高分子科學(xué)導(dǎo)論熱固性樹(shù)脂ppt課件

1、四川大學(xué)化學(xué)學(xué)院,Introduction to polymer science,Thermoset Resin熱固性樹(shù)脂,Thermosetting plastics,Thermosetting plastics (thermosets) are polymer materials that irreversibly cure. The cure may be done through heat (generally above 200oC), through a chemical reaction (two-part epoxy, for example), or irradiation

2、such as electron beam processing. Most often, the cure process involves cross-linking which strengthens the polymer (setting). Thermoset materials are usually liquid or malleable prior to curing and designed to be molded into their final form, or used as adhesives. Others are solids like that of the

3、 molding compound used in semiconductors and integrated circuits,Thermosetting plastics,Thermosetting means the plastic softens when initially heated , but sets permanently rigid once it has cooled or has been chemically It is similar to the relationship between a raw and a cooked egg,Preparation St

4、rategy of thermosets,Multi functional monomer to crosslinked polymer Melamine resin Polyester resin,Prepolymer to crosslinked polymer Phenolic resin Urea resin,Phenolic resin,Dr. Leo Baekeland First totally synthetic plastic (1907) Patented in 1909 By controlling the pressure and temperature applied

5、 to phenol and formaldehyde, he found he could produce his dreamed-of hard moldable plastic: bakelite Replaced rubber for insulation in electrics,Dr. Leo H. Baekeland,In 1872，the famous Germany chemist, Adolf von Bayer had already observed the residue at the bottom of the test tube using for the rea

6、ction of Phenol and formaldehyde, which was very hard to get rid of. However, his interesting was focused on the organic dye, he didnt research this reaction,Phenolic resin,Properties of Phenolic resin,高溫性能 酚醛樹(shù)脂最重要的特征就是耐高溫性，即使在非常高的溫度下，也能保持其結(jié)構(gòu)的整體性和尺寸的穩(wěn)定性。 粘結(jié)強(qiáng)度 酚醛樹(shù)脂一個(gè)重要的應(yīng)用就是作為粘結(jié)劑。酚醛樹(shù)脂是一種多功能，與各種各樣的有機(jī)和無(wú)

7、機(jī)填料都能相容的物質(zhì)。潤(rùn)濕速度特別快，并且在交聯(lián)后可以為磨具、耐火材料，摩擦材料以及電木粉提供所需要的機(jī)械強(qiáng)度，耐熱性能和電性能。 高殘?zhí)悸?在溫度大約為1000 的惰性氣體條件下，酚醛樹(shù)脂會(huì)產(chǎn)生很高的殘?zhí)?，這有利于維持酚醛樹(shù)脂的結(jié)構(gòu)穩(wěn)定性。也是它能用于耐火材料領(lǐng)域的一個(gè)重要原因。 低煙低毒 與其他樹(shù)脂系統(tǒng)相比，酚醛樹(shù)脂具有低煙低毒的優(yōu)勢(shì)。在燃燒的情況下酚醛樹(shù)脂系統(tǒng)將會(huì)緩慢分解產(chǎn)生氫氣、碳?xì)浠衔?、水蒸氣和碳氧化物。分解過(guò)程中所產(chǎn)生的煙相對(duì)少，毒性也相對(duì)低。 抗化學(xué)性 交聯(lián)后的酚醛樹(shù)脂可以抵制大多化學(xué)物質(zhì)的分解。例如汽油，石油，醇，乙二醇和各種碳?xì)浠衔?Application of Phen

8、olic resin,Application of Phenolic resin,酚醛樹(shù)脂主要應(yīng)用于電絕緣體鑄件，用于電器外殼、設(shè)備和汽車(chē)的部件等。也有部分用于木材層板的粘合劑，用于家具和室內(nèi)裝修。通過(guò)浸漬木材和紙板得到的裝飾薄板可用于工作臺(tái)面、印刷電路、墻面裝飾等,Urea formaldehyde resin,Urea-formaldehyde, also known as urea-methanal, named so for its common synthesis pathway and overall structure, is a non-transparent thermose

9、tting resin or plastic, made from urea and formaldehyde heated in the presence of a mild base such as ammonia or pyridine. These resins are used in adhesives, finishes, MDF, and molded objects,Prepolymer,Curing,Properties of Ureaformaldehyde resin,1924年，英國(guó)氰氨公司研制出脲醛樹(shù)脂，1928年始出售產(chǎn)品，30年代中期產(chǎn)量達(dá)千噸，80年代世界年產(chǎn)量

