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CN1958893A - Polythene cross-linking fibers with shape memory, and preparation method - Google Patents

Polythene cross-linking fibers with shape memory, and preparation method Download PDF

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CN1958893A
CN1958893A CN 200510118386 CN200510118386A CN1958893A CN 1958893 A CN1958893 A CN 1958893A CN 200510118386 CN200510118386 CN 200510118386 CN 200510118386 A CN200510118386 A CN 200510118386A CN 1958893 A CN1958893 A CN 1958893A
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fiber
polyethylene
crosslinked
cross
linking
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CN 200510118386
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胡金莲
李加深
刘冶球
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香港理工大学
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Abstract

The present invention relates to a shape memory polyethylene crosslinked fiber and its preparation method. It is characterized by that the restorable deformation temperature of said polyethylene crosslinked fiber is 40-60 deg.C, under the condition of tensioning by 200% the deformation restoration rate of said fiber is 80-99%. Said polyethylene crosslinked fiber is obtained by utilizing polyethylene fiber and making it undergo the process of cross-linking modification treatment under the action of radiation ray.

Description

形状记忆性聚乙烯交联纤维及其制备方法 Shape memory cross-linked polyethylene fiber and its preparation method

技术领域 FIELD

本发明涉及改性聚乙烯交联纤维,更具体的说,涉及一种形状记忆性聚乙烯交联纤维及其制造方法。 The present invention relates to a modified cross-linked polyethylene fiber, more particularly, to a shape memory cross-linked polyethylene fiber and its manufacturing method.

背景技术 Background technique

形状记忆材料是指能够对外界环境(温度、光照、压力或化学物质等)的变化作出响应,并根据这些变化对其自身的力学参数(形状、位置或应变等)进行相应调整,从而回复到预先设定状态的功能性材料。 Means a shape memory material capable of responding to the external environment (temperature, light, pressure or chemicals, etc.) change, and adjust accordingly their own mechanical parameters (shape, location or strain) in accordance with these changes, so that return to preset state functional material. 常用的形状记忆材料有形状记忆合金和形状记忆聚合物,与形状记忆合金相比,形状记忆聚合物具有质量轻、成本低、形状记忆温度易于调节、易着色、形变量大、赋形容易,而且易于激发其形变恢复功能等特点。 Commonly used shape memory materials are shape memory alloys and shape memory polymers, as compared with shape memory alloys, shape memory polymer having a light weight, low cost, easy to adjust the temperature of the shape memory, easy to color, large deformation, easily shaped, and easy to stimulate their deformation recovery characteristics. 目前的形状记忆聚合物主要是基于聚氨酯、聚降冰片烯、反式1,4-聚异戊二烯等的高分子材料。 The current is mainly based on shape memory polymer material such as polyurethane polymer, polynorbornene, trans 1,4-polyisoprene and the like.

形状记忆纤维的原理是,纤维中的固定相(也称硬段)有很好的耐热性,而可逆相(也称软段)在10-50℃温度范围内有明显的结晶熔融温度(Tm)或者玻璃化转变温度(Tg),Tm或Tg可设定为人体穿着不适温度。 Principle shape memory fibers, the fiber of the stationary phase (also referred to as hard segment) has good heat resistance, and a reversible phase (also referred to as soft segment) of a clear crystalline melting temperature in the temperature range 10-50 deg.] C ( Tm) or glass transition temperature (Tg), Tm or Tg may be set to a human body temperature discomfort. 当环境温度低于Tm或Tg时,高分子链段的运动被冻结,分子链的致密排列阻止了热的传递,从而在低温时具有良好的保暖性;当温度高于Tm或Tg时,高分子链之间的间隙明显增大,透湿透气性显著提高。 When the ambient temperature or a Tg of below Tm, the polymer chain motion is frozen, a compact arrangement of molecular chains prevents the transfer of heat, so as to have good heat resistance at low temperatures; when the temperature is higher than Tm or a Tg of, high the gap between molecular chains significantly increased, remarkably improved moisture permeability. 另外,具有合适记忆触发温度的服装面料有良好的抗皱性和耐磨性等性能,当其在使用过程中产生皱痕后,可以通过升高温度使其恢复原来的形状(免熨)。 Further, a suitable memory having a trigger temperature of the fabric with good wrinkle resistance and abrasion resistance properties, which is generated when the creasing during use, so that it can restore the original shape (iron-free) by increasing the temperature.

