WO2011082547A1 - 一种低温热塑材料及其制备方法 - Google Patents

一种低温热塑材料及其制备方法 Download PDF

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WO2011082547A1
WO2011082547A1 PCT/CN2010/070102 CN2010070102W WO2011082547A1 WO 2011082547 A1 WO2011082547 A1 WO 2011082547A1 CN 2010070102 W CN2010070102 W CN 2010070102W WO 2011082547 A1 WO2011082547 A1 WO 2011082547A1
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thermoplastic material
temperature thermoplastic
parts
low temperature
material according
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PCT/CN2010/070102
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English (en)
French (fr)
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章中群
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广州科莱瑞迪医疗器材有限公司
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Application filed by 广州科莱瑞迪医疗器材有限公司 filed Critical 广州科莱瑞迪医疗器材有限公司
Priority to US13/511,284 priority Critical patent/US8859691B2/en
Priority to EP10841891.4A priority patent/EP2492316B1/en
Priority to PCT/CN2010/070102 priority patent/WO2011082547A1/zh
Publication of WO2011082547A1 publication Critical patent/WO2011082547A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the invention relates to a low temperature thermoplastic material, in particular a medical low temperature thermoplastic material and a preparation process.
  • the so-called low-temperature thermoplastic material is made of polycaprolactone as a main component and added with an additive, and is characterized in that it can be softened and molded into any shape at a relatively low temperature (about 65 ° C). At room temperature, it has the physical properties of polyolefins. This feature can be used to accurately position tumor patients during radiotherapy or to create rehabilitation brace for patients who need rehabilitation. At present, low temperature thermoplastic materials have been widely used in radiotherapy positioning, orthopedic fixation, orthopedic brace and rehabilitation brace.
  • the existing polycaprolactone type low-temperature thermoplastic product is convenient to form, but has a large contraction force.
  • a polycaprolactone + carbon fiber composition for medical use which can reduce the contraction force, but the shrinkage force of the product Although it is reduced, it appears to be stiff, and the patient feels uncomfortable when stretching in a tumor patient.
  • the present invention provides a low temperature thermoplastic material having low shrinkage force and comfortable stretching.
  • Another object of the present invention is to provide a method of producing the above low temperature thermoplastic material.
  • thermoplastic material the weight composition of which is: polyurethane having a melting point of 50-70 ° C: 90-10 parts, polycaprolactone: 0-90 parts, crosslinking assistant: 0.1-6 parts.
  • the method for preparing the above low temperature thermoplastic material has the following steps:
  • the obtained sheet is perforated as required, and then irradiated, and the irradiation dose is 3 to 30 Kgy.
  • the invention has the beneficial effects that the low-temperature thermoplastic material produced by the invention has been experimentally verified, and the shrinkage force of the material is smaller and more comfortable after being formed than the existing polycaprolactone-type low-temperature thermoplastic product. Good, more uniform stretching, better fixation strength, so it is more suitable for hospitals or other radiotherapy units, and is used in conjunction with three-dimensional conformal radiotherapy equipment for tumor surgery.
  • a low temperature thermoplastic material the weight composition of which is: polyurethane having a melting point of 50-70 ° C: 90-10 parts, polycaprolactone: 0-90 parts, crosslinking assistant: 0.1-6 parts.
  • the preferred weight ratio is: polyurethane having a melting point of 50-65 ° C: 75-50 parts, polycaprolactone: 25-50 parts, crosslinking assistant: 0.3-2 parts.
  • the crosslinking assistant used in this product is a monofunctional, difunctional or multifunctional group of isooctyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, triallyl iso Cyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate or dipentaerythritol hexaacrylate.
  • the manufacturing method of the above low temperature thermoplastic material is as follows:
  • the sheet is formed by heating the mixture to a molten state; the heating temperature is 65 to 160 °C.
  • the obtained sheet is perforated according to requirements, and then irradiated, the irradiation dose is 3 ⁇ 30Kgy, and the optimal irradiation dose is 5-20.
  • Kgy the irradiated light is: high-energy electron accelerator, cobalt source, X-ray or ultraviolet light. Preferred are high energy electron accelerators and cobalt sources.
  • the low-temperature thermoplastic material prepared by the invention has been experimentally verified that the shrinkage force of the material after molding is smaller, the comfort is better, the stretching is more uniform, and the fixing strength is better than that of the existing polycaprolactone product. Therefore, it is more suitable for hospitals or other radiotherapy units, and is used in conjunction with three-dimensional conformal radiotherapy equipment for tumor surgery, such as facial mask and phantom production for radiotherapy in cancer patients.
  • Mask shrinkage test device Place the pressure sensor connected to the computer (with special software) under the head of the plaster model, and then place the heated film on the face of the plaster model and pull it down. After stretching, the diaphragm is fixed to the base that is not connected to the pressure sensor, and timing and recording are started. In this way, the computer can record the contraction force of the diaphragm.
  • the temperature at room temperature was 24 ° C and the temperature of the heated water was 70 ° C.
  • Based on the shrinkage force measured at 24 hours we tested a polycaprolactone-type low-temperature thermoplastic material with a thickness of 2.4 mm and a mesh space ratio of 36%, and each of the five masks made of the material of the present invention. Contraction force, the specific test data is shown in the following table:
  • the shrinkage force of the material of the present invention is 38.64% lower than that of the polycaprolactone type, and the patient feels comfortable because of the low contraction force. Moreover, since the shrinkage force is small, the mesh formed during stretching is more uniform, so that the fixing strength is better.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Description

