CN106432676A - 一种n/p/纳米协效阻燃水性聚氨酯分散液的制备方法 - Google Patents
一种n/p/纳米协效阻燃水性聚氨酯分散液的制备方法 Download PDFInfo
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Abstract
本发明涉及一种N/P/纳米协效阻燃水性聚氨酯分散液的制备方法,包括以下步骤:(1)DOPO‑丙氨酸酐的合成:以四氢呋喃为溶剂、DOPO和丙氨酸酐为原料,得到DOPO‑丙氨酸酐;(2)一步法合成含N/P聚酯二元醇:以步骤(1)合成的DOPO‑丙氨酸酐、二元酸、二元醇为原料制成;(3)聚氨酯预聚体的合成:计量配比的多异氰酸酯、二元醇、含N/P聚酯二元醇、扩链剂及催化剂反应完全,得到聚氨酯预聚体;(4)水性聚氨酯分散液的制备:聚氨酯预聚体、偶联剂与纳米氧化物溶液反应,加入中和剂得到N/P/纳米协效阻燃水性聚氨酯分散液。该制备方法制成的聚氨酯分散液,具有高效阻燃性、高力学性能。
Description
技术领域
本发明属于高分子复合材料技术领域,具体涉及一种N/P/纳米协效阻燃水性聚氨酯分散液的制备方法。
背景技术
聚氨酯是指在高分子链上含有重复的氨基甲酸酯结构(-NHCOO-)的高分子聚合物,一般是由多异氰酸酯和聚醚或聚酯多元醇在一定条件下反应生成,可以通过选择不同的原料和工艺,制备出性能各异的聚氨酯产品。随着环保要求日益严峻,尤其是对物质中挥发性有机化合物(VOC)排放量的严格要求,水性聚氨酯涂料的研究与应用成为了行业热点。
水性聚氨酯以水作为分散剂,在加工过程中很少使用有机溶剂,因此,具有无毒、气味小等优点,已经广泛应用于墙体涂料、皮革涂饰剂、合成革等行业中,这些行业都存在有易燃的风险,因此,研究开发具有阻燃效果的水性聚氨酯不仅可以保护基材,同时可以保护人们的人身财产安全,拓宽水性聚氨酯的应用领域。
目前阻燃水性聚氨酯的研究主要集中在膨胀型阻燃体系、添加型阻燃水性聚氨酯及反应型阻燃水性聚氨酯。添加型阻燃水性聚氨酯随着阻燃剂的加入,聚氨酯乳液稳定性下降,易发生破乳现象,复配得到的水性聚氨酯制作的涂层不透明。添加型阻燃水性聚氨酯具有阻燃剂添加量大,耐水洗性差等缺点。反应型聚氨酯的合成是将具有活性基团的阻燃单体,加入到水性聚氨酯的合成体系中,以共价键的形式接入水性聚氨酯分子结构中,从而赋予产物优异的阻燃性能,所制得的阻燃水性聚氨酯结构较稳定。
现有研究中,反应型阻燃改性水性聚氨酯多以硬段改性为主,硬段改性虽然可以制备具有较高阻燃性能的水性聚氨酯,但所制备的阻燃聚氨酯的力学性能易被削弱。
发明内容
为解决上述问题,本发明提供一种N/P/纳米协效阻燃水性聚氨酯分散液的制备方法,该制备方法制成的聚氨酯分散液,具有高效阻燃性、高力学性能。
本发明是通过以下技术方案实现的:
9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,以下简称DOPO。
一种N/P/纳米协效阻燃水性聚氨酯分散液的制备方法,包括以下步骤:
(1)DOPO-丙氨酸酐的合成:以四氢呋喃为溶剂、DOPO和丙氨酸酐为原料,在70~95℃下反应12~24h,分液、洗涤、烘干得DOPO-丙氨酸酐;优选地,DOPO与丙氨酸酐的摩尔比为0.8~1.2:1~1.5,DOPO的摩尔浓度为0.9~1.3mol/L,分液洗涤后,产物在110~150℃烘干24~48h。
(2)一步法合成含N/P聚酯二元醇:以步骤(1)合成的DOPO-丙氨酸酐、二元酸、二元醇为原料,在180~230℃反应,酸值降到10mgKOH/g以下停止反应;优选地,二元酸、DOPO-丙氨酸酐与二元醇的物质的量之比为1:0.5~2.5:0.5~2.5。反应过程中需加入催化剂对甲苯磺酸,加入量为DOPO-丙氨酸酐、二元酸与二元醇总质量的0.03%~0.06%。
(3)聚氨酯预聚体的合成:计量配比的多异氰酸酯、二元醇、含N/P聚酯二元醇及催化剂在80~90℃反应1~2h,加入亲水扩链剂及助溶剂,在80~90℃下反应1~2h,降温到55℃左右得到聚氨酯预聚体;优选地,助溶剂为NMP,加入质量为多异氰酸酯、二元醇与含N/P聚酯二元醇总质量的5%~7.5%。
