CN1647904A - Method for preparing polyacrylonitrile pomace - Google Patents

Method for preparing polyacrylonitrile pomace Download PDF

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CN1647904A
CN1647904A CN 200410093262 CN200410093262A CN1647904A CN 1647904 A CN1647904 A CN 1647904A CN 200410093262 CN200410093262 CN 200410093262 CN 200410093262 A CN200410093262 A CN 200410093262A CN 1647904 A CN1647904 A CN 1647904A
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polyacrylonitrile
method
pulp
slurry
producing
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CN100395387C (en
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胡祖明
刘兆峰
尤秀兰
刘永乐
潘婉莲
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东华大学
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Abstract

The production process of polyacrylonitrile pulp includes the following steps: dissolving polyacrylonitrile powder in polar organic solvent to compound homogeneous slurry with polyacrylonitrile content of 14-30 wt% at temperature of 15-80 deg.c; injecting the slurry into solidifying liquid of 0-20 wt% concentration at 15-90 deg.c; and shearing at stirring rate of 700-3500 rpm for 5-60 min to separate polyacrylonitrile pulp. The present invention has simple production process and low production cost, and the prepared polyacrylonitrile pulp with rich fibrillated surface and homogeneous structure.

Description

一种聚丙烯腈浆粕的制备方法 Polyacrylonitrile pulp preparation

技术领域 FIELD

本发明涉及化学纤维材料领域,特别是涉及一种聚丙烯腈浆粕的制备方法。 The present invention relates to the field of chemical fiber material, particularly relates to a process for the preparation of polyacrylonitrile pulp.

背景技术 Background technique

聚丙烯腈浆粕具有抗溶剂性良好,无保存环境限制;更低的潮湿敏感度;较高的使用温度;混合效率高,易于分散,容易加工以及成本低等特点。 Polyacrylonitrile pulp having good solvent resistance, storage environment without limitation; lower moisture sensitivity; high temperature; high mixing efficiency, ease of dispersion, ease of processing and low cost. 目前,聚丙烯腈浆粕的制备技术方面所见报导不多,只有以下三种:腈纶废丝碾磨法、离心纺丝法和增塑熔融挤出研磨法。 Currently, technical polyacrylonitrile pulp seen few reports, only the following three kinds: Acrylic waste silk milling, centrifugal spinning and melt-extruded plasticized polishing method.

美国的Sterling公司利用将腈纶长丝或废丝经切割设备割成一定长度的短纤维,在水中分散进行机械叩解和研磨,纤维被撕裂而原纤化,使其表面产生微纤状毛羽而形成高度原纤化的PAN浆粕,商品名为CTF系列。 US Sterling, waste silk or using the acrylic filament was cut into a length of short fiber cutting device, mechanically beating a dispersion and grinding, the fiber is torn and fibrillated in water, so that the surface hairiness and the like to produce microfibrillated the formation of highly fibrillated PAN pulp trade name CTF series. 该方法得到的聚丙烯腈浆粕存在带状结均匀性较差的缺点,而且工艺比较复杂。 The present method obtained polyacrylonitrile pulp poor uniformity disadvantage strip junction, and the process is more complicated.

USP5296286提出了喷射纺丝法制备聚丙烯腈浆粕,即是将聚丙烯腈的纺丝原液通过一长的狭缝形模口而被挤出,经喷管型的高速成气流装置所拉伸或在狭缝形模品周围开有高速气流喷孔,原液一经模口压出,立即受到周围高速气流的喷吹,从而形成浆粕。 USP5296286 proposed apparatus polyacrylonitrile pulp jet spinning process, i.e., a polyacrylonitrile spinning dope is extruded through a long slit-shaped die, into a high speed through the nozzle-type stretching apparatus airflow or slit-shaped die around the high velocity gas stream article injection hole is opened, a liquid pressed out through the die, by blowing immediately around the high velocity gas stream, to form a pulp. 该方法设备复杂,成本较高。 The method apparatus complex and costly.

