WO2021208192A1 - 一种快速生物降解的微多孔聚酯纤维的生产工艺 - Google Patents

一种快速生物降解的微多孔聚酯纤维的生产工艺 Download PDF

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WO2021208192A1
WO2021208192A1 PCT/CN2020/092413 CN2020092413W WO2021208192A1 WO 2021208192 A1 WO2021208192 A1 WO 2021208192A1 CN 2020092413 W CN2020092413 W CN 2020092413W WO 2021208192 A1 WO2021208192 A1 WO 2021208192A1
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biodegradable
spinning
polyester fiber
monomer
production process
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PCT/CN2020/092413
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English (en)
French (fr)
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余燕平
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博聚(上海)生态科技有限公司
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    • 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
    • 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
    • D01D13/00—Complete machines for producing artificial threads
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F1/10—Other agents for modifying properties

Definitions

  • the invention relates to the technical field of fiber degradation, in particular to a production process of a rapidly biodegradable microporous polyester fiber.
  • polyester fiber a certain proportion of biodegradable additives and polyester chips are mixed and granulated into a biodegradable additive masterbatch. When polyester fiber is spinning, this masterbatch is added. Make polyester fiber a biodegradable polyester fiber.
  • This biodegradable additive has a certain degree of hydrophilicity, which can cause the polyester fiber to undergo chain forging and hydrolysis within a certain period of time, and in an environment where microorganisms exist, it can cooperate with the microorganisms to decompose the polyester fiber into small molecular compounds , To achieve the effect of biodegradation.
  • the degradation time and speed are the most critical factors. At present, the basic degradation can generally occur within 30 weeks to 30 months. And for recycling polyesters with high intrinsic viscosity (IV), there is still no good degradation effect.
  • Biodegradable additives are difficult to be fully and evenly distributed in the fiber.
  • the masterbatch of biodegradable additives is added, but the proportion of addition is not high, generally in the range of 1-5%. This is due to the spinnability of spinning and the cost of biological additives. The reason is that the low proportion of biological additives is added. This small proportion of degradable biological additives is naturally mixed in the spinning fluid and mixed under the action of the spinning screw. Due to the viscosity of the spinning fluid, the small proportion of biodegradable additives, and the natural mixing method, it is difficult for the biological additives to be fully and uniformly dispersed inside the fiber, and there must be a lack of biodegradable additives in some areas . Lead to longer biodegradation time.
  • the fiber After spinning fluid, primordial fiber to drawing and heat setting, the fiber is a closed aggregate with dense crystal structure. This will cause microbial contact only to start from the surface of the fiber, slowly degrading from the outside to the inside, and the dense structure with high crystallinity will also make it difficult for chain forging to break and reach of microorganisms, which makes the degradation rate of microorganisms slow. .
  • the purpose of the present invention is to provide a rapid biodegradable microporous polyester fiber production process.
  • the internal biodegradable additives are fully dispersed and evenly distributed inside the fiber, and the fiber becomes porous.
  • It is a kind of fiber material, which is easy for external microorganisms to reach inside, so that it becomes a fiber with fully dispersed and evenly distributed biodegradable additives and a porous structure to make it easy to biodegrade and accelerate the rate of biodegradation.
  • the technical scheme of the present invention is as follows: a process for producing a rapidly biodegradable microporous polyester fiber, which specifically includes the following steps:
  • the polyester polymer fluid is foamed and decomposed at a high temperature after being discharged from the spinning screw to obtain a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed;
  • S5 The spinning fluid is made into corresponding microporous polyester fiber according to the production requirements.
  • the first monomer is terephthalic acid; and the second monomer is ethylene glycol.
  • the decomposition temperature of the high temperature resistant foaming agent is ⁇ 300° C.
  • CO 2 and nitrogen are released after high temperature thermal decomposition.
  • the melting points of the first monomer and the second monomer are both lower than 280 degrees.
  • the spinning temperature in the spinning screw is lower than 300°C.
  • the step S4 specifically includes the following process: after the polyester polymer fluid containing the biodegradable additives and the high temperature resistant foaming agent is discharged from the spinning screw Enter the foaming zone for high-temperature foaming, and the high-temperature resistant foaming agent will chemically foam.
  • the impact force of the foaming makes the biodegradable additives diffuse more uniformly in the spinning fluid.
