A kind of medical macromolecular materials and preparation method thereof

文档序号:1766766 发布日期:2019-12-03 浏览:33次 中文

阅读说明:本技术 一种医用高分子材料及其制备方法 (A kind of medical macromolecular materials and preparation method thereof ) 是由 朱水寿 刘彦 于 2019-09-02 设计创作,主要内容包括:本发明公开了一种医用高分子材料,其特征在于,是由如下重量份的各组分制成:双(二甲基氨基)二甲基硅烷/2,4-二氯-6-码啉代-1,3,5-三嗪缩聚物30-50份、2,4-双(二甲基氨基)-6-氟嘧啶/4,5-二氯-1,3-二氧五环-2-酮缩聚物20-30份、羧基橡胶25-35份、抗氧剂0.5-1.5份、多羧基笼型倍半硅氧烷10-20份。本发明还公开了所述医用高分子材料的制备方法。本发明公开的医用高分子材料刚性和韧性佳,综合性能优异,耐高温性能和机械力学性能好,抗菌抗静电效果显著,性能稳定性良好,使用寿命长。(The invention discloses a kind of medical macromolecular materials, it is characterized in that, it is made of each component of following parts by weight: bis- (dimethylamino) dimethylsilane/2, the chloro- 6- code quinoline generation of 4- bis- -1,3,5- 30-50 parts of triazine condensation polymers, bis- fluoropyrimidine/4 (dimethylamino) -6- 2,4-, chloro- 20-30 parts of 1, the 3- dioxolane -2- ketone condensation polymer of 5- bis-, 25-35 parts of carboxylic rubber, 0.5-1.5 parts of antioxidant, 10-20 parts of more carboxyl cage-type silsesquioxanes.The invention also discloses the preparation methods of the medical macromolecular materials.Medical macromolecular materials rigidity and toughness disclosed by the invention are good, and excellent combination property, high temperature resistance and mechanical mechanics property are good, and antibacterial antistatic significant effect, stability is good, long service life.)

1. a kind of medical macromolecular materials, which is characterized in that be made of each component of following parts by weight: bis- (dimethylaminos) Dimethylsilane/2,4- bis- chloro- 6- code quinoline generation 30-50 parts of -1,3,5- triazine condensation polymer, bis- (the dimethylamino) -6- fluorine of 2,4- Chloro- 20-30 parts of the 1,3- dioxolane -2- ketone condensation polymer of pyrimidine/4,5- bis-, 25-35 parts of carboxylic rubber, 0.5-1.5 parts of antioxidant, 10-20 parts of more carboxyl cage-type silsesquioxanes.

2. a kind of medical macromolecular materials according to claim 1, which is characterized in that the antioxidant is selected from antioxidant 264, at least one of antioxidant 330, antioxidant 1010, antioxidant 1076, irgasfos 168.

3. a kind of medical macromolecular materials according to claim 1, which is characterized in that the carboxylic rubber is Carboxy At least one of rubber, carboxy nitrile rubber.

4. a kind of medical macromolecular materials according to claim 1, which is characterized in that bis- (dimethylamino) diformazans The preparation method of the chloro- 6- code quinoline generation -1,3,5-triazines condensation polymer of base silane/2,4- bis-, includes the following steps: bis- (dimethyl Amino) dimethylsilane, the chloro- 6- code quinoline generation -1,3,5-triazines of 2,4- bis-, basic catalyst be dissolved in organic solvent, in normal pressure Be stirred to react at 50-70 DEG C lower 2-4 hours, after be warming up to 250-270 DEG C, at 50-150Pa carry out polycondensation reaction 8-12 it is small When, after reaction, be cooled to room temperature, be adjusted to normal pressure, after settle out in ethanol, then rotate removing ethyl alcohol, obtain bis- (dimethyl Amino) dimethylsilane/2,4- bis- chloro- 6- code quinoline generation -1,3,5- triazine condensation polymer.

