CN114045023A - 一种含有生物质填充材料的聚氨酯树脂及其制备和应用 - Google Patents
一种含有生物质填充材料的聚氨酯树脂及其制备和应用 Download PDFInfo
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- CN114045023A CN114045023A CN202111367314.1A CN202111367314A CN114045023A CN 114045023 A CN114045023 A CN 114045023A CN 202111367314 A CN202111367314 A CN 202111367314A CN 114045023 A CN114045023 A CN 114045023A
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Abstract
本发明提供了一种含有生物质填充材料的聚氨酯树脂及其制备和应用,含有生物质填充材料的聚氨酯树脂包括A组分和B组分;所述A组分包括如下重量份组分:
Description
技术领域
本发明涉及高分子材料技术领域,具体涉及一种含有生物质填充材料的聚氨酯树脂及其制备和应用方法。
背景技术
聚氨酯微孔弹性体由于其轻便性、舒适性、回弹性等功能,在鞋垫上的需求与日俱增。为达到较好的舒适性,聚氨酯鞋垫的成型密度较低普遍在0.1~0.3g/cm3,而微孔弹性体的密度较低,鞋垫的支撑性则会变差,容易受压变形且严重会导致行走不适。针对该技术问题,可通过在聚氨酯体系中添加填充材料,可以增加鞋垫支撑性的同时也可以降低原料成本。然而,一方面填充材料与聚氨酯的相容性较差,影响聚氨酯的发泡效果且造成微孔弹性体力学性能的下降;另一方面填充材料的引入过多又会造成鞋垫密度和硬度的增加,回弹效果也变差,影响穿着舒适感;
现有技术中,还无法解决在聚氨酯体系中添加高含量的填充材料的情况下,既能确保填充材料与聚氨酯树脂的相容性,又能保证制备得到的聚氨酯微孔弹性鞋垫同时具备低密度、高回弹及优异的力学性能。
发明内容
技术问题:本发明的目的是提供一种含有生物质填充材料的聚氨酯树脂及其制备和应用,克服现有技术的不足,制备得到的聚氨酯微孔弹性体泡孔结构均匀、产品成型密度低、回弹性好且力学性能优异。
技术方案:本发明的一种含有生物质填充材料的聚氨酯树脂包括A组分和B组分;所述A组分包括如下重量份组分:
所述B组分包括如下重量份组分:
多异氰酸酯 100份;
聚合物多元醇 0~30份;
生物质填充材料添加至A组分或B组分,添加量为聚氨酯树脂质量的15~45%。
其中,
所述A组分中羟基与所述B组分中异氰酸酯基的摩尔比为0.90:1~1.25:1。
所述A组分和所述B组分中的聚合物多元醇各自独立地为乙二醇、一缩二乙二醇或丙三醇中的一种以上为起始剂,由环氧丙烷开环和/或环氧乙烷聚合得到,官能度为2~3,数均分子量为2000~5000;或
所述A组分和所述B组分中的聚合物多元醇各自独立地为己二酸与乙二醇、1,4-丁二醇、一缩二乙二醇、1,3-丙二醇、新戊二醇中的一种及一种以上聚合反应得到,官能度为2~3,数均分子量为2000~5000。
所述的扩链剂为乙二醇、1,4-丁二醇、1,2-丙二醇、1,3-丙二醇或一缩二乙二醇中的中的一种及以上,优选为乙二醇、1,4丁二醇,1,3-丙二醇中的中的一种及以上;
所述的发泡剂包括水、一氟二氯乙烷或环戊烷中的一种及以上;
所述的催化剂包括叔胺类、有机锡类中的一种及以上;
所述的多异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、脲酮亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯或亚甲基二(环己基二异氰酸酯)以及其异构体和/或衍生物和/或改性聚合物中的一种及以上。
所述的生物质填充材料是以多聚糖为壳生物质粉末为核且外表面含有羟基基团的微球;
所述的多聚糖为壳聚糖及其衍生物中的一种及以上;
壳聚糖衍生物包括羧甲化壳聚糖、酰化壳聚糖的一种及两种组合;
