CN114181514A - 用于制造具有低含量的挥发性有机化合物的聚氨酯泡沫的组合物和用其制造聚氨酯的方法 - Google Patents
用于制造具有低含量的挥发性有机化合物的聚氨酯泡沫的组合物和用其制造聚氨酯的方法 Download PDFInfo
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- CN114181514A CN114181514A CN202111073176.6A CN202111073176A CN114181514A CN 114181514 A CN114181514 A CN 114181514A CN 202111073176 A CN202111073176 A CN 202111073176A CN 114181514 A CN114181514 A CN 114181514A
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- composition
- polyol
- polyurethane foam
- reactor
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- 229920002635 polyurethane Polymers 0.000 title description 2
- 239000004814 polyurethane Substances 0.000 title description 2
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- 150000003077 polyols Chemical class 0.000 claims abstract description 87
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- 229920000638 styrene acrylonitrile Polymers 0.000 claims 1
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- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WVVOBOZHTQJXPB-UHFFFAOYSA-N N-anilino-N-nitronitramide Chemical compound [N+](=O)([O-])N(NC1=CC=CC=C1)[N+](=O)[O-] WVVOBOZHTQJXPB-UHFFFAOYSA-N 0.000 description 1
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 238000002144 chemical decomposition reaction Methods 0.000 description 1
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08G18/4825—Polyethers containing two hydroxy groups
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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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- C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Toxicology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
公开一种用于制造具有低含量的诸如乙醛的挥发性有机化合物的聚氨酯泡沫的组合物,和使用所述组合物制造聚氨酯泡沫的方法。用于制造聚氨酯泡沫的组合物包括聚丙二醇含量为0.1ppm或更少并且环氧丙烷含量为16ppm或更少的多元醇组合物、异氰酸酯和挥发性有机化合物(VOC)减少剂。用于制造聚氨酯泡沫的方法包括将原料添加到反应器以使多元醇组合物聚合,从反应器去除杂质;和从去除杂质的反应物获得聚氨酯泡沫。