(4)水性聚氨酯分散液的制备:聚氨酯预聚体、偶联剂在65~75℃反应0.5~1.5h后,加入纳米氧化物溶液继续反应15min~1h,加入中和剂在60~70℃反应15~20min,加入去离子水在高速分散机上进行乳化分散,得到N/P/纳米协效阻燃水性聚氨酯分散液。优选地,纳米氧化物为纳米SiO2、纳米TiO2或纳米ZnO,粒径为100~250nm;偶联剂、聚氨酯预聚体、纳米氧化物摩尔量之比为0.7~1:0.7~1:0.5,纳米氧化物溶液的质量分数为5%~10%。
优选地,所述步骤(3)及步骤(4)中多异氰酸酯、二元醇、含N/P聚酯二元醇、亲水扩链剂与中和剂的摩尔比为2~4:0.3~0.7:0.3~0.7:0.8~1.2:0.9~1.2,催化剂用量为多异氰酸酯、二元醇、含N/P聚酯二元醇、亲水扩链剂及中和剂总质量的0.03%~0.06%。
上述步骤中,步骤(2)中的二元酸为1,6-己二酸、丁二酸、戊二酸、辛二酸或1,4-环己烷二甲酸;所述步骤(2)中二元醇为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、一缩二乙二醇或甲基丙二醇。
优选地,所述步骤(3)中的多异氰酸酯为甲苯二异氰酸脂(TDI)、异佛尔酮二异氰酸酯(IPDI)、萘异氰酸酯(NDI)、二苯基甲烷二异氰酸酯(MDI)、三甲基六亚甲基二异氰酸酯(TMDI)或三甲基-1,6-六亚甲基二异氰酸酯;多元醇为聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚丁二醇或聚乙二醇;催化剂为二月桂酸二丁基锡(DBTDL)、三亚乙基二胺或辛酸亚锡;亲水扩链剂为2,2’-二羟甲基丁酸(DMBA)、1,4-丁二醇或3,3’-二氯-4,4’-二氨基二苯甲烷。
所述步骤(4)中的中和剂为三乙胺(TEA)、N-甲基二乙醇胺(MDEA)、三乙醇胺或氨水;纳米氧化物溶液的溶剂为DMF、丙酮、甲苯、二甲苯、乙酸乙酯或乙酸丁酯;偶联剂为3-氨丙基三乙氧基硅烷或3-缩水甘油基氧基丙基三甲氧基硅烷。
本发明在水性聚氨酯的合成过程中,以含磷阻燃剂部分替代聚酯多元醇,使用软段阻燃改性的方法将阻燃功能元素磷及氮引入水性聚氨酯分子中。在此基础上,引入纳米材料,纳米材料不仅与磷氮阻燃剂形成协效阻燃效应,同时也改善了水性聚氨酯成膜材料的力学性能。
本发明的有益效果:
本发明采用氮磷协效阻燃及纳米材料改性两种方法制备阻燃水性聚氨酯,通过不同阻燃物质之间的协同作用制备具有高效阻燃性能及高力学强度的水性聚氨酯纳米复合新材料。
本发明采用的DOPO由于分子结构中含有以O=P-O键的方式存在的环状磷菲杂环,比一般的、未成环的有机磷酸酯热稳定性和化学稳定性更高,阻燃性能更好。与此同时,选用丙氨酸酐将阻燃功能元素氮元素引入,制成同时具有阻燃功能元素磷及氮的阻燃剂聚酯二元醇,阻燃性能更好。
另外,软段阻燃改性对水性聚氨酯力学性能影响较大,通过无机纳米氧化物的引入改善水性聚氨酯成膜材料的力学性能,即将不同的纳米氧化物(纳米SiO2、纳米TiO2和纳米ZnO)在硅烷偶联剂的作用下,引入水性聚氨酯结构中,采用超声波分散法将纳米氧化物均匀分散后反应,制备出一种具有高效阻燃性、高力学强度的水性聚氨酯纳米复合新材料。
具体实施方式
以下所述仅为本发明较好的实施例,仅仅用于描述本发明,不能理解为对本发明的范围的限制。
实施例1:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为0.8:1.0,DOPO的摩尔浓度为1mol/L,搅拌加热,当温度达到95℃时开始回流,反应12h,向溶液中加入适量的的二甲苯搅拌,分液后洗涤,在110℃烘箱中干燥40h。
(2)含N/P聚酯二元醇的合成