所述的生物质粉末为竹炭粉末、木粉末、玉米秸秆粉末、稻壳粉末、花生壳粉末;
所述的微球粒径为2~50μm。
所述的生物质填充材料通过乳化交联方法制备,将含有生物质粉末和多聚糖的分散水溶液与含有乳化剂的油溶液充分搅拌混合均匀,加入交联剂进行交联反应得到所述的生物质填充材料;
其中,所述的乳化剂包括SPAN-80、SPAN-60、SPAN-40中的一种及以上;
油溶液的油溶剂包括石蜡、植物油、甲苯、石油醚中的一种及以上;
所述的交联剂包括戊二醛、己二醛、京尼平中的一种及以上;
所述的分散水溶液与油溶液的质量比为1:5~20;
所述的分散水溶液中生物质粉末和多聚糖的总质量浓度为6~18%,其中,生物质粉末和多聚糖的质量比为1:1~5:1;
所述的乳化剂添加量为3~10%,基于油溶剂的质量来计算;
所述的交联剂添加量为0.5~2%,基于油溶剂的质量来计算。
所述的A组分的制备原料中还包括添加剂、匀泡剂、阻燃剂、流平剂、表面活性剂、抗氧剂、抗菌剂、颜料、多官交联剂中的至少一种。
所述的B组分的制备原料中还包括磷酸做为副反应阻止剂。
本发明的含有生物质填充材料的聚氨酯树脂的制备方法包括以下步骤:
制备A组分:
将聚合物多元醇、扩链剂、发泡剂、催化剂、生物质填充材料、添加剂在常温下充分混合均匀得到A组分;
制备B组分:
将多异氰酸酯、聚合物多元醇、副反应阻止剂在在60~80℃条件下反应1~3小时,降至常温得到B组分。
本发明的含有生物质填充材料的聚氨酯树脂的应用,是通过将A组分、B组分混合浇注于模具中发泡得到聚氨酯微孔弹性体用于鞋垫、枕头、瑜伽垫的制备;聚氨酯微孔弹性体制品的密度为0.1~0.3g/cm3,拉伸强度为0.2~0.7Mpa,撕裂强度为0.9~1.8KN/m,回弹性为20~45%。
采用本发明的方法得到的聚氨酯微孔弹性体制品的密度为0.1~0.3g/cm3,拉伸强度为0.2~0.7Mpa,撕裂强度为0.9~1.8KN/m,回弹性为20~45%。
有益效果:所述的聚氨酯微孔弹性体制品主要用于鞋垫、枕头、瑜伽垫的制备,生物质填充材料可达30%以上,甚至可达45%,制备得到的聚氨酯微孔弹性体泡孔结构均匀、产品成型密度低、回弹性好且力学性能优异。
1.通过纳米载药微球成型技术,将生物质粉末封装在与聚氨酯原液相容性良好的壳聚糖及其衍生物内,形成表面核壳结构的微米级微球作为含有生物质填充材料。
2.含有生物质填充材料其表面上含有大量的羟基,将其添加至组合物中可进一步参与聚氨酯的反应,更重要的是,在微孔弹性体发泡成型过程中微球可附着在聚氨酯微孔弹性体的孔壁上,填充材料不仅可以作为生物质粉末的运输载体,同时可以作为聚氨酯弹性体的增强相。
3.参与反应的填充材料微球作为交联位点,有效调控泡孔结构,避免了传统聚氨酯制品的易炸泡的问题,有效降低了低密度发泡材料的次品率。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
所述的生物质填充材料为多聚糖为壳生物质粉末为核且外表面含有羟基基团的微球;
所述的多聚糖为壳聚糖及其衍生物中的一种及以上;
进一步的,壳聚糖衍生物包括羧甲化壳聚糖及、酰化壳聚糖的一种及两种组合;
所述的生物质粉末为竹炭粉末、木粉末、玉米秸秆粉末、稻壳粉末、花生壳粉末;
所述的微球粒径为2~50μm;
作为示例的,本申请一些实施例中多聚糖采用壳聚糖,生物质粉末采用竹炭粉末、木粉末;
所述的生物质填充材料通过乳化交联方法制备得到,将含有生物质粉末和多聚糖的分散水溶液与含有乳化剂的油溶液充分搅拌混合均匀,加入交联剂进行交联反应得到所述的生物质填充材料;
其中,所述的乳化剂包括SPAN-80、SPAN-60、SPAN-40中的一种及以上;
所述的油溶液的油溶剂包括石蜡、植物油、甲苯、石油醚中的一种及以上;
所述的交联剂包括戊二醛、己二醛、京尼平中的一种及以上;
所述的分散水溶液与油溶液的质量比为1:5~20;
所述的分散水溶液中生物质粉末和多聚糖的总质量浓度为6~18%,其中,生物质粉末和多聚糖的质量比为1:1~5:1;
所述的乳化剂添加量为3~10%,基于油溶剂的质量来计算;
所述的交联剂添加量为0.5~2%,基于油溶剂的质量来计算;
作为示例,生物质填充材料具体步骤包括:
