瓜儿胶改性及其衍生物在造纸工业的应用

介绍了瓜儿胶的羟烷基及阳离子醚化改性技术,瓜儿胶与丙烯酰胺、丙烯氰等乙烯基单体的接枝共聚改性,总结了各种引发体系下接枝率,接枝效率等指标的优化条件。论述了瓜儿胶衍生物在造纸湿部作为助留助滤剂、增强剂的应用,并指出今后的发展前景。     

商丘市益源科技有限公司

益源科技,河南省高新技术企业,专注天然植物多糖及衍生物的研发、生产和销售。产品覆盖护肤、护发、美容修饰和口腔护理等系列。YJ-3688是具有卓越调理功效的季铵化阳离子瓜耳胶衍生物。在洗发类产品中,可提供良好的干湿手感。其阳离子取代度非常高,胶液透明度良好,系国内首创并已申报国家专利产品,可部分或全部取代阳离子纤维素,且积聚性能小于阳离子纤维素而与普通阳离子瓜尔胶相当。由于其卓越的干湿调理功效,为专业发品首选。     

低浓度瓜胶交联剂(HK-8)在延长油田的应用

低浓度瓜胶交联剂(HK-8)能够将延长中温地层压裂液的瓜胶浓度由0.38%降至0.28%;应用低浓度瓜胶交联剂(HK-8)的压裂液具有与原配方一样良好的携砂性能、耐温抗剪切性能和破胶性能,能够降低对地层伤害率50%以上;现场试验证明,低浓度瓜胶交联剂HK-8可以代替有机硼交联剂,能够满足的压裂要求。     

改性瓜胶压裂液的制备及性能研究

分别以十二烷基和磺酸盐甜菜碱为修饰基团,以瓜胶原粉为主剂,制备了2种改性瓜胶增稠剂:疏水改性羟丙基瓜胶和磺酸盐甜菜碱型瓜胶。模拟现场配方,对其配制的压裂液的抗剪切性能和耐温性能进行评价。通过对比发现磺酸盐甜菜碱型胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有所下降,疏水改性羟丙基胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有明显改善。其中,疏水改性羟丙基瓜胶80℃下剪切60 min后,表观粘度为93.4 m Pa·s,比油田提供CJ2-6瓜胶耐温抗剪切能力有明显改善。可以考虑疏水改性羟丙基瓜胶在压裂液体系的进一步应用。     

改性瓜胶压裂液的制备及性能研究

分别以十二烷基和磺酸盐甜菜碱为修饰基团,以瓜胶原粉为主剂,制备了2种改性瓜胶增稠剂:疏水改性羟丙基瓜胶和磺酸盐甜菜碱型瓜胶。模拟现场配方,对其配制的压裂液的抗剪切性能和耐温性能进行评价。通过对比发现磺酸盐甜菜碱型胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有所下降,疏水改性羟丙基胍胶比油田提供CJ2-6胍胶耐温抗剪切能力有明显改善。其中,疏水改性羟丙基瓜胶80℃下剪切60 min后,表观粘度为93.4 m Pa·s,比油田提供CJ2-6瓜胶耐温抗剪切能力有明显改善。可以考虑疏水改性羟丙基瓜胶在压裂液体系的进一步应用。     

制备接枝共聚羟丙基瓜胶的新工艺

以可聚合的甜菜碱功能单体和羟丙基瓜胶为主要原料,分别使用均相反应法(原工艺)和非均相反应法(新工艺)制备了接枝共聚羟丙基瓜胶。探讨了新工艺的操作条件对反应过程和目标物性能的影响。结果表明,新工艺中m(功能单体)∶m(羟丙基瓜胶)=1∶1,引发剂用量0.12%,溶剂中m(乙醇)∶m(水)=4∶1时,新工艺反应过程较平稳,所得目标物的耐盐性能最好。新工艺目标物符合SY/T 5764—2007《压裂用植物胶通用技术要求》。与原工艺相比,新工艺在不改变目标物主要性能的前提下,能够大幅提高产量、降低生产成本,为实现大规模工业化生产积累了一定经验。     

