有机类PVC热稳定剂的研究现状 翻译

有机类PVC热稳定剂的研究现状 Reserch Progress of Organic PVC Thermal Stabilizer 摘 要:热稳定剂是一类能防止或减少聚合物在加工使用过程中受热而发生降解或交联，延长复合材料 使用寿命的添加剂。常用的PVC稳定剂按照主要成分分类可分为盐基类、脂肪酸皂类、有机锡化合物、 复合型热稳定剂及纯有机化合物类。本文着重对有机化合物类的PVC稳定剂做了总结，得到了PVC在 各种热稳定剂改性后的性能。并对其发展趋势做了客观的预测。 关键词:P VC 热稳定剂 有机化合物 现状 Abstract: Thermal stabilizers is a class of additives to prevent or reduce polymers heat in the processing then to be degradation or cross-linking, to extend the life cycle of composite materials. Commonly, PVC stabilizers can be divided into categories according to the main component of base classes, fatty acid soaps, organic tin compounds, complex organic compounds in heat-stable agents and pure class. This article focuses on the class of pure organic compounds of PVC stabilizer, summarized the obtained PVC heat stabilizer in a variety of modified performance. And on objective forecasts to its development trend. Key words: PVC Thermal, stabilizer Organic compound, Status 前言 聚氯乙烯(PVC)是世界通用的五大合成树脂之一，其制品也是产量较大的一种通用塑料产品，因其 具有自熄、阻燃、耐磨、强度较高、电绝缘性和化学稳定性较好等优点，且价格低廉，广泛用于工、农 业生产的各个领域，目前产量仅次于聚乙烯，居世界第2位。PVC结构中存在缺陷，而PVC是在高温 和高剪切条件下进行加工的，容易脱去分子上的HCI而导致聚合物降解，因其产品变色和制品机械性能 [1]等下降，影响其使用寿命。因此，在PVC的加工过程中必须加入一定量的热稳定剂，与树脂组成有协 同作用的热稳定体系，将分解温度提高到加工温 度以上(一般为180?,200?)。稳定剂能在PVC加工 及使用过程中抑制制品变色、性能变坏。稳定剂可以通过取代不稳定的氯原子，中和氯化氢，与不饱和 部位发生反应等方式抑制PVC的降解。热稳定剂的需求和产量随PVC的需求和产量的增长而增长。由 [1]此可见，对热稳定剂的研究和生产将是一个热门的方向。 preface Polyvinyl chloride (PVC) is the general five synthetic resin, one of its products are also yield a generic large plastic products, because of its from extinguish, flame retardant, wear-resisting, high strength, electrical insulation and chemical stability were as well as good, and the price cheap, widely used in industry, agriculture production each domain, the current production after polyethylene, the highest in the world second. PVC structure defects, and PVC is in high temperature and high shear conditions of processing, easy to take off the HCI and molecular, because of its degradation in polymer product change color and products such as mechanical properties fall, affecting the working life. Therefore, in the process of PVC must be in a certain amount of heat stabilizers, and resin composition have synergy thermal stability of the system, will break temperature increase to processing temperature above 180 ? ~ (usually 200 ?). Stability in PVC agent can use process and processing, and inhibit products discoloration, performance deteriorated. Stabilizers can be replaced by unstable chlorine atom, and hydrogen, and unsaturated parts such as reaction way the degradation of PVC inhibition. Heat stabilizers demand and output of demand and production with PVC increases. This shows, on the heat stabilizers research and production will be a popular direction. PVC热稳定机理 热稳定剂可以通过取代不稳定的氯原子、中和氯化氢、与不饱和部位发生反应等方式抑制PVC分 子的降解。热稳定剂能帮助减少加工条件下的反作用，降解早期阶段释放出HCI被吸收掉，以防止内在 自动催化反应的发生，与HCI的中和反应是大多数金属有机络合物的普遍特征，氯原子则取代金属配位 体而产生一种不易接触反应的物质。