双子型有机硅表面活性剂的合成与活性表征

以二氢四硅氧烷和不饱和聚醚为原料,合成了双子型有机硅表面活性剂;对其表面活性进行了表征,并与三硅氧烷表面活性剂进行了比较。结果发现,乙二醇单元与丙二醇单元的量之比[n（EO）／n（PO）]显著影响有机硅表面活性剂的表面活性;双子型有机硅表面活性剂水溶液的表面张力高于三硅氧烷表面活性剂水溶液的表面张力,其润湿性、渗透性、分散性等落后于三硅氧烷表面活性剂。     

抗水解三硅氧烷表面活性剂的研制

以七甲基三硅氧烷和甲基烯丙基聚醚、炔二醇醚为原料,通过硅氢加成反应合成了2种表面活性剂:甲基烯丙基聚醚改性三硅氧烷SE-429和炔二醇醚改性三硅氧烷SE-640。考察了催化剂种类及用量、温度对反应的影响,确定了较佳的反应条件为:催化剂选用烯丙基铂配合物、催化剂用量为0.02%、温度为110～120℃。研究了产物的表面张力、铺展面积、临界胶束浓度(CMC)、动态表面张力(DST)以及抗水解稳定性。结果表明,这2种三硅氧烷表面活性剂质量分数为0.1%的水溶液表面张力均小于21 mN/m,储存360 d后表面张力增幅分别为78.6%和28.2%,低于常规的烯丙基聚醚改性三硅氧烷SE-90(201.5%);SE-429的CMC为40.7 mg·L,铺展面积与SE-90接近;SE-640水溶液不形成胶束,表面张力能更快达到平衡。两者具有优良的表面活性和抗水解稳定性。     

一种三硅氧烷硫酸盐表面活性剂的合成及性能

以1,1,1,3,5,5,5 -七甲基三硅氧烷(TSO)、甲基丙烯酸羟丙酯和氨基磺酸为原料合成了一种三硅氧烷硫酸盐表面活性剂;通过IR和1HNMR对合成的中间体及最终产物的结构进行了表征,并对其表面活性、泡沫性能和渗透性能等进行了测试.结果表明,三硅氧烷硫酸盐表面活性剂的最低表面张力(γcmc)为23.3 mN· m-1,临界胶束浓度(cmc)为3.16×10-2 tmol·L-1;该表面活性剂有较好的渗透性能,但是起泡性和稳泡性不强.     

三硅氧烷咪唑离子液体表面活性剂的合成与表面活性

以氯丙基甲基二甲氧基硅烷和六甲基二硅氧烷为原料,在浓硫酸催化下合成了氯丙基三硅氧烷,再与1-甲基咪唑进行季铵化反应,制备了三硅氧烷咪唑离子液体表面活性剂.用傅里叶红外光谱仪以及氢谱和碳谱核磁共振仪表征了产物的结构;并对其临界胶束浓度(cmc)及表面张力(γ)进行了测定.结果表明,与长链烷基咪唑类离子液体表面活性剂相比,三硅氧烷咪唑离子液体表面活性剂具有更好的表面活性,其cmc为15.5 mmol/L,γcmc为24.0 mN/m.     

三硅氧烷表面活性剂性能评价

研究了以烯丙基聚醚和七甲基聚三硅氧烷为原料的三硅氧烷表面活性剂中原料烯丙基聚醚中EO的聚合度、产品浓度与产品的表面张力之间的关系。三硅氧烷表面活性剂作为农药喷雾助剂,其最合理的EO聚合度的取值应该在4～8之间。当其浓度达到0.04%aq时,即可使溶液的表面张力达到21～22mN/m,从而使药液在叶片表面获得良好的润湿和铺展。     

高性能低泡农用有机硅增效剂的合成及性能研究

为解决常规表面活性剂带来的多泡问题,以2种不同的烯丙基聚醚和七甲基三硅氧烷为原料合成了农用有机硅增效剂RH-A和RH-B,对比了两者的润湿性、铺展性、表面张力、起泡性以及对农药的增效性。结果表明,RH-B的铺展能力是RH-A的1.3倍,两者的润湿性非常接近,但RH-B的表面张力比RH-A低,表现出更好的表面活性,且RH-B具有低泡性,对农药的增效作用也更好。     

