CN112794985B - 一种透明聚氨酯光学材料及其制备方法 - Google Patents
一种透明聚氨酯光学材料及其制备方法 Download PDFInfo
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- CN112794985B CN112794985B CN202011611033.1A CN202011611033A CN112794985B CN 112794985 B CN112794985 B CN 112794985B CN 202011611033 A CN202011611033 A CN 202011611033A CN 112794985 B CN112794985 B CN 112794985B
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- mixture
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- polyol
- isocyanate
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- BUANSDIEQNBSMT-UHFFFAOYSA-N 4-phenothiazin-10-ylaniline Chemical compound C1=CC(N)=CC=C1N1C2=CC=CC=C2SC2=CC=CC=C21 BUANSDIEQNBSMT-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims abstract description 8
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 8
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- -1 3-amino-2- (4-chlorphenyl) -2-hydroxypropane sodium Chemical compound 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 7
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000376 reactant Substances 0.000 abstract description 3
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- FUVKOERYKPBYQK-UHFFFAOYSA-M sodium 3-amino-2-(4-chlorophenyl)-2-hydroxypropane-1-sulfonate Chemical compound NCC(CS(=O)(=O)[O-])(O)C1=CC=C(C=C1)Cl.[Na+] FUVKOERYKPBYQK-UHFFFAOYSA-M 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种透明聚氨酯光学材料及其制备方法,通过以异氰酸酯和聚合物多元醇作为反应物,同时加入了添加剂等物质反应制得;异氰酸酯上选择了1,4‑双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯,聚合物多元醇上选择了聚四氢呋喃二醇和聚碳酸酯多元醇,添加物上选择了2,3‑双(2‑疏基乙硫基)‑1‑丙硫醇和5‑乙丙基硫代‑1,3,4‑噻二唑‑2‑硫醇;促进剂是由聚甲氢硅氧烷和苯胺类物质反应制得,苯胺类物质上选择了4‑(10H‑吩噻嗪‑10‑基)苯胺和4‑(10H‑吩噻嗪‑10‑基)苯胺;最终制得的聚氨酯材料具有较大的拉伸强度和硬度,机械性能好,同时无色透明,具有较高的折光率,光学性能好,特别适合作为光学材料使用。
Description
技术领域
本发明涉及高分子材料合成领域,更具体的说是涉及一种透明聚氨酯光学材料及其制备方法。
背景技术
