AZOBENZENE POLYMER FILMS FOR OPTICAL STORAGE AND HIGH-ORDER DIFFRACTION (I)——POLY[4''-BIS(N, N-OXYETHYLENE) IMINO-4-NITROAZOBENZENE SUCCINYL] FILM

The properties of phase conjugated (PC) beam and stable optical storage in an azobenzene polymer film were studied by degenerate four-wave mixing. With low-intensity incident waves (peak value of the pulses of the order of W/cm²), the PC beam as well ms diffraction beams were observed and then disappeared after turning off one of the three incident Beams. When the peak intensities of the incidenl beams reached the order of 10 W/cm², the PC beam did not disappear but decreased to some extent after turning off the writing beams. As the peak intensities of incident beams increased to the order of l0³ W/cm², diffraction up to 4th-order was observed. When all of the three incident waves were turned on, three groups of high-order forward and backward diffraction heams were observed. Turning off two of the three incident beams, the diffraction beams of the other incident beams did not decrease obviously, i.e., stable optical storage was realized. After the experiments, brilliant hologram spot was observed and could be maintained over 120 days without obvious change.     

偶氮苯聚合物膜的光致高密度存储及其三维微结构的研究

设计、合成及表征了一种偶氮苯聚合物(PGMAA-20)。研究了该偶氮苯聚合物薄膜中的高密度光学存储和三维微结构,并成功地将20套光栅储存在样品中同一个点上,储存密度是已报道的两倍;用简单的2波混频光路在该材料中刻写出长方格子和六角星型的微结构,在制作多重不同周期不同角度的高密度光栅结构的实验过程中,观察到不同周期光栅的刻写顺序对整个微结构形成的最终结果具有决定性的影响。     

OPTICAL STORAGE MECHANISM AND HIGH-ORDER DIFFRACTION PROPERTIES OF NITROAZOBENZENE-CONTAINING POLYESTER FILMS

Using Nd:YAG second harmonic pulse (100 ps), the optical storage proper-ties of two novel polyesters, poly [4'-bis (N, N-oxyethylene) imino-4-nitroazobenzene suc-cinyl] and poly [2'-chloro-4'-bis (N, N-oxyethylene) iminth-4-nitroazobenzene succiny] havebeen studied by multiwave mixing. The high-order diffractions of the orientation gratingsinduced by anisotropy via the reorientation of nitroazobenzene groups and optical infor-mation storage with long-term stability have been realized by multiwave mixing in theirfilms. Up to 3rd order forward diffraction was detected in two wave mixing, while up to 4thorder backward diffraction was observed in degenerated four wave mixing. The recordingmechanism was explained by the trans-cis-trans isomerization cycles of azobenzene groups.The isomerization of these azobenzene groups probably undergoes with inversion mecha-nism under the experimental conditions. The information recorded in these films has beenkept for more than 6 months.     

偶氮苯聚合物(PGMAA-20)膜光栅结构的分子取向机制

设计合成及表征了一种含偶氮苯聚合物(PGMAA 20)材料.利用两束S偏振光作为泵浦光在PGMAA 20膜上刻写光栅并观察光栅的衍射信号;然后再用相衬显微镜直接观察偶氮苯薄膜上的光栅结构,并以分子取向机制为基础对光栅形成和消除过程提出了新解释,这种观点被实验观察结果进一步证实.     

新型有机/无机聚合物网络的合成与二阶非线性光学

合成了含双官能团的生色团4’-(N,N-二羟乙基)氨基-4-硝基偶氮苯(DR19),采用溶胶-凝胶方法,通过"两端"交联设计合成了光学性能良好的二阶非线性新型有机/无机复合聚合物网络.经过极化交联后,其在室温和较高温度下均具有良好的二次谐波产生(SHG)稳定性,表明该交联聚合体系能形成致密的硅-氧网络,从而有效地抑制生色团分子的取向松弛.     

