WO2020238688A1 - 一种高模低缩型阻燃涤纶工业丝制备方法 - Google Patents

一种高模低缩型阻燃涤纶工业丝制备方法 Download PDF

Info

Publication number
WO2020238688A1
WO2020238688A1 PCT/CN2020/090921 CN2020090921W WO2020238688A1 WO 2020238688 A1 WO2020238688 A1 WO 2020238688A1 CN 2020090921 W CN2020090921 W CN 2020090921W WO 2020238688 A1 WO2020238688 A1 WO 2020238688A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
potassium
spinning
retardant
modulus
Prior art date
Application number
PCT/CN2020/090921
Other languages
English (en)
French (fr)
Inventor
葛骏敏
顾锋
Original Assignee
浙江海利得新材料股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江海利得新材料股份有限公司 filed Critical 浙江海利得新材料股份有限公司
Publication of WO2020238688A1 publication Critical patent/WO2020238688A1/zh

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/04—Melting filament-forming substances
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/08—Interlacing constituent filaments without breakage thereof, e.g. by use of turbulent air streams

Definitions

  • the invention belongs to the technical field of polymer fiber production, and particularly relates to a method for preparing high-modulus low-shrinkage flame-retardant polyester industrial yarn.
  • High modulus and low shrinkage flame-retardant polyester industrial yarns are mainly used in tire cord fabrics, mining conveyor belts, automotive hoses, etc. They require high strength, good dimensional stability, good wear resistance, and excellent flame retardant properties.
  • the limiting oxygen index LOI of polyester is generally 20%-22%, which is a flammable material, and the potential dangers caused by fire are becoming increasingly prominent.
  • the flame retardant modification of polyester at home and abroad is mainly based on phosphorus flame retardants as modifiers (mainly by copolymerization and adding CEPPA), and the phosphorus-containing groups of phosphorus flame retardants are used to produce a large amount of
  • the heat of combustion melts the polyester, reduces the flow viscosity to produce molten drips, takes away heat, and uses the free radical capture effect of the phosphorus-containing flame retardant to extinguish the flame to achieve the purpose of flame retardancy.
  • the flame retardant mechanism is the droplet taking away heat Flame retardant.
  • flame-retardant polyester industrial yarn is prepared by dip coating flame retardant and chip modification before spinning and winding; the flame retardant coating method of yarn before winding is adopted, because it only contains flame retardant on the surface of the yarn In the post-weaving and finishing process, due to the influence of high temperature, solvent, friction and other processes, the flame retardant is easily damaged, which affects the flame retardant performance of the fabric, and the flame retardant performance decreases over time.
  • the flame retardant is a low-molecular substance.
  • the IV value of the chips can reach 1.0 ⁇ 1.2dl/g through the solid-phase thickening method, the crystallization temperature and melting point of the chips are higher than those of pure PET chips. Both must be low, and molecular thermal degradation during the spinning process is severe, which affects spinnability and tensile properties.
  • CEPPA method oxygen index (LOI) 32% flame-retardant polyester industrial yarn
  • the highest strength is generally around 6.5cN/dtex, which is significantly lower than the existing high-strength non-flame-retardant polyester industrial yarn, and the wool yarn and broken ends are also obvious Non-flame retardant polyester industrial yarn higher than similar products. Due to the low strength and many hairs, the cost and difficulty of subsequent applications are increased, thereby limiting the development of the industry.
  • Phosphorus flame retardants are the most effective environmentally friendly flame retardants for polyester.
  • the processing methods introduced by flame retardants can be mainly divided into copolymerization modification and blending modification process routes.
  • Copolymerization modification uses a small molecule flame retardant with reactive functional groups to copolymerize with polyester monomers to introduce flame retardant groups into the polyester molecular chain.
  • the method has the advantages of more stable product quality, less addition of flame retardant, and more durable flame retardant effect.
  • the introduction of reactive phosphorus-based flame retardants will destroy the regularity of the polyester macromolecular chain structure, thereby affecting the crystallization and hydrolysis resistance of polyester fibers, and ultimately lead to the heat resistance, mechanical properties and aging resistance of the product Significant reduction in performance such as sex.
  • Blending modification is to melt and blend the flame retardant with polyester chips or melt, and then spin to obtain flame retardant fiber.
  • This method has better flexibility and diversity, but has disadvantages such as poor dispersion of flame retardants in polyester, easy precipitation of flame retardants, poor flame retardant durability, and poor spinnability, which limits its use in polyester fibers. In the application.
  • the polyphosphate polymer masterbatch selected in this patent has the characteristics of high phosphorus content and good compatibility with polyester, which overcomes the poor dispersion, easy precipitation, poor durability, and poor spinnability of the flame retardant in the blending modification method.
  • the prepared flame-retardant polyester industrial filament has the characteristics of high strength, good flame-retardant performance, and aging resistance.
  • the present invention proposes a high-modulus, low-shrinkage type flame-retardant polyester industrial yarn obtained by melt-spinning a chip blended with an ultra-high molecular phosphorus flame retardant and PET, which contains the following characteristics; high strength , Halogen-free environmental protection, good flame retardant performance, less spinning wool and other characteristics.
  • the fineness range of a high-modulus low-shrinkage flame-retardant polyester industrial yarn of the present invention includes 840 dtex to 3000 dtex, and the thickness (fineness/number of holes) DPF of a single filament includes polyester industrial yarns of 2-10. Its breaking strength range: 6.0 ⁇ 7.5cN/dtex, breaking elongation range: 10.0 ⁇ 20.0%, intermediate elongation (@4.0cN/dtex): 4.5 ⁇ 6.5%; dry heat shrinkage (177°C*10min*0.05cN) /dtex): 2.0-4.0%, limiting oxygen index (LOI) ⁇ 32.0%.