5. a kind of medical macromolecular materials according to claim 4, which is characterized in that bis- (dimethylamino) diformazans Base silane, the chloro- 6- code quinoline of 2,4- bis- are 1:1.61:(0.3- for the mass ratio of -1,3,5- triazine, basic catalyst, organic solvent 0.6):(10-15)。

6. a kind of medical macromolecular materials according to claim 4, which is characterized in that the basic catalyst is selected from hydrogen-oxygen Change at least one of sodium, potassium hydroxide, sodium carbonate, potassium carbonate;The organic solvent is N,N-dimethylformamide, N- methyl At least one of pyrrolidones, dimethyl sulfoxide.

7. a kind of medical macromolecular materials according to claim 1, which is characterized in that the bis- (dimethylaminos of 2,4- Base) -6- fluoropyrimidine/4,5- bis- chloro- 1,3- dioxolane -2- ketone condensation polymer preparation method, include the following steps: 2,4- is bis- (dimethylamino) -6- fluoropyrimidine, chloro- 1, the 3- dioxolane -2- ketone of 4,5- bis-, sodium carbonate are dissolved in N-Methyl pyrrolidone, Be stirred to react 2-4 hours at 50-70 DEG C under normal pressure, after be warming up to 250-270 DEG C, polycondensation reaction 8- is carried out at 50-150Pa 12 hours, after reaction, be cooled to room temperature, be adjusted to normal pressure, after settle out in ethanol, then rotate removing ethyl alcohol, obtain 2,4- The chloro- 1,3- dioxolane -2- ketone condensation polymer of bis- (dimethylamino) -6- fluoropyrimidine/4,5- bis-.

8. a kind of medical macromolecular materials according to claim 7, which is characterized in that the bis- (dimethylaminos of 2,4- Base) -6- fluoropyrimidine, the chloro- 1,3- dioxolane -2- ketone of 4,5- bis-, sodium carbonate, N-Methyl pyrrolidone mass ratio be 1.17: 1:(0.3-0.5):(8-13)。

9. a kind of medical macromolecular materials according to claim 1-8, which is characterized in that the medical high polymer The preparation method of material includes the following steps: each component to obtain mixture for dry-mixed 5-20 minutes in super mixer;Then The mixture is added in dual-screw-stem machine, cooling granulation after melting extrusion is carried out.

10. a kind of medical macromolecular materials according to claim 9, which is characterized in that the melting extrusion is divided into four The temperature in area, first area's temperature are 120-130 DEG C, and second area's temperature is 135-145 DEG C, and third area temperature is 190-200 DEG C, the Four area's temperature are 225-235 DEG C;The screw slenderness ratio of the twin (double) screw extruder is (25-35): 1;Twin (double) screw extruder revolving speed For 45-65r/min.

Technical field

The present invention relates to medical material tech fields more particularly to a kind of medical macromolecular materials and preparation method thereof.

Background technique

With the development of science and technology and the improvement of people's living standards, the usage amount of high molecular material increase year by year, make It is also increasingly wider with range.High molecular material is the substance for constituting life, is the existence form of life, the life of it and modern people It is living inseparable.Being widely used for high molecular material also becomes one of mark of modern civilization.This material is with macromolecule Compound (resin) is matrix, then is equipped with other additives (auxiliary agent) and is constituted, with light, chemical stabilization, will not corrode, The advantages that impact resistance is good, good insulating, is widely used in the fields such as stationery product, food service items, package packing supplies, except this it Outside, it medically applies also quite extensively.

Medical macromolecular materials be it is a kind of with features for artificial organs, surgical repair, and to tissue Dysgenic synthesis high molecular material and natural macromolecular material will not be generated, also includes drug packages material and medical equipment Shell uses material etc..Due to the demand of its use environment, people have higher requirement to the performance of medical macromolecular materials, Other than requiring it to have good characteristic heat-resisting, intensity is high, it is also necessary to its antibacterial, antistatic.

