CN1226123C - Water polyurethane elastic thin-wall products preparation - Google PatentsWater polyurethane elastic thin-wall products preparation Download PDF
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一、技术领域本发明属于聚氨酯弹性薄壁制品及其制备技术领域，具体涉及一种用水性聚氨酯乳液来制备弹性薄壁制品的方法。 I. Technical Field The present invention is in the preparation of polyurethane elastic thin-walled articles and technical field, particularly relates to an aqueous polyurethane emulsion method to prepare elastomeric thin-walled articles.
二、背景技术 Second, the technical background
聚氨酯以其较为优异的物理机械性能，良好的生物相容性和耐挠屈性在替代天然橡胶制备如手套、保险套、袖套、靴子、气球、奶嘴、灌肠器头、充气囊袋和其他管状物等弹性薄壁制品方面获得了广泛的应用，尤其是在医用弹性薄壁制品方面。 Polyurethane its relatively excellent mechanical properties, good biocompatibility and resistance to torsion flexion preparative natural rubber glove Alternatively, condoms, sleeves, boots, balloons, teats, enema head, and the other in the inflatable bladder elastic tubular thin walled articles gained a wide application, particularly in thin-walled elastic medical article. 但是在获得用浸渍、喷涂、流延方式制备弹性薄壁制品的聚氨酯溶液时，通常都是采用有机溶剂来溶解，如申请号为0413467的欧洲专利，公开的即是将模型浸入用有机溶剂溶解的聚氨酯溶液中来制备保险套的方法。 However obtained by dipping, spraying, casting the polyurethane solution was prepared in the way when the elastic thin walled articles are usually dissolved organic solvent, such as European Patent Application No. 0,413,467, the disclosure model that is immersed in an organic solvent for dissolving the method of the polyurethane solution condoms prepared. 这种方法由于必须使用价格较为昂贵的有机溶剂，故既要增加成本，又要带来严重的环境污染，因而正在面临淘汰。 This method is more expensive because of the need to use organic solvents, it is necessary to increase the cost, but also serious environmental pollution, thus being phased out.
目前，能够取而代之的是水性聚氨酯。 At present, it can be replaced by water-based polyurethane. 水性聚氨酯由于其溶剂为水，故安全不燃烧、无毒、无污染、节省能源、易加工且价格低廉，并且它还保留了传统溶剂型聚氨酯的优良性能，如良好的耐磨性、柔韧性、耐低温性、耐疲劳性和耐化学药品性等；加之其溶剂为水，故成本低，生产、运输和使用都很安全，特别适用于制备对有机溶剂使用敏感场合的弹性薄壁制品，因此自问世以来发展非常迅速。 Because of its aqueous polyurethane solvent is water, so the combustion is not safe, non-toxic, energy saving, easy to process and inexpensive, and it retains the excellent performance of the conventional solvent-based polyurethanes, such as good abrasion resistance, flexibility , low temperature resistance, fatigue resistance and chemical resistance and the like; together with its solvent is water, so the low cost of production, transportation, and are safe to use, particularly useful for preparing thin-walled elastomeric articles using the occasion sensitive to organic solvents, Therefore, developing very rapidly since its inception. 如美国专利US4463156公开的用二醇与4，4'-二苯甲基异氰酸酯的混合物制备固含量为20％的聚氨酯悬浮液，再将手套模型浸入悬浮液中以制备手术手套。 As disclosed in U.S. Patent No. US4463156 glycols prepared by solid content of the mixture with 4,4' benzhydryl isocyanate was 20% of a polyurethane suspension, then the glove former dipped in the suspension to prepare a surgical glove. 又如JS.Sadowski，BMartin，P Pgerst等人在“浸入共凝的聚氨酯乳液”(Polyurethane tateies for CoagulationDippingM<弹性体>，1978年10月，11-20)中叙及的聚氨酯手套可用“Anode”方法来制造，即将模型浸入凝固浴中，然后没入水性聚氨酯乳液中。 Another example JS.Sadowski, BMartin, P Pgerst et al., "Co-coagulation of polyurethane emulsion is immersed" (Polyurethane tateies for CoagulationDippingM & lt; elastomeric & gt;, 1978 October 11-20) is recited polyurethane gloves available "Anode "the method of manufacturing, i.e. the model is immersed in the coagulation bath and not into the aqueous polyurethane emulsion. 乳液中的聚氨酯粒子大小从60到300纳米，乳液中还含有非离子表面活性剂。 Particle size of the polyurethane emulsion is from 60 to 300 nm, the emulsion further contains a nonionic surfactant. 但是，尽管在1978年Sadowski宣称这种手套能够被制得，但是迄今为止，通过共凝浸入法来制备聚氨酯手套还未实现工业化生产。 However, despite claims that in 1978, Sadowski gloves can be made, but so far, polyurethane gloves were prepared by co-coagulation method has not been immersed in industrial production. 而不能实现工业化生产的主要原因是水性聚氨酯分散体黏度不能满足浸提成型的要求，成膜性能差。 The main reason is not the industrial production of an aqueous polyurethane dispersion viscosity can not meet the requirements of extraction molding, poor film-forming properties.
