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CN111793842B - A kind of fluorescent brightening dark dyeable polypropylene fiber and preparation method thereof - Google Patents

A kind of fluorescent brightening dark dyeable polypropylene fiber and preparation method thereof Download PDF

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CN111793842B
CN111793842B CN202010669461.3A CN202010669461A CN111793842B CN 111793842 B CN111793842 B CN 111793842B CN 202010669461 A CN202010669461 A CN 202010669461A CN 111793842 B CN111793842 B CN 111793842B
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fluorescent brightening
vinyl
dyeing
polyacrylic acid
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CN111793842A (en
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顾益明
孙宾
黄新强
朱美芳
顾洪达
陈龙
陈珈
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Changshu Polyester Co ltd
Donghua University
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Donghua University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D471/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06Peri-condensed systems
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34Monomers containing two or more unsaturated aliphatic radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/41General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using basic dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)

Abstract

本发明涉及一种荧光增亮深色可染聚丙烯纤维及其制备方法,该方法是先将聚丙烯、聚丙烯酸微球(以1,7‑乙烯基‑苝酰亚胺衍生物作为交联剂制得)混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维,制得的纤维在440~460nm波长的激发下,产生630~645nm的1,7‑乙烯基‑苝酰亚胺衍生物的特征荧光发射峰,荧光量子产率为95~99%,染色性能为:用阳离子黄X‑8GL在125℃下染色,染料上染率为65~95%;染色K/S值为11.41~12.70;本发明的方法选择普通阳离子染色剂即可得到颜色明亮鲜艳的聚丙烯纤维。The invention relates to a fluorescent brightening dark dyeable polypropylene fiber and a preparation method thereof. (prepared by the chemical agent), mixed evenly, dried, and then put into a twin-screw extruder for extrusion to obtain a master batch; finally, the master batch was added to the production equipment for polypropylene melt spinning for spinning to obtain fluorescent Brightening dark dyeable polypropylene fibers, the prepared fibers produce characteristic fluorescence emission peaks of 1,7-vinyl-peryleneimide derivatives at 630-645 nm under excitation at a wavelength of 440-460 nm, and the fluorescence quantum yields The dyeing rate is 95-99%, and the dyeing performance is as follows: dyeing with cationic yellow X-8GL at 125°C, the dye uptake rate is 65-95%; the dyeing K/S value is 11.41-12.70; the method of the present invention selects common cationic The dyeing agent can get bright and bright polypropylene fibers.

Description

一种荧光增亮深色可染聚丙烯纤维及其制备方法A kind of fluorescent brightening dark dyeable polypropylene fiber and preparation method thereof

技术领域technical field

本发明属于聚丙烯纤维技术领域,涉及一种荧光增亮深色可染聚丙烯纤维及其制备方法。The invention belongs to the technical field of polypropylene fibers, and relates to a fluorescent brightening dark dyeable polypropylene fiber and a preparation method thereof.

背景技术Background technique

近年来,在纺织服装领域,随着人们对色彩的要求越来越高,对于亮丽、鲜艳的服装织物具有需求。荧光染料属于一种特殊的功能性染料,它既具有常规染料的着色特性,又能发射出荧光,因而与一般染料相比,荧光染料染色织物的饱和度和鲜艳度相对较高。荧光染料现已被广泛应用于纺织、塑料染色、印刷用颜料等多种行业,如:交通警察、清洁人员着装上的醒目标志,以及高档伞具、箱包、运动服、领带及室外装饰材料等。随着科技的进步,荧光染料也逐步被应用到高端领域,如生物、医药等。In recent years, in the field of textile and clothing, as people have higher and higher requirements for color, there is a demand for bright and bright clothing fabrics. Fluorescent dyes are a special kind of functional dyes, which not only have the coloring properties of conventional dyes, but also emit fluorescence. Therefore, compared with general dyes, fluorescent dyes dye fabrics with relatively high saturation and vividness. Fluorescent dyes have been widely used in textile, plastic dyeing, printing pigments and other industries, such as: traffic police, cleaning staff wearing eye-catching signs, as well as high-end umbrellas, luggage, sportswear, ties and outdoor decoration materials, etc. . With the advancement of science and technology, fluorescent dyes have also been gradually applied to high-end fields, such as biology and medicine.

荧光染料较之非荧光染料呈现更明亮的色彩,提高织物的的饱和度和鲜艳度。但是,目前应用于织物上的荧光染料种类不是很多,主要是由于很大一部分荧光染料不能与纤维产生牢固的结合,其主要应用于涤纶等合成纤维。应用在棉织物上最广泛的是荧光增白剂。荧光增白剂吸收人眼中看不见的紫外光,发出极明亮和艳丽的蓝紫色光,提高织物的白度与鲜艳度。专利CN106758386A公开了一种荧光涤纶面料的加工工艺,包括精练处理、染色整理和后处理步骤;其中,染色整理是采用一浴法将待染织物与染色工作液共浴,浴比为1:10,升温至60℃,升温速率为5℃/min,保持40~50分钟,继续升温至120℃,升温速率为1℃/min,在此温度下保持30~40分钟,完成染色。该荧光涤纶面料既可以作为日常穿着,以满足时尚性的要求,又可以根据需要随意搭配市场上购买的3M反光材料等,从而制成晚上可以使用的高可视性警示服,其荧光性能符合相关标准的要求。Fluorescent dyes exhibit brighter colors than non-fluorescent dyes, increasing the saturation and vividness of fabrics. However, there are not many types of fluorescent dyes currently used on fabrics, mainly because a large part of fluorescent dyes cannot be firmly combined with fibers, and they are mainly used in synthetic fibers such as polyester. The most widely used on cotton fabrics is the fluorescent whitening agent. Fluorescent whitening agent absorbs ultraviolet light invisible to human eyes, emits extremely bright and gorgeous blue-violet light, and improves the whiteness and vividness of fabrics. Patent CN106758386A discloses a processing technology of fluorescent polyester fabric, including scouring treatment, dyeing and finishing and post-treatment steps; wherein, dyeing and finishing is to use one bath method to co-bath the fabric to be dyed with the dyeing working solution, and the bath ratio is 1:10 , heat up to 60°C, the heating rate is 5°C/min, hold for 40-50 minutes, continue to heat up to 120°C, the heating rate is 1°C/min, and keep at this temperature for 30-40 minutes to complete the dyeing. The fluorescent polyester fabric can not only be used for daily wear to meet the requirements of fashion, but also can be freely matched with 3M reflective materials purchased in the market according to needs, so as to make high-visibility warning clothing that can be used at night. requirements of relevant standards.

聚丙烯纤维,名为丙纶,可分为长纤维、短纤维、纺黏无纺布、熔喷无纺布等,具有广泛的用途。但是聚丙烯分子链中不含极性基团或可反应基团,疏水性很强,对一般的染料缺乏亲和力;同时由于聚丙烯纤维结晶度很高(结晶度越高,等规物、间规物所含的比例越高),结构相当紧密,致使染料分子难以扩散到其内部,是目前合成纤维中最难于染色的一种。为了适应生产和应用需要,改善聚丙烯纤维的着色性,国内外许多专家学者作了大量的工作,提出了各种各样的聚丙烯纤维的着色方法。现有技术有在空气中采用低温等离子体对聚丙烯纤维进行处理,再用Ostalan棕BL Supra和Alizarine Chrome红G染色,不但可染性高,而且具有高的耐机械摩擦牢度和水洗牢度。Polypropylene fibers, called polypropylene fibers, can be divided into long fibers, short fibers, spunbond nonwovens, meltblown nonwovens, etc., and have a wide range of uses. However, the polypropylene molecular chain does not contain polar groups or reactive groups, so it has strong hydrophobicity and lacks affinity for general dyes. The higher the proportion of regulated substances), the structure is quite compact, making it difficult for the dye molecules to diffuse into its interior, and it is the most difficult one to dye among synthetic fibers. In order to meet the needs of production and application and improve the colorability of polypropylene fibers, many experts and scholars at home and abroad have done a lot of work and proposed various coloring methods of polypropylene fibers. In the prior art, polypropylene fibers are treated with low-temperature plasma in the air, and then dyed with Ostalan Brown BL Supra and Alizarine Chrome Red G, which not only has high dyeability, but also has high mechanical rubbing fastness and washing fastness. .

为了改进聚丙烯纤维的染色性能,更好地满足印染要求,必须进行改性使其至少具备如下两个条件:改变纤维的紧密结构,使染料易于渗透到纤维基质中;在纤维基体中引入一定数量的、对染料具有足够大亲和力的极性基团。目前,国内外通过改性方法制取可染丙纶大致有下列5种:掺混金属化合物改性法;共混异相聚合物改性法;接枝共聚改性法;复合纤维法和纤维表面处理法。国内有许多针对聚丙烯纤维染色的研究,例如安徽找宝纺织科技有限公司提供了一种聚丙烯纤维的阳离子改性染色方法,包括:纤维改性、预处理、坯布预定型、还原清洗、配制染液、染色、后处理。染色工艺步骤少、染色时间短、染后染料可循环利用、减少环境污染。中科纳米技术工程中心有限公司利用低温等离子体接枝聚合法对聚丙烯纤维或织物进行改性的染色方法,通过在等离子体处理的过程中引入丙烯酸等单体或利用丙烯酸等单体溶液在聚丙烯纤维或织物表面接枝上有利于上染和促进深染的染座,从而使得经此法处理的聚丙烯纤维或织物能采用“常温沸染”工艺染色,然而该改性方法难以连续法生产,而且改性效果不是很好,难以实现产业化生产。In order to improve the dyeing properties of polypropylene fibers and better meet the requirements of printing and dyeing, modification must be carried out to make it at least meet the following two conditions: change the compact structure of the fibers, so that the dyes can easily penetrate into the fiber matrix; A number of polar groups with a sufficiently large affinity for the dye. At present, there are roughly the following five kinds of dyeable polypropylene fibers prepared by modification methods at home and abroad: the modification method of blending metal compounds; the modification method of blending heterogeneous polymers; the modification method of graft copolymerization; the method of composite fiber and fiber surface processing method. There are many domestic researches on polypropylene fiber dyeing. For example, Anhui Zhaobao Textile Technology Co., Ltd. provides a cationic modification dyeing method for polypropylene fibers, including: fiber modification, pretreatment, pre-forming of grey fabrics, reduction cleaning, preparation Dyeing solution, dyeing, post-processing. The dyeing process steps are few, the dyeing time is short, the dyestuff can be recycled after dyeing, and the environmental pollution is reduced. Zhongke Nanotechnology Engineering Center Co., Ltd. uses low-temperature plasma graft polymerization to modify the dyeing method of polypropylene fibers or fabrics, by introducing monomers such as acrylic acid or using monomer solutions such as acrylic acid in the process of plasma treatment. The surface of polypropylene fibers or fabrics is grafted with a dye seat that is conducive to dyeing and promotes deep dyeing, so that polypropylene fibers or fabrics treated by this method can be dyed by the "normal temperature boiling dyeing" process. However, this modification method is difficult to continuously It is produced by the method, and the modification effect is not very good, so it is difficult to realize industrial production.

