing processing more set by step;
(5) will soak in quaternary amine and medical polymer material respectively through enhancing, toughness reinforcing doughnut, airing is standby then;
(6) with epoxy resin many doughnuts are encapsulated, solidify, promptly get the phenolic resins hollow-fibre membrane.
2. according to the preparation method of the described respiratory auxiliary system phenolic resins of claim 1 hollow-fibre membrane, it is characterized in that described step (4) also can adopt at room temperature puts into closed reactor with the doughnut after the charing, feeding pressure is the fluorine of 1～1.5 crust, strengthens, toughness reinforcing.
3. according to the preparation method of claim 1 or 2 described respiratory auxiliary system phenolic resins hollow-fibre membranes, it is characterized in that the quaternary amine described in the above-mentioned steps (5) adopts benzyl alkyl ammonium chloride or cetyl trimethyl ammonium chloride, described medical polymer material is any in liquaemin, taxol or the carboxylated Sulfation shitosan.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021002657A CN1172741C (en) | 2002-01-11 | 2002-01-11 | Process for preparing phenolic resin hollow fibre film for auxiliary respirator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021002657A CN1172741C (en) | 2002-01-11 | 2002-01-11 | Process for preparing phenolic resin hollow fibre film for auxiliary respirator |
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| CN1377726A true CN1377726A (en) | 2002-11-06 |
| CN1172741C CN1172741C (en) | 2004-10-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102162154A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Method for preparing super-energy battery active electrical carbon hollow fibers |
| CN102179217A (en) * | 2011-03-10 | 2011-09-14 | 江苏国正新材料科技有限公司 | Preparation method of hyper-energy active electrical carbon hollow micro ball |
| CN102604320A (en) * | 2012-02-17 | 2012-07-25 | 北京雷特新技术实业公司 | Preparation method and application of resin composition for thermosetting aramid bulletproof composite material |
| CN107281571A (en) * | 2016-04-05 | 2017-10-24 | 裴嘉阳 | A kind of membrane type oxygen exchange device |
-
2002
- 2002-01-11 CN CNB021002657A patent/CN1172741C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102162154A (en) * | 2011-03-10 | 2011-08-24 | 江苏国正新材料科技有限公司 | Method for preparing super-energy battery active electrical carbon hollow fibers |
| CN102179217A (en) * | 2011-03-10 | 2011-09-14 | 江苏国正新材料科技有限公司 | Preparation method of hyper-energy active electrical carbon hollow micro ball |
| CN102162154B (en) * | 2011-03-10 | 2012-08-15 | 江苏国正新材料科技有限公司 | Method for preparing super-energy battery active electrical carbon hollow fibers |
| CN102179217B (en) * | 2011-03-10 | 2013-06-05 | 江苏国正新材料科技有限公司 | Preparation method of hyper-energy active electrical carbon hollow micro ball |
| CN102604320A (en) * | 2012-02-17 | 2012-07-25 | 北京雷特新技术实业公司 | Preparation method and application of resin composition for thermosetting aramid bulletproof composite material |
| CN102604320B (en) * | 2012-02-17 | 2015-10-14 | 北京航天雷特机电工程有限公司 | A kind of preparation method of thermoset aramid bulletproof composite material resin combination and application |
| CN107281571A (en) * | 2016-04-05 | 2017-10-24 | 裴嘉阳 | A kind of membrane type oxygen exchange device |
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| CN1172741C (en) | 2004-10-27 |
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