耐水解型漆酚改性单体对光固化复合树脂综合性能的影响

doi:10.13481/j.1671-587X.20250328

摘要/Abstract

摘要：

目的合成一种耐水解型漆酚改性单体（UMM），以改善光固化复合树脂的耐水解性能，同时减少体积收缩率（VS），提高双键转化率（DC）并减少双酚A双甲基丙烯酸缩水甘油酯（Bis-GMA）单体潜在的生物安全问题。方法通过酰氯反应对漆酚进行改性，合成一种UMM，使用傅里叶变换红外光谱（FT-IR）对其结构进行分析和表征。以不含UMM的Bis-GMA/三乙二醇二甲基丙烯酸酯（TEGDMA）组分作为对照组，10%UMM组、15%UMM组和20%UMM组通过使用UMM部分取代Bis-GMA，其质量分数分别为10%、15%和20%。采用流变仪检测UMM黏度，FT-IR光谱仪检测各组光固化复合树脂DC，计算各组光固化复合树脂VS，悬滴法检测各组光固化复合树脂的接触角并计算吸水值和溶解值，测试各组光固化复合树脂的机械性能，细胞计数试剂盒8（CCK-8）法检测各组光固化复合树脂体外细胞毒性。结果 FT-IR光谱中，3 402 cm^-1处对应羟基基团的吸收峰消失，而1 745和1 637 cm^-1处出现-C=O及-C=C的特征性吸收峰，表明漆酚已成功与丙烯酰氯反应，合成了UMM。UMM的黏度为25.14~29.43 Pa.s。与对照组比较，10%UMM组、15%UMM组和20%UMM组光固化复合树脂DC均明显升高（P<0.05），VS均明显降低（P<0.05），且呈剂量依赖性。与对照组比较，10%UMM组、15%UMM组和20%UMM组光固化复合树脂接触角均明显增大（P<0.05）；与10%UMM组比较，15%UMM组和20%UMM组光固化复合树脂接触角均明显增大（P<0.05）。与对照组比较，10%UMM组、15%UMM组和20%UMM组光固化复合树脂吸水值及溶解值均明显降低（P<0.05），并呈剂量依赖性。水浸泡24 h后，与对照组比较，10%UMM组、15%UMM组和20%UMM组光固化复合树脂挠曲强度（FS）及弹性模量（EM）均明显降低（P<0.05），并呈剂量依赖性。水浸泡7 d后，与对照组比较，10%UMM组光固化复合树脂FS明显升高（P<0.05），20%UMM组光固化复合树脂FS明显降低（P<0.05）；与10%UMM组比较，15%UMM组和20%UMM组光固化复合树脂FS均明显降低（P<0.05），并呈剂量依赖性；与对照组比较，15%UMM组和20%UMM组光固化复合树脂EM均明显降低（P<0.05），并呈剂量依赖性。对照组、10%UMM组、15%UMM组和20%UMM组的L929细胞相对增殖率（RGR）均在90%以上，各组间比较差异均无统计学意义（P>0.05），细胞毒性均为合格。结论本研究合成了一种新型低黏度单体UMM，所有含UMM的光固化复合树脂配方DC较高，VS、吸水值和溶解值较低，耐水解性能较好，细胞毒性较低，UMM可作为一种潜在的树脂单体以提高光固化复合树脂的耐水解性能。

关键词: 光固化复合树脂, 吸水值, 双键转化率, 体积收缩率, 机械性能

Abstract:

Objective To synthesize a hydrolysis-resistant urushiol-modified monomer （UMM） to improve the hydrolysis resistance of light-cured composite resin， while reducing the volume shrinkage rate （VS）， increasing the double bond conversion rate （DC）， and mitigating the potential biosafety concerns of bisphenol A glycidyl methacrylate （Bis-GMA） monomer. Methods UMM was synthesized by modifying urushiol via an acyl chloride reaction， and its structure was analyzed and characterized using Fourier transform infrared spectroscopy （FT-IR）. Control group was consisted of Bis-GMA/triethylene glycol dimethacrylate （TEGDMA） without UMM， while 10%UMM， 15%UMM， and 20%UMM groups were prepared by partially replacing Bis-GMA with UMM at mass fractions of 10%， 15%， and 20%， respectively. The viscosity of UMM was measured using a rheometer. The DC of light-cured composite resin in various groups was detected by FT-IR spectroscopy， and the VS was calculated. The contact angle of light-cured composite resin in various groups was measured using the sessile drop method， and the water sorption and solubility values were calculated. The mechanical properties of light-cured composite resin in various groups were tested. The in vitro cytotoxicity of light-cured composite resin in various groups was evaluated using the cell counting kit-8 （CCK-8） assay. Results The FT-IR spectra results showed that the absorption peak of the hydroxyl group at 3 402 cm^-1 disappeared， while characteristic absorption peaks of -C=O and -C=C appeared at 1 745 and 1 637 cm^-1， indicating that urushiol successfully reacted with acryloyl chloride to form UMM. The viscosity of UMM ranged from 25.14 to 29.43 Pa·s. Compared with control group， the DC of light-cured composite resin in 10%UMM， 15%UMM， and 20%UMM groups was significantly increased （P<0.05）， while the VS was significantly decreased （P<0.05）， both in a dose-dependent manner. Compared with control group， the contact angle of light-cured composite resin in 10%UMM， 15%UMM， and 20%UMM groups was significantly increased （P<0.05）. Compared with 10%UMM group， the contact angle of light-cured composite resin in 15%UMM and 20%UMM groups was further increased （P<0.05）. Compared with control group， the water sorption and solubility values of light-cured composite resin in 10%UMM， 15%UMM， and 20%UMM groups were significantly decreased （P<0.05）， showing a dose-dependent trend. After 24 h of water immersion， compared with control group， the flexural strength （FS） and elastic modulus （EM） of light-cured composite resin in 10%UMM， 15%UMM， and 20%UMM groups were significantly decreased （P<0.05）， also in a dose-dependent manner. After 7 d of water immersion， compared with control group， the FS of light-cured composite resin in 10%UMM group was significantly increased （P<0.05）， while that in 20%UMM group was significantly decreased （P<0.05）. Compared with 10%UMM group， the FS of light-cured composite resin in 15%UMM and 20%UMM groups was significantly decreased （P<0.05）， exhibiting a dose-dependent trend. Compared with control group， the EM of light-cured composite resin in 15%UMM and 20%UMM groups was significantly decreased （P<0.05）， also in a dose-dependent manner. The relative growth rate （RGR） of the L929 cells in control， 10%UMM， 15%UMM， and 20%UMM groups was above 90%， with no statistically significant differences among groups （P>0.05）， and all cytotoxicity results were qualified. Conclusion A novel low-viscosity monomer UMM is successfully synthesized in this study. All UMM-containing light-cured composite resin formulations exhibit higher DC， lower VS， reduced water sorption and solubility values， improved hydrolysis resistance， and low cytotoxicity. UMM can serve as a potential resin monomer to enhance the hydrolysis resistance of light-cured composite resin.

Key words: Light-cured composite resin, Water sorption value, Double bond conversion rate, Volume shrinkage rate, Mechanical properties

中图分类号:

R783.1

杨政远,温雅晴,林令康,林岐,朱松. 耐水解型漆酚改性单体对光固化复合树脂综合性能的影响[J]. 吉林大学学报(医学版), 2025, 51(3): 814-821.

Zhengyuan YANG,Yaqing WEN,Lingkang LIU,Qi LIN,Song ZHU. Effect of hydrolytic resistance urushiol-modified monomer on comprehensive performance of light-curing resin composites[J]. Journal of Jilin University(Medicine Edition), 2025, 51(3): 814-821.

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Group	BisGMA/ TEGDMA	UMM	CQ/4EDMAB	Ba-Al-SiO₂
Control	2.8/1.2	0	0.05/0.05	6
10%UMM	2.4/1.2	0.4	0.05/0.05	6
15%UMM	2.2/1.2	0.6	0.05/0.05	6
20%UMM	2.0/1.2	0.8	0.05/0.05	6

Group	DC	VS
Control	62.70±0.38	2.97±0.02
10%UMM	64.42±0.16^*	2.84±0.02^*
15%UMM	66.34±0.23^*△	2.75±0.02^*△
20%UMM	68.50±0.29^*△#	2.65±0.03^*△#

Group	Contact angle（θ/°）	Water sorption（μg·mm^－3）	Solubility（μg·mm^－3）
Control	77.34±1.47	16.31±0.58	1.53±0.03
10%UMM	94.34±0.66^*	12.54±0.15^*	1.24±0.03^*
15%UMM	98.06±0.38^*△	11.64±0.24^*△	1.14±0.03^*△
20%UMM	99.16±0.50^*△	10.21±0.37^*△#	1.04±0.03^*△#

Group	FS（P/MPa）		EM（P/GPa）
Group	Water immersion for 24 h	Water immersion for 7 d	Water immersion for 24 h	Water immersion for 7 d
Control	144.36±2.82	113.09±4.88	9.38±0.24	7.58±0.29
10%UMM	137.12±2.11^*	123.78±1.22^*	8.19±0.52^*	7.45±0.30
15%UMM	128.38±1.51^*△	115.37±3.00^△	7.44±0.24^*△	6.79±0.34^*△
20%UMM	114.20±4.84^*△#	102.57±2.31^*△#	6.36±0.27^*△#	5.61±0.23^*△#