CN104404645B - A kind of method that aramid fiber spinning slurry directly prepared by PPTA resin - Google Patents
A kind of method that aramid fiber spinning slurry directly prepared by PPTA resin Download PDFInfo
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- CN104404645B CN104404645B CN201410728119.0A CN201410728119A CN104404645B CN 104404645 B CN104404645 B CN 104404645B CN 201410728119 A CN201410728119 A CN 201410728119A CN 104404645 B CN104404645 B CN 104404645B
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- 239000011347 resin Substances 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 77
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 45
- 239000002002 slurry Substances 0.000 title claims abstract description 27
- 238000009987 spinning Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims 2
- 239000001117 sulphuric acid Substances 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- -1 Poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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Abstract
本发明涉及一种PPTA树脂直接制备芳纶纺丝浆液的方法，直接将合成出的PPTA树脂经中和后用水洗涤，然后将PPTA树脂进行脱水，得到脱水后的PPTA树脂；将脱水后的PPTA树脂降温，搅拌条件下通入SO3气体，保持体系温度为11～13℃，得到浓硫酸，然后升温至80‑90℃进行溶解和预脱泡，得到液晶溶液，脱泡，即得。本发明方法混合效果好，溶解效率高，大大缩短从树脂到纺丝浆液的制备时间，并且溶解过程中树脂的降解比较少。The invention relates to a method for directly preparing aramid fiber spinning slurry from PPTA resin. The synthesized PPTA resin is directly washed with water after being neutralized, and then the PPTA resin is dehydrated to obtain dehydrated PPTA resin; the dehydrated PPTA resin is The temperature of the resin is lowered, and SO 3 gas is introduced under the condition of stirring, and the temperature of the system is kept at 11-13°C to obtain concentrated sulfuric acid, and then the temperature is raised to 80-90°C for dissolution and pre-defoaming to obtain a liquid crystal solution, which is then defoamed. The method of the invention has good mixing effect and high dissolution efficiency, greatly shortens the preparation time from resin to spinning slurry, and the degradation of resin is less during the dissolution process.
Description
技术领域technical field
本发明属于纺丝浆液的制备领域，特别涉及一种PPTA树脂直接制备芳纶纺丝浆液的方法。The invention belongs to the field of preparation of spinning slurry, in particular to a method for directly preparing aramid spinning slurry with PPTA resin.
背景技术Background technique
聚对苯二甲酰对苯二胺(PPTA)纤维是一种广泛应用于各个领域的高性能纤维。它由PPTA树脂/浓硫酸的液晶溶液通过干喷湿纺而制得。目前，工业上PPTA树脂/浓硫酸的纺丝浆液的制备方法主要是将充分干燥的树脂与浓硫酸直接混合、剪切、升温溶解。也有专利报道将PPTA树脂先与冷冻浓硫酸混合，接着升温剪切，形成液晶浆液。对于传统的纺丝浆液制备方法来说，树脂与之接触后表面迅速溶胀、发热并相互粘连从而出现严重的结团现象，导致包覆在团块中的树脂很难进一步吸附硫酸，从而很难进一步混合均匀和溶解，阻碍了溶解的顺利进行，需要配合强力的剪切作用加以混合在比较长的时间内完成溶解。由于硫酸的酸性很强，长时间的溶解会导致树脂的剧烈降解。对于树脂与冷冻浓硫酸的混合方法来说，固-固混合的方式有利于降低树脂结团的危害，提高浆液的均匀性。但是由于树脂粉末颗粒较小，比重小于硫酸颗粒，因此形成的混合物形态是硫酸颗粒表面吸附了很多的树脂颗粒，相当于硫酸均匀分散在树脂中，仍会出现一定程度的结团现象。并且需要将浓硫酸冷冻，耗费的时间较长，树脂降解大，能耗也较大，不利于提高生产效率。Poly(p-phenylene terephthalamide) (PPTA) fiber is a high-performance fiber widely used in various fields. It is prepared from liquid crystal solution of PPTA resin/concentrated sulfuric acid by dry jet wet spinning. At present, the industrial preparation method of PPTA resin/concentrated sulfuric acid spinning slurry is mainly to directly mix fully dried resin with concentrated sulfuric acid, shear, and heat up to dissolve. There are also patent reports that PPTA resin is first mixed with frozen concentrated sulfuric acid, and then heated