  • a preparation method of high modulus and low shrinkage flame-retardant polyester industrial yarn which is characterized in that it comprises the following steps: (1) Selection of raw materials
  • Component A high molecular phosphorus flame retardant, the specific parameters are: molecular weight Phosphorus content: Tg; The high molecular phosphorus flame retardant is formed by grafting one or more of copolyphosphonate carbonate, polyphosphonate, and copolyphosphonate to the molecular chain of PET; wherein the molecular weight is controlled in Is the best
  • the intrinsic viscosity of fiber grade PET chips is: The mass content of COOH is The mass content of DEG is The mass ratio of component A to the mixed raw materials is: The effect is better when;
  • step (1) Solid phase thickening: The mixture material in step (1) is preheated in a continuous solid phase thickening device or drum to increase solid phase viscosity until the intrinsic viscosity of the mixed material after treatment is PET flame retardant chips; and the mass content of component A in the mixture is Phosphorus content Phosphorus content
  • Phosphorus content Phosphorus content
  • step (2) the material was dried under N 2 protection, melted raw material is heated in the range of 265 °C ⁇ 310 °C, and then enters the spinning housing, the temperature of the spinning head Control at 265°C ⁇ 310°C;
  • Cooling and forming the spinning yarn sprayed out through the spinneret is cooled into tow by circulating cooling air, and the temperature of the cooling air is controlled at 40 ⁇ 65°C;
  • Winding process control the winding speed
  • the TMT fork-type high-speed winding is used to directly wind the stretched tow on the paper tube, which has the characteristics of beautiful package and uniform tension.
  • the spinning box is heated with biphenyl.
  • the tow is oiled before the drawing process of step (6) of the above-mentioned method for preparing high modulus and low shrinkage flame-retardant polyester industrial yarn, and the oil is composed of monohydric alcohol fatty acid and polyhydric alcohol fatty acid.
  • the oil is composed of monohydric alcohol fatty acid and polyhydric alcohol fatty acid.
  • Organophosphate, dimethylsiloxane or polysiloxane, potassium oleate, fatty acid composition the mass ratio of each component is as follows:
  • the organic phosphates are: potassium methylene phosphonate, sodium methylene phosphonate, magnesium methylene phosphonate, potassium diphosphonate, potassium triphosphonate, potassium tetraphosphonate, potassium pentaphosphonate, diphosphine
  • composition of the oil agent and the mass ratio of each component are as follows:
  • the organic phosphate is one of potassium methylene phosphonate, potassium diphosphonate and potassium pentaphosphonate.
  • step (6) of the above-mentioned preparation method of high modulus and low shrinkage flame-retardant polyester industrial yarn after the stretching process, the tow is passed through the network nozzle under the action of a certain pressure to generate the network node of the tow.
  • the polymer flame retardant described in the flame-retardant chip used in the present invention is a polymer containing phosphorus elements, which can undergo a cross-linking reaction with the PET melt when it is melted at high temperature, so that it can be completely grafted into the PET molecules.
  • the melting point reaches 255°C, while the existing CEPPA flame-retardant chip has a melting point of only 238°C.
  • the thermal degradation rate of PET at high temperature can be greatly reduced, and the obtained melt has good stretchability and heat resistance.
  • the spinning finish used in the present invention is developed in cooperation with foreign manufacturers and is specially used to produce polyester industrial yarn spinning finishes. It has good friction resistance and cohesiveness, and can greatly reduce wool during stretching and post-weaving. The production of silk.
  • Component A high molecular phosphorus flame retardant, specific parameters: molecular weight Phosphorus content: Tg;
  • the high molecular phosphorus flame retardant is formed by grafting one or more of copolyphosphonate carbonate, polyphosphonate, and copolyphosphonate to the molecular chain of PET;
  • the intrinsic viscosity of ordinary PET chips is:
  • step (1) Solid-phase thickening: the mixture material in step (1) is preheated in a continuous solid-phase thickening device or a rotating drum to solid-phase thickening until the treated intrinsic viscosity of the PET flame-retardant chips for And the mass content of component A in the mixture is Phosphorus content
  • step (2) the material was dried under N 2 protection, melted raw material is heated in the range of 265 °C ⁇ 310 °C, and then enters the spinning housing, the temperature of the spinning head control in
  • Cooling and forming the spinning yarn sprayed through the spinneret is cooled into tow by circulating cooling air, and the temperature of the cooling air is controlled at 40 ⁇ 65°C;
  • Winding process control the winding speed
  • the speed control during the winding process directly affects the final performance of the product. Although this speed can be achieved, the causal relationship between the speed and the product performance needs to be understood by technicians before they can consciously realize the speed.
  • the product made by this method has the following test results:
  • the flame-retardant polyester industrial yarn produced by the present invention has significantly higher strength than the polyester industrial yarn spun by using CEPPA flame-retardant chips.
  • the tow is oiled, and the oiling agent is composed of monohydric alcohol fatty acid, polyhydric alcohol fatty acid, organic phosphate, dimethylsiloxane or polysiloxane , Potassium oleate, fatty acid composition, the mass ratio of each component is as follows:
  • Example 6 has the best overall performance.
  • the organic phosphates are: potassium methylene phosphonate, sodium methylene phosphonate, magnesium methylene phosphonate, potassium diphosphonate, potassium triphosphonate, potassium tetraphosphonate, potassium pentaphosphonate, diphosphine
  • the tow is passed through the network nozzle under a certain pressure to generate network nodes to the tow, which can increase the cohesion of the tow.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Fluid Mechanics (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明涉及高分子纤维生产技术领域，特别是涉及一种高模低缩型阻燃涤纶工业丝的制备方法。本发明主要通过选取特定的材料，高分子磷系阻燃剂、高粘PET切片进行混合，并控制混合物的粘度、磷含量等重要参数，然后在每个纺丝环节进行有效参数控制，包括温度、卷绕速度等，最终得到高强型阻燃涤纶工业丝。本发明的优点是采用的纺丝油剂于生产涤纶工业丝纺丝油剂，具有良好的耐摩擦性，抱合性，可以大大减少拉伸和后织造过程中毛丝的产生，强度高，无卤环保，阻燃性能好，纺丝毛丝少等特点。

