CN112095159B - A kind of wet spinning high-strength coarse denier polyvinyl alcohol fiber and preparation method thereof - Google Patents
A kind of wet spinning high-strength coarse denier polyvinyl alcohol fiber and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明所属聚乙烯醇(PVA)纤维的技术领域,涉及一种湿法纺丝的高强粗旦聚乙烯醇纤维及其制备方法。The invention belongs to the technical field of polyvinyl alcohol (PVA) fibers, and relates to a wet spinning high-strength coarse-denier polyvinyl alcohol fiber and a preparation method thereof.
背景技术Background technique
高强度混凝土所具有的特性使其在道路桥梁、水利市政、海工装备、军工国防等领域拥有相当广阔的应用前景。然而,众所周知,普通混凝土本身有脆性开裂、韧性不足等缺点。而高强高模聚乙烯醇纤维因其强度高、模量大、粘合力强等优点,常被用于水泥基增强材料,但由于普通的高强高模聚乙烯醇纤维的纤度较低,每吨混凝土的最大纤维掺量仅为1.5公斤左右,而每吨混凝土的高强粗旦聚乙烯醇纤维的最大纤维掺量可达到20公斤左右,这样能很好地克服脆性大,韧性不足的缺点,从而能够满足高强混凝土的性能要求。The characteristics of high-strength concrete make it have a very broad application prospect in the fields of roads and bridges, water conservancy and municipal administration, marine engineering equipment, military industry and national defense. However, it is well known that ordinary concrete itself has shortcomings such as brittle cracking and insufficient toughness. High-strength and high-modulus polyvinyl alcohol fibers are often used in cement-based reinforcing materials because of their high strength, large modulus, and strong adhesion. The fiber content is only about 1.5 kg, and the maximum fiber content of high-strength coarse denier polyvinyl alcohol fiber per ton of concrete can reach about 20 kg, which can well overcome the shortcomings of high brittleness and insufficient toughness, so as to meet the requirements of high strength Performance requirements for concrete.
目前仅熔融纺丝法可以制备出纤度较高的聚乙烯醇纤维,但也因其制备的聚乙烯醇纤维强度模量不高(断裂强度一般≤10cN/dtex,弹性模量一般≤190cN/dtex),且因生产工艺特殊等原因难以用来工业化制备高强粗旦聚乙烯醇纤维。At present, only the melt spinning method can prepare polyvinyl alcohol fibers with high fineness, but the strength modulus of the prepared polyvinyl alcohol fibers is not high (the breaking strength is generally ≤10cN/dtex, and the elastic modulus is generally ≤190cN/dtex). ), and due to special production process and other reasons, it is difficult to industrially prepare high-strength coarse-denier polyvinyl alcohol fibers.
而普通湿法纺丝工艺中纺丝液浓度低,喷丝板孔径小,且经过凝固、萃取浴及高倍热拉伸等工艺流程使得纤维的纤度较低。在现有设备及工艺的基础上难以采用湿法纺丝制备出兼具高强和粗旦的聚乙烯醇纤维。所以,有必要研究湿法纺丝的高强粗旦聚乙烯醇纤维及其制备方法。In the ordinary wet spinning process, the concentration of spinning solution is low, the diameter of the spinneret is small, and the fineness of the fiber is low after coagulation, extraction bath and high-power thermal drawing. On the basis of the existing equipment and technology, it is difficult to prepare polyvinyl alcohol fibers with both high strength and coarse denier by wet spinning. Therefore, it is necessary to study the wet spinning high-strength coarse-denier polyvinyl alcohol fiber and its preparation method.
发明内容SUMMARY OF THE INVENTION
本发明为了解决现有技术中存在的问题,提供一种湿法纺丝的高强粗旦聚乙烯醇纤维及其制备方法,以粒径为20~40nm的La2O3纳米粒子做交联剂,采用聚合度为3000~3500,醇解度为98~99%的聚乙烯醇做原料进行湿法纺丝,得到的初生纤维依次经两级凝固浴和两次热拉伸后制得高强粗旦聚乙烯醇纤维;In order to solve the problems existing in the prior art, the present invention provides a wet spinning high - strength coarse - denier polyvinyl alcohol fiber and a preparation method thereof. , using polyvinyl alcohol with a degree of polymerization of 3000 to 3500 and a degree of alcoholysis of 98 to 99% as the raw material for wet spinning, and the obtained primary fibers are successively subjected to two-stage coagulation baths and two thermal stretching to obtain high-strength thick denier polyvinyl alcohol fiber;
为了达到上述目的,采用的技术方案如下:In order to achieve the above purpose, the technical solutions adopted are as follows:
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,先将聚合度为3000~3500,醇解度为98~99%的聚乙烯醇溶于DMSO中,加入粒径为20~40nm的La2O3纳米粒子至聚乙烯醇完全溶解后得到高浓度纺丝液;再进行湿法纺丝,得到的初生纤维依次经过第一级凝固浴、第一次拉伸、第二级凝固浴、第一次热拉伸、萃取和第二次热拉伸后制得高强粗旦聚乙烯醇纤维;选用此种中高聚合度的聚乙烯醇纺丝是因为过高聚合度的聚乙烯醇纺丝工艺复杂,生产上比较困难,且经高倍拉伸后纤维直径变细的幅度较大,不利于制备粗旦纤维;而聚合度过低则因末端缺陷多,不利于制备高强度聚乙烯醇纤维。而高醇解度也有利于制备高强度纤维,因醇解度小会因大分子带有较大侧基而影响纤维结晶度的提高,而醇解度再高则工艺上较难实现;A preparation method of wet spinning high-strength coarse-denier polyvinyl alcohol fiber, firstly dissolving polyvinyl alcohol with a polymerization degree of 3000-3500 and an alcoholysis degree of 98-99% in DMSO, adding a particle size of 20- 40nm La 2 O 3 nanoparticles are completely dissolved in polyvinyl alcohol to obtain a high-concentration spinning solution; then wet spinning is carried out, and the obtained primary fibers pass through the first stage coagulation bath, the first stretching, and the second stage in turn. After coagulation bath, first hot drawing, extraction and second hot drawing, high-strength coarse denier polyvinyl alcohol fiber is obtained; this kind of polyvinyl alcohol with medium and high degree of polymerization is selected for spinning because of polyethylene with high degree of polymerization. The alcohol spinning process is complex and difficult to produce, and the diameter of the fiber becomes thinner after high-fold stretching, which is not conducive to the preparation of coarse denier fibers; while the polymerization is too low, it is not conducive to the preparation of high-strength polymer due to many terminal defects. Vinyl fiber. And high alcoholysis degree is also conducive to the preparation of high-strength fibers, because the small alcoholysis degree will affect the increase of fiber crystallinity because the macromolecules have larger side groups, and the higher the alcoholysis degree, it is difficult to achieve technologically;