US5401576、KR9208998等文献提出了增塑熔融挤出研磨法制备聚丙烯浆粕,即将用水增塑的聚丙烯腈升温熔融状态,然后降温到熔点以下,使其成为过冷熔体;挤出后研磨叩解,得到长度为1~20mm、直径为0.1~50μm的聚丙烯腈浆粕。 US5401576, KR9208998 other document proposes plasticized melt extrusion of polypropylene pulp prepared by grinding method, i.e. water plasticized polyacrylonitrile heated molten state, and then cooled to below the melting point, making it a supercooled melt; milled after extrusion beating, to give a length of 1 ~ 20mm, polyacrylonitrile pulp diameter of 0.1 ~ 50μm. 该方法由于需要用水作增塑剂,同时要熔融必须达到130℃以上,因此需要采用高压设备,工艺和设备均比较复杂而且难于控制。 Since this method requires use of water as a plasticizer, while the melt must reach 130 ℃ above and therefore require high pressure equipment, processes and equipment are relatively complicated and difficult to control.

发明内容 SUMMARY

本发明所要解决的技术问题是提供一种聚丙烯腈浆粕的制备方法,以弥补现有技术的不足,满足生产的需要。 The present invention solves the technical problem is to provide a method for preparing polyacrylonitrile pulp, to compensate for deficiencies of the prior art, to meet production needs.

为了解决上述技术问题,本发明所采用的技术方案是:一种聚丙烯腈浆粕的制备方法,包括如下步骤:a.将相对分子质量为30000~100000的聚丙烯腈粉末在极性有机溶剂中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为14%~30%,浆液的温度为15℃~80℃;b.将步骤a得到的浆液注入凝固液中,凝固浴浓度为0%~20%,凝固液的温度为15℃~90℃;c.在搅拌速率为700~3500转/分的强剪切力的作用下,剪切时间为5~60分钟,直接沉析出聚丙烯腈浆粕;作为优选的技术方案,所述的聚丙烯腈的相对分子质量为50000~80000;所述的极性有机溶剂为二甲基甲酰胺(DMF)、二甲基乙酰胺(DMA)、二甲基亚砜(DMSO)、碳酸乙二酯(EC)和丙酮(ACT)中的一种或几种;步骤a所述的浆液中,聚丙烯腈的质量百分含量为18%~25%;所述浆液中可添加少量氯化锂、氯化钙、氯化 To solve the above technical problem, the technical solution employed in the present invention is: a method of preparing polyacrylonitrile pulp, comprising the steps of:. A relative molecular mass of 30,000 to 100,000 polyacrylonitrile powder in a polar organic solvent completely dissolved to prepare a homogeneous slurry, wherein the mass percentage of the polyacrylonitrile is 14% to 30%, temperature of the slurry was 15 ℃ ~ 80 ℃; b injected into the slurry obtained in step a coagulation solution, the coagulation. bath concentration of 0% to 20%, temperature of the coagulation solution is 15 ℃ ~ 90 ℃;. c stirring rate of 700 to 3500 rev / strong shearing force of the sub-shear time of 5 to 60 minutes, the precipitated directly polyacrylonitrile pulp; as a preferred aspect, the polyacrylonitrile molecular weight of 50,000 to 80,000; and the polar organic solvent is dimethylformamide (DMF), dimethyl acetamide (DMA), dimethyl sulfoxide (DMSO), ethylene carbonate (EC) and acetone (ACT) of one or more; a slurry of said step, polyacrylonitrile mass percent content of 18% to 25%; the slurry may be added a small amount of lithium chloride, calcium chloride, 、氯化锌无机盐中的一种或几种,可改善PAN的溶解性能,降低浆液的粘度,无机盐的用量相对于溶剂为1%~8%,无机盐相对于溶剂的最佳用量为2%~4%。 , One or more inorganic salts of zinc, can improve solubility of PAN, reducing the viscosity of the slurry, the inorganic salt relative to the solvent used in an amount of 1% to 8%, relative to the optimum amount of an inorganic salt solvent is 2% to 4%. 步骤a所述浆液的温度为30℃~60℃;步骤b所述的凝固液为H2O、浓度小于10%的二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸乙二酯和丙酮中的一种或几种,凝固液的温度为20℃~60℃;步骤c所述的沉析过程中的搅拌速率为1500~3000转/分,所述的剪切时间为15~30分钟。 The temperature of step a slurry of 30 ℃ ~ 60 ℃; solidifying the liquid of step b is H2O, a concentration of less than 10% of dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, ethylene carbonate one or more ester and acetone, the temperature of the coagulation solution is 20 ℃ ~ 60 ℃; stirring rate during the precipitation in step c 1500 to 3000 rev / min, the shearing time was 15 to 30 minutes.