烯丙基聚醚改性四硅氧烷表面活性剂的表面活性和润湿性能

通过1,1,1,3,5,7,7,7-八甲基四硅氧烷与不同聚合度的烯丙基聚氧乙烯醚反应合成了系列烯丙基聚醚改性四硅氧烷表面活性剂(TESE),用1HNMR和29SiNMR对产物进行了表征。通过对表面张力和接触角的测定,研究了其水溶液的表面活性以及在PET(聚对苯二甲酸乙二醇酯)和PMMA(聚甲基丙烯酸甲酯)基板上的润湿性能,同时探究了其在水中的溶解性以及亲水基结构(聚醚EO链长)对其表面活性和润湿性能的影响。结果显示,这类表面活性剂具有优异的表面活性和良好的润湿性能。随着EO链长的增加,TESE的表面活性存在最佳EO链长(EO单元数为8)。其中,在较短EO链长的一定范围内,TESE水溶液的最低表面张力(γcmc)变化幅度均较小,而EO链长超出一定范围后,γcmc增大幅度较为显著;TESE的润湿性能,在EO单元数小于12时变化不大,当EO单元数超过12时明显减弱。     

新型咪唑盐三硅氧烷表面活性剂的合成及表面活性

以3-巯丙基-1,1,1,3,5,5,5-七甲基三硅氧烷与1-烯烃基-3-甲基咪唑溴盐为原料,通过巯基-烯烃点击反应高效合成含有不同联接基团(—CH 2—)的咪唑盐阳离子三硅氧烷表面活性剂([Si 3-C n-Min]Br).通过表面张力探索—CH 2—链节数量对其表面活性的影响.发现其最低表面张力为27～29 mN/...     

聚醚改性三硅氧烷的合成工艺研究

以烯丙基聚醚与七甲基三硅氧烷为原料,通过硅氢加成反应合成出聚醚改性三硅氧烷。用IR对其结构进行表征,研究了催化剂用量、反应温度、反应时间、烯丙基聚醚与七甲基三硅氧烷的量之比[n(醚)/n(硅)]对七甲基三硅氧烷转化率的影响以及七甲基三硅氧烷转化率与产物表面张力的关系。结果表明,较佳反应条件是n(醚)/n(硅)为1.2、铂原子相对于七甲基三硅氧烷的质量分数为0.00075%、反应时间1 h、反应温度100～110℃。在此条件下合成出的聚醚改性三硅氧烷的0.1%的水溶液的表面张力为20.3 mN/m,七甲基三硅氧烷的转化率为98.1%。     

二甲胺聚醚改性有机硅表面活性剂的合成

以不饱和的聚醚和环氧氯丙烷为原料，合成出环氧不饱和聚醚；再与低含氢硅油进行硅氢加成反应，合成出环氧聚醚改性聚甲基硅氧烷；接着用二甲胺对环氧基开环，得到二甲胺聚醚改性有机硅表面活性剂。研究了硅氢加成反应条件对含氢硅油转化率的影响、用IR谱图表征了关键中间体及产物的结构、测定了产物的表面特性。硅氢加成反应的最佳工艺为：反应温度75℃、反应时间5h、聚醚中的C=C键与含氢硅油中的Si-H基的量之比为1．1：1．0；二甲胺聚醚改性有机硅表面活性荆的表面张力为21．4mN／m，在农纷螟施净水溶液中的临界胶束质量分数为3％，在临界胶束浓度下螟施净水溶液的表面张力值为24．8mN／m，能大幅降低农药的表面张力（降幅这24％）；从亲水亲油平衡（HLB）值看，二甲胺聚醚改性有机硅表面活性荆的亲油性稍强于亲水性，且HLB值在一定范围内随着pH值的降低而提高。     

糖苷改性三硅氧烷表面活性剂及保湿性能

根据表面活性剂结构与性能的关系,将有机硅表面活性剂具有低表面张力的高"效能"与糖基表面活性剂的可生物降解性结合起来,合成了糖苷改性三硅氧烷表面活性剂,通过测定表面张力、临界聚集浓度、聚集体大小和保湿性研究了糖苷改性三硅氧烷表面活性剂的表面活性和在化妆品中的保湿性能。结果表明,糖苷改性三硅氧烷表面活性剂可以显著地降低水的表面张力至约20 mN/m,临界聚集浓度约为1×10-4mol/L,在水溶液中形成的聚集体平均水合半径约为250 nm。在化妆品配方中加入质量分数3%的糖苷改性三硅氧烷表面活性剂,使用2 h后水分含量为33.36%,水合率为31.97%,水分散失为11.21 g/(h.m2),水分散失率为-11.54%,具有明显的补水、锁水效果,且有持续的补水、锁水能力,是一种优良的化妆品保湿剂。     