聚氨酯材料是一种有高机械强度和透明度的材料,具有耐油性好,拉伸强度、断裂强度及撕裂强度高的优异性能。由于其出色的机械性能,在生活中广泛用于制作管材、薄膜、片材、汽车内饰和纤维材料。而其较高的透明度则可以用于制作有机玻璃和眼镜片。目前市面上的聚氨酯材料具有不错的光学性能,但其机械强度和硬度一般,只适合作为普通的镜片使用;而随着科学技术的发展,人们对材料的性能要求也越来越高,在一些特殊领域中,如既要获得具有良好光学性能,又要具有一定的机械强度的防弹玻璃或者是警用防爆盾,或者是要有高透光度和折光率又要保持一定的硬度的特殊眼镜片,但目前现有的聚氨酯材料无法满足市场的需求,这大大限制了透明聚氨酯光学材料的发展。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种透明聚氨酯光学材料及其制备方法,该透明聚氨酯光学材料不仅具有较高的折光率,光学性能好,同时还具有较大的硬度和较高的拉伸强度。
为实现上述目的,本发明提供了如下技术方案:一种透明聚氨酯光学材料,其特征在于:包括下列重量份物质组成:
异氰酸酯10-30份;
聚合物多元醇10-30份;
小分子多元醇5-10份;
催化剂0.1-0.4份;
扩链剂2-6份;
添加剂1-4份;
促进剂1-4份;
所述异氰酸酯为1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯的混合物,其质量比为2:2:1;
所述聚合物多元醇为聚四氢呋喃二醇和聚碳酸酯多元醇的混合物,其质量比为3:1。
作为本发明的进一步改进,所述添加剂为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,其质量比为3:2。
作为本发明的进一步改进,所述促进剂包括下列摩尔份物质组成:
4-(10H-吩噻嗪-10-基)苯胺0.5-1.5份;聚甲氢硅氧烷0.8-2.5份。
作为本发明的进一步改进,所述促进剂的制备方法包括以下步骤:
S1:根据设定的摩尔份配备原料,将4-(10H-吩噻嗪-10-基)苯胺加入到装有第一溶剂的反应容器中搅拌混合,再将温度升高至70-90℃,接着向反应容器中加入铂金催化剂继续搅拌混合,混合均匀后,形成第一混合液;
S2:在氮气氛围下,将聚甲氢硅氧烷加入到第一混合液中搅拌混合,混合均匀后,在温度为140-200℃的条件下进行反应,反应时间为20-30h;反应结束后,过滤提纯烘干,制得促进剂。
本发明中铂金催化剂中铂浓度为5-15ppm,优选10ppm,铂金催化剂可以选自例如Karstedt催化剂溶液(铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液);
作为本发明的进一步改进,第一溶剂为甲苯和四氢呋喃的混合物,其体积比为5:1。
作为本发明的进一步改进,所述小分子多元醇为1,4-二羟基-2-丁烯和1,4-丁二醇的混合物,其质量比为1:2。
作为本发明的进一步改进,所述扩链剂为3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇的混合物,其质量比为1:1:1。
作为本发明的进一步改进,所述催化剂为二月桂酸二丁基锡。
作为本发明的进一步改进,一种透明聚氨酯光学材料的制备方法,其特征在于:包括以下步骤
步骤一:根据设定的重量份配备原料:将聚合物多元醇、小分子多元醇、催化剂和添加剂加入反应容器中搅拌混合,在温度为60-80℃的条件下混合10-30min,形成第一混合物;
步骤二:将异氰酸酯在温度为40-60℃的条件下,预热20-40min再加入到第一混合物中搅拌混合,形成第二混合物;然后在温度为120-150℃的条件下,反应1-3h;
步骤三:接着将扩链剂和促进剂加入到反应容器中搅拌混合物,混合均匀后,在温度为150-200℃的条件下,反应15-25h,制得透明聚氨酯光学材料。
本发明的有益效果:通过以异氰酸酯和聚合物多元醇作为反应物,同时加入了小分子多元醇,扩链剂,添加剂,促进剂以及催化剂这些物质反应制得;在异氰酸酯上选择了1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯,其中异佛尔酮二异氰酸酯简称IPDI,是常见的原料之一,其具有较好的耐化学性,同时不泛黄,易于生产高光学性能的聚氨酯材料,而1,4-双(异氰酸甲酯基)环己烷具有优异的耐黄变性和机械物性,苯二亚甲基二异氰酸酯由于苯环的存在,能够进一步提高聚氨酯材料的机械性能;
在这3种异氰酸酯的共同作用下,能够赋予了聚氨酯优良的物理机械性能以及优异的光学性能,保证材料具有较高的折光率和较大的拉伸强度和硬度;