理想的PVC热稳定剂应是一种多功能物质，或者是一些材料的混 合物，它们能够实现以下功能: PVC thermal stability mechanism Heat stabilizers can be replaced by unstable chlorine atom, and hydrogen, and unsaturated parts such as reaction way the degradation of PVC molecules inhibition. Heat stabilizers can help reduce processing conditions backlash, degradation early stage release HCI be absorbed, in order to prevent the occurrence of inner automatic catalytic reaction, and the neutralization reaction HCI is most common characteristic of the metal organic complex, chlorine atom is replace metal ligand and create a not easy contact reaction of the material. The ideal PVC thermal stabilizer should is a multi-function material, or of some of the material is a mixture, they can achieve the following functions ( 1 )置换活泼、不稳定的取代基，如连接在叔碳原子上的氯原子或烯丙基氯 ，生成稳定的结构; ( 2 )吸收并中和PVC 加工过程中放出的HCI，消除HCI的自动催化降解作用; ( 3 )中和或钝化对降解起催化作用的金属离子及其它有害杂质; ( 4 )通过多种形式的化学反应可阻断不饱和键的继续增长，抑制降解着色; [2]( 5 )对紫外光有防护屏蔽作用。 (1) replacement lively, unstable replace base, such as connection on the carbon atoms in uncle chlorine atom or allyl chloride, generate stable base structure; (2) absorption and PVC processing process and emit HCI, eliminate HCI automatic catalytic degradation function; (3) and passivation degradation or the catalysis of metal ions, and other harmful impurities, (4) through the DuoZhong form of chemical reaction that can block unsaturated double bond continue to grow, restrain degradation coloring; (5) to uv light a protective shield effect. 有机类PVC热稳定剂 有机类热稳定剂由于不含有重金 属，是目前很有发展前景的一类热稳定剂。它包括可以单独使用 [3-5]的主热稳定剂(主要是含N的化合物) 和辅助稳定剂。辅助稳定剂本身稳定化作用很小或不具稳定作 用，但一经与其它热稳定剂共用时，可以发挥良好的协同作用，它们对无镉、铅稳定剂技术进步具有积 [6]极意义。 Organic kind of PVC thermal stabilizer Organic kind of heat stabilizers because do not contain of, is the tone very promising kind of heat stabilizers. It includes can be used alone Lord heat stabilizers (mainly including N compounds) and auxiliary stabilizer. Auxiliary stabilizers itself or do not have a small role of stabilization stable effect, but once and other heat stabilizers share, can play good synergy, they to the no cadmium, lead stabilizers technology progress has the positive significance. 有机热稳定剂分类 环氧化合物类 主要有:环氧大豆油、环氧亚麻子油、环氧妥尔油脂、环氧硬脂酸丁酯、辛酯等，其中环氧大豆油[7]是最常用的PVC辅助稳定剂，对Ba,Zn 、Ca,Zn稳定剂有显著的增效作用。 [8]Egbuchunam T.0.等采用橡胶树子油(RS0) 、环氧橡胶树子油(ERSO)和Zn皂进行复配，并研究 了复配体系对PVC热稳定性的影响。同时利用红外(IR )、X射线衍射(XRD)和差热扫描式量热法(DSC) 等研究了体系的晶体结构、形态和热稳定性等。研究结果明，含ESO的Zn皂很好阻止了PVC凝胶 的初期脱HCI。ERSO单独使用降低了PVC的脱HCI，同时和含有ESO的Zn皂具有较好的协同作用。 亚磷酸酯类 包括亚磷酸三苯酯、亚磷酸三异辛酯、三壬基苯基亚磷酸酯等，亚磷酸(壬基、苯基) 酯通常用于美 国食品和药物管理局所批准的那些非毒性应用中，亚磷酸脂与金属皂有协同作用，可以提高耐热性、透 [7]明性、耐候性、抑制着色性、抑制压折结垢性。缺点是有水解性，不能用于与水接触的PVC制品。 多元醇类 主要有:季戊四醇、甘露醇、山梨醇等，多元醇的作用是通过螯合金属氯化物来抑制劣化，此外多 [7]元醇还可在金属盐的催化作用下置换烯丙基氯。 Organic heat stabilizers classification Epoxy compound class Mainly has: epoxy soybean oil, epoxy flaxseed oil, grease, epoxy, completed epoxy stearic acid, butyl acetate, essien ester etc, with epoxy soybean oil is the most commonly used PVC auxiliary stabilizer for Ba, Zn, Ca / / Zn stabilizer has significant synergistic effect. Egbuchunam t. 0. The son (such as rubber oil RS0), epoxy rubber oil (ERSO) and son Zn soap to get with it, and the complex systems with the influence of thermal stability of PVC. At the same time, infrared (IR) and X-ray diffraction (XRD) and differential thermal scanning calorimetry (DSC) of the