Synthesis and characterization of some novel copolymer resins. III

In continuation of our endeavor to develop synthetic resins of improved properties and performance, we report here the synthesis of mixed copolymer resins by the condensation of resorcinol, aniline, and formaldehyde with ortho-, meta-, and para-phenylenediamine separately. The resins were characterized by infrared (IR) and thermogravimetric analysis (TGA). The mixed copolymer resins were found to have superior thermal stability over conventional phenol–CH₂O and resorcinol–CH₂O resins. The solubility behavior of the resins showed that they are resistant to common solvents. However, they are soluble in concentrated H₂SO₄ and HNO₃, but insoluble in concentrated HCl. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 2183–2187, 1998     

New block copolymers II. Synthesis and characterization of an ABA-type block copolymer

A new regular ABA-type triblock copolymer has been synthesized by polycondensation of the acid chloride of carboxy-terminated butadience-acrylonitrile rubber (CTBN) with hydroxyterminated polyethylene isophthalate (PEI) oligomer. This block copolymer was characterized by elemental (nitrogen) analysis, vapor pressure osmometry, viscometry, and IR and NMR spectroscopy. Quantitative estimation of block segments has been carried out by measuring the area under peaks assigned to various protons in the NMR spectrum of the polymer. NMR spectral analysis has been found to agree well with the nitrogen analysis of the polymer. The solubility and solution viscosity behavior of the polymer has also been studied.     

抗冲共聚PP树脂的结构表征

采用红外光谱、核磁共振碳谱、差示扫描量热法、动态热机械分析以及扫描电子显微镜对抗冲共聚聚丙烯树脂SP179与进口专用基础树脂AW191进行了结构表征。结果表明：SP179和AW191的聚合工艺不同,但两者在分子链结构及相态结构上差异微小．因此它们的物理性能基本相近,都具有优异的抗冲击性能;由于助剂体系不同．两者的热性能表现出较大差异。     

Synthesis and characterization of resorcinol-cinnamaldehyde resins

The mechanisms and kinetics of the reaction between resorcinol and cinnamaldehyde were studied by means of ¹³C-NMR spectroscopy, HPLC, and GPC. In the first step the addition of resorcinol to the double bond and to the carbonyl group of cinnamaldehyde takes place. In the second step of reaction the lower molecular weight oligomers form compounds with groups with molecular weights between 1500 and 2500. The red coloured resin reacts at temperatures above 150°C with crosslinking agents to form an insoluble and highly crosslinked product.     

对苯二酚-果糖树脂的合成与表征

在碱性条件下,使用果糖代替甲醛与对苯二酚反应,成功地制备出环境友好型的对苯二酚-果糖树脂。利用红外、GPC、TGA等对所合成的树脂进行了表征。同时使用响应面优化法优化了反应条件,最优反应条件为:催化剂用量3.99%、反应温度69.97℃、反应时间9.03h、n果糖:n对苯二酚=9.29:1。最优条件时的黏度为222.808mPa?s,拉伸强度15.71～23.61MPa。     

氯乙烯-丙烯酸异辛酯共聚树脂的合成与表征

通过连续滴加预乳化丙烯酸异辛酯(EHA)单体,采用悬浮聚合方法合成了氯乙烯(VC)/EHA共聚树脂,对共聚树脂的颗粒特性、加工性能和力学性能等进行了研究。随着单体配比[m(EHA)∶m(VC)]的增加,共聚树脂颗粒的孔隙率、增塑剂吸收量和玻璃化温度降低,塑化时间和转矩缩短,加工性能逐渐变好,加工试片的硬度和拉伸强度降低,冲击强度略增大。     