在聚合物多元醇上选择了聚四氢呋喃二醇和聚碳酸酯多元醇,其中聚碳酸酯多元醇是一种优异的用于作为光学材料的原料之一,其具有较高的折光率,同时由于链段中含有碳酸酯键,有助于提高聚氨酯材料的拉伸强度和硬度,而聚四氢呋喃二醇不仅能够作为软段存在,还能与聚碳酸酯多元醇相互配合,发生协同作用,让聚碳酸酯多元醇与二异氰酸酯之间发生充分作用,反应更加完全,获得理想性能的聚氨酯材料;通过选择这样的异氰酸酯和聚合物多元醇,使得最终制得的聚氨酯材料已经有了相对较大的拉伸强度和硬度,同时折光率高,光学性能好。
作为本发明的关键点之一,为了进一步提高聚氨酯材料的光学性能和机械性能,本发明中加入了添加剂和促进剂,添加剂主要是进一步改善材料的光学性能,据相关研究发现,硫原子外层有d轨道存在,最外层的两对电子容易受到极化,使得硫原子既具有较低的分子色散性又具有较高的分子折射率;通过加入硫元素,能够有效提高聚氨酯材料的光学性能,本发明中添加物为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,这两种物质均为硫醇类物质,其具有较高的硫含量,在这两种物质的共同作用下,能够进一步改善聚氨酯材料的光学性能,同时这两种物质与体系中的其他物质相容性好,不会对聚氨酯材料的机械性能造成影响;从而保证制得的聚氨酯材料具有较高的折光率,光学性能好,适合用于光学纤维、光学基板、隐形眼镜等方面。
作为本发明的另一个关键点,在聚氨酯材料还加入了促进剂,促进剂主要是进一步提高聚氨酯材料的机械性能,同时也有助于提高聚氨酯材料的光学性能;本发明的促进剂是由聚甲氢硅氧烷和苯胺类物质反应制得,苯胺类物质上选择了4-(10H-吩噻嗪-10-基)苯胺,在铂金催化剂的催化作用下,能够与聚甲氢硅氧烷发生充分反应,最终生产含三苯胺基团的聚硅氧烷物质,因此促进剂是以硅氧作为主链段,同时含有三苯胺基团,碳碳双键等活性基团;由于这些结构的存在,我们惊喜的发现促进剂的加入能够大大提高聚氨酯材料的机械性能,使得聚氨酯材料有较高的拉伸强度和硬度,也一定程度提高了材料的光学性能;并且使得最终制得的聚氨酯材料耐黄变,耐紫外线,稳定性好,应用范围更广。
此外,在扩链剂上选择了3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇这三种低分子量的物质;这些物质中含有氨基,羟基等活性官能团,其中氨基,羟基均能与二异氰酸酯之间发生反应,生成富含-NHCON-,-NHCOO-的硬段,并且会形成氢键聚集区;并且研究发现短链扩链剂与长链扩链剂相搭配,其合成出来的聚氨酯弹性体具有更加良好的力学性能,而这是由于短链扩链剂缩短了硬段之间的距离,从而使硬段之间的氢键作用更加的明显,这也有利于硬段分子的聚集,促进了聚氨酯弹性体分子的微相分离,从而赋予了聚氨酯弹性体具有更好的力学性能;还意外的提高了材料的光学性能。
最终制得的聚氨酯材料具有较大的拉伸强度和硬度,机械性能好,同时无色透明,具有较高的折光率,光学性能好,特别适合作为光学材料使用。
具体实施方式
实施例1:制备促进剂
所述促进剂包括下列摩尔份物质组成:4-(10H-吩噻嗪-10-基)苯胺1份;
聚甲氢硅氧烷1.6份。
所述促进剂的制备方法包括以下步骤:
S1:根据设定的摩尔份配备原料,将4-(10H-吩噻嗪-10-基)苯胺加入到装有第一溶剂的反应容器中搅拌混合,再将温度升高至80℃,接着向反应容器中加入铂金催化剂(浓度为10ppm的Karstedt催化剂溶液)继续搅拌混合,混合均匀后,形成第一混合液;
S2:在氮气氛围下,将聚甲氢硅氧烷加入到第一混合液中搅拌混合,混合均匀后,在温度为160℃的条件下进行反应,反应时间为25h;反应结束后,过滤提纯烘干,制得促进剂。
第一溶剂为甲苯和四氢呋喃的混合物,其体积比为5:1;
每60ml第一溶剂中配有5mlKarstedt催化剂溶液,此时聚甲氢硅氧烷加入的摩尔量为1.6mmol。
实施例2
一种透明聚氨酯光学材料,其特征在于:包括下列重量份物质组成:
异氰酸酯20份;
聚合物多元醇25份;
小分子多元醇7份;
催化剂0.2份;
扩链剂4份;
添加剂3份;
促进剂2份;
所述异氰酸酯为1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯的混合物,其质量比为2:2:1;
所述聚合物多元醇为聚四氢呋喃二醇和聚碳酸酯多元醇的混合物,其质量比为3:1;
所述添加剂为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,其质量比为3:2;