制备接枝共聚羟丙基瓜胶的新工艺

以可聚合的甜菜碱功能单体和羟丙基瓜胶为主要原料,分别使用均相反应法(原工艺)和非均相反应法(新工艺)制备了接枝共聚羟丙基瓜胶。探讨了新工艺的操作条件对反应过程和目标物性能的影响。结果表明,新工艺中m(功能单体)∶m(羟丙基瓜胶)=1∶1,引发剂用量0.12%,溶剂中m(乙醇)∶m(水)=4∶1时,新工艺反应过程较平稳,所得目标物的耐盐性能最好。新工艺目标物符合SY/T 5764—2007《压裂用植物胶通用技术要求》。与原工艺相比,新工艺在不改变目标物主要性能的前提下,能够大幅提高产量、降低生产成本,为实现大规模工业化生产积累了一定经验。     

一种化妆品调理组份：阳离子瓜耳胶

阳离子瓜耳胶(Guar Hydroxypropyltrimonium Chloride)是天然瓜耳胶(Natural Guar Gum)与阳离子化剂经季铵化制得的一种具有调理性的阳离子聚合物。目前,阳离子瓜耳胶在化妆品和盥洗用品中的应用日越增加,尤其是在调理香波、护发素等发用品内得到广泛应用。其主要性能不仅已超过了诸如阳离子纤维素等类聚合物,而且还具备一些十分独特的性能。比如:     

甜菜碱接枝共聚羟丙基瓜胶的制备

以羟丙基瓜胶和甜菜碱单体为原料,硝酸铈铵为引发剂,采用溶液聚合法制备甜菜碱接枝羟丙基瓜胶,对目标物结构进行了IR、质谱表征。考察了接枝反应温度、接枝反应时间、引发剂浓度、原料配比对目标产物增稠性能的影响,结果表明,当反应温度为20℃,引发剂浓度为5 mmol/L,反应时间为24 h,m(甜菜碱单体)∶m(羟丙基瓜胶)=1∶1时,单体转化率为36.5%,相对分子质量为1.28×10~6;常温下,配制目标产物质量分数0.5%的水溶液,20 min内充分溶解,初始黏度为75 m Pa·s;目标产物耐盐性优于羟丙基瓜胶,水溶性和增稠性良好。     

瓜胶压裂返排液配制环保型钻井液的工艺研究

针对瓜胶压裂返排液存在的处理困难、高成本、低效果等问题,本文提出了利用瓜胶压裂返排液配制环保型钻井液的工艺.采用环保型钻井液处理剂,通过单因素分析、正交实验等多种方法,对各类钻井液进行性能检测,以寻找最佳的实验参数,确保瓜胶压裂返排液可以达到使用标准.从线性膨胀率等实验结果可知,利用瓜胶压裂返排液配制钻井液,能够很好地...     

Comparative studies on the flocculation characteristics of polyacrylamide grafted guar gum and hydroxypropyl guar gum

The synthesis of two polysaccharide‐based graft copolymers with acrylamide, guar gum grafted polyacrylamide (GG‐g‐PAM) and hydroxypropyl guar gum grafted polyacrylamide (HPG‐g‐PAM) is described. The graft copolymers have been characterized by viscometry, infrared spectroscopy and thermal analysis. The flocculation characteristics of the graft copolymers have been studied in kaolin, iron ore, and silica suspensions. For the base polysaccharides guar gum (GG) and hydroxypropyl guar gum (HPG), it is observed that GG exhibits better performance than HPG in all three suspensions. For the graft copolymers, HPG‐g‐PAM shows better performance than GG‐g‐PAM. The flocculation characteristics of the best performing graft copolymer (HPG‐g‐PAM) are compared with various commercially available flocculants in the three suspensions mentioned above. © 2001 Society of Chemical Industry     