一种低温热塑材料及其制备方法
技术领域
　　本发明涉及一种低温热塑材料，尤其是医用低温热塑材料以及制备工艺。
背景技术
　　通常所说的低温热塑材料是由聚己内酯为主成份、并加入添加剂而制成的，其特点在于：在较低温度下（65℃左右）可软化并塑成任意形状，而在常温下，其又具有聚烯烃类的物理性质。它们的这一特点可以用于肿瘤病人放疗时的精确定位，或为需要进行康复治疗的患者量身制作康复支具。目前低温热塑材料已广泛用于放射治疗定位、骨外科固定、制作矫形支具和康复支具等。
　　现有聚己内酯型低温热塑产品虽然成形方便，但是收缩力较大，目前有一种可以降低收缩力的用于医疗方面的聚己内酯+碳纤维组合物，但是这种产品的收缩力虽然有所降低，但显得比较僵硬，在肿瘤患者身上拉伸的时候，患者会感觉不舒服。
发明内容
　　为了克服现有技术的不足，本发明提供一种收缩力低、拉伸舒适的低温热塑材料。
　　本发明的另一个目的是要提供一种生产上述低温热塑材料的方法。
　　本发明解决其技术问题所采用的技术方案是：
　　一种低温热塑材料，其重量组成份数为：熔点为50-70℃的聚氨酯：90-10份，聚己内酯：0-90份，交联助剂：0.1~6份。
　　上述低温热塑材料的制作方法，其步骤如下：
1）：按照重量配比称取原料；
2）：将各种原料混合及搅拌均匀；
3）：将混合物加热到熔融状态后进行片材成型；
4）：将所得片材按照需求打孔，然后进行辐照，辐照剂量为3~30Kgy。
　　本发明的有益效果是：通过本发明制作出来的低温热塑材料，经实验验证，与现有聚己内酯型低温热塑产品相比，本材料成形后的收缩力更小、舒适性更好、拉伸更均匀、固定强度更好，因此更适用于医院或其他放疗单位，与三维适形放疗仪器在肿瘤手术配套使用。
具体实施方式
一种低温热塑材料，其重量组成份数为：熔点为50-70℃的聚氨酯：90-10份，聚己内酯：0-90份，交联助剂：0.1~6份。优选的重量比为：熔点为50-65℃的聚氨酯：75-50份，聚己内酯：25-50份，交联助剂：0.3~2份。
　　本产品使用的交联助剂为单官能团的、双官能团的或多功能团的丙烯酸异辛酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三烯丙基异氰尿酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯或二季戊四醇六丙烯酸酯等。
　　制作上述低温热塑材料的制作方法，其步骤为：
1）：按照重量配比称取原料；
2）：将各种原料混合及搅拌均匀；
3）：将混合物加热到熔融状态后进行片材成型；加热温度为65~160℃。
4）：将所得片材按照需求打孔，然后进行辐照，辐照剂量为3~30Kgy，优选辐照剂量为5-20 Kgy，所述的辐照光线为：高能电子加速器、钴源、X-射线或紫外光。优选为高能电子加速器和钴源。
为便于对本发明进一步理解，现结合具体实施例对本发明进行详细描述。
实施例1：
称取熔点为50-70℃的聚氨酯10公斤，聚己内酯90公斤，丙烯酸异辛酯0.3公斤，混合均匀，用双螺杆挤出机造粒，然后用再挤出或注射成板材，根据需要打成不同规格的有孔板，最后用钴源以12KGy的剂量辐照交联，这样就可以制得收缩力小、拉伸舒适的低温热塑产品。
实施例2：
称取熔点为50-70℃的聚氨酯50公斤，聚己内酯50公斤，三羟甲基丙烷三丙烯酸酯 0.5公斤，混合均匀，用双螺杆挤出机造粒，然后用再挤出或注射成板材，然后根据需要打成不同规格的有孔板，最后用电子加速器以8KGy的剂量辐照交联，这样就可以制得收缩力小、拉伸舒适的低温热塑产品。
实施例3：
称取熔点为50-70℃的聚氨酯90公斤，聚己内酯10公斤，三烯丙基异氰尿酸酯0.5公斤，混合均匀，用挤出机挤成板材，然后根据需要打成不同规格的有孔板，最后用钴－60以6KGy的剂量辐照交联，这样就可以制得收缩力小、拉伸舒适的低温热塑产品。
通过本发明制作出来的低温热塑材料，经实验验证，与现有聚己内酯产品相比，本材料成形后的收缩力更小、舒适性更好、拉伸更均匀、固定强度更好，因此更适用于医院或其他放疗单位，与三维适形放疗仪器在肿瘤手术配套使用，例如用于癌症病人放疗时放疗部位的面膜和体模制作。
　　面膜片收缩力测试装置：将与电脑（装有专用软件）相连的压力传感器放在置于石膏模特儿头部下方，再把加热后的膜片放在石膏模特儿面部往下拉伸，拉伸后把膜片固定在与压力传感器不相连的底座上，并开始计时和记录。这样，电脑便可以记录膜片的收缩力。测试时室温24℃，加热水温70℃。以在24小时测定的收缩力为标准，我们分别测试了2.4mm厚，网孔占空率为36%的聚己内酯型低温热塑材料和本发明材料制成的各5个面膜片的收缩力，具体测试数据见下表：
材料 收缩力测定结果（牛） 均值
聚己内酯 52.66 60.60 44.56 52.77 50.88 52.17
本发明材料 26.00 26.37 37.49 35.53 34.68 32.01
由上表可见：本发明材料的收缩力比聚己内酯型降低了38.64%，由于收缩力较低，所以患者会感到舒适。而且，由于收缩力小，也会使得拉伸时形成的网孔更为均匀，这样固定强度就更好。

