CN113861398A - 一种含二苯醚结构聚酯树脂和粉末涂料及其制备方法 - Google Patents
一种含二苯醚结构聚酯树脂和粉末涂料及其制备方法 Download PDFInfo
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- CN113861398A CN113861398A CN202111180053.2A CN202111180053A CN113861398A CN 113861398 A CN113861398 A CN 113861398A CN 202111180053 A CN202111180053 A CN 202111180053A CN 113861398 A CN113861398 A CN 113861398A
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- diphenyl ether
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D5/03—Powdery paints
Abstract
本发明公开了一种含二苯醚结构聚酯树脂和粉末涂料及其制备方法,该树脂内部结构单元含二苯醚结构;按照质量份数,该树脂由以下组分组成:芳香二元酸40‑60份、二元醇30‑40份、支化剂0.01‑2份、酸解剂0.01‑5份、酯化催化剂0.03‑0.2份、抗氧剂0.01‑1.5份、固化促进剂0.01‑1份。本发明通过调控芳香二元酸中二苯醚结构的含量,玻璃化转变温度(Tg)>58℃,5%热失重温度>405.2℃,135℃时零剪切复数粘度<1750Pa.S。本发明的树脂制备的粉末涂料可实现135℃进行低温固化,具有优异的储存稳定性以及漆膜的流平性。
Description
技术领域
本发明属于聚酯树脂制备领域,具体涉及一种含二苯醚结构用聚酯树脂,以及基于该树脂制备的粉末涂料。
背景技术
粉末涂料具有高生产效率、优良涂膜性能、生态环保和经济的特点,得到世界涂料和涂装行业的重视,并成为在各种涂料品种中发展速度最快的品种。其中,聚酯树脂为主要成分的热固性粉末涂料是粉末涂料主要品种,其市场份额已经达到50%左右。随着粉末涂料在新兴领域拓展,对聚酯产品在节能、耐候、耐腐蚀的性能和卷材、木材、集装箱等应用场景也提出了一些新要求。粉末涂料的低温化是限制粉末涂料应用领域拓展的主要瓶颈。通常情况下粉末涂料需要在180~200℃下经过10~20min才能固化,而一般工业用液体涂料在60~120℃下也只需要10~20min便能固化,因此限制了粉末涂料在热敏底材和大型钢结构件等涂装领域的应用。
国内外已有不少粉末涂料低温化专用树脂的专利技术,其中,US6555226通过采用较多(90%)间苯二甲酸单体替代对苯二甲酸来降低玻璃化转变温度和固化温度;US8901250采用混合低玻璃化转变温度(≤45℃)聚酯方法降低固化温度(150℃);US9296917采用通过热自由基引发剂与无定形不饱和聚酯树脂反应的方法降低固化温度(130℃);US9475956通过引入异山梨醇和环烷基二醇单体降低固化温度(140℃);EP20070251729通过引入含磷聚酯降低固化温度;US20150024194合成酸值为约45至65的羧基官能聚酯树脂,实现能够在约120至135℃的温度下完全固化;CN201810327149.9合成的聚酯树脂链段中自带咪唑催化官能团,无需额外添加低温固化促进剂;CN201811320256.5引入8-18mol%丝氨醇单体聚合,丝氨醇中的氨基带有碱性,具有固化促进的作用。
对应粉末涂料用聚酯树脂而言,降低熔融温度(Tm)或熔体粘度是首要指标,其对粉末涂料降低固化温度和提高流平性能具有重要意义;提高或稳定玻璃化转变温度(Tg)是必要指标,其对粉末涂料的储存稳定防止结块上具有指导意义。然而一般聚合物随着结构改变,Tm和Tg发生同时增加或减小的变化,即不能同时满足降低固化温度和提高流平性能和提高储存稳定性的双重要求,这也是聚酯树脂设计的最大困难。
4,4’-二苯醚二甲酸是一种重要的高分子单体,主要用于制备高性能的聚苯并恶唑树脂,聚芳醛树脂,高性能纤维,绝缘材料以及热塑性液晶聚合物。在聚酯合成领域中,CN105440268将其用于合成脂肪族-芳香族-聚乳酸多嵌段共聚物,用于实现改性聚乳酸改性;WO2015016260A1将其用于合成较低分子量聚酯,应用于润滑油领域;CN106835331、CN106801265、CN106835336和CN106835334将其用于合成涤纶纤维,其刚性结构能够减弱纤维的挤出胀大效应,进而制备保形效果较好。