发明内容SUMMARY OF THE INVENTION

本发明针对现有技术中对于鲜艳色彩或高亮聚丙烯纤维染色均使用荧光染料,染料种类选择具有局限性,本发明通过在聚丙烯基体中共混入羧基官能化的高荧光聚丙烯酸微球,增强纤维与阳离子染料的结合,同时微球的加入破坏了聚丙烯本身的结晶性,有利于染料进入,从而实现聚丙烯纤维的深色可染。并且因为荧光微球中苝酰亚胺的发射波长与纤维阳离子染色剂吸收波长的补色波长有重合,有利于得到颜色深且艳丽的荧光增亮深色可染聚丙烯纤维。The present invention uses fluorescent dyes for bright color or high-brightness polypropylene fiber dyeing in the prior art, and the choice of dye types is limited. The present invention mixes carboxyl-functionalized high-fluorescence polyacrylic acid microspheres in the polypropylene matrix to enhance fibers and The combination of cationic dyes and the addition of microspheres destroy the crystallinity of polypropylene itself, which is conducive to the entry of dyes, thereby realizing the dark dyeability of polypropylene fibers. And because the emission wavelength of the peryleneimide in the fluorescent microspheres overlaps with the complementary wavelength of the absorption wavelength of the fiber cationic dye, it is beneficial to obtain deep and bright fluorescent brightening dark dyeable polypropylene fibers.

本发明的目的之一是提供一种荧光增亮深色可染聚丙烯纤维,主要由聚丙烯基体以及分散在其中的聚丙烯酸微球组成;荧光增亮深色可染聚丙烯纤维在440~460nm波长的激发下,产生630-645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰。One of the objectives of the present invention is to provide a fluorescent brightening dark dyeable polypropylene fiber, which is mainly composed of a polypropylene matrix and polyacrylic acid microspheres dispersed therein; Under the excitation of 460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives is generated at 630-645nm.

本发明的目的之二是一种荧光增亮深色可染聚丙烯纤维的制备方法,是先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维。The second purpose of the present invention is a preparation method of fluorescent brightening dark dyeable polypropylene fiber, which is to first mix polypropylene and polyacrylic acid microspheres uniformly, and dry them, and then put them into a twin-screw extruder. Extrusion to obtain master batch; finally, the master batch is added to the production equipment of polypropylene melt spinning for spinning to obtain fluorescent brightening dark dyeable polypropylene fibers.

为达到上述目的,本发明采用的方案如下:For achieving the above object, the scheme that the present invention adopts is as follows:

一种荧光增亮深色可染聚丙烯纤维,主要由聚丙烯基体以及分散在其中的聚丙烯酸微球组成;荧光增亮深色可染聚丙烯纤维荧光增亮深色可染聚丙烯纤维在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰,颜色为橙黄色;A fluorescent brightening dark dyeable polypropylene fiber mainly consists of a polypropylene matrix and polyacrylic acid microspheres dispersed therein; the fluorescent brightening dark dyeable polypropylene fiber is Under the excitation of 440-460 nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645 nm is generated, and the color is orange-yellow;

所述聚丙烯酸微球是以1,7-乙烯基-苝酰亚胺衍生物作为交联剂的聚丙烯酸微球;The polyacrylic acid microspheres are polyacrylic acid microspheres using 1,7-vinyl-peryleneimide derivatives as crosslinking agents;

所述1,7-乙烯基-苝酰亚胺衍生物是指湾位(1,7位)带有乙烯基团的取代基且酰亚胺位带有大体积取代基的苝酰亚胺。The 1,7-vinyl-peryleneimide derivative refers to a peryleneimide having a substituent with a vinyl group at the bay position (1,7 position) and a bulky substituent at the imide position.

1,7-乙烯基-苝酰亚胺衍生物在本发明中的作用是:带有大体积酰亚胺位取代的苝酰亚胺衍生物可以使得该分子在通过π-π相互作用聚集时有很大的位阻,并且在有溶剂的情况下更容易以单分子状态存在在体系中,交联点在微球中存在更为均匀。1,7-乙烯基-苝酰亚胺衍生物同时还具有荧光性能,且由于加入的苝酰亚胺衍生物的量远远小于微球上羧基的量,所以苝酰亚胺本身的颜色会对深色可染纤维颜色影响较小。同时共混聚丙烯酸微球生产出来的纤维有荧光发射,并且因为苝酰亚胺的发射波长与特定阳离子染色剂吸收波长的补色波长有重合,有利于得到颜色深且艳丽的荧光增亮深色可染聚丙烯纤维可以使得该纤维染色更鲜艳明亮;The function of the 1,7-vinyl-perylene imide derivative in the present invention is: the perylene imide derivative with bulky imide position substitution can make the molecule aggregated through π-π interaction. It has great steric hindrance, and in the presence of a solvent, it is easier to exist in the system in a single-molecule state, and the cross-linking point exists more uniformly in the microspheres. The 1,7-vinyl-perylene imide derivative also has fluorescent properties, and since the amount of the perylene imide derivative added is far less than the amount of carboxyl groups on the microspheres, the color of the perylene imide itself will be different. Less impact on dark dyeable fiber color. At the same time, the fibers produced by blending polyacrylic acid microspheres have fluorescence emission, and because the emission wavelength of peryleneimide coincides with the complementary color wavelength of the absorption wavelength of specific cationic dyes, it is beneficial to obtain deep and bright fluorescence brightening dark colors. Dyeable polypropylene fiber can make the fiber dyeing brighter and brighter;

作为优选的技术方案:As the preferred technical solution:

如上所述的一种荧光增亮深色可染聚丙烯纤维,所述的大体积取代基为倍半笼形硅氧烷或带有侧链的长烷基链;A fluorescent brightening dark dyeable polypropylene fiber as described above, wherein the bulky substituent is a silsesquioxane or a long alkyl chain with a side chain;

所述倍半笼形硅氧烷是

Figure BDA0002581717870000031
R为异丁基或异辛基;The silsesquiclathric siloxane is
Figure BDA0002581717870000031
R is isobutyl or isooctyl;

所述带有侧链的长烷基链是

Figure BDA0002581717870000032
The long alkyl chain with side chains is
Figure BDA0002581717870000032

其中

Figure BDA0002581717870000033
表示该化学键链接位置为酰亚胺结构中的N原子;in
Figure BDA0002581717870000033
Indicates that the linking position of the chemical bond is the N atom in the imide structure;

所述乙烯基团的取代基是指端基带有乙烯基团的烷基链,所述烷基链为小于六个碳的烷基链。The substituent of the vinyl group refers to an alkyl chain with a vinyl group at the end, and the alkyl chain is an alkyl chain with less than six carbons.

如上所述的一种荧光增亮深色可染聚丙烯纤维,所述1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为14~21.5:125。由于1,7-乙烯基-苝酰亚胺衍生物的添加量远小于丙烯酸的添加量,纤维中的染座数量大,荧光对于染色的影响较小。In the above-mentioned fluorescent brightening dark dyeable polypropylene fiber, the molar ratio of the 1,7-vinyl-peryleneimide derivative to the acrylic acid structural unit is 14-21.5:125. Since the addition amount of 1,7-vinyl-peryleneimide derivative is much smaller than that of acrylic acid, the number of dye bases in the fiber is large, and the effect of fluorescence on dyeing is small.

如上所述的一种荧光增亮深色可染聚丙烯纤维,所述聚丙烯酸微球的平均直径为150~300nm,平均孔径为10~30nm,孔隙率为35~55%,荧光量子产率为95~99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰,颜色为橙黄色。A fluorescent brightening dark dyeable polypropylene fiber as described above, the polyacrylic acid microspheres have an average diameter of 150-300 nm, an average pore diameter of 10-30 nm, a porosity of 35-55%, and a fluorescence quantum yield. The characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645 nm is produced under the excitation of 440-460 nm wavelength, and the color is orange-yellow.

如上所述的一种荧光增亮深色可染聚丙烯纤维,所述荧光增亮深色可染聚丙烯纤维的断裂强度3.09~3.9cN/dtex,断裂伸长率为17.73~26.6%,熔点为150~180℃;经共混后结晶度降低,为染色创造条件;荧光量子产率为95~99%;A fluorescent brightening dark dyeable polypropylene fiber as described above, the fluorescent brightening dark dyeable polypropylene fiber has a breaking strength of 3.09 to 3.9 cN/dtex, an elongation at break of 17.73 to 26.6%, and a melting point of 3.09 to 3.9 cN/dtex. The temperature is 150~180℃; the crystallinity is reduced after blending, creating conditions for dyeing; the fluorescence quantum yield is 95~99%;

所述荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为65~95%,色泽鲜艳、均匀;染色K/S值为11.41~12.70;随着温度的提高,阳离子黄X-8GL的上染率随之升高,当温度达到120~130℃时达到最高,此后在提高染色温度,上染率变化不明显,The dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 DEG C, the dye uptake rate is 65-95%, the color is bright and uniform; the dyeing K/S value is 11.41~12.70; With the increase of temperature, the dye uptake rate of cationic yellow X-8GL increases, and reaches the highest when the temperature reaches 120~130℃.

