CN1081686C - Wet PVA-crosslinking spinning technology - Google Patents

Wet PVA-crosslinking spinning technology Download PDF

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CN1081686C
CN1081686C CN 98101364 CN98101364A CN1081686C CN 1081686 C CN1081686 C CN 1081686C CN 98101364 CN98101364 CN 98101364 CN 98101364 A CN98101364 A CN 98101364A CN 1081686 C CN1081686 C CN 1081686C
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bath
process
polyvinyl alcohol
spinning
coagulation bath
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CN1197858A (en )
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朱本松
蔡夫柳
李小宁
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中国石油化工总公司
北京服装学院
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本发明为聚乙烯醇湿法交联纺丝工艺,它以普通分子量聚乙烯醇为原料,以锆、硼、钛、硅组成复合交联剂,加水溶解后,在第一凝固浴中纺丝,在第二凝固浴中脱水、凝固。 After the present invention is a crosslinked polyvinyl wet spinning process, it is the molecular weight of polyvinyl alcohol ordinary raw materials, zirconium, boron, titanium, silicon composite crosslinking agent, dissolved in water, in a first coagulation bath spinning , dehydrated in the second coagulation bath, solidification. 然后进行湿热牵伸,在酸浴中进行解交联处理,在中和浴中去除纤维中的酸和硫酸钠,经干燥,最后进行干热牵伸,总牵伸倍数达到15~18倍。 A wet heat drawing and then, de-crosslinking treatment in an acid bath, the fiber is removed and sodium sulfate in the acid bath and, after drying, subjected to dry heat drawing and finally, the total draw ratio of 15 to 18 times. 制得的纤维强度为15克/旦,模量为360克/旦。 Fiber strength obtained was 15 g / denier, modulus 360 g / denier. 本发明可使用现有维纶纺丝装置,工艺简单,便于推广,市场广阔。 The present invention may be used vinylon conventional spinning apparatus, the process is simple, easy to promote a huge market.

Description

聚乙烯醇湿法交联纺丝工艺 Crosslinked polyvinylalcohol wet spinning process

本发明涉及一种制取高强高模合成纤维的方法,具体地说,是由聚乙烯醇配合交联剂纺制一种高强高模聚乙烯醇纤维的纺丝工艺方法。 The present invention relates to a method for preparing high strength and high modulus synthetic fiber, in particular, is made of polyvinyl alcohol with a crosslinking agent spinning a high-strength and high modulus polyvinyl alcohol fiber spinning process method.

聚乙烯醇原料来源广泛,具有广泛的用途,但提高其强度和模量,仍是合成纤维工作者孜孜以求的目标之一。 Polyvinyl wide range of sources of raw materials, having a wide range of uses, but improve the strength and modulus, remains one of the synthetic pursued by workers. 例如聚乙烯醇纤维与水泥有很好的粘合性和固化性,可代替石棉用于制取水泥增强制品,它要求聚乙烯醇纤维具有更高的强度和模量。 Such as polyvinyl alcohol fiber and cement has good adhesiveness and curability can be used to take the place of asbestos reinforced cement products, it requires the polyvinyl alcohol fibers having higher strength and modulus. 目前,国内外多数利用湿法纺丝纺制高强高模的聚乙烯醇纤维,一般以DP=1750±50的普通分子量聚乙烯醇为原料,均使用硼做交联剂,以中国专利公开:CN1031727A“聚乙烯醇长丝束生产工艺”为例,它公开了一种在浓度14~20%下,在聚乙烯醇中加入按重量0.8~5.5%的硼酸和0.05~1.5%的环氧乙烷高聚物,制成纺丝原液。 At present, most domestic and spun by wet spinning of high strength and high modulus polyvinyl alcohol fiber, generally the molecular weight of polyvinyl alcohol ordinary DP = 1750 ± 50 as starting material, are boron crosslinker to Chinese Patent Publication: CN1031727A "polyvinyl long tow production process" for example, it is disclosed at a concentration of 14 to 20% by addition of 0.8 to 5.5 wt% boric acid and 0.05 to 1.5% of ethylene oxide in the polyvinyl alcohol alkoxy polymer to make the spinning dope. 其工艺过程的顺序为,先经过凝固浴、中和浴、湿热牵伸、然后水洗干燥,干热牵伸处理,从而得到6~30万旦的干拉强度为11.6克/旦,初始模量264克/旦,伸度7.7%的高强纤维。 Order in which the process is, after the first coagulating bath, and the bath, wet heat drawing, washing with water and drying, dry heat drawing process to obtain 6 deniers to 300,000 dry tensile strength of 11.6 g / denier, an initial modulus 264 g / denier, an elongation of 7.7% of high-strength fibers. 但经实践认为,其强度,特别是模量还有提高的可能性。 But after practice believes that its strength, particularly in modulus as well as the possibility of improving. 此外,为了提高牵伸性能,纤维中硼酸含量最多不超过0.3%,这就增加了水洗去除硼酸的时间,导致纤维溶胀和并丝,使干热牵伸时容易出现毛丝和断头,影响连续操作和产品的质量。 Further, in order to improve the drawing performance, up to the fiber content of boric acid exceeds 0.3%, which increases the removal of boric acid washing time, and causing the fibers to swell and silk, and the dry and hot bristle breakage prone during drawing, impact continuous operation and product quality. 与此同类的制造方法,如日本专利昭47-42058,昭54-32858,昭59-43112等,皆有此缺欠。 And the method for producing the same, as described in Japanese Patent Sho 47-42058, Sho 54-32858, Sho 59-43112, etc., there are shortcomings to this.

