CN115109249A - 阳离子-非离子型亲水单体及其制备方法和应用 - Google Patents
阳离子-非离子型亲水单体及其制备方法和应用 Download PDFInfo
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- CN115109249A CN115109249A CN202210820665.1A CN202210820665A CN115109249A CN 115109249 A CN115109249 A CN 115109249A CN 202210820665 A CN202210820665 A CN 202210820665A CN 115109249 A CN115109249 A CN 115109249A
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- Prior art keywords
- cationic
- hydrophilic monomer
- nonionic hydrophilic
- mixture
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000004814 polyurethane Substances 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 20
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 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 description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- FYYUTGDAKCRTMZ-UHFFFAOYSA-N 1-[3-aminopropyl(2-hydroxypropyl)amino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)CCCN FYYUTGDAKCRTMZ-UHFFFAOYSA-N 0.000 claims description 4
- CYOIAXUAIXVWMU-UHFFFAOYSA-N 2-[2-aminoethyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCN(CCO)CCO CYOIAXUAIXVWMU-UHFFFAOYSA-N 0.000 claims description 4
- FKJVYOFPTRGCSP-UHFFFAOYSA-N 2-[3-aminopropyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCCN(CCO)CCO FKJVYOFPTRGCSP-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- RAQRYVPHYBAHTA-UHFFFAOYSA-N [3-aminopropyl(hydroxymethyl)amino]methanol Chemical compound NCCCN(CO)CO RAQRYVPHYBAHTA-UHFFFAOYSA-N 0.000 claims 1
- KIOANFZSWZITSQ-UHFFFAOYSA-N [4-aminobutyl(hydroxymethyl)amino]methanol Chemical compound NCCCCN(CO)CO KIOANFZSWZITSQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
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- -1 polyoxyethylene Polymers 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- APHFXVQEHOBENK-UHFFFAOYSA-N 2-[2-aminopropyl(2-hydroxyethyl)amino]ethanol Chemical compound CC(N)CN(CCO)CCO APHFXVQEHOBENK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