所述促进剂由实施例1制得;
所述小分子多元醇为1,4-二羟基-2-丁烯和1,4-丁二醇的混合物,其质量比为1:2;
所述扩链剂为3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇的混合物,其质量比为1:1:1;
所述催化剂为二月桂酸二丁基锡;
一种透明聚氨酯光学材料的制备方法,其特征在于:包括以下步骤
步骤一:根据设定的重量份配备原料:将聚合物多元醇、小分子多元醇、催化剂和添加剂加入反应容器中搅拌混合,在温度为70℃的条件下混合20min,形成第一混合物;
步骤二:将异氰酸酯在温度为50℃的条件下,预热30min后再加入到第一混合物中搅拌混合,形成第二混合物;然后在温度为135℃的条件下,反应2h;
步骤三:接着将扩链剂和促进剂加入到反应容器中搅拌混合物,混合均匀后,在温度为180℃的条件下,反应20h,制得透明聚氨酯光学材料。
实施例3
一种透明聚氨酯光学材料,其特征在于:包括下列重量份物质组成:
异氰酸酯13份;
聚合物多元醇17份;
小分子多元醇5份;
催化剂0.1份;
扩链剂3份;
添加剂2份;
促进剂1份;
所述异氰酸酯为1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯的混合物,其质量比为2:2:1;
所述聚合物多元醇为聚四氢呋喃二醇和聚碳酸酯多元醇的混合物,其质量比为3:1。
所述添加剂为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,其质量比为3:2;
所述促进剂由实施例1制得;
所述小分子多元醇为1,4-二羟基-2-丁烯和1,4-丁二醇的混合物,其质量比为1:2;
所述扩链剂为3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇的混合物,其质量比为1:1:1;
所述催化剂为二月桂酸二丁基锡;
一种透明聚氨酯光学材料的制备方法,其特征在于:包括以下步骤
步骤一:根据设定的重量份配备原料:将聚合物多元醇、小分子多元醇、催化剂和添加剂加入反应容器中搅拌混合,在温度为60℃的条件下混合15min,形成第一混合物;
步骤二:将异氰酸酯在温度为45℃的条件下,预热25min后再加入到第一混合物中搅拌混合,形成第二混合物;然后在温度为125℃的条件下,反应1.5h;
步骤三:接着将扩链剂和促进剂加入到反应容器中搅拌混合物,混合均匀后,在温度为160℃的条件下,反应17h,制得透明聚氨酯光学材料。
实施例4
一种透明聚氨酯光学材料,其特征在于:包括下列重量份物质组成:
异氰酸酯30份;
聚合物多元醇30份;
小分子多元醇9份;
催化剂0.4份;
扩链剂6份;
添加剂4份;
促进剂4份;
所述异氰酸酯为1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯的混合物,其质量比为2:2:1;
所述聚合物多元醇为聚四氢呋喃二醇和聚碳酸酯多元醇的混合物,其质量比为3:1;
所述添加剂为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,其质量比为3:2;
所述促进剂由实施例1制得;
所述小分子多元醇为1,4-二羟基-2-丁烯和1,4-丁二醇的混合物,其质量比为1:2;
所述扩链剂为3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇的混合物,其质量比为1:1:1;
所述催化剂为二月桂酸二丁基锡;
一种透明聚氨酯光学材料的制备方法,其特征在于:包括以下步骤
步骤一:根据设定的重量份配备原料:将聚合物多元醇、小分子多元醇、催化剂和添加剂加入反应容器中搅拌混合,在温度为80℃的条件下混合30min,形成第一混合物;
步骤二:将异氰酸酯在温度为60℃的条件下,预热39min后再加入到第一混合物中搅拌混合,形成第二混合物;然后在温度为150℃的条件下,反应3h;
步骤三:接着将扩链剂和促进剂加入到反应容器中搅拌混合物,混合均匀后,在温度为195℃的条件下,反应24h,制得透明聚氨酯光学材料。
对实施例2-4制得的透明聚氨酯光学材料进行各项性能测试
光学性能测试折光率使用ATAGO(爱拓)的阿贝折光仪直接测得,折光率越大,说明试样的光学性能越好。
