超高相对分子质量聚乙烯纤维粘合涂层用水乳型聚丙烯酸酯微乳液的合成

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)及丙烯酸羟乙酯(HEA)为单体,以十二烷基硫酸钠(SLS)、OP-10和正辛醇的复合物为乳化剂,当m(BA)∶m(MMA)∶m(AA)∶m(HEA)=50∶50∶3∶10、w(乳化剂)=13%、反应温度为80℃及反应时间为3h时,合成了可用于超高相对分子质量聚乙烯纤维粘合涂层的水乳型聚丙烯酸酯微乳液,单体转化率为99 8%,乳胶粒径为30nm,乳液膜的玻璃化温度为-28℃,应用工艺简单,涂层粘附性好、柔软、耐磨。     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

丙烯酸酯乳液胶粘剂的合成及其性能研究

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯腈(AN)和丙烯酸(AA)为单体,十二烷基硫酸钠(SDS)为乳化剂,过硫酸钾(KPS)为引发剂,通过半连续乳液聚合方法合成了丙烯酸酯乳液胶粘剂。研究了软硬单体配比、不同硬单体以及功能单体AA对胶粘剂性能的影响。研究结果表明,当m(BA)∶m(MMA)∶m(AN+St)=75∶15∶10[其中m(AN)∶m(St)=1∶3]、w(AA)=2份时,制备的乳液胶粘剂具有较好的剪切强度、拉伸强度和耐水性。     

聚丙烯酸酯涂料印花黏合剂的合成与性能研究

以过硫酸铵(APS)为引发剂、甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)和丙烯酸异辛酯(EHA)为软单体、丙烯酸(AA)为功能单体和N-羟甲基丙烯酰胺(NMA)为交联单体,采用预乳化法合成出一种聚丙烯酸酯涂料印花黏合剂。讨论了单体滴加方式、预乳化液滴加时间、阴/非离子型乳化剂配比及用量、交联剂和各单体用量等对该黏合剂乳液性能的影响。结果表明:当w(BA)=15%、w(EHA)=8%、w(MMA)=20%、w(NMA)=3.0%、滴加时间为2.5 h、复合乳化剂中m(SDS):m(OP-10)=1:2且w(复合乳化剂)=6%时,该黏合剂乳液具有优良的综合性能,能够满足织物印花的使用要求。     

聚丙烯酸酯涂料的制备

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)为单体,以十二烷基苯磺酸钠为乳化剂,当m(BA)∶m(MMA)∶m(AA)=33∶17∶1,通过乳液聚合制得丙烯酸酯类乳液,再加入填料及各种助剂,经过高速搅拌、均质而出料。并且讨论了乳化剂及引发剂用量对乳液聚合、乳液及涂料性能的影响。     

Effect of the MMA content on the emulsion polymerization process and adhesive properties of poly(BA‐co‐MMA‐co‐AA) latexes

In the past work, the shear resistance of pure poly(n‐butyl acrylate) was low, even incorporation of inorganic filler, silica in the composition. It is well‐known that the copolymerization of n‐butyl acrylate (BA) with methyl methacrylate (MMA) will increase the glass transition temperature, and enhance the shear resistance of acrylic polymers. In the current work, the preparation of a series of acrylic water‐borne pressure‐sensitive adhesives (PSAs) with the controlled composition and structure for the copolymerization of BA and acrylic acid (AA) with different MMA contents, poly(BA‐co‐MMA‐co‐AA) was reported and its effects on adhesive properties of the latices were investigated. The latices of poly(BA‐co‐MMA‐co‐AA) were prepared at a solid content of 50% by two‐stage sequential emulsion polymerization, and this process consisted of a batch seed stage giving a particle diameter of 111 nm, which was then grown by the semicontinuous addition of monomers to final diameter of 303 nm. Dynamic light scattering (DLS) was used to monitor the particle diameters and proved that no new nucleation occurred during the growth stage. Copolymerization of BA with MMA raised the glass transition temperature (T_g) of the soft acrylic polymers, and had the effect of improving shear resistance, while the loop tack and peel adhesion kept relatively high. The relationship between pressure‐sensitive properties and molecular parameters, such as gel content and molecular weight, was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

