• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    During the catalytic hardening of polyurethanic moulding masses, which contain diisocyanates and polyalcohols and/or polyurethanic prepolymers, sorbic acid or cinnamic acid is used as catalyser. These acids produce a quick prehardening and hence a good withdrawing from the mould, which allows to increase the rate of production. Furthermore, these acids are physiologically acceptable, which enables to apply this process of preparation to the shaping of medical instruments. These acids can also be used in a physiologically acceptable mixture with a catalyst containing metals having a high atomic weight.
    公开号:SU1099846A3
    申请号:SU792739601
    申请日:1979-02-15
    公开日:1984-06-23
    发明作者:Леманн Ханс-Дитер
    申请人:Гамбро Диализаторен Гмбх Унд Ко, Кг (Фирма)；
    IPC主号:
    专利说明:

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    a The invention relates to the production of non-toxic biocompatible polyurethane material and can be used in the field of medicine. A known method for producing biocompatible polyurethanes by reacting the isocyanate component with a polyol followed by curing. The curing process is carried out in the absence of a catalyst, since the molding compound should not contain any toxicologically hazardous active parts lj. The disadvantage of this method is the long duration of the curing process and the need to use high temperatures, and the curing process without a catalyst is feasible only with a certain selection of the composition of the molded mass. The closest in technical essence to the present invention is a method for producing biocompatible polyurethane by reacting the isocyanate component with a polyol followed by curing of the reaction composition in the presence of a curing catalyst, for example, octanoic acid f2j. However, the known catalyst has a weak effect, which leads to a decrease in labor productivity. The purpose of the invention is to intensify the curing process and reduce the toxicity of the final product. This goal is achieved by obtaining biocompatible polyurethanes by reacting the isocyanate component with a polyol followed by curing: the reaction composition in the presence of a curing catalyst uses 0.1-2% by weight of the sorbic or cinnamic acid reaction composition as a curing catalyst and the curing process is carried out at 18-70 ° C. According to the proposed method for the catalytic curing of polyurethane molding masses, it is necessary to obtain products that are not poisonous and bio-compatible. we and in contact with, or other body fluids are not isolated by any physiologically opa Sub- stances. It is necessary to accelerate their removal from the form. f0 6 2 The method of catalytic curing of polyurethane molding compounds containing diisocyanates and polyols (and / or polyurethane formolymers with isocyanate or hydroxyl groups) is carried out using sorbinoBoy, i.e. 2,4-hexadienoic acid (may also be added as an intramolecular adduct as para-orbic acid) or cinnamic acid. Used carboxylic acids are not poisonous, odorless and do not form foams. For example, sorbic acid is used as an additive to food products. Used carboxylic acids are soluble in the polyol component, which facilitates its processing. Curing with sorbic or cinnamic acid can be carried out at 18-24 ° C or at elevated temperatures (up to 70 ° C). Sorbic or cinnamic acid can be used either individually or together with catalysts containing heavy metals, as mixtures of carboxylic acids with these heavy metal containing catalysts are biocompatible, Reactive organic polyfunctional polyols, which are used in polyurethanes by introducing into the reaction the polyol with a suitable isocyanate compound These include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like. Glycol polyalkylene aryle esters which have a high molecular weight (400-10000) but differ from the alkylene glycols described in that they contain arylene residues (phenyl or naphtypene) or under known conditions substituted aryle residues, for example substituted with alkyl or aryl groups, or the like Arylene residues in place of some of the alkylene residues in polyalkylene glycols can also be used as the polyol component of the reaction. The