Synthesis and Properties of a Hydrolysis Resistant Cationic Trisiloxane Surfactant

In order to improve the hydrolysis resistant ability (HRA) of trisiloxane surfactants, a new kind of quaternary ammonium salt cationic trisiloxane surfactant (QASCTSS) was synthesized in three steps and investigated. The chemical structure of QASCTSS was characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Compared with normal trisiloxane surfactants, QASCTSS exhibits a lower surface tension, especially under strong acid or alkaline conditions. This was attributed to the protection for Si–O backbone from the quaternized side chain, and some improvement in HRA is seen in acidic conditions with ethyl instead of methyl side chains on the quaternary structure.     

Mixed Micelles of Trisiloxane Based Silicone and Hydrocarbon Surfactants Systems in Aqueous Media: Dilute Aqueous Solution Phase Diagrams, Surface Tension Isotherms, Dilute Solution Viscosities, Critical Micelle Concentrations and Application of Regular Solution Theory

Mixtures of trisiloxane type nonionic silicone surfactant (SS) with sodium dodecylsulfate, tetradecyltrimethylammonium bromide or tert-octylphenol ethoxylated with 9.5 ethylene oxide groups were studied in water at 30 °C by dilute aqueous solution phase diagrams, surface tension and dilute solution viscosity methods. The cloud points for the silicone surfactant aqueous solutions increased upon addition of hydrocarbon surfactants indicating the formation of hydrophilic complexes in mixture solutions. The scrutiny of the surface tension isotherms plotted as a function of SS concentration revealed that competitive adsorption effects are the characteristic features in these mixtures depending upon the SS concentration. Otherwise the isotherms exhibited two break points and the difference of concentration between the two break points increased with the increase in SS concentration indicating the cooperative nature of interactions. The micellar mole fractions of individual surfactants were determined by Rublingh's regular solution theory; interaction parameters and activity coefficients were evaluated and interpreted in terms of synergistic type interactions in these mixtures. The surface active parameters in mixture solutions were estimated and their analysis shows that the molecular species in the mixture solutions have a preferential tendency for adsorption at the air/water interface than in association form in the bulk solution. The effect of hydrocarbon surfactants on the intrinsic viscosity of SS micelles was monitored and related to the enhanced hydration in mixed micelles.     

Synthesis and Properties of Novel Double-Tail Trisiloxane Surfactants

To improve the hydrolysis resistant ability of trisiloxane surfactants, ethoxylated single-tail and double-tail trisiloxane surfactants of the general formulas Me₃SiOSiMeR¹OSiMe₃ (R ¹ = (CH₂)₃NHCH₂CH(OH)CH₂(OCH₂CH₂) _x OCH₃; x = 8.4, 12.9, 17.5, 22) and Me₃SiOSiMeR²OSiMe₃ (R ² = (CH₂)₃NR³CH₂CH(OH)CH₂(OCH₂CH₂) _x OCH₃; R ³ = CH₂(CH₂) _y CH₃; x = 8.4, 12.9, 17.5, 22; y = 2, 6) were synthesized. Their structures were characterized by ¹H NMR and ¹³C NMR. The surface activity and hydrolysis resistant properties of the trisiloxane surfactants prepared were also studied. The values of the critical micelle concentration of all trisiloxane surfactants prepared were at levels of 10⁻⁵ and 10⁻⁴ mol/L. They can reduce the surface tension of water to less than 24 mN/m. The hydrolysis resistant properties of double-tail trisiloxane surfactants are superior to those of single-tail trisiloxane surfactants. The double-tail trisiloxane surfactants 1B (x = 8.4; y = 2) and 2C (x = 12.9; y = 6) can be stable for 8 days in an acidic solution (pH 4.0) and 11 days in an alkaline environment (pH 10.0).     