于是有人试图使用增塑剂来提高乳液的浸提成膜性能。 So someone trying to improve the use of plasticizers leach film-forming properties of the emulsion. 如国际专利WO 96/22009叙述了可以将模型浸入含环氧大豆油增塑剂的聚氨酯乳液中，以浸提生产医用薄壁制品。 As described in International Patent WO 96/22009 describes a model may be immersed in a polyurethane emulsion containing epoxidized soybean oil plasticizer to produce medical leaching thin-walled products. 然而此种方法并不能有效地提高乳液的浸提成膜性能，而且还会导致乳液贮存稳定性的下降。 However, this method does not effectively improve the film forming properties of the emulsion extraction, but also lead to decreased storage stability of the emulsion.
本发明人曾试图用增加固含量的办法来提高其黏度，但是通过大量的实验发现，固含量达到40％以上虽然可明显提高聚氨酯乳液的黏度，但同时也会引起贮存稳定性的大幅下降。 The present inventors have tried to increase the solids content approaches to increase its viscosity, it was found through a lot of experiments, a solids content of more than 40%, although emulsions can significantly increase the viscosity of the polyurethane, but also cause a substantial decline in storage stability.
三、发明内容 III. SUMMARY OF THE INVENTION
本发明的目的是克服已有技术存在的缺点，提供一种水性聚氨酯弹性薄壁制品的制备方法。 Object of the present invention to overcome the shortcomings of the prior art, there is provided a method of preparing an aqueous polyurethane elastic thin-walled products. 该方法可以在提高水性聚氨酯乳液的成膜性能的同时，保持其良好的贮存稳定性。 This method can improve the film forming properties while waterborne polyurethane emulsion maintain its good storage stability.
本发明的另一目的是提供一种能制备性能更为优异的水性聚氨酯弹性薄壁制品的方法。 Another object of the present invention is to provide a more excellent preparing aqueous polyurethane elastomeric thin-walled articles method.
本发明提供的水性聚氨酯弹性薄壁制品的制备方法是先制备或外购水性聚氨酯乳液，然后将薄壁制品的模型浸入乳液中，提出后经干燥、脱模制得成品，其特征在于将薄壁制品的模型浸入乳液前，再在乳液中加入增稠剂。 Preparing an aqueous polyurethane elastic thin-walled articles of the present invention is to provide an aqueous polyurethane emulsion prepared or purchased, and then the thin walled article is immersed in the model emulsion, made after drying, releasing prepared products, characterized in that the thin former model wall products into emulsions, adding a thickening agent in the emulsion. 加入的增稠剂与水性聚氨酯乳液的重量比为0.01～10∶100。 By weight of thickener was added with an aqueous polyurethane emulsion ratio of 0.01 to 10:100. 具体的加入方法是：将增稠剂用0～200倍水溶解后，在水性聚氨酯乳液加热至20～50℃时加入，并在120～250转/分的速度下搅拌5～30分钟即可。 The addition of specific method is: 0 to 200 times the thickening agent dissolved in water, was added upon heating to 20 ~ 50 ℃ use in an aqueous polyurethane emulsion, and stirred at a speed of 120 to 250 revolutions / minute for 5 to 30 minutes .
增稠剂可选用有机天然增稠剂，如琼脂、交叉菜胶、海藻酸盐等或/和改性有机天然增稠剂，如羧甲基纤维素及其衍生物、纤维素醚等或/和有机合成流变增稠剂，如聚丙烯、聚甲基丙烯酸化合物等或/和无机增稠剂，如二氧化硅、膨润土、硬脂酸锌等或/和表面活性剂用增稠剂，如氯化钠、硫酸钠等。 Organic natural thickeners can be selected thickeners, such as agar, carrageenan cross, alginate, etc. and / or modified organic natural thickeners such as carboxymethylcellulose and derivatives thereof, cellulose ether and / or and synthetic organic rheology thickeners, such as polyacrylic, polymethacrylic acid compounds and / or inorganic thickeners, such as silica, bentonite, zinc stearate and / or thickener and a surfactant, such as sodium chloride and sodium sulfate. 如果用于制备与人体密切接触的生物医用类薄壁制品，如安全套，医用手套等，则应使用其中的食用级增稠剂以达到其生物安全性要求。 If the class biomedical thin-walled articles in close contact with the human body, such as condoms, medical gloves for the preparation should be used wherein the food grade thickener to achieve biosafety requirements. 可选用的食用级增稠剂为海藻酸及其盐、海藻酸丙二醇酯、琼脂、卡拉胶、洋槐豆胶、瓜尔豆胶、阿拉伯胶、刺梧桐胶、黄蓍胶、果胶、黄原胶、羧甲基纤维素及其衍生物、改性淀粉和明胶中的至少一种。 Optional food grade thickeners alginic acid and its salts, propylene glycol alginate, agar, carrageenan, locust bean gum, guar gum, gum arabic, karaya gum, tragacanth, pectin, xanthan gum, carboxymethylcellulose and derivatives thereof, at least one modified starch and gelatin. 这些食用增稠剂均属欧共体食品立法机构批准的。 These edible food thickeners belong to the approval of the Community legislature.
