CN109679130A - 包含六氟丁烯和有机醇胺盐化合物的复合发泡剂 - Google Patents
包含六氟丁烯和有机醇胺盐化合物的复合发泡剂 Download PDFInfo
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- CN109679130A CN109679130A CN201710980334.3A CN201710980334A CN109679130A CN 109679130 A CN109679130 A CN 109679130A CN 201710980334 A CN201710980334 A CN 201710980334A CN 109679130 A CN109679130 A CN 109679130A
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Abstract
一种复合发泡剂,它包括:1)六氟丁烯;和2)一种醇胺盐混合物(MAA),该醇胺盐混合物(MAA)包含具有以下通式(I)的有机胺盐化合物:An‑[Bm+]p(I);其中An‑是选自于下列阴离子中的一种或两种或三种:(b)碳酸根:CO3 2‑;(c)甲酸根:HCOO‑;(d)碳酸氢根:HO‑COO‑。复合发泡剂适合作为聚氨酯发泡剂,所获得的聚氨酯泡沫材料具有良好的绝热性能和深冷绝热性能,以及良好的尺寸稳定性。
Description
技术领域
本发明涉及包含六氟丁烯和有机醇胺盐化合物的复合发泡剂,及其在发泡材料如聚氨酯泡沫体或PVC发泡材料或聚苯乙烯发泡等材料中的应用。
技术背景
聚氨酯硬泡作为一种高分子新材料,其质量轻、强度高并具有极低的热导率,是优质的绝热保温材料,广泛应用于冷藏保温、尤其化学武器冷藏保温、建筑节能、太阳能、汽车、冰箱冰柜等家电等产业。聚氨酯硬泡生产中最重要的原料是发泡剂。目前这些发泡剂除了环戊烷以外都是含氯氟烃物质,由于它们对大气臭氧层的破坏所以各国政府早已签订了“蒙特利尔协定书”的国际公约,限制和逐步淘汰、禁止该类产品的生产和使用,中国也是该协定书的签约国。
目前还在使用的是第二代含氯氟烃发泡剂HCFC-141b(一氟二氯乙烷)和环戊烷,欧美等发达国家早已禁止使用HCFC-141b。目前欧美等发达国家使用的是第三代发泡剂五氟丙烷(HFC-245fa)和五氟丁烷(HFC-365),第二、三代发泡剂的GWP(温室效应潜能值)都很高,对大气臭氧层的破坏严重,因此欧美将在2017年以前禁止第三代发泡剂的使用。为此美国霍尼韦尔公司又开发出了第四代物理发泡剂一氯三氟丙烯(LBA),但该产品价格昂贵,ODP(对臭氧层的破坏的潜能值)虽然为零,但GWP仍然较高,比第三代相对环保。总之除了环戊烷以外的这些物理发泡剂都是破坏大气臭氧层的罪魁祸首,因为都含氯氟元素,都将被淘汰。
(HFC-365),第二、三代发泡剂的GWP(温室效应潜能值)都很高,对大气臭氧层的破坏严重,因此欧美将在2017年以前禁止第三代发泡剂的使用。为此美国霍尼韦尔公司又开发出了第四代物理发泡剂一氯三氟丙烯(LBA),但该产品价格昂贵,ODP(对臭氧层的破坏的潜能值)虽然为零,但GWP仍然较高,比第三代相对环保。总之除了环戊烷以外的这些物理发泡剂都是破坏大气臭氧层的罪魁祸首,因为都含氯氟元素,都将被淘汰。
现有技术公开了直接将CO2作为聚氨酯发泡剂,但是,鉴于CO2气体的逃逸和它在原料MDI和聚酯多元醇和/或聚醚多元醇中的溶解度不好,使得CO2气体在发泡组合物中无法均匀地分散,并且发泡过程不容易控制。
另外,现有技术公开了直接将少量的水作为聚氨酯发泡剂,但是,鉴于水分子的氢键作用和水在聚酯多元醇和/或聚醚多元醇中的溶解度不好,水分子以微滴的形式存在于发泡组合物(如聚醚多元醇组分)中,在发泡材料中造成局部过度反应和发泡。如果用水作为发泡剂,则在聚氨酯泡沫材料中包含较多的脲键,大大影响泡沫材料的强度和绝热性能。此外,如果作为发泡剂的水的用量稍稍提高,则会显著影响到聚氨酯泡沫体的性能和尺寸稳定性。如果将水作为唯一的发泡剂,则聚氨酯泡沫体会遭遇收缩、焦烧和绝热性能差的问题(shrinkage,scorching,inadequate heat insulation)。
总之,现有技术中的发泡剂无法以分子水平被分散到发泡组合物中,从而造成泡孔的分布不均匀和泡孔的尺寸不均匀,最终影响到发泡材料的强度性能和绝热性质。
另外,现有技术中使用六氟丁烯(沸点约33℃,商品名FEA-1100)作为聚氨酯发泡剂,但是,它的生产成本和销售价格以及用它作为发泡剂所制备的聚氨酯泡沫材料在性能上仍然有不足,尤其在低温或超低温条件下的绝热性能显著下降以及在低温或超低温下的变形(由于发泡剂变成液体,使得泡孔内的蒸汽压变低,瘪泡现象突出)非常严重。
发明内容
为克服现有技术中存在的缺点,本发明的发明目的是提供一种用于聚氨酯泡沫材料的复合发泡剂。
本申请的发明人出乎预料地发现,当将六氟丁烯与有机醇胺盐混合物(MAA)相结合作为聚氨酯发泡剂时,所获得的聚氨酯泡沫材料不仅具有更好的在常温下的绝热性能,而且具有良好的在低温或超低温下的抗变形性能和绝热性能。这对于聚氨酯泡沫材料在深冷领域中的应用具有重大意义。