聚乙烯属于典型的结晶性聚合物,有比较明确的熔点,在熔点以下,大分子链受晶格能的束缚,链段难于自由运动,处于玻璃态;一旦温度到达到其熔点以上,大分子热运动突破晶格结构束缚,成为粘流态。 Polyethylene is a typical crystalline polymer, a relatively clear melting point below the melting point, the macromolecular chains bound lattice energy of the segment is difficult to move freely in the glassy state; once the temperature reaches above its melting point to, macromolecules breakthrough thermal lattice structure bound to become viscous flow state. 这种聚乙烯不具有形状记忆效应,但是在对聚乙烯进行交联后,聚合物被加热到其熔点以上时则不再是粘流态,而是高弹态,此时可以通过施加外力使其变形,在其变形状态下进行冷却,结晶复出,冻结应力。 Such polyethylenes having no shape memory effect, but after crosslinking of the polyethylene, the polymer is heated to above its melting point is no longer a viscous flow state, but the high elastic state, when external force is applied can be made deformation, in its deformed state cooling and crystallization back, the frozen stresses. 当聚合物再被加热到熔点以上时,结晶熔化,应力释放,材料恢复原来的形态,完成一个记忆循环。 When the polymer is then heated to above the melting point, crystalline melting, stress relief material recovers its original shape, completing a memory cycle. 因而交联聚乙烯可以作为制备形状记忆纤维的材料。 XLPE thus prepared can be used as a material of the shape memory fibers.

利用不同的辐照方法对聚乙烯树脂或者聚乙烯纤维进行处理可以提高和改善它们的耐热性、抗蠕变性和表面粘接性,但是目前所有的技术都没有涉及到聚乙烯纤维的形状记忆性。 Using different irradiation method of a polyethylene resin or the polyethylene fibers may be treated to enhance and improve their heat resistance, creep resistance and surface adhesion, but all current technologies do not address the shape of the polyethylene fibers memory.

发明内容 SUMMARY

本发明要解决的技术问题在于,针对现有技术的上述不足,提供一种改性聚乙烯交联纤维,通过改性赋予聚乙烯纤维以形状记忆功能,同时提高了聚乙烯纤维的耐热性、抗蠕变性等。 The present invention is to solve the technical problem, the prior art problems mentioned above, there is provided a cross-linked modified polyethylene fibers, polyethylene fibers imparted by modifying a shape memory, while improving the heat resistance of polyethylene fibers , creep resistance and so on.

本发明的另一目的还在于提供一种形状记忆性聚乙烯交联纤维的制备方法。 Another object of the present invention is to provide a method for preparing a shape memory cross-linked polyethylene fibers.

本发明提供的形状记忆性聚乙烯交联纤维,其特征是,该聚乙烯交联纤维的可恢复变形温度为40~60℃,在拉伸200%以下,纤维的变形恢复率在80~99%。 The present invention provides a shape memory cross-linked polyethylene fiber, characterized in that the crosslinked fibers of the polyethylene recoverable deformation temperature is 40 ~ 60 ℃, stretched at 200%, the strain recovery rate of 80 to 99 fibers %. 该聚乙烯交联纤维是通过将聚乙烯纤维在辐照射线的作用下进行交联改性而制得的。 The crosslinked polyethylene fibers are polyethylene fibers by crosslinking under the effect of modifying ray irradiation is prepared.

本发明使用的聚乙烯的包括高密度聚乙烯(HDPE)、线形低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)或超高分子量聚乙烯(UHMWPE)。 In the present invention include polyethylene, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) or ultrahigh molecular weight polyethylene (UHMWPE). 不同的聚乙烯具有不同的分子链结构。 Polyethylenes having different molecular chains of different structures. HDPE是线形分子结构,分子链上支链少;LLDPE分子链上有较多的短支链,基本无长支链,仍属线形结构;LDPE具有长支链支化结构,也有部分分子内转移反咬形成的短支链,其结晶性能、熔点及力学性能都低于HDPE;UHMWPE为线形直链结构,重均相对分子量可达100-500万。 HDPE is a linear molecular structure, branched chain molecular less; have more short chain branched LLDPE molecular chain substantially free of long chain branching, is still linear structure; of LDPE having a branched long-chain branched structure, but also the transfer of the molecule short chain branches formed bite, crystallization properties, and mechanical properties are lower than the melting point of the HDPE; UHMWPE is a linear straight chain structure, the relative weight average molecular weight of up to 100-500 million.