  • the high-temperature resistant foaming agent After the high-temperature resistant foaming agent is foamed, it is released CO 2 and nitrogen make the polymer form a porous polymer with fine pores, so that the biodegradable additives are uniformly distributed in the porous polymer, and a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed is obtained.
  • the foaming zone is a pipe zone of a non-woven screw, and the temperature of this zone is ⁇ 300°C.
  • the production process of the fast biodegradable microporous polyester fiber wherein, in the step S5, the spinning fluid is subjected to spinning, drafting, shaping, and cutting processes through a spinneret to obtain short fibers ,
  • the short fiber is a fast biodegradable microporous fiber.
  • the production process of the rapid biodegradable microporous polyester fiber wherein, in the step S5, the spinning fluid is passed through a spinneret for spinning, drawing, and setting processes to obtain filaments.
  • the filament is a fast biodegradable microporous fiber; or the spinning fluid is processed by spinning, drawing, setting, and crimping through a spinneret to obtain a filament, which is a fast biodegradable filament Of microporous fibers.
  • the beneficial effects of the present invention provides a rapid biodegradable microporous polyester fiber production process, and by adding high-temperature foaming agent and biodegradable additives, the biodegradable additives are foamed and decomposed at high temperature.
  • the biodegradable additives in the microporous polyester fiber are fully dispersed and evenly distributed, and at the same time, the microporous polyester fiber becomes a porous fiber material, so that the microporous polyester fiber becomes a fully dispersed biodegradable additive.
  • evenly distributed fibers with loose structure the fibers are easy to biodegrade, accelerate the speed of biodegradation, and shorten the degradation cycle exponentially.
  • Fig. 1 is a flow chart of the production process of the rapid biodegradable microporous polyester fiber of the present invention.
  • first and second are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with “first” and “second” may explicitly or implicitly include one or more of the features. In the description of the present invention, “plurality” means two or more than two, unless otherwise specifically defined.
  • the "above” or “below” of the first feature of the second feature may include direct contact between the first and second features, or may include the first and second features Not in direct contact but through other features between them.
  • the "above”, “above” and “above” of the first feature on the second feature include the first feature directly above and obliquely above the second feature, or it simply means that the first feature is higher in level than the second feature.
  • the “below”, “below” and “below” of the second feature of the first feature include the first feature directly below and obliquely below the second feature, or it simply means that the level of the first feature is smaller than the second feature.
  • a process for producing a rapidly biodegradable microporous polyester fiber specifically includes the following steps:
  • the high temperature resistant foaming agent is a combination of an anionic surfactant and other additives (such as AGES, AGS8 type, PMP-1 type, commercial foaming agent F240B, etc.), or Sulfonate anionic surfactants are compounded with other additives (such as a high temperature resistant drilling fluid foaming agent disclosed in patent CN107841295 A, etc.), or KGF-1 high temperature foaming agent (such as heavy oil Steam soaking high temperature foaming agent, etc.), etc.
  • an anionic surfactant such as AGES, AGS8 type, PMP-1 type, commercial foaming agent F240B, etc.
  • Sulfonate anionic surfactants are compounded with other additives (such as a high temperature resistant drilling fluid foaming agent disclosed in patent CN107841295 A, etc.), or KGF-1 high temperature foaming agent (such as heavy oil Steam soaking high temperature foaming agent, etc.), etc.
  • the first monomer is terephthalic acid; and the second monomer is ethylene glycol.
  • the decomposition temperature of the high-temperature resistant foaming agent is ⁇ 300°C, and CO 2 and nitrogen are released after high-temperature thermal decomposition.
  • the melting points of the first monomer and the second monomer are both lower than 280 degrees.
  • the spinning temperature in the spinning screw is lower than 300°C.
  • the biodegradable additives include natural polymer cellulose, synthetic polycaprolactone, polyvinyl alcohol, aliphatic-aromatic lipids, modified polylactic acid, monosaccharides, hexyl Any one or more combinations of aldose, etc., can also use existing biodegradable additives (such as a biodegradable agent, biodegradable fiber and preparation method disclosed in patent CN 110644066 A).
  • the step S4 specifically includes the following process: the polyester polymer fluid containing biodegradable additives and high temperature resistant foaming agent is discharged from the spinning screw and enters the foaming zone for high temperature foaming.
  • the high-temperature foaming agent produces chemical foam, and the impact of foaming makes the biodegradable additives diffuse more uniformly in the spinning fluid.
