Preparation and characterization of polyacrylate/polymerized rosin composite emulsions by seeded semicontinuous emulsion polymerization

Polyacrylate/polymerized rosin composite emulsions were prepared by seeded semicontinuous emulsion polymerization of acrylate monomers in which polymerized rosin was dissolved. The effects of polymerized rosin content on the polymerization stability, monomer conversion, polymer structure, and adhesive properties were studied. Polyacrylate/polymerized rosin composites were characterized by gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogracvimetry (TG). The results showed that with an increase of polymerized rosin content from 0 to 6 wt %, gel fraction and sol molecular weight decreased obviously but monomer conversion was basically unchanged. In contrast, with a further increase of polymerized rosin content, the decreasing rates of gel fraction, and sol molecular weight were slowed down. Meanwhile, monomer conversion decreased remarkably. Moreover, interface failure changed into cohesive failure after the addition of polymerized rosin, and the peel adhesion and shear resistance of composite latex films declined with the increase of polymerized rosin content. Thermal analysis showed that polymerized rosin and polyacrylate were compatible and the composite latex films had good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ synthesis and properties of hydrogenated rosin/polyacrylate composite miniemulsions-based pressure sensitive adhesives

Hydrogenated rosin/polyacrylate composite miniemulsions-based pressure sensitive adhesives were synthesized by in situ miniemulsion polymerization method. The effect of HR amount on the monomer conversion rate, particle size and its polydispersity, coagulum rate, Zeta potential, and stability of the composite miniemulsions were studied, the effect of HR and crosslinker amount on the adhesion properties of the composite latex films were also investigated, and the composites were characterized by differential scanning calorimetry (DSC) and gel permeation chromatograph. The results showed that with HR amount increasing, the monomer conversion rate decreased, and the absolute value of Zeta potential and the molecular weight of the sol in the composite latex films also decreased, while the particle size and its polydispersity were almost unaffected. DSC analysis indicated that HR had relative good compatibility with polyacrylate. However, excess HR amount led to the decrease of the centrifugal stability and storage stability of the composite miniemulsions. Furthermore, with HR amount increasing, the ball tack of the latex films increased gradually, 180^o peel strength first increased and then decreased, and holding force decreased constantly. When HR amount exceeded 10 wt%, the failure style changed from interface failure to cohesion failure. The crosslinker CX-100 was helpful for the improvement of 180^o peel strength and holding force. When HR and CX-100 amount were 10 and 0.6 wt%, the ball tack, 180^o peel strength, and holding force were 9 #, 8.9 N/25 mm, and 178 h, respectively.     

可聚合阳离子含氟表面活性剂在含氟丙烯酸酯乳液聚合中的应用

以可聚合阳离子含氟表面活性剂N-(乙酸全氟辛基乙基酯)-N-(乙醇丙烯酸酯)二甲基溴化铵(PF8DM)为乳化剂,进行含氟丙烯酸酯的细乳液聚合研究,考察了PF8DM用量对单体转化率和凝胶率的影响,PF8DM用量对乳液的稳定性和表面性能的影响;分别采用PF8DM和十六烷基三甲基溴化铵作为乳化剂考察其对乳胶膜性能的影响。结果表明,当PF8DM含量为单体总质量的4%时,单体转化率达95%,凝胶率为0.6%;所得乳液具有优异的贮存、稀释、离心稳定性;当PF8DM用量为单体总质量的6%时得到的乳胶膜接触角达118.6°。在总含氟量相同的条件下,采用PF8DM为乳化剂制备的含氟丙烯酸酯乳液,其乳胶膜的吸水率大大降低,拒水性也明显增强。     

Preparation and properties of polydimethylsiloxane/polyacrylate composite latex initiated by 60Co γ‐ray irradiation