本发明的有益效果是:直接用聚丙烯腈浆液沉析制备浆粕,省略了纺丝、切断、打浆等工序,可以大幅度降低制造成本;本发明所制备的聚丙烯腈浆粕表面原纤化丰富,结构比较均匀。 Advantageous effects of the present invention are: direct polyacrylonitrile pulp slurry prepared coagulation omitted spinning, cutting, beating and other processes, can greatly reduce the manufacturing cost; polyacrylonitrile pulp surface fibrils prepared according to the invention of the rich, relatively uniform structure.

附图说明 BRIEF DESCRIPTION

图1为本发明PAN浆粕的工艺流程图图2为本发明PAN浆粕的扫描电镜照片图3为Sterling公司的产品CTF的电镜照片具体实施方式下面结合实施例对本发明作进一步详细阐述。 PAN pulp SEM photograph of FIG. 1 process flow diagram of the present invention, PAN 2 of the present invention, the pulp is Sterling, product 3 is an electron micrograph CTF particular embodiments in conjunction with embodiments of the present invention will be explained in further detail below manner.

实施例1将相对分子质量为30000的聚丙烯腈粉末在极性有机溶剂二甲基甲酰胺中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为16%,浆液的温度为33℃;将步骤a得到的浆液注入浓度为8%的凝固液二甲基甲酰胺中,凝固浴浓度为3%,凝固液的温度为23℃;在搅拌速率为2500转/分的强剪切力的作用下,剪切时间为6分钟,直接沉析出聚丙烯腈浆粕,根据国标测定,其比表面积为63m2/g。 Example 1 The relative molecular mass of 30,000 embodiment of polyacrylonitrile powder was completely dissolved in a polar organic solvent, dimethyl formamide to prepare a uniform slurry, wherein the mass percentage of 16% polyacrylonitrile, temperature of the slurry of 33 ℃; slurry obtained in step a implant concentration of 8% solution in dimethylformamide coagulation, the coagulation bath at a concentration of 3%, the temperature of the coagulating liquid was 23 ℃; stirring rate of 2500 rpm / min strong under the action of shear forces, shear time of 6 minutes, is directly precipitated on polyacrylonitrile pulp, measured according to the national standard, a specific surface area of ​​63m2 / g.

实施例2将相对分子质量为100000的聚丙烯腈粉末在极性有机溶剂二甲基乙酰胺中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为17.7%,浆液的温度为31℃;将步骤a得到的浆液注入浓度为6%的凝固液二甲基乙酰胺中,凝固浴浓度为3%,凝固液的温度为28℃;在搅拌速率为2800转/分的强剪切力的作用下,剪切时间为10分钟,直接沉析出聚丙烯腈浆粕,根据国标测定,其比表面积为65.7m2/g。 Example 2 The relative molecular mass of 100,000 embodiments of polyacrylonitrile powder was completely dissolved in a polar organic solvent is dimethyl acetamide to prepare a uniform slurry, wherein the mass percentage of 17.7% of polyacrylonitrile, the temperature of the slurry of 31 ℃; slurry obtained in step a concentration of 6% of the injected liquid dimethylacetamide coagulation in the coagulation bath at a concentration of 3%, the temperature of the coagulating liquid was 28 deg.] C; at a stirring rate of 2800 rpm / min strong under the action of shear force, shearing time was 10 minutes, and directly precipitated on polyacrylonitrile pulp, measured according to the national standard, a specific surface area of ​​65.7m2 / g.