羧甲基纤维素钠/阳离子瓜尔胶共混膜用作药物缓释材料的研究

以可生物降解和生物相容的羧甲基纤维素钠(NaCMC)与阳离子瓜尔胶(GG)为原料,制得系列不同配比的多糖共混膜。以此共混膜作为药物布洛芬的载体,考察了共混比、药物浓度以及pH值对药物释放的影响,并研究了其药物释放机理。结果发现,对布洛芬药物释放影响最大的是介质的pH值,其次是共混膜的共混比例,药物含量在弱碱介质中有一定的影响,在酸性介质中基本无影响。大部分的药物释放n>0.89,为非Fick扩散(骨架溶蚀机制),药物以零级进行释放。共混膜对疏水性药物布洛芬具有较好的缓释性能。     

Guar gum methyl ethers. Part I. Synthesis and macromolecular characterization

Guar gum (GG) has been partially methyl-etherified under heterogeneous reaction conditions. The resulting products, (methyl ether guar: MG) with different degrees of substitution, have been characterized by means of viscosity, ¹H NMR, and FTIR measurements. The introduction of methoxyl groups along the polysaccharidic chains reduces the hydrogen bonding sites on the guar backbone reducing primarely the extent of hydrogen bonding between guar macromolecules, hence their aggregation tendency. A comparative analysis of Mark–Houwink–Sakurada parameters and of the characteristic ratio (C_∞) of GG and MG samples in aqueous solution has been carried out using the Burchard–Stockmayer–Fixman method for flexible and semiflexible chains. The MG chains exhibit more flexibility than those of native guar gum which is traceable to a disruption of intrachain hydrogen bonds.     

瓜尔胶的改性及其透光性能研究

瓜尔豆片为原料,经羟丙基提纯后阳离子改性,得到透明性较好的阳离子瓜尔胶（CGG）。经分析碱法水解除蛋白质最优工艺为：豆片25g,NaOH5g,98℃下反应3h：蛋白质去除率为98．24％,透光率达77％。羟丙基化较优工艺为：环氧丙烷8mL。60℃反应4h;羟丙基取代度为0．2650,透光率为89％e阳离子化最优工艺为：醚化剂10mL,60℃反应3～5h,取代度（DS）为0．1701,透光率达97％。用IR对产蹦结构进行了表征,用TG和DSC对瓜尔胶、羟丙基瓜尔胶和阳离子瓜尔胶的对比研究表明,接枝的阳离子基团对瓜尔胶的相态稳定温度有影响,阳离予瓜尔胶的水分含量和结合水含量有所降低,利于储存。此产品用于对透光率要求较高的领域。     

pH敏感瓜胶/聚丙烯酸半互穿网络水凝胶研究

制备了瓜胶/聚丙烯酸(GG/PAA)的半互穿网络(sem i-IPN)水凝胶,以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,考察了加料量、溶胀介质pH对平衡溶胀率(ESR)的影响。结果表明:GG/PAA半互穿网络水凝胶的ESR在pH≤3时较小,pH>4后增加较快,pH=8.2时达最大值,继续增加pH,ESR又呈下降趋势,体系具有pH敏感性。在pH相同条件下,ESR随GG用量增加而减小,随丙烯酸(AA)用量增加而增大。pH=8.2、ρ(GG)从5 g/L增加到25 g/L时,ESR从3 142降低到1 026;当ρ(AA)用量从125 g/L增加到375 g/L时,ESR从1 195增加到2 611。m(MBA)∶m(AA)=(0.5∶100)~(1.2∶100)时,ESR略有增加。GG/PAA半互穿网络水凝胶的溶胀动力学表明,该类凝胶满足在胃液pH环境中溶胀率较小、小肠部位pH环境中溶胀率较高的要求,因此,通过调整配方,结合瓜胶只被结肠部位细菌降解的特性,GG/PAA半互穿网络水凝胶有望成为一种理想的靶向结肠给药载体。     

瓜尔胶的化学改性

简要介绍了瓜尔胶的结构及其化学改性的原理和方法;综述了国内外瓜尔胶化学改性的研究工作;详细介绍了非离子瓜尔胶、阳离子瓜尔胶、阴离子瓜尔胶、羟烷基阴离子瓜尔胶和羟烷基阳离子瓜尔胶以及两性瓜尔胶的合成方法。瓜尔胶通过改性改善了水溶性、大大降低了水不溶物的含量、提高了电解质的兼容性、增加了黏度的稳定性、从而扩大了瓜尔胶的应用领域,使得改性瓜尔胶广泛应用于化妆品、个人护理品、造纸、油田和增稠剂等众多领域。     