所述第一级凝固浴的温度为-12~-10℃;第二级凝固浴的温度为-2~0℃;第一级凝固浴和第二级凝固浴的溶剂均为甲醇或乙醇;The temperature of the first-stage coagulation bath is -12 to -10°C; the temperature of the second-stage coagulation bath is -2 to 0°C; the solvents of the first-stage coagulation bath and the second-stage coagulation bath are methanol or ethanol;
所述高浓度纺丝液中,聚乙烯醇的质量分数为20~22wt%,La2O3纳米粒子的质量分数为0.8~1.0wt%;湿法纺丝工艺中,喷丝孔孔径为0.42~0.45mm;In the high-concentration spinning solution, the mass fraction of polyvinyl alcohol is 20-22 wt %, and the mass fraction of La 2 O 3 nanoparticles is 0.8-1.0 wt %; in the wet spinning process, the diameter of the spinneret hole is 0.42 ~0.45mm;
所述第一次拉伸的拉伸倍数为2.0~2.2倍。此时为了保持大分子链的伸展性需要施加一定的张力,由于该初生纤维较粗,需稍大一些的张力才能克服纤维的回缩,从而尽可能的保持大分子链的伸直状态,但纤维刚从低温凝固浴中出来,拉伸倍数过高容易导致脆断。The stretching ratio of the first stretching is 2.0 to 2.2 times. At this time, in order to maintain the stretchability of the macromolecular chain, a certain tension needs to be applied. Since the primary fiber is relatively thick, a slightly larger tension is required to overcome the retraction of the fiber, so as to maintain the straight state of the macromolecular chain as much as possible, but The fiber has just come out of the low temperature coagulation bath, and the stretching ratio is too high to easily lead to brittle fracture.
作为优选的技术方案:As the preferred technical solution:
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述第一级凝固浴的固化时间为2.8~3.0min;第二级凝固浴的固化时间为2.8~3.0min。因该初生纤维纤度较大,相比普通纤度的纤维短时间内较难固化彻底,所以延长固化时间能够在第一级和第二级凝固浴中起到更好的固化效果,但固化时间过长对生产效率不利。In the above-mentioned preparation method of wet spinning high-strength coarse-denier polyvinyl alcohol fiber, the curing time of the first-stage coagulation bath is 2.8-3.0 min; the curing time of the second-stage coagulation bath is 2.8-3.0 min min. Due to the larger fineness of the primary fiber, it is more difficult to cure completely in a short time than the fiber of ordinary fineness, so prolonging the curing time can achieve better curing effect in the first and second stage coagulation baths, but the curing time is too long. Long is not good for production efficiency.
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述第一次热拉伸的温度为190~200℃。与普通纤度的聚乙烯醇相比,粗旦聚乙烯醇纤维纤度更大,为使纤维内外层大分子受温度及应力的作用能形成均匀的折叠链结晶,温度需略高于普通纤维,但温度过高容易导致纤维熔融,从而不利于后续拉伸倍数的提高;第二次热拉伸的温度为200~210℃,因在一定范围内,热拉伸温度越高,纤维热拉伸倍数越大,总拉伸倍数越大,粗旦纤维可以适当升高第二次的热拉伸温度,但温度过高时,纤维也会出现熔断,无法连续性拉伸。这主要是因为随着热拉伸温度的升高,聚乙烯醇纤维内大分子链的活化能增加,链段的运动加快,由于主链上单键的内旋转和链段的运动会改变大分子构象,从而使纤维大分子链在外力作用下更容易伸直取向,使纤维的热拉伸倍数增加,纤维的取向度和结晶度也随之增大,最终使纤维力学性能提高,但温度过高时,纤维容易出现局部熔解并断裂,反而会影响纤维力学性能。In the above-mentioned preparation method of wet spinning high-strength coarse-denier polyvinyl alcohol fiber, the temperature of the first thermal drawing is 190-200°C. Compared with polyvinyl alcohol with ordinary fineness, the fineness of coarse denier polyvinyl alcohol fiber is larger. In order to make the macromolecules in the inner and outer layers of the fiber form uniform folded chain crystallization under the action of temperature and stress, the temperature needs to be slightly higher than that of ordinary fibers, but If the temperature is too high, it is easy to cause the fiber to melt, which is not conducive to the improvement of the subsequent stretching ratio; the temperature of the second thermal stretching is 200-210 °C, because within a certain range, the higher the thermal stretching temperature, the higher the thermal stretching ratio of the fiber. The larger the value, the greater the total draw ratio, and the coarse denier fiber can appropriately increase the second hot drawing temperature, but when the temperature is too high, the fiber will also melt and cannot be continuously drawn. This is mainly because with the increase of the hot stretching temperature, the activation energy of the macromolecular chain in the polyvinyl alcohol fiber increases, and the movement of the chain segment is accelerated. Due to the internal rotation of the single bond on the main chain and the movement of the chain segment, the macromolecules will be changed. Conformation, so that the fiber macromolecular chain is easier to straighten and orientate under the action of external force, so that the thermal stretching ratio of the fiber increases, the degree of orientation and crystallinity of the fiber also increases, and finally the mechanical properties of the fiber are improved, but the temperature is too high. When it is high, the fiber is prone to local melting and breaking, which will affect the mechanical properties of the fiber.