水性聚氨酯乳液可以自己生产制备，也可以购买市场上的产品。 The aqueous polyurethane dispersions can prepare their own production, can also be purchased on the market. 如果是购买市场上的产品，其选择指标主要是乳液的固含量和成膜后的力学性能。 If you bought the product on the market, their choice of indicators is mainly mechanical properties of solids content and film-forming emulsion. 水性聚氨酯乳液的固含量可以选择的范围为15～40％，更好为20％～35％。 Aqueous polyurethane emulsion had a solids content may be selected in the range of 15 to 40%, more preferably 20% to 35%. 水性聚氨酯乳液成膜后的力学强度可以选择15～40Mpa，而20～40Mpa则更好。 The aqueous polyurethane emulsion of mechanical strength after the film formation may be selected 15 ~ 40Mpa, and even better 20 ~ 40Mpa. 如果是自己生产制备，选用的水性聚氨酯可以为聚醚型水性聚氨酯或聚酯型水性聚氨酯，而最好的是聚醚/聚酯型水性聚氨酯。 If their production is prepared, may be selected aqueous polyurethane aqueous polyurethane polyether or polyester polyurethane, and preferably is a polyether / polyester aqueous polyurethane. 这是因为聚醚是亲水结构而聚酯是疏水结构，以聚酯聚醚共同做软段的聚氨酯则具有亲-疏水的两相交替结构，目前生物相容性领域研究成果表明这种亲-疏水的两相交替结构具有最优的生物相容性，因此这种聚酯/聚醚型聚氨酯比起单纯的聚酯或聚醚型聚氨酯更适用于制作生物医用制品。 This is because the polyether is hydrophilic structure is hydrophobic polyester, polyether polyester polyurethane soft segments do together with the pro - a two-phase structure of alternating hydrophobic, biocompatible art research results show that the pro - two alternate optimal structure having a hydrophobic biocompatible, so that the polyester / polyether polyurethane compared to pure polyester or polyether polyurethane is more suitable for the production of biomedical products. 其制备的配方(重量百分比)为：二异氰酸酯17～40％，聚醚多元醇0～60％，聚酯多元醇0-60％(但两者不能同时为零)，扩链剂1～5％，成盐剂1～5％，其中二异氰酸酯可用芳香族二异氰酸酯或脂肪族二异氰酸酯，但脂肪族二异氰酸酯更好，因其拥有更加良好的生物相容性和更小的毒性，如考虑能提供给聚氨酯乳液良好分散性和稳定性的二异氰酸酯，则选用2，6-二异氰酸酯(LDI)和异佛尔酮二异氰酸酯(IPDI)等；聚醚多元醇可选用聚环氧丙烷二醇、聚环氧乙烷二醇、聚环氧乙烷环氧丙烷共聚二醇、聚丁烯二醇中的任意一种，分子量控制在1000～2000；聚酯多元醇可以选用聚ε-己内酯二醇、聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸丁二醇酯中的任意一种，分子量控制在1000～2000；扩链剂可以选用1，4-丁二醇、1，6-己二醇、双羟甲基丙酸中的任一种；而 Their preparation formulation (percentage by weight) of: a diisocyanate 17 to 40%, the polyether polyol 0-60%, 0-60% polyester polyol (but not both zero), a chain extender having 1 to 5 %, salt forming agent 1-5%, wherein the diisocyanate available aromatic diisocyanates or aliphatic diisocyanates, the aliphatic diisocyanates better, because of its toxicity have a more biocompatible and less, such considerations diisocyanate polyurethane emulsion can provide excellent dispersibility and stability, the selection of 2,6-diisocyanate (the LDI) and isophorone diisocyanate (IPDI) and the like; polyether polyol is polypropylene oxide diol may be chosen , polyoxyethylene glycols, polyethylene oxide propylene oxide copolymer diol, any of the polybutylene glycol, molecular weight control at 1000 to 2000; polyester polyol can be selected poly ε- caprolactone diol, polyethylene adipate, polypropylene adipate glycol, propylene glycol, any one of the polybutylene adipate, molecular weight control at 1000 to 2000; the chain extender may be selected 1 1,4-butanediol, 1,6-hexanediol, bis-hydroxymethyl propionic any one of; and 成盐剂为胺类，如二乙醇胺、吗啉等，或阳离子类，如钠、钾、铵等。 Salt-forming agent is an amine, such as diethanolamine, morpholine, or a cationic species such as sodium, potassium, ammonium and the like. 较适合的胺包括叔胺特别是烷基叔胺，如三乙胺。 Suitable tertiary amines include more particularly alkyl tertiary amines, such as triethylamine.
而制备水性聚氨酯乳液的工艺为常规的聚氨酯合成和水乳化工艺，这些都是这一领域技术人员公知的技术，故不一一赘述。 Preparation of an aqueous polyurethane emulsion for the conventional processes of polyurethane synthesis and water emulsification process, which are well known to those skilled in this art, it is not enumerate.