Description

一种高模低缩型阻燃涤纶工业丝制备方法 技术领域
本发明属于高分子纤维生产技术领域，特别是涉及一种高模低缩型阻燃涤纶工业丝制备方法。
背景技术
高模低缩型阻燃涤纶工业丝主要应用于轮胎帘子布，矿用输送带，车用胶管等，要求强度高，尺寸稳定性好，耐磨性好，阻燃性能优异。
涤纶的极限氧指数LOI一般为20％-22％，属于易燃材料，其发生火灾所带来的潜在危险也日益突出。目前国内外的涤纶阻燃改性主要是以磷系的阻燃剂作为改性剂(主要是共聚添加CEPPA为主)，利用磷系阻燃剂的含磷基团在燃烧过程中产生大量的燃烧热，使聚酯熔融，降低流动粘度产生熔融滴落，带走热量，并利用含磷阻燃剂的自由基捕捉作用熄灭火焰，达到阻燃目的，其阻燃机理为熔滴带走热量阻燃。一般有纺丝卷绕前浸涂阻燃剂和切片改性的方法来制备阻燃涤纶工业丝；采用卷绕前纱线浸涂阻燃剂的方法，由于其只在纱线表面含有阻燃剂，在后织造，整理过程中由于受高温，溶剂，磨擦等过程的影响，阻燃剂易被损橇，影响了织物的阻燃性能，且阻燃性能随着时间推移而降低。
采用PET改性生产CEPPA磷系阻燃切片，其阻燃剂属于低分子物，虽然切片IV值通过固相增粘的方法达到1.0～1.2dl/g，但切片结晶温度和熔点比纯PET切片均要低，纺丝过程中分子热降解严重，从而影响了可纺性和拉伸性能。当前应用CEPPA的方法氧指数(LOI)在32％的阻燃涤纶工业丝最高强度一般在6.5cN/dtex左右，明显低于现有高强非阻燃涤纶工业丝，而且毛丝、断头也明显高于同类产品的非阻燃涤纶工业丝。由于强度的低且毛丝多，增加了后道应用的成本和难度，从而限制了产业的发展。
磷系阻燃剂是涤纶最有效的环保型阻燃剂，阻燃剂引入的加工方法主要可分为共聚改性和共混改性工艺路线。共聚改性是利用带反应性官能团的小分子阻燃剂与聚酯单体进行共聚反应，在聚酯分子链中引入阻燃基团。该方法具有产品质量更稳定、添加阻燃剂少、阻燃效果更耐久的优势。但反应性的磷系阻燃剂的引入，会破坏聚酯大分子链结构的规整型，从而影响聚酯纤维的结晶性能和耐水解性能等，最终导致产品耐热性能、力学性能和耐老化性等性能的显著降低。
共混改性是将阻燃剂与聚酯切片或熔体进行熔融共混，再经纺丝得到阻燃纤维。该方法具有更好的灵活性和多样性，但是具有阻燃剂在聚酯中的分散性差、阻燃剂易析出、阻燃耐久性差、可纺性差等劣势，从而限制了其在聚酯纤维中的应用。
本专利所选聚磷酸酯聚合物母粒，具有磷含量高、与聚酯相容性好的特点，克服了共混改性方法阻燃剂分散性差、易析出、耐久性差、可纺性差等缺点，所制备的阻燃涤纶工业长丝具有强度高、阻燃性能好、耐老化等特点。
发明内容
本发明提出了一种使用超高分子磷系阻燃剂与PET共混的切片，经融熔纺丝得到的一种高模低缩型阻燃涤纶工业丝，其包含的特点有；强度高，无卤环保，阻燃性能好，纺丝毛丝少等特点。
本发明所述的一种高模低缩型阻燃涤纶工业丝纤度范围包括：840dtex～3000dtex，单根丝的粗细(纤度/孔数)DPF范围包括2～10的涤纶工业丝。其断裂强度范围：6.0～7.5cN/dtex，断裂伸长范围：10.0～20.0％，中间伸长(@4.0cN/dtex)：4.5～6.5％；干热收缩率(177℃*10min*0.05cN/dtex)：2.0～4.0％，极限氧指数(LOI)≥32.0％。
本发明是通过下述技术方案得以实现的：
一种高模低缩型阻燃涤纶工业丝的制备方法，其特征在于，包括下述步骤：(1)原料选用
组分A：高分子磷系阻燃剂，具体参数为：分子量
Figure PCTCN2020090921-appb-000001
磷含量：
Figure PCTCN2020090921-appb-000002
Tg；
Figure PCTCN2020090921-appb-000003
所述高分子磷系阻燃剂是一种含有共聚膦酸酯碳酸酯，聚膦酸酯，共聚膦酸酯的一种或多种，枝接到PET分子链上所形成的；其中分子量控制在