本发明的目的在于避免上述存在的不足之处,提供一种采用聚乙烯醇普通纺丝工艺,可纺性好,水洗时间短,纤维强度和模量较高的聚乙烯醇湿法交联纺丝工艺。 Object of the present invention is to avoid the above shortcomings exist, there is provided a use of polyvinyl alcohol ordinary spinning process, good spinnability, the washing time is short, a higher fiber strength and modulus of crosslinked polyvinyl wet spinning wire process.

本发明的目的可以用如下方法来实现,其聚乙烯醇湿法交联纺丝工艺首先将聚乙烯醇和交联剂配制成纺丝溶液,其原液组成为:聚乙烯醇浓度为12~16%,交联剂加入浓度0.5~5%,所用交联剂由水溶性的锆化合物、钛盐、硼酸盐、硅酸盐中的两种或两种以上组成,加入的重量比例顺次为3~5∶2~3.5∶1~2.5∶1~2.5,纺丝温度95~98℃;溶液经喷丝孔喷入凝固浴成丝,其凝固浴由第一凝固浴和第二凝固浴构成,第一凝固浴组成为:氢氧化钠:15~50克/升,硫酸钠:300~380克/升,控制温度:40~45℃;第二凝固浴组成为:氢氧化钠:10~30克/升,硫酸钠:330~410克/升,控制温度为:45~50℃,同时进行牵伸2~4倍;然后顺序经过湿热牵伸、酸浴、中和浴、干燥、干热牵伸得到高强高模长丝。 The object of the present invention can be achieved by the following method, which is cross-linked polyvinyl wet spinning process and the crosslinking agent of polyvinyl alcohol is first formulated as a spinning solution, which stock solution consisting of: a polyvinyl alcohol concentration of 12 to 16% the weight ratio of the crosslinking agent added to a concentration of 0.5 to 5%, of a water-soluble crosslinking agent used by the zirconium compound, titanium, borate, silicate consisting of two or more, was added sequentially 3 5:2 ~ ~ 2.5 ~ 2.5 ~ 3.5:1 spinning temperature 95 ~ 98 ℃; solution was sprayed into a coagulation bath through the spinneret orifices into filaments, the coagulation bath which is constituted by a first coagulation bath and second coagulation bath, The first coagulation bath consisting of: sodium hydroxide: 15 - 50 g / l, sodium sulfate: 300 to 380 g / l, temperature control: 40 ~ 45 ℃; second coagulation bath consisting of: sodium: 10 to 30 g / l, sodium sulfate: 330 to 410 g / l, the temperature is controlled: 45 ~ 50 ℃, simultaneously drawn 2 to 4 times; then sequentially through heat drawing, acid bath, and the bath, drying, dry heat drafting obtain high strength high modulus filaments.