为了达到获得性能更为优异的水性聚氨酯弹性薄壁制品的目的，本发明提供的制备方法是在上述方法的基础上，对配方中所用的二异氰酸酯选用了侧链上带苯基的脂肪族二异氰酸酯，具体为苯二亚甲基二异氰酸酯、戊基苯基-3-庚烯-2，4-二壬基异氰酸酯的任一种。 To achieve the purpose of obtaining more excellent performance aqueous polyurethane elastic thin walled articles, the present invention provides a method of preparing the above-described method is based on the formulation of the diisocyanate used in the selection of an aliphatic dicarboxylic with a phenyl side chain isocyanates, particularly as xylylene diisocyanate, pentyl-phenyl-3-heptene-2,4-nonyl isocyanate according to any one ester.
用上述方法获得的增稠水性聚氨酯乳液除可用于用浸提方式制备弹性薄壁制品外，还可用喷涂、流延方式制备弹性薄壁制品。 Thickened aqueous polyurethane emulsion obtained by the above methods, the preparation of thin-walled elastomeric articles can be used in addition to elastomeric thin-walled articles may also be prepared by spraying the outer leaching manner, casting method.
为了考查用本发明方法获得的增稠水性聚氨酯乳液的黏度变化，以及所获弹性薄壁制品的物理机械性能、生物相容性和溶血性，本发明人对按实施例3的配方和工艺制备的基础上添加了不同量增稠剂的聚酯/聚醚型聚氨酯乳液及薄膜进行了测试，其测试方法如下，结果见表1、2、3、4：1.薄膜的拉伸强度与断裂伸长率测试将聚氨酯薄膜压制成长2cm厚约为1mm的样品。 In order to examine the change in viscosity of a thickened aqueous polyurethane emulsion obtained by the process of the present invention, and the resulting physical and mechanical properties of an elastic thin-walled products, biocompatibility and hemolytic, formulation and preparation process of Example 3 according to the embodiment of the present invention, on the basis of the added polyester / polyether urethane film, and varying amounts of emulsion thickeners were tested, following the test method, the results in Table 1, 2: 1 and fracture tensile strength of the film elongation test pressing the polyurethane film growth thickness of about 2cm sample of 1mm. 按GB 1040-92，在广州材料试验机厂的XLL-100型拉力试验机上测定，拉伸速率为250mm/min。 According to GB 1040-92, on a material testing machine plant in Guangzhou XLL-100-type tensile testing machine was measured, the stretching rate was 250mm / min.
2.乳液的粘度测试用上海天平仪器厂的NDJ-1型转子粘度计在常温下对乳液粘度进行测试。 2. Emulsion Viscosity Test NDJ-1 with rotor viscosity meter Shanghai Balance Instrument viscosity of the emulsion was tested at room temperature.
3.薄膜的水接触角测试采用Eyma(Japan)接触角测定仪其接触角。 3. The water contact angle test of the film using Eyma (Japan) the contact angle of the contact angle meter. 操作方法是用微量移液器取约5ul蒸馏水加到试样表面，每个样品取三点的平均值作为测试结果，测定温度为28℃，湿度为55％。 The method of operation is about to take a micropipette 5ul distilled water were added the sample surface, the average value of three points of each sample taken as the test result, the measurement temperature was 28 ℃, humidity of 55%.
4.薄膜的溶血性测试按照国家标准GB/T 16886.1-1997进行测试。 4. The film hemolytic tests according to national standard GB / T 16886.1-1997 test.
表1增稠水性聚氨酯弹性薄壁制品的力学性能测试 Table 1 Mechanical Properties Test thickened aqueous polyurethane elastic thin-walled products
表2粘度的测试 Table 2 Viscosity test
表3水接触角的测试 Table 3 Test water contact angle
表4水性聚氨酯弹性薄壁制品溶血实验结果 The results in Table 4 elastomeric thin-walled articles aqueous polyurethane hemolysis
值得说明的是，水接触角测试是考查本发明的水性聚氨酯弹性薄壁制品的表面亲水性。 It should be noted that the water contact angle test is a test of the present invention the surface of the hydrophilic aqueous polyurethane elastomeric thin-walled articles. 而表面亲水性考查是基于血液是个含水的体系，而生物材料的亲水性好坏则可从一个侧面来反映其生物相容性的好坏。 The test is based on the hydrophilic surface of the blood is an aqueous system, the biological material can be a hydrophilic quality from one side to reflect the quality of their biocompatibility. 水接触角越小，表明表面亲水性越好，也就从一个侧面反映该制品具有更良好的生物相容性。 The smaller the water contact angle indicates better surface hydrophilicity, it will reflect from a side surface of the article having more excellent biocompatibility. 结果发现增稠后的聚氨酯乳液成膜后其水接触角较原样明显降低，并随着增稠剂量的增加呈现出递减趋势。 The results found after forming the polyurethane emulsion thickened water contact angle decreased as compared with, and with the increase in the amount of thickening agent exhibits a decreasing trend.
另外，溶血实验是用水性聚氨酯乳液弹性薄壁制品做体外试验，测定红细胞溶解和血红蛋白游离的程度，对其的体外溶血性进行评价。 Further, hemolysis is an aqueous emulsion of a polyurethane elastomeric thin-walled articles made in vitro test to measure the degree of red blood cell lysis and free hemoglobin, hemolysis in vitro evaluation thereof. 本发明的水性聚氨酯弹性薄壁制品的样品测定的溶血率均小于5％，说明材料对红细胞的破坏很小，符合生物材料的溶血性要求，因此可以安全的用来做医用手套等。 Hemolytic assay sample rate of the aqueous polyurethane elastomeric thin-walled articles of the present invention is less than 5%, indicating little material damage to erythrocytes, hemolytic meet the requirements of biological material and thus can be safely used for medical gloves.