system of the crystal structure, shape and thermal stability, etc. The results of the study show that, including the soap is very good ESO Zn to stop the PVC gel in the early stages of the take off HCI. ERSO used alone reduce the PVC, at the same time and the take off HCI containing the ESO Zn soap has good synergy. The phosphate ester Including benzene ester, phosphite three phosphite three different essien ester, three I base benzene, phosphite had phosphate ester (I base, phenyl) ester normally used for the U.S. food and drug administration approved the application of the toxicity, phosphite with metal soap fat have synergy, can improve the heat resistance, transparency, and weather resistance, inhibit shading sex, inhibit crushing knot dirty sex. Defect is to have sex, hydrolysis cannot be used in contact with water PVC products. DuoYuan alcohol Mainly has: pentaerythritol, mannitol, sorbitol, DuoYuan alcohol's role is through the chelating metal chloride to curb degradation, in addition DuoYuan alcohol still can be in metal salt under the catalysis of displacement allyl chloride base. [9]Hiro his O Iked等研究了季戊四醇二磷酸酯与Ca,Zn皂作为PVC稳定 剂时的协同效应。研究表明，季戊四醇二聚酯在PVC中显示良好的分散性，稳定效果比使用小分子的 [10]多元醇好。他们还研究了以大分子的多羟基化合物聚乙烯醇( PVA )作为第二稳定剂与Ca,Zn皂的协 同作用，发现PVA在PVC中的分散程度与其稳定效果密切相关。 Hiro his O the Iked the pentaerythritol two phosphate and Ca/Zn soap as PVC stabilizer of synergy effect. Research shows that, pentaerythritol two polyester in PVC shows good dispersion, stable effect than using small molecules DuoYuan alcohol. They also studied with macromolecules polyol polyvinyl alcohol (PVA) as a second stabilizer and Ca/Zn soap as the coordination with PVA, found in the dispersion degree of PVC is closely related with its stable effect. [11]许家友等通过荧光发射光谱、红外光谱和光电子能谱研究了季戊四醇与ZnSt和ZnCI的络合作22 用，以及PVC,ZnSt,季戊四醇体系在170?共混过程中的结构变化。结果表明，季戊四醇与ZnSt和22 ZnCI， 形成络合物，在加工过程中无游离的ZnCI生成，季戊四醇与ZnCI;形成的络合物抑制了ZnCI2222 对PVC 的催化降解，从而抑制了“锌烧”。 [12]蒋金博等采用环己二醇二缩水甘油醚作为辅助热稳定剂，与Ca,Zn稳定剂复配，通过刚果红热 稳定测试，研究了它们相互间协同作用及机理。结果表明，环己二醇二缩水甘油醚与Ca,Zn复合稳定 剂有很好的协同作用 ，能有效地抑制Ca,Zn复合稳定剂在使用中的“锌烧”现象;其中Ca:Zn为3: 1 时热稳定性最好，热稳定时间为38 min。 [13]2008年l2月，郭爱花等人首先通过刚果红实验筛选本身具有较好热稳定性或具有协同热稳定作 用的多元醇类化合物为先导物，再采用结构修饰的，对选取的多元醇进行酯化和醚化修饰，引入具 有稳定活性的环氧基团和增加与PVC相溶性和分散性的酯基或醚键基团，并且对这些结构修饰物进行 稳定性能的考察，得到了稳定性和应用性能更优的三甘醇二缩水甘油醚(2,2-( 2,5,8,11-四氧杂-l,1 2-十二 烷二基) 双环氧乙烷)、甘油三缩水甘油醚(1,2,3-TriS(2,3-epoxypropoxy) propane)，其结构式为 和双酚A二缩水甘油醚等多元醇衍生物，为有机热稳定剂的深入研究提供了参考。 通过实验筛选本身具有一定稳定性或具有协同稳定作用的多元醇类化合物为先导物，采用结构修饰 的方法，对选取的多元醇化合物中的羟基进行酯化和醚化反应，引入具有稳定活性或增加与PVC相溶 性和分散性的基团，并通过刚果红试纸法，对这些结构修饰物进行稳定性能的考察，得到了稳定性和应 用性能更优的多元醇衍生物。二甘醇二缩水甘油醚、三甘醇二缩水甘油醚、甘油三缩水甘油醚和双酚A 二缩水甘油醚等与季戊四醇热稳定性相当或优于季戊四醇的有机稳定物。 XuGuYou etc through the fluorescence emission spectrum, infrared spectrum and light electronic energy spectrum research the pentaerythritol with ZnSt2 and ZnCI2 complex function, as well as PVC/ZnSt2 / pentaerythritol system in 170 ? blending process of structural change. The results show that pentaerythritol with ZnSt2 and ZnCI2, form complex, in the machining process of the formation, ZnCI2 without free pentaerythritol with ZnCI2; The complex ZnCI2 inhibit the formation of catalytic degradation of PVC, thus