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述第一次热拉伸的拉伸倍数为2.4~2.5倍,第二次热拉伸的拉伸倍数为3.0~3.5倍。当第一次拉伸的拉伸倍数过低时,纤维的预取向度不足,晶型容易变成较难拉伸的单斜晶,从而导致第二次拉伸不匀,又因为纤维内交联点的作用,导致纤维伸长率低,高倍拉伸时则分子链容易断裂;在两次合理分配拉伸倍数的情况下,能使总拉伸倍数尽可能提高。第二次热拉伸倍数为纤维此次所能承受的最大拉伸倍数,纤维的总拉伸倍数为三次拉伸倍数的乘积。The above-mentioned preparation method of a wet spinning high-strength coarse denier polyvinyl alcohol fiber, wherein the stretching ratio of the first thermal stretching is 2.4 to 2.5 times, and the stretching ratio of the second thermal stretching is 2.4 to 2.5 times. 3.0 to 3.5 times. When the drawing ratio of the first drawing is too low, the pre-orientation degree of the fiber is insufficient, and the crystal form easily becomes a monoclinic crystal that is difficult to draw, resulting in uneven drawing in the second drawing. The effect of the junction point leads to low fiber elongation, and the molecular chain is easily broken when stretched at high times; in the case of two reasonable distribution of stretch ratios, the total stretch ratio can be increased as much as possible. The second thermal stretching ratio is the maximum stretching ratio that the fiber can bear this time, and the total stretching ratio of the fiber is the product of the three stretching ratios.
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述萃取的溶剂为甲醇或乙醇,温度为25~30℃,时间为23~24h(可以每隔12h左右更换一次溶剂,增加萃取的效率),较高的温度下萃取的目的是为了最大程度地去除粗旦纤维中的溶剂,增加热拉伸倍数。The above-mentioned preparation method of a wet spinning high-strength coarse denier polyvinyl alcohol fiber, the solvent for the extraction is methanol or ethanol, the temperature is 25-30°C, and the time is 23-24h (it can be about every 12h). Replace the solvent once to increase the extraction efficiency). The purpose of extraction at a higher temperature is to remove the solvent in the coarse denier fiber to the greatest extent and increase the thermal drawing ratio.
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述湿法纺丝工艺为:喷丝孔挤出速率为4.0~4.2ml/min,纺丝温度为85~90℃。The above-mentioned preparation method of a wet spinning high-strength coarse denier polyvinyl alcohol fiber, the wet spinning process is: the extrusion rate of the spinneret hole is 4.0~4.2ml/min, and the spinning temperature is 85 ~90°C.
如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,所述纺丝液在湿法纺丝前还在温度为78~80℃条件下脱泡处理3.0~3.5h。纺丝液如果含有气泡会导致纤维粗细不匀,影响拉伸倍数,且会对纺丝设备造成一定损坏。较高浓度纺丝液脱泡困难,需适当延长脱泡时间,待充分脱泡以后再延长时间则无意义。The above-mentioned preparation method of wet spinning high-strength coarse denier polyvinyl alcohol fiber, the spinning solution is defoamed at a temperature of 78-80° C. for 3.0-3.5 hours before wet-spinning . If the spinning solution contains air bubbles, it will cause uneven fiber thickness, affect the stretching ratio, and cause certain damage to the spinning equipment. High concentration spinning solution is difficult to defoam, and it is necessary to appropriately extend the defoaming time, and it is meaningless to extend the time after sufficient defoaming.
本发明还提供如上所述的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法制备的高强粗旦聚乙烯醇纤维,所述高强粗旦聚乙烯醇纤维的纤度为19.2~21.1dtex,断裂强度为13.1~14.6cN/dtex,弹性模量为320~339cN/dtex。The present invention also provides high-strength and coarse-denier polyvinyl alcohol fibers prepared by the above-mentioned preparation method of wet-spinning high-strength coarse-denier polyvinyl alcohol fibers, wherein the fineness of the high-strength coarse-denier polyvinyl alcohol fibers is 19.2-21.1 dtex, the breaking strength is 13.1~14.6cN/dtex, and the elastic modulus is 320~339cN/dtex.