苯乙烯改性丙烯酸酯乳液压敏胶的研制

以丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸-2-羟乙酯、丙烯酸为反应单体,十二烷基硫酸钠与聚乙二醇辛基苯基醚按质量比2：1组成复合乳化剂,过硫酸钾为引发剂,采用乳液聚合法,制备了苯乙烯改性丙烯酸酯乳液型压敏胶;对乳液型压敏胶进行了粒度分布、初粘性、180°剥离强度测试。研究结果表明,在反应温度为83±2℃、反应时间为6h、复合乳化剂用量为单体总质量的3～5％、引发剂用量为单体总质量的0．6～0．8％、单体质量比BA：MMA：St：HEA：AA为80：5：10：2：3的工艺条件下,可制得粒径分布窄、平均粒径小、初粘性好、剥离强度高的乳液型压敏胶。     

Kinetic investigations of acrylic–polyurethane composite latex

The effect of various reaction parameters on the rate of polymerization, R_p, and on the particle size and morphology of aqueous acrylic–polyurethane hybrid dispersions, prepared by semibatch emulsion polymerization, was investigated. The particles of polyurethane dispersion were used as seeds during the polymerization of acrylic component: methyl methacrylate (MMA), butyl acrylate (BA), and a mixture of MMA and BA with the ratio of 1:1. These emulsions were found to form structured polymer particles in aqueous media using scanning electron microscopy. The kinetics of the emulsion polymerization was studied on the basis of Wessling's model. The influence of emulsifier and initiator concentrations, including the monomer feed rates, R_m, on the rates of polymerization and on the properties of the resulting dispersions were studied. The number of particles and the particle size were also measured during the polymerization process. The final values were found to be independent of the concentration of the emulsifier, initiator and the monomer feed rate in monomer starved conditions. In the steady‐state conditions, during the seeded semibatch hybrid emulsion polymerization, the rate of polymerization and the monomer feed rate followed the Wessling relationship 1/R_p = 1/K + 1/R_m. The dispersions MMA/PU, BA/PU, and MMA/BA/PU have K values of 0.0441, 0.0419 and 0.0436 mol/min, respectively. The seeded BA/PU hybrid polymerization proceeded according to Smith‐Ewart Case I kinetics, while the MMA/PU hybrid emulsions demonstrate Case II of the Smith‐Ewart kinetic model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2639–2649, 2002     

氟碳铝型材保护膜用压敏胶的制备与性能

以丙烯酸丁酯(BA)和丙烯酸异辛酯(2-EHA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸(AA)和丙烯酸羟丙酯(HPA)为功能单体,采用降低PSA(压敏胶)的Tg(玻璃化转变温度)和预乳化半连续乳液聚合法合成了丙烯酸酯PSA乳液。研究结果表明:当m(软单体)∶m(硬单体)∶m(功能单体)=90∶5∶5、m(BA)∶m(2-EHA)=1∶2、w(AA)=1.0%、w(HPA)=5%、w(缓冲剂)=0.25%、w(引发剂)=w(复合乳化剂)=0.6%且m(阴离子型乳化剂)∶m(非离子型乳化剂)=1∶1时,PSA乳液的综合性能相对最好,用该PSA制成的保护膜对氟碳铝型材具有良好的附着力,并且其耐湿热老化性能和耐热老化性能俱佳。     

乳液型丙烯酸酯压敏胶的研究

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和丙烯酸(AA)为反应单体,过硫酸铵(APS)为引发剂,非离子型乳化剂(OP-10)/十二烷基硫酸钠(SDS)为复合乳化剂,硫酸铝为化学交联剂,采用乳液聚合法合成了丙烯酸酯PSA(压敏胶)。研究结果表明:当w(BA)=80%、w(MMA)=14%、w(AA)=6%、w(APS)=0.4%、w(硫酸铝)=2.0%、w(复合乳化剂)=6%且m(OP-10)∶m(SDS)=2∶1时,相应PSA的固含量(54.41%)较高、黏度(140 mPa.s)较低以及耐热性良好,并且其180°剥离强度(2.79 N/mm)、初粘力(16号钢球)和持粘力(>24.0 h)俱佳。     

