Preparation and radiation resistance of thermoplastic elastomer for medical devices

doi:10.16085/j.issn.1000-6613.2023-1589

Chemical Industry and Engineering Progress ›› 2024, Vol. 43 ›› Issue (2): 1047-1053.DOI: 10.16085/j.issn.1000-6613.2023-1589

• Materials science and technology • Previous Articles

Preparation and radiation resistance of thermoplastic elastomer for medical devices

LIU Haihong¹^,²(), LUO Lu¹^,², ZHANG Yuancheng¹^,²^,³(), ZHANG Xiaomeng¹^,²^,³, CUI Zhe¹^,²^,³, FU Peng¹^,²^,³(), PANG Xinchang¹^,²^,³, LIU Minying¹^,²^,³

^1.School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.Henan Provincial Key Laboratory of Advanced Nylon Materials and Applications, Zhengzhou 450001, Henan, China
^3.Zhengzhou University Industrial Technology Research Institute Co. , Ltd. , Zhengzhou 450001, Henan, China

Received:2023-09-08 Revised:2023-12-22 Online:2024-03-07 Published:2024-02-25
Contact: ZHANG Yuancheng, FU Peng

医疗器械用热塑性弹性体的制备及耐辐照性能

刘海洪¹^,²(), 罗璐¹^,², 张袁铖¹^,²^,³(), 张晓朦¹^,²^,³, 崔喆¹^,²^,³, 付鹏¹^,²^,³(), 庞新厂¹^,²^,³, 刘民英¹^,²^,³

^1.郑州大学材料科学与工程学院，河南郑州 450001
^2.河南省先进尼龙材料及应用重点实验室，河南郑州 450001
^3.郑州大学产业技术研究院有限公司，河南郑州 450001

通讯作者: 张袁铖,付鹏
作者简介:刘海洪（1974—），男，博士研究生，高级工程师，研究方向为各种药用弹性体制品的配方设计、工艺开发、新材料应用等。E-mail：bestlhh@126.com。
基金资助:
2022年郑州市科技惠民计划(2022KJHM0030);2022年河南省留学人员科研择优资助项目(22180035);2023年度河南省重点研发与推广专项（科技攻关）(232102230138)

Abstract

Abstract:

In this work, a thermoplastic elastomer blend (TPV) with irradiation resistance for medical devices was prepared by the dynamic vulcanization of the blends of brominized poly(isobutene-co-p-methylstyrene) (BIMS) and styrene ethylene butylene styrene copolymer (SEBS). Besides, alkyl phenol disulfide was used as vulcanizing crosslinker and bio-based plasticizer was also added. After irradiated by different doses, basic physicochemical properties, headspace gas chromatography, Fourier transform infrared spectra, thermal stability, dynamic mechanical properties and mechanical properties of irradiated TPV were analyzed. The experimental results indicated that the performance of TPV irradiated within 40kGy dose did not change which met the irradiation resistance requirements of the normal elastomers for medical devices.

Key words: radiation resistance, thermoplastic elastomer, radiation sterilization, dynamic vulcanization

摘要：

采用具有耐辐照特性的溴化聚（异丁烯-对甲基苯乙烯）（BIMS）为基体橡胶，与苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物（SEBS）共混，以烷基苯酚二硫化物作为硫化交联剂，并配合一种生物基增塑剂，采用动态硫化工艺，制备了一种医疗器械用耐辐照动态硫化热塑性弹性体（TPV）。通过对不同剂量辐照后TPV的基本理化性质、顶空气相色谱、红外图谱、热稳定性、动态机械性能和力学性能对比分析研究发现，在辐照灭菌（≤40 kGy）后，产品性能未发生变化，可满足常规医疗器械用弹性体制品对耐辐照性能的要求。

关键词: 耐辐照性, 热塑性弹性体, 辐照灭菌, 动态硫化

CLC Number:

TQ334

LIU Haihong, LUO Lu, ZHANG Yuancheng, ZHANG Xiaomeng, CUI Zhe, FU Peng, PANG Xinchang, LIU Minying. Preparation and radiation resistance of thermoplastic elastomer for medical devices[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 1047-1053.