本发明主要是针对不同的聚乙烯纤维,利用各种射线和紫外光进行辐照交联改性,控制适当的条件,可以在基本不影响聚乙烯纤维力学性能的基础上,赋予聚乙烯纤维具有形状记忆功能。 The present invention is directed to various polyethylene fibers, using a variety of ultraviolet ray irradiation and the crosslinking modification, control of appropriate conditions, can not affect the basic mechanical properties of the polyethylene fibers, polyethylene fibers have imparted shape memory function.

本发明提供的形状记忆性聚乙烯交联纤维的制备方法,包含如下步骤:a)将聚乙烯纤维放置在密闭容器中,并将容器抽真空至6.5×10-2pa;b)通过自动循环系统将装载有聚乙烯纤维的容器送入辐照系统,在辐射源发出的辐照射线的作用下进行交联改性;c)将经辐照后的聚乙烯纤维取出,置于真空干燥箱内在80~90℃下退火1小时。 The method of preparing a shape memory polyethylene, crosslinked fibers of the present invention provided, comprising the steps of: a) polyethylene fibers is placed in a closed vessel, and the vessel was evacuated to 6.5 × 10-2pa; b) by an automatic circulation system the container loaded with polyethylene fibers into the irradiation system, under the effect of modifying the crosslinking radiation in the radiation source emits radiation; c) a polyethylene fiber was taken out after irradiation, positioned internal vacuum oven 80 ~ 90 ℃ annealed for 1 hour.

其中,在步骤a)将聚乙烯纤维放置入密闭容器前,还可以将该聚乙烯纤维浸泡在光敏剂和交联剂溶液中一定时间,然后再放置于密闭容器中。 Before wherein in step a) is placed into a closed container polyethylene fibers, polyethylene fibers may also be soaked in the photosensitizer and the crosslinking agent solution certain time, then add placed in a sealed container.

本发明提供的通过射线辐照制备形状记忆性聚乙烯交联纤维的工艺特征还在于,将聚乙烯纤维放置于密闭容器中,抽真空至6.5×10-2Pa,或者抽真空之后再充入乙炔气或者高纯氮气,最好在高真空或完全无氧状态下进行;在将盛有聚乙烯纤维容器送入辐照系统后,由电脑监控辐照强度等各项参数,当以电子加速器作为辐射源时,控制辐照强度在0.04~1.6J/cm2之间;当以放射源作为辐射源时,辐照剂量为25~250kGy,当辐照剂量大于100kGy时,每辐照100kGy,把样品从辐照系统中取出2-3分钟,防止样品温度太高而引起解取向。 Acetylene refilling provided by the present invention, memory ray irradiation process wherein polyethylene, crosslinked fibers prepared shape in that the polyethylene fiber is placed in a closed vessel evacuated to 6.5 × 10-2Pa, or after evacuation purity nitrogen gas or, preferably carried out under high vacuum or oxygen-free state completely; after the container filled with polyethylene fibers into the irradiation system, the computer monitoring the parameters of the radiation intensity and the like, when the electronic accelerator as radiation source, to control the radiation intensity between 0.04 ~ 1.6J / cm2; when as a radiation source to the radiation source, the radiation dose is 25 ~ 250kGy, when the radiation dose greater than 100 kGy, 100 kGy per irradiation, the sample 2-3 minutes, removed from the irradiation system, prevent the sample temperature is too high and cause disorientation.

本发明中的辐照射线可以是等离子体、紫外线、电子射线、放射源射线或其它任何适合的辐照射线。 The present invention may be a plasma radiation rays, ultraviolet rays, electron rays, radiation source, or any other suitable radiation ray irradiation.

实施本发明提供的形状记忆性聚乙烯交联纤维及其制备方法的有益效果是,利用辐照对聚乙烯纤维进行交联改性,从而赋予聚乙烯纤维以形状记忆功能,同时提高了聚乙烯纤维的耐热性、抗蠕变性等。 Embodiment crosslinked polyethylene fiber and the beneficial effects of the preparation method of the present invention, the shape memory is provided, polyethylene fibers crosslinking modification of irradiation, polyethylene fibers to impart shape memory, while increasing the polyethylene heat resistance, creep resistance and the like fibers.