  • the high-temperature foaming agent foams, it releases CO 2 and nitrogen to make the polymer form fine
  • the porous polymer with pores enables the biodegradable additives to be evenly distributed in the porous polymer to obtain a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed.
  • the foaming zone is a duct zone of a non-woven screw, and the temperature of this zone is ⁇ 300°C.
  • the foaming zone adopts a foaming box, and the temperature in the foaming box is ⁇ 300°C.
  • S5 The spinning fluid is made into corresponding microporous polyester fiber according to the production requirements.
  • the spinning fluid in the step S5, is subjected to spinning, drawing, shaping, and cutting processes through a spinneret to obtain short fibers, which are rapidly biodegradable fibers. Microporous fibers.
  • the fiber is a fast biodegradable microporous fiber.
  • the spinning fluid is passed through a spinneret for spinning, drawing, and setting processes to obtain filaments (FDY (full drawn yarn, full name: FULL)
  • the fiber is a fast biodegradable microporous fiber.
  • the spinning fluid is passed through a spinneret for spinning, drawing, setting, and crimping processes to obtain filaments (DTY (DTY) Full name: DRAW
  • the microbial fully dispersed and uniformly distributed loose structure fiber produced by this production process has greatly accelerated its biodegradability and shortened its degradation cycle by more than one time (the traditional degradation cycle ranges from several weeks to 30 months, but the use of The biodegradable rate of the fiber made by this technical solution is 1/2 of the traditional degradation rate.
  • the first monomer is terephthalic acid: the second monomer is ethylene glycol: 2/1.
  • a high temperature resistant commercial foaming agent F240B is added.
  • the decomposition temperature of the high-temperature resistant foaming agent is ⁇ 300°C, and CO 2 and nitrogen are released after high-temperature thermal decomposition.
  • the proportion of foaming agent is 1/97 of the whole.
  • the biodegradable additive is a biodegradable agent, biodegradable fiber and biodegradable fiber disclosed in patent CN 110644066 A.
  • the biodegradation agent disclosed in the preparation method is added in an amount of 2% of the total weight of the rapid biodegradable microporous polyester fiber, and a polyester polymer fluid containing biodegradable additives and a high temperature resistant foaming agent is prepared.
  • the spinning temperature of the polyester polymer fluid spinning screw containing biodegradable additives and high temperature resistant foaming agent is 290 degrees. After being discharged, it enters the foaming zone for high-temperature foaming, and the temperature of the foaming zone is 305 Degree; high temperature resistant foaming agent chemically foams, the impact of foaming makes the biodegradable additives more uniformly diffused in the spinning fluid, after the high temperature resistant foaming agent foams, it releases CO 2 and nitrogen to make polymerization
  • the material forms a porous polymer with micropores, so that the biodegradable additives are uniformly distributed in the porous polymer, and a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed is obtained.
  • the spinning fluid with a bubble structure is prepared into DTY through a conventional spinning process.
  • DTY 100D/96F.
  • the strength is 3.1 cn/dtex, and the elongation at break is 33%.
  • the fiber can be biodegraded by 90% in 90 days under ordinary soil environment.
  • the first monomer is terephthalic acid and the second monomer is ethylene glycol: 3/1.
  • the high temperature resistant KGF-1 high temperature foaming agent is added.
  • the decomposition temperature of the high-temperature resistant foaming agent is ⁇ 300°C, and CO 2 and nitrogen are released after high-temperature thermal decomposition.
  • the ratio of foaming agent to the whole is 1/95.
  • the dried polymer is fed into the spinning screw, and the biodegradable additive is injected from the spinning syringe.
  • the biodegradable additive is a biodegradable agent, biodegradable fiber, and biodegradable fiber disclosed in patent CN 110644066 A.
  • the biodegradation agent disclosed in the preparation method is added in an amount of 5% of the total weight of the rapid biodegradable microporous polyester fiber.
  • the polyester polymer fluid containing biodegradable additives and high temperature resistant foaming agent is prepared.
  • the spinning temperature of the polyester polymer fluid spinning screw containing biodegradable additives and high temperature resistant foaming agent is 290 degrees. After being discharged, it enters the foaming zone for high-temperature foaming, and the temperature of the foaming zone is 305 Degree; high temperature resistant foaming agent chemically foams, the impact of foaming makes the biodegradable additives more uniformly diffused in the spinning fluid, after the high temperature resistant foaming agent foams, it releases CO 2 and nitrogen to make polymerization
  • the material forms a porous polymer with micropores, so that the biodegradable additives are uniformly distributed in the porous polymer, and a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed is obtained.