10、已超過(guò)1.5Mt。 脲醛樹(shù)脂成本低廉，顏色淺，硬度高，耐油，抗霉，有較好的絕緣性和耐溫性，是開(kāi)發(fā)較早的熱固性樹(shù)脂之一。 脲醛樹(shù)脂堅(jiān)硬，耐刮傷，耐弱酸弱堿及油脂等介質(zhì)，價(jià)格便宜，具有一定的韌性，但它易于吸水，因而耐水性和電性能較差，耐熱性也不高。 脲醛樹(shù)脂可用于耐水性和介電性能要求不高的制品，如插線板、開(kāi)關(guān)、機(jī)器手柄、儀表外殼、旋紐、日用品、裝飾品、麻將牌、便桶蓋，也可用于部分餐具的制造。 脲醛樹(shù)脂是國(guó)內(nèi)外木材工業(yè)的主要粘合劑。由于它膠合強(qiáng)度高、固化快、操作性好、生產(chǎn)成本低、原料豐富易得等一系列優(yōu)點(diǎn)而得到廣泛應(yīng)用。但是脲醛樹(shù)脂所含的游離甲醛具有毒性，樹(shù)脂中的游離甲醛含量越低，其毒性就越小,App

11、lication of Ureaformaldehyde resin,Melamine formaldehyde resin,Thermosetting resins of the amino resin family, made by reacting melamine with formaldehyde. The lower molecular weight, uncured melamine resins are water soluble used for impregnating or laminating. Glass fiber reinforced melamine can b

12、e processed by compression molding. Also known as MELAMINE PLASTICS or MELAMINE RESINS,Melamine formaldehyde resin,Properties of melamineformaldehyde resin,蜜胺樹(shù)脂（三聚氰胺甲醛樹(shù)脂）單體具有較大的化學(xué)活性，很高的膠接強(qiáng)度，耐水能力高，能經(jīng)歷三小時(shí)以上的沸水，熱穩(wěn)定性高，耐磨性好，固化快。 蜜胺樹(shù)脂成品比脲醛樹(shù)脂成品硬度和耐磨性好，對(duì)化學(xué)藥物的抵抗能力，電絕緣性能等都好。但是固化后膠層容易破裂不宜單獨(dú)使用。 儲(chǔ)存期短，易變質(zhì)，制成粉狀可延長(zhǎng)

13、儲(chǔ)存期限,蜜胺樹(shù)脂加無(wú)機(jī)填料后制成模塑制品，色彩豐富，大多用于裝飾板、餐具、日用品。餐具外觀酷似瓷器或象牙，不易脆裂又適宜機(jī)械洗滌。 蜜胺樹(shù)脂與脲醛樹(shù)脂混合可配制成膠粘劑，用于制造層壓材料。用丁醇改性的密胺樹(shù)脂可作涂料和熱固性漆,Application of melamineformaldehyde resin,Polyester resin,Polyester resin, also known as alkyd resin, are resin formed by the reaction of polyols (also known as polyhydric alcohols, org

14、anic compounds with multiple alcohol or hydroxy functional groups) and polycarboxylic. the term alk-yd from alcohol and acid or anhydride. Typical polyols used are glycols such as ethylene glycol. The usual polycarboxylic acids used are unsaturated carboxylic acid such as phthalic acid, maleic acid,

15、 oleic acid. Water, which is a by-product of this esterification reaction, is removed from the reaction mass as soon as it is formed to drive the reaction to completion. the unsaturated groups react with oxygen from the air, causing the oils to crosslink and harden,Glyptal resin,在適當(dāng)?shù)臏囟葪l件下，甘油的兩個(gè)伯羥基先與

16、二酸反應(yīng)得到的線性預(yù)聚物，而當(dāng)溫度升高后，預(yù)聚物中殘留的仲羥基將繼續(xù)發(fā)生反應(yīng)將線形的分子鏈交聯(lián),Unsaturated polyester,Unsaturated polyester resins may be obtained by polymerization of unsaturated acids (e.g., maleic anhydride) with a diol such as propylene glycol or diethylene glycol. Corporation of the saturated acid serves to decrease crosslink

17、 density and consequently resin brittleness. Fumaric acid may be used in place of maleic acid to increase impact resistance. The low-molecular-weight prepolymer is soluble in styrene, which can then participate in a crosslinking step with the double bonds of the prepolymer during initiation by perox