Figure PCTCN2020090921-appb-000004
为最佳；
将组分A与纤维级PET切片混合，A组份占混合后原料的质量比例为：
Figure PCTCN2020090921-appb-000005
其中纤维级PET切片的特性粘度为：
Figure PCTCN2020090921-appb-000006
COOH的质量含量为
Figure PCTCN2020090921-appb-000007
Figure PCTCN2020090921-appb-000008
DEG的质量含量为
Figure PCTCN2020090921-appb-000009
A组份占混合后原料的质量比例为：
Figure PCTCN2020090921-appb-000010
Figure PCTCN2020090921-appb-000011
时的效果更好；
(2)固相增粘：将步骤(1)中的混合物料，在连续式固相增粘装置或转鼓中经 过预热，固相增粘，直至混合物料经处理后的特性粘度为
Figure PCTCN2020090921-appb-000012
的PET阻燃切片；且组分A在混合物料中的质量含量为
Figure PCTCN2020090921-appb-000013
其中的磷含量
Figure PCTCN2020090921-appb-000014
Figure PCTCN2020090921-appb-000015
其中的磷含量
Figure PCTCN2020090921-appb-000016
为更佳；
(3)融熔过程：将步骤(2)中经干燥原料在N 2保护下，在265℃～310℃范围内对原料进行加热融熔，再进入纺丝箱体内，纺丝箱体的温度控制在265℃～310℃；
(4)计量纺丝过程：经充分融熔的熔体经过计量泵进行纺丝；经充分融熔的熔体经过计量泵按照设定的纤度要求精确计量，计量泵转速根据所纺产品纤度和纺速计算得到；
(5)冷却成型：经喷丝孔喷出的纺丝经环吹冷却风进行冷却成丝束，冷却风控制温度为40～65℃；；
(6)拉伸过程：将冷却后的丝束进行拉伸和热定型，拉伸总倍率
Figure PCTCN2020090921-appb-000017
定型温度235℃～260℃；以达到要求强度，伸长，干热收缩等各项物于是数据。
(7)卷绕过程：控制卷绕速度
Figure PCTCN2020090921-appb-000018
采用TMT拨叉式的高速卷绕方面将拉伸后的丝束直接卷绕在纸管上，具有卷装漂亮，张力均匀的特点。
作为优选，上述的一种高模低缩型阻燃涤纶工业丝的制备方法的步骤(4)的融熔过程中，纺丝箱体用联苯加热。
作为优选，上述的一种高模低缩型阻燃涤纶工业丝的制备方法的步骤(6)的拉伸过程前，对丝束进行上油，所述油剂由一元醇脂肪酸，多元醇脂肪酸，有机磷酸盐，二甲基硅氧烷或聚硅氧烷，油酸钾，脂肪酸组成，各组份的质量比例如下：
Figure PCTCN2020090921-appb-000019
其中的有机磷酸盐为：亚甲基膦酸钾、亚甲基膦酸钠、亚甲基膦酸镁，二膦酸钾、三膦酸钾、四膦酸钾、五膦酸钾，二膦酸钠、三膦酸钠、四膦酸钠、五膦酸钠，二膦酸镁、三膦酸镁、四膦酸镁、五膦酸镁中的一种或几种。
作为更佳选择，油剂的组成及各组份的质量比例如下：
Figure PCTCN2020090921-appb-000020
其中的有机磷酸盐为：亚甲基膦酸钾、二膦酸钾、五膦酸钾中的一种。
作为优选，上述的一种高模低缩型阻燃涤纶工业丝的制备方法的步骤(6)拉伸过程后，对丝束通过网络喷嘴在一定压空的作用下使丝束产生网络节点。
本发明采用的阻燃切片中所述的高分子阻燃剂是一种含有磷元素的高分子，它高温熔融时能与PET熔本发生交联反应，使其完全嫁接下PET分子中，其熔点达到了255℃，而现有的CEPPA阻燃切片的熔点仅为238℃。可使PET在高温时的热降解速率大幅下降，所得的熔体具有良好可拉伸性和耐热性能。
