Functional Mechanism of Polymers for Papermaking : Fundamental Research Using Fluorescently Labeled Polymers.

造纸聚合物的功能机制：使用荧光标记聚合物的基础研究。

• 批准号: 63470119
• 负责人: TANAKA Hiroo
• 金额: $ 4.8万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470119/
• 关键词: Fluorescent polymer; Polymer adsorption; Polymer desorption; Polymer conformation; Polymer exchange; Polymer transfer; 蛍光標識高分子; 高分子の吸脱着; 高分子交換反応; 吸着鎖のコンホメ-ション; 繊維細孔への高分子の浸透; 高分子の固体間転移; 繊維細孔への高分子の進入; 吸着鎖のコンフォメーション; 固体表面での高分子の交換反応; 繊維素細孔中への高分

Cationic polyacrylamides (C-PAM) which contain both primary and quaternary amines were prepared according to the Hofmann reaction by adding choline chloride to a solution of PAM in water. The reaction was 90 % complete after 60 min at 20ﾟC. The degree of aniNation was over 70 % and the proportion of primary and quaternary amines could be altered widely by controlling the relative concentrations of NaOH, NaOCl and choline chloride.C-PAM was dansylated (fluorescently labeled) in a homogeneous system using aqueous dimethylformamide as solvent. The optimum excitation wavelength for dansylated C-PAM (DC-PAM) in water was 333 nm and the corresponding emission wavelength 540 nm.Series of C-PAMs in which (a) the molecular weight (MW) was constant (4x10*5) and the charge densities (CD) varied (0.65, 1.4 and 2.5 meq/g) and (b) the CD was constant (1.4 meq/g) and MWs varied (2x10*4, 4x10*5 and 8x10*6) were prepared with and without a fluorescent label.The adsorption of these C-PAMs onto monodispe … More rse polystyrene latex (PSL) was very rapid regardless of MW and CD, but the adsorption rate onto cellulose fibers were significantly influenced by MW and CD due to the porous nature of fibers. A considerable degree of adsorption was, however, also rapidlyachieved in the case of fibers. The ratio of the charge of the adsorbed polymer to the charge of the substrate is discussed on the basis of the adsorption isotherms obtained. The fluorescent labeling had little effect on the adsorptivity of C-PAM on either PSL or fibers, probably because of the low degree of substitution.The exchange reaction of C-PAMs on PSL and cellulose fibers have been studied using with the same MW and CD except that the pre-adsorbed polymers were fluorescently labeled. For C-PAM with the highest MW no significant exchange could be detected on PSL or on fibers. When C-PAM with the highest CD was used a slight exchange occurred on both PSL and fibers. On PSL the level of exchange was influenced only slightly by the time before displacement started (pre-adsorption time), and after 2 hr there was no further reduction in deabsorption. On fibers, on the other hand, the levels of exchange were affected significantly by the pre-absorption time, and the degree in exchange continued even after 3 weeks. The rates and levels of exchange were also influenced by the MW and CD.For DC-PAM with different MWs, the rate of transfer from fibers to PSL 1 hr pre-adsorption time was in the following order, medium > high > low. It is interesting to note that DC-PAM with highest MW is transfered fairly easily considering that an exchange reaction for such a high MW does not take ple on PSL or on fibers described above. The effects of the CD of the polymer on polymer transfer were not great. When polymers transferred the cleavage of polymer chain occurred. The transferred fraction converged approximately to the ratio of charges of fibers and PSL. Less