inhibiting the "burn" zinc. The ring has JiangJinBo, glycol two glycidyl ether as the auxiliary heat stabilizers, and Ca/Zn stabilizers blends with red-hot stability test, through the Congo, the synergy between them and the mechanism. The results show that, the ring has glycol two glycidyl ether and Ca/Zn composite stabilizer has very good synergy, can effectively restrain Ca/Zn composite stabilizer in use of the "zinc burning," phenomenon; One Ca: Zn 3:1 in thermal stability, best when the thermal stability of time for 38 min. 2008 years on l2, guo love flowers such as first people through the Congo red experiment selection itself has a good thermal stability or has cooperative heat-stable function of DuoYuan alcohol compound for the pilot thing, and then using structure, the method of selection of modified the DuoYuan alcohol for esterification and etherification decorate, introducing has the stable of epoxy groups and increased activity and PVC XiangRongXing and dispersion, or ether ester key group, and the structure of the accessories, the investigation of the stable performance, get the stability and application performance better three glycol two glycidyl ether (2, 2-(2,5,8,11-four oxygen miscellaneous-l, 1 2-(2) and 12 double epoxy ethane), glycerine three glycidyl ether (one, two, three-TriS (2, 3-epoxypropoxy) propane), its structured for And bisphenol A second glycidyl ether etc DuoYuan alcohol derivatives, for organic heat stabilizers research provides reference. Through the experiment selection itself has certain stability has cooperative or stabilizing DuoYuan alcohol compound for the pilot thing, the structure of the modification methods, to the selection DuoYuan alcohol hydroxyl compound for esterification and etherification reaction, introducing has the stable or increase the activity and PVC XiangRongXing and dispersion, and through the Congo red groups dipstick methods, the structure of the accessories, the investigation of the stable performance, get the stability and application performance better DuoYuan alcohol derivatives. Really diethylene glycol two glycidyl ether, three glycol two glycidyl ether, glycerine three glycidyl ether and bisphenol A second glycidyl ether with pentaerythritol thermal stability quite or better than the pentaerythritol organic stable content. 含氮辅助类(β-氨基巴豆酸酯、α-苯基吲哚和二苯基硫脲) Nitrogen auxiliary class (beta amino acid esters, BaDou alpha phenyl indole and ErBenJi thiourea) 曾作为无毒主体稳定剂使用，但其耐高温性、长期耐热性、耐光性较差，目前已很少使用。α-苯基 合使用。由于其易早期着色，所吲哚与Ca,Zn等稳定剂复合使用;β-氨基巴豆酸酯多半与Ca,Zn配 [7]以在其他地方用的很少;二苯基硫脲曾在欧洲几个国家被用于食品卫生级PVC，但现在使用较少。 1998年12月，金陵石油化工公司化工一厂的陈平轩以顺丁烯二酸酐和苯胺为原料，选择二步法合 成了N-苯基马来酰亚胺，试验表明N-苯基马来酰亚胺是PVC塑料有效的热稳定剂，与月桂酸二丁基锡 [14]类热稳定剂有很好的协同效应。 2000年，美国科聚亚公司(德国熊牌公司近日收购其有机热稳定剂产品业务) 最初用于PVC硬 制品加工方面的有机稳定剂，可以从有机碱类化合物( 如氨基尿嘧啶、二氢吡啶、五节环1,3,4-恶二唑 衍生物等)中提取 ，这类物质具有价格竞争性，同时在性能上有优势，有低迁移性、低气味、良好前期 色相、极佳的透明性。有机稳定剂由于抑制了分子链交联，在加工PVC制品时，在高温和高剪切作用 下的加工时间明显优于铅类和钙, 锌皂类稳定剂体系，国内已有多家企业投入了大量的人、财、物 ， [15]取得了一定的成绩。 