分散水溶液制备:在温度30~60℃下,将羧甲多聚糖溶于去离子水得到多聚糖溶液,再加入生物质粉末与羧甲多聚糖溶液搅拌混合均匀得到分散水溶液;
油溶液制备:在温度下30~60℃,将乳化剂加入到油溶剂的中搅拌混合得到油溶液;
在室温下,将分散水溶液与油溶液搅拌混合均匀后,加入交联剂后继续搅拌反应,最后离心洗涤并干燥后得到生物质填充材料。
所述的含有所述的生物质填充材料的聚氨酯,包括A、B组分;
所述A组分的制备原料包括如下重量份组分:
所述B组分的制备原料包括如下重量份组分:
多异氰酸酯 100份;
聚合物多元醇 0~30份;
所述的生物质填充材料可添加至A组分或B组分,优选添加至A组分中,添加量为15~45%,基于聚氨酯的质量来计算;
所述A组分中羟基和所述B组分中异氰酸酯基的摩尔比为0.90:1~1.25:1;
所述A组分和所述B组分中的聚合物多元醇各自独立地为乙二醇、一缩二乙二醇或丙三醇中的一种以上为起始剂,由环氧丙烷开环和/或环氧乙烷聚合得到的聚醚多元醇,官能度为2~3,数均分子量为2000~5000;
所述A组分和所述B组分中的聚合物多元醇各自独立地为己二酸与乙二醇、1,4-丁二醇、一缩二乙二醇、1,3-丙二醇、新戊二醇中的一种及一种以上聚合反应得到,官能度为2~3,数均分子量为2000~5000;
所述的扩链剂为乙二醇、1,4-丁二醇、1,2-丙二醇、1,3-丙二醇或一缩二乙二醇中的中的一种及以上,优选为乙二醇、1,4丁二醇,1,3-丙二醇中的中的一种及以上;
所述的交联剂为三羟甲基丙烷、甘油、三乙醇胺、二乙醇胺中的一种及以上;
所述的发泡剂包括水、一氟二氯乙烷或环戊烷中的一种及以上;
所述的催化剂包括叔胺类、有机锡类中的一种及以上;
例如,三乙烯二胺、辛酸亚锡、双(二甲氨基乙基)醚中的一种及以上;
所述的多异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、脲酮亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯或亚甲基二(环己基二异氰酸酯)以及其异构体和/或衍生物和/或改性聚合物中的一种及以上;
优选的,所述A组分的制备原料中还包括为本领域常用添加剂,包括匀泡剂、阻燃剂、流平剂、表面活性剂、抗氧剂、抗菌剂、颜料、多官交联剂中的至少一种;
对于添加剂的量没有明确要求,可根据本领域常规使用来进行添加,不对聚氨酯的性能造成劣化即可;
优选地,所述B组分的制备原料中还包括副反应阻止剂;
优选地,所述副反应阻止剂为磷酸。
所述的聚氨酯树脂的制备方法,其特征在于包括以下步骤:
制备A组分:
将聚合物多元醇、扩链剂、发泡剂、催化剂、任选的添加剂在常温下充分混合均匀得到A组分;
制备B组分:
将多异氰酸酯、聚合物多元醇、任选的副反应阻止剂在在60~80℃条件下反应1~3小时,降至常温得到B组分;
所述的生物质填充材料添加至A组分或B组分,优选添加至A组分中。
本发明还提供由所述的聚氨酯树脂得到聚氨酯微孔弹性体,通过将A、B组分混合浇注与模具中发泡得到。
在本发明中,A、B组分分别加入发泡浇筑机中,A组分维持温度35~45℃,B组分维持温度35~45℃,通过浇注机将两组分混合均匀后注入模具中,发泡反应成型后即得聚氨酯微孔弹性体制品。
作为示例的,聚氨酯微孔弹性体的具体制备:
A组分中的温度控制在35~45℃,B组分的温度在35~45℃,控制A组分中羟基和所述B组分中异氰酸酯基的摩尔比为0.90:1~1.25:1混合后注入35~45℃模具反应2~6min成型,脱模,熟化45~50h,得到所述的聚氨酯微孔弹性体制品。
以下结合具体实施例进一步描述本发明,但不限制本发明范围。
生物质填充材料的制备:
生物质填充材料1:
分散水溶液制备:在温度45℃下,将多聚糖溶于去离子水得到5%的多聚糖溶液,再加入生物质粉末与多聚糖溶液搅拌混合均匀得到分散水溶液,其中,生物质粉末和多聚糖的质量比为1:1;
油溶液制备:在温度下45℃,将乳化剂加入到油溶剂的中搅拌混合得到1%的油溶液;
在室温下,将分散水溶液与油溶液按照质量比为1:10搅拌混合均匀后,加入0.5%交联剂后(基于油溶剂的质量),继续搅拌反应60min,离心洗涤并干燥后得到生物质填充材料。