本发明与已有技术相比，具有以下优点： Compared with the prior art the present invention has the following advantages:
1、由于本发明提供的方法可使水性聚氨酯乳液在未进行浸提等方式生产制品时可保持其良好的稳定性，而需要进行时，只要即时加入增稠剂增稠便可立刻满足浸提等方式生产对乳液黏度的要求，且操作简便经济易行，为水性聚氨酯弹性薄壁制品工业化生产提供了一条切实可行的途径。 1, can maintain its good stability due to the method of the present invention to provide aqueous polyurethane emulsion can not be leached to produce manufactured articles and the like, and when required, as long as the thickener is added to thicken instantly leaching can be satisfied immediately etc. production requirements on the emulsion viscosity, and easy to operate economically feasible, provide a feasible approach for water-based polyurethane elastic thin-walled products for industrial production.
2、由于本发明提供方法选用的增稠剂范围大，因而不仅可用于制备一般的水性聚氨酯弹性薄壁制品，还可用于制备具有良好生物相容性的医用级水性聚氨酯弹性薄壁制品。 2, since the present invention provides a method for a large range of optional thickener, and therefore not only useful for the preparation of general aqueous polyurethane elastic thin walled articles, may also be used to prepare aqueous polyurethane medical grade elastomeric thin-walled articles having good biocompatibility.
3、由于用本发明提供的添加增稠剂方法可大大提高水性聚氨酯乳液黏度，因而可减少反复浸提的次数，缩短工艺流程，减小乳液损耗，降低成本。 3, since the method of adding a thickening agent provided by the present invention can greatly increase the viscosity of the aqueous polyurethane emulsion, thereby reducing the number of repeated leaching, shorten the process, the emulsion is reduced losses and reduce costs.
4、用本发明提供的方法制备的水性聚氨酯弹性薄壁制品，从后期的一系列测试中可看出其具有更优异的力学性能、亲水性能和抗溶血性等。 4, the aqueous polyurethane elastomeric thin-walled articles prepared by the process provided by the present invention, from series of tests can be seen later with more excellent mechanical properties, hydrophilic properties, and anti-hemolytic like.
四、具体实施方式 IV DETAILED DESCRIPTION
下面给出实施例以对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员根据本发明内容对本发明作出的一些非本质的改进和调整仍属本发明的保护范围。 Given below embodiments to the present invention will be specifically described, it is necessary to point out that the following examples are only for the present invention is further illustrated not to be construed as limiting the scope of the invention, the skilled in the art of the present Some non-essential modifications and adaptations of the present invention SUMMARY oF tHE iNVENTION still made to the scope of the present invention.
实施例11、聚酯/聚醚型聚氨酯乳液的制备将70克聚环氧丙烷二醇(Mn＝1000)和70克聚己二酸丁二醇酯二醇(Mn＝1000)加到250ml三颈瓶中，加热至60℃搅拌溶解10分钟后，在105℃下抽真空，脱水10分钟；降温至90℃，再将16.59克甲苯二异氰酸酯(TDI)加入，保持在90℃下反应2个小时左右，测NCO％，若NCO％小于或等于理论值6.8时，再将5.03克扩链剂双羟甲基丙酸(DMPA)加入，在90℃下反应25分钟，降温至75℃继续反应40分钟后开始测NCO％，每隔15分钟测一次，直至NCO％小于或等于理论值0.7时为止；降温至60℃下加入90ml丙酮搅拌10分钟，再加入5克三乙胺搅拌10分钟后，将聚氨酯预聚物倒入装有488毫升蒸馏水的乳化装置中猛烈搅拌，乳化3～4个小时即可出料，获得固含量为25％的聚酯/聚醚型聚氨酯乳液，备用； Example 11, a polyester / polyether polyurethane emulsion 70 g of polypropylene oxide diol (Mn = 1000) and 70 grams of polyethylene adipate diol (Mn = 1000) was added to 250ml three neck flask, was heated to 60 deg.] C and dissolved under stirring for 10 minutes, evacuated and dehydrated at 105 deg.] C 10 minutes; cooling to 90 ℃, then 16.59 grams of toluene diisocyanate (TDI) was added, maintaining the reaction at 90 ℃ 2 th about hours, measured NCO%, when the theoretical NCO% value equal to or less than 6.8, the chain extender and then 5.03 g bis dimethylol propionic acid (DMPA) was added, reacted at 90 ℃ 25 minutes and cooled to 75 deg.] C the reaction was continued after cooling down to 90ml of acetone was added and stirred for 10 minutes at 60 ℃, then added 5 g of triethylamine was stirred for 10 min; measured beginning 40 minutes NCO%, measured once every 15 minutes, until NCO% until the theoretical value equal to or less than 0.7 emulsifying apparatus, the urethane prepolymer was poured into 488 ml of distilled water with vigorous stirring, emulsified 3-4 hours to the material, a solids content of 25% polyester / polyether polyurethane dispersion for standby;
2、增稠聚酯聚醚型聚氨酯乳液的制备称取100克制备的聚酯/聚醚型聚氨酯乳液加入三颈瓶中加热至30℃，将0.3克的海藻酸丙二醇酯用50倍蒸馏水溶解后加入，开动搅拌，在250转/分的速度下搅拌5分钟，即得；此种增稠型乳液可以用做生产手套、保险套等产品，因具体制备工艺为已有的，故略去不述。 2. Preparation of polyester-polyether polyurethane thickening emulsion weighed polyester / polyether polyurethane emulsion prepared three-necked flask were added 100 g was heated to 30 ℃, 0.3 g of propylene glycol alginate with distilled water 50 times after the addition, stirring was started, with stirring at 250 rpm / min for 5 minutes to obtain; such thickening emulsions produced can be used as gloves, condoms, and other products, particularly due to existing manufacturing process, so is omitted its description.