Claims (7)

  1. 一种低温热塑材料，其特征在于：重量组成份数为：熔点为50-70℃的聚氨酯：90-10份，聚己内酯：0-90份，交联助剂：0.1~6份。
  2. 根据权利要求1所述的一种低温热塑材料，其特征在于：重量组成份数为：熔点为50-65℃的聚氨酯：75-50份，聚己内酯：25-50份，交联助剂：0.3~2份。
  3. 根据权利要求1或2所述的一种低温热塑材料，其特征在于：所述的交联助剂为单官能团的、双官能团的或多功能团的丙烯酸异辛酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三烯丙基异氰尿酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯或二季戊四醇六丙烯酸酯。
  4. 一种如权利要求1或2所述低温热塑材料的制作方法，其特征在于：步骤如下：
    1）：按照重量配比称取原料；
    2）：将各种原料混合及搅拌均匀；
    3）：将混合物加热到熔融状态后进行片材成型；
    4）：将所得片材按照需求打孔，然后进行辐照，辐照剂量为3~30Kgy。
  5. 根据权利要求4所述的一种低温热塑材料的制作方法，其特征在于：所述步骤3）的加热温度为65~160℃。
  6. 根据权利要求4所述的一种低温热塑材料的制作方法，其特征在于：所述步骤4）辐照光线为：高能电子加速器、钴源、X-射线或紫外光。
  7. 根据权利要求4所述的一种低温热塑材料的制作方法，其特征在于：所述步骤4）的辐照剂量5-20 Kgy。
PCT/CN2010/070102 2010-01-09 2010-01-09 一种低温热塑材料及其制备方法 WO2011082547A1 (zh)

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Application Number Priority Date Filing Date Title
US13/511,284 US8859691B2 (en) 2010-01-09 2010-01-09 Low temperature thermoplastic material and preparing method thereof
EP10841891.4A EP2492316B1 (en) 2010-01-09 2010-01-09 Low temperature thermoplastic material and preparing method thereof
PCT/CN2010/070102 WO2011082547A1 (zh) 2010-01-09 2010-01-09 一种低温热塑材料及其制备方法

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US8859691B2 (en) 2014-10-14
EP2492316A1 (en) 2012-08-29
EP2492316B1 (en) 2015-07-29
US20120271007A1 (en) 2012-10-25
EP2492316A4 (en) 2013-10-30

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