刘海洪, 罗璐, 张袁铖, 张晓朦, 崔喆, 付鹏, 庞新厂, 刘民英. 医疗器械用热塑性弹性体的制备及耐辐照性能[J]. 化工进展, 2024, 43(2): 1047-1053.

Figures/Tables 16

References 19

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原料	质量分数（PHR）	投料量/g
BIMS	100	1700.0
SEBS	100	1700.0
纳米氧化锌	3.0	51.0
硫化剂	2.6	7.8
钛白粉	3	51.0
炭黑	0.5	1.5
生物基增塑剂	40	680
总量	249.1	4234.7

原料	质量分数（PHR）	投料量/g
BIMS	100	1700.0
SEBS	100	1700.0
纳米氧化锌	3.0	51.0
硫化剂	2.6	7.8
钛白粉	3	51.0
炭黑	0.5	1.5
生物基增塑剂	40	680
总量	249.1	4234.7

元素	质量分数/%	原子分数/%
C	92.37	95.33
O	5.43	4.21
Si	0.18	0.08
Ti	0.36	0.09
Zn	0.90	0.17
Br	0.76	0.12

元素	质量分数/%	原子分数/%
C	92.37	95.33
O	5.43	4.21
Si	0.18	0.08
Ti	0.36	0.09
Zn	0.90	0.17
Br	0.76	0.12

辐照剂量 /kGy	电导率 /μS·cm^-1	pH变化值	澄清度 /级	颜色	铵离子 /%	锌离子 /%	重金属 /mg·kg^-1	吸收度(220nm)	易氧化物 /mL	不挥发物 /mg	挥发性硫化物 /µg Na₂S·（20 cm²）^-1
0	3.7	0.12	<0.5	无色	<0.0002	<0.0003	<0.5	0.038	0.08	0.2	<25
20	3.0	0.10	<0.5	无色	<0.0002	<0.0003	<0.5	0.036	0.14	0.2	<25
30	3.5	0.17	<0.5	无色	<0.0002	<0.0003	<0.5	0.039	0.04	0.2	<25
40	4.5	0.18	<0.5	无色	<0.0002	<0.0003	<0.5	0.049	0.05	0.2	<25

Preparation and radiation resistance of thermoplastic elastomer for medical devices

医疗器械用热塑性弹性体的制备及耐辐照性能

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Figures/Tables 16

References 19

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辐照剂量/kGy	邵尔A型硬度	断裂伸长率/%	拉伸强度/MPa	100%定伸应力/MPa	300%定伸应力/MPa	撕裂强度/kN·m^-1
0	40	10.4	3.2	0.7	1.5	14
20	40	10.2	3.2	0.7	1.5	14
30	39	9.6	3.5	0.7	1.5	14
40	38	9.9	3.2	0.7	1.4	12

辐照剂量/kGy	穿刺力/N	密合性	自密封性
0	4.8	无渗漏	无渗漏
20	5.2	无渗漏	无渗漏
30	5.4	无渗漏	无渗漏
40	5.3	无渗漏	无渗漏

辐照剂量/kGy	初始分解温度T_d,5%/℃	最大分解温度T_d,max/℃
0	322	416
20	315	415
30	312	415
40	320	416

辐照剂量/kGy	初始分解温度T_d,5%/℃	最大分解温度T_d,max/℃
0	322	416
20	315	415
30	312	415
40	320	416

辐照剂量/kGy	玻璃化转变温度T_g/℃
0	-40.9
20	-40.6
30	-41.1
40	-41.0

辐照剂量/kGy	玻璃化转变温度T_g/℃
0	-40.9
20	-40.6
30	-41.1
40	-41.0