and sheared to form a liquid crystal slurry. For the traditional spinning slurry preparation method, the surface of the resin swells rapidly after being in contact with it, heats up and sticks to each other, resulting in serious agglomeration, which makes it difficult for the resin coated in the agglomerate to further absorb sulfuric acid, making it difficult Further mixing evenly and dissolving hinders the smooth progress of dissolving, and needs to be mixed with strong shearing to complete the dissolving in a relatively long period of time. Due to the strong acidity of sulfuric acid, long-term dissolution will lead to severe degradation of the resin. For the mixing method of resin and frozen concentrated sulfuric acid, the solid-solid mixing method is beneficial to reduce the harm of resin agglomeration and improve the uniformity of the slurry. However, since the resin powder particles are smaller and the specific gravity is smaller than that of sulfuric acid particles, the form of the formed mixture is that many resin particles are adsorbed on the surface of the sulfuric acid particles, which is equivalent to the uniform dispersion of sulfuric acid in the resin, and a certain degree of agglomeration will still occur. And the concentrated sulfuric acid needs to be frozen, which takes a long time, causes large resin degradation, and consumes a lot of energy, which is not conducive to improving production efficiency.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种PPTA树脂直接制备芳纶纺丝浆液的方法，本发明采用未完全干燥的PPTA树脂作为原料，其多孔结构有利于硫酸向树脂内部的渗透，加速树脂的溶解，同时也有利于提高浆液的均匀性和防止PPTA的剧烈降解。The technical problem to be solved by the present invention is to provide a method for directly preparing aramid fiber spinning slurry with PPTA resin. The present invention uses incompletely dried PPTA resin as raw material, and its porous structure is conducive to the penetration of sulfuric acid into the resin and accelerates the resin's dehydration. Dissolving is also beneficial to improve the uniformity of the slurry and prevent the severe degradation of PPTA.
本发明的一种PPTA树脂直接制备芳纶纺丝浆液的方法，包括：A kind of PPTA resin of the present invention directly prepares the method for aramid fiber spinning slurry, comprising:
(1)直接将合成出的含有大量微孔的PPTA树脂经中和后用水洗涤，交换出树脂中的溶剂和盐分，然后将PPTA树脂进行脱水，但是水分不完全脱除，得到脱水后的PPTA树脂；其中脱水后的PPTA树脂中水和树脂的质量比为1:1.0～1:1.6；(1) Directly wash the synthesized PPTA resin containing a large number of micropores with water after neutralization, exchange the solvent and salt in the resin, and then dehydrate the PPTA resin, but the water is not completely removed, and the dehydrated PPTA is obtained Resin; wherein the mass ratio of water and resin in the dehydrated PPTA resin is 1:1.0～1:1.6;
(2)将脱水后的PPTA树脂降温，搅拌条件下通入SO3气体，保持体系温度为11～13℃，使气体逐渐被水吸收形成浓硫酸，SO3气体吸收结束后，然后升温至80-90℃进行溶解和预脱泡，得到液晶溶液，脱泡，即得芳纶纺丝浆液。( 2 ) Cool down the dehydrated PPTA resin, feed SO gas under stirring conditions, keep the system temperature at 11-13 ° C, make the gas gradually absorbed by water to form concentrated sulfuric acid , and then heat up to 80 Dissolving and pre-defoaming are carried out at -90°C to obtain a liquid crystal solution, and after defoaming, aramid fiber spinning slurry is obtained.
所述步骤(1)中合成出的PPTA树脂的比浓对数粘度为4.0-8.0dl/g。The inherent viscosity of the PPTA resin synthesized in the step (1) is 4.0-8.0dl/g.
所述步骤(2)中降温至0-2℃。In the step (2), the temperature is lowered to 0-2°C.