实施例3将相对分子质量为50000的聚丙烯腈粉末在极性有机溶剂丙酮中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为22%,浆液的温度为40℃;将步骤a得到的浆液注入浓度为5%的凝固液丙酮中,凝固浴浓度为3.7%,凝固液的温度为28℃;在搅拌速率为2780转/分的强剪切力的作用下,剪切时间为10.5分钟,直接沉析出聚丙烯腈浆粕,根据国标测定,其比表面积为62m2/g。 Embodiment 3 The embodiment of 50,000 relative molecular mass of polyacrylonitrile powder was completely dissolved in a polar organic solvent such as acetone, to prepare a uniform slurry, wherein the mass percentage of 22% polyacrylonitrile, temperature of the slurry was 40 ℃; the resulting slurry is injected in step a concentration of 5% acetone coagulation solution, the coagulation bath concentration 3.7%, temperature of the coagulation solution is 28 deg.] C; under the effect of stirring rate 2780 rpm / min strong shear forces, shear cutting time was 10.5 minutes, and directly precipitated on polyacrylonitrile pulp, measured according to the national standard, a specific surface area of ​​62m2 / g.

实施例4将相对分子质量为80000的聚丙烯腈粉末在极性有机溶剂二甲基亚砜中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为30%,浆液的温度为45℃;将步骤a得到的浆液注入浓度为5%的凝固液碳酸乙二酯中,凝固浴浓度为6.5%,凝固液的温度为35℃;在搅拌速率为2600转/分的强剪切力的作用下,剪切时间为14分钟,直接沉析出聚丙烯腈浆粕,根据国标测定,其比表面积为70m2/g。 Example 4 The relative molecular mass of 80,000 embodiment of polyacrylonitrile powder was completely dissolved in a polar organic solvent dimethyl sulfoxide to prepare a uniform slurry, wherein the mass percentage of 30% polyacrylonitrile, temperature of the slurry to 45 deg.] C; the slurry obtained in step a coagulation liquid injection ethylene carbonate in a concentration of 5%, 6.5% concentration of the coagulation bath, the temperature of the coagulating liquid was 35 ℃; stirring rate of 2600 rev / min shear strength under the action of shear forces, shear time of 14 minutes, polyacrylonitrile directly precipitated on the pulp, measured according to the national standard, a specific surface area of ​​70m2 / g.

Claims (11)

