聚氨酯凝胶预聚物对传统树脂基质体积收缩的影响及对其综合性能的改善作用

doi:10.13481/j.1671-587X.20210401

摘要/Abstract

摘要： 目的

合成一种光反应性聚氨酯（PU）凝胶预聚物IBGBMA，并探讨其对传统树脂基质体积收缩和机械性能的影响。

方法

通过溶液法，以异氟尔酮二异氰酸酯、双酚-A和甲基丙烯酸羟乙酯等为原料，以1，4-丁二醇和三羟基甲基丙烷为扩链剂和交联剂合成一种光反应性PU凝胶预聚物IBGBMA，实现其与光固化树脂基质的化学结合，通过傅里叶变换红外光谱仪（FT-IR）对其结构进行表征。以不添加IBGBMA的Bis-GMA/TEGDMA（7∶3）传统树脂基质制备的试件为对照组，以添加5%、10%、15%和20%IBGBMA的传统树脂基质制备的试件为实验组。通过密度瓶法检测各组树脂基质固化后的体积收缩率，万能试验机检测各组试件挠曲强度（FS）和弹性模量（EM），维氏硬度仪检测各组试件维氏硬度，FT-IR峰面积法检测各组树脂基质双键转化率。

结果

FT-IR检测出终产物碳碳（C=C）双键（1 638 cm^－1）和氨基甲酸酯基团（－NHCOO－）（3 310 cm^－1）特征性吸收峰，表明合成了具有反应性的目标产物IBGBMA，光固化时可与树脂基质发生聚合反应。随着IBGBMA添加量的增加，各实验组树脂基质固化后体积收缩率逐渐降低，且均低于对照组（P<0.05）。与对照组比较，20%IBGBMA实验组试件FS和EM明显降低（P<0.05），其余各组间比较差异均无统计学意义（P>0.05）。与对照组比较，15%和20%IBGBMA实验组试件维氏硬度明显增加（P<0.05）。各实验组树脂基质双键转化率随IBGBMA添加量的增加而降低，15%和20%IBGBMA实验组树脂基质双键转化率低于对照组（P<0.05）。

结论

成功合成了可光固化的反应性聚氨酯凝胶预聚物，其中添加了15%IBGBMA的实验组树脂基质固化后所制备的试件体积收缩率明显降低，维氏硬度增强，而FS和EM不受影响，其综合性能得到改善。

关键词: 聚氨酯凝胶, 聚合反应, 体积收缩率, 机械性能, 挠曲强度, 弹性模量

Abstract: Objective

To synthesize an photo-active polyurethane-gel prepolymer named IBGBMA， and to explore its influence in the volume shrinkage and mechanical properties of the traditional resin matrix.

Methods

By solution polymerization，isophorone diisocyanate， bisphenol-A and hydroxyethyl methacrylate，etc.were used as the raw materials，and 1，4-butanediol and trihydroxymethylpropane were used as the chain extenders and crosslinkers， an photo-active polyurethane-gel prepolymer（IBGBMA） which could realize the chemical bond combination with the light-curable resin matrix was synthesied， and its structure was characterized by Fourier transform infrared spectroscopy（FT-IR）.The Bis-GMA/TEGDMA （7∶3） resin matrix without IBGBMA was used as control group， and the matrixes added with 5%， 10%， 15% and 20% IBGBMA were used as experimental groups. The volume shrinkage rates of each group after curing were detected by the density bottle method， and the universal testing machine was used to detect the flexural strength（FS） and elastic modulus（EM）， the Vickers hardness tester was used to detect the Vickers hardness， and the FT-IR peak area method was used to detect the double bonds conversion rate.

Results

The FT-IR results showed the characteristic absorption peaks of a photo-curable group （C=C） at 1 638 cm^－1 as well as the group （－NHCOO－） at 3 310 cm^－1， indicating that the active target product IBGBMA was synthesized，which can polymerize with the resin matrix during light curing. With the increase of IBGBMA addition amount， the volume shrinkage rates in each experimental group were decreased， and they were all lower than those in control group （P<0.05）.Compared with control group，the FS and EM in 20%IBGBMA experiment group were decreased（P<0.05），but there was no statistically differences in the other experimental groups（P>0.05）.The Vickers hardness in various experimental groups was increased （P<0.05）.The double bond conversion rates in various experimental groups were decreased with the increase of IBGBMA addition amount， and they were all lower than that in control group（P<0.05）.

Conclusion

The light-curable active polyurethane-gel prepolymer is successfully synthesized which reduces the volume shrinkage. And the volume shrinkage rate in 15%IBGBMA group is significantly reduced， the Vickers hardness is significantly increased， while the EM and FS are not affected， so the comprehensive properties are improved.

Key words: polyurethane-gel, polymerization reaction, volume shrinkage rate, mechanical properties, flexural strength, elastic modulus

中图分类号:

R783.1

于改改, 王惠敏, 田子璐, 杨宇斌, 朱轩言, 朱松. 聚氨酯凝胶预聚物对传统树脂基质体积收缩的影响及对其综合性能的改善作用[J]. 吉林大学学报(医学版), 2021, 47(4): 819-825.

Gaigai YU, Huimin WANG, Zilu TIAN, Yubin YANG, Xuanyan ZHU, Song ZHU. Influence of polyurethane-gel prepolymer on volume shrinkage and its improvement effect on comprehensive properties of traditional resin matrix[J]. Journal of Jilin University(Medicine Edition), 2021, 47(4): 819-825.

图/表 4

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Group	Bis-GMA/TEGDMA	IBGBMA	CQ/ 4-EDMAB	HEMA
Control	7.00/3.00	0.00	0.06/0.14	0.10
Experiment
5%IBGBMA	6.65/2.85	0.50	0.06/0.14	0.10
10%IBGBMA	6.30/2.70	1.00	0.06/0.14	0.10
15%IBGBMA	5.95/2.55	1.50	0.06/0.14	0.10
20%IBGBMA	5.60/2.40	2.00	0.06/0.14	0.10

Group	Volume shrinkage rate (η/%)	Flexural strength (P/MPa)	Elastic modulus (P/GPa)	Vickers hardness （N·mm^－2)	Double bond conversion rate(η/%)
Control	7.41±0.39	126.61±24.37	3.37±0.39	23.58±1.19	51.26±2.20
Experiment
5%IBGBMA	7.40±0.30	121.61±10.88	3.37±0.19	24.25±0.59	49.90±4.65
10%IBGBMA	6.30±0.55^*△	113.56±6.57	3.37±0.18	24.49±0.96	47.65±4.07
15%IBGBMA	5.15±0.16^*△#	119.53±4.47	3.47±0.16	25.45±0.99^*	45.05±2.21^*
20%IBGBMA	4.00±0.48^*△#○	91.98±7.21^*	2.50±0.29^*	26.18±1.53^*△#	39.11±3.11^*△#○
^*P<0.05 compared with control group;^△P<0.05 compared with 5% IBGBMA experiment group;^#P<0.05 compared with 10%IBGBMA experiment group;^○P<0.05 compared with 15%IBGBMA experiment group.

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