有益效果：本发明采用的纺丝油剂是与国外厂商合作开发的专门于生产涤纶工业丝纺丝油剂，具有良好的耐摩擦性，抱合性，可以大大减少拉伸和后织造过程中毛丝的产生。
具体实施方式
下面对本发明的实施作具体说明：
实施例1
首先确定原料：
A组分：高分子磷系阻燃剂，具体参数为：分子量
Figure PCTCN2020090921-appb-000021
磷含量：
Figure PCTCN2020090921-appb-000022
Tg；
Figure PCTCN2020090921-appb-000023
所述高分子磷系阻燃剂是一种含有共聚膦酸酯碳酸酯，聚膦酸酯，共聚膦酸酯的一种或多种，枝接到PET分子链上所形成的；
将组分A与普通PET切片混合，组分A占混合后原料的质量比例为：
Figure PCTCN2020090921-appb-000024
其中普通PET切片的特性粘度为：
Figure PCTCN2020090921-appb-000025
(2)固相增粘：将步骤(1)中的混合物料，在连续式固相增粘装置或转鼓中经过预热，固相增粘，直至PET阻燃切片经处理后的特性粘度为
Figure PCTCN2020090921-appb-000026
且组分A在混合物料中的质量含量为
Figure PCTCN2020090921-appb-000027
其中的磷含量
Figure PCTCN2020090921-appb-000028
(3)融熔过程：将步骤(2)中经干燥原料在N 2保护下，在265℃～310℃范围内对原料进行加热融熔，再进入纺丝箱体内，纺丝箱体的温度控制在
Figure PCTCN2020090921-appb-000029
Figure PCTCN2020090921-appb-000030
(4)计量纺丝过程：经充分融熔的熔体经过计量泵进行纺丝；
(5)冷却成型：经喷丝孔喷出的纺丝经环吹冷却风进行冷却成丝束，冷却风控制温度为40～65℃；
(6)拉伸过程：将冷却后的丝束进行拉伸和热定型，拉伸总倍率
Figure PCTCN2020090921-appb-000031
定型温度235℃～260℃；
(7)卷绕过程：控制卷绕速度
Figure PCTCN2020090921-appb-000032
卷绕过程中的速度控制直接影响到产品最后的性能，虽然这个速度可以实现，但对该速度与产品性能之间的因果关系需要技术人员的事先了解，才会有意识去实现该速度。
一种高模低缩型阻燃涤纶工业丝制造方法
Figure PCTCN2020090921-appb-000033
通过该方法所制得的产品，经检测的结果如下：
项目 单位 测试值
线密度 dtex 1115
强力 N 83.6
断裂强度 cN/dtx 7.05
断裂伸长率 ％ 13.0％
中间伸长(4.0cN/dtex) ％ 5.8
干热收缩率(177℃*10min*0.05cN/dtex) ％ 3.0
网络度(针刺法) 个/m 5.0
含油率 ％ 0.60
极限氧指数(LOI) ％ 33.4
从表中可以明显看出本发明生产的阻燃涤纶工业丝其强度明显高于使用CEPPA阻燃切片纺制的涤纶工业丝。
Figure PCTCN2020090921-appb-000034
实施例2-6
在实施例中，步骤(6)的拉伸过程前，对丝束进行上油，所述油剂由一元醇脂肪酸，多元醇脂肪酸，有机磷酸盐，二甲基硅氧烷或聚硅氧烷，油酸钾，脂肪酸组成，各组份的质量比例如下：
Figure PCTCN2020090921-appb-000035
上述实施例2——6经试验所得结果，与现有产品相比，具有更好的性能。 其中实施例6的综合性能最佳。
其中的有机磷酸盐为：亚甲基膦酸钾、亚甲基膦酸钠、亚甲基膦酸镁，二膦酸钾、三膦酸钾、四膦酸钾、五膦酸钾，二膦酸钠、三膦酸钠、四膦酸钠、五膦酸钠，二膦酸镁、三膦酸镁、四膦酸镁、五膦酸镁中的一种或几种。
进一步，在步骤(6)拉伸过程后，对丝束通过网络喷嘴在一定压空的作用下使丝束产生网络节点，可以增加丝束的抱合性。