生物质填充材料2:
在温度45℃下,将多聚糖溶于去离子水得到5%的多聚糖溶液,再加入生物质粉末与多聚糖溶液搅拌混合均匀得到分散水溶液,其中,生物质粉末和多聚糖的质量比为1:1,离心洗涤并干燥后得到生物质填充材料2。
本发明实施例、对比例的聚氨酯制备所用到的原料具体如下:
本发明实施例和对比例聚氨酯的原料组分如下:
实施例1
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
聚合MDI 100份;
所述的生物质填充材料1添加至A组分,添加量为35%,基于聚氨酯的质量来计算。
实施例2
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
聚合MDI 100份;
EG-5000 20份;
所述的生物质填充材料1添加至A组分,添加量为15%,基于聚氨酯的质量来计算。
实施例3
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 12份;
聚合MDI 88份;
PBEA-2000 30份;
所述的生物质填充材料1添加至A组分,添加量为30%,基于聚氨酯的质量来计算。
实施例4
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 100份;
PBA-2000 10份;
所述的生物质填充材料1添加至A组分,添加量为45%,基于聚氨酯的质量来计算。
实施例5
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 8份;
聚合MDI 92份;
所述的生物质填充材料1添加至A组分,添加量为20%,基于聚氨酯的质量来计算。
实施例6
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 8份;
聚合MDI 92份;
所述的生物质填充材料1添加至A组分,添加量为20%,基于聚氨酯的质量来计算。
实施例7
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 8份;
聚合MDI 92份;
所述的生物质填充材料1添加至A组分,添加量为20%,基于聚氨酯的质量来计算。
实施例8
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
MDI 100份;
所述的生物质填充材料1添加至A组分,添加量为35%,基于聚氨酯的质量来计算。
实施例9
A组分的制备原料包括如下重量份组分:
B组分的制备原料包括如下重量份组分:
聚合MDI 100份;
所述的生物质填充材料1添加至B组分,添加量为35%,基于聚氨酯的质量来计算。
对比例1
与实施例1的差别在于,A组分中不添加生物质填充材料1,其他一致。
对比例2
与实施例4的差别在于,将生物质填充材料1替换为常规竹炭粉末,其他一致。
对比例3
与实施例4的差别在于,将生物质填充材料1替换为生物质填充材料2,其他一致。
聚氨酯微孔弹性体的制备:
将生物质粉末添加至A组分或B组分中搅拌均匀,A组分的温度控制在35~45℃,B组分的温度在35~45℃,控制A组分中羟基和所述B组分中异氰酸酯基的摩尔比为0.90:1~1.25:1混合后注入35~45℃模具反应2~6min成型,脱模,熟化45~50h,得到所述的聚氨酯微孔弹性体制品。
为明确说明本发明技术效果,实施例和对比例的A组分温度为35℃,B组分温度为35℃,并且控制A组分中羟基和所述B组分中异氰酸酯基的摩尔比为1:1,注入模具的组分的质量保持一致从而得到发泡平均密度为0.15g/cm3的样品。
将成型得到的聚氨酯微孔弹性体进行性能测试,测试项目如下:
注:拉伸强度、撕裂强度、断裂伸长率的试样厚度为6mm。
根据上述实施例及对比例的数据表明,采用本发明方法得到的聚氨酯微孔弹性体产品表现出十分优异的性能。
Claims (10)
2.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述A组分中羟基与所述B组分中异氰酸酯基的摩尔比为0.90:1~1.25:1。