Summary of the invention

Present invention seek to address that the above problem, a kind of medical macromolecular materials and preparation method thereof, the preparation method are provided Simple process, easy to operate, preparation process is easy to control, and energy consumption is few, and preparation efficiency and product qualified rate are high, and environmental pollution is small, It is suitble to large-scale production demand, market value, social value and the ecological value with higher;The medical high polymer being prepared Material stiffness and toughness are good, excellent combination property, and high temperature resistance and mechanical mechanics property are good, antibacterial antistatic significant effect, Stability is good, long service life.

To achieve the above object, the technical solution adopted by the present invention are as follows:

A kind of medical macromolecular materials, which is characterized in that be made of each component of following parts by weight: bis- (dimethylaminos Base) dimethylsilane/2,4- bis- chloro- 6- code quinoline generation 30-50 parts of -1,3,5- triazine condensation polymer, bis- (the dimethylamino) -6- of 2,4- Chloro- 20-30 parts of the 1,3- dioxolane -2- ketone condensation polymer of fluoropyrimidine/4,5- bis-, 25-35 parts of carboxylic rubber, antioxidant 0.5-1.5 Part, 10-20 parts of more carboxyl cage-type silsesquioxanes.

Further, the antioxidant is selected from antioxidant 264, antioxidant 330, antioxidant 1010, antioxidant 1076, antioxygen At least one of agent 168.

Further, the carboxylic rubber is at least one of carboxylic styrene-butadiene rubber, carboxy nitrile rubber.

Preferably, more carboxyl cage-type silsesquioxanes are previously prepared, preparation method reference: more carboxyl cage model sesquialters Siloxanes/silicon rubber hybrid nano-material Evaluation of Biocompatibility, Li Xiang etc., modern medicine health, 2019,35 (1): 16- 20。

Further, the chloro- 6- code quinoline generation -1,3,5-triazines of bis- (dimethylamino) dimethylsilanes/2,4- bis- contracts The preparation method of polymers includes the following steps: bis- (dimethylamino) dimethylsilanes, 2,4- bis- chloro- 6- code quinoline generation -1,3, 5- triazine, basic catalyst are dissolved in organic solvent, are stirred to react 2-4 hours at 50-70 DEG C under normal pressure, after be warming up to 250- 270 DEG C, carried out polycondensation reaction 8-12 hours at 50-150Pa, after reaction, be cooled to room temperature, be adjusted to normal pressure, after in second It settles out in alcohol, then rotates removing ethyl alcohol, obtain bis- (dimethylamino) dimethylsilanes/2,4- bis- chloro- 6- code quinoline generation -1,3,5- Triazine condensation polymer.

Preferably, bis- (dimethylamino) dimethylsilanes, the chloro- 6- code quinoline generation -1,3,5-triazines of 2,4- bis-, alkalinity Catalyst, organic solvent mass ratio be 1:1.61:(0.3-0.6): (10-15).

Preferably, the basic catalyst is selected from least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.

Preferably, the organic solvent be n,N-Dimethylformamide, N-Methyl pyrrolidone, in dimethyl sulfoxide at least It is a kind of.

Further, 2, the 4- chloro- 1, the 3- dioxolane -2- ketone of bis- (dimethylamino) -6- fluoropyrimidines/4,5- bis- contracts The preparation method of polymers includes the following steps: bis- (the dimethylamino) -6- fluoropyrimidines of 2,4-, chloro- 1, the 3- dioxy five of 4,5- bis- Ring -2- ketone, sodium carbonate are dissolved in N-Methyl pyrrolidone, are stirred to react 2-4 hours at 50-70 DEG C under normal pressure, after be warming up to It 250-270 DEG C, is carried out polycondensation reaction 8-12 hours at 50-150Pa, after reaction, is cooled to room temperature, is adjusted to normal pressure, after It settles out in ethanol, then rotates removing ethyl alcohol, obtain chloro- 1, the 3- dioxy of bis- (the dimethylamino) -6- fluoropyrimidines/4,5- bis- of 2,4- Five rings -2- ketone condensation polymer.