根据本发明的第一个实施方案,提供一种复合发泡剂(即包含六氟丁烯和有机醇胺盐化合物的复合发泡剂),它包括:
1)六氟丁烯;和
2)一种醇胺盐混合物(MAA,alkanolamine),
该醇胺盐混合物(MAA)包含具有以下通式(I)的有机胺盐化合物:
An-[Bm+]p (I)
式中,An-是作为CO2给体的具有-n价的阴离子,其中n=1或2;Bm+包含或各Bm+独立地是:+1价的铵离子,+1价的肼离子(H3 +N-NH2),+2价的肼离子(H3 +N-NH3 +),和/或,具有m个的-+NR3R4H基团和/或-+NR3H-基团的一种或多种有机胺(B)的阳离子;
其中m=1-5;和
其中An-是选自于下列阴离子中的一种或两种或三种:
(b)碳酸根:CO3 2-;
(c)甲酸根:HCOO-;
(d)碳酸氢根:HO-COO-;
其中,R3或R4独立地选自:H,R,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
前提条件是:所述通式(I)的化合物具有至少一个(例如一个或两个)与N键接的R基团(即-N-R基团),并且,醇胺盐混合物(MAA)含有50-99wt%(余量是水和任选的杂质)的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐,基于醇胺盐混合物(MAA)的总重量;
其中该R基团选自于下列基团中的一种或多种:
(1a)H[OCH(R1a)CH(R2a)]q-;
(2a)H[OCH(R1a)CH(R2a)CH(R3a)]q-;或
(3a)H[OCH(R1a)CH(R2a)CH(R3a)CH(R4a)]q-;
其中q的值或平均值是q=1-2;R1a、R2a、R3a或R4a各自独立地选自:H,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
其中:在醇胺盐混合物(MAA)中水的含量为>0wt%至40wt%,和,所述有机胺化合物(B)是具有2-50个碳原子的有机胺化合物;
其中,在复合发泡剂中六氟丁烯与醇胺盐混合物(MAA)的重量之比是0.1-10:1。
优选,An-是(b)碳酸根:CO3 2-;或者,An-是(b)碳酸根(CO3 2-)与(c)甲酸根(HCOO-)和/或(d)碳酸氢根(HO-COO-)之间的结合物或混合物。
优选,在上述复合发泡剂中,(1a)H[OCH(R1a)CH(R2a)]q-是H(OCH2CH2)q-、H(OCH2CH(CH3))q-、H(OCH(CH3)CH2)q-、H(OCH2CH(C6H5))q-、H(OCH(C6H5)CH2)q-、H(OCH2CH(CH2Cl))q-、H(OCH(CH2Cl)CH2)q-或H(OCH2CH(CBr3))q-。
优选,在复合发泡剂中六氟丁烯与醇胺盐混合物(MAA)的重量之比是0.2-5:1,更优选0.3-4:1,更优选0.4-3:1,更优选0.5-2:1,更优选0.7-1.3:1。
优选,在醇胺盐混合物(MAA)中水的含量为5-35wt%。
优选,该醇胺盐混合物(MAA)含有60-98wt%的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐。
优选,醇胺盐混合物(MAA)的pH为7.5-10。
进一步优选,在醇胺盐混合物(MAA)中水的含量为10-30wt%以及该醇胺盐混合物(MAA)含有70-97wt%的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐。
进一步优选,醇胺盐混合物(MAA)的pH为7.8-9.5。
进一步优选,在醇胺盐混合物(MAA)中水的含量为15-25wt%以及该醇胺盐混合物(MAA)含有80-96wt%的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐。
进一步优选,醇胺盐混合物(MAA)的pH为8-9.5。
优选,在醇胺盐混合物(MAA)中,通式(I)化合物和水的总含量是基于醇胺盐混合物(MAA)总重量的70-100%,优选80-99.5%,更优选85-99.0%。
优选,上述醇胺盐混合物(MAA)是通过第一原料与第二原料在水存在下(优选,水的用量是以第一原料的重量为基础计算的70-250wt%、优选85-200wt%、更优选100-170wt%、更优选110-160wt%),任选地在催化剂存在下,进行反应所制备的,其中第一原料是选自于下列这些化合物中的一种或多种(例如两种或三种):
H2N-COONH4,
(NH4)2CO3,碳酸肼,碳酸铵肼,或碳酸有机胺类化合物(M)盐,
HCOONH4,甲酸肼,或甲酸有机胺类化合物(M)盐,
HO-COONH4,碳酸氢肼,或有机胺类化合物(M)的碳酸氢盐;
第二原料是选自于下列这些环氧化物中的一种或多种(例如两种或三种):
或苯乙烯氧化物;其中R1a、R2a、R3a或R4a各自独立地选自:H,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
