CN1057780C - Synthesis process of prepolymer for medical polymer bandage - Google Patents

Synthesis process of prepolymer for medical polymer bandage Download PDF

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CN1057780C
CN1057780C CN 96116854 CN96116854A CN1057780C CN 1057780 C CN1057780 C CN 1057780C CN 96116854 CN96116854 CN 96116854 CN 96116854 A CN96116854 A CN 96116854A CN 1057780 C CN1057780 C CN 1057780C
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temperature
prepolymer
heating
dihydroxy
diphenylmethane
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CN1158868A (en
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臧德耿
张云芳
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无锡锡美低温医疗设备有限公司
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Abstract

本发明是一种医用高分子绷带的预聚体合成工艺,它依次包括以下步骤:先将二苯基甲烷-4,4′-二异氰酸酯和二羟基聚醚分别投入两个反应锅内,在氮封、搅拌的情况下对其间断加热,进行预处理,然后,在氮封、搅拌的情况下,将处理过的二羟基聚醚滴入二苯基甲烷-4,4′-二异氰酸酯内,并添加各种助剂,合成为预聚体。 The present invention is a medical polymer bandage prepolymer synthesis process, which in turn comprises the steps of: first diphenylmethane-4,4'-diisocyanate and dihydroxy polyethers were put two pot reaction, in dihydroxy polyether its intermittent heating pretreated under a nitrogen blanket, stirring conditions, and then, under a nitrogen blanket, with stirring, treated dropwise diphenylmethane-4,4'-diisocyanate inner ester and various additives such as a prepolymer synthesis. 采用本发明的合成工艺生产出的预聚体涂敷在基布上制成医用高分子绷带,保存期长、无发泡层、强度高、透气性好,可广泛用于临床上的断肢复位固定。 The synthetic process of the present invention to produce the prepolymer coated on a base fabric made of medical polymer bandage, long shelf life, non-foamed layer, a high strength, permeability, and can be widely used clinically limb fixation.

Description

一种医用高分子绷带的预聚体合成工艺 A medical polymer bandage prepolymer synthesis

本发明涉及一种医用高分子绷带的预聚体合成工艺。 The present invention relates to a medical polymer bandage prepolymer synthesis.

在骨科临床上,采用石膏对断肢进行复位固定已逐渐为用高分子绷带固定所取代。 In orthopedics, plaster for fixation of the limb has gradually been replaced with the polymer bandage. 如上海医疗器械研究所生产的SGB-I型医用高分子绷带,它是在基布上涂敷预聚体而制成。 The medical device produced by Shanghai Institute SGB-I type of medical polymer bandage, which is applied on the base fabric made prepolymer. 这种绷带轻便,耐磨性和耐水性强,能给医护人员和伤者带来方便。 This bandage lightweight, abrasion resistance and water resistance, easy to give health care workers and bring the wounded. 但由于其预聚体的合成工艺中,对二苯基甲烷-4,4′-二异氰酸酯和聚醚没有进行预处理,且所用聚醚为聚醚多元醇,致使二苯基甲烷-4,4′-二异氰酸酯部分沉淀,聚醚部分带水;合成时,反应温度低,反应不完全;添加的助剂品种少,二苯基甲烷-4,4′-二异氰酸酯与聚醚的配比不合理;制成的预聚体没有进行氮封,致使用这种预聚体制成的绷带在包装袋内易自聚固化、保存期短,一般只有6个月,发泡层厚、强度低、透气性差,光照后还易变黄。 But because synthesis process in which the prepolymer of diphenylmethane-4,4'-diisocyanate and a polyether without pretreatment, and the polyether is a polyether polyol, resulting diphenylmethane -4, 4'-diisocyanate partial precipitation, polyether moiety with water; the synthesis, the reaction temperature is low, incomplete reaction; less aid species added, diphenylmethane-4,4'-diisocyanate and a polyether ratio unreasonable; prepolymer formed is not sealed with nitrogen, activated using such prepolymer bandages easily made into self-polymerization curing in the packaging bag, short-term storage, typically only six months, the layer thickness of the foamed, low intensity , poor ventilation, the light is also easy to turn yellow.