In this study, polydimethylsiloxane (PDMS)/polyacrylate composite polymer latex was synthesized via polymerization of the acrylate monomer in the presence of vinyl‐containing PDMS seeded latex. The polymerization was initiated by ⁶⁰Co γ‐ray irradiation. The morphology of the PDMS/polyacrylate composite polymer latex was a core–shell structure with PDMS as the core and polyacrylate as the shell. There was an interpenetration layer between the PDMS core and the polyacrylate shell. The composition of the vinyl‐containing PDMS and the PDMS/polyacrylate composite latex were investigated with NMR and Fourier transform infrared spectroscopy, respectively. The effect of irradiation dose on the seeded emulsion polymerization conversion is discussed. Finally, the mechanical properties of latex film, such as water‐absorption ratio, tensile strength, pendulum hardness, and heat‐decomposed temperature, were tested. The results showed that the mechanical properties of the PDMS/polyacrylate film were remarkably improved when compared to the polyacrylate film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2732–2736, 2003     

核壳型聚丙烯酸酯乳液的耐水性能研究

采用种子乳液二阶段聚合法,制备了经丙烯酸(AA)/丙烯酰胺(AM)交联、具有核壳结构的甲基丙烯酸甲酯(MMA)/丙烯酸丁酯(BA)/丙烯腈(AN)复合乳液,研究了核壳软硬单体比、AN及壳层中交联单体AM含量对乳胶膜吸水率的影响。结果表明:乳胶膜吸水率主要受壳层软硬单体比例的影响,软硬单体比值越小,乳胶膜的吸水率越低;丙烯酸/丙烯酰胺复合交联剂对乳胶膜吸水率的影响不明显;功能单体丙烯腈可明显降低乳胶膜的吸水率,乳胶膜吸水率随丙烯腈含量的增加而逐渐降低,最低达到9.40%。     

Preparation and properties of soapless poly(styrene–butyl acrylate–acrylic acid)/SiO2 composite emulsion

Soapless emulsion polymerization of styrene-butyl acrylate-acrylic acid was carried out using single or combined polymerizable emulsifiers, such as hydroxypropyl methacrylate sodium sulfate (HPMAS), sodium vinyl sulfate, and vinyl alkylphenol polyether sulfates (NRS-10), in the presence of colloidal nano-SiO₂ solution in order to obtain films with high degree of hardness and water-resistance. Monomer conversion, formation of coagulum, viscosity, particle size, size distribution, and surface tension of the emulsions, as well as the film properties, were determined and compared with those of an emulsion prepared with the conventional emulsifier sodium dodecyl sulfate and polyoxyethylene octylphenol ether. Emulsions prepared from a mixture of two polymerizable emulsifiers NRS-10 and HPMAS (1:1, weight ratio) have presented high monomer conversion, low coagulum, and small particle sizes. When the emulsifier level increased within a certain level, the monomer conversion increased but particles size decreased. Increased amounts of reactive emulsifiers led to low monomer conversion, large amount of coagulum and small particle sizes. With the increase of nano-SiO₂ the particle sizes and the viscosity of the emulsion also increased. The introduction of reactive emulsifiers improved the water-resistance of the resulting films, and the addition of nano-SiO₂ increased the hardness of the coatings. Under optimal conditions, the coatings made from emulsions produced from a combination of reactive emulsifiers such as NRS-10 and HPMAS (1:1, weight ratio) at 2?% level (based on monomer weight) exhibited remarkable hardness, adhesion force and water-resistance.     

Kinetics and effect of surfactant and cosurfactant on miniemulsion polymerization of acrylate monomers

The effects of the type and amount of the surfactant and cosurfactant on the miniemulsion polymerization of acrylate monomers were studied, and the comparison of the kinetics between miniemulsion polymerization and conventional emulsion polymerization was discussed in the presence of reactive surfactant allyloxy nonylphenol propyl polyoxyethylene (10), ether sulfate (DNS-86), and reactive cosurfactant stearyl methacrylate (SMA). The results showed that the obtained polyacrylate miniemulsion had a high monomer conversion rate and a low coagulum fraction, which were affected little by the surfactant and cosurfactant type. When the surfactant and cosurfactant amounts were all 2 wt%, the contact angle of the prepared polyacrylate miniemulsion with DNS-86/SMA and the water absorption fraction of the latex film were 39° and 8.3 wt%, respectively. FTIR results confirmed that DNS-86 and SMA took part in the polymerization of acrylate monomers. In the miniemulsion polymerization of acrylate monomers with DNS-86/SMA, monomer droplet nucleation was the main nucleation style.     