染色色牢度为:皂洗牢度:原样变色4级、白布沾色3~5级,摩擦牢度:干4~5级、湿3~5级,汗渍色牢度:原样变色4~5级、白布沾色4~5级,升华色牢度:原样变色4~5级,白布沾色4~5级;The color fastness of dyeing is: soaping fastness: the original discoloration level 4, white cloth staining level 3-5, rubbing fastness: dry level 4-5, wet level 3-5, perspiration color fastness: original discoloration 4-5 4-5 grades, white cloth staining, sublimation color fastness: 4-5 grades for discoloration as it is, 4-5 grades for white cloth staining;

由所述荧光增亮深色可染聚丙烯纤维制成的织物的反射率为95~145%,染色织物的色度坐标值为:x=0.45~0.5,y=0.42~0.52,处于黄色区域;The reflectivity of the fabric made of the fluorescent brightening dark dyeable polypropylene fiber is 95-145%, and the chromaticity coordinates of the dyed fabric are: x=0.45-0.5, y=0.42-0.52, in the yellow region ;

阳离子黄X-8GL的染色过程如下:The dyeing process of Cationic Yellow X-8GL is as follows:

(1)将荧光增亮深色可染聚丙烯纤维置于染色浴中,按浴比为l:20~50的重量比加水后,加入已经溶解好的染料阳离子黄X-8GL为0.05~2%、匀染剂1277加入量为0.3~2%、元明粉0~10%和醋酸0.5~2%,5~25℃运转10~20min;(1) Put the fluorescent brightening dark dyeable polypropylene fiber in the dyeing bath, add water according to the weight ratio of the bath ratio of 1:20~50, add the dissolved dye cationic yellow X-8GL to 0.05~2 %, the leveling agent 1277 is added in an amount of 0.3-2%, Yuanming powder is 0-10% and acetic acid is 0.5-2%, and the operation is carried out at 5-25°C for 10-20min;

元明粉和醋酸加入量均以共混丙纶的重量计。The amount of Yuan Mingfen and acetic acid added is based on the weight of the blended polypropylene.

(2)以0.5~4℃/min的速率升温到50~80℃后运转10~30min;(2) Raise the temperature to 50-80°C at a rate of 0.5-4°C/min and run for 10-30min;

(3)以1~2℃/min的速率升温到95~100℃运转30~60min;(3) Raise the temperature to 95-100°C at a rate of 1-2°C/min and run for 30-60min;

(4)以2~4℃/min的速率下降到35~45℃后放掉残液,用20~40℃清水洗,然后采用本领域共知的方法干燥或功能整理。(4) After dropping to 35-45°C at a rate of 2-4°C/min, let off the residual liquid, wash with water at 20-40°C, and then dry or perform functional finishing by methods known in the art.

本发明还提供如上所述的一种荧光增亮深色可染聚丙烯纤维的制备方法,先将聚丙烯、聚丙烯酸微球加入到搅拌机中搅拌混合均匀,并进行干燥(干燥温度为160~180℃,时间为30~60min)处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上,调整生产设备不同位置的参数,进行纺丝,得到荧光增亮深色可染聚丙烯纤维;The present invention also provides the above-mentioned preparation method of fluorescent brightening dark dyeable polypropylene fibers. First, polypropylene and polyacrylic acid microspheres are added into a mixer, stirred and mixed evenly, and dried (the drying temperature is 160-100 ℃). 180°C for 30-60min) treatment, and then put it into a twin-screw extruder for extrusion to obtain a masterbatch; finally, add the masterbatch to the production equipment of polypropylene melt spinning, and adjust the different positions of the production equipment. parameters, spinning to obtain fluorescent brightening dark dyeable polypropylene fibers;

所述高荧光聚丙烯酸微球的制备方法为:The preparation method of the high-fluorescence polyacrylic acid microspheres is:

(1)将乳化剂和去离子水在温度T1下混合形成体系I;(1) emulsifier and deionized water are mixed at temperature T1 to form system I;

(2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物溶于有机溶剂中,再加入到体系I中在温度T2下混合得到体系II;(2) first dissolving methyl acrylate and 1,7-vinyl-perylene imide derivative in an organic solvent, then adding to system I and mixing at temperature T2 to obtain system II;

(3)先将体系II搅拌一定时间后,在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温(23±2℃)后过滤、水洗和烘干得到聚丙烯酸酯微球;(3) After stirring the system II for a certain period of time, adding potassium persulfate to the system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature (23±2°C), filtering, washing with water and drying to obtain polyacrylate microspheres;

(4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到高荧光聚丙烯酸微球(固体粉末)。(4) Mixing the polyacrylate microspheres with sodium hydroxide ethanol solution, heating to reflux, cooling, filtering and drying to obtain high-fluorescence polyacrylic acid microspheres (solid powder).

作为优选的技术方案:As the preferred technical solution:

如上所述的方法,所述双螺杆挤出机(TSE-3Q)的螺杆转速为150~200r/min,螺杆温度为200~220℃;双螺杆挤出机反向旋转的螺杆呈上下水平平行布置在沿纵向大小孔径不等的8字形挤出笼腔室内,在喂料段螺旋完全啮合而在主基础段上不啮合,挤出笼沿纵向分成4段不同出丝缝隙的出粒孔;In the method described above, the screw speed of the twin-screw extruder (TSE-3Q) is 150-200 r/min, and the screw temperature is 200-220°C; the counter-rotating screw of the twin-screw extruder is horizontal and parallel It is arranged in the figure-8 extrusion cage chamber with different diameters along the longitudinal direction. The screw is fully meshed in the feeding section but not meshed on the main base section. The extrusion cage is divided into 4 sections of pellet outlet holes with different wire outlet gaps in the longitudinal direction;

所述母粒中,按重量份数计,聚丙烯为80~120份,聚丙烯酸微球为40~60份;纺丝过程中,母粒的添加量为7~8wt%;In the master batch, in parts by weight, polypropylene is 80-120 parts, and polyacrylic acid microspheres are 40-60 parts; in the spinning process, the addition amount of the master batch is 7-8 wt%;

所述纺丝的工艺参数为:熔体输送管道的温度200~260℃,熔体过滤器温度220~260℃,纺丝箱体的温度220~260℃,侧吹风风速0.5~0.7m/s,风温15±2℃,热辊温度110±10℃,纺丝速度2500~2800m/min,卷绕角7~8°。随着纺丝速度的提高,纺程中张力不断升高,纤维强力随之提高,伸长减小,但结晶度及其取向在纺速2500m/min时达到饱和。The spinning process parameters are as follows: the temperature of the melt conveying pipe is 200-260°C, the temperature of the melt filter is 220-260°C, the temperature of the spinning box is 220-260°C, and the side blowing wind speed is 0.5-0.7m/s , the wind temperature is 15±2℃, the temperature of the hot roller is 110±10℃, the spinning speed is 2500~2800m/min, and the winding angle is 7~8°. With the increase of the spinning speed, the tension in the spinning process increases continuously, the fiber strength increases and the elongation decreases, but the crystallinity and its orientation reach saturation at the spinning speed of 2500 m/min.

如上所述的方法,所述乳化剂为月桂酸钾、十二烷基硫酸钠或者丁二酸二辛酯磺酸钠;所述有机溶剂为甲苯或者二甲苯。In the above method, the emulsifier is potassium laurate, sodium lauryl sulfate or sodium dioctyl succinate sulfonate; and the organic solvent is toluene or xylene.

如上所述的方法,步骤(1)中,T1为35~55℃,混合时间为3~8min;In the above-mentioned method, in step (1), T1 is 35~55 ℃, and mixing time is 3~8min;

步骤(2)的体系II中,乳化剂的含量为0.4~0.7wt%;丙烯酸甲酯的含量为4~6wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为9~15wt%,有机溶剂的含量为6~10wt%;T2为75~95℃;In the system II of step (2), the content of the emulsifier is 0.4-0.7 wt %; the content of methyl acrylate is 4-6 wt %, and the content of the 1,7-vinyl-perylene imide derivative is 9-15 wt % %, the content of organic solvent is 6~10wt%; T2 is 75~95℃;

步骤(3)中过硫酸钾的质量分数为丙烯酸酯分散液的0.06~0.12%;搅拌速率为300~500r/min,搅拌时间为15~35min;聚合时间为4~8h,聚合温度为75~95℃;烘干温度为90~140℃;The mass fraction of potassium persulfate in step (3) is 0.06-0.12% of the acrylate dispersion; the stirring rate is 300-500 r/min, the stirring time is 15-35 min; the polymerization time is 4-8 h, and the polymerization temperature is 75- 95℃; drying temperature is 90~140℃;

步骤(4)中的氢氧化钠乙醇溶液的浓度为1~2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:1~3;所述加热回流的时间为9~11h,干燥温度为90~110℃。The concentration of the sodium hydroxide ethanol solution in step (4) is 1~2mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1:1~3; the time of the heating and refluxing is 9~2 mol/L. 11h, drying temperature is 90~110 ℃.

本发明的原理如下:The principle of the present invention is as follows:

本发明采用以1,7-乙烯基-苝酰亚胺衍生物作为交联点制备聚丙烯酸酯微球,后将聚丙烯酸酯水解为聚丙烯酸得到聚丙烯酸微球。该聚丙烯酸微球具有多孔结构,比表面积大,裸露出可反应羧基多。由于聚丙烯纤维结构中没有极性基团,纤维结构紧密,很难染色。由于许多染料带有阳离子基团,阳离子基团与基体中如果带有羧基基团,羧基与阳离子之间会产生静电相互作用,增加了阳离子染料与基体的相互作用。因此,本发明在聚丙烯纤维生产的过程中加入具有羧基基团的聚丙烯酸微球,在聚丙烯纤维中引入了极性羧基基团,增强纤维与阳离子染料的结合。且聚丙烯酸微球是多孔的,从微球结构上增加了裸露出的极性羧基基团,进一步增加染座。同时,由于聚丙烯与聚丙烯酸微球中的聚丙烯酸主链结构相似,聚丙烯酸微球在聚丙烯切片和聚丙烯纤维中分散良好(分散主要是微球基体和纤维基体间的问题,交联剂的影响很小),对于纤维力学性能影响较小。The invention adopts 1,7-vinyl-perylene imide derivative as a cross-linking point to prepare polyacrylate microspheres, and then hydrolyzes the polyacrylate into polyacrylic acid to obtain polyacrylic acid microspheres. The polyacrylic acid microspheres have a porous structure, a large specific surface area, and many exposed reactive carboxyl groups. Since there are no polar groups in the polypropylene fiber structure, the fiber structure is tight and difficult to dye. Since many dyes have cationic groups, if there are carboxyl groups in the cationic groups and the matrix, there will be electrostatic interactions between the carboxyl groups and the cations, which increases the interaction between the cationic dyes and the matrix. Therefore, in the present invention, polyacrylic acid microspheres with carboxyl groups are added in the process of producing polypropylene fibers, and polar carboxyl groups are introduced into polypropylene fibers to enhance the combination of fibers and cationic dyes. And the polyacrylic acid microspheres are porous, and the exposed polar carboxyl groups are added from the microsphere structure, which further increases the dye base. At the same time, due to the similarity of the main chain structure of polyacrylic acid in polypropylene and polyacrylic acid microspheres, polyacrylic acid microspheres are well dispersed in polypropylene chips and polypropylene fibers (dispersion is mainly a problem between the microsphere matrix and the fiber matrix, cross-linking The effect of the agent is small), and the effect on the mechanical properties of the fiber is small.