采用步骤(1)合成的DOPO-丙氨酸酐、1,6-己二酸、乙二醇作为原材料,一步法合成含N/P聚酯二元醇。其中,1,6-己二酸、DOPO-丙氨酸酐及乙二醇的物质的量之比为1:0.5:0.5,对甲苯磺酸的加入量为1,6-己二酸、DOPO-丙氨酸酐与乙二醇总质量的0.03%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入1,6-己二酸、DOPO-丙氨酸酐、乙二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,升温至120℃后采用阶梯升温法(30℃/30min)继续升温至200℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.09MPa,直至酸值降到10mgKOH/g以下停止反应。根据GB/T5530-2005国家标准测酸值,用吡啶-高氯酸法测羟值。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入TDI、PPG1000、含N/P聚酯二元醇,三者摩尔比为3:0.5:0.5,加入催化剂DBTDL,在85℃下反应1.5h后,加入DMBA(TDI与DMBA 摩尔比为3:1),再加入助溶剂NMP,继续反应1.5h。降温到55℃左右得到水性聚氨酯的预聚体。其中DBTDL的加入量为TDI、PPG1000、含N/P聚酯二元醇、DMBA及中和剂三乙胺总质量的0.03%,助溶剂NMP的加入量为TDI、PPG1000与含N/P聚酯二元醇总质量的5%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将KH-550与含N/P阻燃水性聚氨酯预聚体在70℃下反应0.5h, KH550、含N/P阻燃水性聚氨酯及纳米SiO2的摩尔比为0.8:0.9:0.5,将平均粒径为250nm的质量分数为8%的纳米SiO2的 DMF溶液超声分散10min后加入,反应0.5h;然后加入三乙胺,TDI与三乙胺摩尔比为3:1,在60℃下中和反应15min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化20min(分散机转速为1000r/min),得到N/P/纳米协效阻燃水性聚氨酯分散液。
实施例2:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为0.8:1.2,DOPO的摩尔浓度为1mol/L,搅拌加热,当温度达到85℃时开始回流,反应15h,向溶液中加入适量的二甲苯搅拌,分液后洗涤,在120℃烘箱中干燥48h。
(2)含N/P聚酯二元醇的合成
丁二酸、DOPO-丙氨酸酐及1,2-丙二醇的物质的量之比为1:1:1,对甲苯磺酸的加入量为丁二酸、DOPO-丙氨酸酐与1,2-丙二醇总质量的0.04%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入丁二酸、DOPO-丙氨酸酐、1,2-丙二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,升温至120℃后采用阶梯升温法(30℃/30min)继续升温至190℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.08MPa,直至酸值降到10mgKOH/g以下停止反应。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入IPDI、PTMG2000、含N/P聚酯二元醇到反应体系中,三者摩尔比为3:0.4:0.6,加入催化剂三亚乙基二胺,在85℃下反应1.5h,加入亲水扩链剂1,4-丁二醇(IPDI与1,4-丁二醇的摩尔比为3:1),再加入NMP,继续反应2h,降温到55℃左右得到聚氨酯预聚体。其中三亚乙基二胺的加入量为IPDI、PTMG2000、含N/P聚酯二元醇、1,4-丁二醇与三乙胺总质量的0.04%,NMP的加入量为IPDI、PTMG2000与含N/P聚酯二元醇总质量的5%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将KH-560与聚氨酯预聚体65℃下反应0.5h,KH550、含N/P阻燃水性聚氨酯及纳米TiO2的摩尔比为0.7:0.9:0.5,将平均粒径为250nm的质量分数为10%的纳米TiO2的 DMF溶液超声分散10min后加入反应体系中,反应0.5h后,加入三乙胺,IPDI与三乙胺摩尔比为3:1,在70℃下进行中和反应20min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到N/P/纳米协效阻燃水性聚氨酯分散液。