  • the spinning fluid with bubble structure is prepared into FDY through a conventional spinning process.
  • FDY 100D/96F.
  • the strength is 2.9 cn/dtex, and the elongation at break is 35%.
  • the fiber can be biodegraded by 90% in 80 days under ordinary soil environment.
  • the first monomer is terephthalic acid and the second monomer is ethylene glycol: 4/1.
  • a high-temperature resistant PMP-1 foaming agent is added.
  • the decomposition temperature of the high-temperature resistant foaming agent is ⁇ 300°C, and CO 2 and nitrogen are released after high-temperature thermal decomposition.
  • the ratio of foaming agent to the whole is 1/98.
  • biodegradable additives include synthetic polycaprolactone, polyvinyl alcohol, and aliphatic-aromatic A mixture of tri-group lipids, modified polylactic acid, monosaccharides, and aldohexose, added in an amount of 3% of the total weight of the rapid biodegradable microporous polyester fiber.
  • the polyester polymer fluid containing biodegradable additives and high temperature resistant foaming agent is prepared.
  • the spinning temperature of the polyester polymer fluid spinning screw containing biodegradable additives and high temperature resistant foaming agent is 290 degrees. After being discharged, it enters the foaming zone for high-temperature foaming, and the temperature of the foaming zone is 305 Degree; high temperature resistant foaming agent chemically foams, the impact of foaming makes the biodegradable additives more uniformly diffused in the spinning fluid, after the high temperature resistant foaming agent foams, it releases CO 2 and nitrogen to make polymerization
  • the material forms a porous polymer with micropores, so that the biodegradable additives are uniformly distributed in the porous polymer, and a spinning fluid with a bubble structure in which the biodegradable additives are fully dispersed and evenly distributed is obtained.
  • the spinning fluid with a bubble structure is prepared into short fibers through a conventional spinning process.
  • the short fiber is 1.5D*38mm, the strength is 3.5 cn/dtex, and the elongation at break is 29%.
  • the fiber can be biodegraded by 90% in 102 days under ordinary soil environment.
  • the description with reference to the terms “one embodiment”, “certain embodiments”, “exemplary embodiments”, “examples”, “specific examples”, or “some examples” etc. means to combine The specific features, structures, materials or characteristics described in the embodiments or examples are included in at least one embodiment or example of the present invention.