所述步骤(2)中通入5～10MPa的SO3气体；通入时间为0.1-1h。In the step (2), 5-10 MPa of SO 3 gas is fed; the feeding time is 0.1-1 h.
所述步骤(2)中在搅拌条件下通入SO3气体；其中，首先以较慢的速度通入潮湿的树脂中(脱水后的树脂)，有利于体系的散热，当水吸收SO3气体后生产的硫酸浓度达到80％后，放热减少，可以加快气体的通入速度。In the described step ( 2 ), feed SO gas under agitation; Wherein, at first pass in the wet resin (resin after dehydration) at a slower speed, which is conducive to the heat dissipation of the system, when water absorbs SO gas After the concentration of sulfuric acid produced in the end reaches 80%, the heat release is reduced, and the gas feeding speed can be accelerated.
所述步骤(2)中浓硫酸的浓度为99.8～100.2％。The concentration of concentrated sulfuric acid in the step (2) is 99.8-100.2%.
所述步骤(2)中芳纶纺丝浆液的质量百分浓度为15.5～23％。The mass percent concentration of the aramid fiber spinning slurry in the step (2) is 15.5-23%.
所述步骤(2)中溶解和预脱泡共0.2-0.8h。Dissolving and pre-defoaming in the step (2) took 0.2-0.8h in total.
本发明直接向将洗涤后半干树脂中通入高压的SO3气体，树脂微孔中的水吸收SO3生成浓硫酸，再进行升温溶解，节省了树脂干燥和混合的时间。本发明的优点还在于，刚合成的树脂是一种多孔洞的结构，清洗过程中水置换出了孔洞中的溶剂并进入孔洞中，因此在水吸收SO3生成浓硫酸后，树脂与浓硫酸已经达到混合均匀的效果。The present invention directly feeds high - pressure SO3 gas into the semi-dried resin after washing, and the water in the resin micropores absorbs SO3 to generate concentrated sulfuric acid , which is then heated and dissolved, saving the time for resin drying and mixing. The present invention also has the advantage that the just-synthesized resin has a porous structure, and in the cleaning process, water has replaced the solvent in the pores and entered the pores, so water absorbs SO after generating concentrated sulfuric acid , resin and concentrated sulfuric acid A uniform effect has been achieved.
有益效果Beneficial effect
本发明采用未完全干燥的PPTA树脂作为原料，其多孔结构有利于硫酸向树脂内部的渗透，加速树脂的溶解，同时也有利于提高浆液的均匀性和防止PPTA的剧烈降解；The present invention uses incompletely dried PPTA resin as a raw material, and its porous structure is conducive to the penetration of sulfuric acid into the resin, accelerating the dissolution of the resin, and is also conducive to improving the uniformity of the slurry and preventing the violent degradation of PPTA;
本发明方法混合效果好，溶解效率高，大大缩短从树脂到纺丝浆液的制备时间，并且溶解过程中树脂的降解比较少。The method of the invention has good mixing effect and high dissolution efficiency, greatly shortens the preparation time from resin to spinning slurry, and the degradation of resin is less during the dissolution process.
具体实施方式detailed description
下面结合具体实施例，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。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of 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
将经过水清洗的100公斤比浓对数粘度为6.0dl/g、水与树脂的质量比为1：1.2的PPTA树脂加入多轴行星搅拌器进行搅拌，其中，向行星搅拌器的夹套中通入冷冻液，将潮湿树脂的温度控制在1℃左右。Add 100 kg of PPTA resin with an inherent viscosity of 6.0dl/g and a water-to-resin mass ratio of 1:1.2 after washing with water into a multi-axis planetary mixer for stirring. Pass through the freezing liquid to control the temperature of the wet resin at about 1°C.
向潮湿树脂中缓慢通入5MPa的SO3气体，保持体系温度在11℃。0.8h后，树脂中的水吸收SO3浓度达到80％，将SO3气体的量增大，10min后，硫酸的浓度达到99.8％。Slowly feed 5MPa SO 3 gas into the wet resin, keeping the system temperature at 11°C. After 0.8h, the water in the resin absorbs the SO 3 concentration to reach 80%, increase the amount of SO 3 gas, and after 10min, the sulfuric acid concentration reaches 99.8%.