实施例3:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为1.0:1.0,DOPO的摩尔浓度为1.3mol/L,搅拌加热,当温度达到85℃时开始回流,反应18h,向溶液中加入适量的二甲苯搅拌,分液后洗涤,在140℃烘箱中干燥45h。
(2)含N/P聚酯二元醇的合成
戊二酸、DOPO-丙氨酸酐及1,4-丁二醇的物质的量之比为1:1.5:1.5,对甲苯磺酸的加入量为戊二酸、DOPO-丙氨酸酐与1,4-丁二醇总质量的0.03%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入戊二酸、DOPO-丙氨酸酐、1,4-丁二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,继续缓慢升温至120℃后采用阶梯升温法(30℃/30min)继续升温至210℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.08MPa,直至酸值降到10mgKOH/g以下停止反应。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入NDI、PEG和含N/P聚酯二元醇,三者摩尔比为2:0.3:0.7,加入辛酸亚锡,在80℃下反应1.5h,然后加入亲水扩链剂MOCA(NDI与MOCA摩尔比为2:1),再加入NMP,搅拌反应1.5h。降温到55℃左右得到聚氨酯预聚体。辛酸亚锡的加入量为NDI、PEG、含N/P聚酯二元醇、MOCA与三乙醇胺总质量的0.04%,NMP的加入量为NDI、PEG与含N/P聚酯二元醇总质量的6%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将偶联剂KH550与含N/P阻燃水性聚氨酯预聚体75℃下反应1h,KH550、含N/P阻燃水性聚氨酯及纳米ZnO的摩尔比为0.8:0.7:0.5,将平均粒径为100nm的质量分数为10%的纳米ZnO的甲苯溶液超声分散10min后加入,反应0.5h后,加入三乙醇胺(NDI与三乙醇胺摩尔比为2:1),65℃进行中和反应20min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到N/P/纳米协效阻燃水性聚氨酯分散液。
实施例4:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为0.9:1.0,DOPO的摩尔浓度为0.9mol/L,搅拌加热,当温度达到70℃时开始回流,反应24h,向溶液中加入适量的二甲苯搅拌,分液后洗涤,在130℃烘箱中干燥28h。
(2)含N/P聚酯二元醇的合成
辛二酸、DOPO-丙氨酸酐及1,6-己二醇的物质的量之比为1:1.5:1.5,对甲苯磺酸的加入量为辛二酸、DOPO-丙氨酸酐及1,4-丁二醇总质量的0.06%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入辛二酸、DOPO-丙氨酸酐、1,6-己二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,继续缓慢升温至120℃后采用阶梯升温法反应(30℃/30min)升温至180℃反应,当出水量接近理论值时,抽真空,真空度逐渐增大,最后达到0.08MPa,直至酸值降到10mgKOH/g以下停止反应。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入MDI、PPG2000和含N/P聚酯二元醇,三者摩尔比为4:0.4:0.6,加入催化剂DBTDL,在85℃下反应2h,然后加入亲水扩链剂DMBA(MDI与DMBA 摩尔比为4:0.8),再加入NMP,搅拌反应2h。降温到55℃左右得到聚氨酯预聚体。