本发明的机理是:The mechanism of the present invention is:
为了采用湿法纺丝工艺制备高强粗旦聚乙烯醇纤维,本发明首先配制的纺丝液浓度(20~22wt%)高于一般DMSO为溶剂的湿法纺丝时的浓度(12~15wt%),相应地,采用的喷丝孔孔径(0.42~0.45mm)也高于普通湿法纺丝时的喷丝孔孔径(0.2~0.3mm),此种情况下满足了初生纤维具有的大直径的要求,其次,纺丝液中还加入了较高浓度的La2O3纳米粒子(0.8~1.0wt%)做交联剂,高于普纺丝时使用的交联剂量(0.5~0.8wt%);In order to prepare high-strength coarse denier polyvinyl alcohol fibers by wet spinning process, the concentration of spinning solution (20-22wt%) prepared in the present invention is higher than the concentration (12-15wt%) of general wet spinning with DMSO as solvent ), correspondingly, the diameter of the spinneret hole (0.42-0.45mm) used is also higher than the spinneret hole diameter (0.2-0.3mm) during ordinary wet spinning, which satisfies the large diameter of the primary fiber in this case. Second, a higher concentration of La 2 O 3 nanoparticles (0.8-1.0wt%) is added to the spinning solution as a cross-linking agent, which is higher than the cross-linking amount used in ordinary spinning (0.5-0.8wt%). %);
本发明采用带有一定拉伸倍数的两级凝固浴对初生纤维进行固化,具体为:聚乙烯醇纺丝液由喷丝孔挤出时大分子链会受到喷丝孔剪切力的作用而趋向于伸直链状态,当直接进入到低温的第一级凝固浴时,由于温差较大,大分子链的热运动迅速减小,初生纤维瞬间固化,使得大分子链的伸直状态得以保持;在第一级凝固浴和第二级凝固浴之间做了较低倍数的机械拉伸,该拉伸是为了避免纤维进入空气时因温度的升高,使得大分子链会发生较大程度的回缩;进入第二级中温(温度介于第一级凝固浴及室温之间)凝固浴后随着温度的缓慢升高大分子链也会有少部分的回缩,纤维直径变粗,溶剂被初步地去除,纤维被进一步固化,此时进入室温不会因温度的剧烈变化而导致大分子链的大幅度回缩与缠结,从而有利于强度的提高;The invention adopts a two-stage coagulation bath with a certain stretching ratio to solidify the nascent fibers, specifically: when the polyvinyl alcohol spinning solution is extruded from the spinneret hole, the macromolecular chain will be affected by the shearing force of the spinneret hole and be formed. It tends to be in a straight chain state. When directly entering the first-stage coagulation bath at low temperature, due to the large temperature difference, the thermal motion of the macromolecular chain decreases rapidly, and the primary fibers are instantly solidified, so that the straight state of the macromolecular chain can be maintained. ; A lower multiple mechanical stretching is done between the first-stage coagulation bath and the second-stage coagulation bath. This stretching is to prevent the macromolecular chain from occurring to a greater extent due to the temperature increase when the fiber enters the air. After entering the second-stage medium-temperature coagulation bath (the temperature is between the first-stage coagulation bath and room temperature), the macromolecular chain will also shrink in a small part with the slow increase of the temperature, the fiber diameter becomes thicker, and the solvent It is initially removed, and the fiber is further solidified. At this time, entering room temperature will not cause the macromolecular chain to shrink and entangle greatly due to the drastic change of temperature, which is beneficial to the improvement of strength;
与此同时,本发明中加入的La2O3纳米粒子因其具有较好的分散性,可以在纺丝液中均匀分散,且La2O3纳米粒子粒径小(20~40nm),比表面积大,活性高,表面含有大量羟基,在固浴中去除部分纺丝液中的溶剂以后,纤维内的La2O3纳米粒子可以与聚乙烯醇大分子链上的羟基产生大量的氢键交联,能够抑制大分子链自身及相互间氢键的形成;且在上述的两级凝固浴对初生纤维进行固化的过程中,可以避免大分子链之间的缠结,有利于保持分子链的伸直链状态;另外,在有机凝固浴中La2O3溶解性一般,不容易被去除,这样留在纤维内部的La2O3纳米粒子会在纤维中形成永久交联点,与大分子链之间形成网络交联,这样既能保证纤维具有较高的纤度,又能因网络交联作用,分散纤维受到的外力,从而提高纤维的强度。At the same time, the La 2 O 3 nanoparticles added in the present invention can be uniformly dispersed in the spinning solution because of their good dispersibility, and the La 2 O 3 nanoparticles have a small particle size (20-40 nm), which is smaller than The surface area is large, the activity is high, and the surface contains a large number of hydroxyl groups. After removing the solvent in part of the spinning solution in the solid bath, the La 2 O 3 nanoparticles in the fiber can generate a large number of hydrogen bonds with the hydroxyl groups on the polyvinyl alcohol macromolecular chain. Cross-linking can inhibit the formation of hydrogen bonds between the macromolecular chains themselves and each other; and in the process of curing the nascent fibers in the above-mentioned two-stage coagulation bath, the entanglement between the macromolecular chains can be avoided, which is conducive to maintaining the molecular chains. In addition, the solubility of La 2 O 3 in the organic coagulation bath is general, and it is not easy to be removed, so that the La 2 O 3 nanoparticles left in the fiber will form permanent cross-linking points in the fiber, which is different from the large Network cross-linking is formed between molecular chains, which can not only ensure that the fiber has a high fineness, but also disperse the external force on the fiber due to the network cross-linking effect, thereby improving the strength of the fiber.
有益效果:Beneficial effects:
(1)本发明的一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,采用高浓度纺丝液,特殊的交联剂,大孔径的喷丝板,以及含有一定拉伸倍数的两级凝固浴凝固的纺丝,制得了纤度为19.2~21.1dtex,断裂强度为13.1~14.6cN/dtex,弹性模量为320~339cN/dtex的高强粗旦聚乙烯醇纤维;(1) A preparation method of a wet spinning high-strength coarse-denier polyvinyl alcohol fiber of the present invention adopts a high-concentration spinning solution, a special cross-linking agent, a spinneret with a large aperture, and a spinneret containing a certain stretching ratio. The spinning coagulated by the two-stage coagulation bath produced high-strength coarse-denier polyvinyl alcohol fibers with a fineness of 19.2-21.1 dtex, a breaking strength of 13.1-14.6 cN/dtex, and an elastic modulus of 320-339 cN/dtex;
(2)本发明方法制备的高强粗旦聚乙烯醇纤维,可在道路桥梁、水利市政、海工装备、军工国防等领域拥有相当广阔的应用前景。(2) The high-strength coarse-denier polyvinyl alcohol fiber prepared by the method of the present invention can have quite broad application prospects in the fields of roads and bridges, water conservancy and municipal administration, marine engineering equipment, military industry and national defense.