Biodegradable blend films based on two polysaccharide derivatives and their use as ibuprofen‐releasing matrices

Differential scanning calorimetry (DSC), FTIR, X‐ray diffraction (XRD), and viscosity methods were used to examine the miscibility, interaction, and degradability of cationic guar gum (GG) and sodium carboxymethylcellulose (NaCMC) in their blend films. The experiment results prove that there exist electrostatic interactions and hydrogen bonding between GG and NaCMC. Blend films degrade quicker than pure GG or NaCMC film. Furthermore, the degradation rate of blend films is related to the interactions between GG and NaCMC. Based on the research of blend films as the drug carriers for Ibuprofen, it is found that the blend composition, initial drug concentration, and pH value affect the drug release and the GG/NaCMC blend films have good sustained release performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3553–3559, 2007     

阳离子羟乙基瓜尔胶的合成及其造纸湿部应用

对一步泥浆法合成新型助留助滤剂———阳离子羟乙基瓜尔胶(CEG),及将其用于废新闻纸浆的抄造过程进行了探讨。悬浮于醇/水体系中的瓜尔胶,先与阳离子单体发生醚化反应,然后与氯乙醇在微过量碱催化剂存在下进行羟乙基化反应,阳离子中间产物不必分离。重点研究了阳离子醚化产物的黏度及氮质量分数的影响因素,确定了阳离子化反应优化条件为:m(阳离子单体)∶m(瓜尔胶)=0.4∶1,m(NaOH)∶m(瓜尔胶)=0.25∶1,反应温度60℃,反应时间2.5 h。经红外光谱分析,证实了接枝产物中季铵阳离子基团的存在。由于CEG分子结构同时含有季铵阳离子和非离子的活性羟基,CEG常温水合作用进一步强化,w(CEG)=1%的水溶液的透光率增加到80%。当以w(CEG)=0.2%(以绝干浆计)的用量添加到废新闻纸浆中,细小组分的单程留着率提高了40%,打浆度减少了37%。     

瓜尔胶/丙烯酰胺的反相乳液接枝共聚

以硝酸铈铵/硝酸为引发剂,在反相乳液中引发瓜尔胶/丙烯酰胺的接枝共聚反应。考察了m(丙烯酰胺AM)∶m(瓜尔胶GG)、引发剂浓度、反应温度和反应时间对接枝聚合的影响。结果表明,当m(AM)∶m(GG)=3∶2,引发剂浓度为4 mmol/L,反应时间为4 h,反应温度为45℃时,接枝共聚反应的接枝率和单体转化率分别为147.05%和87.7%。接枝共聚物的最大相对分子质量(简称分子量,下同)可达到1.73×106。红外光谱(IR)分析证明了AM确实接枝到GG分子链上,热重分析(TGA)显示接枝的AM单体并未影响GG的热稳定性。     

Thermal stability enhancement of guar-based hydraulic fracturing fluids by phosphate treatment

Guar gum (GG), along with its derivatives [e.g., hydroxypropyl guar (HPG)], is an important thickening agent in the hydraulic fracturing fluid system. However, as the oil reservoir gets deeper, GG is unable to tolerate the elevated temperature. In this study, the thermal stability of GG and HPG can be increased up to 95% and 80%, respectively, when phosphates are used as thermal stabilizer. The thermal stability is highest when the usage of phosphate is 1.84 mmol L⁻¹ KH₂PO₄ for GG and 2.27 mmol L⁻¹ K₂HPO₄ for HPG and the pH is 6.25–6.90 for GG and 6.25–8.75 for HPG. Furthermore, the heated GG with phosphate treatment demonstrates excellent crosslinking ability, which suggests that phosphate can be a good alternative for current thermal stabilizers and has potential application in the high-temperature formation oil or gas production. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47119.