其中,催化剂DBTDL的加入量为MDI、PPG2000、含N/P聚酯二元醇、DMBA与三乙胺总质量的0.05%,NMP的加入量为MDI、PPG2000与含N/P聚酯二元醇总质量的6.5%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将偶联剂KH560与聚氨酯预聚体70℃下反应1.5h,KH560、含N/P阻燃水性聚氨酯及纳米TiO2的摩尔比为1.0:1.0:0.5,将平均粒径为200nm质量分数为10%的纳米TiO2的二甲苯溶液超声分散10min后加入,反应1h,加入三乙胺(MDI与三乙胺摩尔比为4:1.1)在65℃下进行中和反应20min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到N/P/纳米协效复合阻燃水性聚氨酯分散液。
实施例5:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为0.9:1.5,DOPO的摩尔浓度为1mol/L,搅拌加热,当温度达到95℃时开始回流,反应20h,向溶液中加入适量的二甲苯搅拌,分液后洗涤,在150℃烘箱中干燥30h。
(2)含N/P聚酯二元醇的合成
1,4-环己烷二甲酸、DOPO-丙氨酸酐及新戊二醇的物质的量之比为1:1.5:2,对甲苯磺酸的加入量为戊二酸、DOPO-丙氨酸酐与1,4-丁二醇总质量的0.05%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入1,4-环己烷二甲酸、DOPO-丙氨酸酐、新戊二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,继续缓慢升温至120℃后采用阶梯升温法反应(30℃/min)升温至230℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.08MPa,直至酸值降到10mgKOH/g以下停止反应。根据GB/T5530-2005国家标准测酸值,用吡啶-高氯酸法测羟值。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入TMDI、PTMG和含N/P聚酯二元醇,三者摩尔比为3:0.7:0.3,加入催化剂辛酸亚锡,在90℃下反应1h,然后加入MOCA(TMDI与MOCA摩尔比为3:1.2),与此同时,加入NMP搅拌反应1.5h。降温到55℃左右得到含N/P阻燃水性聚氨酯预聚体。其中,辛酸亚锡的加入量为TMDI、PTMG、含N/P聚酯二元醇、MOCA与三乙胺的总质量的0.06%,NMP的加入量为TMDI、PTMG与含N/P聚酯二元醇总质量的7%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将KH560与含N/P阻燃水性聚氨酯预聚体75℃下反应1.5h,KH550、含N/P阻燃水性聚氨酯及纳米SiO2的摩尔比为1:1:0.5,将平均粒径为200nm的质量分数为10%的纳米TiO2的乙酸乙酯溶液超声分散10min后加入,反应1h,加入三乙胺,TMDI与三乙胺摩尔比为3:0.9,65℃进行反应20min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到N/P/纳米协效阻燃水性聚氨酯分散液。
实施例6:
(1)含N/P单体DOPO-丙氨酸酐的合成
在装有搅拌器、温度计、冷凝管的三口烧瓶中,加入四氢呋喃、DOPO和丙氨酸酐,DOPO和丙氨酸酐摩尔比为1.2:1.5,DOPO的摩尔浓度为1mol/L,当温度达到85℃时开始回流,反应14h,向溶液中加入适量的二甲苯搅拌,分液后洗涤,在110℃烘箱中干燥40h。
(2)含N/P聚酯二元醇的合成
1,6-己二酸、DOPO-丙氨酸酐及甲基丙二醇的物质的量之比为1:2.5:2.5,对甲苯磺酸的加入量为戊二酸、DOPO-丙氨酸酐及1,4-丁二醇总质量的0.05%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入1,6-己二酸、DOPO-丙氨酸酐、甲基丙二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,继续缓慢升温至120℃后采用阶梯升温法(30℃/30min)升温至200℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.09MPa,直至酸值降到10mgKOH/g以下停止反应。根据GB/T5530-2005国家标准测酸值,用吡啶-高氯酸法测羟值。