苝酰亚胺衍生物同时还具有荧光性能,且由于加入的苝酰亚胺衍生物的量远远小于微球上羧基的量,所以苝酰亚胺本身的颜色会对深色可染纤维颜色影响较小。并且因为苝酰亚胺的发射波长与特定阳离子染色剂吸收波长的补色波长有重合,有利于得到颜色深且艳丽的荧光增亮深色可染聚丙烯纤维可以使得该纤维染色更鲜艳明亮,可媲美荧光染料的作用。以此可以得到可深染并且具有高亮鲜艳色彩的聚丙烯纤维。The peryleneimide derivatives also have fluorescent properties, and since the amount of the peryleneimide derivatives added is far less than the amount of carboxyl groups on the microspheres, the color of the peryleneimide itself will affect the color of dark dyeable fibers. Less affected. And because the emission wavelength of peryleneimide coincides with the complementary wavelength of the absorption wavelength of a specific cationic dye, it is beneficial to obtain a deep and bright fluorescent brightening dark dyeable polypropylene fiber, which can make the fiber dyeing more bright and bright, and can be Comparable to the effect of fluorescent dyes. In this way, deep-dyeable polypropylene fibers with bright and vivid colors can be obtained.

有益效果:Beneficial effects:

(1)本发明一种荧光增亮深色可染聚丙烯纤维,可深染并且具有高亮鲜艳色彩;(1) a fluorescent brightening dark dyeable polypropylene fiber of the present invention can be deep dyed and has bright and bright colors;

(2)本发明的一种荧光增亮深色可染聚丙烯纤维的制备方法,不需要使用荧光染色剂,可选择普通阳离子染色剂得到颜色明亮鲜艳的聚丙烯纤维。(2) The preparation method of the fluorescent brightening dark dyeable polypropylene fiber of the present invention does not require the use of fluorescent dyes, and ordinary cationic dyes can be selected to obtain bright and bright polypropylene fibers.

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1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000061
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入2-乙基己胺
Figure BDA0002581717870000062
(4.5mmol),冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000061
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. 2-ethylhexylamine was then added
Figure BDA0002581717870000062
(4.5 mmol), glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000063
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were pipetted with a pipette.
Figure BDA0002581717870000063
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例2Example 2

一种1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000071
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入
Figure BDA0002581717870000072
(4.5mmol),R为异丁基,冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000071
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. then join
Figure BDA0002581717870000072
(4.5 mmol), R is isobutyl, glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000073
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were pipetted with a pipette.
Figure BDA0002581717870000073
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例3Example 3

一种1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000081
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入2-乙基己胺
Figure BDA0002581717870000082
(4.5mmol),冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000081
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. 2-ethylhexylamine was then added
Figure BDA0002581717870000082
(4.5 mmol), glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000083
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were removed with a pipette
Figure BDA0002581717870000083
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例4Example 4

一种1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000084
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入、
Figure BDA0002581717870000085
(4.5mmol),冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000084
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. then join,
Figure BDA0002581717870000085
(4.5 mmol), glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000091
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were removed with a pipette
Figure BDA0002581717870000091
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例5Example 5

一种1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000092
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入2-乙基己胺
Figure BDA0002581717870000093
(4.5mmol),冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000092
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. 2-ethylhexylamine was then added
Figure BDA0002581717870000093
(4.5 mmol), glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000101
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were pipetted with a pipette.
Figure BDA0002581717870000101
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例6Example 6

一种1,7-乙烯基-苝酰亚胺衍生物的制备方法如下:A preparation method of 1,7-vinyl-perylene imide derivative is as follows:

酰亚胺位大体积取代基接入方法:Access method of bulky substituent at imide position:

在250mL三颈烧瓶中加入粗产物PTCDA-Br

Figure BDA0002581717870000102
(0.50g,0.91mmol)和1-甲基-2-吡咯烷酮(NMP)15.00mL并将固体溶解后在25℃下搅拌1h。随后加入
Figure BDA0002581717870000103
(4.5mmol),R为异丁基,冰醋酸(16mL,140mmol)。在氮气保护下升温至85℃,继续反应7h。反应结束后,冷却至室温,然后向其中加入120.00mL甲醇,隔夜搅拌。抽滤,得到红色固体,真空干燥24h,85℃,柱层析后得到1,7-Br-PDI-X。Add the crude product PTCDA-Br to a 250mL three-necked flask
Figure BDA0002581717870000102
(0.50 g, 0.91 mmol) and 15.00 mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25° C. for 1 h. then join
Figure BDA0002581717870000103
(4.5 mmol), R is isobutyl, glacial acetic acid (16 mL, 140 mmol). The temperature was raised to 85°C under nitrogen protection, and the reaction was continued for 7h. After the reaction was completed, the mixture was cooled to room temperature, 120.00 mL of methanol was added thereto, and the mixture was stirred overnight. Suction filtration to obtain a red solid, vacuum-dried for 24 h at 85 °C, and 1,7-Br-PDI-X was obtained after column chromatography.

湾位双键取代基接入方法:Bay position double bond substituent access method:

取1,7-Br-PDI-X(77.4mg,0.10mmol)于50mL茄形烧瓶中,加入HPLC级THF(20mL)并搅拌使其充分溶解,45℃加热,此时体系呈橙黄色。随后向体系中加入无水碳酸钾(55.4mg,0.40mmol)、18-冠-6-醚(105.73mg,0.40mmol),并用移液枪移取

Figure BDA0002581717870000104
(0.50mmol)添加到体系中,整个反应过程中密切关注体系颜色变化并间隔15min进行一次TLC点板观察。Take 1,7-Br-PDI-X (77.4 mg, 0.10 mmol) in a 50 mL eggplant-shaped flask, add HPLC grade THF (20 mL) and stir to fully dissolve, and heat at 45°C, at this time, the system is orange-yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40 mmol) and 18-crown-6-ether (105.73 mg, 0.40 mmol) were added to the system, and were removed with a pipette
Figure BDA0002581717870000104
(0.50 mmol) was added to the system, and the color change of the system was closely monitored during the entire reaction process and a TLC spot plate observation was carried out at intervals of 15 min.

反应开始15min后体系变为橙红色,30min后体系变为鲜红色,45min后变为深红色,最后变为紫红色,1h时TLC点板显示原料点消失,继续反应2h后停止反应。旋干溶剂后用三氯甲烷和水对产物进行萃取,用水移除体系中的无水碳酸钾、18-冠-6-醚以及未反应的3-丁烯-1-醇。分液漏斗中下层为有机相,上层为水相,有机相呈紫红色,水相呈粉淡色。将萃取后的三氯甲烷溶液旋干,得到1,7-乙烯基-苝酰亚胺衍生物粗产物后柱层析得到产物1,7-乙烯基-苝酰亚胺衍生物。The system turned orange-red after 15 min of the reaction, bright red after 30 min, dark red after 45 min, and finally purple-red, and the TLC dot plate showed that the starting material disappeared at 1 h, and the reaction was stopped after continuing the reaction for 2 h. After spin-drying the solvent, the product was extracted with chloroform and water, and the anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system were removed with water. The middle and lower layers of the separatory funnel are the organic phase, the upper layer is the aqueous phase, the organic phase is purple-red, and the aqueous phase is pinkish. The extracted chloroform solution was spin-dried to obtain a crude product of 1,7-vinyl-peryleneimide derivative, and the product 1,7-vinyl-peryleneimide derivative was obtained by column chromatography.

实施例7Example 7

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将月桂酸钾和去离子水在温度T1(35℃)下混合形成体系I;-(1.1) Mixing potassium laurate and deionized water at temperature T1 (35°C) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例1制得)溶于甲苯中,再加入到体系I中在温度T2(75℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为4wt%,1,7-乙烯基-(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 1) were first dissolved in toluene, then added to system I and mixed at temperature T2 (75°C) System II is obtained; in system II, the content of methyl acrylate is 4wt%, 1,7-vinyl-

苝酰亚胺衍生物的含量为13.6wt%,甲苯的含量为10wt%,月桂酸钾的含量为0.4wt%;The content of the perylene imide derivative is 13.6 wt%, the content of toluene is 10 wt%, and the content of potassium laurate is 0.4 wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.06%,聚合时间为4h,聚合温度为75℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction of acrylate dispersion liquid is 0.06%, the polymerization time is 4h, and the polymerization temperature is 75℃;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为1mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:1;加热回流的时间为9h,干燥温度为90℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 1mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:1; the heating and refluxing time is 9h, and the drying temperature is 90°C;

制得的聚丙烯酸微球的平均直径为150nm,平均孔径为10nm,孔隙率为35%,荧光量子产率为95%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 150 nm, an average pore diameter of 10 nm, a porosity of 35%, and a fluorescence quantum yield of 95%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为150r/min,螺杆温度为200℃;所述母粒中,按重量份数计,聚丙烯为80份,聚丙烯酸微球为40份;纺丝过程中,母粒的添加量为7wt%;所述聚丙烯的分子量为146200,分子量分布指数为2.5,熔体指数为10g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly, and dried, and then put into a twin-screw extruder for extrusion to obtain a masterbatch; finally, the masterbatch is added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 150 r/min, and the screw temperature is 200 ° C; in the masterbatch, in parts by weight, polypropylene It is 80 parts, and the polyacrylic acid microspheres are 40 parts; during the spinning process, the addition amount of the masterbatch is 7wt%; the molecular weight of the polypropylene is 146200, the molecular weight distribution index is 2.5, and the melt index is 10g/10min;