  • the schematic representation of the above-mentioned terms does not necessarily refer to the same embodiment or example.
  • the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner.

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  • Mechanical Engineering (AREA)
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Abstract

一种快速生物降解的微多孔聚酯纤维的生产工艺，通过加入由高温发泡剂与生物降解添加物，使生物降解添加物在高温发泡和分解的过程中，在微多孔聚酯纤维内部的生物降解添加物充分分散且均匀分布，同时使该微多孔聚酯纤维成为多孔性纤维材料，从而使本微多孔聚酯纤维成为生物降解添加物充分分散且均匀分布的结构松散的纤维，该纤维易于生物降解，加速生物降解的速度，成倍缩短降解周期。

Description

一种快速生物降解的微多孔聚酯纤维的生产工艺 技术领域
本发明涉及纤维降解技术领域，尤其涉及的是一种快速生物降解的微多孔聚酯纤维的生产工艺。
背景技术
利用微生物，对涤纶进行生物降解，以保护环境，已经有很多年的研究和应用了。目前的方法，是在聚酯纤维生产中，先将一定比例的生物降解添加物与聚酯切片混合造粒为生物降解添加物母粒，在聚酯纤维纺丝时候，加入这种母粒而使聚酯纤维成为生物可降解的聚酯纤维。
该生物降解添加物，具有一定的亲水性，在一定时间内，能够使聚酯纤维发生链锻水解，且在有微生物存在的环境下，能够与微生物协同使聚酯纤维分解为小分子化合物，达到生物降解的效果。而降解时间、速度，是最关键因素。目前，一般能够在30周至30个月的不等时间而发生基本降解。且对于高的特性粘度(IV)的回收用聚酯，还没有良好的降解效果。
但有以下因素，影响聚酯纤维的生物降解速度和效率，及回收用聚酯：
1.生物降解添加物，在纤维中难于充分均匀分布。
目前，在纺丝流体中，添加的生物降解添加物的母粒，但添加的比例都不高，一般在1-5％的范围，这是由于纺丝的可纺性以及生物添加物的成本原因，导致生物添加物的低比例添加。这种小比例的可降解生物添加物，是自然的混于纺丝流体中，在纺丝螺杆作用下，进行混合。由于纺丝流体的粘稠性，及小比例的生物降解添加物成分，和自然混合的混合方式，使生物添加物难于充分的、均匀的分散于纤维内部，必然有部分区域缺少生物降解添加物。导致生物降解时间变长。
2.致密纤维结构问题
纺丝流体，初原纤维到牵伸及热定型的成型后，纤维是结晶结构致密的封闭集合体。这会导致微生物接触只能从纤维表面开始，从外到内的缓慢降解，且高结晶度的致密结构，也使链锻的断裂及微生物的触及，变得很困难，使微生物的降解速度缓慢。
因此，现有的聚酯纤维生物降解技术还有待于改进和发展。
发明内容
本发明的目的在于提供一种快速生物降解的微多孔聚酯纤维的生产工艺，在纤维生 产成型过程中，使内部的生物降解添加物充分分散且均匀分布在纤维内部，同时使该纤维成为多孔性纤维材料，外界微生物容易触及内部，从而使其成为生物降解添加物充分分散且均匀分布、结构多孔的纤维，以使其易于生物降解，加速生物降解的速度。
本发明的技术方案如下：一种快速生物降解的微多孔聚酯纤维的生产工艺，其中，具体包括以下步骤：
S1：在第一单体与第二单体发生聚合反应的过程中，添加耐高温发泡剂，以得到在含高温发泡剂的聚酯聚合物；
S2：对聚合物进行预结晶处理，然后干燥；
S3：将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物，制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体；
S4：该聚酯聚合物流体从纺丝螺杆排出后进行高温发泡和分解，得到生物降解添加物充分分散且均匀分布的、具有气泡结构的纺丝流体；
S5：将纺丝流体根据生产要求制成相应的微多孔聚酯纤维。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述第一单体为对苯二甲酸；所述第二单体为乙二醇。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述第一单体、第二单体和耐高温发泡剂的重量比为：(第一单体+第二单体)：发泡剂＝X/100-X，其中X为0.1～3。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述第一单体、第二单体的熔点均低于280度。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述纺丝螺杆内的纺丝温度低于300℃。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述步骤S4具体包括以下过程：含生物降解添加物和耐高温发泡剂的聚酯聚合物流体从纺丝螺杆排出后进入发泡区进行高温发泡，耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述发泡区为一无纺丝螺杆的管道区，该区域的温度≥300℃。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型、切断工艺处理后，制得短纤维，该短纤维为快速生物降解的的多微孔的纤维。
所述的快速生物降解的微多孔聚酯纤维的生产工艺，其中，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型工艺处理后，制得长丝，该长丝为快速生物降解的的多微孔的纤维；或将纺丝流体经过喷丝板进行喷丝、牵伸、定型、卷曲工艺处理后，制得长丝，该长丝为快速生物降解的的多微孔的纤维。