Was used as a non-toxic subject stabilizers use, but their resistance to high temperature sex, long-term heat resistance, resistance to light the gender is poorer, has rarely used. Alpha phenyl indole and Ca/Zn and stabilizer composite use; Beta BaDou amino acid esters and Ca/Zn most used together. Because it tends to be early coloring, so in other place with a few; ErBenJi thiourea worked in several European countries are used to the food sanitation PVC, but use less now. In December 1998, jinling petrochemical company chemical factory ChenPingXuan of maleic anhydride and aniline as raw materials, to choose two footwork synthesized N-phenyl Malay imide), test indicated that N-phenyl Malay imide) is PVC plastic effective heat stabilizers, and bay acid two of butyltin compounds heat stabilizers have very good synergy effect. In 2000, American families get together and company (Germany bear recently acquired its brand organic heat stabilizers product business) originally designed for PVC hard products processing of organic stabilizer, can from the organic compounds alkali (such as amino uracil, two hydrogen pyridine ring, five section 1, 3-oxadiazoles derivatives), this kind of substance extracted with competitive prices, and the performance advantage, have low transference, low smell, the good hue, preferably transparency. Organic stabilizers due to inhibit the molecular chain crosslinking, PVC products in machining, high temperature and high shear function in the processing time obviously better than the lead class and calcium/zinc soap class stabilizer system, domestic enterprises have invested a lot of human, financial, material, has obtained some achievements. 2000年，吴茂英研究了N (取代苯基) 马来酰亚胺( N-RPMI) 对PVC的热稳定作用。N-PRMI具有 类似于马来酸(酯)有机锡的热稳定特性，能较好地抑制初期着色且不存在突然变黑现象。N-RPMI既可 大部分代替BaSt - CdSt复合物中的CdSt，而不降低热稳定性，又可少量代替CdSt-ZnSt，复合物中22222 的CdSt以明显提高热稳定效能。复合N-RPMI- BaSt-CdSt的热稳定性随N-RPMI中取代基的拉电子效222 应 (用取代基常数D表示)的增强而提高，而N-RPMI-CdSt-ZnSt的热稳定性基本上不受N-RPMI中取22[16]代基的影响。 2004年，吴茂英研究了N-环己基马来酰亚胺(N-CHMI)对PVC的热稳定作用。N-CHMI具有类似于 C-10，的中旬型热稳定特性。根据N- CHMI的分子结构特征分析，N-CHMI之所以具有一定的抑制PVC2 初期着色的能力，可能是由于它类似于马来酸(酯)有机锡，作为亲双烯试剂，可与PVC链上的共轭多烯 链发生Diels-Alder加成反应而阻断其增长。因N-CHMI不产生对PVC热降解有催化作用的转化产物， 故不会PVC产生突然变黑现象，但又由于缺乏吸收HCI的能力，所以长期热稳定效能不如C-10。N-CHMI2 具有与Ba、Ca、Cd、Zn皂不同的热稳定功能，其并用可能具有协同效应。 N- CHMI,BaSt,CdSt并用。BaSt、CdSt与N-CHMI并用均存在协同效应:BaSt与N-CHMI并22222 用，抑制初期着色效能得到提高;CdSt与N-CHMI并用，长期热稳定性得以改进。N-CHMI与复合BaSt22 ,CdSt存在协同效应，替代比约5,时并用效果最佳，替代比可高至约50,而不导致热稳定效能下降。2 这一结果表明，可以通过并用N-CHMI以降低复合Ba,Cd热稳定剂中Ba、Cd的比例，从而达到减轻 PVC工业重金属毒害和污染的目的。 N-CHMI,CaSt,ZnSt并用。CaSt与N-CHMI并用存在较明显的协同效应(所稳定PVC试片在整222 个受热过程的着色均较两者单独稳定者轻);而与ZnSt并用，N-CHMI的效果明显不如CaSt。据此推22 测可以N-CHMI部分替代复合CaSt,ZnSt中CaSt，以改进其热稳定效能，用N-CHMI部分替代复合222 CaSt,ZnSt中CaSt，可在非常宽的替代比范围内改进其抑制PVC初期着色的效能。 222 结果表明，N-CHMI具有中间型热稳定剂的热稳定作用特性，能在一定程度上抑制PVC初期着色， [17]与复合Ba,Cd和Ca,Zn皂均存在协同效应。 