Claims (5)

  1. 一种高模低缩型阻燃涤纶工业丝制备方法，其特征在于，包括下述步骤：
    (1)原料选用
    组分A：高分子磷系阻燃剂，具体参数为：分子量
    Figure PCTCN2020090921-appb-100001
    磷含量：
    Figure PCTCN2020090921-appb-100002
    Tg；
    Figure PCTCN2020090921-appb-100003
    所述高分子磷系阻燃剂是一种含有共聚膦酸酯碳酸酯，聚膦酸酯，共聚膦酸酯的一种或多种，枝接到PET分子链上所形成的；
    将组分A与纤维级PET切片混合，A组份占混合后原料的质量比例为：
    Figure PCTCN2020090921-appb-100004
    其中纤维级PET切片的特性粘度为：
    Figure PCTCN2020090921-appb-100005
    COOH的质量含量为
    Figure PCTCN2020090921-appb-100006
    Figure PCTCN2020090921-appb-100007
    DEG的质量含量为
    Figure PCTCN2020090921-appb-100008
    (2)固相增粘：将步骤(1)中的混合物料，在连续式固相增粘装置或转鼓中经过预热，固相增粘，直至混合物料经处理后的特性粘度为
    Figure PCTCN2020090921-appb-100009
    的PET阻燃切片；且组分A在混合物料中的质量含量为
    Figure PCTCN2020090921-appb-100010
    其中的磷含量
    Figure PCTCN2020090921-appb-100011
    Figure PCTCN2020090921-appb-100012
    (3)融熔过程：将步骤(2)中经干燥原料在N 2保护下，在265℃～310℃范围内对原料进行加热融熔，再进入纺丝箱体内，纺丝箱体的温度控制在
    Figure PCTCN2020090921-appb-100013
    Figure PCTCN2020090921-appb-100014
    (4)计量纺丝过程：经充分融熔的熔体经过计量泵进行纺丝；
    (5)冷却成型：经喷丝孔喷出的纺丝由环吹冷却风进行冷却成丝束，冷却风控制温度为40～65℃；
    (6)拉伸过程：将冷却后的丝束进行拉伸和热定型，拉伸总倍率
    Figure PCTCN2020090921-appb-100015
    定型温度235℃～260℃；
    (7)卷绕过程：控制卷绕速度
    Figure PCTCN2020090921-appb-100016
  2. 根据权利要求1所述的一种高模低缩型阻燃涤纶工业丝的制备方法，其特征在于，步骤(3)的融熔过程中，纺丝箱体用联苯加热。
  3. 根据权利要求1所述的一种高模低缩型阻燃涤纶工业丝的制备方法，其特征在于，步骤(6)的拉伸过程前，对丝束进行上油，所述油剂由一元醇脂肪酸，多元醇脂肪酸，有机磷酸盐，二甲基硅氧烷或聚硅氧烷，油酸钾，脂肪酸组成，各组份的质量比例如下：
    Figure PCTCN2020090921-appb-100017
    Figure PCTCN2020090921-appb-100018
    其中的有机磷酸盐为：亚甲基膦酸钾、亚甲基膦酸钠、亚甲基膦酸镁，二膦酸钾、三膦酸钾、四膦酸钾、五膦酸钾，二膦酸钠、三膦酸钠、四膦酸钠、五膦酸钠，二膦酸镁、三膦酸镁、四膦酸镁、五膦酸镁中的一种或几种。
  4. 根据权利要求3所述的一种高模低缩型阻燃涤纶工业丝的制备方法，其特征在于，所述油剂的组成及各组份的质量比例如下：
    Figure PCTCN2020090921-appb-100019
    其中的有机磷酸盐为：亚甲基膦酸钾、二膦酸钾、五膦酸钾中的一种。
  5. 根据权利要求1所述的一种高模低缩型阻燃涤纶工业丝的制备方法，其特征在于，步骤(7)拉伸过程后，对丝束通过网络喷嘴在一定压空的作用下使丝束产生网络节点。
PCT/CN2020/090921 2019-05-27 2020-05-18 一种高模低缩型阻燃涤纶工业丝制备方法 WO2020238688A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910448026.5 2019-05-27
CN201910448026.5A CN110172750A (zh) 2019-05-27 2019-05-27 一种高模低缩型阻燃涤纶工业丝制备方法

