Application of Macromonomers for Pressure Sensitive Adhesives II. Phase Separation and Adhesive Properties

Pressure sensitive adhesives (PSA) were prepared by copolymerization of butyl acrylate, methyl methacrylate and styrene macromer and the effects of macromer on the adhesive properties and phase separated structures were investigated. The results are as follows:

(1) The cohesion of the PSA increased as the quantity of the styrene macromer increased.

(2) The reason why the cohesion of the PSA increased seemed to be that the polystyrene phase, as the graft chain, was separated from the polybutyl acrylate phase as matrix.

(3) When styrene was used instead of styrene macromer, there were not these effects on the adhesive properties.     

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。     

丙烯酸酯类水基压敏胶研究进展

对近年来用接枝、核／壳、有机硅、交联、共混、反应性或高分子乳化剂改性丙烯酸酯类水基压敏胶的研究进展和发展趋势进行了综述。     

A Study on the Properties and Structure of polyether-Sulfone-Modified Epoxy Adhesives

Properties and morphology of PES-modified epoxy adhesives were studied in this paper. These systems have excellent mechanical properties and can be used as heat-resistant adhesives. SEM and EDX observations showed that the system has a two-phase structure. At lower PES content, there is a PES dispersed phase and a epoxy continuous phase. At higher PES content, there are two continuous phases. From these results, the relationship between structure and properties of this system were discussed.     

外交联型丙烯酸酯乳液压敏胶的制备与性能研究

以丙烯酸丁酯(BA)、醋酸乙烯酯(VAc)、丙烯酸(AA)单体为基础,采用双丙酮丙烯酰胺(DAAM)/己二酸二酰肼(ADH)外交联体系,通过预乳化和半连续加料工艺制备了外交联型丙烯酸酯乳液压敏胶.采用红外光谱(FTIR)、透射电镜(TEM)、热重分析(TGA)等手段对其进行了表征和分析.并研究了软硬单体配比[m(BA)∶m(VAc)]、官能单体(AA)用量及外交联体系(DAAM/ADH)用量对压敏胶性能的影响.结果表明,通过调节软硬单体配比和官能单体用量可以使压敏胶性能达到一个较优的水平.当m(BA)∶m(VAc)=85∶15,w(AA)=3％时,压敏胶初粘力为17号球,180°剥离强度为504 N/m,室温持粘力＞30 d,高温(100℃)持粘力为140 min.外交联体系DAAM/ADH的引入可以在对初粘力和180°剥离强度影响较小的情况下显著提高压敏胶的高温持粘力到540 min,从而得到高温持粘力优异的外交联型丙烯酸酯乳液压敏胶.     

玻璃珠抛光新型热熔胶的制备

利用丙烯酸丁酯与苯乙烯共聚物为主要原料制得玻璃珠抛光用的新型热熔胶,同时研究了部分助剂、填充剂、溶剂等对热熔胶性能的影响,从而优化得到了一种新型热熔胶的生产工艺过程。通过实验研究表明,该热熔胶克服了聚丙烯酸树脂热熔胶在应用过程中存在的诸多问题,而且易于清洗,可在较高温度下以粉末状态存放,不结块、不易碳化,完全适用于玻璃珠抛光热熔胶所需的高温操作工艺。     

皮肤用亲水性聚氨酯压敏胶的制备及性能研究

针对目前我国透皮制剂所用橡胶类压敏胶的缺点,制备了一种亲水性聚氨酯压敏胶,并对其性能进行了研究。该压敏胶是由二异氰酸酯与多元醇的混合物进行反应生成预聚体,再经扩链制得的。通过在聚氨酯主链上引入亲水的聚乙二醇嵌段来赋予压敏胶亲水性。研究结果表明该聚氨酯压敏胶具有优良的粘结性能及反复揭帖性,具有良好的药物、皮肤相容性及良好的药物控释性能。     

Pressure Sensitive Adhesives Based on VectorR SIS Polymers I. Rheological Model and Adhesive Design Pathways