其中所述的有机胺类化合物(M)是选自下列这些中的有机胺类化合物:
C1-C24烃基胺类;
二(C1-C16烃基)胺类;
C2-C14亚烃基二胺类;
C4-C16多亚烷基多胺类;
具有三个伯胺基的C3-C18有机三胺类或具有四个伯胺基的C5-C18有机四胺类;或
C2-C10醇胺类。
在本申请中,优选,有机胺化合物(B)是具有N-R基团的有机胺类化合物,并且,具有N-R基团的有机胺化合物(B)是通过在氨上或在所述有机胺类化合物(M)的至少一个N原子上被上述一个或多个R基团所取代而形成的,其中R的定义与权利要求1中相同。
优选,q=1-2.5、更优选q=1-2.0,按q的平均值计算。
一般,有机胺(B)具有m至m+3个的伯胺、仲胺和/或叔胺基团,和任选地具有季铵基团。
优选,所述有机胺化合物(B)是具有2-20个碳原子的有机胺化合物。
优选,Bm+是两种以上的上述有机胺阳离子的结合或混合物。
优选,所述有机胺化合物(B)是具有3-12个碳原子的有机胺化合物。
优选,R3或R4独立地选自:H,R,任选被羟基或氨基或卤素取代的C1-C4脂肪族烃基,任选被羟基或氨基或卤素取代的环丁基或环己基,或,任选被羟基或氨基或卤素取代的苯基或甲基苯基;并且,R1a、R2a、R3a或R4a各自独立地选自:H,甲基或任选被羟基或氨基或卤素取代的乙基,或任选被羟基或者氨基或卤素取代的丙基或异丙基,任选被羟基或氨基或卤素取代的环己基,或,任选被羟基或氨基或卤素取代的苯基或甲基苯基。
优选,R1a、R2a、R3a或R4a各自独立地选自:H,甲基,氯甲基,溴甲基,乙基,环己基,或,苯基。
优选,在复合发泡剂中,它的碱金属和碱土金属的质量含量为0-200ppm。
优选,通式(I)的化合物平均每分子含有1.3-5个R基团,例如1.4-4个(例如3个)R基团,优选1.5-2个R基团。
优选,上述环氧化物是:环氧乙烷、环氧丙烷、环氧氯丙烷、环氧溴丙烷、环氧丁烷、或环氧氯丁烷或苯乙烯氧化物,或它们中任何两种或多种的混合物。
上述催化剂是氨水。
根据本发明的第二个实施方案,还提供聚氨酯发泡组合物,它包含:
0.1-100重量%、优选1-80重量%、更优选3-60wt%的根据权利要求1-18中任何一项所述的复合发泡剂;
0-50重量%、优选0-40重量%、更优选0-30重量%的除六氟丁烯以外的物理发泡剂;
0-6重量%、优选0-5重量%、更优选0-4重量%的水,和
0.0-99.9重量%、优选20.0-99重量%、更优选40-97wt%的聚合物多元醇;其中,所述重量百分比基于聚氨酯发泡组合物的总重量。
优选,所述聚氨酯发泡组合物含有总共0.4-6wt%、0.5-5wt%、优选0.8-4wt%、进一步优选1-3wt%的水。
优选,所述的发泡组合物进一步包含:泡沫稳定剂、催化剂和阻燃剂等。这些助剂是聚氨酯领域中常用的。
优选,聚合物多元醇选自:聚醚多元醇、聚酯多元醇、聚醚-聚酯多元醇、聚碳酸酯二醇、聚碳酸酯-聚酯多元醇、聚碳酸酯-聚醚多元醇、聚丁二烯多元醇或聚硅氧烷多元醇。聚合物多元醇的平均官能度一般为2-16,优选为2.5-10,更优选3-8。
优选,所述物理发泡剂选自下组中的至少一种:正戊烷,异戊烷,环戊烷,沸点在0-100℃范围内的其它烷烃,HCFC-141b,HFC-245fa,HFC-365mfc,LBA,沸点在0-100℃范围内的其它氟氯烃,甲酸甲酯。
根据本发明的第三个实施方案,还提供聚氨酯泡沫材料,其通过以上所述的聚氨酯发泡组合物与多异氰酸酯单体或异氰酸酯封端的预聚物进行混合后发生反应而形成。
本发明的通式(I)化合物的分解温度一般是在45-120℃之间,优选50-70℃之间,或者,当接触到异氰酸酯时它的分解温度是在45-70℃之间。
在本申请中,醇胺盐混合物(MAA)与通式(I)的化合物或化合物混合物可互换使用。
对于本申请中未详细描述的内容,可以参考CN107089927A或CN107089910A,它们的说明书中的内容被引入本申请中供参考。
本发明的有益技术效果或优点
1、通过将醇胺盐混合物(MAA)与六氟丁烯相结合用作聚氨酯发泡剂,所制备聚氨酯泡沫材料不仅在常温下具有更良好的绝热性能,而且,具有良好的在低温或超低温下的抗变形性能和绝热性能。在深冷领域中的应用具有重大的优势。
2、通过将醇胺盐混合物(MAA)与六氟丁烯相结合用作聚氨酯发泡剂,在发泡过程中,前段由六氟丁烯发泡,后段由醇胺盐混合物(MAA)中的通式(I)化合物分解释放二氧化碳进行二次发泡,发泡过程呈现“双峰”型过程,两种气体有力地支撑泡孔、避免瘪泡,使得泡沫材料中的泡孔尺寸相对均匀,并且通过通式(I)化合物分解产物(醇胺)的交联和扩链作用,泡沫内的微观结构得到增强,抗变形的性能非常突出。
3、用本发明的复合发泡剂作为发泡剂所制备的聚氨酯泡沫材料的尺寸变化率或收缩率≤0.3%、甚至≤0.2%(按照中国国家标准GB/T 8811-2008,放置时间可按照该标准中所要求)。另外,例如在34-42Kg/m3的泡沫体密度下,导热系数w/m·k(10℃)或w/m·k(22.5℃)是在0.01830-0.01895之间,优选是在0.01850-0.01885之间。而现有技术的聚氨酯泡沫体在此密度下的导热系数一般高于0.01900,更通常是高于0.02200。另外,在此密度范围内,本发明泡沫体的压缩强度是在110-220Kpa范围,优选150-200Kpa范围。