本法主要目的是使纤维在初生态时保持结构的均匀性和良好的牵伸性能,初生纤维外观近似呈圆形截面,为此采用双凝固浴:在第一凝固浴,使大分子产生一定的交联,避免了分子间的无规缠绕,使初生纤维维持凝胶状态并缓慢凝固,在第二凝固浴减少氢氧化钠量,适当增加硫酸钠浓度,使大分子聚乙烯醇进一步脱水、交联,形成结构均匀的初生纤维,并进行首次牵伸。 Law main purpose is to maintain the uniformity of the fibers and good drawing properties in the nascent structure, spun fibers appearance approximately circular cross section, double coagulation bath used for this purpose: the first coagulation bath, so that a certain macromolecules crosslinking avoid random molecules of the wound, so to maintain the fibers spun slowly solidified gel state and, in the second coagulation bath to reduce the amount of sodium hydroxide, an appropriate increase in the concentration of sodium sulfate, polyvinyl alcohol further dehydrated macromolecules, crosslinking spun fibers to form a uniform structure, and the first drawing. 为配合本工艺,其交联剂的选择应使聚乙烯醇分子交联容易,并要满足纺丝工艺对纤维的要求。 With this process is that the crosslinking agent is selected so readily cross-linked polyvinyl alcohol molecules, and to meet the requirements for the fiber spinning process. 交联剂应用水溶性的锆化合物、钛盐、硼酸盐和硅酸盐。 Application of the water-soluble crosslinking agent is a zirconium compound, titanium, borate and silicate. 此外,本发明中由于采用二个凝固浴形成了结构均匀的初生纤维,有很好的牵伸性能。 Further, since the present invention uses two coagulation bath formed a uniform structure spun fibers, has good drawing properties.

本发明的目的还可以用如下的方法来实现,在首次牵伸后纤维进入湿热牵伸浴,浴中维持硫酸钠浓度:340~380克/升,在温度80~95℃下,牵伸2~4倍。 Object of the present invention may also be achieved by the following method proceeds after the first heat drawing bath drawing the fibers, the bath is maintained over sodium concentration: 340 to 380 g / l, at a temperature of 80 ~ 95 ℃, drawing 2 to 4 times. 接着进入酸浴,酸浴中维持硫酸钠浓度:280~320克/升,硫酸浓度:10~40克/升,在硫酸作用下使聚乙烯醇大分子已产生交联发生部分解交联,目的在于提高纤维的干热牵伸性能。 Then into the acid bath, the acid bath is maintained over sodium concentration: 280 to 320 g / l, sulfuric acid concentration: 10 to 40 g / l, the polyvinyl alcohol molecules in the presence of sulfuric acid solution has been partially crosslinked to produce crosslinked, dry heat drawing object is to improve the properties of the fibers. 在中和浴中纤维停留时间为:20~90秒,目的在于洗去硫酸和硫酸钠,使纤维呈中性,这一过程停留时间比对比专利技术水洗时间短,避免纤维发生溶胀,保证了纤维的高倍牵伸即保证了高倍牵伸所具有的高强特性,虽然仍带有一定的交联分子,但不影响牵伸性能且能增加产品的强度。 In the fiber and the bath residence time: 20 to 90 seconds, and the object is to wash away the sodium sulfate, neutral fiber, the residence time is shorter than the comparison process patented washing time, prevent the fibers swell, to ensure that the drawing the fibers to ensure high power, i.e., the high power draw has high strength properties, although still with a certain degree of cross-linking molecules, but does not affect the performance of the drawing and can increase the strength of the product. 再经干燥箱控制温度120~150℃进行干燥,干燥时间为:1~5分钟。 Then dried over a drying oven controlled temperature 120 ~ 150 ℃, drying time: 1 to 5 minutes. 最后,在225~245℃下进行干热牵伸,总的牵伸倍数可达15~18倍。 Finally, subjected to dry heat drawing at 225 ~ 245 ℃, the total draw ratio of up to 15 ~ 18 times. 其干燥及牵伸可采用现有技术,其所用装置采用现有技术所用的装置稍加改造即可。 Drafting and can be dried prior art that uses the device, a device used in the prior art can be slightly modified.