(3)聚氨酯预聚体的合成
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入计量配比的TMHDI、PTMG和含N/P聚酯二元醇,三者摩尔比为3:0.5:0.5,加入催化剂辛酸亚锡,在85℃下反应2h,然后加入亲水扩链剂DMBA(TMHDI与DMBA 摩尔比为3:1.2),及NMP,搅拌反应2h。降温到55℃左右得到聚氨酯预聚体。其中,辛酸亚锡的加入量为TMHDI、PTMG、含N/P聚酯二元醇、DMBA与三乙胺的总质量的0.03%,NMP的加入量为TMHDI、PTMG与含N/P聚酯二元醇总质量的7.5%。
(4)N/P/纳米协效阻燃水性聚氨酯分散液的制备
将KH560与聚氨酯预聚体70℃下反应1.5h,KH560、含N/P阻燃水性聚氨酯及纳米ZnO的摩尔比为1:0.9:0.5,将平均粒径为250nm的质量分数为10%的纳米ZnO乙酸丁酯溶液超声分散10min后加入,反应0.5h,加入三乙胺(TMHDI与三乙胺摩尔比为3:1.2),65℃下反应20min,加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到N/P/纳米协效阻燃水性聚氨酯分散液。
对比例1
1,6-己二酸、乙二醇的物质的量之比为1:2.5,对甲苯磺酸为二元酸与二元醇总质量的0.03%。
在装有搅拌器、温度计、冷凝管、分水器的三口烧瓶中加入1,6-己二酸、乙二醇、带水剂二甲苯、对甲苯磺酸,缓慢升温,待固体全部溶解后,开始搅拌,继续缓慢升温至120℃后采用阶梯升温法升温至200℃反应,当出水量接近理论值时,降温至180℃,抽真空,真空度逐渐增大,最后达到0.08MPa,直至酸值降到10mgKOH/g以下停止反应,即为含DOPO聚酯二元醇。根据GB/T5530-2005国家标准测酸值,用吡啶-高氯酸法测羟值。
在装有搅拌器、回流冷凝管和温度计的四口烧瓶中加入TDI、PPG1000,两者摩尔比为3:0.5,再加入催化剂DBTDL,在85℃下反应1.5h。然后加入DMBA(TDI与DMBA 摩尔比为3:1),及助溶剂NMP,在85℃下搅拌反应2h。降温至65℃后,加入三乙胺(TDI与三乙胺摩尔比为3:1.2),反应20min后得到聚氨酯预聚体。加入去离子水(配制固含量为30%的水性聚氨酯分散液)进行乳化分散20min(分散机转速为1000r/min),得到水性聚氨酯分散液。其中催化剂的加入量为TDI、PPG1000与DMBA总质量的0.03%。NMP的加入量为TDI及PPG1000总质量的5%。
性能测试
实施例1~6所制备的N/P/纳米协效阻燃水性聚氨酯分散液,具有高效阻燃性、高力学性能,材料的有焰燃烧时间明显缩短,阻燃效果达到了UL-94 V0级;残炭率测定结果表明,纳米氧化物的加入,提高了膨胀炭层的热稳定性,力学性能提高,拉伸强度在60~63MPa。而对比例未引入氮元素和纳米氧化物改性,阻燃效果明显低于实施例,力学性能也较差。
Claims (10)
1.一种N/P/纳米协效阻燃水性聚氨酯分散液的制备方法,其特征在于,包括以下步骤:
(1)DOPO-丙氨酸酐的合成:以四氢呋喃为溶剂、DOPO和丙氨酸酐为原料,在70~95℃下反应12~24小时,分液、洗涤、烘干得DOPO-丙氨酸酐;
(2)一步法合成含N/P聚酯二元醇:以步骤(1)合成的DOPO-丙氨酸酐、二元酸、二元醇为原料,在180~230℃反应,酸值降到10mgKOH/g以下停止反应;
(3)聚氨酯预聚体的合成:计量配比的多异氰酸酯、二元醇 、含N/P聚酯二元醇及催化剂在80~90℃反应1~2h,加入亲水扩链剂及助溶剂,在80~90℃下反应1~2h,降温到55℃得到聚氨酯预聚体;
(4)水性聚氨酯分散液的制备:聚氨酯预聚体、偶联剂在65℃~75℃反应0.5~1.5h后,加入纳米氧化物溶液继续反应15min~1h,加入中和剂在60~70℃反应15~20min,加入去离子水在分散机上进行乳化分散,得到N/P/纳米协效阻燃水性聚氨酯分散液。