本发明的有益效果：本发明通过提供一种快速生物降解的微多孔聚酯纤维的生产工艺，通过加入由高温发泡剂与生物降解添加物，使生物降解添加物在高温发泡和分解的过程中，在微多孔聚酯纤维内部的生物降解添加物充分分散且均匀分布，同时使该微多孔聚酯纤维成为多孔性纤维材料，从而使本微多孔聚酯纤维成为生物降解添加物充分分散且均匀分布的结构松散的纤维，该纤维易于生物降解，加速生物降解的速度，成倍缩短降解周期。
附图说明
图1是本发明中快速生物降解的微多孔聚酯纤维的生产工艺的步骤流程图。
具体实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个所述特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、 “相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接或可以相互通讯；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本发明。此外，本发明可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。此外，本发明提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。
如图1所示，一种快速生物降解的微多孔聚酯纤维的生产工艺，具体包括以下步骤：
S1：在第一单体与第二单体发生聚合反应的过程中，添加耐高温发泡剂，以得到在含高温发泡剂的聚酯聚合物，其中，第一单体与第二单体的添加比例为重量比2：1～4：1。
在某些具体实施例中，所述耐高温发泡剂为阴离子表面活性剂与其他助剂复配而成(如AGES、AGS8型、PMP-1型、商业发泡剂F240B，等)，或磺酸盐类阴离子表面活性剂与其他助剂复配(如专利CN 107841295 A公开的一种耐高温钻井液发泡剂，等)而成，或KGF-1高温起泡剂(如，稠油蒸汽吞吐高温起泡剂，等)，等。
在某些具体实施例中，所述第一单体为对苯二甲酸；所述第二单体为乙二醇。
在某些具体实施例中，所述耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。
在某些具体实施例中，所述第一单体、第二单体和耐高温发泡剂的重量比为：(第一单体+第二单体)：发泡剂＝X/100-X，其中X为0.1-3的范围，即(第一单体+第二单体)：发泡剂＝0.1/99.9～3/97。
在某些具体实施例中，所述第一单体、第二单体的熔点均低于280度。
S2：对聚合物进行预结晶处理，然后干燥。
S3：将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物，制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体，其中，生物降解添加物的添加比例为快速生物降解的微多孔聚酯纤维总体重量的0.5-5％。
在某些具体实施例中，所述纺丝螺杆内的纺丝温度低于300℃。
在某些具体实施例中，所述生物降解添加物包括天然高分子纤维素、人工合成的聚己内酯、聚乙烯醇、脂肪族-芳香族的脂、改性聚乳酸、单糖、己醛醣等任一或多种组合，也可采用现有的生物降解添加物(如专利CN 110644066 A公开的一种生物降解剂、生物降解纤维及制备方法)。
S4：该聚酯聚合物流体从纺丝螺杆排出后进行高温发泡和分解，得到生物降解添加物充分分散且均匀分布的、具有气泡结构的纺丝流体。
在某些具体实施例中，所述步骤S4具体包括以下过程：含生物降解添加物和耐高温发泡剂的聚酯聚合物流体从纺丝螺杆排出后进入发泡区进行高温发泡，耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
在某些具体实施例中，所述发泡区为一无纺丝螺杆的管道区，该区域的温度≥300℃。
优选的，所述发泡区采用发泡箱，发泡箱内的温度≥300℃。
S5：将纺丝流体根据生产要求制成相应的微多孔聚酯纤维。
在某些具体实施例中，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型、切断工艺处理后，制得短纤维，该纤维为快速生物降解的的多微孔的纤维。
YARN，采用纺丝拉伸进一步制得的合成纤维长丝))，该纤维为快速生物降解的的多微孔的纤维。DRAW在某些具体实施例中，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型工艺处理后，制得长丝(FDY(全拉伸丝，全称：FULL
YARN，是利用POY做原丝，进行拉伸和假捻变形加工制成))，该纤维为快速生物降解的的多微孔的纤维。TEXTURED在某些具体实施例中，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型、卷曲工艺处理后，制得长丝(DTY(是拉伸变形丝，全称：DRAW
经过本生产工艺制得的微生物充分分散且均匀分布的结构松散的纤维，其生物可降解速度大大加快，降解周期缩短一倍以上(传统的降解周期在几周到30个月不等，而使用本技术方案制成的纤维的生物可降解速度为传统降解速度的1/2)。
根据上述所述的快速生物降解的微多孔聚酯纤维的生产工艺，现列举以下实施例加以说明：
实施例1
(1)聚合物的制备
其中，第一单体为对苯二甲酸：第二单体为乙二醇：2/1。在第一单体与第二单体发生聚合反应的过程中，添加耐高温的商业发泡剂F240B。该耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。其中发泡剂的比例，占整体的比例为1/97。
(2)对聚合物进行预结晶处理，然后干燥。
(3)将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物，该生物降解添加物为专利CN 110644066 A公开的一种生物降解剂、生物降解纤维及制备方法中公开的生物降解剂，添加量为本快速生物降解的微多孔聚酯纤维总体重量的2％，制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体。