本发明相比现有技术具有以下优点:1,以DP1750±50国产普通聚乙烯醇为原料,采用锆、钛、硼、硅型复合交联剂和双凝固浴湿法交联纺丝工艺,可以达到15克/旦高强度,360克/旦高模量的聚乙烯醇纤维,比对比专利技术分别提高30%和36%;牵伸性能好,可达到15~18倍,比对比专利高约2~5倍。 Compared with the prior art the present invention has the following advantages: 1 to DP1750 ± 50 made of ordinary PVA as raw material, zirconium, titanium, boron, silicon type compound and a crosslinking agent crosslinking bis wet coagulation bath spinning process, can reach 15 g / denier high strength, 360 g / denier high modulus polyvinyl alcohol fibers, patented technology to increase contrast ratio were 30% and 36%; good drawing properties, may be from 15 to 18 times higher than the comparative Patent from about 2 to 5 times. 2,在中和浴中不刻意洗去纤维中剩余的交联剂,不但可以避免纤维发生溶胀,而且可以保留少量交联,从而提高纤维的模量。 2, in the bath and washed fibers are not deliberately cross-linking agent remaining, not only avoid the fiber swells, but may retain a small amount of cross-linking, thereby increasing the modulus of the fiber. 3,可用于加工高强度的产品,如绳索、蓬盖布、水龙带、工业缝纫线、土工布、安全带、吊装袋、运输带、滤芯材料、阻燃制品等,还可以作为石棉代用品,用于生产水泥以及其他增强水泥复合材料,在国内外具有广泛的市场。 3, can be used for processing high-strength products such as ropes, tarpaulins, hoses, industrial sewing thread, geotextiles, webbing, lifting the bag, conveyor belts, filter materials, flame retardant products, etc., may also be used as a substitute for asbestos for the production of cement and other cement composite materials at home and abroad with a wide range of markets.

本发明附图的图面说明如下:附图为本发明工艺流程简图。 Drawing figures of the present invention is described as follows: BRIEF process diagram of the present invention.

下面配合附图以实施例说明本发明,为了更易推广,我们使用最常用的聚合度DP 1750±50,醇解度99.9%聚乙烯醇,制成浓度14%的水溶液。 With the following drawings illustrate embodiments of the present invention, in order to promote easier, we used the most commonly used polymerization degree DP 1750 ± 50, 99.9% alcoholysis degree of polyvinyl alcohol, an aqueous solution of 14% concentration. 将聚乙烯醇重量的2%的复合交联剂添加到溶液中,复合交联剂选用硫酸锆、四硼酸钠,其组成为硫酸锆∶四硼酸钠=3∶2。 The addition of 2% by weight of the composite crosslinking agent to the solution of polyvinyl alcohol, the crosslinking agent selected composite zirconium sulfate, sodium tetraborate, consisting of zirconium sulfate: sodium tetraborate = 3:2. 聚乙烯醇纺丝原液通过孔径为0.08毫米的喷丝孔1挤入含硫酸钠370克/升、氢氧化钠30克/升,温度为45℃的第一凝固浴2,形成凝胶状初生纤维,其工艺流程示意图见附图,接着进入硫酸钠400克/升,氢氧化钠15克/升,温度45℃的第二凝固浴3,进一步脱水、凝固,并牵伸2.5倍。 Polyvinyl alcohol dope through spinning holes of 0.08 mm, a pore-containing extruded over sodium sulfate 370 g / l, sodium hydroxide 30 g / l, a temperature of the first coagulating bath at 45 ℃ 2, to form a gelatinous primary fibers, which process see attached drawing, then into 400 g sodium / liter, 15 g NaOH / l, temperature 45 ℃ second coagulation bath 3, further dehydration, freezing, and drawn 2.5 times. 湿热牵伸浴4中硫酸钠360克/升,温度90℃,牵伸2倍。 Heat drawing bath 4 sodium sulfate 360 ​​g / l, temperature 90 ℃, drawn two times. 然后进入含硫酸钠280克/升,硫酸15克/升的酸浴5,室温牵伸1.4倍,在牵伸中使纤维中大量的交联解除。 Containing 280 g sodium sulphate and then enter / liter, sulfuric acid 15 g / l of acid bath 5, drawn 1.4 times at room temperature, releasing a large amount of crosslinking in the fiber drawing manipulation. 然后进入室温的中和浴6,洗去纤维中的硫酸钠和硫酸,在中和浴中停留30秒。 And then into a bath of room temperature 6, and the washed fibers sodium sulfate, and stay in the bath for 30 seconds. 接着在140℃干燥箱7中干燥,之后进入235℃干热牵伸箱8进行干热牵伸,使纤维总牵伸倍数达到16倍。 7 deg.] C drying oven at 140 followed by drying, after entering the dry heat drawing tank 235 ℃ 8 was dry heat drawing the fiber total draft ratio of 16 times. 制成纤维经测定,强度为15克/旦,模量360克/旦,断裂伸长为6.0%,纤度为1.48分特。 The determination is made of fiber strength of 15 g / denier, modulus 360 g / denier, an elongation at break of 6.0%, a fineness of 1.48 dtex. 整个工艺连续操作,由于与现有国产维纶的纺丝工艺基本一致,可利用原维纶生产装置,稍加改动即可生产高强高模聚乙烯醇纤维。 Continuous operation throughout the process, since the spinning process is consistent with the existing domestic polyvinyl alcohol, polyvinyl alcohol can be produced using the original device, a little change can produce high strength high modulus polyvinyl alcohol fiber.