3.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述A组分和所述B组分中的聚合物多元醇各自独立地为乙二醇、一缩二乙二醇或丙三醇中的一种以上为起始剂,由环氧丙烷开环和/或环氧乙烷聚合得到,官能度为2~3,数均分子量为2000~5000;或
所述A组分和所述B组分中的聚合物多元醇各自独立地为己二酸与乙二醇、1,4-丁二醇、一缩二乙二醇、1,3-丙二醇、新戊二醇中的一种及一种以上聚合反应得到,官能度为2~3,数均分子量为2000~5000。
4.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述的扩链剂为乙二醇、1,4-丁二醇、1,2-丙二醇、1,3-丙二醇或一缩二乙二醇中的中的一种及以上,优选为乙二醇、1,4丁二醇,1,3-丙二醇中的中的一种及以上;
所述的发泡剂包括水、一氟二氯乙烷或环戊烷中的一种及以上;
所述的催化剂包括叔胺类、有机锡类中的一种及以上;
所述的多异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、脲酮亚胺改性二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯或亚甲基二(环己基二异氰酸酯)以及其异构体和/或衍生物和/或改性聚合物中的一种及以上。
5.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述的生物质填充材料是以多聚糖为壳生物质粉末为核且外表面含有羟基基团的微球;
所述的多聚糖为壳聚糖及其衍生物中的一种及以上;
壳聚糖衍生物包括羧甲化壳聚糖、酰化壳聚糖的一种及两种组合;
所述的生物质粉末为竹炭粉末、木粉末、玉米秸秆粉末、稻壳粉末、花生壳粉末;
所述的微球粒径为2~50μm。
6.根据权利要求5所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述的生物质填充材料通过乳化交联方法制备,将含有生物质粉末和多聚糖的分散水溶液与含有乳化剂的油溶液充分搅拌混合均匀,加入交联剂进行交联反应得到所述的生物质填充材料;
其中,所述的乳化剂包括SPAN-80、SPAN-60、SPAN-40中的一种及以上;
油溶液的油溶剂包括石蜡、植物油、甲苯、石油醚中的一种及以上;
所述的交联剂包括戊二醛、己二醛、京尼平中的一种及以上;
所述的分散水溶液与油溶液的质量比为1:5~20;
所述的分散水溶液中生物质粉末和多聚糖的总质量浓度为6~18%,其中,生物质粉末和多聚糖的质量比为1:1~5:1;
所述的乳化剂添加量为3~10%,基于油溶剂的质量来计算;
所述的交联剂添加量为0.5~2%,基于油溶剂的质量来计算。
7.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述的A组分的制备原料中还包括添加剂、匀泡剂、阻燃剂、流平剂、表面活性剂、抗氧剂、抗菌剂、颜料、多官交联剂中的至少一种。
8.根据权利要求1所述的含有生物质填充材料的聚氨酯树脂,其特征在于所述的B组分的制备原料中还包括磷酸做为副反应阻止剂。
9.一种如权利要求1、7或8所述的含有生物质填充材料的聚氨酯树脂的制备方法,其特征在于该制备方法包括以下步骤:
制备A组分:
将聚合物多元醇、扩链剂、发泡剂、催化剂、生物质填充材料、添加剂在常温下充分混合均匀得到A组分;
制备B组分:
将多异氰酸酯、聚合物多元醇、副反应阻止剂在在60~80℃条件下反应1~3小时,降至常温得到B组分。
10.一种如权利要求1所述的含有生物质填充材料的聚氨酯树脂的应用,其特征在于通过将A组分、B组分混合浇注于模具中发泡得到聚氨酯微孔弹性体用于鞋垫、枕头、瑜伽垫的制备;聚氨酯微孔弹性体制品的密度为0.1~0.3g/cm3,拉伸强度为0.2~0.7Mpa,撕裂强度为0.9~1.8KN/m,回弹性为20~45%。
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