通过Hofmann反应，在阳离子聚丙烯酰胺(PAM)的水溶液中加入氯化胆碱，制备了同时含有伯胺和季胺的阳离子聚丙烯酰胺(C-PAM)。在20ﾟC下反应60min，反应完成率为90%，阴离子度在70%以上，伯胺和季胺的比例可通过控制氢氧化钠、氯化氢钠和氯化胆碱的相对浓度进行较大幅度的改变。丹酚化C-PAM在水中的最佳激发波长为333 nm，相应的发射波长为540 nm。制备了(A)分子量恒定(4×10~(*5))、电荷密度(Cd)变化(0.65、1.4和2.5meq/g)和(B)Cd恒定(1.4meq/g)、分子量(2×10~(*4)、4×10~(*5)和8×10~(*6))变化(2×10~(*4)、4×10~(*5)和8×10~(*6))的C-PAM在…上的吸附更多的RSE聚苯乙烯胶乳(PSL)是非常迅速的，但由于纤维的多孔性，其在纤维素纤维上的吸附速率受分子量和Cd的影响很大。然而，在纤维的情况下，也很快实现了相当程度的吸附。在得到吸附等温线的基础上，讨论了吸附聚合物的电荷与基质电荷的比值。荧光标记对C-PAM在PSL和纤维上的吸附几乎没有影响，可能是因为取代度较低。除了预吸附的聚合物被荧光标记外，C-PAM在PSL和纤维素纤维上的交换反应已被研究。对于相对分子质量最高的C-PAM，在PSL或纤维上没有检测到明显的交换。当使用Cd含量最高的C-PAM时，PSL和纤维都发生了轻微的交换。在PSL上，置换开始前的时间(预吸附时间)对交换水平的影响很小，2小时后解吸没有进一步的减少。另一方面，纤维的交换程度受预吸收时间的影响很大，即使在3周后，交换程度仍在继续。对于不同相对分子质量的DC-PAM，预吸附时间为1小时时，纤维向PSL的转移速率大小顺序为：中>高>低。有趣的是，考虑到如此高相对分子质量的交换反应不会在上述PSL或纤维上发生，具有最高相对分子质量的DC-PAM被相当容易地转移。聚合物中的Cd对聚合物转移的影响不大。当聚合物转移时，聚合物链发生断裂。转移分数接近于纤维和PSL的电荷之比。较少

项目成果

Hiroo Tanaka, Lars Odberg, Lars Wagberg and Tom Lindstrom: "Adsorption of Cationic Polyacrylamides onto Monodisperse Polystyrene Latices and Cellulose Fibers : Effect of Molecular Weight and Charge Density of Cationic Polyacrylamides" J. Colloid Interface

Hiroo Tanaka、Lars Odberg、Lars Wagberg 和 Tom Lindstrom：“阳离子聚丙烯酰胺在单分散聚苯乙烯胶乳和纤维素纤维上的吸附：阳离子聚丙烯酰胺的分子量和电荷密度的影响”J. 胶体界面

Hiroo Tanaka, Lars Odberg, Lars Wagberg and Tom Lindstrom: "Exchange of Cationic Polyacrylamides Adsorbed on Monodisperse Polystyrene Latex and Cellulose Fibers : Effect of Molecular Weight" J. Colloid Interface Sci.134-1. 229-234 (1990)

Hiroo Tanaka、Lars Odberg、Lars Wagberg 和 Tom Lindstrom：“单分散聚苯乙烯乳胶和纤维素纤维上吸附的阳离子聚丙烯酰胺的交换：分子量的影响”J. 胶体界面 Sci.134-1。

Hirro Tanaka: "Cleavage of Polymer Chain during Transter of Cationic Polyacrylamides from Cellulose Fibers to Polystyrene Latex" J.Colloid Interface Sci.

Hirro Tanaka：“阳离子聚丙烯酰胺从纤维素纤维转移到聚苯乙烯乳胶期间聚合物链的断裂”J.Colloid Interface Sci。

Hiroo Tanaka: "Adsorption of Cationic Polyacrylamides onto Monodisperse Polystyrene Latices and Cellulose Fiber:Effect of Molecular Weight and Charge Density of Cationic Polyacrylamides." J.Colloid Interface Sci.134. 219-228 (1990)

Hiroo Tanaka：“阳离子聚丙烯酰胺在单分散聚苯乙烯胶乳和纤维素纤维上的吸附：阳离子聚丙烯酰胺的分子量和电荷密度的影响”。

田中 浩雄: "カチオン性ポリマ-のセルロ-ス繊維細孔への浸透" 紙パ技協誌. 44. 911-917 (1990)

Hiroo Tanaka：“阳离子聚合物渗透到纤维素纤维孔中”造纸和造纸技术协会杂志 44. 911-917 (1990)。