(4)该含生物降解添加物和耐高温发泡剂的聚酯聚合物流体纺丝螺杆的纺丝温度为290度，排出后进入发泡区进行高温发泡，发泡区的温度为305度；耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
(5)将该具有气泡结构的纺丝流体经常规的纺丝工艺，制备为DTY。
(6)DTY为100D/96F.强度为3.1cn/dtex,断裂伸长率为33％。
(7)该纤维在普通的土壤环境下，90天可以生物降解90％。
实施例2
(1)聚合物的制备
其中，第一单体为对苯二甲酸：第二单体为乙二醇:3/1。在第一单体与第二单体发生聚合反应的过程中，添加耐高温的KGF-1高温起泡剂。该耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。其中发泡剂的比例，占整体的比例为1/95。
(2)对聚合物进行预结晶处理，然后干燥。
(3)将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物， 该生物降解添加物为专利CN 110644066 A公开的一种生物降解剂、生物降解纤维及制备方法中公开的生物降解剂，添加量为本快速生物降解的微多孔聚酯纤维总体重量的5％。制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体。
(4)该含生物降解添加物和耐高温发泡剂的聚酯聚合物流体纺丝螺杆的纺丝温度为290度，排出后进入发泡区进行高温发泡，发泡区的温度为305度；耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
(5)将该具有气泡结构的纺丝流体经常规的纺丝工艺，制备为FDY。
(6)FDY为100D/96F.强度为2.9cn/dtex,断裂伸长率为35％。
(7)该纤维在普通的土壤环境下，80天可以生物降解90％。
实施例3
(1)聚合物的制备
其中，第一单体为对苯二甲酸：第二单体为乙二醇:4/1。在第一单体与第二单体发生聚合反应的过程中，添加耐高温的PMP-1型发泡剂。该耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。其中发泡剂的比例，占整体的比例为1/98。
(2)对聚合物进行预结晶处理，然后干燥。
(3)将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物，该生物降解添加物包括人工合成的聚己内酯、聚乙烯醇、脂肪族-芳香族的脂、改性聚乳酸、单糖、己醛醣的混合物，添加量为本快速生物降解的微多孔聚酯纤维总体重量的3％。制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体。
(4)该含生物降解添加物和耐高温发泡剂的聚酯聚合物流体纺丝螺杆的纺丝温度为290度，排出后进入发泡区进行高温发泡，发泡区的温度为305度；耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
(5)将该具有气泡结构的纺丝流体经常规的纺丝工艺，制备为短纤维。
(6)该短纤维为1.5D*38mm.强度为3.5cn/dtex,断裂伸长率为29％。
(7)该纤维在普通的土壤环境下，102天可以生物降解90％。
在本说明书的描述中，参考术语“一个实施方式”、“某些实施方式”、“示意性实施 方式”、“示例”、“具体示例”、或“一些示例”等的描述意指结合所述实施方式或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施方式或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施方式或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施方式或示例中以合适的方式结合。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

  1. 一种快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，具体包括以下步骤：
    S1：在第一单体与第二单体发生聚合反应的过程中，添加耐高温发泡剂，以得到在含高温发泡剂的聚酯聚合物；
    S2：对聚合物进行预结晶处理，然后干燥；
    S3：将干燥后的聚合物送进纺丝螺杆，并从纺丝注射器中，注入生物降解添加物，制备得到含生物降解添加物和耐高温发泡剂的聚酯聚合物流体；
    S4：该聚酯聚合物流体从纺丝螺杆排出后进行高温发泡和分解，得到生物降解添加物充分分散且均匀分布的、具有气泡结构的纺丝流体；
    S5：将纺丝流体根据生产要求制成相应的微多孔聚酯纤维。
  2. 根据权利要求1所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述第一单体为对苯二甲酸；所述第二单体为乙二醇。
  3. 根据权利要求1所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述耐高温发泡剂的分解温度≥300℃，经高温热分解后释放CO 2和氮气。
  4. 根据权利要求1所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述第一单体、第二单体和耐高温发泡剂的重量比为：(第一单体+第二单体)：发泡剂＝X/100-X，其中X为0.1～3。
  5. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述第一单体、第二单体的熔点均低于280度。
  6. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述纺丝螺杆内的纺丝温度低于300℃。