附图说明
图1是实施例2的泡沫体的扫描电子显微镜照片(SEM)。
具体实施方式
下面结合实施例对本发明做进一步的描述。
在本申请中,用于制备聚氨酯泡沫体或用于发泡组合物中的常用聚醚多元醇和聚酯多元醇选自下列品种:聚醚4110、450、400A、MN500、SU380、SA380、403、SA460、G350;聚酯CF6320、DM2003、YD6004、AKS7004、CF6255。常用催化剂选自:33LV(A-33):33%三乙烯二胺的二丙二醇溶液、N,N-二甲基乙醇胺、N,N-二甲基苄胺、70%双(二甲胺基乙基)醚的二丙二醇溶液、70%辛酸钾于二乙二醇溶液、二月桂酸二丁基锡、PT303、PT304、醋酸钾、PC-8(N,N-二甲基环己胺)、PC-5、PC-41、三乙醇胺、JXP-508、JXP-509、TMR-2、TMR-3、TMR-4。常用阻燃剂:TCPP、TCEP、DMMP、氯化铵、氢氧化铝粉末、DM1201、DM1301、四溴苯酐二醇。常用硅烷表面活性剂:DC8545、AK-158、AK-8805、AK-8812、AK-8809、AK-8818、AK-8860、DCI990、DC5188、DC6070、DC3042、DC3201。非硅烷表面活性剂:LK-221,LK-443。
安全说明:在本发明中凡是涉及使用环氧化合物的情况,为了安全起见,在将反应物加入反应器之前和之后必须经过惰性气体(如氮气或氩气)处理和保护下进行反应,防止爆炸。另外,对于加入环氧乙烷的情况,为了安全起见,优选的是分批加入反应器中,而环氧丙烷可以一次性加入反应器中,也可以分批。反应器一般为装有冷却设备的压力反应器,除非另有说明。环氧化合物要分批地慢慢地加入到反应器中,而对于那些相对安全的环氧化合物也要分批分次地慢慢地加入到反应器中,控制反应速度等反应条件,确保安全。水合肼也是易燃易爆的有毒的化合物,因此在使用的时候也必须按照相关要求和规定进行。
在实施例中根据中国国家标准GB/T 26689-2011(冰箱、冰柜用硬质聚氨酯泡沫塑料)测试泡沫体的各项性能。样品的尺寸一般为10*10*2.5cm。
导热系数按照GB/T 10294-2008或GB/T 10295-2008进行。平均温度为10℃,冷热板温差15~20℃。表观(芯)密度按照GB/T 6343-2009测试。低温尺寸稳定性按照GB/T8811-2008,在-30℃±2℃下测试。压缩强度按照GB/T 8813-2008进行测试。闭孔率(即闭孔体积百分率)按照GB/T 10799-2008进行测试。
对于通式(I)的化合物或化合物混合物中各种醇胺(例如单乙醇胺、二乙醇胺、三乙醇胺、单丙醇胺、二丙醇胺或三丙醇胺)的含量的测量方法,可采用气相色谱法。其中气相色谱仪配有氢火焰离子化检测器(FID),通式(I)化合物的质量浓度为大约10mg/mL,为标准溶液。气相色谱条件:HP-5毛细管色谱柱(30m×0.32mm i.d.×0.25μm,5%phenyl methyl-siloxane);柱温为程序升温,初始温度为80℃,保持3min后以25℃/min的速率升至250℃,保持5min;进样口温度250℃;检测器温度260℃;载气为高纯氮,流速为1.5mL/min;燃气为氢气,流速为30mL/min;助燃气为空气,流速为300mL/min;尾吹气为氮气,流速为25mL/min;进样方式为分流进样,分流比:30:1;进样量为1μL。
A)从氨基酸铵盐制备通式(I)化合物
实施例A-1
将1.4吨的氨基甲酸铵(分子量78.07)、1.2吨的水加入到带有冷却水夹套的不锈钢高压反应釜(在下面的其它实施例中简称反应器)中,开动搅拌器,使得氨基甲酸铵溶解,用氮气吹扫反应器,然后封闭反应器并开动搅拌,通入总共1.90吨的环氧丙烷(分子量58.08,沸点34℃),控制环氧丙烷的加料速度以便控制反应器内的压力不高于0.6MPa,在不断搅拌下慢慢升温,控温在70℃以下反应15小时,反应完成,慢慢降低温度到50℃后控制真空度在600毫米汞柱以下(优选低于500mmHg)慢慢脱除不必要的水(例如达到低于20wt%的水含量)和未反应的环氧丙烷,然后放掉真空,降温到40℃以下后放出反应物,获得化合物A-1(即,醇胺盐混合物MAA)。粘度200厘泊,pH=9,化合物A-1的分解温度为45-70℃(从45℃开始极其缓慢地分解,峰值分解温度为57-62℃)。用原子吸收分光光度计(SeikoInstruments,Inc.;SAS/727)测定碱金属和碱土金属离子的含量为低于检测极限。气相色谱分析,单丙醇胺与二丙醇胺的摩尔比是1:0.18。化合物A-1含有约74wt%的单丙醇胺和二丙醇胺两者的盐。还含有一部分的水。另外,化合物A-1含有约55wt%的单丙醇胺和二丙醇胺(在加热化合物A-1以释放二氧化碳之后对残留物进行分析),基于加热分解之前的化合物A-1的总重量。