In 2000, WuMaoYing research N (phenyl) instead of the Malay imide) (N-RPMI) on PVC thermal stability of the role. N-PRMI are similar with the Malay acid (ester) organic tin thermal stability of the characteristic, can better inhibition colouring and early does not exist suddenly become black phenomenon. N-RPMI as can be most BaSt2-the CdSt2 complex instead of CdSt2, not lower the heat stability, and small CdSt2-ZnSt2, instead of the complex CdSt2 obviously improve the efficiency in the thermal stability. Composite N-RPMI-BaSt2-CdSt2 thermal stability with N-RPMI replace the pull electronic effects (with the constant D said) to replace the enhance and improve, and N-RPMI-CdSt2-ZnSt2 thermal stability basically from N-RPMI replaced the influence of the yankees in. In 2004, WuMaoYing research the N-ring has the Malay imide) (N-CHMI) on PVC thermal stability of the role. N-CHMI are similar with C-102, in the middle of the thermal stability of properties. According to N-CHMI the molecular structure characteristics of analysis, N-CHMI that have certain inhibit the ability of PVC initial period coloration, probably because it is similar to the Malay acid (ester) of organic tin, as a double agent, can kiss fullerenes and PVC chain conjugated fullerenes Diels happened more than chain-Alder addition reaction and block the growth. For N-CHMI does not produce PVC thermal degradation to have a catalytic effect, so the conversion of the products will not suddenly become black produced PVC phenomenon, but also because of the lack of the ability of absorbing HCI, so long as the thermal stability of C-102. Performance N-CHMI has and Ba, Ca, CDS, Zn soap different thermal stability of the function, its and may have a synergy effect. N-CHMI/BaSt2 / CdSt2 and. BaSt2, CdSt2 and N-CHMI and there are synergies: BaSt2 and N-CHMI, restrain the initial period coloration and improve efficiency; CdSt2 and N-CHMI and thermal stability, long to improve. N-CHMI and compound BaSt2 / CdSt2 there existed synergetic effects, alternative is about 5% and the best effect when, alternative can be higher than to about 50% do not cause heat-stable potency decline. The results show that, by using N-CHMI to reduce composite Ba/Cd heat stabilizers, the proportion of Ba in Cd, in order to reduce PVC industry heavy metal poisoning and the purpose of the pollution. N-CHMI/CaSt2 / ZnSt2 and. CaSt2 and N-CHMI and there are obvious synergy (PVC specimens, the stable in the whole process of heated color than both light); the stable alone And with ZnSt2 and, N-CHMI effect obvious not equal to CaSt2. To infer can N-CHMI partly replace composite CaSt2 / ZnSt2 CaSt2 in to improve its heat-stable potency, with N-CHMI partly replace composite CaSt2 / ZnSt2 CaSt2 in, can be in a very wide range of alternative than improvement the inhibition of the initial colouring of PVC efficiency. The results show that, N-CHMI have middle typal heat stabilizers thermal stability of the interaction characteristics, to a certain extent, and the early suppression PVC color composite Ba/Cd and Ca/Zn soap there are synergies. 含硫辅助类(硫醇化合物，硫代二丙酸酯及硫代酸酐) Sulfur auxiliary class (mercaptan compounds, sulfur and two propionic acid ester and sulfur generation anhydride) 硫代酸酐，初期易变黄，但是能提供良好的长期稳定性。而且能通过少量的巯基酯有机锡共稳定剂 [7]增强其效率。 [18]江以桦等合成了马来酸二巯酯，其合成方法是在催化剂存在的条件下，将马来酸酐和巯基醇溶解 在溶剂中，回流后用水洗涤 ，经干燥后蒸 出溶剂，即得马来酸二巯酯。产品具有甲基锡系列的无毒性、 高透明性、高热稳定性，且在保持有机锡稳定剂的热稳定性和透明性的同时，尽可能降低锡含量，以达 到价廉的目的。另外 ，还同时起到协同稳定效果的有机稳定剂也能具有润滑剂的功效 ，使得原甲基锡 在加工时不会粘辊，不易渗出。 