稀土催化剂本体聚合异戊二烯的生胶性能

本体聚合与溶液聚合相比,具有能耗低,反应平稳,转化率高等特点。杨彩云等用稀土催化剂对异戊二烯(Ip)进行本体聚合,聚合转化率达80%以上,聚合物中无疑胶,且分子量分布较窄(M_w/M?<2)。本文报道和讨论本体聚合放大试验胶样的生胶特性。 异戊二烯胶样(BLn-IR)本所自制。溶液钛催化聚异戊二烯IR-1Q为日本JSR生产。天然橡胶(NR)系海南岛3~#烟片。门尼粘度按GB1232测定。应力-应变性能(23℃),用DL-1000B型电子拉力机测定,拉速500mm/min。玻璃化温度(T_g)用PE DSC-2C型仪测定,升温速率

STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

MOSSBAUER-EFFECT STUDIES ON SOME BIOINORGANIC COMPLEXES OF EUROPIUM

The bioinorganic complexes of europium with N-acetyl-DL-alanine, N-acetyl-DL-valine, and DL-alanyl-DL-alanine have been synthesized and the Mossbauer spectra at room temperature have been measured for these solid state complexes. The Mossbauer parameters indicate that the water molecules in these complexes are not directly linked to the central europium ion and are outside the coordination sphere of europium and biological ligands, and that the chemical bond between the europium ion and the ligands may be predominantly ionic in character, with the possibility of partial covalent contribution.

THERMAL DECOMPOSITIONS OF SOME BIOINORGANIC COMPLEXES OF EUROPIUM

Thermogravimetric and derivative thermogravimetric investigations for three kinds of bioinorganic complexes of europium with N-acetyl-DL-alanine, N-acetyl-DL-valine and DL-alanyl-DL-alanine have been performed. It was found that the water molecules in these solid state complexes are not directly coordinated to the europium ion and that there may be three or four steps in the thermal decomposition process of these complexes after dehydration. The possible thermal decomposition reactions of these bioinorganic complexes have been suggested and discussed.

界面层结构对填充聚丙烯力学性能及流变行为的影响

本文采用各类偶联剂处理填充改性聚丙烯的无机填料。实验结果表明,硅烷类 KH-550偶联剂在界面层形成刚性架的有机硅烷膜复盖层结构,使填充聚丙烯屈服强度明显提高,断裂面形貌为界面结合较好的脆性断裂。TSC,NDZ-201,OLT-671和 DL-411等酯类偶联剂在界面形成线型柔性链的单分子层结构,使填充聚丙烯冲击强度、断裂仲长率提高,加工流动性能明显改善。

本体聚合稀土异戊橡胶的加工性能

对2L釜合成的5个本体聚合稀土异戊橡胶(LnIR)胶样([η]=2.38～8.10 dL/g)的辊筒行为、挤出行为,硫化特性和硫化胶性能进行了研究。结果表明,LnIR具有明显的素炼降解行为,混炼辊筒温度不宜低于70℃,混炼行为与NR和溶液聚合钛系异戊橡胶(IR-10)相当,在110～130℃时,胶料的挤出性能可达良级;口型膨胀(B)位随温度和生胶[η]的增大而略有增加,在[η]相同时,B值与IR-10胶料相近。但小于NR胶料。硫化湿度为143℃时,LnIR硫化胶的性能除拉伸强度和扯断伸长率外,其他均对硫化时间不敏感,从综合性能考虑,硫化时间应为20～40min,LnIR硫化胶的拉伸强度和撕裂强度稍低于IR-10和NR硫化胶,而回弹性、低温性能、生热和抗湿滑性等均优于或相当于后两者。为获得良好综合性能的硫化胶。LnIR[η]应为4.0～6.0dL/g。

CHARACTERIZATION OF GAMMA-IRRADIATED CRYSTALLINE POLYMER .3. THERMAL-BEHAVIOR OF GAMMA-IRRADIATED POLYAMIDE-1010

Thermal behaviour of gamma-irradiated plain PA1010 and PA1010 containing different amounts of difunctional cross-linking agent BMI was investigated. In DSC endo- and exotherm, it was found that during irradiation, the presence of BMI markedly changes the melting and crystallisation characteristics of PA1010. A supposition that the network of BMI-containing specimens is rather loose in structure was proposed to explain the discrepancy in thermal behaviour between these two kinds of specimens. The supposition was further ascertained by the less brittleness in mechanical property of specimens containing BMI. Besides, the complexity of the thermal behaviour of gamma-irradiated PA1010 was discussed and attributed mainly to the increase in sigma-e, the fold surface free energy of chain fold crystals.

MOLECULAR-WEIGHT DEPENDENCE OF THE GLASS-TRANSITION OF CYCLIC POLYSTYRENE

The glass transition temperature (T(g)) of cyclic polystyrene was measured by differential scanning calorimetry. There was a marked difference in the glass transition behaviour between cyclic and linear polystyrene. In the low molecular weight region (M(n) < 5 x 10(3)), the T(g) of the cyclic polystyrene increased with decreasing M(n), contrary to that of linear polystyrene. With M(n) higher than 5 x 10(3), the T(g) of cyclic polystyrene increased with increasing M(n). The T(g) of cyclic and linear polystyrene approached the same constant value when the M(n) was high enough (M(n) > 10(5)). Combining the results of specific volume, it is believed that the variation of T(g) with molecular weight does not depend only on free volume effects but that configurational entropy is also an important factor.