乙烯-辛烯共聚物接枝苯乙烯-丙烯腈共聚物的合成及其表征

用苯乙烯(St)、丙烯腈(AN)2种单体和乙烯一辛烯共聚物(POE)进行溶液接枝共聚合反应,制备了乙烯-辛烯共聚物接枝苯乙烯-丙烯腈共聚物(POE-g-SAN),探讨了接枝共聚反应条件,并对POE-g-SAN进行了表征.结果表明,接枝共聚反应的接枝率(GR)和接枝效率(GE)均随着St/AN(质量比)的减小而稍有增大,当POE/St-AN(质量比)为50/50时,GR与GE达到最大值;增加BPO用量有利于接枝反应;当反应物POE与St-AN在甲苯中的质量分数为27.5%时,GR与GE达到最大值;在反应前10 h,随着反应时间的延长,GR增大,GE在4 h时达到最大值77.8%,在反应10 h后,接枝反应几乎不再进行;在POE与St-AN接枝共聚反应中,POE已接枝了SAN支链,且GR越大,SAN支链越多;POE-g-SAN有2个玻璃化转变温度(Tg),约为-50℃和110℃;随着GR的增大,POE-g-SAN中POE相的Tg升高,熔融温度和熔融热均降低;随着共单体中AN配比量的增加,POE-g-SAN中SAN相的Tg升高.     

官能化丁苯渐变嵌段共聚物树脂的合成与表征

采用溶液聚合法,以官能化偶联剂合成了带有HN-,HO-,HS-的官能化丁二烯-苯乙烯渐变嵌段共聚物.结果表明,该聚合物为单形态的三臂或四臂星形共聚物,具有良好的透光率和耐环境开裂性以及较好的耐氧化性、耐热性和表面粘接性,可应用于医疗器械、儿童玩具、食品容器等行业.     

Synthesis and characterization of the epoxyfumarate resins

The synthesis and properties of the new epoxyfumarate and epoxymaleate resins obtained by the addition of acidic allyl maleate to the commercially available resin Epidian 5 are presented. The resins were synthesized in one‐ and two‐step procedures and properties of the obtained resins are compared. It should be noted that the use of allyl alcohol in the synthesis of unsaturated resins has an advantageous influence on their properties. Glass‐transition temperatures of the epoxyfumarate resins exceed 100°C, whereas those of epoxymaleates are higher than 70°C. The resins are also characterized by good chemical resistance. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 716–722, 2002; DOI 10.1002/app.10067     

Synthesis and characterization of novel dihydrobenzoxazine resins

Three dihydrobenzoxazines are synthesized from bisphenol A (BPA), 4,4′‐biphenol (BIP), and dicyclopentadiene phenol adduct (DCPD). Polydihydrobenzoxazine containing 4,4′‐biphenol (BIPDB) had the most rigid structure of the three and was found to possess the best mechanical and thermal properties. The glass transition temperature of BIPDB was 206°C, and that of BPA‐type polydihydrobenzoxazine (BPADB) and dicyclopentadiene type polydihydrobenzoxazine (DCPDDB) were 184 and 183°C, respectively. DCPDDB, with a rigid hydrophobic cycloaliphatic structure, was found to possess excellent properties such as low moisture absorption, low dielectric constant, low polarization. The resulted polymer from DCPDDB had a dielectric constant of 2.94U, which was better than that of polymers derived from BPA (3.31U), BIP (3.45U), and traditional phenolic resin (3.9–4.0U). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 342–347, 2006     

Synthesis and characterization of MQ silicone resins

MQ silicone resins, which represent a broad range of hydrolytic condensation products of monofunctional silane (M) and tetrafunctional silane (Q), were synthesized by reaction of water glass with hexamethyldisiloxane. The optimum reaction time and the optimal reaction temperature is 30 min and 30–40°C, respectively. Concentrated hydrochloric acid is the best one among those catalysts tested. In large-scale experiments (420–1680 mL), the favorable feeding order is catalyst first, and then water glass, the mixture of hexamethyldisiloxane and ethanol last and most MQ silicone resin was observed. The structure of MQ silicone resin was characterized by FT-IR and GPC spectra. The MQ silicone resin shows narrow molecular weight distribution and the number average molecular weight of MQ silicone resin is 2917. The silicone pressure sensitive adhesive prepared from as-synthesized MQ resin has good tack (29#) and 180° peel adhesion (5.630N/20 mm). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of a PE-g-LCP copolymer