通常二苯醚结构具有较多芳环,被认为是刚性结构。研究认为部分刚性结构的引入会破坏了分子链的有序排列,因而增大了分子链间距离,导致分子间相互作用减弱粘度下降;但随着刚性结构持续增加,分子间摩擦阻力会显著提升反而会致使粘度增大。
发明内容
本发明的目的是提供一种含二苯醚结构聚酯树脂和粉末涂料及其制备方法,将二苯醚结构引入粉末涂料用聚酯树脂中,通过调控结构的含量,实现玻璃化转变温度(Tg)变化不大的情况下,降低低温固化条件下的熔融粘度,较高的热稳定性。由该树脂制备的粉末涂料实现135℃进行低温固化,具有优异的储存稳定性以及漆膜的流平性,能解决了背景技术中出现的问题。
为实现上述目的,本发明采用如下技术方案:
一种含二苯醚结构聚酯树脂,该树脂内部结构单元含二苯醚结构;按照质量份数,该树脂由以下组分组成:芳香二元酸40-60份、二元醇30-40份、支化剂0.01-2份、酸解剂0.01-5份、酯化催化剂0.03-0.2份、抗氧剂0.01-1.5份、固化促进剂0.01-1份。
所述树脂是端羧基聚酯树脂,其酸值范围为25-55mgKOH/g。
优选的,所述芳香多元酸为对苯二甲酸和4,4'-二苯醚二甲酸中的一种或者两者的混合物;若芳香多元酸为混合物,则芳香多元酸中4,4'-二苯醚二甲酸的摩尔百分含量为0.01-50%。
优选的,所述多元醇为新戊二醇、乙二醇、一缩二乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、1,4-丁二醇中的一种或多种的混合。
优选的,所述支化剂为三羟甲基丙烷、三羟甲基乙烷、1,2,5-戊三醇、季戊四醇、一缩二丙三醇中的一种或者多种的混合。
优选的,所述酸解剂为间苯二甲酸、己二酸、偏苯三酸酐和马来酸酐中的一种或者多种的混合。
优选的,所述酯化催化剂为二丁基氧化锡、三丁基氧化锡、二羟基丁基氯化锡、草酸亚锡、单丁基氧化锡中的一种或者多种的混合,酯化催化剂的用量是树脂的总质量的0.03-0.2%wt。
优选的,所述抗氧剂为三(2,4-二叔丁基苯基)亚磷酸酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯的一种或者多种的混合,抗氧剂的使用量是树脂总质量的0.01-1.5%wt。
优选的,所述固化促进剂为三苯基膦、三苯基乙基溴化膦;四乙基溴化铵、四丁基溴化铵、四丁基氯化铵,二月桂酸二丁基锡的一种或者多种的混合,固化促进剂的使用量是树脂总质量的0.01-1%wt。
所述树脂的玻璃化转变温度Tg≥58℃,5%热失重温度>405.2℃,135℃时零剪切复数粘度<1750Pa.S。
一种含二苯醚结构聚酯树脂的制备方法,包括以下步骤:
(1)在氮气氛围下,将二元醇、支化剂、酯化催化剂、一部分抗氧剂加入反应器中;
(2)升温加热至130℃,再加入芳香二元酸,搅拌均匀;
(3)加热升温至180℃开始反应,随后以10-15℃/h的速度升温至250℃,在此温度下,保温至反应体系澄清;
(4)取样检测酸值(AV)达到5-20mgKOH/g时,降低反应体系温度至220℃;
(5)加入酸解剂,然后再升温至240℃,保温2h后,在真空度为-0.09~-0.099Mpa的条件下继续反应2~4h;
(6)取样分析酸值、粘度,其中:酸值控制在25-55mg KOH/g、200℃时粘度控制在35~55pa.s,指标合格后,投加固化促进剂和剩余的另一部分抗氧剂,搅拌0.5h后出料。
一种基于所述含二苯醚结构聚酯树脂的粉末涂料,所述粉末涂料由以下重量份的组分组成:含二苯醚结构聚酯树脂50-60份、异氰尿酸三缩水甘油酯2-4.5份、钛白粉10-18份、硫酸钡8-16份、流平剂1-2份、增光剂0.5-1份、安息香0.2-0.6份。
优选的,所述流平剂为流平剂GLP503/588,增光剂为促进剂BLC701,安息香为二苯乙醇酮。
一种粉末涂料的制备方法,包括以下步骤:将各原料经混合机混合后通过双螺杆挤出机在各110℃的条件下经熔融挤出成片,然后用磨机磨制成粉,最后过200目筛筛选后得到所述粉末涂料;通过静电喷枪将所述粉末涂料喷涂于样板上,经烘箱在135℃下保温20min固化成型。