本发明提供的聚乙烯形状记忆交联纤维具有以下一些特点:1.在高于定形温度时(制造过程中)给予纤维所需的形状,之后降低温度到定形温度以下,所得形状将被记住;2.在定形温度以下和转变温度以上使用时表现为弹性纤维;3.如果在使用过程中(一般在转变温度以下)纤维形状因外力发生变化(如折皱),在转变温度(如洗衣和干衣温度)以上并在定形温度以下时,纤维会恢复到原来的形状,这就是典型的形状记忆。 The present invention provides a shape memory polyethylene crosslinked fibers have the following characteristics: 1 at a temperature higher than the setting (during manufacture) to give desired fiber shape, after the temperature was lowered to the temperature setting, the resulting shape will be remembered ;. 2 performance when used in the above setting temperature and transition temperature of elastomeric fibers; 3. If during use (typically below the transition temperature) fiber shape change (e.g., wrinkles) occurred due to an external force, the transition temperature (e.g., laundry and drying temperature) and at the setting temperature or less, the fiber will return to its original shape, which is a typical shape memory.

4.纤维在常温(转变温度以下)表现为玻璃态,模量较高,弹性比普通纤维好,但比弹性纤维低;5.耐热性较好;6.制备聚乙烯形状记忆交联纤维的原料与制备普通弹性纤维的原料有所不同,改变原料配比和组成,可以调节形状记忆性能和转变温度;7.形状记忆可以多次反复设计。 4. fibers at room temperature (transition temperature) showed a glassy, ​​high modulus of elasticity than ordinary fibers, but lower than the elastic fibers; 5. good heat resistance; 6 Preparation of crosslinked polyethylene shape memory fibers the raw material prepared with different common elastic fiber, and changing the composition ratio of raw materials, and can adjust the transition temperature of the shape memory properties;. 7 can be repeatedly shape memory design.

具体实施方式 detailed description

下面通过具体的实施例对本发明进行更加详细的描述。 It described below in more detail of the present invention through specific embodiments.

实施例1取超高分子量聚乙烯(UHMWPE)纤维放入密闭容器中,抽真空到6.5×10-2pa,密封后放在传送带上自动进入辐照室,以γ射线作为放射源进行辐照,当电脑显示辐照剂量为50kGy时,取出聚乙烯纤维,然后在真空干燥箱内80℃下退火1小时。 EXAMPLE 1 ultra high molecular weight polyethylene (UHMWPE) fibers were placed in a sealed vessel, evacuated to 6.5 × 10-2pa, automatically on a conveyor belt into the irradiation chamber sealed to γ-ray irradiation as a radiation source, when the computer display irradiation dose is 50 kGy, polyethylene fibers removed, and then annealed in a vacuum oven for 1 hour at 80 ℃.

实施例2取高密度聚乙烯(HDPE)、线形低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)或超高分子量聚乙烯(UHMWPE),以γ射线为辐照射线,累积辐照强度为100kGy,气氛为乙炔气,进行辐照交联反应。 EXAMPLE 2 High density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) or ultrahigh molecular weight polyethylene (the UHMWPE), to γ ​​rays ray irradiation, the cumulative radiation intensity to 100 kGy, acetylene gas atmosphere, irradiation crosslinking reaction. 其它条件同实施例1。 Other conditions were the same as in Example 1. 交联前后聚乙烯纤维的力学性能见表1。 Mechanical properties before and after cross-linked polyethylene fibers shown in Table 1.

表1交联前后聚乙烯纤维的力学性能*1 Table polyethylene fibers the mechanical properties before and after cross-linking 1 * 1

*1纤维的力学性能采用INSTRON纤维强度测试机测定,拉伸速度为50mm/min,每个样品测5根丝束,取平均值。 * The mechanical properties of a fiber using a fiber strength testing machine measured INSTRON tensile speed of 50mm / min, each sample was measured five strands, averaged.

实施例3取超高分子量聚乙烯(UHMWPE)在乙炔气氛下,以等离子体为辐照射线,辐照强度分别为25、50、100、150、200和250kGy,其它条件同实施例1。 Example 3 taken ultrahigh molecular weight polyethylene (UHMWPE) under an atmosphere of acetylene, a plasma radiation was irradiated, and irradiation intensity of 250 kGy 25,50,100,150,200 respectively, other conditions were the same as in Example 1. 所得纤维在110℃下拉伸150%,在40℃下定形,然后再加热到60℃,其变形恢复率见表2。 The resulting fiber was drawn at 110 ℃ 150%, setting at 40 ℃, then heated to 60 ℃, deformation recovery rate shown in Table 2.