纺丝的工艺参数为:熔体输送管道的温度200℃,熔体过滤器温度220℃,纺丝箱体的温度220℃,侧吹风风速0.5m/s,风温13℃,热辊温度100℃,纺丝速度2500m/min,卷绕角7°。The spinning process parameters are: the temperature of the melt conveying pipe is 200°C, the temperature of the melt filter is 220°C, the temperature of the spinning box is 220°C, the side blowing wind speed is 0.5m/s, the air temperature is 13°C, and the temperature of the hot roller is 100°C. ℃, spinning speed 2500m/min, winding angle 7°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为14:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为95%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.09cN/dtex,断裂伸长率为26.6%,熔点为150℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为65%;染色K/S值为11.41;染色色牢度为:皂洗牢度:原样变色4级、白布沾色3级,摩擦牢度:干4级、湿3级,汗渍色牢度:原样变色4级、白布沾色4级,升华色牢度:原样变色4级,白布沾色4级;织物反射率为95%,染色织物的色度坐标值为:x=0.45,y=0.42。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic acid structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 14:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 95%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fiber is 3.09cN/dtex, the breaking elongation is 26.6%, and the melting point is 150℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fiber are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 65%; the K/S value of dyeing is 11.41; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 3, rubbing fastness: dry level 4, wet level 3 , Color fastness to perspiration: 4 grades of discoloration as original, 4 grades of white cloth staining, sublimation color fastness: 4 grades of original discoloration, 4 grades of white cloth staining; fabric reflectivity is 95%, and the chromaticity coordinates of dyed fabrics are: x = 0.45, y = 0.42.

实施例8Example 8

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将月桂酸钾和去离子水在温度T1(48℃)下混合形成体系I;-(1.1) Mix potassium laurate and deionized water at temperature T1 (48°C) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例4制得)溶于二甲苯中,再加入到体系I中在温度T2(84℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为5wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为14.6wt%,二甲苯的含量为9wt%,月桂酸钾的含量为0.4wt%;(1.2) Methyl acrylate and 1,7-vinyl-peryleneimide derivative (prepared from Example 4) were first dissolved in xylene, and then added to system I at temperature T2 (84°C) Mixing to obtain system II; in system II, the content of methyl acrylate is 5 wt %, the content of 1,7-vinyl-peryleneimide derivative is 14.6 wt %, the content of xylene is 9 wt %, and the content of potassium laurate is 9 wt %. The content is 0.4wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.07%,聚合时间为5h,聚合温度为84℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.07% of the acrylate dispersion, the polymerization time is 5h, and the polymerization temperature is 84°C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为1mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:1;加热回流的时间为9h,干燥温度为101℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 1mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:1; the heating and refluxing time is 9h, and the drying temperature is 101°C;

制得的聚丙烯酸微球的平均直径为207nm,平均孔径为27nm,孔隙率为50%,荧光量子产率为97%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The obtained polyacrylic acid microspheres have an average diameter of 207 nm, an average pore diameter of 27 nm, a porosity of 50%, and a fluorescence quantum yield of 97%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为159r/min,螺杆温度为208℃;所述母粒中,按重量份数计,聚丙烯为117份,聚丙烯酸微球为41份;纺丝过程中,母粒的添加量为7wt%;所述聚丙烯的分子量为146300,分子量分布指数为2.6,熔体指数为17g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 159r/min, and the screw temperature is 208°C; in the masterbatch, in parts by weight, polypropylene It is 117 parts, and the polyacrylic acid microsphere is 41 parts; during the spinning process, the addition amount of the masterbatch is 7wt%; the molecular weight of the polypropylene is 146300, the molecular weight distribution index is 2.6, and the melt index is 17g/10min;

纺丝的工艺参数为:熔体输送管道的温度241℃,熔体过滤器温度220℃,纺丝箱体的温度233℃,侧吹风风速0.5m/s,风温14℃,热辊温度114℃,纺丝速度2569m/min,卷绕角7°。The spinning process parameters are: the temperature of the melt conveying pipe is 241°C, the temperature of the melt filter is 220°C, the temperature of the spinning box is 233°C, the side blowing air speed is 0.5m/s, the air temperature is 14°C, and the temperature of the hot roller is 114°C. ℃, spinning speed 2569m/min, winding angle 7°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为16:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为97%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.2cN/dtex,断裂伸长率为24.36%,熔点为179℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为67%;染色K/S值为11.56;染色色牢度为:皂洗牢度:原样变色4级、白布沾色3级,摩擦牢度:干4级、湿4级,汗渍色牢度:原样变色4级、白布沾色4级,升华色牢度:原样变色4级,白布沾色4级;织物反射率为138%,染色织物的色度坐标值为:x=0.46,y=0.47。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 16:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 97%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fibers is 3.2cN/dtex, the elongation at break is 24.36%, and the melting point is 179℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fibers are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 67%; the dyeing K/S value is 11.56; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 3, rubbing fastness: dry level 4, wet level 4 , Color fastness to perspiration: the original discoloration level 4, white cloth staining level 4, sublimation color fastness: the original color change level 4, white cloth staining level 4; the fabric reflectivity is 138%, and the chromaticity coordinates of the dyed fabric are: x = 0.46, y = 0.47.

实施例9Example 9

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将月桂酸钾和去离子水在温度T1(40℃)下混合形成体系I;-(1.1) Mix potassium laurate and deionized water at temperature T1 (40°C) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例2制得)溶于甲苯中,再加入到体系I中在温度T2(80℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为4wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为12.5wt%,甲苯的含量为9wt%,月桂酸钾的含量为0.5wt%;(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 2) were first dissolved in toluene, and then added to system I and mixed at temperature T2 (80°C) System II is obtained; in system II, the content of methyl acrylate is 4wt%, the content of 1,7-vinyl-peryleneimide derivative is 12.5wt%, the content of toluene is 9wt%, and the content of potassium laurate is 0.5wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.06%,聚合时间为8h,聚合温度为78℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.06% of the acrylate dispersion, the polymerization time is 8h, and the polymerization temperature is 78°C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为1mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:1.2;加热回流的时间为9h,干燥温度为106℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 1mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:1.2; the heating and refluxing time is 9h, and the drying temperature is 106°C;

制得的聚丙烯酸微球的平均直径为235nm,平均孔径为19nm,孔隙率为53%,荧光量子产率为99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 235 nm, an average pore diameter of 19 nm, a porosity of 53%, and a fluorescence quantum yield of 99%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为200r/min,螺杆温度为202℃;所述母粒中,按重量份数计,聚丙烯为120份,聚丙烯酸微球为51份;纺丝过程中,母粒的添加量为7wt%;所述聚丙烯的分子量为148800,分子量分布指数为2.8,熔体指数为18g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 200 r/min, and the screw temperature is 202 ° C; in the masterbatch, in parts by weight, polypropylene It is 120 parts, and the polyacrylic acid microsphere is 51 parts; during the spinning process, the addition amount of the masterbatch is 7wt%; the molecular weight of the polypropylene is 148800, the molecular weight distribution index is 2.8, and the melt index is 18g/10min;

纺丝的工艺参数为:熔体输送管道的温度205℃,熔体过滤器温度228℃,纺丝箱体的温度257℃,侧吹风风速0.6m/s,风温15℃,热辊温度107℃,纺丝速度2584m/min,卷绕角7°。The spinning process parameters are: the temperature of the melt conveying pipe is 205°C, the temperature of the melt filter is 228°C, the temperature of the spinning box is 257°C, the wind speed of the side blowing is 0.6m/s, the air temperature is 15°C, and the temperature of the hot roller is 107°C. ℃, spinning speed 2584m/min, winding angle 7°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为20:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为96%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.46cN/dtex,断裂伸长率为19.45%,熔点为172℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为95%;染色K/S值为11.48;染色色牢度为:皂洗牢度:原样变色4级、白布沾色5级,摩擦牢度:干5级、湿5级,汗渍色牢度:原样变色4级、白布沾色5级,升华色牢度:原样变色4级,白布沾色5级;织物反射率为140%,染色织物的色度坐标值为:x=0.48,y=0.52。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 20:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 96%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fiber is 3.46cN/dtex, the elongation at break is 19.45%, and the melting point is 172 °C; the dyeing properties of fluorescent brightening dark dyeable polypropylene fiber are: dyeing with cationic yellow X-8GL at 125 °C , the dye uptake rate is 95%; the dyeing K/S value is 11.48; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 5, rubbing fastness: dry level 5, wet level 5 , Color fastness to perspiration: 4 grades of discoloration as it is, 5 grades of white cloth staining, sublimation color fastness: 4 grades of original discoloration, 5 grades of white cloth staining; fabric reflectivity is 140%, and the chromaticity coordinates of dyed fabrics are: x = 0.48, y = 0.52.