Role of acrylic acid in the synthesis of core‐shell fluorine‐containing polyacrylate latex with spherical and plum blossom‐like morphology

The core‐shell fluorine‐containing polyacrylate latex was successfully synthesized by two‐stage semicontinuous emulsion copolymerization of methyl methacrylate (MMA), butylacrylate (BA), acrylic acid (AA), and dodecafluoroheptyl methacrylate (DFMA). The fluorine‐containing polyacrylate latex was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC). The effects of AA content on monomer conversion, polymerization stability, particle size, corsslinking degree, carboxyl groups distributions (latex surface, aqueous phase or buried in latex), as well as mechanical properties and water absorption rate of latex film were investigated. The obtained fluorine‐containing polyacrylate latex exhibited core‐shell structure with a particle size of 120–150 nm. The introduction of AA was beneficial for the increase of monomer conversion and the polymerization stability, and had little effects on the mechanical property of latex film. However, the hydrophilicity of AA made the water resistance of latex film get bad. With the increase of AA content, the carboxyl groups preferred to distribute on aqueous phase, and the possibility of homogeneous nucleation increased and more oligomers particles were formed. Moreover, the oligomers would distribute to the latex and continued to grow up, making the latex morphology changed from spherical to plum blossom‐like. The core‐shell latex had two T_g corresponding to the rubber polyacrylate core and hard fluorine‐containing polyacrylate shell, and the latex film possessed excellent thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42527.     

N-羟甲基丙烯酰胺改性核壳型丙烯酸酯乳液的制备与表征

采用甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸为反应单体,以N-羟甲基丙烯酰胺(NMA)为功能单体,通过预乳化半连续种子乳液聚合工艺制备了NMA改性核壳型丙烯酸酯乳液,讨论了NMA用量对乳液的凝胶率及离心稳定性和贮存稳定性的影响,并对乳胶膜的吸水性、力学性能及耐热性进行了表征。结果表明:当NMA的用量为1.5%(wt)时,乳液的凝胶率仅为0.23%(wt),具有良好的离心稳定性和贮存稳定性,乳胶膜的吸水性由6.0%(wt)下降至4.5%(wt),铅笔硬度和冲击强度分别由1 H和52 cm提高至2 H和55 cm以上,弯曲强度、附着力及耐热性俱佳。     

细乳液聚合制备纳米SiO2／含氟丙烯酸酯复合乳液及其性能研究

采用溶胶-凝胶法,以正硅酸乙酯为前驱物,在丙烯酸酯单体为油相介质中原位生成纳米SiO2粒子,并通过细乳液聚合,制备出纳米Si02／含氟丙烯酸酯复合乳液。研究了含氟单体和SiO2的用量对复合乳胶膜性能的影响,并采用FT-IR,DSL等分析手段对产物进行了表征。结果表明：该乳液具有良好的稳定性,粒径分布较窄。当（甲基丙烯酸十二氟庚酯）FA与SiO2的用量分别为6％和5．5％时,乳胶膜表现出良好的疏水性能,对水的接触角达到了102．7°,吸水性降低到6．9％。     

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.     

含巯基有机硅改性水性苯丙乳液的制备及性能

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)和丙烯酸(AA)为反应单体,利用羟基硅油(SO)与3?巯丙基甲基二甲氧基硅烷(MPDMS)制备的含巯基有机硅(PMMS)为改性剂,通过种子乳液聚合的方法,制备了一系列有机硅改性水性苯丙复合乳液.通过红外光谱(FTIR)、核磁共振(NMR)和凝胶渗透色谱(GP...     