polyalkylene aryl glycols used for the type used for this purpose contain at least one alkylene ether residue in mol. weighing about 500 per arylene present. Linear polyesters, which contain several hydroxyl-reactive isocyanate groups, are another class of reactive organic polyfunctional polyols that can be used in the preparation of polyurethane. Linear or branched chain polyesters that are commonly used to make polyurethane resins have a mol. weight in the limit of 750-3000. In addition, they have relatively low acid numbers, for example, not exceeding 60, relatively high hydroxyl numbers, for example, about 30-700. Another class of suitable organic polyfunctional polyol reaction components include polyalkylene ether polyols with more than two reactive hydroxyl groups, such as polyalkylene ether, triols, tetrales, and the like, which are obtained, for example, by reacting polyols such as glycerin, trimethyl ethane, trimethylol propane, pentaerythritol, dipentaerythritol, sorbitol, and the like, with low molecular weight alkylene oxides, such as ethylene oxide, propylene oxide, and the like. Castor oil and polyols may be used as the polyol component. based on castor oil, which is obtained, for example, by chemical modification of castor oil. It is also possible to use mixtures of the various reactive organic polyfunctional polyols described in the preparation of polyurethane prepolymers that are necessary for carrying out the proposed process. In addition, complex or simple polyether polyols can be combined with a slight excess of any polyisocyanate to produce a polyurethane prepolymer. Preferred polyisocyanates are, for example, 1-methoxyphenyl-2, 4-diisocyanate, 1-methyl-4-methoxyphenyl-2, 5-diisocyanate, 1-ethoxyphenyl-2, 4-diisocyanate, 1,3-dimethoxyphenyl-4 , 6-diisocyanate, 1,4-dimethylsphenyl-2, 5-diisocyanate, 1-propoxyphenyl-2, 4-diisocyanate, 1-isobutoxyphenyl-2, 4-diisocyanate, 1,4-diethoxyphenyl-2, 5-diisocyanate, toluene -2,4-diisocyanate, toluene-256-diisocyanate, diphenyl ether-2,4-diisocyanate, naphthalene-1,4-diisocyanate, 1,1-dinaphthalene-2, 2-diisocyanate, biphenyl-2,4-diisvacyanate, 3, 3-dimethyldiphenyl-4, 4-diisocyanate, 3,3-dimethoxyphenyl-4, 4-diisocyanate, di Enylmethane-4,4-diisocyanate, diphenylmethane-2,4-diisocyanate, diphenylmethane-2,2-diisocyanate, 3, 3-dimethoxydiphenylmethane-4, 4-diisocyanate, benzophenone-353 -diisocyanate, ethylene diisocyanate, propylene diisocyanate, and a bottle, and a bottle, and a diisocyanate; methyl butylenediisocyanate, tetramethylenediisocyanate, pentamethylene diisocyanate, ciphers, dehydrochemicscapes, dehydropyisocyanate-ether, hectamethylenediisocyanate, 2,2-dimethylamine diisocyanate, 3-methoxyhexamethylene diisocyanate, octamethylenediisocyanate, 2,2-dimethylamine diisocyanate, 3-methoxyhexamethylene diisocyanate, octamethylene diisocyanate, 2,2-dimethylamine diisocyanate, 3-methoxyhexamethylene diisocyanate, octamethylenediisocyanate, 2,2-dimethylamine diisocyanate, 3-methoxyhexamethylene diisocyanate, octamethylenediisocyanates etilendiizotsianat, 1,3-dimetildiizotsianata, benzoldiizotsianat 1,4-dimethyl-1,2-dimetiltsiklogeksandiizotsianyt, 1,4-dimetiltsiklogeksandiizotsianat, 1,4-dietilenbenzoldiizotsianat, 1,4-dimetilnaftalindiizotsianat, 1,5-dimetilnaftalindiizotsianat, cyclohexane-1, 3-diisocyanate, cyclohexane-1,4-diisocyanate. 1-meth-cyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2J 5-diisocyanate; 1-ethylcyclohexane-2,4-diisocyanate, dicyclohexylmethane-4,4 -diizotsianat, ditsiklogeksimetilmetan-4,4 -diizotsianat, ditsiklogeksildimetilmetan -diizotsianat-4,4, 2,2-dimetilditsiklogeksilmetan-4, 4-diisocyanate, 3,3, 5.5 -tetrametilditsiklogeksilmetan-4, 4 -diizotsianat, 4,4-methylene-bis-cyclohexylisocyanate, etilidindiizotsianat, propylene-1,2-diisocyanate, 4,4 -difenildiizotsianat, dianizidindiizo1schanat, 1,5-naphthalene diisocyanate, 4,4 - diphenol ether-diisocyanate, M- and P-phenylene diisocyanate, 4,4-toluidine diisocyanate, isopropylidene-bis- (phenyl or cyclohexyl-iso-tdia nat), 1,3-cycloam-1lenediisocyanate, 1.3 cyclohexylene diisocyanate, 1,4-cyclohexyl diisocyanate, chlorodiphenyldiisocyanate, 4,4,4 -triphenylmethanethrisocyanate, 1,3,5-triisocyanatobenzene or phenylethylene diisocyanate.