The possibility of reinforcing polyethylene (PE) by blending it with a liquid crystalline polymer (LCP) rests on the successful improvement of phase compatibility and interfacial adhesion of these two structurally unlike polymers. The approach that is being considered in our laboratories consists of the synthesis of PE–LCP block or graft copolymers and of their use as compatibilizing agents for PE/LCP blends. In this work, the melt polycon-densation of sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) has been carried out at temperatures up to 280°C in the presence of an oxidized low molar mass PE sample containing free carboxylic groups (PEox), with the main scope of demonstrating that a PE-g-LCP copolymer may be synthesized by this route. The polycon-densation product has been fractionated by successive extractions with boiling toluene and xylene. The soluble fractions and the residues have been characterized by IR and NMR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TG, DTG), and scanning electron microscopy (SEM). The extractions and the analyses have been repeated on a PEox/LCP blend prepared by melt mixing PEox and preformed LCP (SBH 112, by Eniricerche). The results show that, whereas for the blend a fairly clean separation of PEox and SBH can be obtained by solvent extraction, this is not so for the polycondensation product. All analytical procedures concordantly show that a PEox-g-SBH copolymer has, in fact, been obtained. In effect, both PEox and SBH chain segments are present, with different relative ratios, in all fractions of the polycondensate. Moreover, a fairly quantitative esterification of the PEox carboxyl groups has been shown by IR analysis to take place in the adopted conditions. Preliminary morphological investigations carried out by SEM have shown that the addition of the synthesized graft copolymer into HDPE/SBH blends leads to an improvement of the interfacial adhesion. © 1996 John Wiley & Sons, Inc.     

NVF-DADMAC阳离子共聚物的合成与表征

以N-乙烯基甲酰胺(NVF)和二甲基二烯丙基氯化铵(DADMAC)为原料,通过水溶液聚合法合成了NVF-DADMAC阳离子共聚物。用FTIR和DSC-TG对共聚产物进行了表征,用胶体滴定法测定了共聚物的阳离子度,考察了引发剂浓度、反应温度对聚合过程中转化率以及聚合物的阳离子度和特性粘数的影响。研究结果表明:NVF与DADMAC发生了共聚,且该共聚物的热稳定性比NVF的均聚物高,DADMAC的转化率可达90%以上。     

Methyl nadimide resins: Synthesis and characterization

This article describes the synthesis and characterization of several methyl nadimides endcapped resins based on tris(3-aminophenyl)phosphine oxide. These resins were prepared by reacting methyl-5-norbornene 2,3-dicarboxylic anhydride (methyl nadic anhydride) (MNA), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6F), and tris(3-aminophenyl)phosphine oxide (TAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, IR, and ¹H-NMR. Thermal characterization of uncured resins using DSC and TGA techniques revealed an exothermic transition accompanied by a weight loss in the temperature range of 200–350°C. Residual weight at 800°C in nitrogen was found to be 47–55%. Isothermal curing of the resins was done at 340°C for 1 h in an air atmosphere. The cured resins were stable up to 400 ± 20°C. © 1994 John Wiley & Sons, Inc.     

丙烯酸酯-富马酸酯共聚乳液的合成及表征

采用半连续乳液聚合方法,以甲基丙烯酸甲酯（MMA）、富马酸二丁酯（DBF）为主单体,丙烯酸（AA）为功能单体,十二烷基硫酸钠（SDS）为乳化剂,过硫酸钾（KPS）为引发剂,合成了固含量为30%的共聚物乳液。探讨了单体配比、SDS用量、KPS用量对乳液及胶膜性能的影响。结果表明,乳胶粒子有核壳结构,当DBF/MMA比例为1/1.5,SDS为单体总质量的3%,KPS为0.4%时,乳液涂料综合性能达到最佳,涂膜光泽度、附着力良好,力学性能及耐化学试剂性能优良。     

Multifunctional epoxy resins: Synthesis and characterization

The tetrafunctional epoxy resins were prepared starting from diaminodiphenylmethane, diaminodiphenylether, and diaminobibenzyl. The obtained resins were characterized by IR and ¹H‐NMR spectroscopy, rheological and thermal techniques. The polymerization reaction was investigated by viscosimetry. The flow activation energy and the polymerization activation energy were evaluated from the rheological data and from the critical parameters (critical time and critical viscosity at gel point). The viscosity measurements and gel time determination showed slight differences between the synthesized resins. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2430–2436, 2000     