实施例10Example 10

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将十二烷基硫酸钠和去离子水在温度T1(39℃)下混合形成体系I;(1.1) Sodium dodecyl sulfate and deionized water are mixed at temperature T1 (39° C.) to form system I;

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例6制得)溶于甲苯中,再加入到体系I中在温度T2(93℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为5wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为14.5wt%,甲苯的含量为10wt%,十二烷基硫酸钠的含量为0.5wt%;(1.2) First, methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 6) were dissolved in toluene, and then added to system I and mixed at temperature T2 (93° C.) System II is obtained; in system II, the content of methyl acrylate is 5wt%, the content of 1,7-vinyl-peryleneimide derivative is 14.5wt%, the content of toluene is 10wt%, sodium lauryl sulfate is The content is 0.5wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.08%,聚合时间为8h,聚合温度为81℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.08% of the acrylate dispersion, the polymerization time is 8h, and the polymerization temperature is 81°C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为1.5mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:2;加热回流的时间为9h,干燥温度为105℃;(1.4) Mix polyacrylate microspheres with sodium hydroxide ethanol solution, and cool, filter and dry after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 1.5mol/L, and the polyacrylate The volume ratio of microspheres to sodium hydroxide ethanol solution is 1:2; the heating and refluxing time is 9h, and the drying temperature is 105°C;

制得的聚丙烯酸微球的平均直径为201nm,平均孔径为21nm,孔隙率为48%,荧光量子产率为98%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 201 nm, an average pore diameter of 21 nm, a porosity of 48%, and a fluorescence quantum yield of 98%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为170r/min,螺杆温度为206℃;所述母粒中,按重量份数计,聚丙烯为87份,聚丙烯酸微球为57份;纺丝过程中,母粒的添加量为8wt%;所述聚丙烯的分子量为149200,分子量分布指数为3.2,熔体指数为12g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 170r/min, and the screw temperature is 206°C; in the masterbatch, in parts by weight, polypropylene It is 87 parts, and the polyacrylic acid microsphere is 57 parts; during the spinning process, the addition amount of the masterbatch is 8wt%; the molecular weight of the polypropylene is 149200, the molecular weight distribution index is 3.2, and the melt index is 12g/10min;

纺丝的工艺参数为:熔体输送管道的温度205℃,熔体过滤器温度246℃,纺丝箱体的温度231℃,侧吹风风速0.6m/s,风温17℃,热辊温度108℃,纺丝速度2790m/min,卷绕角8°。The spinning process parameters are: the temperature of the melt conveying pipe is 205°C, the temperature of the melt filter is 246°C, the temperature of the spinning box is 231°C, the side blowing wind speed is 0.6m/s, the air temperature is 17°C, and the temperature of the hot roller is 108°C. ℃, spinning speed 2790m/min, winding angle 8°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为21.5:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为98%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.9cN/dtex,断裂伸长率为17.73%,熔点为169℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为71%;染色K/S值为12.70;染色色牢度为:皂洗牢度:原样变色4级、白布沾色4级,摩擦牢度:干4级、湿4级,汗渍色牢度:原样变色4级、白布沾色4级,升华色牢度:原样变色4级,白布沾色4级;织物反射率为107%,染色织物的色度坐标值为:x=0.5,y=0.52。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 21.5:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 98%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fiber is 3.9cN/dtex, the elongation at break is 17.73%, and the melting point is 169 ℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fiber are: dyeing with cationic yellow X-8GL at 125 ℃ , the dye uptake rate is 71%; the dyeing K/S value is 12.70; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 4, rubbing fastness: dry level 4, wet level 4 , Color fastness to perspiration: 4 grades of discoloration as original, 4 grades of white cloth staining, sublimation color fastness: 4 grades of original discoloration, 4 grades of white cloth staining; fabric reflectance is 107%, and the chromaticity coordinates of dyed fabrics are: x = 0.5, y = 0.52.

实施例11Example 11

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将十二烷基硫酸钠和去离子水在温度T1(55℃)下混合形成体系I;-(1.1) Sodium lauryl sulfate and deionized water are mixed at temperature T1 (55° C.) to form System I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例3制得)溶于甲苯中,再加入到体系I中在温度T2(93℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为6wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为10.4wt%,甲苯的含量为8wt%,十二烷基硫酸钠的含量为0.6wt%;(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 3) were first dissolved in toluene, and then added to system I and mixed at temperature T2 (93°C) System II is obtained; in system II, the content of methyl acrylate is 6wt%, the content of 1,7-vinyl-peryleneimide derivative is 10.4wt%, the content of toluene is 8wt%, sodium lauryl sulfate is The content is 0.6wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.08%,聚合时间为7h,聚合温度为89℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.08% of the acrylate dispersion, the polymerization time is 7h, and the polymerization temperature is 89°C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:2.2;加热回流的时间为11h,干燥温度为94℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 2mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:2.2; the heating and refluxing time is 11h, and the drying temperature is 94°C;

制得的聚丙烯酸微球的平均直径为290nm,平均孔径为17nm,孔隙率为55%,荧光量子产率为98%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The obtained polyacrylic acid microspheres have an average diameter of 290 nm, an average pore diameter of 17 nm, a porosity of 55%, and a fluorescence quantum yield of 98%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为172r/min,螺杆温度为202℃;所述母粒中,按重量份数计,聚丙烯为94份,聚丙烯酸微球为57份;纺丝过程中,母粒的添加量为7wt%;所述聚丙烯的分子量为150000,分子量分布指数为3.1,熔体指数为12g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 172r/min, and the screw temperature is 202°C; in the masterbatch, in parts by weight, polypropylene 94 parts, and 57 parts of polyacrylic acid microspheres; during the spinning process, the addition amount of masterbatch is 7wt%; the molecular weight of the polypropylene is 150000, the molecular weight distribution index is 3.1, and the melt index is 12g/10min;

纺丝的工艺参数为:熔体输送管道的温度237℃,熔体过滤器温度238℃,纺丝箱体的温度221℃,侧吹风风速0.6m/s,风温13℃,热辊温度106℃,纺丝速度2688m/min,卷绕角8°。The process parameters of spinning are: the temperature of the melt conveying pipe is 237°C, the temperature of the melt filter is 238°C, the temperature of the spinning box is 221°C, the side blowing wind speed is 0.6m/s, the air temperature is 13°C, and the temperature of the hot roller is 106°C. ℃, spinning speed 2688m/min, winding angle 8°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为14.5:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为98%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.6cN/dtex,断裂伸长率为25.12%,熔点为176℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为90%;染色K/S值为11.89;染色色牢度为:皂洗牢度:原样变色4级、白布沾色5级,摩擦牢度:干5级、湿4级,汗渍色牢度:原样变色4级、白布沾色5级,升华色牢度:原样变色5级,白布沾色4级;织物反射率为96%,染色织物的色度坐标值为:x=0.45,y=0.49。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 14.5:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 98%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fibers is 3.6cN/dtex, the elongation at break is 25.12%, and the melting point is 176℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fibers are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 90%; the dyeing K/S value is 11.89; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 5, rubbing fastness: dry level 5, wet level 4 , Color fastness to perspiration: the original discoloration level 4, white cloth staining level 5, sublimation color fastness: the original color change level 5, white cloth staining level 4; the fabric reflectivity is 96%, and the chromaticity coordinates of the dyed fabric are: x = 0.45, y = 0.49.

实施例12Example 12

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将丁二酸二辛酯磺酸钠和去离子水在温度T1(38℃)下混合形成体系I;-(1.1) Mixing sodium dioctyl succinate sulfonate and deionized water at temperature T1 (38° C.) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例2制得)溶于甲苯中,再加入到体系I中在温度T2(94℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为6wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为11.4wt%,甲苯的含量为7wt%,丁二酸二辛酯磺酸钠的含量为0.6wt%;(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 2) were first dissolved in toluene, and then added to system I and mixed at temperature T2 (94°C) System II is obtained; in system II, the content of methyl acrylate is 6 wt %, the content of 1,7-vinyl-perylene imide derivative is 11.4 wt %, the content of toluene is 7 wt %, and the content of dioctyl succinate is 6 wt %. The content of sodium sulfonate is 0.6wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.12%,聚合时间为4h,聚合温度为80℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.12% of the acrylate dispersion, the polymerization time is 4h, and the polymerization temperature is 80 °C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:2.8;加热回流的时间为11h,干燥温度为96℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 2mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:2.8; the heating and refluxing time is 11h, and the drying temperature is 96°C;

制得的聚丙烯酸微球的平均直径为288nm,平均孔径为25nm,孔隙率为47%,荧光量子产率为97%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 288 nm, an average pore diameter of 25 nm, a porosity of 47%, and a fluorescence quantum yield of 97%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为188r/min,螺杆温度为216℃;所述母粒中,按重量份数计,聚丙烯为96份,聚丙烯酸微球为40份;纺丝过程中,母粒的添加量为7wt%;所述聚丙烯的分子量为149500,分子量分布指数为4,熔体指数为16g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly, and dried, and then put into a twin-screw extruder for extrusion to obtain a masterbatch; finally, the masterbatch is added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 188r/min, and the screw temperature is 216°C; in the masterbatch, in parts by weight, polypropylene It is 96 parts, and the polyacrylic acid microsphere is 40 parts; during the spinning process, the addition amount of the masterbatch is 7wt%; the molecular weight of the polypropylene is 149500, the molecular weight distribution index is 4, and the melt index is 16g/10min;

纺丝的工艺参数为:熔体输送管道的温度237℃,熔体过滤器温度229℃,纺丝箱体的温度241℃,侧吹风风速0.7m/s,风温15℃,热辊温度116℃,纺丝速度2707m/min,卷绕角7°。The spinning process parameters are: the temperature of the melt conveying pipe is 237°C, the temperature of the melt filter is 229°C, the temperature of the spinning box is 241°C, the side blowing air speed is 0.7m/s, the air temperature is 15°C, and the temperature of the hot roller is 116°C. ℃, spinning speed 2707m/min, winding angle 7°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为14.3:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为96%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.8cN/dtex,断裂伸长率为25.98%,熔点为153℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为66%;染色K/S值为12.34;染色色牢度为:皂洗牢度:原样变色4级、白布沾色3级,摩擦牢度:干4级、湿3级,汗渍色牢度:原样变色4级、白布沾色4级,升华色牢度:原样变色4级,白布沾色4级;织物反射率为115%,染色织物的色度坐标值为:x=0.49,y=0.46。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic acid structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 14.3:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 96%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fibers is 3.8cN/dtex, the elongation at break is 25.98%, and the melting point is 153℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fibers are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 66%; the dyeing K/S value is 12.34; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 3, rubbing fastness: dry level 4, wet level 3 , Color fastness to perspiration: 4 grades of discoloration as it is, 4 grades of white cloth staining, sublimation color fastness: 4 grades of original discoloration, 4 grades of white cloth staining; fabric reflectivity is 115%, and the chromaticity coordinates of dyed fabrics are: x = 0.49, y = 0.46.