2.根据权利要求1所述的制备方法,其特征在于,
所述步骤(1)中DOPO与丙氨酸酐的摩尔比为0.8~1.2:1~1.5,DOPO的摩尔浓度为0.9~1.3mol/L;
所述步骤(1)中产物分液洗涤后,在110~150℃烘干24~48h。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中二元酸、DOPO-丙氨酸酐与二元醇的物质的量之比为1:0.5~2.5:0.5~2.5。
4.根据权利要求1或3所述的制备方法,其特征在于,
所述步骤(2)中的二元酸为1,6-己二酸、丁二酸、戊二酸、辛二酸或1,4-环己烷二甲酸;
所述步骤(2)中二元醇为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、一缩二乙二醇或甲基丙二醇。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)一步法合成含N/P的聚酯二元醇的反应过程中需加入催化剂对甲苯磺酸,加入量为DOPO-丙氨酸酐、二元酸与二元醇总质量的0.03%~0.06%。
6.根据权利要求1所述的制备方法,其特征在于,所述步骤(3)及步骤(4)中多异氰酸酯、二元醇、含N/P聚酯二元醇、亲水扩链剂与中和剂的摩尔比为2~4:0.3~0.7:0.3~0.7:0.8~1.2:0.9~1.2,助溶剂为NMP,加入质量为多异氰酸酯、二元醇与含N/P聚酯二元醇总质量的5%~7.5%;催化剂用量为多异氰酸酯、二元醇、含N/P聚酯二元醇、亲水扩链剂及中和剂总质量的0.03%~0.06%。
7.根据权利要求1所述的制备方法,其特征在于,所述步骤(4)中纳米氧化物为纳米SiO2、纳米TiO2或纳米ZnO,粒径为100~250nm。
8.根据权利要求1所述的制备方法,其特征在于,步骤(4)中偶联剂、聚氨酯预聚体、纳米氧化物摩尔量之比为0.7~1:0.7~1:0.5,纳米氧化物溶液的质量分数为5%~10%。
9.根据权利要求1所述的制备方法,其特征在于,
所述步骤(3)中的助溶剂为NMP,加入质量为多异氰酸酯、二元醇与含N/P聚酯二元醇总质量的1%~1.5%;
所述步骤(4)中的中和剂为三乙胺、N-甲基二乙醇胺、三乙醇胺或氨水。
10.根据权利要求1-9之一所述的制备方法,其特征在于,
所述步骤(3)中的多异氰酸酯为甲苯二异氰酸脂、异佛尔酮二异氰酸酯、萘异氰酸酯、二苯基甲烷二异氰酸酯、三甲基六亚甲基二异氰酸酯或三甲基-1,6-六亚甲基二异氰酸酯;
所述步骤(3)中多元醇为聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚丁二醇或聚乙二醇;
所述步骤(3)中所述的催化剂为二月桂酸二丁基锡、三亚乙基二胺或辛酸亚锡;
所述步骤(3)中亲水扩链剂为2,2’-二羟甲基丁酸、1,4-丁二醇或3,3’-二氯-4,4’-二氨基二苯甲烷;
所述步骤(4)中的纳米氧化物溶液的溶剂为DMF、丙酮、甲苯、二甲苯、乙酸乙酯或乙酸丁酯;
所述步骤(4)中偶联剂为3-氨丙基三乙氧基硅烷或3-缩水甘油基氧基丙基三甲氧基硅烷。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107417898A (zh) * | 2017-06-19 | 2017-12-01 | 河北科技大学 | 一种磷氮协效阻燃聚酯二元醇及其制备方法 |
CN109721704A (zh) * | 2019-01-11 | 2019-05-07 | 北京理工大学 | 一种光屏蔽阻燃水性聚氨酯及其制备方法 |
CN110229308A (zh) * | 2019-05-20 | 2019-09-13 | 齐鲁工业大学 | 一种水性聚氨酯改性胶原蛋白基混凝土发泡剂的制备方法 |
CN111410729A (zh) * | 2020-04-24 | 2020-07-14 | 黎哲华 | 一种高耐热阻燃型磷氮协效反应型聚氨酯材料及其制法 |