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- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
Description
技术领域
本发明涉及水性聚氨酯技术领域,特别是涉及一种阳离子-非离子型亲水单体及其制备方法和应用。
背景技术
水性聚氨酯分散体(WPUD)是以水为分散介质的二元胶体体系,是一种VOC含量极低、环境友好型材料。由于聚氨酯分子具有“可裁剪性”,结合新的合成和交联改性技术,可以有效控制其组成与结构,从而具有高的力学性能和热性能等,因此WPUD产品已在织物、皮革涂饰、涂料、粘合剂和制革等许多领域得到了广泛的应用。
根据亲水基团的电荷性质,WPUD主要分为阴离子型、阳离子型和非离子型水性聚氨酯三种类型。其中,阳离子型水性聚氨酯主要采用N-甲基二乙醇胺(MDEA)为亲水单体,将潜在亲水基团叔胺结构(-NR3)引入到聚氨酯分子链上,再经酸性中和剂中和,将分子链上的叔胺结构中和成盐变成季铵盐亲水基团(-NR4 +),从而实现聚氨酯的自乳化分散,得到阳离子型聚氨酯分散体。但是,阳离子亲水基团赋予聚氨酯分子链的自乳化能力明显不如阴离子亲水基团,所以在实际生产制备过程中,制备相同粒径、外观的聚氨酯分散体时,阳离子亲水单体的用量要明显高于阴离子亲水单体用量。另外,阳离子型聚氨酯分散体在耐电解质和配伍性方面都相对较差。
虽然,传统技术中采用同时引入阳离子型亲水单体和非离子型亲水单体两种亲水扩链剂,通过共聚到聚氨酯分子链上可以在一定程度上改善聚氨酯的耐电解质性能和配伍性,但该方法需要使用大量的非离子型亲水单体才能实现,并且采用两种亲水扩链剂共聚制备得到的聚氨酯仍然存在乳化分散效果不佳等问题。
发明内容
基于此,有必要针对上述问题,提供一种阳离子-非离子型亲水单体及其制备方法和应用;所述阳离子-非离子型亲水单体具有较高的乳化分散性,能够提高聚氨酯的自乳化分散能力,同时使聚氨酯具有良好的耐电解质性能、配伍性和力学性能。
一种阳离子-非离子型亲水单体,所述阳离子-非离子型亲水单体的结构式如下式(1)所示,
式(1)中,R1选自烷基、环烷基或者芳烷基中的至少一种,R2、R3、R4分别独立的选自碳原子数为1-4的烷基,n为整数,n=3-20。
本发明所述的阳离子-非离子型亲水单体的结构式中,通过非离子型的聚氧乙基亲水基团与潜在阳离子型的叔胺亲水基团的协同乳化分散作用,使阳离子-非离子型亲水单体具有较高的乳化分散性。同时,所述阳离子-非离子型亲水单体的结构式中不仅含有双羟基活性基团,而且还具有氨基甲酸酯和脲键结构,进而有利于提升阳离子-非离子型亲水单体与合成聚氨酯其他组分的相容性。
在其中一个实施例中,R1选自碳原子数为4-14的烷基、环烷基或者芳烷基中的至少一种。
一种如上所述的阳离子-非离子型亲水单体的制备方法,包括如下步骤:
在保护气氛下,将二异氰酸酯、聚乙二醇单甲醚以及催化剂混合得到第一混合物,将所述第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%,得到中间产物;以及
在保护气氛下,将所述中间产物与双羟基二元胺混合得到第二混合物,将所述第二混合物反应至异氰酸根在所述第二混合物中的含量为0,得到阳离子-非离子型亲水单体。
在其中一个实施例中,所述二异氰酸酯、所述聚乙二醇单甲醚与所述双羟基二元胺的摩尔比为1:(0.98-1.05):(0.95-1.02)。
在其中一个实施例中,所述二异氰酸酯选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯中的至少一种。
在其中一个实施例中,所述双羟基二元胺选自N,N-双(2-羟乙基)乙二胺、[(4-氨基丁基)亚氨基]双甲醇、N-(3-氨基丙基)二乙醇胺、2,2'-[(2-氨基丙基)亚氨基]二乙醇、[(3-氨基丙基)亚氨基]双甲醇、1-[(3-氨基丙基)-(2-羟基丙基)-氨基]-2-丙醇中的至少一种。
在其中一个实施例中,所述聚乙二醇单甲醚的聚合度为3-20。