Sulfur generation anhydride, easy to become yellow, early but can provide a good long-term stability. And a small amount of sulphur acetate through total organic tin stabilizer enhance its efficiency. Jiang to synthesis the constituent of the Malay acid ester, the two Qiu synthesis method is in the presence of catalyst, maleic anhydride and sulphur alcohol will be dissolved in solvent, with water after washing the backflow, dry evaporate out for a quick Malay acid solvent, two Qiu ester. The product has the methyl tin series of non-toxic, high transparency, high heat stability, and keep in organic tin stabilizers thermal stability and transparency at the same time, as low as possible, so as to tin content and purpose. In addition, also have the effect of collaborative stable organic stabilizers also can have the effect of lubricants, makes the original methyl tin in the process will not stick roller, is not easy to seep out. β -二酮辅助类 Beta 2 ketone auxiliary class β-二酮，在金属盐的催化作用下迅速置换烯丙基，具有良好的抑制初期着色的能力。特别是十八烷 酰基苯甲酰基甲烷被美国食品和药物管理局批准用于食品卫生级PVC，它是优良的辅助稳定剂，现在使 [19]用较多。 [20-21]林美娟等合成了与β-二酮及Ca,Zn皂之间有良好协同稳定作用的螯合剂，并将Ca,Zn皂、 螯合剂等多种组分复配制备出高效Ca,Zn复合热稳定剂，同时研究了螯合剂对热稳定性能的影响，考 察了Ca,Zn复合热稳定剂在软质、硬质PVC配方中的应用，着重研究了体系的静态热稳定性和抗紫外 性能。结果表明，所研制的螯合剂能显著改善体系的长期热稳定性，并与β-二酮和Ca,Zn皂间有良好 的协同稳定作用;Ca皂、Zn皂的静态、动态热稳定时间分别为CaSt、ZnSt的2倍，当w (Ca):w (Zn) = 22 6:4时，PVC试样于195?条件下刚果红变色时间为27 min，初期着色性好，长期稳定性高，且有很好 的抗紫外老化性能。 [22]徐竞等将新型β-二酮类辅助热稳定剂DBM (二苯甲酰甲烷)-S和SBM (硬脂酰苯甲酰甲烷)-S分 别与传统的β-二酮辅助热稳定剂DBM和SBM应用效果进行对比，结果表明，在粉状钙锌复合热稳定 剂中，用新型辅助热稳定剂代替传统的辅助热稳定剂，热稳定效能基本不变，但添加新型辅助热稳定剂 的复合热稳定剂及其所稳定的PVC制品的存放变色情况明显减轻，同时能显著提高PVC制品的耐候性。 Beta 2 ketones, metal salt in the catalysis of rapidly replacement allyl base, has the good inhibit the ability of the initial period coloration. Especially 18 (dibenzyloxyphosphoiyl benjia acyl methane by the us food and drug administration approval for the food sanitation PVC, it is excellent auxiliary stabilizer, used more now. LinMeiJuan synthesis with beta 2 ketone and Ca/Zn fine coordination between the soap stabilizing chelating, and will Ca/Zn soap, chelating DuoZhong components such as complex configuration for a high efficiency Ca/Zn composite heat stabilizers, and research on the thermal stability of chelating influence on the performance of the investigation, the Ca/Zn composite heat stabilizers in soft, hard PVC formula, this paper studies the application of the system of the static thermal stability and ultraviolet performance. The results showed that the developed chelating agent can markedly improve the system for a long time, and thermal stability and beta 2 ketone and Ca/Zn soap has good coordination between stable effect; Ca soap, soap Zn static and dynamic thermal stability, respectively, ZnSt2 CaSt2 time of 2 times, when w (Ca) : w (Zn) = 6:4, PVC sample in 195 ? conditions Congo red color time for 27 min, initial period coloration of long-term stability and high, have very good ultraviolet aging performance. XuJing will be new beta diketones auxiliary heat stabilizers DBM (2 benzoyl methane)-S and SBM (stearic acid benzoyl methane)-S respectively with the traditional beta 2 ketone auxiliary heat stabilizers DBM SBM and application effect were compared, the results showed that, in the powdery calcium zinc composite heat stabilizers, use new auxiliary heat stabilizers instead of the traditional auxiliary heat stabilizers, heat stability performance basic remain unchanged, but add new auxiliary heat stabilizers composite heat stabilizers and the stability of the products of the storage conditions change color PVC significantly reduce, at the same time it can remarkably improve the PVC products market. 