中空聚合物乳液的制备及其性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸(AA)、丙烯酸丁酯(BA)、丙烯腈(AN)和苯乙烯(St)为共聚单体,过硫酸铵(APS)为引发剂,十二烷基硫酸钠(SDS)和非离子型乳化剂(OP-10)为阴/非离子型复合乳化剂,采用种子乳液聚合法和碱溶胀后处理法制备了P(MMA/AA/BA)为核、P(St/AA/AN)为壳的纸张施胶用中空聚合物乳液。研究结果表明:当w(引发剂)=0.80%、m(SDS)∶m(OP-10)=2∶1和w(乳化剂)=1.5%时,中空乳液的综合性能较好,其单体转化率较高、乳液黏度适中、粒径较小且分布较窄。     

丙烯酸酯系水溶性压敏胶的制备及性能研究

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和丙烯酸(AA)为共聚单体,采用半连续乳液聚合工艺,制取了性能优良的丙烯酸酯系水溶性压敏胶(PSA)。讨论了单体、乳化剂、引发剂、反应温度、反应时间和搅拌速率等对该PSA的固含量、黏度、初粘性、持粘性和水溶性等性能的影响。研究结果表明,丙烯酸酯系水溶性PSA的最佳合成工艺条件是:w(引发剂)=0.7%～0.8%、w(乳化剂)=3.0%,搅拌速率为200r/min,反应温度为85～92℃,反应时间为3.5～4h,保温时间为0.5～1h;在此条件下制取的丙烯酸酯系水溶性PSA具有较好的综合性能。     

自交联型涂料印花黏合剂的制备与性能研究

以甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)为软单体、丙烯酸(AA)为功能单体、N-羟甲基丙烯酰胺(NMA)为交联单体、过硫酸铵(APS)为引发剂、十二烷基硫酸钠(SDS)和壬基酚聚氧乙烯醚(NP-40)为复合乳化剂,采用预乳化半连续乳液聚合法合成了自交联型丙烯酸酯涂料印花黏合剂。研究结果表明:当m(MMA)∶m(BA)=0.38∶1、w(NMA)=3%、w(AA)=2.5%～3.0%、w(复合乳化剂)=3.0%且m(SDS)∶m(NP-40)=1∶(1.5~2.0)、w(APS)=0.8%、75~80℃聚合3 h和85℃保温1 h时,相应乳液的综合性能相对最好。     

Emulsifier‐minor emulsion copolymerization of BA‐MMA‐St‐MAA (or AA)‐N‐MA

A novel emulsion polymerization technique referred to as emulsifier‐minor emulsion polymerization was achieved by the copolymerization of methyl methacrylate, butyl acrylate, and styrene (MMA‐BA‐St) with a combination of water‐soluble ionic monomers [methacrylic acid (MAA) or acrylic acid (AA)] and nonionic monomers (N‐methylol acrylamide). In the technique, water‐soluble monomers play a crucial role in the stabilization of the latex particles as they can be bound to the particle surface and form a hydrate protective layer, which exhibits steric and/or electrostatic effects to prevent particle coagulation. The minor but over its critical micelle concentration emulsifier sodium alkylated diphenyl ether disulfonate (DSB) results in the nucleation of particles mainly by the micelle nucleation mechanism and thus determines the polymerization rate, the particle size, and the number. The film water resistance of the latices can be improved, and the foaming capacity of can be lowered by using technique instead of conventional emulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2923–2929, 2004     

食品包装材料用无毒干法覆膜胶乳液的研制

以醋酸乙烯酯(VAc)和甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)为软单体、交联单体(TM-200)/丙烯酸(AA)为复合交联剂、叔丁基过氧化氢(TBHP)/甲醛合次硫酸钠(吊白块)为氧化-还原型引发剂、可聚合型阴离子乳化剂(SVS-25)为环保型乳化剂和Gohsefimer Z-210为改性保护胶体,采用乳液聚合法制备出食品包装材料用无毒干法覆膜胶。研究结果表明:采用减压脱除及后添加氧化-还原型引发剂,可使覆膜胶中残余单体含量降至0.01%以下;当m(VAc)∶m(MMA)∶m(BA)=30∶10∶60、乳化剂中m(SVS-25)∶m(Gohsefimer Z-210)=1∶1、w(乳化剂)=2.0%和w(氧化-还原型引发剂)=0.20%时,覆膜胶的综合性能相对最好。     