Preferably, bis- (the dimethylamino) -6- fluoropyrimidines of 2, the 4-, chloro- 1, the 3- dioxolane -2- ketone of 4,5- bis-, carbon Sour sodium, N-Methyl pyrrolidone mass ratio be 1.17:1:(0.3-0.5): (8-13).

Further, the preparation method of the medical macromolecular materials, includes the following steps: each component in mixed at high speed Mixture is obtained for dry-mixed 5-20 minutes in device;Then the mixture is added in dual-screw-stem machine, carries out cooling after melting extrusion Granulation.

Further, the melting extrusion is divided into the temperature in four areas, and first area's temperature is 120-130 DEG C, second area's temperature Degree is 135-145 DEG C, and third area temperature is 190-200 DEG C, and the 4th area's temperature is 225-235 DEG C.

Further, the screw slenderness ratio of the twin (double) screw extruder is (25-35): 1;Twin (double) screw extruder revolving speed is 45-65r/min。

The beneficial effects of adopting the technical scheme are that

(1) medical macromolecular materials provided by the invention, preparation method simple process, easy to operate, preparation process is easily-controllable System, energy consumption is few, and preparation efficiency and product qualified rate are high, and environmental pollution is small, is suitble to large-scale production demand, city with higher Field value, social value and the ecological value.

(2) medical macromolecular materials provided by the invention, overcome medical macromolecular materials in the prior art or it is more or Few existing transparency is inadequate, and antistatic effect is poor, and impact strength is low, and the stability of photo-thermal is poor, and impact strength is lower, toughness compared with Difference, be easy to appear at thin-walled in use notch or fracture the case where defect, have rigidity and toughness it is good, it is comprehensive Can be excellent, high temperature resistance and mechanical mechanics property are good, and antibacterial antistatic significant effect, stability is good, service life Long advantage.

(3) medical macromolecular materials provided by the invention introduce bis- (dimethylamino) dimethyl-silicons by polycondensation reaction The chloro- 6- code quinoline generation -1,3,5-triazines condensation polymer of alkane/2,4- bis-, quaternary ammonium salt structure is introduced on backbone structure, can effectively improve material The antibiotic property and antistatic property of material;Silicon N structure is introduced on main chain, is conducive to the anti-flammability and weatherability that improve material;Draw Entering triazine structure can make material resistance to UV aging and weather resistance largely be improved.

(4) medical macromolecular materials provided by the invention introduce bis- (the dimethylamino) -6- fluorine of 2,4- by polycondensation reaction Chloro- 1, the 3- dioxolane -2- ketone condensation polymer of pyrimidine/4,5- bis-, the fluorine-containing pyrimidine structure of introducing, so that material has fluorine silicon materials Possessed performance, excellent combination property;Structural carbonate is introduced, the color and transparency and biology of material can be effectively increased Compatibility;Quaternary ammonium salt structure on its strand can also improve the antibiotic property and antistatic property of material;Bis- (dimethylaminos Base) dimethylsilane/2,4- bis- chloro- 6- code quinolines generation -1,3,5- triazine condensation polymer and bis- (the dimethylamino) -6- fluorine of 2,4- it is phonetic Quaternary ammonium salt group on the chloro- 1,3- dioxolane -2- ketone condensation polymer of pyridine/4,5- bis- at the time of molding with carboxylic rubber and more carboxyl cages The anti-raw ion-exchange reactions of carboxyl on type silsesquioxane forms ionomer structure, improves the comprehensive performance of material;Draw The toughness of the rubber structure energy reinforcing material entered, more carboxyl cage-type silsesquioxanes of addition can improve the lubricity of material, resistance to Mill property and intensity.

Specific embodiment

In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention, Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for It is bright the present invention rather than limit the scope of the invention.

The more carboxyl cage-type silsesquioxanes of institute being related in the following embodiments of the present invention are previously prepared, preparation method ginseng Examine: the Evaluation of Biocompatibility of more carboxyl cage-type silsesquioxane/silicon rubber hybrid nano-materials, Li Xiang etc., modern medicine is defended It is raw, 2019,35 (1): 16-20;Other raw materials are commercially available.

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