18、ides,Properties of unsaturatedpolyester resin,工藝性能優(yōu)良。這是不飽和聚酯樹(shù)脂最大的優(yōu)點(diǎn)?？梢栽谑覝叵鹿袒合鲁尚?，工藝性能靈活，特別適合大型和現(xiàn)場(chǎng)制造玻璃鋼制品。 固化后樹(shù)脂綜合性能好。力學(xué)性能指標(biāo)略低于環(huán)氧樹(shù)脂，但優(yōu)于酚醛樹(shù)脂。耐腐蝕性，電性能和阻燃性可以通過(guò)選擇適當(dāng)牌號(hào)的樹(shù)脂來(lái)滿足要求，樹(shù)脂顏色淺，可以制成透明制品。 品種多，適應(yīng)廣泛，價(jià)格較低。 缺點(diǎn)是固化時(shí)收縮率較大，貯存期限短，含苯乙烯，有刺激性氣體，長(zhǎng)期接觸對(duì)身體健康不利。 聚酯樹(shù)脂主要用于膠粘玻璃鋼、硬質(zhì)塑料、混凝土、電氣罐封等,FRP (Fiberglass Reinforce

19、d Plastics 亦稱作GRP，Glass Reinforced Plastics，或Glass fibre reinforced plastics (GFRP) 即纖維強(qiáng)化塑料，一般指用玻璃纖維增強(qiáng)不飽和聚脂、環(huán)氧樹(shù)脂與酚醛樹(shù)脂基體。 最為廣泛使用的醇酸樹(shù)脂是玻纖增強(qiáng)的不飽和聚酯樹(shù)脂，是熱固性樹(shù)脂中用量最大的，也是玻璃鋼復(fù)合材料制品生產(chǎn)中用得最多的樹(shù)脂。雖然隸屬于醇酸樹(shù)脂，但是因?yàn)槎嘤猛竞透呤褂昧?，已?jīng)發(fā)展成為一個(gè)單獨(dú)的行業(yè),Application of unsaturatedpolyester resin,Application of unsaturatedpolyester resi

20、n,Epoxy resin,Epoxy or polyepoxide is a thermosetting polymer formed from reaction of an epoxide “prepolymer with polyamine or cyclic anhydride as hardener. Epoxy has a wide range of applications, including fiber-reinforced plastic materials and general purpose adhesives,Structure of unmodified bisp

21、henol-A epoxy prepolymer. n denotes the number of polymerized subunits and is in the range from 0 to about 25,Toughness,Toughness,High temperature performance and Rigidity,Reactive sites, Adhesion, and Wetability,Reactive sites,Curing agent of epoxy resin,常用環(huán)氧樹(shù)脂固化劑有 胺類固化劑 包括脂肪胺、脂環(huán)胺、芳香胺等 酸酐類固化劑 低分子量聚

22、酰胺類固化劑 咪唑類固化劑 三級(jí)胺類固化劑 常溫或低溫固化一般選用胺類固化劑，加溫固化則常用酸酐、芳香類固化劑,Curing of epoxy resin,polyamine as hardener,Maleic anhydride and styrene as hardener,Properties of epoxy resin,形式多樣。各種基體、固化劑、改性劑體系幾乎可以適應(yīng)各種應(yīng)用對(duì)形式提出的要求，其范圍可以從極低的粘度到高熔點(diǎn)固體。 固化方便。選用各種不同的固化劑，環(huán)氧樹(shù)脂體系幾乎可以在0180溫度范圍內(nèi)固化。 粘附力強(qiáng)。環(huán)氧樹(shù)脂分子鏈中固有的極性羥基和醚鍵的存在，使其對(duì)各種物質(zhì)具有

23、很高的粘附力。環(huán)氧樹(shù)脂固化時(shí)的收縮性低，產(chǎn)生的內(nèi)應(yīng)力小，這也有助于提高粘附強(qiáng)度。 收縮性低。環(huán)氧樹(shù)脂和所用的固化劑的反應(yīng)是通過(guò)直接加成反應(yīng)或樹(shù)脂分子中環(huán)氧基的開(kāi)環(huán)聚合反應(yīng)來(lái)進(jìn)行的，沒(méi)有水或其它揮發(fā)性副產(chǎn)物放出。它們和不飽和聚酯樹(shù)脂、酚醛樹(shù)脂相比，在固化過(guò)程中顯示出很低的收縮性（小于2%）。 力學(xué)性能。固化后的環(huán)氧樹(shù)脂體系具有優(yōu)良的力學(xué)性能。 電性能。固化后的環(huán)氧樹(shù)脂體系是一種具有高介電性能、耐表面漏電、耐電弧的優(yōu)良絕緣材料。 化學(xué)穩(wěn)定性。通常，固化后的環(huán)氧樹(shù)脂體系具有優(yōu)良的耐堿性、耐酸性和耐溶劑性。像固化環(huán)氧體系的其它性能一樣，化學(xué)穩(wěn)定性也取決于所選用的樹(shù)脂和固化劑。適當(dāng)?shù)剡x用環(huán)氧樹(shù)脂和固化劑