核壳型丙烯酸酯乳液的制备与性能研究

采用甲基丙烯酸甲酯／丙烯酸丁酯作复合单体,丙烯酸为功能单体,通过预乳化半连续种子乳液聚合工艺合成了核壳型丙烯酸酯乳液,讨论了反应温度、乳化剂用量、核壳单体质量比以及丙烯酸加入量对乳液性能以及漆膜力学性能的影响,并用TEM对乳胶粒子进行了表征。结果表明：采用预乳化半连续滴加法,当复合乳化剂SDS与OP-10质量比为2：1且总用量为4％,核、壳层中甲基丙烯酸甲酯与丙烯酸丁酯的质量比分别为3：7和4：1,核壳总单体质量比为1：1,丙烯酸质量分数为4％,核层和壳层反应温度分别为70℃和80％时,可以合成黏度适中、乳胶粒粒径分布均匀、稳定性好和漆膜力学性能优良的核壳型丙烯酸酯乳液。     

新型丙烯酸酯乳液胶粘剂的应用研究

以丙烯酸乙酯(EA)和丙烯酸丁酯(BA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、甲基丙烯酸(MAA)和丙烯酸(AA)为功能单体,采用种子乳液聚合法制备出一种新型丙烯酸酯乳液胶粘剂。结果表明:当m(EA)∶m(BA)∶m(MMA)=19.2∶6.4∶6.4、m(MAA)∶m(AA)=2.00∶1、w(MAA+AA)=w(BA)=6%～8%以及经氨水中和后胶液的pH为7~8时,该胶粘剂具有良好的综合性能,其初粘强度大、干燥速率快、耐冷藏性能好、不起皱、不掉标且易清洗,完全满足啤酒瓶贴标用胶粘剂的使用要求。     

叔碳酸乙烯酯改性醋丙乳液的制备与性能研究

采用半连续种子乳液聚合,以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、乙酸乙烯酯(VAc)为主单体,丙烯酸(AA)为功能单体,叔碳酸乙烯酯(VeoVa10)为改性单体,合成了核壳型丙烯酸酯乳液。探讨了聚合温度、乳化剂、引发剂及功能单体与乳液性能的关系。通过单因素实验探讨了乳化剂用量、配比,改性单体用量等与乳液性能的关系。FT-IR和DSC测试结果表明,各单体之间发生了自由基共聚反应,乳液粒子为核壳结构。     

结合磷阻燃型苯丙共聚乳液胶粘剂的合成及性能研究

以苯乙烯(St)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)和含磷单体为共聚单体,采用预乳化种子乳液聚合法制备PSA(结合磷型苯丙共聚乳液胶粘剂),并在PSA中添加少量无机阻燃剂APP(聚磷酸铵)制备CPSA(复合型阻燃胶粘剂)。系统研究了含磷单体和APP含量对乳液稳定性、胶膜剥离强度、涂层阻燃性和热性能等影响。结果表明:当m(St+BA+EA+MMA+AA)=40 g、m(St)∶m(BA)∶m(EA)∶m(MMA)∶m(AA)=16∶90∶60∶24∶5、w(含磷单体)=4%和w(APP)=12%(相对于单体总质量而言)时,可制成稳定性、剥离强度和阻燃性能俱佳的CPSA。     

乳液型CPP-g-MAH复膜胶的研制

以酯溶性CPP-g-MAH(马来酸酐接枝改性氯化聚丙烯)、BA(丙烯酸丁酯)、HEA(丙烯酸羟乙酯)和β-CEA(β-羧乙基丙烯酸酯)为共聚单体,DNS-86[烯丙氧基壬基酚丙醇聚氧乙烯(10)醚硫酸铵]为反应型乳化剂,采用半连续预乳化乳液聚合法制备乳液型CPP-g-MAH复膜胶。研究结果表明:当m(BA)∶m(CPP-g-MAH)=9∶4、聚合温度为82⁸5℃、聚合时间为4 h、w(DNS-86)=3.0%(相对于配方中各物料总质量而言)和w(引发剂)=0.5%(相对于聚合单体总质量而言)时,制得的乳液型复膜胶具有环保、成本低等优势,并且其黏度、初粘力(2.5 cm)和180°剥离强度(5.1 N/cm)俱佳。