有益效果:本发明的树脂原料采用芳香二元酸、二元醇、支化剂、酸解剂、酯化催化剂、抗氧剂、和固化促进剂。通过调控芳香二元酸中二苯醚结构的含量,玻璃化转变温度(Tg)>58℃,5%热失重温度>405.2℃,135℃时零剪切复数粘度<1750Pa.S。本发明的树脂制备的粉末涂料可实现135℃进行低温固化,具有优异的储存稳定性以及漆膜的流平性。
附图说明
图1是实施例1-6所制备的聚酯的FTIR谱图;
图2是实施例5所制备的聚酯的H-NMR谱图;
图3是实施例1-6所制备的聚酯的的DSC谱图;
图4为实施例1-6所制备的聚酯的XRD图谱;
图5是实施例1-6所制备的聚酯的TGA谱图;
图6是实施例1-6所制备的聚酯在115-135℃五个温度条件下剪切频率与复数黏度谱图。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
聚酯树脂A0,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入442克对苯二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为34.1mg KOH/g、粘度为32.1pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯2克、四丙酸季戊四醇酯1克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为405.2℃。由DSC检测玻璃化转变温度为59.4℃。由流变仪测定零剪切粘度9033pa.s(115℃),5458pa.s(120℃),3150pa.s(125℃),1745pa.s(130℃),1149pa.s(135℃)。
实施例2
聚酯树脂A10,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入398克对苯二甲酸和69克4,4'-二苯醚二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为34.3mg KOH/g、粘度为22.7pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯1克、四丙酸季戊四醇酯2克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为423.6℃。由DSC检测玻璃化转变温度为64.6℃。由流变仪测定零剪切粘度6310pa.s(115℃),4426pa.s(120℃),4481pa.s(125℃),1449pa.s(130℃),888pa.s(135℃)。
实施例3
聚酯树脂A20,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入354克对苯二甲酸和137克4,4'-二苯醚二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为33.8mg KOH/g、粘度为14.7pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯1克、四丙酸季戊四醇酯2克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为428.9℃。由DSC检测玻璃化转变温度为61.9℃。由流变仪测定零剪切粘度3432pa.s(115℃),2051pa.s(120℃),1170pa.s(125℃),709pa.s(130℃),368pa.s(135℃)。
实施例4
聚酯树脂A30,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入310克对苯二甲酸和206克4,4'-二苯醚二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为35.1mg KOH/g、粘度为43.1pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯1克、四丙酸季戊四醇酯2克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为434.5℃。由DSC检测玻璃化转变温度为58.2℃。由流变仪测定零剪切粘度15589pa.s(115℃),8458pa.s(120℃),4560pa.s(125℃),3301pa.s(130℃),1432pa.s(135℃)。