该乳液增稠前成膜材料拉伸强度34Mpa，断裂伸长率540％；增稠后成膜材料拉伸强度38Mpa，断裂伸长率520％。 The emulsion is thickened before film tensile strength 34Mpa, elongation at break of 540%; tensile strength after forming thickening 38Mpa, elongation at break of 520%.
实施例21、购买Bayer公司的Desmocoll KA 8066号水性聚氨酯乳液，该乳液固含量为40％，拉伸强度37Mpa，断裂伸长率500％；2、称取1000克的聚氨酯乳液加入三颈瓶中加热至30℃，将海藻酸钠1克，明胶4克，淀粉15克的复配增稠剂用120倍蒸馏水溶解后加入，开动搅拌，在120转/分的速度下搅拌30分钟，即得；此种增稠型乳液可以用做生产手套，保险套等产品，因具体制备工艺为已有的，故略去不述。 Example 21, purchased from Bayer number Desmocoll KA 8066 aqueous polyurethane emulsion embodiment, the emulsion has a solid content of 40%, a tensile strength of 37 MPa, elongation at break of 500%; 2, weighed 1000 g polyurethane emulsion three-necked flask were added was heated to 30 ℃, added 1 g of sodium alginate, gelatin 4 g, starch 15 g compound 120-fold with distilled water and thickener dissolved, stirring was started, at a stirring speed of 120 rev / min for 30 minutes, to obtain ; such thickening emulsions produced can be used as gloves, condoms, and other products, particularly due to existing manufacturing process, it is omitted. 该乳液增稠后成膜材料拉伸强度40Mpa，断裂伸长率460％。 After forming the emulsion thickened tensile strength 40Mpa, elongation at break of 460%.
实施例31、聚酯/聚醚型聚氨酯乳液的制备将聚己二酸乙二醇丙二醇酯(Mn＝1000)350克放入反应釜中，在60℃下熔解后，搅拌降温至50℃，加入聚环氧乙烷环氧丙烷共聚二醇(Mn＝1000)350克混合均匀；再加入异佛尔酮二异氰酸酯(IPDI)110克，在75℃下预聚反应50分钟，再加入40克双羟甲基丙酸先在90℃下反应25分钟，然后降温至75℃反应40分钟后开始测NCO％，每隔15分钟测一次，直至NCO％小于或等于理论值0.7为止；在60℃下加入100毫升丙酮搅拌10分钟，再加入35克三乙胺搅拌10分钟后，将聚氨酯预聚物倒入装有1354毫升的乳化装置中猛烈搅拌，乳化3～4个小时即可出料，获得固含量为30％的聚酯/聚醚型聚氨酯乳液，备用；2、增稠聚酯/聚醚型聚氨酯乳液的制备称取1000克制备的聚酯/聚醚型聚氨酯乳液加入三颈瓶中，加热至40℃，然后将丙烯酸14.85克，丙烯酸乙酯13.20克，丙 Example 31, a polyester / polyether polyurethane emulsion of the polyethylene adipate glycol diacrylate (Mn = 1000) 350 grams into the autoclave, after melting at 60 deg.] C, cooled with stirring to 50 ℃, Add propylene oxide copolymer of polyethylene oxide glycol (Mn = 1000) 350 g of mixed; was added isophorone diisocyanate (IPDI) 110 grams, the prepolymerization at 75 ℃ 50 minutes, then 40 g bis-hydroxymethyl propionic acid is first reacted at 90 ℃ 25 minutes and then cooled to 75 deg.] C for 40 minutes the reaction starts measuring the NCO%, measured once every 15 minutes, until NCO% of theory far less than or equal 0.7; at 60 deg.] C after the addition of 100 ml of acetone was stirred for 10 minutes and then added 35 g of triethylamine was stirred for 10 minutes and the polyurethane prepolymer was poured into 1354 ml emulsifying device equipped with a violently stirred, emulsified 3-4 hours to the material, a solids content of 30% polyester / polyether urethane emulsion standby; 2, prepared thickened polyester / polyether type polyurethane emulsion was weighed polyester / polyether polyurethane emulsion prepared 3-necked flask was added 1000 g and heated to 40 ℃, and then 14.85 g of acrylic acid, 13.20 g ethyl acrylate, propyl 腈2.64克，邻苯二甲酸二烯丙酯1.65克，十二烷基硫酸钠0.693克，O∏-70.693克，过硫酸钾0.264克，羟胺0.033克的复配增稠剂用130倍蒸馏水溶解后加入，开动搅拌，在150转/分的速度下搅拌25分钟，即得；此种乳液可以用做袖套，充气囊袋，靴子，气球等产品，因具体制备工艺为已有的，故略去不述。 Nitrile 2.64 g, diallyl phthalate, 1.65 g, 0.693 g sodium lauryl sulfate, OΠ-70.693 g, 0.264 g of potassium persulfate, 0.033 grams of hydroxylamine compound 130-fold with distilled water thickener after the addition, stirring was started at a stirring speed of 150 rev / min for 25 minutes to obtain; such emulsions can be used as the cuff, the inflatable bladder, boots, balloons and other products, particularly due to existing manufacturing process, so omitted.