POSS/有机硅改性聚丙烯酸酯无氟防水剂的合成与应用研究

通过无皂乳液聚合技术合成了POSS/有机硅改性聚丙烯酸酯无氟防水剂,并将其应用于棉织物整理。考察了软硬单体配比对乳液、乳胶膜及其应用性能的影响。利用傅里叶红外光谱(FT-IR)和傅里叶红外光谱(DLS)对聚丙烯酸酯的结构及乳胶粒的粒径大小进行了表征,利用伺服材料多功能高低温控制试验机、柔软度仪、SEM对整理织物的应用性能及表面形貌进行了表征。结果表明：当m(BA):m(MMA)为6:4时,单体的转化率最大为96.97%,乳液的凝胶率为0.14%,乳胶粒的粒径最小为104.8 nm,乳胶膜对水的接触角最大可达114.3?,并具有优异的耐水性。整理棉织物表现出优异的力学性能和良好的柔软度,其对水的接触角可达161?。SEM结果表明棉织物纤维表面存在功能化POSS纳米颗粒。无氟防水剂赋予棉织物纤维表面低的的表面能和一定的粗糙结构,从而使整理棉织物表现出超疏水性能。     

反应型乳化剂在核壳丙烯酸酯乳液合成中的应用

本研究采用种子乳液聚合法,将反应型乳化剂、非离子型乳化剂和阴离子型乳化剂进行复配,以BA、St、MMA、AA为单体合成了具有核壳结构的聚丙烯酸酯类乳液。试验表明：乳化剂用量为2.5%,G-30∶NP40∶HAPS比例为1∶2∶1,乳化剂在核壳中的比例为2∶1,得到的乳液具有核壳结构,胶膜综合性能良好。     

有机硅烷偶联剂改性紫外光固化超支化聚醚基水性聚氨酯的性能

采用超支化聚酯Boltorn H 20与丁二酸酐反应,制备了亲水性超支化聚酯,然后与甲基丙烯酸酯基改性的聚醚基聚氨酯预聚体和3-异氰酸酯基丙基三乙氧基硅烷(IPTS)反应,合成了有机硅烷偶联剂改性紫外光固化聚醚基超支化水性聚氨酯(WHPU)。考察了有机硅烷偶联剂用量对WHPU的耐酸性、固化时间、凝胶质量分数、附着力、水接触角、水吸附率、乳液粒径分布及热稳定性的影响。结果表明,当IPTS与Boltorn H 20中羟基的摩尔比为6/16时,固化后的WHPU膜的凝胶质量分数为92%,在玻璃表面的附着力达到0级;与不含有机硅烷偶联剂的WHPU相比,该涂膜的水接触角和热稳定性分别提高了34°和22℃,其吸水率从13.8%降低到4.3%。     

用阴离子Gemini 9 B-6-9 B乳化剂合成苯乙烯-丙烯酸丁酯共聚物纳米乳液

以壬基酚、1,6-二溴己烷、氯磺酸为主要原料合成的阴离子Gemini磺酸盐表面活性剂9 B-6-9 B为乳化剂,苯乙烯(St)、丙烯酸丁酯(BA)为单体,合成了乳胶粒径小于100 nm且分布均匀的苯乙烯-丙烯酸丁酯共聚物纳米乳液,考察了聚合温度、乳化剂用量、引发剂用量、单体配比、单体含量对乳液的影响,探讨了乳胶粒子成核机理。结果表明,随着温度的升高,乳胶粒子的平均粒径减小,转化率与凝胶率增大;随着乳化剂或引发剂用量的增加,乳胶粒子的平均粒径和凝胶率减小,转化率增大;随着软单体比例的增加,乳胶粒子的平均粒径与转化率增大,粒径分布变宽,凝胶率减小;单体用量增大,乳胶粒子的平均粒径与凝胶率增大,转化率降低;乳胶粒子的粒径呈单峰分布,可能是按胶束成核机理形成的。     