在其中一个实施例中,所述将第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%的步骤中,反应温度为60℃-90℃;
及/或,所述将第二混合物反应至异氰酸根在所述第二混合物中的含量为0的步骤中,反应温度为30℃-50℃。
本发明所述的阳离子-非离子型亲水单体的制备方法中,先通过聚乙二醇单甲醚中的羟基与部分异氰酸根活性基团反应,引入非离子型的聚氧乙基亲水基团,再利用剩余部分的异氰酸根活性基团与双羟基二元胺反应,引入包含潜在阳离子亲水基团的叔胺结构和双羟基活性基团,从而使所述阳离子-非离子型亲水单体的分子链上同时含有非离子型的聚氧乙基亲水基团和阳离子型的叔胺亲水基团,而且还引入了氨基甲酸酯、脲键结构和双羟基活性基团,使阳离子-非离子型亲水单体具有多元化的结构,有利于进一步提升聚氨酯的力学性能。
一种如上所述的阳离子-非离子型亲水单体在制备聚氨酯中的应用。
在其中一个实施例中,所述阳离子-非离子型亲水单体的质量为所述聚氨酯原料总质量的1%-6%。
本发明提供一种具有较高的乳化分散性的阳离子-非离子型亲水单体,可以作为亲水扩链剂、中和剂或者乳化剂等用于制备聚氨酯,有利于提高聚氨酯的自乳化分散能力,进而使聚氨酯分子结构具有更强的“可裁剪设计性”,同时使聚氨酯具有良好的耐电解质性能、配伍性和力学性能,具有较高的实际应用价值。
附图说明
图1为实施例6制备得到阳离子-非离子型亲水单体的红外光谱图。
具体实施方式
为了便于理解本发明,下面将对本发明进行更详细的描述。但是,应当理解,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式或实施例。相反地,提供这些实施方式或实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式或实施例的目的,不是旨在于限制本发明。
本发明提供一种阳离子-非离子型亲水单体,所述阳离子-非离子型亲水单体的结构式如下式(1)所示,
式(1)中,R1选自烷基、环烷基或者芳烷基中的至少一种,R2、R3、R4分别独立的选自碳原子数为1-4的烷基,n为整数,n=3-20。
本发明所述的阳离子-非离子型亲水单体的结构式中,通过非离子型的聚氧乙基亲水基团与潜在阳离子型的叔胺亲水基团的协同乳化分散作用,使阳离子-非离子型亲水单体具有较高的乳化分散性。同时,所述阳离子-非离子型亲水单体的结构式中不仅含有双羟基活性基团,而且还具有氨基甲酸酯和脲键结构,进而有利于提升阳离子-非离子型亲水单体与合成聚氨酯其他组分的相容性。
予以说明的是,R2、R3、R4的结构单元可以相同,也可以不同,本发明中不作限定。
具体地,R1选自碳原子数为4-14的烷基、环烷基或者芳烷基中的至少一种。
在一实施方式中,当R1选自甲苯基,R2选自正丙基,R3、R4分别独立的选自亚甲基,n=16时,所述阳离子-非离子型亲水单体的结构式如下式(1-1)所示,
在一实施方式中,当R1选自二环己基甲烷基,R2选自异丙基,R3、R4分别独立的选自乙基,n=12时,所述阳离子-非离子型亲水单体的结构式如下式(1-2)所示,
在一实施方式中,当R1选自六亚甲基,R2选自正丙基,R3、R4分别独立的选自异丙基,n=8时,所述阳离子-非离子型亲水单体的结构式如下式(1-3)所示,
在一实施方式中,当R1选自3,3,5-三甲基环己基,R2选自正丙基,R3、R4分别独立的选自乙基,n=4时,所述阳离子-非离子型亲水单体的结构式如下式(1-4)所示,
在一实施方式中,当R1选自甲苯基,R2选自正丙基,R3、R4分别独立的选自亚甲基,n=10时,所述阳离子-非离子型亲水单体的结构式如下式(1-5)所示,
在一实施方式中,当R1选自3,3,5-三甲基环己基,R2选自乙基,R3、R4分别独立的选自乙基,n=6时,所述阳离子-非离子型亲水单体的结构式如下式(1-6)所示,
本发明还提供一种如上所述的阳离子-非离子型亲水单体的制备方法,包括如下步骤:
S1,在保护气氛下,将二异氰酸酯、聚乙二醇单甲醚以及催化剂混合得到第一混合物,将所述第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%,得到中间产物;以及
S2,在保护气氛下,将所述中间产物与双羟基二元胺混合得到第二混合物,将所述第二混合物反应至异氰酸根在所述第二混合物中的含量为0,得到阳离子-非离子型亲水单体。