化合物A-1是一种在室温下或在环境条件比较稳定的透明或澄清液体,适合作为聚氨酯发泡剂,它与HFC-245fa、LBA、五氟丁烷的基本特性对比如下表:
化合物A-1 | HFC245fa | 五氟丁烷 | LBA | |
ODP | 0 | 0 | 0 | 0 |
GWP | 1 | 1030.01 | 793.98 | 5.00 |
沸点(℃) | 45℃开始慢分解 | 15.3 | 40.2 | 19.3 |
从上表可以看出,化合物A-1的GWP(温室效应潜能值)等于1,分解温度比较高,克服了某些低沸点(低于20℃的)物理发泡剂如HFC-245fa、LBA、五氟丁烷等的很多缺点,如GWP远大于1、沸点比较低、易挥发,而本发明化合物A-1的GWP等于1、沸点比较高、不易挥发,并且ODP(对臭氧层的破坏的潜能值)为0,不会破坏大气臭氧层;不易挥发便于运输和存储。
实施例A-2
将1kg的氨基甲酸铵、1.1kg的水加入到反应器中,在搅拌下溶解,用氮气吹扫反应器,然后加入2.1kg的环氧丙烷到透明的石英玻璃反应器中,开动搅拌,在不断搅拌下慢慢升温,控温在50-60℃之间,压力不高于0.6MPa条件下进行反应,当反应进行到大约2小时时突然出现了奇妙的现象:混浊、不透明的混合物瞬间变成透明或澄明溶液,继续反应8小时,然后降温到50℃,在真空度为600毫米汞柱以下脱出不必要的水和未反应的环氧丙烷,降温到40℃以下后放出产物。反应时间确保反应按照摩尔比完成。获得化合物A-2。粘度200厘泊,pH=9.1,分解温度在45-70℃范围。液相色谱分析以及气相色谱分析,表明化合物A-2是包含多种醇胺的混合物。水含量为20.5wt%。
实施例A-3
将7kg的碳酸铵和7kg的氨基甲酸铵、15kg的水加入到反应器中,在搅拌下溶解,用氮气吹扫反应器,然后再分批加入32kg的环氧丙烷,在不断搅拌下慢慢升温,控温在45-70℃之间,控制压力不高于0.6MPa,反应10小时,然后降温到50℃,控温在50℃以下,真空度为600毫米汞柱以下脱出不必要的水和未反应的环氧丙烷,降温到40℃以下后放掉真空、放出产物,即获得化合物A-3。粘度大约250厘泊,pH=9,分解温度在45-70℃范围。
实施例A-4
将16kg的氨基甲酸一乙醇胺盐、18kg的水加入到反应器中,用氮气清扫反应器,搅拌溶解,分批加入13kg的环氧丙烷到反应器中,开动搅拌,控制压力不高于0.6MPa,在不断搅拌下慢慢升温,当温度升高到70℃时控温反应5小时,然后降低温度到50℃以下,控制真空度600毫米汞柱以下脱除不必要的水和未反应的环氧丙烷,降温到40℃以下后放掉真空、放出产物,即可获得化合物A-4。粘度280厘泊。pH=9。分解温度在45-70℃范围。
实施例A-5
将21kg的氨基甲酸二亚乙基三胺盐、15kg的水加入到反应器中,搅拌溶解,用氮气吹扫反应器,在搅拌下,控制压力不高于0.6MPa,温度在45-70℃之间,分批加入16kg的环氧丙烷到反应器中,加完环氧丙烷后控温反应5小时,然后降温到50℃下,真空度在600毫米汞柱以下减压下脱除不必要的水和未反应的环氧丙烷,降温到40℃以下后放掉真空、放出产物即可获得化合物A-5。粘度大约350厘泊。pH=9,分解温度在45-70℃范围。
实施例A-6
将1.2kg的碳酸铵和1.2kg的氨基甲酸铵、2.7kg的水加入到反应器中,在搅拌下溶解,用氮气吹扫反应器,然后再加入7.1kg的苯乙烯氧化物(styrene oxide,分子量120.15),在不断搅拌下慢慢升温,控温在45-70℃之间,控制压力不高于0.6MPa,反应10小时,然后降温到50℃,控温在50℃以下,真空度为600毫米汞柱以下脱出不必要的水,降温到40℃以下后放掉真空、放出产物,即获得化合物A-6。粘度大约460厘泊,pH=9,分解温度在45-70℃范围。
B)从碳酸铵或碳酸肼盐制备通式(I)化合物
实施例B-1
将16kg的碳酸铵(分子量96)和15.5kg的水加入到反应器中,开动搅拌,使得碳酸铵溶解,用氮气吹扫反应器,加入28kg的环氧丙烷,开动搅拌,控制压力不高于0.6MPa,在不断搅拌下慢慢升温,控温在70℃以下反应12小时,反应完成,慢慢降低温度到50℃后控制真空度在600毫米汞柱以下慢慢脱除不必要的水和未反应的环氧丙烷,然后放掉真空,降温到40℃以下后放出反应物,获得化合物获得化合物B-1。粘度大约300厘泊,pH=8.9,化合物B-1的分解温度为45-70℃。液相色谱分析以及气相色谱分析,表明化合物B-1是包含多种醇胺的混合物。用原子吸收分光光度计(Seiko Instruments,Inc.;SAS/727)测定碱金属和碱土金属离子的含量为低于检测极限。气相色谱分析,单丙醇胺与二丙醇胺的摩尔比是1:0.28。化合物B-1含有约79wt%的单丙醇胺和二丙醇胺两者的盐。化合物B-1含有约59wt%的单丙醇胺和二丙醇胺(在加热化合物A-1以释放二氧化碳之后对残留物进行分析),基于加热分解之前的化合物B-1的总重量。
实施例B-2