实施例13Example 13

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将丁二酸二辛酯磺酸钠和去离子水在温度T1(36℃)下混合形成体系I;-(1.1) Mixing sodium dioctyl succinate sulfonate and deionized water at temperature T1 (36° C.) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例5制得)溶于二甲苯中,再加入到体系I中在温度T2(92℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为5wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为15wt%,二甲苯的含量为6wt%,丁二酸二辛酯磺酸钠的含量为0.7wt%;(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 5) were first dissolved in xylene, and then added to system I at temperature T2 (92°C) Mixing to obtain system II; in system II, the content of methyl acrylate is 5 wt %, the content of 1,7-vinyl-perylene imide derivative is 15 wt %, the content of xylene is 6 wt %, and the content of dioctyl succinate is 6 wt %. The content of sodium ester sulfonate is 0.7wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.07%,聚合时间为7h,聚合温度为93℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction of acrylic ester dispersion is 0.07%, the polymerization time is 7h, and the polymerization temperature is 93℃;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:3;加热回流的时间为11h,干燥温度为109℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 2mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:3; the heating and refluxing time is 11h, and the drying temperature is 109°C;

制得的聚丙烯酸微球的平均直径为290nm,平均孔径为19nm,孔隙率为50%,荧光量子产率为99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 290 nm, an average pore diameter of 19 nm, a porosity of 50%, and a fluorescence quantum yield of 99%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为150r/min,螺杆温度为217℃;所述母粒中,按重量份数计,聚丙烯为108份,聚丙烯酸微球为44份;纺丝过程中,母粒的添加量为8wt%;所述聚丙烯的分子量为150200,分子量分布指数为3.7,熔体指数为17g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 150 r/min, and the screw temperature is 217 ° C; in the masterbatch, in parts by weight, polypropylene It is 108 parts, and the polyacrylic acid microspheres are 44 parts; during the spinning process, the addition amount of the masterbatch is 8wt%; the molecular weight of the polypropylene is 150200, the molecular weight distribution index is 3.7, and the melt index is 17g/10min;

纺丝的工艺参数为:熔体输送管道的温度243℃,熔体过滤器温度241℃,纺丝箱体的温度239℃,侧吹风风速0.7m/s,风温14℃,热辊温度117℃,纺丝速度2748m/min,卷绕角7°。The spinning process parameters are: the temperature of the melt conveying pipe is 243°C, the temperature of the melt filter is 241°C, the temperature of the spinning box is 239°C, the wind speed of the side blower is 0.7m/s, the air temperature is 14°C, and the temperature of the hot roller is 117°C. ℃, spinning speed 2748m/min, winding angle 7°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为15:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为95%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.87cN/dtex,断裂伸长率为24.3%,熔点为164℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为74%;染色K/S值为12.23;染色色牢度为:皂洗牢度:原样变色4级、白布沾色4级,摩擦牢度:干4级、湿4级,汗渍色牢度:原样变色4级、白布沾色4级,升华色牢度:原样变色4级,白布沾色4级;织物反射率为105%,染色织物的色度坐标值为:x=0.49,y=0.42。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 15:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 95%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fibers is 3.87cN/dtex, the elongation at break is 24.3%, and the melting point is 164℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fibers are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 74%; the dyeing K/S value is 12.23; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 4, rubbing fastness: dry level 4, wet level 4 , Color fastness to perspiration: 4 grades of discoloration as original, 4 grades of white cloth staining, sublimation color fastness: 4 grades of original discoloration, 4 grades of white cloth staining; fabric reflectivity is 105%, and the chromaticity coordinates of dyed fabrics are: x = 0.49, y = 0.42.

实施例14Example 14

一种荧光增亮深色可染聚丙烯纤维的制备方法,步骤如下:A preparation method of fluorescent brightening dark dyeable polypropylene fiber, the steps are as follows:

(1)制备聚丙烯酸微球:(1) Preparation of polyacrylic acid microspheres:

(1.1)将丁二酸二辛酯磺酸钠和去离子水在温度T1(55℃)下混合形成体系I;-(1.1) Mixing sodium dioctyl succinate sulfonate and deionized water at temperature T1 (55°C) to form system I;-

(1.2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物(由实施例6制得)溶于二甲苯中,再加入到体系I中在温度T2(95℃)下混合得到体系II;体系II中,丙烯酸甲酯的含量为6wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为9wt%,二甲苯的含量为9.3wt%,丁二酸二辛酯磺酸钠的含量为0.7wt%;(1.2) Methyl acrylate and 1,7-vinyl-perylene imide derivative (prepared from Example 6) were first dissolved in xylene, and then added to system I at temperature T2 (95°C) Mixing to obtain system II; in system II, the content of methyl acrylate is 6wt%, the content of 1,7-vinyl-peryleneimide derivative is 9wt%, the content of xylene is 9.3wt%, the content of succinic acid di The content of sodium octyl sulfonate is 0.7wt%;

(1.3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;其中,过硫酸钾的质量分数为丙烯酸酯分散液的0.12%,聚合时间为8h,聚合温度为95℃;(1.3) firstly adding potassium persulfate in system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein, potassium persulfate The mass fraction is 0.12% of the acrylate dispersion, the polymerization time is 8h, and the polymerization temperature is 95°C;

(1.4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球;其中,氢氧化钠乙醇溶液的浓度为2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:3;加热回流的时间为11h,干燥温度为110℃;(1.4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, and cooling, filtering and drying after heating to reflux to obtain polyacrylic acid microspheres; wherein, the concentration of sodium hydroxide ethanol solution is 2mol/L, and the polyacrylate microspheres are The volume ratio of the ball to the sodium hydroxide ethanol solution is 1:3; the heating and refluxing time is 11h, and the drying temperature is 110°C;

制得的聚丙烯酸微球的平均直径为300nm,平均孔径为30nm,孔隙率为55%,荧光量子产率为99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;The prepared polyacrylic acid microspheres have an average diameter of 300 nm, an average pore diameter of 30 nm, a porosity of 55%, and a fluorescence quantum yield of 99%. Under the excitation at a wavelength of 440 to 460 nm, 1,7- Characteristic fluorescence emission peaks of vinyl-peryleneimide derivatives;

(2)制备荧光增亮深色可染聚丙烯纤维:(2) Preparation of fluorescent brightening dark dyeable polypropylene fibers:

先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;其中,双螺杆挤出机的螺杆转速为200r/min,螺杆温度为220℃;所述母粒中,按重量份数计,聚丙烯为120份,聚丙烯酸微球为60份;纺丝过程中,母粒的添加量为8wt%;所述聚丙烯的分子量为150700,分子量分布指数为4.5,熔体指数为20g/10min;First, the polypropylene and polyacrylic acid microspheres are mixed uniformly and dried, and then put into a twin-screw extruder for extrusion to obtain masterbatches; finally, the masterbatches are added to the production equipment for polypropylene melt spinning. Spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; wherein, the screw speed of the twin-screw extruder is 200 r/min, and the screw temperature is 220 ° C; in the masterbatch, in parts by weight, polypropylene It is 120 parts, and the polyacrylic acid microspheres are 60 parts; during the spinning process, the addition amount of the masterbatch is 8wt%; the molecular weight of the polypropylene is 150700, the molecular weight distribution index is 4.5, and the melt index is 20g/10min;

纺丝的工艺参数为:熔体输送管道的温度260℃,熔体过滤器温度260℃,纺丝箱体的温度260℃,侧吹风风速0.7m/s,风温17℃,热辊温度120℃,纺丝速度2800m/min,卷绕角8°。The spinning process parameters are: the temperature of the melt conveying pipe is 260°C, the temperature of the melt filter is 260°C, the temperature of the spinning box is 260°C, the side blowing air speed is 0.7m/s, the air temperature is 17°C, and the temperature of the hot roller is 120°C. ℃, spinning speed 2800m/min, winding angle 8°.

最终制得的荧光增亮深色可染聚丙烯纤维中1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为21:125;荧光增亮深色可染聚丙烯纤维的荧光量子产率为99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;荧光增亮深色可染聚丙烯纤维的断裂强度为3.5cN/dtex,断裂伸长率为20.8%,熔点为180℃;荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为95%;染色K/S值为12.70;染色色牢度为:皂洗牢度:原样变色4级、白布沾色5级,摩擦牢度:干5级、湿4级,汗渍色牢度:原样变色5级、白布沾色5级,升华色牢度:原样变色5级,白布沾色5级;织物反射率为145%,染色织物的色度坐标值为:x=0.45,y=0.52。The molar ratio of 1,7-vinyl-peryleneimide derivative to acrylic acid structural unit in the final fluorescent brightening dark dyeable polypropylene fiber is 21:125; the fluorescent brightening dark dyeable polypropylene fiber The fluorescence quantum yield is 99%. Under the excitation of 440-460nm wavelength, the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives at 630-645nm is generated; the fluorescence brightens the dark dyeable polymer The breaking strength of propylene fiber is 3.5cN/dtex, the elongation at break is 20.8%, and the melting point is 180℃; the dyeing properties of fluorescent brightening dark dyeable polypropylene fiber are: dyeing with cationic yellow X-8GL at 125℃ , the dye uptake rate is 95%; the dyeing K/S value is 12.70; the color fastness is: soaping fastness: the original discoloration level 4, white cloth staining level 5, rubbing fastness: dry level 5, wet level 4 , Color fastness to perspiration: the original discoloration level 5, white cloth staining level 5, sublimation color fastness: the original color change level 5, white cloth staining level 5; the fabric reflectivity is 145%, and the chromaticity coordinates of the dyed fabric are: x = 0.45, y = 0.52.