将仪器校准后,取样品溶解于丙酮溶液中滴2-3滴液体于进光棱镜的磨砂面上。调整旋转手轮,使得视场中黑白分界线与叉丝交点重合为止。在井筒中读出读数。
力学性能测试拉伸性能使用万能材料试验机,使用样品厚度为4mm,拉伸速度为5mm/min。拉伸强度和拉伸断裂应力、拉伸屈服应力、偏执屈服应力按下式计算:
式中:σt——拉伸强度或拉伸断裂应力、拉伸屈服应力、偏置屈服应力,MPa;
P——最大负荷或断裂负荷、屈服负荷、偏置屈服负荷,N;
B——试样宽度,m;
D——试样厚度,m
硬度测试
硬度性能使用浇注Ф50mmⅹ10mm硬度块,采用邵A橡胶硬度计参照GB/T 528—1999进行测试。
取厚度均匀的实验样品,厚度为5mm。在同一样品上取3个测试点,各组测量点之间的距离不少于5mm,最后取其平均值。
拉伸强度越大,硬度越大,说明该试样的机械性能越好。
测试结果如下:
试样 | 折光率nD(20) | 拉伸强度/MPa | 邵氏硬度A | 外观 |
实施例2 | 1.77 | 68 | 95 | 无色透明 |
实施例3 | 1.75 | 62 | 90 | 无色透明 |
实施例4 | 1.74 | 74 | 97 | 无色透明 |
由上表可知,实施例2-4制得的透明聚氨酯光学材料,具有较大的折光率,较高的硬度和拉伸强度,从而说明其光学性能和机械性能均较好。
将实施例2-4制得的试样先在紫外灯下照射48h,再进行各项性能测试,其结果如下:
试样 | 折光率nD(20) | 拉伸强度/MPa | 邵氏硬度A | 外观 |
实施例2 | 1.76 | 66 | 94 | 无色透明 |
实施例3 | 1.74 | 61 | 90 | 无色透明 |
实施例4 | 1.73 | 72 | 96 | 无色透明 |
由上表可知,实施例2-4制得的透明聚氨酯光学材料,在经过紫外线长时间照射后,依然具有较大的折光率,较高的硬度和拉伸强度,从而说明其耐紫外性,耐黄变,性质稳定,应用范围广。
本发明的透明聚氨酯光学材料,以异氰酸酯和聚合物多元醇作为反应物,同时加入了小分子多元醇,扩链剂,添加剂,促进剂以及催化剂这些物质反应制得;在异氰酸酯上选择了1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯,其中异佛尔酮二异氰酸酯简称IPDI,是常见的原料之一,其具有较好的耐化学性,同时不泛黄,易于生产高光学性能的聚氨酯材料,而1,4-双(异氰酸甲酯基)环己烷具有优异的耐黄变性和机械物性,苯二亚甲基二异氰酸酯由于苯环的存在,能够进一步提高聚氨酯材料的机械性能;在这3种异氰酸酯的共同作用下,能够赋予了聚氨酯优良的物理机械性能以及优异的光学性能,保证材料具有较高的折光率和较大的拉伸强度和硬度;
在聚合物多元醇上选择了聚四氢呋喃二醇和聚碳酸酯多元醇,其中聚碳酸酯多元醇是一种优异的用于作为光学材料的原料之一,其具有较高的折光率,同时由于链段中含有碳酸酯键,有助于提高聚氨酯材料的拉伸强度和硬度,而聚四氢呋喃二醇不仅能够作为软段存在,还能与聚碳酸酯多元醇相互配合,发生协同作用,让聚碳酸酯多元醇与二异氰酸酯之间发生充分作用,反应更加完全,获得理想性能的聚氨酯材料;通过选择这样的异氰酸酯和聚合物多元醇,使得最终制得的聚氨酯材料已经有了相对较大的拉伸强度和硬度,同时折光率高,光学性能好。
作为本发明的关键点之一,为了进一步提高聚氨酯材料的光学性能和机械性能,本发明中加入了添加剂和促进剂,添加剂主要是进一步改善材料的光学性能,据相关研究发现,硫原子外层有d轨道存在,最外层的两对电子容易受到极化,使得硫原子既具有较低的分子色散性又具有较高的分子折射率;通过加入硫元素,能够有效提高聚氨酯材料的光学性能,本发明中添加物为2,3-双(2-疏基乙硫基)-1-丙硫醇和5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,这两种物质均为硫醇类物质,其具有较高的硫含量,在这两种物质的共同作用下,能够进一步改善聚氨酯材料的光学性能,同时这两种物质与体系中的其他物质相容性好,不会对聚氨酯材料的机械性能造成影响;从而保证制得的聚氨酯材料具有较高的折光率,光学性能好,适合用于光学纤维、光学基板、隐形眼镜等方面。