New epoxy resins. II. The preparation,characterization, and curing of epoxy resins and their copolymers

A polymer having high aromaticity and/or cyclic ring structures in the chain backbone usually gives high heat resistance and flame resistance. Five glycidyl ether-type epoxy resins are prepared from bisphenol A (DGEBA), 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF), 3,6-dihydroxyspiro-[fluorene-9,9′-xanthane] (DGEFX), 10,10-bis(4-hydroxyphenyl) anthrone (DGEA), and 9,9,10,10-tetrakis(4-hydroxyphenyl)anthracene (TGETA) in order to study structure–thermal stability–flame resistance property relationships. In this study, trimethoxyboroxine (TMB) and diaminodiphenylsulfone (DDS) are employed as the curing agents. The char yield at 700°C under a nitrogen atmosphere and the glass transition temperature (T_g) for the uncured resins decrease according to the sequence TGETA > DGEFX > DGEA > DGEBF > DGEBA. The Tg values for these cured epoxy resins are DGEBA < DGEBF < DGEFX < DGEA. A T_g for the TGETA is not obtainable but would be expected to be the highest. The char yields at 700°C of these cured epoxy resins have the same trend as the uncured resins. DGEBF, DGEFX, DGEA, and TGETA added to the DGEBA system show increases in the char yield, T_g, and oxygen index with increasing concentration of these novel epoxy resins.     

Synthesis and characterization of thermosetting polyacetylene-terminated silicone resins

A novel polyacetylene-terminated silicone (PTS) resins possessing low curing temperature and high heat resistance has been prepared by Grignard reaction using m-diacetylenylbenzene (DEB), 1,3,5-triacetylenylbenzene(TEB), and dichlorosilane as original materials. The reaction of the functional groups was characterized by in situ Fourier transform infrared spectrometer. The experimental results indicated that Si─H and C≡CH bonds are almost exclusively involved in the crosslinking reaction, while ─C≡C─ bonds only partially react. Further, Si─H and C≡CH bonds can participate in the curing reaction at relatively low temperatures, but ─C≡C─ bonds require higher temperature, indicating the higher activity of Si─H and C≡CH bonds than ─C≡C─ bonds. As determined by differential scanning calorimetry, PTS resins have low peak exothermic temperature at 184.5 °C, which is lower than MSP resin (~ 210 °C); in addition, rheological test showed that PTS resins have a very wide processing window from 40 to 163.3 °C, indicating that the PTS resins have excellent processability with a low curing temperature and wide processing window. What is more, TGA results of thermal-cured PTS resins revealed that T_d5 (5% weight loss temperature) of PTS-H10 reached the highest of 684.4 °C. Compared with PTS-H0 resin, there is an increase of 124.2 °C and the remarkably increased heat resistance correlated with a higher m-DEB input ratio. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48783.     

Synthesis and characterization of epoxy resins containing bismuth

The synthesis of epoxy resins in the presence of Bi as bismuth acrylate (BiA₃) showed that the properties such as epoxide equivalent weight (eq/100 g), molecular weight, and viscosity (η_sp) increased; whereas hydrolyzable chlorine content, hydroxyl content, and refractive index decreased in the presence of BiA₃. The metal forms a complex with ether linkage of epoxy resins, as evidenced from infrared spectroscopy. The presence of Bi in epoxy resins has been confirmed by scanning electron microscopy (SEM) and qualitative analysis. The glass transition temperature (T_g) of epoxy resins containing 1.18 × 10⁻⁵ and 2.8 × 10⁻⁵ molar equivalent of BiA₃ is 131.58 and 190°C, respectively, and is greater than that of blank (130°C). The heat of reactions for epoxy resins containing 1.18 × 10⁻⁵ molar equivalent of BiA₃, calculated by differential scanning calorimetry, is 4.75 J g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1359–1365, 1997     

Synthetic resins: II: Preparation and characterization of resins prepared from aminoacetophenone

A number of resins were prepared by condensing m-aminoacetophenone with substituted aromatic compounds and formaldehyde in the presence of acids and bases as catalyst. The resins were characterized by infrared spectra. The solubility parameters were calculated from Small's group contribution which agreed well with the experimental value. The bacteriocidal properties of the resins have been studied.