24、，可以使其具有特殊的化學(xué)穩(wěn)定性能。 尺寸穩(wěn)定性。上述的許多性能的綜合，使環(huán)氧樹(shù)脂體系具有突出的尺寸穩(wěn)定性和耐久性。 耐霉菌。固化的環(huán)氧樹(shù)脂體系耐大多數(shù)霉菌，可以在苛刻的熱帶條件下使用,Application of epoxy resin,Silicon resin,Silicone resins are a type of silicone material which is formed by branched, cage-like oligosiloxanes with the general formula of Rn-Si-Xm-Oy, where R is a non reactiv

25、e substituent, usually Me or Ph, and X is a functional group H, OH, Cl or OR. These groups are further condensed in many applications, to give highly crosslinked, insoluble polysiloxane networks,Silicone resins are prepared by hydrolytic condensation of various silicone precursors. In early processe

26、s of preparation of silicone resins sodium silicate and various chlorosilanes were used as starting materials,Preparation of silicon resin,Crosslinked,Linear,R = CH3, C2H5, Ph, H, etc,Properties of Silicon resin,熱穩(wěn)定性。硅樹(shù)脂的 Si-O 鍵有較高的鍵能（363kJ/mol），所以比較穩(wěn)定，耐熱性和耐高溫性能均很高。一般說(shuō)來(lái)其熱穩(wěn)定性范圍可達(dá)200250，特殊類型的樹(shù)脂可以更高一些。

27、 力學(xué)性能。硅樹(shù)脂固化后的力學(xué)性能不高，若在大分子主鏈上引進(jìn)氯代苯基，可提高力學(xué)性能。硅樹(shù)脂玻璃纖維層壓板的層間粘接強(qiáng)度較差，受熱時(shí)彎曲強(qiáng)度有較大幅度的下降。若在主鏈中引入亞苯基，可提高剛性、強(qiáng)度及使用溫度。 電性能。硅樹(shù)脂具有優(yōu)良的電絕緣性能，它的擊穿強(qiáng)度、耐高壓電弧及電火花性能均較優(yōu)異。受電弧及電火花作用時(shí)，樹(shù)脂即使裂解而除去有機(jī)基團(tuán)，表面剩下的二氧化硅同樣具有良好的介電性能。 憎水性。硅樹(shù)脂的吸水性很低，水珠在其表面只能滾落而不能潤(rùn)濕。因此，在潮濕的環(huán)境條件下，有機(jī)硅樹(shù)脂玻璃纖維增強(qiáng)復(fù)合材料仍能保持其優(yōu)良的性能。 耐腐蝕性能。硅樹(shù)脂玻璃纖維增強(qiáng)復(fù)合材料可而濃度（質(zhì)量）10%30%硫酸、1

28、0%鹽酸、10%15%氫氧化鈉、2%碳酸鈉及3%過(guò)氧化氫。醇類、脂肪烴和潤(rùn)滑油對(duì)它的影響較小，但耐濃硫酸及某些溶劑（如四氯化碳、丙酮和甲苯）的能力較差,Application of silicon resin,Urethane resin,A polyurethane, IUPAC abbreviation PUR, but commonly abbreviated PU, is any polymer consisting of a chain of organic units joined by urethane (carbamate) links (-O-CO-NH-). Polyure

29、thane polymers are formed through step-growth polymerization by reacting a monomer containing at least two isocyanate functional groups with another monomer containing at least two hydroxyl (alcohol) groups in the presence of a catalyst. Reaction of multi-functional monomers (number of functional group of the monomer 3) will result in a cross-linked urethane resin,polyurethane,Diisocyanate,toluene diisocyanate (TDI,diphenylmethane diisocyanate (MDI,p-phenylene diisocyante (PPDI,nap