Publications (1)

Publication Number Publication Date
WO2020238688A1 true WO2020238688A1 (zh) 2020-12-03

Family

ID=67696143

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/090921 WO2020238688A1 (zh) 2019-05-27 2020-05-18 一种高模低缩型阻燃涤纶工业丝制备方法

Country Status (2)

Country Link
CN (1) CN110172750A (zh)
WO (1) WO2020238688A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110172750A (zh) * 2019-05-27 2019-08-27 浙江海利得新材料股份有限公司 一种高模低缩型阻燃涤纶工业丝制备方法
CN110528109B (zh) * 2019-08-28 2021-02-19 江苏索力得新材料集团有限公司 一种高强阻燃涤纶工业丝及其制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003129368A (ja) * 2001-10-18 2003-05-08 Toyobo Co Ltd 意匠性に富む難燃性ポリエステル布帛の染色加工方法
CN101298703A (zh) * 2008-06-19 2008-11-05 浙江海利得新材料股份有限公司 单头纺高模量低收缩聚酯工业长丝生产工艺
CN102400342A (zh) * 2010-09-14 2012-04-04 李文娟 化纤热拉伸纺丝油剂
CN102675618A (zh) * 2005-08-11 2012-09-19 Frx聚合物股份有限公司 聚(嵌段-膦酰氧基-酯)和聚(嵌段-膦酰氧基-碳酸酯)及其制备方法
CN102912640A (zh) * 2012-10-25 2013-02-06 上虞市皇马化学有限公司 一种原油型涤纶工业丝油剂及其制备方法
CN102995155A (zh) * 2012-12-15 2013-03-27 浙江海利得新材料股份有限公司 一种活化型高模低收缩涤纶工业丝及其制备方法
CN104603176A (zh) * 2012-06-29 2015-05-06 Frx聚合物股份有限公司 聚酯共-膦酸酯
CN105504241A (zh) * 2015-12-29 2016-04-20 江苏恒力化纤股份有限公司 一种高模低缩聚酯工业丝及其制备方法
CN109735942A (zh) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 高模低缩活化型涤纶工业丝及其制备方法
CN110158189A (zh) * 2019-05-27 2019-08-23 浙江海利得新材料股份有限公司 一种高模低缩型阻燃涤纶工业丝的制备方法
CN110172750A (zh) * 2019-05-27 2019-08-27 浙江海利得新材料股份有限公司 一种高模低缩型阻燃涤纶工业丝制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105862152A (zh) * 2016-06-06 2016-08-17 浙江尤夫高新纤维股份有限公司 一种高速纺低拉伸高模量低收缩涤纶工业丝生产方法
CN108677269A (zh) * 2018-05-14 2018-10-19 无锡索力得科技发展有限公司 一种高品质阻燃涤纶工业丝的生产方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003129368A (ja) * 2001-10-18 2003-05-08 Toyobo Co Ltd 意匠性に富む難燃性ポリエステル布帛の染色加工方法
CN102675618A (zh) * 2005-08-11 2012-09-19 Frx聚合物股份有限公司 聚(嵌段-膦酰氧基-酯)和聚(嵌段-膦酰氧基-碳酸酯)及其制备方法
CN101298703A (zh) * 2008-06-19 2008-11-05 浙江海利得新材料股份有限公司 单头纺高模量低收缩聚酯工业长丝生产工艺
CN102400342A (zh) * 2010-09-14 2012-04-04 李文娟 化纤热拉伸纺丝油剂
CN104603176A (zh) * 2012-06-29 2015-05-06 Frx聚合物股份有限公司 聚酯共-膦酸酯
CN102912640A (zh) * 2012-10-25 2013-02-06 上虞市皇马化学有限公司 一种原油型涤纶工业丝油剂及其制备方法
CN102995155A (zh) * 2012-12-15 2013-03-27 浙江海利得新材料股份有限公司 一种活化型高模低收缩涤纶工业丝及其制备方法
CN105504241A (zh) * 2015-12-29 2016-04-20 江苏恒力化纤股份有限公司 一种高模低缩聚酯工业丝及其制备方法
CN109735942A (zh) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 高模低缩活化型涤纶工业丝及其制备方法
CN110158189A (zh) * 2019-05-27 2019-08-23 浙江海利得新材料股份有限公司 一种高模低缩型阻燃涤纶工业丝的制备方法
CN110172750A (zh) * 2019-05-27 2019-08-27 浙江海利得新材料股份有限公司 一种高模低缩型阻燃涤纶工业丝制备方法