注:本发明所指“%”皆为重量百分比。 NOTE: The present invention is referred to "%" are all by weight.

Claims (2)

  1. 1.一种聚乙烯醇湿法交联纺丝工艺,由聚乙烯醇和交联剂配制成纺丝溶液,经喷丝孔(1)成丝后,进入凝固浴(2)、(3)并牵伸,然后经湿热牵伸浴(4)、酸浴(5)、中和浴(6)、干燥(7),干热牵伸(8)工艺过程得到高强高模长丝,其特征在于:①纺丝原液重量百分比组成为:聚乙烯醇浓度为12-16%,交联剂加入浓度0.5~5%,纺丝温度95~98℃;②其前部工艺过程为:纺丝溶液经喷丝孔(1)后,顺序经过第一、第二凝固浴(2)、(3)、湿热牵伸浴(4)、酸浴(5)、中和浴(6);③其凝固浴由第一凝固浴(2)和第二凝固浴(3)组成,第一凝固浴(2)含:氢氧化钠:15~50克/升,硫酸钠:300~380克/升,控制温度:40~45℃;第二凝固浴(3)含:氢氧化钠:10~30克/升,硫酸钠:330~410克/升,控制温度为:45~50℃,同时牵伸2-4倍;④所用交联剂由水溶性的锆化合物、钛盐、硼酸盐、硅酸盐中的 A crosslinked polyvinyl wet spinning process, and a crosslinking agent into a polyvinyl alcohol prepared spinning solution through the spinneret orifices (1) into the wire, into a coagulation bath (2), (3) and drawing, and then by heat drawing bath (4), an acid bath (5), and the bath (6), dried (7), the dry heat drawing (8) a process to obtain high strength and high modulus filaments, wherein : ① dope of percent by weight: 12-16% of a polyvinyl alcohol concentration of the crosslinking agent added to a concentration of 0.5 to 5%, the spinning temperature is 95 ~ 98 ℃; ② the process which is the front portion: spinning solution was after the nozzle orifice (1), sequentially through the first, second coagulation bath (2), (3), wet heat drawing bath (4), an acid bath (5), and the bath (6); ③ solidifying bath a first coagulation bath (2) and the second coagulation bath (3) composed of a first coagulation bath (2) containing: NaOH: 15 to 50 g / l, sodium sulfate: 300 to 380 g / l, temperature control : 40 ~ 45 ℃; second coagulation bath (3) containing: NaOH: 10 to 30 g / l, sodium sulfate: 330 to 410 g / l, the temperature is controlled: 45 ~ 50 ℃, simultaneous draw 2- 4 times; ④ a water-soluble crosslinking agent used by the zirconium compound, titanium, borate, silicate 种或两种以上组成,加入的重量比例顺次为:3~5∶2~3.5∶1~2.5∶1~2.5。 One or two or more at a ratio by weight of added sequentially: 5:2 ~ 3 ~ 2.5 ~ 2.5 ~ 3.5:1.
  2. 2.如权利要求1所述之聚乙烯醇湿法交联纺丝工艺,其特征在于纤维在中和浴(6)中和时间为:20~90秒。 2. The polyvinyl alcohol as claimed in claim 1 of the crosslinked wet spinning process, characterized in that the fibers and the bath (6), and time: 20 to 90 seconds.
CN 98101364 1998-04-14 1998-04-14 Wet PVA-crosslinking spinning technology CN1081686C (en)

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CN100422404C (en) 2006-07-27 2008-10-01 中国石化集团资产经营管理有限公司重庆天然气化工分公司;中国人民解放军总后勤部军需装备研究所士兵系统研究中心;四川大学 Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use

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