表2不同辐照强度下UHMWPE纤维的变形恢复率 Table 2 Deformation recovery rate under different irradiance UHMWPE fibers

实施例4取超高分子量聚乙烯(UHMWPE)纤维在有光敏剂(二苯甲酮及其衍生物,1.0wt%)和交联剂(丙烯酸酯,20wt%)的二甲苯溶液中浸泡20分钟。 EXAMPLE 4 ultrahigh molecular weight polyethylene (UHMWPE) fibers soaked in a photosensitizer (benzophenone and derivatives thereof, 1.0wt%) and a crosslinking agent (acrylate, 20wt%) in xylene solution for 20 minutes . 将浸泡好的纤维放置在密闭容器中,抽真空到6.5×10-2Pa,然后通入高纯氮气,放入紫外交联反应器中,平均辐照强度为0.3J/cm2进行交联改性,辐照完成后,取出聚乙烯纤维,在真空干燥箱内90℃下退火1小时,即得具有形状记忆性聚乙烯交联纤维。 The soaked fibers are placed in a closed vessel, evacuated to 6.5 × 10-2Pa, and high pure nitrogen gas into the reactor UV crosslinking, the average radiation intensity of 0.3J / cm2 crosslinked modified after irradiation is completed, remove the polyethylene fiber, in a vacuum oven at 90 deg.] C annealing for 1 hour to obtain a shape memory cross-linked polyethylene fibers.

需要指出的是,上述实施例只用于对本发明作进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员可以根据本发明的内容,在不超出发明的保护范围内,对发明内容做出一些非本质的和其它方面的改进和调整。 It should be noted that the above embodiments are provided for the present invention will be further described, can not be construed as limiting the scope of the invention, those skilled in the art according to the present invention, within the scope without departing from the invention, of the invention content and make some nonessential improvements and adjustments in other areas.

Claims (10)