附图说明Description of drawings
图1凝固浴及拉伸示意图;Fig. 1 Schematic diagram of coagulation bath and stretching;
图2热拉伸示意图;Figure 2 is a schematic diagram of thermal stretching;
其中,1-推进泵,2-喷丝头,3-导辊I,4-导辊II,5-导辊III,6-第一级凝固浴,7-第二级凝固浴。Among them, 1-propulsion pump, 2-spinneret, 3-guide roll I, 4-guide roll II, 5-guide roll III, 6-first-stage coagulation bath, 7-second-stage coagulation bath.
具体实施方式Detailed ways
下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,其过程如下:A kind of preparation method of the high-strength coarse denier polyvinyl alcohol fiber of wet spinning, its process is as follows:
(1)先将聚合度为3200、醇解度为98%的聚乙烯醇溶于DMSO中,加入La2O3纳米粒子配制高浓度纺丝液;高浓度纺丝液中,聚乙烯醇的质量分数为21wt%,La2O3纳米粒子的质量分数为0.9wt%;(1) First, dissolve polyvinyl alcohol with a degree of polymerization of 3200 and a degree of alcoholysis of 98% in DMSO, and add La 2 O 3 nanoparticles to prepare a high-concentration spinning solution; in the high-concentration spinning solution, the polyvinyl alcohol The mass fraction is 21wt%, and the mass fraction of La2O3 nanoparticles is 0.9wt %;
(2)纺丝液在温度为79℃条件下脱泡处理3.2h;(2) The spinning solution was defoamed for 3.2 hours at a temperature of 79°C;
(3)进行湿法纺丝,得到的初生纤维依次经过温度为-11℃的第一级凝固浴(溶剂为甲醇,固化时间为2.9min)、第一次拉伸(拉伸倍数为2.1倍)、第二级温度为-1℃的凝固浴(溶剂为甲醇,固化时间为2.8min);如图1所示,由推进泵1对纺丝液进行挤出,经过大孔径喷丝头2挤出初生纤维,进入第一级凝固浴6,接着进行第一次拉伸(通过导辊I 3和II 4的转速调节来控制拉伸倍数),然后进入第二级凝固浴7,第二次凝固完成后经过导辊III 5进行后续的热拉伸;(3) Wet spinning is carried out, and the obtained spun fibers are successively subjected to a first-stage coagulation bath with a temperature of -11° C. (the solvent is methanol, and the curing time is 2.9 min), the first stretching (the stretching ratio is 2.1 times) ), a coagulation bath with a temperature of -1°C in the second stage (the solvent is methanol, and the curing time is 2.8min); as shown in Figure 1, the spinning solution is extruded by the propeller pump 1, and passed through the large-aperture spinneret 2 The spun fibers are extruded into the first-stage coagulation bath 6, followed by the first drawing (the stretching ratio is controlled by the speed adjustment of the guide rollers I 3 and II 4), and then into the second-stage coagulation bath 7, the second After the secondary solidification is completed, the subsequent hot stretching is carried out through the guide roller III 5;
热拉伸的过程为凝固后的纤维经过温度为198℃的第一次热拉伸(拉伸倍数为2.5倍)、萃取(溶剂为甲醇,温度为26℃,时间为24h)和温度为205℃的第二次热拉伸(拉伸倍数为3.2倍)处理后制得高强粗旦聚乙烯醇纤维;其中,湿法纺丝工艺为:喷丝板挤出速率为4.1ml/min,纺丝温度为86℃,喷丝孔孔径为0.43mm;其中,如图2所示,为第一次热拉伸和第二次热拉伸的拉伸装置示意图。The process of thermal drawing is that the coagulated fibers undergo the first thermal drawing at a temperature of 198°C (the draw ratio is 2.5 times), extraction (the solvent is methanol, the temperature is 26°C, and the time is 24h) and the temperature is 205°C. The high-strength coarse-denier polyvinyl alcohol fiber was obtained after the second hot drawing at ℃ (the draw ratio was 3.2 times); wherein, the wet spinning process was as follows: the spinneret extrusion rate was 4.1 ml/min, and the spinning process was 4.1 ml/min. The silk temperature was 86° C., and the diameter of the spinneret hole was 0.43 mm; among them, as shown in FIG. 2 , it was a schematic diagram of the drawing device for the first thermal drawing and the second thermal drawing.
制得的高强粗旦聚乙烯醇纤维的纤度为19.9dtex,断裂强度为13.9cN/dtex,弹性模量为331cN/dtex。The obtained high-strength coarse-denier polyvinyl alcohol fiber has a fineness of 19.9 dtex, a breaking strength of 13.9 cN/dtex and an elastic modulus of 331 cN/dtex.