    The amounts of curing catalysts added are typically 0.1-2.0%, preferably 0.4-1.0% of the molding composition. The time after which the curing mixture, at ambient or twisted temperature (approximately 40 ° C), reaches a Shore L hardness value of 20-30 and then can be removed from the mold, depends on the catalyst concentration, mass, and type of polyurethane system. For small masses (10-50 g) it ranges from a few minutes to two hours, for example, 15-30 minutes. The target hardness of these casting masses is reached at room temperature for a time from several hours to several days.
    The proposed method can be used for the manufacture of products used in medicine, for example, for pouring and bonding separate parts of dialysis and filtration devices. Since the hardness required for demoulding is achieved relatively quickly, high productivity can be achieved with this method.
    Examples 1 and 2. 64 weight.h. containing catalyst polyol component, consisting of 90% castor oil, 10% polyether (mol. weight, 2600) and 0.5% of the test acid, is mixed with 36 parts by weight. a diphenylmethane-4, 4 -diisocyanate-polyether prepolymer and the mixture is degassed under vacuum, -40 g of the sample is drunk into a paper cup and cured at 40 ° C. At this temperature, after 30 min, the trod A. capacity is measured. Forms consider Shore A hardness as a critical value. In the case of octane and oleic acids, strong foaming is observed. This also explains the low final hardness. Sorbinic and o-tolyl acid practically do not lead to the formation of bubbles.
    The intensity of the process of curing polyurethanes in the presence of pg of catalyzed catalysts is given in the table.
    The data in the table show that after 30 minutes only with sorbic and cinnamic acid, a hardness value of 25, which is critical for removal from the mold, is reached.
    Example 3. 90 weight.h. castor oil and 10 weight, h polyester (mol. weight 2600), heated to 70 ° C, mixed with 2 weight,% sorbic acid (calculated on the total weight of the mass). 64 wt. h, this catalyst-containing polyol component is shifted from 36 parts by weight, diphenylmethane-4,4-diisocyanate-polyester prepolymer and the mixture is degassed under vacuum. 40 g of the resulting mixture is poured into paper cups and cured at 18 ° C. After about 6 minutes, a hardness of Shore A mass of 25 is reached to get out of the mold. It is equal to 25. No foaming of the solidified mass is observed.
    Example 4 The same operations are repeated as in Example 3, but instead of sorbic, 2.0% by weight (based on the weight of the molding mass) of cinnamic acid is taken. Curing is carried out with tackles at 18 ° C. The hardness of Shore A mass, equal to 25, is critical for removing from the mold, is reached after 8 minutes. No foaming is observed.
    Example 5. The same operations are repeated as in Example 3, but with the following changes: 0.1 wt.% (Calculated on weight. Mass) of sorbic acid as a catalyst is added to the mixture of castor oil and polyester. Curing is carried out at 70 ° C. At this temperature, the hardness of the mass according to Shore A, equal to 23, is critical for removal from the forg-y, is reached in about 30 minutes. No foaming of the cured sample is observed.
    Example 6. The same operations are repeated as in example 5, but instead of sorbic acid, 0.1% cinnamic acid (based on the weight of the molding material) is taken. Curing is carried out at 70 ° C. And in this case it is critical to remove From the form, the hardness of the mass according to Shore A is reached after 30 min. Foaming is not observed even in this case.
    Catalyst
    Example
    Shore A hardness after 30 min
    Sorbic acid
    Cinnamic acid
    Oleic acid
    Octanoic acid
    2-Methoxybenzoic acid O-Tolyl acid m-Tolyl acid P-Tolyl acid
    Examples 1-6 are comparative.
    27 25 Not measurable
    15
    Not measurable
    22
    20
    15
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING BIO-COMPATIBLE POLYURETHANES by reacting an isocyanate component with a polyol followed by curing the reaction composition in the presence of a curing catalyst, which entails that, in order to intensify the curing process and reduce the toxicity of the final product, 0.1 is used as a curing catalyst -2.0% by weight of the reaction composition of sorbic or cinnamic acid and the curing process is carried out in an iris of 18-70 ° C.
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    法律状态:
    优先权:
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