  1. 1)一种形状记忆性聚乙烯交联纤维,其特征在于,该聚乙烯交联纤维的可恢复变形温度为40~60℃,在拉伸200%以下,纤维的变形恢复率在80~99%。 1) A shape memory cross-linked polyethylene fiber, characterized in that the crosslinked fibers of the polyethylene recoverable deformation temperature is 40 ~ 60 ℃, stretched at 200%, the strain recovery rate of 80 to 99 fibers %.
  2. 2)根据权利要求1所述的形状记忆性聚乙烯交联纤维,其特征在于,该聚乙烯交联纤维是通过将聚乙烯纤维在辐照射线的作用下进行交联改性而制得的。 2) The shape memory according to claim 1 crosslinked polyethylene fibers, wherein the polyethylene fibers are crosslinked by crosslinking polyethylene fibers under the effect of modifying ray irradiation and the obtained .
  3. 3)根据权利要求1所述的形状记忆性聚乙烯交联纤维,其特征在于,其中的聚乙烯是选自高密度聚乙烯、低密度聚乙烯、线形低密度聚乙烯或超高分子量聚乙烯。 3) The shape memory cross-linked polyethylene fiber according to claim 1, wherein, wherein the polyethylene is selected from high density polyethylene, low density polyethylene, linear low density polyethylene or ultrahigh molecular weight polyethylene .
  4. 4)一种形状记忆性聚乙烯交联纤维的制备方法,其特征在于,包含如下工艺步骤:a)将聚乙烯纤维放置在密闭容器中,并将容器抽真空至6.5×10-2Pa;b)通过自动循环系统将装载有聚乙烯纤维的容器送入辐照系统,在辐射源发出的辐照射线的作用下进行交联改性;c)将经辐照后的聚乙烯纤维取出,置于真空干燥箱内在80~90℃下退火1小时。 4) A shape memory cross-linked polyethylene fiber production method, wherein, the process comprising the steps of: a) polyethylene fibers is placed in a closed vessel, and the vessel was evacuated to 6.5 × 10-2Pa; b ) circulation system by automatically loaded with containers fed polyethylene fibers irradiation system, modified crosslinked under the action of radiation rays emitted from radiation source; c) polyethylene fiber was taken out after irradiation, set internal annealed in a vacuum oven for 1 hour at 80 ~ 90 ℃.
  5. 5)根据权利要求4所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中还包括在将聚乙烯纤维放置入密闭容器前,对其进行浸泡的步骤,浸泡采用的溶液是由光敏剂和交联剂组成的混合溶液。 5) The method of preparing a shape memory polyethylene crosslinked fibers according to claim 4, characterized in that, further comprising prior to the polyethylene fiber placed into the sealed container, its soaking step is performed, using the soaking solution a mixed solution of the photosensitizing agent and the crosslinking agent.
  6. 6)根据权利要求5所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中的光敏剂是重量百分含量为1.0%的二苯甲酮及其衍生物溶液,其中的交联剂是重量百分含量为20%的丙烯酸酯溶液。 6) The shape memory as claimed in claim 5, wherein the preparation of cross-linked polyethylene fiber, wherein, wherein the photosensitizer is a weight percent of 1.0% solution of benzophenone and derivatives thereof, wherein a weight percent of the crosslinking agent is 20% acrylate solution.
  7. 7)根据权利要求4所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中步骤a)中还可以包括在将容器抽真空之后,向容器中充入乙炔气或高纯氮气的步骤。 7) The method of preparing a shape memory polyethylene crosslinked fibers according to claim 4, characterized in that, wherein in step a) may further comprise, after the container is evacuated, the vessel was charged with high-purity acetylene gas or step nitrogen.
  8. 8)根据权利要求4所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中的辐射源是电子加速器或放射源。 8) The method of preparing a shape memory polyethylene crosslinked fibers according to claim 4, characterized in that, where the radiation source is an electron accelerator or radioactive sources.
  9. 9)根据权利要求4所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中的辐照射线是等离子体、紫外线、电子射线或放射源射线。 9) The method of preparing a shape memory polyethylene crosslinked fibers according to claim 4, characterized in that, where the plasma is irradiated rays, ultraviolet rays, electron rays or radioactive sources rays.
  10. 10)根据权利要求4所述的形状记忆性聚乙烯交联纤维的制备方法,其特征在于,其中当采用放射源作为辐射源时,辐照强度为0.04~1.6J/cm2;当采用电子加速器作为辐射源时,辐照强度为25~250kGy。 10) The method of preparing a shape memory polyethylene crosslinked fibers according to claim 4, wherein, when the radiation source when measured as a radiation source, the radiation intensity of 0.04 ~ 1.6J / cm2; when using an electron accelerator as the radiation source, the radiation intensity of 25 ~ 250kGy.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102356191A (en) * 2009-03-18 2012-02-15 鲍姆胡特挤出有限责任公司 Polyethylene fiber, its use and process for its manufacture
CN102400375A (en) * 2010-09-14 2012-04-04 上海斯瑞聚合体科技有限公司 Method for producing modified ultrahigh molecular weight polyethylene fiber by using mutual radiation grafting technology
CN102517672A (en) * 2011-11-09 2012-06-27 武汉纺织大学 Preparation method for high-modulus and high-tensile-resilience special fiber
CN101768868B (en) 2010-01-04 2013-02-20 广东省均安牛仔服装研究院 Resin styling liquid and denim crumpling process method
CN105399966A (en) * 2015-12-29 2016-03-16 哈尔滨工业大学 Preparation of shape-memory polymer and application of shape-memory polymer to 4D printing

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102356191A (en) * 2009-03-18 2012-02-15 鲍姆胡特挤出有限责任公司 Polyethylene fiber, its use and process for its manufacture
CN101768868B (en) 2010-01-04 2013-02-20 广东省均安牛仔服装研究院 Resin styling liquid and denim crumpling process method
CN102400375A (en) * 2010-09-14 2012-04-04 上海斯瑞聚合体科技有限公司 Method for producing modified ultrahigh molecular weight polyethylene fiber by using mutual radiation grafting technology
CN102517672A (en) * 2011-11-09 2012-06-27 武汉纺织大学 Preparation method for high-modulus and high-tensile-resilience special fiber
CN102517672B (en) 2011-11-09 2013-07-03 武汉纺织大学 Preparation method for high-modulus and high-tensile-resilience special fiber
CN105399966A (en) * 2015-12-29 2016-03-16 哈尔滨工业大学 Preparation of shape-memory polymer and application of shape-memory polymer to 4D printing

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