Also Published As

Publication number Publication date
CN110172750A (zh) 2019-08-27

Similar Documents

Publication Publication Date Title
WO2020238687A1 (zh) 一种高强型阻燃涤纶工业丝制备方法
CN102653890B (zh) 一种高可纺性无卤阻燃锦纶纤维的制备方法
WO2020238688A1 (zh) 一种高模低缩型阻燃涤纶工业丝制备方法
CN102560716B (zh) 高可纺性对位芳纶短纤维及其生产方法
CN113529200A (zh) 一种防切割聚乙烯纤维的制备方法
CN110158174B (zh) 一种阻燃剂、阻燃合成纤维及其制造方法
JP2007056392A (ja) 難燃性ポリアミド繊維および難燃性布帛
WO2020238686A1 (zh) 一种低缩型阻燃涤纶工业丝制备方法
CN112458583B (zh) 一种对位芳纶纤维及其制备方法和在制备熔融金属飞溅防护服装方面的应用
CN110158190A (zh) 一种高强型阻燃涤纶工业丝的制备方法
CN110241475A (zh) 一种低缩型阻燃涤纶工业丝的制备方法
CN110158189A (zh) 一种高模低缩型阻燃涤纶工业丝的制备方法
CN112501710A (zh) 一种阻燃涤纶低弹丝的制备方法
CN109477248B (zh) 聚烯烃系纤维及其制造方法
JP7028682B2 (ja) 原着メタ型全芳香族ポリアミド繊維及びその製造方法、並びに該繊維からなる難燃性紡績糸及び難燃性牽切紡績糸
KR100663254B1 (ko) 카펫용 폴리에틸렌테레프탈레이트 벌키 연속 필라멘트의제조방법
KR102113535B1 (ko) 탄소섬유 스테이플을 포함하는 방적사 및 그의 제조방법
CN103361870B (zh) 聚芳噁二唑与阻燃粘胶的混纺织物
CN113308889B (zh) 一种无卤阻燃涤棉面料及其制备方法
JP2014001467A (ja) 難燃ポリエステル繊維の製造方法
CN112779619B (zh) 一种锦纶阻燃纤维及其制品
EP3692189A1 (en) Flame retardant lyocell filament
CN115704116A (zh) 一种芳香族聚砜酰胺纤维的制造方法
JP3296456B2 (ja) 耐熱、耐炎布帛
JP2023023305A (ja) 難燃性布帛および繊維製品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20812633

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20812633

Country of ref document: EP

Kind code of ref document: A1