本发明的目的在于提供一种医用高分子绷带的预聚体合成工艺,使用本发明的合成工艺生产出的预聚体涂敷在基布上制成绷带,保存期长,无发泡层、强度高、透气性好,而且光照后不易变色。 Object of the present invention to provide a process for the synthesis of prepolymer medical polymer bandage, using the synthetic process of the invention is produced prepolymer coating was made on the base fabric bandage, long shelf life, non-foamed layer, high strength, permeability, and easy to change color after exposure.

为实现上述目的,采用以下技术解决方案:本发明的医用高分子绷带的预聚体合成工艺依次包括以下步骤:1.对二苯基甲烷-4,4′-二异氰酸酯的预处理。 To achieve the above object, the following technical solutions: the medical bandage of the present invention, the polymer prepolymer synthesis process comprising the following steps: 1. Pretreatment of 4,4'-diphenylmethane diisocyanate. 将二苯基甲烷-4,4′-二异氰酸酯投入一个反应锅内,在氮封、搅拌的情况下,对其加热;当其温度升至80℃时,停止加热并使其恒温60分钟;之后,让其自然冷却至60℃,使其变成澄清透明的液体,待用。 Diphenylmethane-4,4'-diisocyanate into a reaction pot, sealed under nitrogen, with stirring, it is heated; when its temperature was raised to 80 ℃, heating was stopped and allowed constant temperature of 60 min; Thereafter, let it cool to 60 ℃, so that it becomes clear and transparent liquid, inactive. 2.对二羟基聚醚的预处理。 2. Pretreatment of dihydroxy polyethers. 将二羟基聚醚投入另一反应锅内,在反应锅内的压力为-0.09~-0.1MPa的情况下,对其加热;当其温度升至80℃时,恒温30分钟;然后,继续加热,当其温度升至100℃时,恒温30分钟;之后,再继续加热,当其温度升至120℃时,恒温60分钟,待用。 Dihydroxy polyether into another pot reaction, the reaction pressure in the case where the pot is -0.09 ~ -0.1MPa, and it is heated; when its temperature was raised to 80 ℃, constant temperature of 30 min; then, heating was continued when the temperature was raised to 100 deg.] C, the thermostat 30 minutes; then, heating was continued, when the temperature was raised to 120 deg.] C, the thermostat 60 minutes stand. 3.合成。 3. Synthesis. 在氮封、搅拌的情况下,按照二苯基甲烷-4,4′-二异氰酸酯∶三羟基聚醚=1.5∶1的比例,先将经过预处理的二羟基聚醚以滴加的方式滴入预处理过的二苯基甲烷-4,4′-二异氰酸酯中,其中的二羟基聚醚的滴加速度为20~25L/h,滴加时搅拌机的转速为150~200转/分钟;然后,对其加热,当其温度升至70℃时,加聚合抑制剂,继续加热至85~90℃,使其反应;当温度下降2℃反应完全后,对其进行空气冷却;当温度降至75℃时,对其进行水冷却;当温度降至55℃时,分别加入防老剂、抗氧剂、表面活性剂、泡孔调节剂、催化剂和稀释剂等助剂;当其温度降至45℃时,使用氮气进行封装,制成本发明的预聚体。 Under a nitrogen blanket, with stirring, in accordance with diphenylmethane-4,4'-diisocyanate: polyether triol ratio = 1.5, the first through the dihydroxy polyether pretreated in a dropwise manner drops the pretreated diphenylmethane-4,4'-diisocyanate, in which the dihydroxy polyether dropping of 20 ~ 25L / h, when added dropwise stirrer speed of 150 to 200 revolutions / minutes; , it is heated, when the temperature was raised to 70 ℃, a polymerization inhibitor was added, heating was continued to 85 ~ 90 ℃, reacted; 2 ℃ when the temperature drops after completion of the reaction, subjected to air cooling; when the temperature is lowered when 75 ℃, subjected to water cooling; when the temperature was lowered to 55 ℃, antioxidant were added, antioxidants, surfactants, cell regulators, catalysts and other additives and diluents; when its temperature is lowered to 45 when ℃, encapsulation using nitrogen, prepared prepolymer of the invention.