Description
技术领域
本公开涉及一种用于制造具有低含量的诸如乙醛的挥发性有机化合物的聚氨酯泡沫的组合物,和使用所述组合物制造聚氨酯泡沫的方法。
背景技术
车辆的座椅是允许乘员坐在其上并驾驶车辆的部件。座椅占据了车辆内饰材料的大部分体积。座椅中包括的座垫根据诸如缓冲性、回弹性、经济可行性和量产可行性等要求大部分使用聚氨酯泡沫制造。
用于片材的聚氨酯泡沫使用多元醇体系之间的加成聚合反应制造,该多元醇体系包括催化剂、表面活性剂、发泡剂和异氰酸酯。然而,挥发性有机化合物(VOC),诸如苯和甲苯醛,在短时间内和/或连续地从制造的聚氨酯泡沫中释放出来。
挥发性有机化合物(VOC)为烃化合物并且为致癌材料。此外,挥发性有机化合物(VOC)气味难闻,并通过呼吸吸入引起神经系统疾病和病屋综合症。因此,国土交通省自2011年以来评估和管理车辆的空气质量,以减少新车辆内饰材料中使用的材料和粘合剂产生的挥发性有机化合物(VOC)的量。
国土交通省2019年在现有的七项有害物质管理标准中新增一项有害物质(乙醛),因此确定总共八种要管理的组分,从而强化了国土交通省公布的标准(第2019-144号)。
因此,所有车辆制造商都需要对车辆内饰材料的质量进行管理,以便满足上述八种组分的标准。
发明内容
本公开的目的是提供一种聚氨酯泡沫,其通过对包括VOC减少剂的原料进行升级和优化混合,能够符合管理挥发性有机化合物的法律法规。
本公开的目的不限于上述目的,并且通过以下描述可理解其它目的,并且通过权利要求中描述的组合物和方法和其组合来实现。
用于制造根据本公开的聚氨酯泡沫的组合物包括聚丙二醇含量为0.1ppm或更少并且环氧丙烷含量为16ppm或更少的多元醇组合物、异氰酸酯和挥发性有机化合物(VOC)减少剂。
多元醇组合物的羟值可为20至30毫克(mg)KOH/g。
多元醇组合物在25℃下的粘度可为1000至2000厘泊(cps)。
多元醇组合物可包括至少一种选自以下的多元醇:第一多元醇,其分子量为7000至8000g/mol,羟值为20至26mg KOH/g,并且在25℃下的粘度为为1200至1600cps;第二多元醇,其分子量为4000至5000g/mol、羟值为32至38mg KOH/g,并且在25℃下的粘度为800至1000cps;第三多元醇,其分子量为5500至6500g/mol,羟值为22至30mg KOH/g,并且在25℃下的粘度为1000至1400cps;第四多元醇,其分子量为3500至4500g/mol,羟值为40至45mgKOH/g,并且在25℃下的粘度为900至1000cps;和其组合。
多元醇组合物还可包括多元醇聚合物(POP),并且该多元醇聚合物可包括接枝有苯乙烯丙烯腈(SAN)的多元醇。
VOC减少剂可包括选自以下的至少一种试剂:羟胺、硫酸羟胺、N-甲基乙醇胺、乙醇胺、三(羟甲基)氨基甲烷和其组合。
用于制造聚氨酯泡沫的组合物可包括100重量份的多元醇组合物、40至60重量份的异氰酸酯和0.1至2重量份的VOC减少剂。
制造根据本公开的聚氨酯泡沫的方法包括将原料添加到反应器以使多元醇组合物聚合,从反应器去除杂质,和从去除杂质且含有多元醇组合物、异氰酸酯和VOC减少剂的反应物获得聚氨酯泡沫。
在制造方法中,可将选自以下的至少一种流体供应到反应器以去除杂质:CO2、N2、蒸汽、蒸馏水、硫酸、盐酸和其组合。
在制造方法中,可以20至200kg/小时的流速供应流体1至2小时。
在制造方法中,可供应流体,将反应器的温度调节到80至100℃,并且可将压力调节到0.5至1巴。
在制造方法中,可将流体供应到反应器以与杂质反应,并且由于反应产生的气体可释放到外部,由此去除杂质。
在制造方法中,在杂质和流体之间的反应完成后,可将反应器的压力调节到0.5至0.97巴,由此将气体释放到外部。
根据本公开,可获得一种聚氨酯泡沫,其通过对包括VOC减少剂的原料进行升级和优化混合,能够符合管理挥发性有机化合物的法律法规。
本公开的效果不限于前述效果,并且应当理解为包括可从以下描述中合理地预期的所有效果。
具体实施方式
通过以下实施例,可更清楚地理解本公开的上述和其它目的、特征和优点。然而,本公开不限于本文公开的实施例并且可被修改成不同的形式。提供这些实施例以彻底解释本公开并且将本公开的精神充分传达给本领域技术人员。