Ageing of trisiloxane solutions

Surfactants are commonly employed in numerous industrial applications and everyday products due to their enhancing wetting abilities. Trisiloxane surfactants in particular have proved to be matchless in reducing the surface tension of the liquid and consequently in enhanced wetting on even highly hydrophobic surfaces. In many practical applications trisiloxanes are frequently used as water-based solution. For convenience and reduced cost they are often pre-mixed with water and left for long periods of time in aqueous environment. We provide evidence that ageing of trisiloxane surfactants in water solutions may lead to loss of their interfacial activity. A mechanism for the observed behaviour is suggested and the phenomenon quantified. Along with a detailed explanation of the problem, we shed light on the dynamics of the process and provide some limitations of pre-mixed solutions.     

Synthesis and Properties of Novel Double-Tail Trisiloxane Surfactants with High Spreading Ability

A new type of double-tail trisiloxane surfactants of the general formula R¹NR²CH₂CH(OH)CH₂O(CH₂CH₂O)xCH₃ (x = 8.4, 12.9, 17.5, 22; R ¹ = Me₃SiOSiMe(CH₂)₃OSiMe₃, R ² = CH₂CH(OH)CH₂OR³, R ³ = CH₂CH(C₂H₅)CH₂(CH₂)₂CH₃) has been synthesized by reacting single-tail trisiloxane surfactants with 2-ethylhexyl glycidyl ether. Their structures were characterized with ¹H-NMR and ¹³C-NMR spectroscopy. These double-tail trisiloxane surfactants reduce the surface tension of water to less than 24 mN/m at a level of 10⁻⁵ mol/L. The spreading ability (SA) of the double-tail trisiloxane surfactant solution on Parafilm (or Ficus microcarpa leaf) surfaces is better than that on polyethylene terephthalate surface. The SA of the solution of the double-tail trisiloxane surfactants 1J with average ethoxy units of 8.4 is far better than the others, and its solution (5.0 × 10⁻³ mol/L) possesses an SA value of over 15 within 10 min on Parafilm and Ficus microcarpa leaf surfaces. The surface tension values of aqueous solutions (1.0 × 10⁻³ mol/L) of the double-tail trisiloxane surfactants 1J are still less than 25 mN/m over 21 days in an acidic environment (pH 4.0) and 139 days in an alkaline environment (pH 10.0), respectively. It is suggested that the SA and hydrolysis resistance of double-tail trisiloxane surfactants are able to be improved by changing the structure of the hydrophobic group, such as increasing the molar ratio of methyl to methylene.     

Synthesis and Characterization of Glycoside-Based Trisiloxane Surfactant

The synthesis of glycoside-based trisiloxane surfactants of the general formula Me₃SiOSiMeR¹OSiMe₃ (R¹ = (CH₂)₃(OCH₂CH₂)₂OR², R² = glycosyl) is described, and the surface activity properties of the surfactant are studied. Diethylene glycol monoallyl ether glycoside is synthesized by reacting the diethylene glycol monoallyl ether with glucose. The glycoside-based trisiloxane surfactant is prepared by hydrosilylation of the precursor glycoside with hydrogen-containing trisiloxane. The product is structurally characterized by IR, ¹H NMR and MS. The surface tension of an aqueous solution is reduced to approximately 20 mN m⁻¹ at concentration level of 10⁻⁴ mol L⁻¹.     

Synthesis and Solution Properties of Novel Sugar-Based Polysiloxane Surfactants

Two sugar‐based polysiloxane surfactants with well‐defined structures, 3‐(2‐aminoethylamino)propyl functional polysiloxane glucosamide grafted (AEAPFPS‐GA) and 3‐(2‐aminoethylamino)propyl functional polysiloxane lactobionamide grafted (AEAPFPS‐LA), were successfully synthesized and characterized by FT‐IR and ¹H NMR. Their surface activities and aggregation behavior in aqueous solution were investigated by surface tension measurements, dynamic light scattering (DLS) and negative‐stain transmission electron microscopy (TEM). The surface tension measurements provided the critical micelle concentration (CMC) and the surface tension at the CMC (γ_CMC), which revealed that these two surfactants have a much higher surface activity than those of conventional hydrocarbon surfactants. DLS and TEM analysis of the two polysiloxane surfactants aqueous solutions revealed that the AEAPFPS‐GA can self‐assemble into collapsed spherical micelles, and the AEAPFPS‐LA can self‐assemble into spherical micelles.