由于本发明的预聚体合成工艺对二苯基甲烷-4,4′-二异氰酸酯二羟基聚醚进行过预处理,且使用的聚醚为二羟基聚醚,使得二苯基甲烷-4,4′-二异氰酸酯无沉淀,聚醚不带水;合成时,反应温度较高,反应完全。 Since the prepolymer synthesis process of the present invention is 4,4'-diphenylmethane diisocyanate which had been pre-dihydroxy polyethers, polyether and dihydroxy polyethers used, such diphenylmethane -4, 4'-diisocyanate no precipitation, polyethers without water; synthesis, higher reaction temperature, the reaction was complete. 添加的助剂品种较多,二苯基甲烷-4,4′-二异氰酸酯与二羟基聚醚的配比合理。 Add more auxiliary species, a reasonable diphenylmethane-4,4'-diisocyanate with a dihydroxy polyether ratio. 而且使用氯气进行封装。 And the use of chlorine gas encapsulation. 因而,用本发明的合成工艺生产的预聚体涂敷在基布上制成医用高分子绷带,在包装袋内不会自聚固化,保存期长,可达一年以上,而且无发泡层、强度高、透气性好,光照后不变色。 Thus, coated with a prepolymer synthesis process of the present invention is produced in the base fabric is made of medical polymer bandage, the packaging bag will not self-polymerization curing, long shelf life, up to one year, and no foam layer, a high strength, permeability, and does not change color after exposure.

下面结合实施例对本发明作进一步的详细说明。 Below in connection with embodiments of the present invention will be further described in detail.

本发明的医用高分子绷带的预聚体合成工艺依次包括以下步骤:先将二苯基甲烷-4,4′-二异氰酸酯投入反应锅内,并将高强度的氮气连续不断地通入反应锅内,对其实行氮封,以防空气中的氧和水侵入。 The medical bandage of the present invention, the polymer of prepolymer synthesis process comprising the following steps: first diphenylmethane-4,4'-diisocyanate into the reaction pot, and the high strength nitrogen continuously into Fanyingguo inner, imposed a nitrogen blanket, to prevent oxygen in the air and water intrusion. 在不断搅拌的情况下,对其加热。 Under constant stirring, it is heated. 当其温度升至80℃,停止加热,并借助温度自动控制器使其恒温60分钟,之后,让其自然冷却至60℃,使其变成澄清透明的液体,待用。 When the temperature was raised to 80 ℃, heating was stopped, and the automatic temperature control means so that temperature for 60 minutes and then, allowed to cool naturally to 60 ℃, so that it becomes clear and transparent liquid, inactive.

再将二羟基聚醚投入另一反应锅内,在反应锅内的压力为-0.09~-0.1MPa的情况下,对其加热。 Then dihydroxy polyether into another pot reaction, the reaction pressure in the case where the pot is -0.09 ~ -0.1MPa, and it is heated. 当其温度升至80℃时,借助于温度自动控制器使其恒温30分钟。 When the temperature was raised to 80 ℃, so that by means of automatic temperature control thermostat for 30 minutes. 然后继续加热,当其温度升至100℃时,再恒温30分钟。 Then heating was continued, when the temperature was raised to 100 deg.] C, then 30 minutes constant. 之后再继续加热,当其温度升至120℃时,使其恒温60分钟,待用。 After the heating was continued, when the temperature was raised to 120 deg.] C, allowed temperature for 60 minutes stand.