铁-芳烃配合物引发环氧化合物的光引发阳离子聚合

以环戊二烯基异丙苯铁六氟磷酸盐为光引发剂,用等温差示扫描量热法(DSC)研究了对甲苯基缩水甘油醚(CGE)的光引发阳离子聚合的温度效应及聚合反应动力学。研究表明CGE聚合时,反应速率及最终转化率随温度变化在550℃及450℃左右有一个峰值。CGE光聚合反应速率与单体浓度的一次方成比例,其反应机理包括两个基本反应,即:引发剂光解产物与单体的配合反应以及在该配合物中单体的开环反应,而这两个反应具有相反的温度效应,升高温度有利于后者而不利于前者。     

含对硝基偶氮苯胺生色团的键合型有机／无机复合材料的合成及其二阶非线性

以γ－缩水甘油氧丙基三甲氧基硅烷（ＫＨ５６０）作中间体,用溶胶－凝胶（Ｓｏｌ－Ｇｅｌ）法合成了含对硝基偶氮苯胺（ＤＯ３）生色团的新型键合型有机／无机复合非线性光学（ＮＬＯ）材料,在这种有机生色团与无机玻璃键合成形成的交联网络结构中,无机玻璃的刚性三维结构和优良的高温稳定性能有效抑制ＮＬＯ生色图的极化松驰,二次谐波售（ＳＨＧ）测量表明,合成的键合型聚合物膜的二阶非线性光学系数（ｄ３３）值达５．７９＊１０＾－７ｅｓｕ,ＮＬＯ稳定性也较好;在室温下放置９０天后,其ｄ３３值能维持初始值的９３．５％,在１００℃下放置３００ｍｉｎ后,其ｄ３３值仍能维持初始值的６０％。     

新型偶氮苯侧链共聚物的超快光致双折射特性

采用抽运探测方法测量了一种新型的含 4 偶氮苯 4′ 偶氮苯酚侧链的共聚物 (DAP PGMA)的光致异构特性。实验结果表明DAP PGMA比含单偶氮苯侧链共聚物P (MMA co MAZ)有较大的光致双折射效应 ,Δn～ 6 .6 0× 10 -4 ;同时DAP PGMA比P(MMA co MAZ)具有更快的开启速度 ,光致向向异性上升时间为 40 ps,这种皮秒量级的快过程对应于双偶氮苯生色团的顺反异构过程。     

甲基丙烯酸β羟乙酯的感光聚合动力学的研究

本文用自动记录膨胀计研究了在紫外光照射下30℃时,以安息香醚类作光敏剂,甲基丙烯酸β-羟乙酯(HEMA)的感光聚合反应动力学。测得了在水溶液中,以羟甲基安息香甲醚或安息香乙醚作光敏剂时,单体的起始聚合速率与光敏剂浓度、单体浓度及起始光强的关系。动力学的研究表明:聚合速率与光敏剂浓度及起始光强有平方根的依赖关系,这近似于一般的游离基聚合的动力学规律,但是单体的反应级数远小于1。根据动力学的研究,得到了聚合反应动力学方程式,并讨论了其聚合反应历程。同时研究了温度、溶剂对聚合速率及暗反应聚合速率的影响,井计算了其感光聚合总活化能(E_p-E_t/2)值接近于零。     

铁-芳烃络合物引发氧化环己烯阳离子光聚合反应动力学研究

以环戊二烯异丙苯铁六氟磷酸盐为引发剂,用示差扫描量热法研究了氧化环己烯(CHO)阳离子聚合反应动力学.实验结果表明,温度对CHO聚合反应影响很大.CHO在一系列温度下等温聚合时,放热量和转化率均在40℃左右最高,而聚合反应速率则随着温度的升高而降低.CHO聚合反应属一级反应,活化能为-9.87kJ/mol,并对聚合反应历程进行了理论推导,其结果与实验结果相符合.