结束语 热稳定剂作为PVC加工时不可缺少的助剂，加强对其性能深入了解，开发出高效、无毒、价廉的 品种对发展PVC加工有着重要的意义。大部分PVC热稳定剂都具有一定的毒性，因此，在食品、医药、 包装、玩具等方面的应用受到一定程度的限制。近年来，国内外稀土类，金属皂特别是Ca,Zn复合类 热稳定剂在无毒、高效方面的研究应用取得了一定的进展。同时，无毒高效的PVC热稳定剂新品种不 [23]断出现，相应的专用复合热稳定剂也得到了发展。 PVC稳定剂发展至今天，金属稳定剂的进展相对缓慢，而辅助热稳定剂的研究与开发空前活跃，已 构成PVC稳定剂领域的一大潮流。辅助热稳定剂极少单独使用，常与主稳定剂配合使用，改善初期着 色，或者改善长期稳定性能。有机化合物类稳定剂是90年代PVC稳定化助剂中品种开发最活跃的领域 [24]之一，对实现PVC热稳定剂无毒、无害化具有划时代的意义。 从上文中可以看出，多元醇类、含氮辅助类、β-二酮辅助类的品种较多，而亚磷酸酯类、含硫辅助 类的发展前景较好，有待进一步加深。其总的发展趋势是:低毒、无毒热稳定是发展的主要方向;高分 子化、多功能化也是热稳定剂研究的方向;环保型有机化合物类热稳定剂具有极大的研究价值和应用前[25]景。 Last word Heat stabilizers as PVC processing indispensable assistant, strengthen its performance understanding, develop more efficient, non-toxic, cheap varieties to development PVC processing are of important significance. Most of the PVC thermal stabilizer all have certain of toxicity, therefore, in food, medicine, packaging, toys, the application of the limit by certain degree. In recent years, both at home and abroad, rare earth metal soap especially Ca/Zn composite kind of heat stabilizers non-toxic, efficient aspects in research and application of made progress. At the same time, non-toxic and efficient PVC heat stabilizers continue to occur, the corresponding new special composite heat stabilizers also obtained the development. PVC stabilizers development to today, metal stabilizers relatively slow progress, and the auxiliary heat stabilizers research and development, has constituted an active PVC stabilizers field of the big trend. The auxiliary heat stabilizers rarely used alone, often with the Lord used together to improve the stabilizer, color, or improve the early long-term stable performance. Organic compounds class stabilizer is the 90 s PVC stabilization additives products development in one of the most active areas and to realize the PVC thermal stabilizer avirulent, harmless epoch-making significance. In this paper can see, from DuoYuan alcohols, nitrogen auxiliary class, beta 2 ketone auxiliary class more, and the varieties and phosphate ester, sulfur auxiliary class is good, the development prospect of the further deepen. The general development trend is: low toxicity and non-toxic hot stability is the main development direction of; The polymer, muti_function change is also heat stabilizers research direction; Environmental protection of organic compounds heat stabilizers is of great value for study and application prospect. 参考文献reference [1] 王振华，田美珠，秦梅.PVC热稳定剂的现状及发展方向[ P ]. 化学师1002-1124 (2006) 08-0015-03 [2] 刘岭梅，候学军. PVC热稳定剂现状及发展态势[J].聚氯乙烯，2004，(3):6-8 [3] Mohamed N A,Sabaa M W，Kha1il K De t a l Organic thermal stabilizers for rigid polyvinyl chloride)? 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