Preparation of Detachable UV Curing Adhesive Based on Oxime-Carbamate Bond
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摘要: 以聚四氢呋喃醚二醇(PTMEG)、异佛尔酮二异氰酸酯（IPDI）、丁二酮肟（DMG）和丙烯酸羟乙酯（HEA）为原料合成了聚氨酯丙烯酸酯预聚物。将上述预聚物与光引发剂2-羟基-2-甲基-1-苯基-1-丙酮（HMPP）及活性稀释剂HEA混合，制备了紫外光（UV）固化胶黏剂。利用傅里叶变换红外光谱和核磁共振氢谱表征了聚氨酯丙烯酸酯预聚物的结构，考察了胶黏剂在UV辐照下的双键转化率和固化后的凝胶含量，以钢化玻璃为黏结基材探究了HEA和DMG的含量对胶黏剂拉伸剪切强度的影响，并通过原位变温红外光谱测试、自修复实验及热失重分析验证了氨基甲酸肟酯键的热可逆性。结果表明：当活性稀释剂HEA的质量分数为30%（以胶黏剂总质量计）且DMG与PTMEG的物质的量之比为1.5∶1时，胶黏剂经UV辐照3 min后其拉伸剪切强度可达3.72 MPa。氨基甲酸肟酯键的热可逆性赋予了胶黏剂良好的热可拆卸性能，在150 °C下加热3 min即可实现胶黏剂与基材的分离。Abstract: Polyurethane acrylate prepolymer was synthesized from polytetrahydrofuran ether glycol (PTMEG), isoflurone diisocyanate (IPDI), dimethylglyoxime (DMG) and hydroxyethyl acrylate (HEA). The prepolymer was mixed with photoinitiator 2-hydroxy-2-methylpropiophenone (HMPP) and active diluent HEA to prepare ultraviolet (UV) curing adhesive. The structure of polyurethane acrylate prepolymer was characterized by Fourier-transform infrared (FT-IR) spectroscopy and 1H-nuclear magnetic resonance (1H-NMR) spectroscopy. The double bond conversion and gel content of the adhesive under UV irradiation were investigated. The effects of contents of HEA and DMG on the tensile shear strength of the adhesive were also investigated, using toughened glass as a bonding substrate. In addition, the thermo-reversible behavior of oxime-carbamate bond was studied by in-situ variable temperature infrared spectroscopy, self-healing experiment and thermogravimetric analysis. The results show that when the mass fraction of HEA is 30% of UV curing adhesive and the molar ratio of DMG to PTMEG is 1.5∶1, the tensile shear strength of the adhesive can reach 3.72 MPa after UV irradiation for 3 min. The in-situ variable temperature infrared spectroscopy shows that the oxime-carbamate groups of the adhesive can be thermally decomposed to produce ―NCO groups above 120 °C. The self-healing experiments reveal that the scratches on the surface of the adhesive can disappear and be healed after heat treatment at 150 °C for 30 min, owing to enhancement of chain segmental motion by thermo-reversibility of oxime-carbamate bond. The TGA curves of the adhesive display a thermal decomposition stage at 160—240 °C, belonging to the decomposition of oxime carbamate. The thermal reversibility of oxime-carbamate bond gives the adhesive good thermal detachability. The adhesive can be separated from the substrate by heating at 150 °C for 3 min. Therefore, the adhesive demonstrates a promising prospect for application in the fields requiring UV rapid curing and thermal disassembly performance.
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Key words:
- adhesive /
- UV curing /
- thermal detachability /
- oxime-carbamate /
- thermal reversibility
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图 2 UV固化胶黏剂的制备及热拆卸过程示意图
Figure 2. Schematic diagram of preparation and thermal detachment process of UV curable adhesive
图 4 PreDMG1.0-PUA和PreBDO1.0-PUA的核磁共振氢谱图
Figure 4. 1H-NMR spectra of PreDMG1.0-PUA and PreBDO1.0-PUA
图 5 （a）光引发剂用量及（b）DMG含量对胶黏剂双键转化率的影响
Figure 5. Effect of (a) photoinitiator content and (b) DMG content on double bond conversion of adhesives
图 7 （a）HEA含量和（b）DMG含量对胶黏剂拉伸剪切强度的影响
Figure 7. Effect of (a) HEA content and (b) DMG content on tensile shear strength of adhesives
图 8 由DMG1.5-PUA胶黏剂黏接的两片玻璃基材承重1 kg时的数码照片
Figure 8. Digital photos of two glass sheets bonded by DMG1.5-PUA adhesive held a 1 kg weight
图 9 胶黏剂结构中的氨基甲酸肟酯键的热可逆机理图
Figure 9. Schematic illustration of the thermal reversible mechanism of oxime-carbamate bond of adhesive
图 10 DMG1.5-PUA胶膜的表面划痕在150 °C下热处理不同时间的自修复图片
Figure 10. Images of self-healing process of DMG1.5-PUA adhesive film with scratch on the surface by heating at 150 °C for different time
图 11 DMG1.5-PUA胶黏剂的原位变温傅里叶变换红外光谱
Figure 11. In situ variable temperature FT-IR spectra of DMG1.5-PUA adhesive
图 12 UV固化胶黏剂的（a）DSC和（b）TGA曲线
Figure 12. (a) DSC and (b) TGA curves of UV curing adhesive
表 1 制备PUA预聚物的原料配比
Table 1. Formulas of preparation of PUA prepolymers
Sample m (PTMEG) / g m (DMG) / g n (DMG) / n (PTMEG) m (BDO) / g PreDMG0.5-PUA 30 1.161 0.5 — PreDMG1.0-PUA 20 2.322 1.0 — PreDMG1.5-PUA 10 3.484 1.5 — PreBDO1.0-PUA 20 — — 1.802 m (IPDI) = 13.337 g；m (HEA) = 4.643 g 
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