该乳液增稠前成膜材料拉伸强度33.73Mpa，断裂伸长率540％；增稠后成膜材料拉伸强度38.45Mpa，断裂伸长率480％。 The emulsion is thickened before film tensile strength 33.73Mpa, elongation at break of 540%; tensile strength after forming thickening 38.45Mpa, elongation at break of 480%.
实施例41、聚酯/聚醚型聚氨酯乳液的制备将聚己二酸乙二醇丙二醇酯(Mn＝1000)200克放入反应釜中，在60℃下熔解后，搅拌降温至40℃，加入聚环氧乙烷环氧丙烷共聚二醇(Mn＝1000)200克混合均匀；再加入苯二亚甲基二异氰酸酯(XDI)54克，在75℃下预聚反应80分钟，再加入21克双羟甲基丙酸先在90℃下反应35分钟，然后降温至60℃反应40分钟后开始测NCO％，每隔15分钟测一次，直至NCO％小于或等于理论值0.9为止；在60℃下加入75毫升丙酮搅拌10分钟，再加入20克三乙胺搅拌10分钟后，将聚氨酯预聚物倒入装有1096毫升的乳化装置中猛烈搅拌，乳化3～4个小时即可出料，获得固含量为30％的聚酯/聚醚型聚氨酯乳液，备用；2、增稠聚酯/聚醚型聚氨酯乳液的制备称取100克制备的聚酯/聚醚型聚氨酯乳液加入三颈瓶中，加热至30℃，然后将4.5克的卡拉胶增稠剂用150倍蒸馏水溶解 Example 41, a polyester / polyether polyurethane emulsion of the polyethylene adipate glycol diacrylate (Mn = 1000) 200 grams into the autoclave, after melting at 60 deg.] C, cooled with stirring to 40 ℃, Add propylene oxide copolymer of polyethylene oxide glycol (Mn = 1000) 200 g of mixed; adding xylylene diisocyanate (XDI) 54 grams, the prepolymerization at 75 ℃ 80 minutes, then add 21 g bis-hydroxymethyl propionic acid is first reacted at 90 ℃ 35 minutes and then cooled to 60 deg.] C for 40 minutes the reaction starts measuring the NCO%, measured once every 15 minutes, until NCO% is less than or equal to the theoretical value of 0.9; at 60 after addition of 75 ml of acetone was stirred for 10 minutes at ℃, then added 20 g of triethylamine was stirred for 10 minutes and the polyurethane prepolymer was poured into 1096 ml emulsifying device equipped with a violently stirred, emulsified 3-4 hours to discharge to obtain a solid content of 30% polyester / polyether urethane emulsion standby; 2, prepared thickened polyester / polyether type polyurethane emulsion was weighed polyester / polyether polyurethane emulsion prepared three-neck 100 g bottle, heated to 30 ℃, carrageenan and 4.5 g of distilled water was dissolved 150 times thickener 后加入，开动搅拌，在120转/分的速度下搅拌25分钟，即得；此种乳液可以用做袖套，充气囊袋，靴子，气球等产品，因具体制备工艺为已有的，故略去不述。 After the addition, stirring was started, at a stirring speed of 120 rev / min for 25 minutes to obtain; such emulsions can be used as the cuff, the inflatable bladder, boots, balloons and other products, particularly due to existing manufacturing process, so omitted.
该乳液增稠前成膜材料拉伸强度35Mpa，断裂伸长率500％；增稠后成膜材料拉伸强度38Mpa，断裂伸长率450％。 The emulsion is thickened before film tensile strength 35Mpa, elongation at break of 500%; tensile strength after forming thickening 38Mpa, elongation at break of 450%.
实施例5：1、购买Bayer公司的Badur型水性聚氨酯乳液，该乳液固含量40％，拉伸强度为22Mpa，断裂伸长率600％；2、称取100克的聚氨酯乳液加入三颈瓶中加热至30℃，将6.5克的阿拉伯胶增稠剂用160倍蒸馏水溶解后加入，开动搅拌，在150转/分的速度下搅拌27分钟，即得；此种增稠型乳液可以用做生产手套，保险套等产品，因具体制备工艺为已有的，故略去不述。 Example 5: 1, from Bayer Badur purchase type aqueous polyurethane emulsion, the emulsion solids of 40%, a tensile strength 22Mpa, elongation at break of 600%; 2 weighed 100 g polyurethane emulsion three-necked flask were added was heated to 30 ℃, after 6.5 g of gum arabic dissolved in 160 times thickener distilled water was added, stirring the mixture was stirred at a speed of 150 rev / min in 27 minutes, to obtain; such thickening emulsions produced can be used gloves, condoms, and other products, particularly due to existing manufacturing process, it is omitted. 该乳液增稠后成膜材料拉伸强度28Mpa，断裂伸长率600％。 After forming the emulsion thickened tensile strength 28Mpa, elongation at break of 600%.