虽然本文可使用诸如“第一”、“第二”等术语来描述各种元件,但是这些元件不限于这些术语。这些术语仅用于将一个元件与另一个元件区分。例如,在不脱离本公开的范围的情况下,下文讨论的“第一”元件可被称为“第二”元件。类似地,“第二”元件也可被称为“第一”元件。如本文所用,除非上下文另外明确指出,否则单数形式也旨在包括复数形式。
当在本说明书中使用时,术语“包含(comprise)”、“包括(include)”、“具有”等规定存在所陈述的特征、整数、步骤、操作、元件、部件或其组合,但是不排除存在或增加一个或多个其它特征、整数、步骤、操作、元件、部件或其组合。此外,应当理解,当诸如层、膜、区域或片材的元件被称为在另一个元件“上”时,它可直接在另一个元件上,或可在其间存在中间元件。类似地,当诸如层、膜、区域或片材的元件被称为在另一个元素“下方”时,它可直接在另一个元件下方,或可在其间存在中间元件。
除非另有指明,否则表示本文所用的组分、反应条件、聚合物组合物和混合物的量的所有数字、值和/或表示将被视为包括影响测量的各种不确定性的近似值,这些不确定性固有地发生在获得这些值时,以及因此在所有情况下都应理解为由术语“约”修饰。此外,除非另外指明,否则当本说明书中公开数值范围时,所述范围为连续的,并且包括从所述范围的最小值到其最大值的所有值。此外,除非另外指明,否则当此类范围涉及整数值时,包括最小值到最大值的所有整数。
已知从聚氨酯泡沫释放乙醛的原因是在多元醇聚合期间产生的杂质引起与异氰酸酯的副反应而直接变成乙醛,或产品由于暴露于高温或紫紫外线发生化学分解,由此生成乙醛。
在本公开中,在多元醇组合物的聚合期间添加汽提工艺以从多元醇组合物去除杂质,这可能是产生乙醛的直接原因。另外,在本公开中,将VOC减少剂以用于制造聚氨酯泡沫的组合物的原料添加,由此减少释放的乙醛的量。
在下文中,参考本公开的具体细节来描述本公开。
制造根据本公开的聚氨酯泡沫的方法包括将原料添加到反应器以使多元醇组合物聚合,从反应器去除杂质,和从去除杂质且含有多元醇组合物、异氰酸酯和VOC减少剂的反应物获得聚氨酯泡沫。
原料没有特别限制。原料的实例可包括乙二醇、二甘醇、二丙二醇、甘油、三羟甲基丙烷、乙二胺、三乙醇胺、甲苯二胺、山梨糖醇和蔗糖。
多元醇组合物可通过使原料聚合来制造。例如,可将诸如环氧乙烷和环氧丙烷的扩链材料、诸如氢氧化钾(KOH)、氢氧化铯(CsOH)的催化剂添加到原料,并且然后反应以由此获得多元醇组合物。
多元醇组合物的聚合时间没有特别限制。例如,聚合时间可为足以使原料充分反应的时间,并且聚合可进行约20至35小时。
此后,从如上聚合的多元醇组合物去除杂质。具体地,可将选自以下的至少一种流体供应到反应器以去除杂质:二氧化碳(CO2)、氮气(N2)、蒸汽、蒸馏水、硫酸、盐酸和其组合。将流体供应到反应器,使得多元醇组合物聚合过程中生成的杂质与流体反应,并且使其产物挥发。
可以20至200kg/hr的流速供应流体1至2小时。然而,流体的流速和供应时间可根据反应器的大小和原料的量适当地调节。
可供应流体,将反应器的温度调节到80至100℃,并且可将压力调节到0.5至1巴,使得流体与杂质反应,并且使所得材料挥发。
在杂质和流体之间的反应完成后,可将反应器的压力调节到0.5至0.97巴,使得挥发的所得材料释放到外部,由此被去除。
此后,可通过脱水过程从已经去除杂质的多元醇组合物去除水分,并且然后可将多元醇组合物转移到储存罐中进行储存。多元醇组合物的储存温度可为50至70℃。然而,可将多元醇组合物直接转移到后续阶段以制造聚氨酯泡沫而无需存储。
如上所述获得的已去除杂质的多元醇组合物具有以下特征。
多元醇组合物的聚丙二醇(PPG)含量为0.1ppm或更少,并且环氧丙烷(PO)含量为16ppm或更少。
聚丙二醇和环氧丙烷的含量的下限没有特别限制,并且例如各自可大于0ppm。
由于上述多元醇组合物的聚丙二醇(PPG)和环氧丙烷(PO)的含量低于常规组合物,因此减少后续与异氰酸酯反应期间由于副反应而释放的乙醛量。
同时,多元醇组合物的羟值可为20至30mg KOH/g,并且在25℃下的粘度为1000至2000cps。
由于多元醇组合物的羟值和粘度等于常规组合物,因此使用所述多元醇组合物制造的聚氨酯泡沫的理化特性与常规组合物相同或相似。