将0.95kg的碳酸肼(以碳酸肼水溶液形式使用,该水溶液的体积为1.8L)、0.8kg的水加入到反应器中,在搅拌下溶解30分钟,用氮气吹扫反应器,然后分批加入1.8kg的环氧丙烷到透明的石英玻璃反应器中,开动搅拌,在不断搅拌下慢慢升温,控温在50-70℃之间,压力不高于0.6MPa条件下进行反应,当反应进行到大约2小时左右回出现奇妙的现象:混浊、不透明的混合物瞬间变成透明或澄明溶液,继续反应5小时,然后降温到50℃,在真空度为600毫米汞柱以下脱出一部分的水和未反应的环氧丙烷,降温到40℃以下后放出产物。反应时间确保反应按照摩尔比完成。获得化合物B-2。pH=9.1,分解温度在45-70℃范围。
实施例B-4
将10kg的碳酸铵、11kg的水加入到透明的石英玻璃反应器中,搅拌溶解,用氮气吹扫反应器,在不断搅拌下,控制温度在45-70℃之间,控制压力不高于0.6MPa,将22kg的环氧丙烷加入到反应器中,加完后控温反应,当反应进行到大约2小时左右时突然出现了奇妙的现象:混浊、不透明的混合物瞬间变成透明或澄明溶液,继续反应8小时,然后降温到50℃,控制真空在600mHg以下减压下脱除不必要的水和未反应的环氧丙烷,降温到40℃以下后放掉真空、放出产物即可。获得化合物B-4。粘度大约为340厘泊。pH=9.1。分解温度在45-70℃。
C)制备具有甲酸根(HCOO-)的通式(I)化合物
实施例C-1
将15kg的甲酸铵、1kg的甲胺催化剂,10kg的水、5kg的乙二醇加入到反应器中,开动搅拌,用氮气吹扫反应器,控制压力不高于0.5MPa,控温在120℃以下,将12kg的环氧乙烷分批加入到反应器中,反应5小时。反应完成后降温,然后控制真空度为600毫米汞柱以下,温度100℃以下减压脱除不必要的水和未反应的环氧乙烷,去掉真空,降温到50℃以下后放出产品即可。获得化合物C-1。粘度为大约200厘泊,pH=8.5,分解温度高于100℃。
实施例C-2
重复实施例C-1,只是使用15kg的环氧丙烷代替12kg的环氧乙烷,并且环氧丙烷不是分批次加入反应器中,而是一次性加入其中。获得化合物C-2。粘度为大约350厘泊,pH=8.6,分解温度高于100℃。
D)制备具有碳酸氢根(HO-COO-)的通式(I)化合物
实施例D-1
将10kg的碳酸氢铵(分子量79.06)、9.0kg的水和1kg乙二胺加入到透明的石英玻璃反应器中,搅拌溶解(允许存在不溶解的碳酸氢铵),用氮气吹扫反应器,密封反应器,然后在不断搅拌下,控制温度在45-65℃之间,控制压力不高于0.6MPa,将20kg的环氧丙烷分批加入到反应器中,加完后控温反应10小时,然后降温到50℃,控制真空在600mHg以下减压下脱除不必要的水和未反应的环氧丙烷,降温到40℃以下后放掉真空、放出产物即可。获得化合物D-1。粘度大约为250厘泊。pH=8,分解温度在36-42℃。
发明人意外地发现,当将化合物D-1与聚醚多元醇和/或聚酯多元醇混合,例如配制发泡组合物(“白料”)时,溶解在白料中的化合物D-1的分解温度能够提高至45-65℃。这使得化合物D-1具有合适的分解温度,因此,适合用于聚氨酯发泡。
应用实施例
实施例1
将5重量份的作为发泡剂的由以上实施例A-1制备的化合物A-1、4重量份的六氟丁烯(杜邦公司,商品名FEA-1100)、50重量份的聚醚多元醇4110(由山东省滨州市的滨化集团生产)、1重量份的泡沫稳定剂DC3201(美国空气化工公司生产)、12.5重量份的阻燃剂TCPP(江苏雅克化工有限公司生产)和2重量份催化剂A33(33LV,美国空气化工公司生产)混合均匀后获得透明的发泡组合物,然后在其中加入95.5份异氰酸酯MDI(PM200,烟台万华化学集团股份有限公司),经搅拌均匀后发泡制得聚氨酯泡沫材料。
实施例2
将3重量份的作为发泡剂的由以上实施例B-1制备的化合物B-1和、6重量份的六氟丁烯(杜邦公司,商品名FEA-1100)、30重量份的聚醚多元醇4110、20重量份的聚酯多元醇CF6320(江苏富盛新材料有限公司)和1重量份的泡沫稳定剂DC3201、12.5重量份的阻燃剂TCPP和2重量份催化剂A33混合均匀后获得透明的发泡组合物,然后在其中加入95.5份异氰酸酯MDI(PM200),经搅拌均匀后发泡制得聚氨酯泡沫。
取样品,用刀片切片后利用SEM放大100倍观察泡孔。如图1中所示,泡孔直径为207微米。
实施例3
将3重量份的作为发泡剂的由以上实施例B-1制备的化合物B-1和2重量份的作为发泡剂的由以上实施例B-2制备的化合物B-2和4重量份的作为发泡剂的六氟丁烯(杜邦公司,商品名FEA-1100)、30重量份的聚醚多元醇4110、20重量份的聚酯多元醇CF6320(江苏富盛新材料有限公司)和1重量份的泡沫稳定剂DC3201、12.5重量份的阻燃剂TCPP和2重量份催化剂A33混合均匀后获得透明的发泡组合物,然后在其中加入95.5份异氰酸酯MDI(PM200),经搅拌均匀后发泡制得聚氨酯泡沫。
取样品,用刀片切片后利用SEM放大100倍观察泡孔。泡孔直径为209微米。
实施例4