实施例6：1、购买Bayer公司的Impranil DLN型水性聚氨酯乳液，该乳液固含量40％，拉伸强度为25Mpa，断裂伸长率700％；2、称取100克的聚氨酯乳液加入三颈瓶中加热至30℃，将8.4g的琼脂增稠剂用180倍蒸馏水溶解后加入，开动搅拌，在150转/分的速度下搅拌25分钟，即得；此种增稠型乳液可以用做生产手套，保险套等产品，因具体制备工艺为已有的，故略去不述。 Example 6: 1, purchased from Bayer Impranil DLN waterborne polyurethane emulsion, which emulsion has a solid content of 40%, a tensile strength 25Mpa, elongation at break of 700%; 2 weighed 100 g polyurethane emulsion was added 3-necked flask heated to 30 ℃, 8.4g agar thickener to 180 times of distilled water and dissolved, stirring was started at a stirring speed of 150 rev / min for 25 minutes to obtain; such thickening emulsions produced can be used gloves, condoms, and other products, particularly due to existing manufacturing process, it is omitted. 该乳液增稠后成膜材料拉伸强度30Mpa，断裂伸长率700％。 After forming the emulsion thickened tensile strength 30Mpa, elongation at break of 700%.
- 1.一种水性聚氨酯弹性薄壁制品的制备方法，该方法是先制备或外购水性聚氨酯乳液，然后将薄壁制品的模型浸入乳液中，提出后经干燥、脱模制得成品，其特征在于将薄壁制品的模型浸入乳液前，再在乳液中加入增稠剂，增稠剂是用0～200倍水溶解后，在水性聚氨酯乳液加热至20～50℃时加入，并在120～250转/分的速度下搅拌5～30分钟；加入的增稠剂与水性聚氨酯乳液的重量比为0.01～10∶100；增稠剂选用海藻酸及其盐、海藻酸丙二醇酯、琼脂、卡拉胶、洋槐豆胶、瓜尔豆胶、阿拉伯胶、刺梧桐胶、黄蓍胶、果胶、黄原胶、羧甲基纤维素及其衍生物、改性淀粉和明胶中的至少一种。 1. A method for preparing an aqueous polyurethane elastic thin-walled article, which is to be prepared or purchased an aqueous polyurethane emulsion, then thin-walled articles immersed model emulsion, made after drying, releasing prepared products, characterized in in that the model thin walled articles before immersing the emulsion, the emulsion was added thickener, the thickener is dissolved in water, 0 to 200 times, followed by heating in an aqueous polyurethane emulsion when added to 20 ~ 50 ℃, and 120 ~ stirring 250 rpm / min for 5 to 30 minutes; the weight ratio of thickener added to the aqueous polyurethane emulsion is from 0.01 to 10:100; thickener selected alginic acid and salts thereof, propylene glycol alginate, agar, karaoke plastic, at least one of locust bean gum, guar gum, acacia gum, karaya gum, gum tragacanth, pectin, xanthan gum, carboxymethylcellulose and derivatives thereof, modified starches and gelatin.
- 2.根据权利要求1所述的水性聚氨酯弹性薄壁制品的制备方法，其特征在于水性聚氨酯选自聚醚/聚酯型水性聚氨酯；在合成水性聚氨酯时，所用的二异氰酸酯为侧链上带苯基的脂肪族二异氰酸酯。 The method of preparing aqueous polyurethane elastomeric thin-walled articles according to claim 1, characterized in that the aqueous polyurethane selected from polyether / polyester waterborne polyurethane; in the synthesis of polyurethane, the diisocyanate is used on the side chain phenyl aliphatic diisocyanates.
- 3.根据权利要求2所述的水性聚氨酯弹性薄壁制品的制备方法，其特征在于侧链上带苯基的脂肪族二异氰酸酯为苯二亚甲基二异氰酸酯、戊基苯基-3-庚烯-2，4-二壬基异氰酸酯的任一种。 The method of preparing aqueous polyurethane elastomeric thin-walled articles according to claim 2, characterized in that with the aliphatic diisocyanate is phenyl xylylene diisocyanate side chain pentyl-heptyl-phenyl-3- ene-2,4-nonyl isocyanate according to any one ester.
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|US7901740B2 (en)||2004-11-05||2011-03-08||Tamicare Ltd.||Methods to produce stretchable products|
|ES2335694T3 (en)||2005-08-26||2010-03-31||Goldendip Sdn. Bhd.||Glove with polyurethane coated textile lining with aqueous base and process for their manufacture.|
|CN102078233A (en) *||2011-03-10||2011-06-01||中国化工橡胶株洲研究设计院||Condom and preparation method thereof|
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