Dexco Polymers (a Dow/Exxon partnership) has been manufacturing Vector^R SIS polymers since 1990.¹ This paper describes experiments carried out to study Vector SIS polymers and model pressure sensitive adhesive (PSA) formulations based on Exxon Chemical's Escorez^R 1310LC tackifier. The adhesive behavior of tackified polymers was quantitatively analyzed by applying the rheological principle of time-temperature superposition² and the mapping approach,^3,4 and the pressure sensitive rheological model⁵ developed earlier. This model⁵ was developed by expanding and modifying an equation [adhesive fracture strength = (intrinsic adhesion) × (bulk energy dissipation)] proposed by Gent et al.^6,7 and Andrews et al.^8,9 This study delivers two key results. The first is that the fracture strength of the PSA/steel bond is the multiplication of three terms: the intrinsic (or interfacial) adhesion, the bonding and the debonding terms (Fig. 1). The debonding term is correlated with the logarithm of the loss modulus at the PSA debonding frequency or with the logarithm of the monomeric friction coefficient of the block copolymer/tackifier system. Both the loss modulus and the monomeric friction coefficient measure the energy dissipation in the bulk adhesive. The second is that PSA design pathways can be established by a mapping approach in the rheological space of the plateau modulus versus the loss modulus peak position in the frequency scale (Fig. 2). Plateau modulus is the bonding parameter because it measures the wetting capability of the adhesive with the substrate surface. The loss modulus peak position is the debonding parameter because it corresponds approximately to the time scale (or the frequency scale) in which one deforms the adhesive to maximize energy dissipation. Therefore, the tackifier and oil combination lowers the plateau modulus, but increases the T_g of the polyisoprene phase of the SIS polymer. This increase in T_g is equivalent to the lowering of the rate of local rearrangement (frequency of segment jumps) of the polyisoprene chains of the block copolymer. An optimal “tackification pathway” in this rheological space is achieved by tailoring the tackifier type and T_g, and the amount of oil used in the PSA.

In brief, the PSA rheological model and mapping approach described in this work for Vector SIS polymers give a comprehensive understanding and adhesive design pathways. This concept and approach not only allow raw material suppliers to improve and design better tackifier and polymer products, but also provide PSA formulators a quantitative tool to achieve PSA end property results.     

溶剂型丙烯酸酯压敏胶的制备与性能研究

以丙烯酸丁酯(BA),丙烯酸异辛酯(2-EHA),丙烯酸羟丙酯(HPA)以及甲基丙烯酸甲酯(MMA)为聚合单体,采用普通自由基聚合合成了一系列溶剂型丙烯酸酯共聚物压敏胶.讨论了交联剂MDI用量不同对压敏胶热性能与使用性能的影响,并研究了加入氢化松香树脂对压敏胶性能的影响.用TGA以及DSC对其热性能进行了表征,并测试了...     

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。     

反应性乳化剂对丙烯酸酯乳液压敏胶性能影响的研究

选择了几种不同的乳化剂体系,采用预乳化种子聚合工艺,制备了丙烯酸酯乳液压敏胶.比较了常规乳化剂和反应性乳化剂对乳液的各项物理性能,胶膜的耐水性、力学性能以及压敏胶的初黏力、持黏力、180°剥离强度等的影响,并进行了分析.研究结果表明:与常规乳化剂相比,使用反应性乳化剂(Er-30、Se-10N复配体系)能显著提高胶膜的耐水性,并对单体转化率、持黏力、180°剥离强度等性能有所改善,获得综合性能较好的乳液压敏胶.     

汽车膜用单组份丙烯酸酯压敏胶的合成研究

以丙烯酸酯类单体为原料,通过溶液聚合,合成了一种溶剂型汽车膜用单组份丙烯酸酯压敏胶。并对影响压敏胶性能的诸多因素,如单体浓度、溶剂、聚合反应温度、反应时间等进行了研究,结果表明:甲苯、乙酸乙酯、甲醇比例为6∶2∶2,单体含量40%,反应温度80℃,反应时间6~7 h,合成的丙烯酸酯压敏胶粘剂综合性能较好,DSC测试玻璃化温度Tg:-32.48℃,数均分子量Mn:122 189,重均分子量Mw:556 863。     

乳液压敏胶的耐热耐水性研究

采用预乳化种子聚合工艺,在多元丙烯酸酯中添加自交联功能单体N-羟甲基丙烯酰胺和反应型乳化剂2-丙烯酰胺基-2-甲基-丙基磺酸铵盐,研制出性能优异的耐热耐水型乳液压敏胶。同时讨论了自交联功能单体、反应型乳化剂、种子乳液的用量对压敏性能的影响。     

溶剂型有机硅压敏胶的制备及性能研究

以正硅酸乙酯和六甲基二硅氧烷为原料制得MQ硅树脂,MQ硅树脂再与107硅橡胶进行缩合反应,制备了107-MQ;再加入过氧化苯甲酰（BPO）及辅料配成有机硅压敏胶。考察了MQ硅树脂与107硅橡胶的质量比、BPO用量、外加辅料对压敏胶性能的影响。较佳工艺为：MQ与107硅橡胶的质量比为0．75：1．1．75：1、BPO用量2份、丙烯酸羟乙酯用量0．5份（MQ与107硅橡胶总用量100份）,此时有机硅压敏胶液稳定,可长时间放置,初粘32#钢球,剥离强度12N／25mm。     

偏光片用压敏胶粘剂的合成及性能研究

采用聚合物共混改性的方法,以高、低分子量共聚物共混,使其分子量分布变宽,在保持较好的持粘力的情况下,改善初粘力和剥离强度。实验以丙烯酸丁酯、丙烯酸乙酯为软单体,甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯等为硬单体,以过氧化苯甲酰BPO为引发剂,甲苯和乙酸乙酯为溶剂,合成了一系列高、低分子量丙烯酸酯共聚物,再通过调节功能性单体丙烯酸AA的含量以及高、低分子量共聚物的共混配比,使压敏胶粘剂的性能得到了很好的改善。     