不同粒径含氟丙烯酸酯共聚乳液的合成及膜表面疏水性能研究

采用半连续种子乳液聚合的方式,以丙烯酸丁酯、甲基丙烯酸甲酯和甲基丙烯酸六氟丁酯为原料制备了粒径分别为30nm、75nm、210nm左右的含氟丙烯酸酯共聚物乳液。通过乳胶粒核壳结构设计与大小粒径乳液机械共混改性2种方法研究了如何在较少含氟单体用量的情况下达到较好的表面疏水性能。利用X射线光电子能谱、动态光散射仪、接触角测定仪等分析手段,研究了共聚物膜的表面性能和共聚物乳液粒径的大小及分布,测试结果表明,核壳结构乳液成膜后壳层含氟量较高,膜表面接触角大于90,°疏水性能强;而大小粒径乳液共混物成膜后表面含氟量较低,却仍能得到90°以上的接触角,表明乳胶膜表面具有粗糙结构,具有一定的仿荷叶效应。     

Double in-situ synthesis of polyacrylate/nano-TiO2 composite latex

Polyacrylate/nano-TiO₂ composite latex was prepared via double in-situ polymerization using acrylamide (AM), vinyl acetate (VAc), butyl acrylate (BA) and methyl methacrylate (MMA) as monomers, tetrabutyl titanate (Ti(OBu)₄) as precursor of TiO₂. The morphology, structure and distribution of composite latex were characterized by Transmission Electron Microscope (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Light Scattering (DLS) and X-Ray Diffraction (XRD). The thermal stability, anti-yellowing and antibacterial properties of composite latex were also investigated. The results showed that nano-TiO₂ consisted in polyacrylate latex and it was located on the surface of latex particles. The average particle size of polyacrylate/nano-TiO₂ composite latex was 156.6 nm, which was bigger than that of pure polyacrylate (125.1 nm). The introduction of nano-TiO₂ improved the thermal stability, anti-yellowing and antibacterial properties of the latex film. At last, the polyacrylate/nano-TiO₂ composite latex was applied in leather finishing. Compared with polyacrylate latex, the properties of the leather finished by polyacrylate/nano-TiO₂ composite latex were enhanced: water vapor permeability increased by 58% and water uptake decreased by 3.52%.     

氢化丙烯酸松香/丙烯酸酯复合乳液的制备及其压敏胶的性能

以氢化丙烯酸松香为增黏树脂,将其溶解在丙烯酸酯单体中,预乳化后采用半连续乳液聚合工艺制备了氢化丙烯酸松香/丙烯酸酯复合乳液。研究了氢化丙烯酸松香的用量对单体转化率、凝胶率、溶胶相对分子质量及其分布、乳胶膜的玻璃化温度(Tg)和压敏胶粘接性能等的影响。结果表明,氢化丙烯酸松香对单体聚合具有一定的阻聚作用,随着氢化丙烯酸松香用量的增加,单体转化率、凝胶率及相对分子质量下降,相对分子质量分布变窄。氢化丙烯酸松香的合适用量为8.0%wt,此时压敏胶的初黏力为15#,180°剥离强度为10.6N.25mm-1,持黏力大于120h。     

Self-assembled nanostructure of polybenzoxazine resins from reaction-induced microphase separation with poly(styrene-b-4-vinylpyridine) copolymer

Self-crosslinkable aqueous polyurethane (PU)/polyacrylate (PA) composite emulsion was obtained by radical copolymerization. Fourier transform infrared spectroscopy (FT-IR) result shows that the cross-linking reaction between the carbonyl group and the hydrazine group has happened. The influence of the hydrazide-carbonyl molar ratio and the PA content on the properties of the composite emulsions and their films were investigated. The results show that, under the optimal hydrazide-carbonyl molar ratio (n (hydrazine group)/n (carbonyl group) =1:1), the water absorption is 10.56 %, and the mechanical properties and thermal stabilities are both improved. As the PA content increases from 0 wt% to 15 wt%, the tensile strength increases from 5.7 MPa to 7.3 MPa and the gel content increases from 70.3 % to 87 %.