Claims (8)

1.一种荧光增亮深色可染聚丙烯纤维,其特征是:主要由聚丙烯基体以及分散在其中的聚丙烯酸微球组成;荧光增亮深色可染聚丙烯纤维在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰;1. a fluorescent brightening dark dyeable polypropylene fiber is characterized in that: mainly consists of a polypropylene matrix and polyacrylic acid microspheres dispersed therein; the fluorescent brightening dark dyeable polypropylene fiber is at a wavelength of 440~460nm Under the excitation of , the characteristic fluorescence emission peak of 1,7-vinyl-peryleneimide derivatives is generated at 630-645 nm; 所述聚丙烯酸微球是以1,7-乙烯基-苝酰亚胺衍生物作为交联剂的聚丙烯酸微球;The polyacrylic acid microspheres are polyacrylic acid microspheres using 1,7-vinyl-peryleneimide derivatives as crosslinking agents; 所述1,7-乙烯基-苝酰亚胺衍生物是指湾位带有乙烯基团的取代基且酰亚胺位带有大体积取代基的苝酰亚胺;The 1,7-vinyl-perylene imide derivative refers to a perylene imide with a vinyl group at the bay position and a bulky substituent at the imide position; 所述的大体积取代基为倍半笼形硅氧烷或带有侧链的长烷基链;Described bulky substituent is silsesquioxane or long alkyl chain with side chain; 所述倍半笼形硅氧烷是
Figure FDA0003629233590000011
R为异丁基或异辛基;
The silsesquiclathric siloxane is
Figure FDA0003629233590000011
R is isobutyl or isooctyl;
所述带有侧链的长烷基链是
Figure FDA0003629233590000012
The long alkyl chain with side chains is
Figure FDA0003629233590000012
其中
Figure FDA0003629233590000013
表示该化学键链接位置为酰亚胺结构中的N原子;
in
Figure FDA0003629233590000013
Indicates that the linking position of the chemical bond is the N atom in the imide structure;
所述乙烯基团的取代基是指端基带有乙烯基团的烷基链,所述烷基链为小于六个碳的烷基链。The substituent of the vinyl group refers to an alkyl chain with a vinyl group at the end, and the alkyl chain is an alkyl chain with less than six carbons.
2.根据权利要求1所述的一种荧光增亮深色可染聚丙烯纤维,其特征在于,所述1,7-乙烯基-苝酰亚胺衍生物与丙烯酸结构单元的摩尔比为14~21.5:125。2. a kind of fluorescent brightening dark dyeable polypropylene fiber according to claim 1 is characterized in that, the molar ratio of described 1,7-vinyl-perylene imide derivative and acrylic acid structural unit is 14 ~21.5:125. 3.根据权利要求1所述的一种荧光增亮深色可染聚丙烯纤维,其特征在于,所述聚丙烯酸微球的平均直径为150~300nm,平均孔径为10~30nm,孔隙率为35~55%,荧光量子产率为95~99%,在440~460nm波长的激发下,产生630~645nm的1,7-乙烯基-苝酰亚胺衍生物的特征荧光发射峰。3. The fluorescent brightening dark dyeable polypropylene fiber according to claim 1, wherein the polyacrylic acid microspheres have an average diameter of 150-300 nm, an average pore diameter of 10-30 nm, and a porosity of 150-300 nm. 35-55%, the fluorescence quantum yield is 95-99%, and the characteristic fluorescence emission peak of the 1,7-vinyl-peryleneimide derivative at 630-645 nm is generated under the excitation of the wavelength of 440-460 nm. 4.根据权利要求1所述的一种荧光增亮深色可染聚丙烯纤维,其特征在于,所述荧光增亮深色可染聚丙烯纤维的断裂强度3.09~3.9cN/dtex,断裂伸长率为17.73~26.6%,熔点为150~180℃;荧光量子产率为95~99%;4 . The fluorescent brightening dark dyeable polypropylene fiber according to claim 1 , wherein the fluorescent brightening dark dyeable polypropylene fiber has a breaking strength of 3.09 to 3.9 cN/dtex, and a breaking elongation of 3.09 to 3.9 cN/dtex. The length is 17.73-26.6%, the melting point is 150-180°C; the fluorescence quantum yield is 95-99%; 所述荧光增亮深色可染聚丙烯纤维的染色性能为:用阳离子黄X-8GL在125℃下染色,染料上染率为65~95%;染色K/S值为11.41~12.70;The dyeing properties of the fluorescent brightening dark dyeable polypropylene fiber are: dyeing with cationic yellow X-8GL at 125 DEG C, the dye uptake rate is 65-95%; the dyeing K/S value is 11.41-12.70; 染色色牢度为:皂洗牢度:原样变色4级、白布沾色3~5级,摩擦牢度:干4~5级、湿3~5级,汗渍色牢度:原样变色4~5级、白布沾色4~5级,升华色牢度:原样变色4~5级,白布沾色4~5级;The color fastness of dyeing is: soaping fastness: the original discoloration level 4, white cloth staining level 3-5, rubbing fastness: dry level 4-5, wet level 3-5, perspiration color fastness: original discoloration 4-5 4-5 grades, white cloth staining, sublimation color fastness: 4-5 grades for discoloration as it is, 4-5 grades for white cloth staining; 织物反射率为95~145%,染色织物的色度坐标值为:x=0.45~0.5,y=0.42~0.52。The reflectivity of the fabric is 95-145%, and the chromaticity coordinates of the dyed fabric are: x=0.45-0.5, y=0.42-0.52. 5.制备如权利要求1~4任一项所述的一种荧光增亮深色可染聚丙烯纤维的方法,其特征是:先将聚丙烯和聚丙烯酸微球混合均匀,并进行干燥处理,再投入到双螺杆挤出机中挤出,制得母粒;最后将母粒添加到聚丙烯熔融纺丝的生产设备上进行纺丝,得到荧光增亮深色可染聚丙烯纤维;5. The method for preparing a fluorescent brightening dark dyeable polypropylene fiber according to any one of claims 1 to 4, wherein the polypropylene and the polyacrylic acid microspheres are firstly mixed uniformly, and then dried , and then put it into the twin-screw extruder for extrusion to obtain the masterbatch; finally, the masterbatch is added to the production equipment of polypropylene melt spinning for spinning to obtain fluorescent brightening dark dyeable polypropylene fibers; 所述聚丙烯酸微球的制备方法为:The preparation method of the polyacrylic acid microspheres is: (1)将乳化剂和去离子水在温度T1下混合形成体系I;(1) emulsifier and deionized water are mixed at temperature T1 to form system I; (2)先将丙烯酸甲酯和1,7-乙烯基-苝酰亚胺衍生物溶于有机溶剂中,再加入到体系I中在温度T2下混合得到体系II;(2) first dissolving methyl acrylate and 1,7-vinyl-perylene imide derivative in an organic solvent, then adding to system I and mixing at temperature T2 to obtain system II; (3)先在体系II中加入过硫酸钾引发聚合得到聚丙烯酸酯分散液;再将聚丙烯酸酯分散液冷却至室温后过滤、水洗和烘干得到聚丙烯酸酯微球;(3) first adding potassium persulfate to system II to initiate polymerization to obtain a polyacrylate dispersion; then cooling the polyacrylate dispersion to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; (4)将聚丙烯酸酯微球与氢氧化钠乙醇溶液混合,并加热回流后冷却、过滤和干燥得到聚丙烯酸微球。(4) The polyacrylate microspheres are mixed with sodium hydroxide ethanol solution, heated to reflux, cooled, filtered and dried to obtain polyacrylic acid microspheres. 6.根据权利要求5所述的一种荧光增亮深色可染聚丙烯纤维的制备方法,其特征在于,所述双螺杆挤出机的螺杆转速为150~200r/min,螺杆温度为200~220℃;6 . The preparation method of fluorescent brightening dark dyeable polypropylene fiber according to claim 5 , wherein the screw speed of the twin-screw extruder is 150-200 r/min, and the screw temperature is 200 rpm. 7 . ~220℃; 所述母粒中,按重量份数计,聚丙烯为80~120份,聚丙烯酸微球为40~60份;纺丝过程中,母粒的添加量为7~8wt%;所述聚丙烯的分子量为146200~150700,分子量分布指数为2.5~4.5,熔体指数为10~20g/10min;In the master batch, in parts by weight, polypropylene is 80-120 parts, and polyacrylic acid microspheres are 40-60 parts; in the spinning process, the addition amount of the master batch is 7-8 wt%; the polypropylene The molecular weight is 146200~150700, the molecular weight distribution index is 2.5~4.5, and the melt index is 10~20g/10min; 所述纺丝的工艺参数为:熔体输送管道的温度200~260℃,熔体过滤器温度220~260℃,纺丝箱体的温度220~260℃,侧吹风风速0.5~0.7m/s,风温15±2℃,热辊温度110±10℃,纺丝速度2500~2800m/min,卷绕角7~8°。The spinning process parameters are as follows: the temperature of the melt conveying pipe is 200-260°C, the temperature of the melt filter is 220-260°C, the temperature of the spinning box is 220-260°C, and the side blowing wind speed is 0.5-0.7m/s , the wind temperature is 15±2℃, the temperature of the hot roller is 110±10℃, the spinning speed is 2500~2800m/min, and the winding angle is 7~8°. 7.根据权利要求5所述的一种荧光增亮深色可染聚丙烯纤维的制备方法,其特征在于,所述乳化剂为月桂酸钾、十二烷基硫酸钠或者丁二酸二辛酯磺酸钠;所述有机溶剂为甲苯或者二甲苯。7. the preparation method of a kind of fluorescent brightening dark dyeable polypropylene fiber according to claim 5, is characterized in that, described emulsifier is potassium laurate, sodium lauryl sulfate or dioctyl succinate Sodium ester sulfonate; the organic solvent is toluene or xylene. 8.根据权利要求5所述的一种荧光增亮深色可染聚丙烯纤维的制备方法,其特征在于,步骤(1)中,T1为35~55℃;8 . The method for preparing a fluorescent brightening dark dyeable polypropylene fiber according to claim 5 , wherein in step (1), T1 is 35 to 55° C. 9 . 步骤(2)的体系II中,乳化剂的含量为0.4~0.7wt%;丙烯酸甲酯的含量为4~6wt%,1,7-乙烯基-苝酰亚胺衍生物的含量为9~15wt%,有机溶剂的含量为6~10wt%;T2为75~95℃;In the system II of step (2), the content of the emulsifier is 0.4-0.7 wt %; the content of methyl acrylate is 4-6 wt %, and the content of the 1,7-vinyl-perylene imide derivative is 9-15 wt % %, the content of organic solvent is 6~10wt%; T2 is 75~95℃; 步骤(3)中过硫酸钾的质量分数为丙烯酸酯分散液的0.06~0.12%;聚合时间为4~8h,聚合温度为75~95℃;In step (3), the mass fraction of potassium persulfate is 0.06-0.12% of the acrylate dispersion; the polymerization time is 4-8h, and the polymerization temperature is 75-95°C; 步骤(4)中的氢氧化钠乙醇溶液的浓度为1~2mol/L,聚丙烯酸酯微球与氢氧化钠乙醇溶液的体积比为1:1~3;所述加热回流的时间为9~11h,干燥温度为90~110℃。The concentration of the sodium hydroxide ethanol solution in step (4) is 1~2mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1:1~3; the time of the heating and refluxing is 9~2 mol/L. 11h, drying temperature is 90~110 ℃.
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