对比例1Comparative Example 1
一种湿法纺丝的聚乙烯醇纤维的制备方法,其过程与实施例1基本相同,不同之处仅在于,湿法纺丝时,高浓度纺丝液改变为质量分数为14%的较低浓度的纺丝液,制得的聚乙烯醇纤维的纤度为13.9dtex,断裂强度为10.2cN/dtex,弹性模量为287cN/dtex;将对比例1与实施例1进行对比可以看出,对比例1中的纤度,断裂强度及弹性模量均更小,这是因为在相同纺丝条件下,随着纺丝液浓度的降低,单根纤维内含有的聚乙烯醇分子链数目减少,纤维凝固成形时,因溶剂向凝固浴扩散而形成的孔洞增加,纤维内部的缺陷增加,从而导致纤维的力学性能降低。相反,较高的纺丝液浓度有利于纤维力学性能的提高,但当纺丝液浓度过高时,溶液粘度过大,也会导致纤维无法稳定连续地生产。A preparation method of wet-spinning polyvinyl alcohol fiber, the process is basically the same as that of Example 1, the only difference is that during wet-spinning, the high-concentration spinning solution is changed to a relatively high concentration of 14% by mass fraction. Low concentration spinning solution, the obtained polyvinyl alcohol fiber has a fineness of 13.9dtex, a breaking strength of 10.2cN/dtex, and an elastic modulus of 287cN/dtex; it can be seen from the comparison between Comparative Example 1 and Example 1, The fineness, breaking strength and elastic modulus in Comparative Example 1 are all smaller, because under the same spinning conditions, with the decrease of spinning solution concentration, the number of polyvinyl alcohol molecular chains contained in a single fiber decreases, When the fiber is coagulated and formed, the pores formed due to the diffusion of the solvent into the coagulation bath increase, and the defects inside the fiber increase, resulting in a decrease in the mechanical properties of the fiber. On the contrary, a higher spinning solution concentration is beneficial to the improvement of fiber mechanical properties, but when the spinning solution concentration is too high, the solution viscosity is too large, which will also lead to the inability to stably and continuously produce fibers.
对比例2Comparative Example 2
一种湿法纺丝的聚乙烯醇纤维的制备方法,其过程与实施例1基本相同,不同之处仅在于,湿法纺丝原料中不含有La2O3纳米粒子,制得的聚乙烯醇纤维的的纤度为15.9dtex,断裂强度为11.4cN/dtex,弹性模量为295cN/dtex;将对比例2与实施例1进行对比可以看出,对比例2中的纤度,断裂强度及弹性模量均更小,这是因为La2O3纳米粒子的使用能与聚乙烯醇大分子形成络合物,起到了永久交联的作用,不仅可以减少大分子内及大分子间的相互交联,克服大分子链的缠结,且一定数量的交联点可以起到分散外力的作用,从而有利于纤维力学性能的提高,同时也会使纤维直径变得更粗,最终有利于制备高强粗旦聚乙烯醇纤维。A preparation method of wet-spinning polyvinyl alcohol fiber, the process is basically the same as that of Example 1, the difference is only that the wet-spinning raw material does not contain La 2 O 3 nanoparticles, the obtained polyethylene The fineness of the alcohol fiber is 15.9dtex, the breaking strength is 11.4cN/dtex, and the elastic modulus is 295cN/dtex; comparing Example 2 with Example 1, it can be seen that the fineness, breaking strength and elasticity in Comparative Example 2 The modulus is smaller, because the use of La 2 O 3 nanoparticles can form complexes with polyvinyl alcohol macromolecules, which play a role of permanent cross-linking, which can not only reduce the interaction between macromolecules and macromolecules. It can overcome the entanglement of macromolecular chains, and a certain number of cross-linking points can play the role of dispersing external force, which is conducive to the improvement of fiber mechanical properties, and also makes the fiber diameter thicker, which is ultimately conducive to the preparation of high-strength fibers. Coarse denier polyvinyl alcohol fibers.
对比例3Comparative Example 3
一种湿法纺丝的聚乙烯醇纤维的制备方法,其过程与实施例1基本相同,不同之处仅在于,湿法纺丝时纤维只经过一级凝固浴凝固,其一级凝固浴的温度及凝固时间与实施例1均形同,最终制得的聚乙烯醇纤维的纤度为20.3dtex,断裂强度为12.5cN/dtex,弹性模量为312cN/dtex;将对比例3与实施例1进行对比可以看出,对比例3中的纤度略有增加,但强度和模量均更小,这是因为一级凝固浴与两级凝固浴相比,中间缺少一道拉伸及较大的温差作用,使得纤维更容易回缩,且纤维内含有大量的溶剂没有去除会影响拉伸倍数的提高,从而会使纤维直径变粗,并且不利于纤维力学性能的提高。A preparation method of a wet spinning polyvinyl alcohol fiber, the process is basically the same as that of Example 1, the difference is only that the fiber is only coagulated by a first-stage coagulation bath during wet spinning, and the first-stage coagulation bath is coagulated. The temperature and coagulation time are the same as in Example 1. The final obtained polyvinyl alcohol fiber has a fineness of 20.3dtex, a breaking strength of 12.5cN/dtex, and an elastic modulus of 312cN/dtex; Comparative Example 3 and Example 1 It can be seen from the comparison that the fineness in Comparative Example 3 is slightly increased, but the strength and modulus are smaller. This is because the one-stage coagulation bath lacks a stretch and a larger temperature difference compared with the two-stage coagulation bath. It makes the fiber easier to retract, and the fiber contains a large amount of solvent without removal, which will affect the increase of the stretching ratio, thereby making the fiber diameter thicker, and is not conducive to the improvement of the mechanical properties of the fiber.