可移性压敏标签的制备及性能研究

在相同的原料配比下,通过三种不同溶液聚合工艺制得丙烯酸酯高聚物A01,A02和A03.它们的初黏性,180°剥离强度和固含量相差不大,然而A01和A02的黏度太大,导致涂布困难,而A03的持黏性较低.通过引入交联剂Al-acac和GA-240进行改性,大大提高了A03的持黏性.交联改性后的A03涂布于PET膜和铜版纸上制得压敏胶签,其中PET膜类标签可剥离性能良好,在不锈钢板,有机玻璃板、环氧板等材料上均可无损剥离.而制得铜版纸标签进行实物黏贴表明,在部分常见日用品(如水杯、手机壳,苹果等)均可无损剥离,但在鸡蛋揭离标签时会发生纸张撕裂现象.     

可移性压敏标签的制备及性能研究

在相同的原料配比下,通过三种不同溶液聚合工艺制得丙烯酸酯高聚物A01,A02和A03.它们的初黏性,180°剥离强度和固含量相差不大,然而A01和A02的黏度太大,导致涂布困难,而A03的持黏性较低.通过引入交联剂Al-acac和GA-240进行改性,大大提高了A03的持黏性.交联改性后的A03涂布于PET膜和铜版纸上制得压敏胶签,其中PET膜类标签可剥离性能良好,在不锈钢板,有机玻璃板、环氧板等材料上均可无损剥离.而制得铜版纸标签进行实物黏贴表明,在部分常见日用品(如水杯、手机壳,苹果等)均可无损剥离,但在鸡蛋揭离标签时会发生纸张撕裂现象.     

Relaxation Properties of Pressure-sensitive Adhesives upon Withdrawal of Bonding Pressure

Relaxation properties of pressure-sensitive adhesives (PSA) have been studied with the squeeze-recoil tester used in the regime of parallel-plate dilatometer under conditions imitating the removal of compressive force in the course of adhesive bond formation. The relaxation properties of PSAs are compared with their adhesive behavior measured using the 180-Deg Peel Test. Two classes of PSAs are considered: 1) conventional rubbery adhesives based on the mixtures of styrene-isoprene-styrene (SIS) block copolymer with a tackifier resin and a plasticizer, and butyl rubber plasticized with low-molecular-weight polyisobutylene, and 2) hydrophilic PSAs composed of the blends of high-molecular-weight poly(N-vinyl pyrrolidone) (PVP) with oligomeric polyethylene glycol (PEG). By comparing the adhesive and relaxation behaviors of different PSAs, the relaxation criteria for pressure-sensitive adhesion have been stated. Relaxation behavior of the examined PSAs demonstrates two values of retardation time: the shorter retardation time of 10–70?sec and the longer time of 300–660?sec. These times can be associated, respectively, with small- and large-scale mechanisms of strain recovery. By comparing the relaxation and adhesive properties of PVP-PEG blend (which involves the formation of a hydrogen-bonded network through both terminal hydroxyl groups in PEG short chains) with the properties of covalently crosslinked copolymers of vinyl pyrrolidone (VP) with PEG-diacrylate and comb-like VP copolymers with PEG-monomethacrylate, the contributions of covalent crosslinking and H-bonding network have been characterized.     

有机硅压敏胶的性能及影响因素

对有机硅压敏胶的几个影响因素进行了考察,在此基础上研制出一种有机硅压敏胶。乙烯基含量为0.3%的MQ硅树脂和相对分子质量为4.0×105的硅橡胶等比例配合,经1.0%的二丁基二月桂酸锡催化缩合,再以1.5%的BPO交联剂200℃下交联10min制得的有机硅压敏胶性能优异,初黏力25#,室温持黏力960min,剥离强度13.45N/25mm。     

反应型乳化剂对保护膜用丙烯酸酯乳液型压敏胶性能的影响

采用预乳化法制备了丙烯酸酯压敏胶乳液,探讨了不同乳化剂体系对压敏胶物理性能的影响。FTIR测试表明,反应型乳化剂参与了反应;TEM测试显示,反应型乳化剂体系所得乳液粒径小,分布均匀。实验结果表明:当w(复合乳化剂)=3%,m(ANPEO10)∶m(DNS-458)∶m(DNS-501)=1.5∶1.1∶0.4时,所得乳液的固体分质量分数为48.03%,单体转化率达到97.66%,乳液黏度为38.8 s,平均粒径为238 nm,压敏胶的初粘力能吸住8号钢球,持黏性大于24 h,180°剥离强度达到0.304 N/mm。贴在不锈钢表面的保护膜经80℃烘烤24 h后,不锈钢表面无残胶和雾影。