最后合成。 Finally synthesis. 在氮封、不断搅拌的情况下,按照二苯基甲烷-4,4′-二异氰酸酯∶二羟基聚醚=1.5∶1的比例,利用液位差,先将经过预处理的二羟基聚醚以滴加的方式滴入预处理过的二苯基甲烷-4,4′-二异氰酸酯中。 Under a nitrogen blanket, under constant stirring, in accordance with diphenylmethane-4,4'-diisocyanate: the dihydroxy polyether ratio = 1.5, the use of level difference, after a first pre-dihydroxy polyethers in a dropwise manner added dropwise pretreated diphenylmethane-4,4'-diisocyanate in. 利用阀门调节使其滴加的速度控制在20~25L/h范围内。 Adjustment means of the valve so that speed control was added dropwise within 20 ~ 25L / h range. 然后对其加热,当其温度升至70℃时,加入占总重量为0.2~0.4的聚合抑制剂,继续加热至85~90℃,使其反应。 Then subjected to heat, when the temperature was raised to 70 ℃, a polymerization inhibitor is added to the total weight of 0.2 to 0.4, and heating was continued to 85 ~ 90 ℃, reacted. 当温度下降2℃反应完全后,利用空气使其自然冷却。 When the temperature dropped 2 ℃ reaction was complete, naturally cooled by air. 当其温度降至75℃时,在反应锅四周通自来水,对其进行水冷却。 When the temperature dropped to 75 ℃, 11:50 four weeks through water, subjected to water cooling. 当温度降至55℃时,分别加入占总重量为0.05~0.15%的防老剂、0.10~0.20%的抗氧剂、0.05~0.15%的表面活性剂、0.05~0.15%的泡孔调节剂、0.15~0.25%的稀释剂和1.0~1 2%的催化剂。 When the temperature dropped to 55 ℃, were added to the total of 0.05 to 0.15% by weight of antioxidant, 0.10 to 0.20% of an antioxidant, 0.05 to 0.15% of a surfactant, 0.05 to 0.15% of the cell regulators, 0.15 to 0.25% diluent and 1.0 to 12% of the catalyst. 当其温度降至45℃时,进行封装。 When the temperature dropped to 45 ℃, encapsulation. 封装时,先将氮气通入包装容器内,再将预聚体加入,以达到氮封之目的,使得本发明的预聚体不含氧和水分。 When packaged, the first packaging container into the nitrogen gas, and then the prepolymer was added, in order to achieve closure of the nitrogen, so that the prepolymer of the present invention are free of oxygen and moisture.

本发明上述实施例中,添加助剂时搅拌机的转速为300~350转/分钟。 In the present invention, the above-described embodiment, when adding additives stirrer speed of 300 to 350 revolutions / minute.

本发明上述实施例中,聚合抑制剂是苯甲酰氯,防老剂是2,2′-亚甲基双(4-甲基-6-特丁基苯酚),抗氧剂是2,6-二叔丁基-4-甲基苯酚、表面活性剂是烷基酚聚氧乙烯醚,泡孔调节剂是聚二甲基硅氧烷,稀释剂是丙酮,催化剂是占总重量0.1%的双(2,-二甲基胺基乙基)醚和占总重量1.0%的NN-二甲基乙醇胺混合液。 The above-described embodiments of the present invention, the polymerization inhibitor is a chloride, the antioxidant is 2,2'-methylenebis (4-methyl-6-t-butyl phenol), an antioxidant is 2,6- tert-butyl-4-methylphenol, the surfactant is polyoxyethylene alkylphenol ether, cell regulator is polydimethylsiloxane, the diluent is acetone, the catalyst is 0.1% of the total weight of bis ( 2 - dimethylamino ethyl) ether and 1.0% by weight of the total NN- dimethylethanolamine mixture.

Claims (3)