DE102021002539A1 (de) | 2021-05-14 | 2022-11-17 | Schill + Seilacher Gmbh | Verfahren zum Herstellen eines flammgeschützten Polyesters |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103275309A (zh) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | 含磷阻燃不饱和聚酯树脂及其制备方法 |
CN104004171A (zh) * | 2014-06-16 | 2014-08-27 | 旭川化学(苏州)有限公司 | 一种含磷无卤环保阻燃聚酯多元醇的制备方法 |
CN104592475A (zh) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | 含有磷杂菲和/或苯基磷酸酯基的阻燃水性聚氨酯的制法 |
CN104927038A (zh) * | 2015-06-18 | 2015-09-23 | 福建师范大学泉港石化研究院 | 一种无溶剂制备dopo基阻燃聚酯多元醇的方法 |
-
2016
- 2016-09-28 CN CN201610858303.6A patent/CN106432676B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103275309A (zh) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | 含磷阻燃不饱和聚酯树脂及其制备方法 |
CN104004171A (zh) * | 2014-06-16 | 2014-08-27 | 旭川化学(苏州)有限公司 | 一种含磷无卤环保阻燃聚酯多元醇的制备方法 |
CN104592475A (zh) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | 含有磷杂菲和/或苯基磷酸酯基的阻燃水性聚氨酯的制法 |
CN104927038A (zh) * | 2015-06-18 | 2015-09-23 | 福建师范大学泉港石化研究院 | 一种无溶剂制备dopo基阻燃聚酯多元醇的方法 |
Non-Patent Citations (3)
Title |
---|
张五一等: ""新型DOPO基反应型阻燃剂在聚氨酯中的应用"", 《塑料》 * |
张斐斐等: ""阻燃水性聚氨酯研究进展"", 《齐鲁工业大学学报》 * |
王浩等: ""DAM-DOPO的合成及其阻燃性能"", 《中国塑料》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107417898A (zh) * | 2017-06-19 | 2017-12-01 | 河北科技大学 | 一种磷氮协效阻燃聚酯二元醇及其制备方法 |
CN109721704A (zh) * | 2019-01-11 | 2019-05-07 | 北京理工大学 | 一种光屏蔽阻燃水性聚氨酯及其制备方法 |
CN110229308A (zh) * | 2019-05-20 | 2019-09-13 | 齐鲁工业大学 | 一种水性聚氨酯改性胶原蛋白基混凝土发泡剂的制备方法 |
CN110229308B (zh) * | 2019-05-20 | 2021-04-06 | 齐鲁工业大学 | 一种水性聚氨酯改性胶原蛋白基混凝土发泡剂的制备方法 |
CN111410729A (zh) * | 2020-04-24 | 2020-07-14 | 黎哲华 | 一种高耐热阻燃型磷氮协效反应型聚氨酯材料及其制法 |
DE102021002539A1 (de) | 2021-05-14 | 2022-11-17 | Schill + Seilacher Gmbh | Verfahren zum Herstellen eines flammgeschützten Polyesters |
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