  7. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述步骤S4具体包括以下过程：含生物降解添加物和耐高温发泡剂的聚酯聚合物流体从纺丝螺杆排出后进入发泡区进行高温发泡，耐高温发泡剂发生化学发泡，发泡的冲击力使生物降解添加物更加均匀的扩散于纺丝流体中，耐高温发泡剂产生发泡后，释放CO 2和氮气，使聚合物形成微细孔的多孔聚合物，使生物降解添加物均匀分布在多孔聚合物中，获得生物降解添加物充分分散且均匀分布的具有气泡结构的纺丝流体。
  8. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述发泡区为一无纺丝螺杆的管道区，该区域的温度≥300℃。
  9. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型、切断工艺处理后，制 得短纤维，该短纤维为快速生物降解的的多微孔的纤维。
  10. 根据权利要求1至4任一所述的快速生物降解的微多孔聚酯纤维的生产工艺，其特征在于，所述步骤S5中，将纺丝流体经过喷丝板进行喷丝、牵伸、定型工艺处理后，制得长丝，该长丝为快速生物降解的的多微孔的纤维；或将纺丝流体经过喷丝板进行喷丝、牵伸、定型、卷曲工艺处理后，制得长丝，该长丝为快速生物降解的的多微孔的纤维。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115852515A (zh) * 2022-11-29 2023-03-28 上海水星家用纺织品股份有限公司 低致敏抗菌聚酯纤维及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113318044B (zh) * 2021-05-28 2023-06-20 广州艾菲芭美容科技有限公司 一种可软化死皮的聚丙烯干态无纺面膜
CN113304081B (zh) * 2021-06-10 2023-08-18 菲诗倾城(广州)生物科技有限公司 一种可降解保湿自发热聚酯基干态面膜

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065870A (zh) * 1991-04-18 1992-11-04 纳幕尔杜邦公司 含氢氟烃发泡剂的微孔和超微孔材料
WO2009113288A1 (ja) * 2008-03-11 2009-09-17 株式会社カネカ 樹脂組成物
WO2011036272A2 (en) * 2009-09-25 2011-03-31 Novamont S.P.A. Biodegradable polyester
CN102828276A (zh) * 2012-09-04 2012-12-19 福建鑫华股份有限公司 一种可生物降解再生涤纶短纤维的制备方法
CN109322002A (zh) * 2018-10-10 2019-02-12 无锡沛莱斯纺织有限公司 一种生物可降解聚酯织物及其制备方法
CN110644066A (zh) * 2019-09-12 2020-01-03 中山尚洋科技股份有限公司 生物降解剂、生物降解纤维及制备方法
CN110832124A (zh) * 2018-01-02 2020-02-21 普莱玛有限公司 生物降解增强的合成纤维及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008280649A (ja) * 2007-05-11 2008-11-20 Toray Ind Inc 発泡繊維の製造方法と該方法により得られる発泡繊維
CN101284225A (zh) * 2007-12-21 2008-10-15 北京科技大学 一种波聚合技术制备疏水性聚合物整体柱材料的方法
CN102174717B (zh) * 2011-03-15 2013-06-05 浙江理工大学 一种多微孔发泡聚丙烯纤维及制备方法
CN102229707B (zh) * 2011-05-16 2013-05-08 四川大学 生物可降解的聚己二酸-对苯二甲酸-丁二醇酯高发泡倍率微孔发泡粒子及其制备方法
CN109304834A (zh) * 2017-07-26 2019-02-05 威海维赛新材料科技有限公司 Pvc泡沫塑料的制备方法
CN110685025A (zh) * 2019-11-08 2020-01-14 张家港市金鹰纺织有限公司 一种多孔涤纶短纤维的生产工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065870A (zh) * 1991-04-18 1992-11-04 纳幕尔杜邦公司 含氢氟烃发泡剂的微孔和超微孔材料
WO2009113288A1 (ja) * 2008-03-11 2009-09-17 株式会社カネカ 樹脂組成物
WO2011036272A2 (en) * 2009-09-25 2011-03-31 Novamont S.P.A. Biodegradable polyester
CN102828276A (zh) * 2012-09-04 2012-12-19 福建鑫华股份有限公司 一种可生物降解再生涤纶短纤维的制备方法
CN110832124A (zh) * 2018-01-02 2020-02-21 普莱玛有限公司 生物降解增强的合成纤维及其制备方法
CN109322002A (zh) * 2018-10-10 2019-02-12 无锡沛莱斯纺织有限公司 一种生物可降解聚酯织物及其制备方法
CN110644066A (zh) * 2019-09-12 2020-01-03 中山尚洋科技股份有限公司 生物降解剂、生物降解纤维及制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115852515A (zh) * 2022-11-29 2023-03-28 上海水星家用纺织品股份有限公司 低致敏抗菌聚酯纤维及其制备方法
CN115852515B (zh) * 2022-11-29 2024-06-11 上海水星家用纺织品股份有限公司 低致敏抗菌聚酯纤维及其制备方法

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