在以下条件下,多元醇组合物可包括选自以下的至少一种:第一多元醇、第二多元醇、第三多元醇、第四多元醇和其组合。
第一多元醇为分子量为7000至8000g/mol,羟值为20至26mg KOH/g,并且在25℃下的粘度为1200至1600cps的多元醇;
第二多元醇为分子量为4000至5000g/mol,羟值为32至38mg KOH/g,并且在25℃下的粘度为800至1000cps的多元醇;
第三多元醇为分子量为5500至6500g/mol,羟值为22至30mg KOH/g,并且在25℃下的粘度为1000至1400cps的多元醇;
第四多元醇为分子量为3500至4500g/mol,羟值为40至45mg KOH/g,并且在25℃下的粘度为900至1000cps的多元醇。
然而,本公开的特征在于降低聚丙二醇(PPG)和环氧丙烷(PO)的含量,其导致从如上所述的多元醇组合的多元醇组合物中产生乙醛。因此,尽管多元醇的具体组合和混合比例有所变化,但是如果满足本公开的特征,那么应认为它们属于本公开的范围。
同时,多元醇组合物还可包括多元醇聚合物(POP)。多元醇聚合物(POP)为提高聚氨酯泡沫硬度的成分。其类型没有特别限制,但是其实例可包括接枝有苯乙烯丙烯腈(SAN)的多元醇。
以多元醇组合物的总重量计,多元醇聚合物(POP)的含量可为30wt%或更少。当多元醇聚合物(POP)的含量大于30wt%时,由于聚氨酯泡沫的硬度变得非常高,乘员可能会抱怨座椅不舒服。
最后,聚氨酯泡沫可由含有已从中去除杂质的多元醇组合物、异氰酸酯和VOC减少剂的反应物获得。
异氰酸酯的类型没有特别限制。其实例可包括芳族异氰酸酯(例如甲苯二异氰酸酯)和/或脂肪族异氰酸酯(例如六亚甲基二异氰酸酯)。
在本公开中,将VOC减少剂应用到用于制造聚氨酯泡沫的组合物,从而防止由于多元醇组合物的未反应的材料未去除而生成乙醛。
VOC减少剂用于减少甲醛和丙烯醛的释放。具体地,VOC减少剂可具有液体形式,并且可以包括具有胺基的化合物、抗氧化剂、表面活性剂和具有羟基的溶剂。
为了提高减少乙醛的效率,可使用基于羟基的胺作为具有胺基的化合物。基于羟基的胺在碱性条件下可具有优异的反应性并且可与醛化合物键合以转化成肟,使得在氨酯合成期间醛被减少的效率能够最大化。
基于羟基的胺可包括选自以下的至少一种胺:羟胺、硫酸羟胺、N-甲基乙醇胺、乙醇胺、三(羟甲基)氨基甲烷和其组合。
聚氨酯泡沫的反应物可包括100重量份的多元醇组合物、40至60重量份的异氰酸酯和0.1至2重量份的VOC减少剂。
当VOC减少剂的含量大于2重量份时,高反应性VOC减少剂可能参与氨酯反应,这可能导致聚氨酯泡沫不成型或刚性变差。
反应物还可包括添加剂,诸如催化剂、表面活性剂和发泡剂。
在下文中,基于实例更详细地描述本公开,但是本公开不受以下实例限制。
实施例1、实施例2、比较例1和比较例2
基于根据下表1的组合物制备用于制造聚氨酯泡沫的组合物。
[表1]
在表1中,多元醇组合物1进行根据本公开的杂质去除过程,而多元醇组合物2没有进行。
如下对每种组合物进行发泡,由此制造用于片材的聚氨酯泡沫。
将每种组合物注射到模具的下部。当注射完成时,闭合模具顶板,并且在模具温度为55至65℃下进行固化4至6分钟。将聚氨酯泡沫从模具脱模,然后在50RH%的条件下,在25℃下稳定12小时或更长。
如上制造的聚氨酯泡沫的每种物理特性如下测量。
实验实例1-发泡特性
测量沉降和上升时间以检查根据实施例1和2以及比较例1和2的组合物的发泡特性的差异。
“沉降”是指通过聚氨酯泡沫自由发泡获得的最大高度和由于二氧化碳从聚氨酯泡沫释放到外部而导致的高度下降之间的下降率。
上升时间是聚氨酯泡沫发泡反应完成所需的时间,其与聚氨酯泡沫的化学反应速率有关。
上述发泡特性影响最终产品的特性。
结果在下表2示出。
[表2]
参考表2,实施例的发泡特性与比较例的发泡特性相似。因此,可间接证实,即使当如在本公开中使用进行杂质去除过程的多元醇组合物,最终产品的理化特性将不发生变化。
实验实例2–理化特性
测量使用根据实施例1和2以及比较例1和2的组合物制造的聚氨酯泡沫的硬度和永久压缩收缩率。结果在下表3示出。
[表3]
