【作者】 杨柳；

【导师】 刘平； 蒋传煜；

【作者基本信息】 华南理工大学 ， 材料工程（专业学位）， 2020， 硕士

【摘要】 聚氨酯(polyurethane,PU),就是分子链中含有重复氨基甲酸酯(-NHCOO-)基团的嵌段共聚物。PU不仅具有良好的耐冲击性、耐化学药品性和耐低温性,还具有优异的柔韧性和粘弹性,被广泛应用于轻工、电子、汽车和国防等领域。选择不同的聚合方式及调整配方设计可制备出不同粘弹性的PU压敏胶(PU-PSA)。目前PU-PSA已成为胶粘剂中发展最快的胶种之一。但PU易燃,使得其在一些特殊领域(如航空和电子电器设备等)的应用受到了限制,因此对PU-PSA提出了阻燃要求。本课题的目的是制备具有阻燃性能的PU-PSA。在本论文中,作者通过改变单体分子量、种类和配比等方法制备了PU预聚体,利用聚磷酸铵(APP)和氢氧化铝(ATH)为添加型阻燃剂,10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPOHQ)、N,N-双(羟乙基)氨基亚甲基磷酸二乙酯(FRC-6)和(6-氧代-6H-二苯并[C,E][1,2]氧磷杂己环-6-基)羟甲基噻吩(DOPO-SF)为反应型阻燃剂对PU进行改性,制备了阻燃PU-PSA,通过红外光谱、热重、氧指数、垂直燃烧、锥形量热、180°剥离和斜面滚球法的测试,表征和考察了阻燃PU-PSA的阻燃性能和粘结性能。结果如下:(1)以分子量3000的聚丙二醇(PPG3000)和甲苯二异氰酸酯(TDI)作为原料,在n(-NCO):n(-OH)为2.5(R=2.5)时,制备了PU预聚体。利用PU预聚体制备的PUPSA,当交联剂为三羟甲基丙烷(TMP),固化剂(氨基树脂)为10 wt%时可实现快速表干。当增粘剂(萜烯树脂,TR)为40wt%,增塑剂(环氧大豆油,ESO)为5 wt%时,PU-PSA具有良好的粘结性能,剥离强度可达到8.60±0.2 N/25 mm。(2)利用APP和ATH作为添加型阻燃剂制备的阻燃PU-PSA,其中PU/15 wt%A-PP/5 wt%ATH的极限氧指数(LOI)值可达到30.5%,并通过了UL 94 V-0等级,其峰值放热率(PHRR)、总放热率(THR)和平均有效热燃烧率(av-EHC)较纯PU分别降低了43.1%、21.0%和29.4%。然而PSA的初粘性和剥离强度随着添加型阻燃剂的含量增多而下降;利用DOPO-HQ、FRC-6和DOPO-SF作为反应型阻燃剂制备的阻燃P U-PSA,PU/50 mol%DOPO-HQ、PU/50 mol%FRC-6和PU/20 wt%DOPO-SF的LOI值分别为30.7%、29.3%和25.0%,均通过UL 94 V-1等级,其中PU/50 mol%DOPO-HQ和PU/50 mol%FRC-6的剥离强度分别为3.88 N/25 mm和3.42 N/25 mm。(3)为了进一步提高反应型阻燃PU-PSA的阻燃性,利用PU/50 mol%DOPO-HQ和PU/50 mol%FRC-6分别与5 wt%、10 wt%添加型阻燃剂(APP与ATH质量比3:1)制备了复合阻燃PSA。当添加型阻燃剂为10 wt%时,复合PSA的LOI值大于33,达到了UL 94 V-0等级。商用PSA制品的剥离强度为0.10～4.15 N/25 mm,本论文中作者所制备的反应型阻燃PU-PSA和复合PU-PSA可以满足不同商用PSA制品的粘结强度而实现应用。更多还原

【Abstract】 Polyurethane(PU)is multifunctional block copolymer containing repeating carbamate(-NHCOO-)groups in the molecular chain.PU has good impact resistance,chemical resistance and low temperature resistance,excellent flexibility and viscoelasticity.Therefore,it is widely used in light industry,electronics,textile,automobile,national defense and other fields.Polyurethane pressure-sensitive adhesive(PU-PSA)with different viscoelasticity could be prepared by selecting different polymerization methods and adjusting formula design of PU.At present,PU-PSA had become one of the fastest growing adhesives.However,PU is easy to burn,which limits its application in some special fields(such as aviation and electrical equipment,etc.),so the requirements for PU-PSA are put forward.The purpose of this project is to prepare PU-PSA with flame retardancy.In this paper,PU-PSA was prepared by changing the molecular weight,type and ratio of mo-nomer.Then,Ammonium polyphosphate(APP)and Aluminum hydroxide(ATH)were used as additive flame retardants,10-(2,5-dihydroxyphenyl)-10-H-9-oxo-10-phosphenanthrene-10-oxide(DOPO-HQ),N,N-bis(hydroxyethyl)aminomethylene phosphate diethyl ester(FRC-6)and(6-oxo-6H-dibenzo[c,e][1,2]oxphosphine-6-yl)hydroxymethylthiophene(DOPO-SF)were used as reactive flame retardant to modify PU,and the flame retardant PU-PSA was prepared.The flame retardant and adhesion properties of PU-PSA were characterized by FTIR,TG,oxygen index test,vertical combustion,cone,180° peeling and inclined ball rolling method.The results were as follows:(1)Using PPG3000 and TDI as raw materials,PU prepolymer was prepared at n(-NCO):n(-OH)=2.5(R=2.5).When the crosslinking agent was trimethylolpropane(TMP)and the curing agent(amino resin)was 10wt%,the rapid surface drying of PU-PSA prepared by PU prepolymer could be realized.When Tackifier(terpene resin,TR)was 40 wt% and Plasticizer(epoxy soybean oil,ESO)was 5w t%,PU-PSA had good adhesive property,and the peel strength could reach 8.60±0.2 N/25 mm.(2)The additive flame retardant PU-PSA was prepared with APP and ATH,the limiting oxygen index(LOI)value of PU/15 wt%APP/5 wt%ATH was 30.5%,reached UL 94 V-0rating.Compared with pure PU,the peak heat release rate(PHRR),total heat release(THR)and average mass lost rate(av-EHC)were 43.1%,21.0% and 29.4% respectively.However,the initial viscosity and peel strength of PSA decreased with the increase of the content of flame retardant;The reactive flame retardant PU-PSA was prepared by DOPO-HQ,FRC-6and DOPO-SF.The LOI values of PU/50 mol%DOPO-HQ,PU/50 mol%FRC-6 and PU/20wt%DOPO-SF could reach 30.7%,29.3% and 25.0%,and the vertical combustion could reach UL 94 V-1 rating.The peel strength of PU/50 mol%DOPO-HQ and PU/50 mol%FRC-6 was3.88 N/25 mm and 3.42 N/25 mm,and the initial viscosity was also good.(3)In order to further improve the flame retardancy of reactive flame retardant PSA,the composite PSA was prepared by PU/50 mol%DOPO-HQ and PU/50 mol%FRC-6 with 5 wt%and 10 wt% additive flame retardants(the mass ratio of APP to ATH is 3:1).When the flame retardant was 10 wt%,the composite PSA passed UL 94 V-0 rating,and the LOI value was greater than 33.The peel strength of commercial PSA products was 0.10～4.15 N/25 mm,reactive flame retardant PU-PSA and composite PU-PSA prepared by the author in this paper could meet the peel strength of different commercial PSA products and realized the application.更多还原