作为本发明的另一个关键点,在聚氨酯材料还加入了促进剂,促进剂主要是进一步提高聚氨酯材料的机械性能,同时也有助于提高聚氨酯材料的光学性能;本发明的促进剂是由聚甲氢硅氧烷和苯胺类物质反应制得,苯胺类物质上选择了4-(10H-吩噻嗪-10-基)苯胺,在铂金催化剂的催化作用下,能够与聚甲氢硅氧烷发生充分反应,最终生产含三苯胺基团的聚硅氧烷物质,因此促进剂是以硅氧作为主链段,同时含有三苯胺基团,碳碳双键等活性基团;由于这些结构的存在,我们惊喜的发现促进剂的加入能够大大提高聚氨酯材料的机械性能,使得聚氨酯材料有较高的拉伸强度和硬度,也一定程度提高了材料的光学性能;并且使得最终制得的聚氨酯材料耐黄变,耐紫外线,稳定性好,应用范围更广。
此外,在扩链剂上选择了3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和1,4-环己烷二甲醇这三种低分子量的物质;这些物质中含有氨基,羟基等活性官能团,其中氨基,羟基均能与二异氰酸酯之间发生反应,生成富含-NHCON-,-NHCOO-的硬段,并且会形成氢键聚集区;并且研究发现短链扩链剂与长链扩链剂相搭配,其合成出来的聚氨酯弹性体具有更加良好的力学性能,而这是由于短链扩链剂缩短了硬段之间的距离,从而使硬段之间的氢键作用更加的明显,这也有利于硬段分子的聚集,促进了聚氨酯弹性体分子的微相分离,从而赋予了聚氨酯弹性体具有更好的力学性能;还意外的提高了材料的光学性能。
最终制得的聚氨酯材料具有较大的拉伸强度和硬度,机械性能好,同时无色透明,具有较高的折光率,光学性能好,特别适合作为光学材料使用。
以上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。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前提下的若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种透明聚氨酯光学材料,其特征在于:包括下列重量份物质组成:异氰酸酯 10-30份;
聚合物多元醇 10-30 份;
小分子多元醇 5-10 份;
催化剂 0.1-0.4 份;
扩链剂 2-6 份;
添加剂 1-4 份;
促进剂 1-4 份;
所述异氰酸酯为 1,4-双(异氰酸甲酯基)环己烷、异佛尔酮二异氰酸酯和对苯撑二异氰酸酯的混合物,其质量比为 2:2:1;
所述聚合物多元醇为聚四氢呋喃二醇和聚碳酸酯多元醇的混合物,其质量比为 3:1;
所述添加剂为 2,3-双(2-疏基乙硫基)-1-丙硫醇和 5-乙丙基硫代-1,3,4-噻二唑-2-硫醇的混合物,其质量比为 3:2;
所述促进剂包括下列摩尔份物质组成:4-(10H-吩噻嗪-10-基)苯胺 0.5-1.5份;聚甲氢硅氧烷 0.8-2.5 份;
所述小分子多元醇为 1,4-二羟基-2-丁烯和 1,4-丁二醇的混合物,其质量比为 1:2;
所述扩链剂为 3,4'-二氨基二苯醚、3-氨基-2-(4-氯苯基)-2-羟基丙烷磺酸钠和 1,4-环己烷二甲醇的混合物,其质量比为 1:1:1;
所述促进剂的制备方法包括以下步骤:
S1:根据设定的摩尔份配备原料,将 4-(10H-吩噻嗪-10-基)苯胺加入到装有
第一溶剂的反应容器中搅拌混合,再将温度升高至 70-90℃,接着向反应容器中加入铂金催化剂继续搅拌混合,混合均匀后,形成第一混合液;
S2:在氮气氛围下,将聚甲氢硅氧烷加入到第一混合液中搅拌混合,混合均匀后,在温度为 140-200℃的条件下进行反应,反应时间为 20-30h;反应结束后,过滤提纯烘干,制得促进剂。
2.根据权利要求 1 所述的一种透明聚氨酯光学材料,其特征在于:第一溶剂为甲苯和四氢呋喃的混合物,其体积比为 5:1。
3.根据权利要求 1 所述的一种透明聚氨酯光学材料,其特征在于:所述催化剂为二月桂酸二丁基锡。
4.根据权利要求 1-3任意一项所述的一种透明聚氨酯光学材料的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料:将聚合物多元醇、小分子多元醇、催化剂和添加剂加入反应容器中搅拌混合,在温度为 60-80℃的条件下混合 10-30min,形成第一混合物;
步骤二:将异氰酸酯在温度为 40-60℃的条件下,预热 20-40min 再加入到第一混合物中搅拌混合,形成第二混合物;然后在温度为 120-150℃的条件下,反应 1-3h;
步骤三:接着将扩链剂和促进剂加入到反应容器中搅拌混合物,混合均匀后,在温度为150-200℃的条件下,反应 15-25h,制得透明聚氨光学材料。
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