1.一种医用高分子绷带的预聚体合成工艺,其特征在于依次包括以下步骤:(1)对二苯基甲烷-4,4′-二异氰酸酯的预处理将二苯基甲烷-4,4′-二异氰酸酯投入反应锅内,在氮封、搅拌的情况下,对其加热;当其温度升至80℃时,停止加热并使其恒温60分钟;之后让其自然冷却至60℃,使其变成澄清透明的液体,待用;(2)对二羟基聚醚的预处理将二羟基聚醚投入另一反应锅内,在反应锅内的压力为-0.09~-0.1MPa的情况下,对二羟基聚醚加热,当其温度升至80℃时,恒温30分钟;然后继续加热,当其温度升至100℃时,再恒温30分钟;之后,再继续加热,当其温度升至120℃时,恒温60分钟,待用;(3)合成在氮封、搅拌的情况下,按二苯基甲烷-4,4′-二异氰酸酯∶二羟基聚醚=1.5∶1的重量比例,先将经过预处理的二羟基聚醚以滴加的方式滴入预处理过的二苯基甲 1. A medical polymer bandage prepolymer synthesis process, characterized by comprising the following steps: (1) Pretreatment of diphenylmethane-4,4'-diisocyanate diphenylmethane -4, 4'-diisocyanate into the reaction pot, under a nitrogen blanket, under stirring, it is heated; when its temperature was raised to 80 ℃, heating was stopped and allowed constant temperature of 60 min; then allowed to cool naturally to 60 ℃, it became a clear transparent liquid, stand; (2) pretreatment dihydroxy polyethers dihydroxy polyether into another pot reaction, the reaction pressure in the pot is the case of -0.09 ~ -0.1MPa next, heating of a dihydroxy polyether, when the temperature was raised to 80 ℃, constant temperature of 30 min; then heating was continued, when its temperature was raised to 100 deg.] C, then the thermostat 30 minutes; then, heating was continued, when the temperature rise when deg.] C to 120, thermostat 60 minutes stand; (3) synthesis of nitrogen blanket, stirring conditions, by diphenylmethane-4,4'-diisocyanate: the weight ratio of the dihydroxy polyethers = 1.5 , dihydroxy polyether after first pretreated in a dropwise manner added dropwise pretreated diphenylmethyl -4,4′-二异氰酸酯中,其中,二羟基聚醚的滴加速度为20~25L/h,滴加时搅拌机的转速为150~200转/分钟;然后,对其加热,当其温度升至70℃时,加聚合抑制剂,继续加热至85~90℃,使其反应;当温度下降2℃反应完全后,对其进行空气冷却;当温度降至75℃时,对其进行水冷却;当温度降至55℃时,分别加入防老剂、抗氧剂、表面活性剂、泡孔调节剂、催化剂和稀释剂;当其温度降至45℃时,使用氮气进行封袋,制成本发明的预聚体。 4,4'-isocyanate, wherein the dihydroxy polyether dropping of 20 ~ 25L / h, stirrer speed during the dropwise addition of 150 to 200 revolutions / min; then, heating it, when the temperature rise Between 70 ℃, a polymerization inhibitor was added, heating was continued to 85 ~ 90 ℃, reacted; 2 ℃ when the temperature drops the reaction was complete, be air-cooled; when the temperature was lowered to 75 ℃, subjected to water cooling ; when the temperature was lowered to 55 ℃, antioxidant were added, antioxidants, surfactants, cell regulators, catalysts and diluents; when its temperature was lowered to 45 ℃, using nitrogen gas envelope, the cost of system prepolymer invention.
2.根据权利要求1所述的预聚体,其特征在于添加助剂时搅拌机的转速为300~350转/分钟。 The prepolymer according to claim 1, characterized in that the stirrer when adding auxiliaries speed of 300 to 350 revolutions / minute.
3.根据权利要求1或2所述的预聚体,其特征在于所述的聚合抑制剂是苯甲酰氯,防老剂是2,2′-亚甲基双(4-甲基-6-特丁基苯酚),抗氧剂是2,6-二叔丁基-4-甲基苯酚,表面活性剂是烷基酚聚氧乙烯醚;泡孔调节剂是聚二甲基硅氧烷,稀释剂是丙酮,催化剂是双(2,-二甲基胺基乙基)醚和NN-二甲基乙醇胺。 The prepolymer of claim 1 or claim 2, wherein said polymerization inhibitor is a chloride, the antioxidant is 2,2'-methylenebis (4-methyl-6- Laid butylphenol), antioxidant is 2,6-di-butyl-4-methylphenol, the surfactant is a polyoxyethylene alkylphenol ether; cell regulators are polydimethyl siloxane, diluted agent is acetone, the catalyst is bis (2 - dimethylamino ethyl) ether and NN- dimethylethanolamine.
CN 96116854 1996-03-06 1996-03-06 Synthesis process of prepolymer for medical polymer bandage CN1057780C (en)

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US5447492A (en) * 1993-12-20 1995-09-05 New Dimensions In Medicine, Inc. External fixation dressing for accommodating a retaining pin

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US5447492A (en) * 1993-12-20 1995-09-05 New Dimensions In Medicine, Inc. External fixation dressing for accommodating a retaining pin

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