将3重量份的作为发泡剂的由以上实施例B-2制备的化合物B-2和2重量份的作为发泡剂的由以上实施例C-2制备的化合物C-2、2重量份的作为发泡剂的由以上实施例D-1制备的化合物D-1和2重量份的作为发泡剂的六氟丁烯(杜邦公司,商品名FEA-1100)、50重量份的聚醚多元醇4110(山东滨州市滨化集团)、1重量份的泡沫稳定剂DC3201(美国空气化工)、12.5重量份的阻燃剂TCPP(江苏雅克化工有限公司)和2重量份催化剂A33(33LV,美国空气化工)混合均匀后获得透明的发泡组合物,然后在其中加入95.5份异氰酸酯MDI(PM200),经搅拌均匀后发泡制得聚氨酯泡沫材料。
对比例1
重复实施例1,只是仅仅采用9重量份的六氟丁烯作为发泡剂。
对比例2
重复实施例2,只是仅仅采用9重量份的由以上实施例B-1制备的化合物B-1作为发泡剂。
表1:聚氨酯泡沫体的性能
说明:以上列表中的检测数据是采用常规发泡箱和自制发泡模型制备的泡沫样品所做的检测数据,是手工制备的自由泡样品。
其中收缩率(尺寸变化率)按照中国国家标准GB/T 8811-2008测量。
从表1中数据可以清楚看出,醇胺盐混合物(MAA)与六氟丁烯相结合,能够降低常温下导热系数,与对比例1相比。另外,泡沫材料的尺寸稳定性显著提高。
对于深冷(-160℃)下导热系数,本发明的产品表现尤为突出。
另外,深冷(-160℃)下,通过目测,本发明的产品的收缩率较低,而对比例1的产品变形非常严重,收缩率几乎达到40%。
Claims (14)
1.一种复合发泡剂,它包括:
1)六氟丁烯;和
2)一种醇胺盐混合物(MAA),
该醇胺盐混合物(MAA)包含具有以下通式(I)的有机胺盐化合物:
An- [Bm+]p (I)
式中,An-是作为CO2给体的具有-n价的阴离子,其中n=1或2;
Bm+包含或各Bm+独立地是:+1价的铵离子,+1价的肼离子(H3 +N-NH2),+2价的肼离子(H3 +N-NH3 +),和/或,具有m个的-+NR3R4H基团和/或-+NR3H-基团的一种或多种有机胺(B)的阳离子;
其中m=1-5;和
其中An-是选自于下列阴离子中的一种或两种或三种:
(b)碳酸根:CO3 2-;
(c)甲酸根:HCOO-;
(d)碳酸氢根:HO-COO-;
其中,R3或R4独立地选自:H,R,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
前提条件是:所述通式(I)的化合物具有至少一个(例如一个或两个)与N键接的R基团(即-N-R基团),并且,醇胺盐混合物(MAA)含有50-99wt%的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐,基于醇胺盐混合物(MAA)的总重量;
其中该R基团选自于下列基团中的一种或多种:
(1a)H[OCH(R1a)CH(R2a)]q-;
(2a)H[OCH(R1a)CH(R2a)CH(R3a)]q-;或
(3a)H[OCH(R1a)CH(R2a)CH(R3a)CH(R4a)]q-;
其中q的值或平均值是q=1-2;R1a、R2a、R3a或R4a各自独立地选自:H,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
其中:在醇胺盐混合物(MAA)中水的含量为>0wt%至40wt%,和,所述有机胺化合物(B)是具有2-50个碳原子的有机胺化合物;
其中,在复合发泡剂中六氟丁烯与醇胺盐混合物(MAA)的重量之比是0.1-10:1。
2.根据权利要求1所述的复合发泡剂,其中:
(1a)H[OCH(R1a)CH(R2a)]q-是H(OCH2CH2)q-、H(OCH2CH(CH3))q-、H(OCH(CH3)CH2)q-、H(OCH2CH(C6H5))q-、H(OCH(C6H5)CH2)q-、H(OCH2CH(CH2Cl))q-、H(OCH(CH2Cl)CH2)q-或H(OCH2CH(CBr3))q-,和/或
在复合发泡剂中六氟丁烯与醇胺盐混合物(MAA)的重量之比是0.2-5:1,更优选0.3-4:1,更优选0.4-3:1,更优选0.5-2:1,更优选0.7-1.3:1。
3.根据权利要求1或2所述的复合发泡剂,其中:在醇胺盐混合物(MAA)中水的含量为5-35wt%(优选10-30wt%,更优选15-25wt%)以及该醇胺盐混合物(MAA)含有60-98wt%(优选70-97wt%,更优选80-96wt%)的单醇胺(例如单乙醇胺和/或单丙醇胺)的盐和二醇胺(例如二乙醇胺、乙醇丙醇胺和/或二丙醇胺)的盐;和/或
醇胺盐混合物(MAA)的pH为7.5-10(优选7.8-9.5,更优选8-9.0)。
4.根据权利要求1-3中任何一项所述的复合发泡剂,其中:在醇胺盐混合物(MAA)中,通式(I)化合物和水的总含量是基于醇胺盐混合物(MAA)总重量的70-100%,优选80-99.5%,更优选85-99.0%。
5.根据权利要求1-4中任何一项所述的复合发泡剂,其中该醇胺盐混合物(MAA)是通过第一原料与第二原料在水存在下,任选地在催化剂存在下,进行反应所制备的,其中第一原料是选自于下列这些化合物中的一种或多种:
H2N-COONH4,
(NH4)2CO3,碳酸肼,碳酸铵肼,或碳酸有机胺类化合物(M)盐,
HCOONH4,甲酸肼,或甲酸有机胺类化合物(M)盐,
HO-COONH4,碳酸氢肼,或有机胺类化合物(M)的碳酸氢盐;
第二原料是选自于下列这些环氧化物中的一种或多种:
或苯乙烯氧化物;其中R1a、R2a、R3a或R4a各自独立地选自:H,任选被羟基或氨基或卤素取代的C1-C7脂肪族烃基,任选被羟基或氨基或卤素取代的C3-C7环脂族烃基,或,任选被羟基或氨基或卤素取代的C6-C10芳族烃基;
其中所述的有机胺类化合物(M)是选自下列这些中的有机胺类化合物:
C1-C24烃基胺类;
二(C1-C16烃基)胺类;
C2-C14亚烃基二胺类;
C4-C16多亚烷基多胺类;
具有三个伯胺基的C3-C18有机三胺类或具有四个伯胺基的C5-C18有机四胺类;或
C2-C10醇胺类;
优选,水的用量是以第一原料的重量为基础计算的70-250wt%、优选85-200wt%、更优选100-170wt%、更优选110-160wt%。
6.根据权利要求5所述的复合发泡剂,其中有机胺化合物(B)是具有N-R基团的有机胺类化合物,并且,具有N-R基团的有机胺化合物(B)是通过在氨上或在所述有机胺类化合物(M)的至少一个N原子上被上述一个或多个R基团所取代而形成的,其中R的定义与权利要求1中相同。
7.根据权利要求1-6中任何一项所要求的复合发泡剂,其中q=1-2.5,优选q=1-2.0,按q的平均值计算;;和/或
所述有机胺化合物(B)是具有2-20个碳原子(优选3-12个碳原子)的有机胺化合物。
8.根据权利要求1-7中任何一项所述的复合发泡剂,其中R3或R4独立地选自:H,R,任选被羟基或氨基或卤素取代的C1-C4脂肪族烃基,任选被羟基或氨基或卤素取代的环丁基或环己基,或,任选被羟基或氨基或卤素取代的苯基或甲基苯基;并且,R1a、R2a、R3a或R4a各自独立地选自:H,甲基或任选被羟基或氨基或卤素取代的乙基,或任选被羟基或者氨基或卤素取代的丙基或异丙基,任选被羟基或氨基或卤素取代的环己基,或,任选被羟基或氨基或卤素取代的苯基或甲基苯基。
9.根据权利要求8所述的复合发泡剂,其中R1a、R2a、R3a或R4a各自独立地选自:H,甲基,氯甲基,溴甲基,乙基,环己基,或,苯基。
10.根据权利要求1-9中任何一项所述的复合发泡剂,其特征在于它的碱金属和碱土金属的质量含量为0-200ppm;和/或,通式(I)的化合物平均每分子含有1.3-5个R基团,例如1.4-4个R基团,优选1.5-2个R基团。
11.根据权利要求5-10中任何一项所述的复合发泡剂,其中该环氧化物是:环氧乙烷、环氧丙烷、环氧氯丙烷、环氧溴丙烷、环氧丁烷、或环氧氯丁烷或苯乙烯氧化物,或它们中任何两种或多种的混合物;和/或
催化剂是氨水。
12.聚氨酯发泡组合物,它包含:
0.1-100重量%、优选1-80重量%、更优选3-60wt%的根据权利要求1-11中任何一项所述的复合发泡剂;
0-50重量%、优选0-40重量%、更优选0-30重量%的除六氟丁烯以外的物理发泡剂;
0-6重量%、优选0-5重量%、更优选0-4重量%的水,和
0.0-99.9重量%、优选20.0-99重量%、更优选40-97wt%的聚合物多元醇;其中,所述重量百分比基于聚氨酯发泡组合物的总重量。
13.根据权利要求12所述的聚氨酯发泡组合物,其特征在于它含有总共0.4-6wt%、0.5-5wt%、优选0.8-4wt%、进一步优选1-3wt%的水。
14.聚氨酯泡沫材料,其通过权利要求12或13所述的聚氨酯发泡组合物与多异氰酸酯单体或异氰酸酯封端的预聚物进行混合后发生反应而形成。
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EP3719064A4 (en) | 2022-06-29 |
JP7036913B2 (ja) | 2022-03-15 |
CN109679130B (zh) | 2021-09-07 |
RU2020115026A3 (zh) | 2021-11-19 |
EP3719064A1 (en) | 2020-10-07 |
KR20200060475A (ko) | 2020-05-29 |
JP2022088402A (ja) | 2022-06-14 |
JP2020537702A (ja) | 2020-12-24 |
CA3078648C (en) | 2023-03-28 |
WO2019075875A1 (zh) | 2019-04-25 |
AU2017436626A1 (en) | 2020-04-16 |
KR20220137156A (ko) | 2022-10-11 |
RU2020115026A (ru) | 2021-11-19 |
CA3078648A1 (en) | 2019-04-25 |
KR102528271B1 (ko) | 2023-05-02 |
KR102540982B1 (ko) | 2023-06-07 |
US20200291199A1 (en) | 2020-09-17 |
AU2017436626B2 (en) | 2021-11-18 |
US11634552B2 (en) | 2023-04-25 |
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