1.一种聚丙烯腈浆粕的制备方法,其特征在于包括如下步骤:a.将相对分子质量为30000~100000的聚丙烯腈粉末在极性有机溶剂中完全溶解,配制成均匀的浆液,其中聚丙烯腈的质量百分含量为14%~30%,浆液的温度为15℃~80℃;b.将步骤a得到的浆液注入凝固液中,凝固浴浓度为0%~20%,凝固液的温度为15℃~90℃;c.在搅拌速率为700~3500转/分的强剪切力的作用下,剪切时间为5~60分钟,直接沉析出聚丙烯腈浆粕; 1. A method for preparing poly acrylonitrile pulp, comprising the steps of:. A relative molecular mass of 30,000 to 100,000 polyacrylonitrile powder was completely dissolved in a polar organic solvent to prepare a homogeneous slurry, wherein the mass percentage of the polyacrylonitrile is 14% to 30%, temperature of the slurry was 15 ℃ ~ 80 ℃; b injected into the slurry obtained in step a coagulation solution, the coagulation bath concentration of 0% to 20%, solidified. liquid temperature was 15 ℃ ~ 90 ℃;. c stirring rate of 700 to 3500 rev / min under the action of strong shear forces, shear time of 5 to 60 minutes, and directly precipitated on polyacrylonitrile pulp;
2.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述的聚丙烯腈的相对分子质量为50000~80000。 2. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: the molecular weight polyacrylonitrile of 50,000 to 80,000.
3.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述的极性有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸乙二酯和丙酮中的一种或几种。 3. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: said polar organic solvent is dimethylformamide, dimethylacetamide, dimethylsulfoxide, one or more of ethylene carbonate and acetone.
4.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:步骤a所述的浆液中,聚丙烯腈的质量百分含量为18%~25%。 4. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: said step of a slurry, the mass percentage of the polyacrylonitrile is 18% to 25%.
5.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:步骤a所述浆液中添加氯化锂、氯化钙、氯化镁、氯化锌无机盐中的一种或几种,无机盐的用量相对于溶剂为1%~8%。 5. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: a lithium chloride, calcium chloride, magnesium chloride, zinc salts in the step of adding a slurry of the or more, the inorganic salt relative to the solvent used in an amount of 1% to 8%.
6.根据权利要求5所述的一种聚丙烯腈浆粕的制备方法,其特征在于:无机盐的用量相对于溶剂为2%~4%。 6. A method for producing a polyacrylonitrile pulp as claimed in claim 5, wherein: the inorganic salt relative to the solvent used in an amount of 2% to 4%.
7.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述浆液的温度为30℃~60℃。 7. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: the temperature of the slurry is 30 ℃ ~ 60 ℃.
8.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述的凝固液为H2O、浓度小于10%的二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸乙二酯和丙酮中的一种或几种。 8. A method for the preparation of a polyacrylonitrile pulp claim, wherein: said coagulation liquid is H2O, a concentration of less than 10% of dimethyl formamide, dimethyl acetamide, bis methyl sulfoxide, ethylene carbonate and one or more of acetone.
9.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述的凝固液的温度为20℃~60℃。 9. A method for the preparation of a polyacrylonitrile pulp claim, wherein: the temperature of the coagulating liquid was 20 ℃ ~ 60 ℃.
10.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:步骤c所述的沉析过程中的搅拌速率为1500~3000转/分。 10. A method for producing a polyacrylonitrile pulp according to claim 1, wherein: step c the stirring rate during the precipitation of 1500 to 3000 rev / min.
11.根据权利要求1所述的一种聚丙烯腈浆粕的制备方法,其特征在于:所述的剪切时间为15~30分钟。 According to claim 1, wherein one of the preparation of polyacrylonitrile pulp, characterized in that: the shearing time was 15 to 30 minutes.
CN 200410093262 2004-12-21 2004-12-21 Method for preparing polyacrylonitrile pomace CN100395387C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280470B (en) 2007-04-02 2012-04-25 上海兰邦工业纤维有限公司 Method for continuously producing polyacryl-nitrile pulp-like fibre
CN101058896B (en) 2006-04-17 2012-06-20 上海兰邦工业纤维有限公司 Preparation of polyacrylonitrile pulp-shape fibre

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
KR950005429B1 (en) 1991-03-27 1995-05-24 박원희 Heat-resistant acrylic short fibers without spinning
GB9518798D0 (en) 1995-09-14 1995-11-15 Secr Defence Apparatus and method for spinning hollow polymeric fibres
JP2002309479A (en) 2001-04-11 2002-10-23 Oji Paper Co Ltd Method for producing very fine fiber
CN1180143C (en) 2001-04-27 2004-12-15 中国科学院化学研究所 Method for making superfine fibres
JP2003020516A (en) 2001-07-04 2003-01-24 Toray Ind Inc Polyacrylonitrile precursor fiber for carbon fiber and method for producing the same
CN1187393C (en) 2002-08-12 2005-02-02 东华大学 Preparation method of preparing p- phenylene terephthamide pulp fibre

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058896B (en) 2006-04-17 2012-06-20 上海兰邦工业纤维有限公司 Preparation of polyacrylonitrile pulp-shape fibre
CN101280470B (en) 2007-04-02 2012-04-25 上海兰邦工业纤维有限公司 Method for continuously producing polyacryl-nitrile pulp-like fibre

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