实施例2Example 2
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,其过程如下:A kind of preparation method of the high-strength coarse denier polyvinyl alcohol fiber of wet spinning, its process is as follows:
(1)先将聚合度为3400、醇解度为98%的聚乙烯醇溶于DMSO中,加入La2O3纳米粒子得到高浓度纺丝液;高浓度纺丝液中,聚乙烯醇的质量分数为21wt%,La2O3纳米粒子的质量分数为0.8wt%;(1) Dissolve polyvinyl alcohol with a polymerization degree of 3400 and an alcoholysis degree of 98% in DMSO, and add La 2 O 3 nanoparticles to obtain a high-concentration spinning solution; in the high-concentration spinning solution, the polyvinyl alcohol The mass fraction is 21wt%, and the mass fraction of La2O3 nanoparticles is 0.8wt%;
(2)纺丝液在温度为78℃条件下脱泡处理3.4h;(2) The spinning solution was defoamed for 3.4 hours at a temperature of 78°C;
(3)进行湿法纺丝,得到的初生纤维依次经过温度为-12℃的第一级凝固浴(溶剂为甲醇,固化时间为2.8min)、第一次拉伸(拉伸倍数为2.0倍)、第二级温度为0℃的凝固浴(溶剂为甲醇,固化时间为2.9min)、温度为199℃的第一次热拉伸(拉伸倍数为2.4倍)、萃取(溶剂为甲醇,温度为27℃,时间为24h)和温度为203℃的第二次热拉伸(拉伸倍数为3.3倍)处理后制得高强粗旦聚乙烯醇纤维;其中,湿法纺丝工艺为:喷丝板挤出速率为4ml/min,纺丝温度为86℃,喷丝孔孔径为0.44mm;(3) Carry out wet spinning, and the obtained spun fibers are successively subjected to a first-stage coagulation bath (the solvent is methanol, and the curing time is 2.8 min) at a temperature of -12° C., the first stretching (the stretching ratio is 2.0 times) ), the second-stage coagulation bath at 0°C (solvent is methanol, curing time is 2.9min), the first thermal stretching at 199°C (stretching ratio is 2.4 times), extraction (solvent is methanol, The high-strength coarse denier polyvinyl alcohol fiber is obtained after the temperature is 27 ° C, the time is 24 h) and the second hot drawing at a temperature of 203 ° C (the stretching ratio is 3.3 times); wherein, the wet spinning process is: The extrusion rate of the spinneret is 4ml/min, the spinning temperature is 86°C, and the diameter of the spinneret hole is 0.44mm;
制得的高强粗旦聚乙烯醇纤维的纤度为20.1dtex,断裂强度为14.1cN/dtex,弹性模量为334cN/dtex。The obtained high-strength coarse-denier polyvinyl alcohol fiber has a fineness of 20.1 dtex, a breaking strength of 14.1 cN/dtex and an elastic modulus of 334 cN/dtex.
实施例3Example 3
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,其过程如下:A kind of preparation method of the high-strength coarse denier polyvinyl alcohol fiber of wet spinning, its process is as follows:
(1)先将聚合度为3500、醇解度为99%的聚乙烯醇溶于DMSO中,加入La2O3纳米粒子得到高浓度纺丝液;高浓度纺丝液中,聚乙烯醇的质量分数为22wt%,La2O3纳米粒子的质量分数为1.0wt%;(1) First, dissolve polyvinyl alcohol with a degree of polymerization of 3500 and an alcoholysis degree of 99% in DMSO, and add La 2 O 3 nanoparticles to obtain a high-concentration spinning solution; in the high-concentration spinning solution, the polyvinyl alcohol The mass fraction is 22wt%, and the mass fraction of La2O3 nanoparticles is 1.0wt%;
(2)纺丝液在温度为80℃条件下脱泡处理3.5h;(2) The spinning solution was defoamed for 3.5 hours at a temperature of 80 °C;
(3)进行湿法纺丝,得到的初生纤维依次经过温度为-11℃的第一级凝固浴(溶剂为甲醇,固化时间为3min)、第一次拉伸(拉伸倍数为2.2倍)、第二级温度为0℃的凝固浴(溶剂为甲醇,固化时间为2.8min)、温度为200℃的第一次热拉伸(拉伸倍数为2.4倍)、萃取(溶剂为乙醇,温度为28℃,时间为23h)和温度为210℃的第二次热拉伸(拉伸倍数为3.5倍)处理后制得高强粗旦聚乙烯醇纤维;其中,湿法纺丝工艺为:喷丝板挤出速率为4.2ml/min,纺丝温度为87℃,喷丝孔孔径为0.42mm;(3) Wet spinning is carried out, and the obtained spun fibers are successively subjected to a first-stage coagulation bath with a temperature of -11° C. (the solvent is methanol, and the curing time is 3 min), and the first stretching (the stretching ratio is 2.2 times) , the coagulation bath at the second stage temperature is 0 ℃ (the solvent is methanol, the curing time is 2.8min), the temperature is 200 ℃ for the first thermal stretching (stretching ratio is 2.4 times), extraction (the solvent is ethanol, the temperature is 2.4 times) High-strength coarse-denier polyvinyl alcohol fibers were obtained after the second thermal stretching (stretching ratio of 3.5 times) at 28°C for 23h) and a temperature of 210°C; wherein, the wet spinning process was: spraying The extrusion rate of the spinneret is 4.2ml/min, the spinning temperature is 87°C, and the diameter of the spinneret hole is 0.42mm;
制得的高强粗旦聚乙烯醇纤维的纤度为19.2dtex,断裂强度为14.6cN/dtex,弹性模量为339cN/dtex。The obtained high-strength coarse-denier polyvinyl alcohol fiber has a fineness of 19.2 dtex, a breaking strength of 14.6 cN/dtex and an elastic modulus of 339 cN/dtex.