将混合物升温至85℃进行溶解和预脱泡，0.5h后得到浓度为18.1％的PPTA/硫酸的液晶溶液。The temperature of the mixture was raised to 85° C. for dissolution and pre-defoaming, and a 18.1% PPTA/sulfuric acid liquid crystal solution was obtained after 0.5 h.
实施例2Example 2
将经过水清洗的100公斤比浓对数粘度为5.8dl/g、水与树脂的质量比为1：1.6的PPTA树脂加入多轴行星搅拌器进行搅拌，其中，向行星搅拌器的夹套中通入冷冻液，将潮湿树脂的温度控制在1℃左右。Add 100 kg of PPTA resin with an inherent viscosity of 5.8dl/g and a water-to-resin mass ratio of 1:1.6 after washing with water into a multi-axis planetary agitator for stirring. Pass through the freezing liquid to control the temperature of the wet resin at about 1°C.
向潮湿树脂中缓慢通入5MPa的SO3气体，保持体系温度在11℃。0.6h后，树脂中的水吸收SO3浓度达到80％，将SO3气体的量增大，10min后，硫酸的浓度达到99.9％。Slowly feed 5MPa SO 3 gas into the wet resin and keep the system temperature at 11°C. After 0.6h, the water in the resin absorbs the SO 3 concentration to reach 80%, increase the amount of SO 3 gas, and after 10min, the sulfuric acid concentration reaches 99.9%.
将混合物升温至85℃进行溶解和预脱泡，0.4h后得到PPTA/硫酸的液晶溶液，将得到的液晶溶液泵入后道进行脱泡，得到均匀的浓度为22.7％的浓度为PPTA/硫酸纺丝浆液。The mixture is heated to 85°C for dissolving and pre-defoaming. After 0.4h, a liquid crystal solution of PPTA/sulfuric acid is obtained. The obtained liquid crystal solution is pumped into the subsequent channel for defoaming, and a uniform concentration of 22.7% is obtained as PPTA/sulfuric acid. Spinning slurry.
实施例3Example 3
将经过水清洗的100公斤比浓对数粘度为7.8dl/g、水与树脂的质量比为1：1.1的PPTA树脂加入多轴行星搅拌器进行搅拌，其中，向行星搅拌器的夹套中通入冷冻液，将潮湿树脂的温度控制在1℃左右。Add 100 kg of PPTA resin with an inherent viscosity of 7.8dl/g and a water-to-resin mass ratio of 1:1.1 that has been washed with water into a multi-axis planetary mixer for stirring. Pass through the freezing liquid to control the temperature of the wet resin at about 1°C.
向潮湿树脂中缓慢通入10MPa的SO3气体，保持体系温度在13℃。0.5h后，树脂中的水吸收SO3浓度达到80％，将SO3气体的量增大，10min后，硫酸的浓度达到100.1％。Slowly feed 10MPa SO 3 gas into the wet resin and keep the system temperature at 13°C. After 0.5h, the water in the resin absorbs the SO 3 concentration to reach 80%, increase the amount of SO 3 gas, and after 10min, the sulfuric acid concentration reaches 100.1%.
将混合物升温至85℃进行溶解和预脱泡，0.5h后得到PPTA/硫酸的液晶溶液，将得到的液晶溶液泵入后道进行脱泡，得到均匀稳定的浓度为16.8％的PPTA/硫酸纺丝浆液。The mixture was heated to 85°C for dissolving and pre-defoaming. After 0.5h, a liquid crystal solution of PPTA/sulfuric acid was obtained. The obtained liquid crystal solution was pumped into the subsequent channel for defoaming, and a uniform and stable concentration of 16.8% PPTA/sulfuric acid was obtained. silk slurry.
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| Title |
|---|
| PPTA低温硫酸溶解工艺研究;杨拯等;《高科技纤维与应用》;20100430;第35卷(第02期);第6-9页 * |
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| CN104404645A (en) | 2015-03-11 |
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