实施例5
聚酯树脂A40,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入265克对苯二甲酸和275克4,4'-二苯醚二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为33.7mg KOH/g、粘度为43.7pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯1克、四丙酸季戊四醇酯2克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为437.9℃。由DSC检测玻璃化转变温度为66.3℃。由流变仪测定零剪切粘度11323pa.s(115℃),6122pa.s(120℃),3711pa.s(125℃),2155pa.s(130℃),1374pa.s(135℃)。
实施例6
聚酯树脂A50,在氮气氛围下,将245克新戊二醇、40克乙二醇、10克三羟甲基丙烷、1克催化剂单丁基氧化锡和1克亚磷酸三苯酯加入反应器中,升温加热至130℃。再加入221克对苯二甲酸和343克4,4'-二苯醚二甲酸,搅拌均匀。加热升温至250℃,在此反应条件下,保温至反应体系澄清,随后降低反应体系温度至220℃,加入30克间苯二甲酸、20克己二酸,随后升温至240℃,保温2小时后,真空缩聚3小时。取样分析酸值、粘度,酸值为36.8mg KOH/g、粘度为43.9pa.s(200℃,78.5rad/s),指标合格,投加抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯1克、四丙酸季戊四醇酯2克,搅拌半小时后出料。由XRD检测,15~25°有宽吸收峰为无定型态树脂。由TGA检测5%热失重温度为438.5℃。由DSC检测玻璃化转变温度为66.9℃。由流变仪测定零剪切粘度21564pa.s(115℃),10933pa.s(120℃),5863pa.s(125℃),2351pa.s(130℃),1750pa.s(135℃)。
图1是实施例1-6所制备的聚酯的FTIR谱图。其中1721cm-1处出现较高和尖锐峰,是C=O的伸缩振动特征吸收峰,说明聚合物中含有酯基;1596cm-1和1101cm-1处的峰是苯环骨架结构的振动吸收峰,说明聚合物中含有苯环结构;1163cm-1处为的C-O-C吸收峰,发现随着4,4’-二苯醚二甲酸用量的增加,该峰的强度及峰面积也呈现逐步增大趋势,说明该合成方法实现了二苯醚结构的有效定量引入。
图2是实施例5所制备的聚酯的H-NMR谱图。在2处的峰为δ=8.07,5处的峰为δ=7.07出现对应4,4’-二苯醚二甲苯环H的化学位移,表明着合成的聚酯产品分子链上存在4,4’-二苯醚的结构单元,根据积分面积和氢的个数比对,谱图与设计分子一致。
图3是实施例1-6所制备的聚酯的的DSC谱图。玻璃化转变温度在>58℃具有较好的常温储存性能。
图4为实施例1-6所制备的聚酯的XRD图谱,从图中可以发现,各组样品只有在衍射角为15~25°的范围里才有明显的特征峰,这说明了合成的树脂的结晶能力比较小。并且各组样品的XRD峰形相似,并且没有突变的峰,说明引入二苯醚结构对合成聚酯树脂的结晶性能影响不大。
图5是实施例1-6所制备的聚酯的TGA谱图。随着二苯醚含量的增加5%热失重温度逐步由405.2℃增加到438.5℃,说明树脂的耐热老化性能增加。
图6是实施例1-6所制备的聚酯在115-135℃五个温度条件下剪切频率与复数黏度谱图。A20的曲线明显低于其他曲线,说明在低温时的流动性最好,在135℃聚酯A20的η0最低,仅为368Pa.S。
用本发明方法合成的聚酯树脂的性能可通过制作成的粉末涂料的性能来体现。将上述实施例1-6、对比例7合成的聚酯树脂50-60份,分别与异氰尿酸三缩水甘油酯2-4.5份;钛白粉10-20份;硫酸钡8-20份;流平剂1-2份;增光剂0.5-1份;安息香0.2-0.6份。按表1中的比例称好后混匀,通过双螺杆挤出机在各110℃的条件下经熔融挤出成片,然后用磨机磨制成粉,最后过200目筛筛选后制成粉末涂料。粉末涂料采用静电喷枪喷涂在经表面处理(磷化)的金属板上,经135℃/20min固化,然后进行各种性能测试,性能测试结果如表1所示。