参考表3,实施例的每种聚氨酯泡沫的硬度和永久压缩收缩率与各比较例的硬度和永久压缩收缩率相同或相似。因此,可看出,即使当如在本公开中使用进行杂质去除过程的多元醇组合物并且使用添加VOC减少剂的反应物时,最终产品所需的特性也能够保持。
实验实例3–释放的醛的量
如下测量从使用根据实施例1和2以及比较例1和2的组合物制造的聚氨酯泡沫释放的醛的量。
将每种聚氨酯泡沫放入满足KS I ISO 12219-4‘车内空气-第4部分:测量从车辆内部部件释放的挥发性有机化合物的方法-小室测试方法’的测试条件的1m3室中。使聚氨酯泡沫在室温度为约65℃并且相对湿度为约5%的条件下静置约2小时。室中的空气被吸附到DNPH(二硝基苯肼)料盒上。使用HPLC分析来分析释放的醛组分的量。
结果在下表4示出。
[表4]
参考表4,从实施例的聚氨酯泡沫释放的醛化合物(例如乙醛、甲醛和丙烯醛)的量大大减少。将实施例1和比较例1相比,乙醛的释放减少83%,甲醛减少98%,丙烯醛减少80%。因此,可看出,如在本公开中使用进行杂质去除过程的多元醇组合物和使用添加VOC减少剂的反应物,大大减少从聚氨酯泡沫释放的乙醛的量。
尽管本文已描述本公开的具体实施例,但是本领域技术人员将理解,本公开可以其它具体形式实施而不改变其技术精神或基本特征。因此,上述实施例应被理解为在各个方面都是非限制性和说明性的。
Claims (13)
1.一种用于制造聚氨酯泡沫的组合物,所述组合物包含:
多元醇组合物,其聚丙二醇含量为0.1ppm或更少,并且环氧丙烷含量为16ppm或更少;
异氰酸酯;和
挥发性有机化合物减少剂。
2.根据权利要求1所述的组合物,其中所述多元醇组合物的羟值为20至30mg KOH/g。
3.根据权利要求1所述的组合物,其中所述多元醇组合物在25℃下的粘度为1000至2000cps。
4.根据权利要求1所述的组合物,其中所述多元醇组合物包括选自以下的至少一种多元醇:
第一多元醇,其分子量为7000至8000g/mol,羟值为20至26mg KOH/g,并且在25℃下的粘度为1200至1600cps;
第二多元醇,其分子量为4000至5000g/mol,羟值为32至38mg KOH/g,并且在25℃下的粘度为800至1000cps;
第三多元醇,其分子量为5500至6500g/mol,羟值为22至30mg KOH/g,并且在25℃下的粘度为1000至1400cps;
第四多元醇,其分子量为3500至4500g/mol,羟值为40至45mg KOH/g,并且在25℃下的粘度为900至1000cps;和
其组合。
5.根据权利要求1所述的组合物,其中所述多元醇组合物还包括多元醇聚合物,且所述多元醇聚合物包括接枝有苯乙烯丙烯腈的多元醇。
6.根据权利要求1所述的组合物,其中所述挥发性有机化合物减少剂包括选自以下的至少一种试剂:羟胺、硫酸羟胺、N-甲基乙醇胺、乙醇胺、三(羟甲基)氨基甲烷和其组合。
7.根据权利要求1所述的组合物,其中所述组合物包括100重量份的所述多元醇组合物、40至60重量份的所述异氰酸酯和0.1至2重量份的所述挥发性有机化合物减少剂。
8.一种制造聚氨酯泡沫的方法,所述方法包括以下步骤:
将原料添加到反应器以使多元醇组合物聚合;
从所述反应器去除杂质;和
从去除杂质并含有所述多元醇组合物、异氰酸酯和挥发性有机化合物减少剂的反应物获得聚氨酯泡沫,所述多元醇组合物中的聚丙二醇含量为0.1ppm或更少,并且环氧丙烷含量为16ppm或更少。
9.根据权利要求8所述的方法,其还包括以下步骤:
将至少一种流体供应到所述反应器以去除所述杂质,
其中所述至少一种流体选自:CO2、N2、蒸汽、蒸馏水、硫酸、盐酸和其组合。
10.根据权利要求9所述的方法,其中以20至200kg/hr的流速供应所述至少一种流体1至2小时。
11.根据权利要求9所述的方法,其中当供应所述至少一种流体时,将所述反应器的温度调节到80至100℃,并且将压力调节到0.5至1巴。
12.根据权利要求9所述的方法,其中供应到所述反应器的所述至少一种流体与所述杂质反应,并生成气体,并且
其中所述气体释放到所述反应器的外部,由此去除所述杂质。
13.根据权利要求12所述的方法,其中在所述杂质与所述至少一种流体之间的反应之后,将所述反应器的压力调节到0.5至0.97巴,由此将所述气体释放到外部。
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