异戊二烯均相聚合催化剂

分别用C_6H_5CH_2Cl,CH_2-CHSiCl_3,CH_ SiHCl_2,(CH_3)_2SiCl_2,(CH_3)_3CCl,CH_2—CHCH_2Cl,Cl_3SiCH_2CH_2SiCl_3代替非均相催化剂Nd(naph)_3-Al_2Et_3Cl-Al(i-Bu)_2H(简称Nd-Cl-Al)中的助催化剂后,除C_6H_5CH_2Cl,CH_2=CHSiCl_3,CH_SiHCl_2形成悬浊催化剂外,在Cl/Nd<8(mol比)时,其他氯化物均形成均相催化剂,并能催化异戊二烯均相聚合,得到顺式-1,4含量约95％,[η]约3 dL/g的聚合物。分别用(CH_3)_3CCl和(CH_3)_2SiCl_2代替Cl所组成的两催化剂,其催化活性接近,最佳Al/Nd和Cl/Nd值分别为40和2.5;异戊二烯浓度为10％—20％时,转化率不随其浓度的改变而变化。符合一级反应动力学特征。

CHARACTERIZATION OF GAMMA-RADIATION CROSS-LINKED CRYSTALLINE POLYMERS BY CRYSTALLIZATION TEMPERATURE

The effect of gamma-radlatlon on plain crystalline polymers and crystalline polymers containing different amounts of difunctional monomer both in vacuum and in air at room temperature has been investigated with DSC. It was found that the crystallization temperature T_c of crosslinked sample measured on DSC at a constant cooling rate decreases with increasing radiation dose. The difference between T_c before and after crosslinking (T_(c_0)-T_(c_R)) is linearly related to the radiation dose for plain polymer....

苯乙烯存在下的稀土催化丁二烯聚合

研究了在不同量St(St/Bd=0.02—0.50,mol比)的存在下,稀土催化剂对Bd溶液聚合的影响,Sdt/Bd=0.50时,Bd转化率大于76％,得到不含凝胶的聚丁二烯,其中顺式-1,4含量在95 ％左右,[η]=4—5 dL/g;在无链终止条件下使聚丁二烯和St热引发共聚,可得Bd和St的接枝(或嵌段)共聚物。用 IR、NMR、DSC 和透射电子显微镜等方法对聚合物进行了表征。

Identification of Porphyra lines (Rhodophyta) by AFLP DNA fingerprinting and molecular markers

Twenty-seven Porphyra lines from 5 classes, including lines widely used in China, wild lines, and lines introduced to China from abroad in recent years, were screened by means of amplified fragment length polymorphism (AFLP) with 24 primer pairs. From the generated AFLP products, 13 bands that showed stable and repeatable AFLP patterns amplified by primer pairs M-CGA/E-AA and M-CGA/E-TA were scored and used to develop the DNA fingerprints of the 27 Porphyra lines. Moreover, the DNA fingerprinting patterns were converted into computer language expressed with digitals 1 and 0, which represented the presence (numbered as 1) or absence (numbered as 0) of the corresponding band. On the basis of these results, computerized AFLP DNA fingerprints were constructed in which each of the 27 Porphyra lines has its unique AFLP,fingerprinting pattern and can be easily distinguished from others. Software called PGI-AFLP (Porphyra germplasm identification-AFLP) was designed for identification of the 27 Porphyra lines. In addition, 21 specific AFLP markers from 15 Porphyra lines were identified; 6 AFLP markers from 4 Porphyra lines were sequenced, and 2 of them were successfully converted into SCAR (sequence characterized amplification region) markers. The developed AFLP DNA fingerprinting and specific molecular markers provide useful ways for the identification, classification, and resource protection of the Porphyra lines.

A simple method for DNA extraction from sporophyte in the brown alga Laminaria japonica

A simple method was developed for extracting DNA from brown algae Laminaria japonica, which possess large amounts of acidic polysaccharides. Firstly, the sporophyte were washed by eliminating polysaccaride buffer to remove the polysaccharides and then ground in liquid nitrogen. Secondly, the powders were treated with lysing buffer. Thirdly, KAc was used to eliminate the remaining acidic polysaccharides. The extracted DNA was purified using a chloroform-isoamyl alcohol ( 24: 1 v/v), and precipitated in cold isopropanol. The yield was from 18.7 to 37.5 mu g g(-1) (wet weight) and the purity of total DNA was determined spectrophotometrically as the ratio of A(260)/A(280), which was about 1.7 - 1.9. The extracted DNA was of high quality and suitable for molecular analyses, such as PCR, restriction enzyme digestion. This method is a reproducible, simple, and rapid technique for routine DNA extraction from sporophyte in Laminaria japonica. Furthermore, the low cost of this method makes it attractive for large-scale studies.