对比例江苏达美瑞新材料有限公司现有产品DM7101,其产品指标为酸值为32.8mgKOH/g、粘度为51pa.s(200℃)。
表1
以上所述仅是本发明的优选实施方式,应当指出:对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种含二苯醚结构聚酯树脂,其特征在于:该树脂内部结构单元含二苯醚结构;按照质量份数,该树脂由以下组分组成:芳香二元酸40-60份、二元醇30-40份、支化剂0.01-2份、酸解剂0.01-5份、酯化催化剂0.03-0.2份、抗氧剂0.01-1.5份、固化促进剂0.01-1份。
2.根据权利要求1所述的含二苯醚结构聚酯树脂,其特征在于:所述树脂是端羧基聚酯树脂,其酸值范围为25-55mgKOH/g。
3.根据权利要求1所述的含二苯醚结构聚酯树脂,其特征在于:所述芳香多元酸为对苯二甲酸和4,4'-二苯醚二甲酸中的一种或者两者的混合物;若芳香多元酸为混合物,则芳香多元酸中4,4'-二苯醚二甲酸的摩尔百分含量为0.01-50%。
4.根据权利要求1所述的含二苯醚结构聚酯树脂,其特征在于:所述多元醇为新戊二醇、乙二醇、一缩二乙二醇、三缩四乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、1,4-丁二醇中的一种或多种的混合。
5.根据权利要求1所述的含二苯醚结构聚酯树脂,其特征在于:所述支化剂为三羟甲基丙烷、三羟甲基乙烷、1,2,5-戊三醇、季戊四醇、一缩二丙三醇中的一种或者多种的混合;
所述酸解剂为间苯二甲酸、己二酸、偏苯三酸酐和马来酸酐中的一种或者多种的混合;
所述酯化催化剂为二丁基氧化锡、三丁基氧化锡、二羟基丁基氯化锡、草酸亚锡、单丁基氧化锡中的一种或者多种的混合,酯化催化剂的用量是树脂的总质量的0.03-0.2%wt;
所述抗氧剂为三(2,4-二叔丁基苯基)亚磷酸酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯的一种或者多种的混合,抗氧剂的使用量是树脂总质量的0.01-1.5%wt;
所述固化促进剂为三苯基膦、三苯基乙基溴化膦;四乙基溴化铵、四丁基溴化铵、四丁基氯化铵,二月桂酸二丁基锡的一种或者多种的混合,固化促进剂的使用量是树脂总质量的0.01-1%wt。
6.根据权利要求1所述的含二苯醚结构聚酯树脂,其特征在于:所述树脂的玻璃化转变温度Tg≥58℃,5%热失重温度>405.2℃,135℃时零剪切复数粘度<1750Pa.S。
7.一种权利要求1所述的含二苯醚结构聚酯树脂的制备方法,其特征在于:包括以下步骤:
(1)在氮气氛围下,将二元醇、支化剂、酯化催化剂、一部分抗氧剂加入反应器中;
(2)升温加热至130℃,再加入芳香二元酸,搅拌均匀;
(3)加热升温至180℃开始反应,随后以10-15℃/h的速度升温至250℃,在此温度下,保温至反应体系澄清;
(4)取样检测酸值(AV)达到5-20mgKOH/g时,降低反应体系温度至220℃;
(5)加入酸解剂,然后再升温至240℃,保温2h后,在真空度为-0.09~-0.099Mpa的条件下继续反应2~4h;
(6)取样分析酸值、粘度,其中:酸值控制在25-55mg KOH/g、200℃时粘度控制在35~55pa.s,指标合格后,投加固化促进剂和剩余的另一部分抗氧剂,搅拌0.5h后出料。
8.一种基于权利要求1所述含二苯醚结构聚酯树脂的粉末涂料,其特征在于:所述粉末涂料由以下重量份的组分组成:含二苯醚结构聚酯树脂50-60份、异氰尿酸三缩水甘油酯2-4.5份、钛白粉10-18份、硫酸钡8-16份、流平剂1-2份、增光剂0.5-1份、安息香0.2-0.6份。
9.根据权利要求8所述的粉末涂料,其特征在于:所述流平剂为流平剂GLP503/588,增光剂为促进剂BLC701,安息香为二苯乙醇酮。
10.一种权利要求8所述的粉末涂料的制备方法,其特征在于:包括以下步骤:将各原料经混合机混合后通过双螺杆挤出机在各110℃的条件下经熔融挤出成片,然后用磨机磨制成粉,最后过200目筛筛选后得到所述粉末涂料;通过静电喷枪将所述粉末涂料喷涂于样板上,经烘箱在135℃下保温20min固化成型。
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