实施例4Example 4
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,其过程如下:A kind of preparation method of the high-strength coarse denier polyvinyl alcohol fiber of wet spinning, its process is as follows:
(1)先将聚合度为3000、醇解度为99%的聚乙烯醇溶于DMSO中,加入La2O3纳米粒子得到高浓度纺丝液;高浓度纺丝液中,聚乙烯醇的质量分数为20wt%,La2O3纳米粒子的质量分数为0.8wt%;(1) First, dissolve polyvinyl alcohol with a degree of polymerization of 3000 and an alcoholysis degree of 99% in DMSO, and add La 2 O 3 nanoparticles to obtain a high-concentration spinning solution; in the high-concentration spinning solution, the polyvinyl alcohol The mass fraction is 20wt%, and the mass fraction of La2O3 nanoparticles is 0.8wt%;
(2)纺丝液在温度为78℃条件下脱泡处理3.0h;(2) The spinning solution was defoamed for 3.0h at a temperature of 78°C;
(3)进行湿法纺丝,得到的初生纤维依次经过温度为-10℃的第一级凝固浴(溶剂为乙醇,固化时间为2.9min)、第一次拉伸(拉伸倍数为2.0倍)、第二级温度为-2℃的凝固浴(溶剂为乙醇,固化时间为2.9min)、温度为190℃的第一次热拉伸(拉伸倍数为2.5倍)、萃取(溶剂为甲醇,温度为30℃,时间为24h)和温度为200℃的第二次热拉伸(拉伸倍数为3.0倍)处理后制得高强粗旦聚乙烯醇纤维;其中,湿法纺丝工艺为:喷丝板挤出速率为4.1ml/min,纺丝温度为88℃,喷丝孔孔径为0.45mm;(3) Wet spinning is carried out, and the obtained spun fibers are successively subjected to a first-stage coagulation bath (the solvent is ethanol, and the curing time is 2.9 min) with a temperature of -10° C., the first stretching (the stretching ratio is 2.0 times) ), second-stage coagulation bath at -2°C (solvent is ethanol, curing time is 2.9min), first thermal stretching at 190°C (stretching ratio is 2.5 times), extraction (solvent is methanol) , the temperature is 30 ° C, the time is 24 h) and the second hot drawing (the stretching ratio is 3.0 times) at the temperature of 200 ° C is processed to obtain high-strength coarse denier polyvinyl alcohol fibers; wherein, the wet spinning process is: : The extrusion rate of the spinneret is 4.1ml/min, the spinning temperature is 88℃, and the diameter of the spinneret hole is 0.45mm;
制得的高强粗旦聚乙烯醇纤维的纤度为21.1dtex,断裂强度为13.1cN/dtex,弹性模量为320cN/dtex。The obtained high-strength coarse-denier polyvinyl alcohol fiber has a fineness of 21.1 dtex, a breaking strength of 13.1 cN/dtex and an elastic modulus of 320 cN/dtex.
实施例5Example 5
一种湿法纺丝的高强粗旦聚乙烯醇纤维的制备方法,其过程如下:A kind of preparation method of the high-strength coarse denier polyvinyl alcohol fiber of wet spinning, its process is as follows:
(1)先将聚合度为3100、醇解度为99%的聚乙烯醇溶于DMSO中,加入La2O3纳米粒子得到高浓度纺丝液;高浓度纺丝液中,聚乙烯醇的质量分数为22wt%,La2O3纳米粒子的质量分数为0.9wt%;(1) Dissolve polyvinyl alcohol with a polymerization degree of 3100 and an alcoholysis degree of 99% in DMSO, and add La 2 O 3 nanoparticles to obtain a high-concentration spinning solution; in the high-concentration spinning solution, the polyvinyl alcohol The mass fraction is 22wt%, and the mass fraction of La2O3 nanoparticles is 0.9wt %;
(2)纺丝液在温度为78℃条件下脱泡处理3.5h;(2) The spinning solution was defoamed for 3.5h at a temperature of 78°C;
(3)进行湿法纺丝,得到的初生纤维依次经过温度为-10℃的第一级凝固浴(溶剂为甲醇,固化时间为3min)、第一次拉伸(拉伸倍数为2.1倍)、第二级温度为-1℃的凝固浴(溶剂为甲醇,固化时间为3min)、温度为194℃的第一次热拉伸(拉伸倍数为2.5倍)、萃取(溶剂为乙醇,温度为25℃,时间为24h)和温度为202℃的第二次热拉伸(拉伸倍数为3.0倍)处理后制得高强粗旦聚乙烯醇纤维;其中,湿法纺丝工艺为:喷丝板挤出速率为4.1ml/min,纺丝温度为90℃,喷丝孔孔径为0.43mm;(3) Wet spinning is carried out, and the obtained spun fibers are successively subjected to a first-stage coagulation bath at a temperature of -10° C. (the solvent is methanol, and the curing time is 3 min), and the first stretching (the stretching ratio is 2.1 times) , the second stage temperature is -1 ℃ of coagulation bath (solvent is methanol, curing time is 3min), the temperature is 194 ℃ the first thermal stretching (stretching ratio is 2.5 times), extraction (solvent is ethanol, temperature High-strength coarse denier polyvinyl alcohol fiber was obtained after treatment at 25 ℃, time 24h) and the second hot drawing at 202 ℃ (stretching ratio was 3.0 times); wherein, the wet spinning process was: spraying The extrusion rate of the silk plate is 4.1ml/min, the spinning temperature is 90℃, and the diameter of the spinneret hole is 0.43mm;
制得的高强粗旦聚乙烯醇纤维的纤度为20.7dtex,断裂强度为13.7cN/dtex,弹性模量为325cN/dtex。The obtained high-strength coarse-denier polyvinyl alcohol fiber has a fineness of 20.7 dtex, a breaking strength of 13.7 cN/dtex and an elastic modulus of 325 cN/dtex.
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