步骤S1中,为了引入非离子型的聚氧乙基亲水基团,使二异氰酸酯具有半封端结构,将二异氰酸酯、聚乙二醇单甲醚以及催化剂反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%。
具体地,所述二异氰酸酯选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯中的至少一种。
需要说明的是,所述聚乙二醇单甲醚是由环氧乙烷聚合得到的。为了得到具有不同电解质稳定性、冻/融稳定性和硬度的聚氨酯分散体,控制聚乙二醇单甲醚的聚合度为3-20。
在一实施方式中,所述催化剂在所述第一混合物中的质量分数为0.5‰-3‰。
具体地,所述催化剂选自二月桂酸二丁基锡、辛酸亚锡、有机铋催化剂中的至少一种。
在一实施方式中,所述将第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%的步骤中,反应温度为60℃-90℃,时间为1h-3h。
步骤S2中,为了引入亲水性的叔胺基团,同时使具有半封端结构的中间产物中的活性异氰酸根与叔胺基团反应完全,调控所述二异氰酸酯、所述聚乙二醇单甲醚与所述双羟基二元胺的摩尔比为1:(0.98-1.05):(0.95-1.02),优选为1:1:1。
具体地,所述双羟基二元胺选自N,N-双(2-羟乙基)乙二胺、[(4-氨基丁基)亚氨基]双甲醇、N-(3-氨基丙基)二乙醇胺、2,2'-[(2-氨基丙基)亚氨基]二乙醇、[(3-氨基丙基)亚氨基]双甲醇、1-[(3-氨基丙基)-(2-羟基丙基)-氨基]-2-丙醇中的至少一种。
在一实施方式中,所述将第二混合物反应至异氰酸根在所述第二混合物中的含量为0的步骤中,反应温度为30℃-50℃,时间为0.5h-1h。
本发明还提供一种如上所述的阳离子-非离子型亲水单体在制备聚氨酯中的应用。
该阳离子-非离子型亲水单体可用作羧酸型聚氨酯分散体合成的中和剂,分子上的叔胺结构可作为成盐基团,而分子上的非离子型的聚环氧乙烷亲水链段可作为外乳化剂起到协同乳化分散作用并分布在聚氨酯乳胶粒表面。另外,分子上的双羟基活性基团在水性聚氨酯分散体成膜时,还可与固化剂发生反应、固化交联,进一步提升聚氨酯胶膜的力学性能。
该阳离子-非离子型亲水单体也可用作阳非离子型外乳化剂,通过外乳化法制备聚氨酯分散体,分子上的叔胺结构和非离子型的聚环氧乙烷亲水链段作为亲水基团,二异氰酸酯结构作为具有锚定作用的疏水基团,该单体用作外乳化剂时,其与聚氨酯相容性好,且分子上具有反应活性羟基,也还可与固化剂发生反应、固化交联,进一步提升聚氨酯胶膜的力学性能。
该阳离子-非离子型亲水单体还适用于所有阳离子型聚氨酯分散体的合成,可以单独使用作为唯一的亲水单体,也可与其他一般阳离子、非离子亲水单体配合使用,适用范围广泛、操作简单,能明显提升水性聚氨酯材料的性能。
具体地,将阳离子-非离子型亲水单体与多异氰酸酯、聚多元醇、小分子多元醇进行聚合,得到含有叔胺基和非离子聚氧乙基亲水基团的聚氨酯预聚体,然后采用酸性中和剂进行中和,将叔胺基中和变成季铵盐阳离子亲水基团,最后再经加水分散乳化、扩链、减压蒸馏脱除溶剂,得到阳性-非离子型聚氨酯。
在其中一个实施例中,所述阳离子-非离子型亲水单体的质量为所述聚氨酯原料总质量的1%-6%。
因此,本发明提供一种具有较高的乳化分散性的阳离子-非离子型亲水单体,可以作为亲水扩链剂、中和剂或者乳化剂等用于制备聚氨酯,有利于提高聚氨酯的自乳化分散能力,进而使聚氨酯分子结构具有更强的“可裁剪设计性”,同时使聚氨酯具有良好的耐电解质性能、配伍性和力学性能,具有较高的实际应用价值。
以下,将通过以下具体实施例对所述阳离子-非离子型亲水单体及其制备方法和应用做进一步的说明。
实施例1
在有氮气保护的条件下,将87g的甲苯二异氰酸酯与368g的聚乙二醇单甲醚(n=16)搅拌均匀,加入0.68g的有机铋催化剂,在65℃下反应3h,直至异氰酸根的含量达到4.62%,得到中间产物。
将含有中间产物的反应体系降温到45℃,加入67g的[(3-氨基丙基)亚氨基]双甲醇,反应0.5h,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-1)所示,
实施例2
在有氮气保护的条件下,将131g的二环己基甲烷二异氰酸酯与280g的聚乙二醇单甲醚(n=12)搅拌均匀,加入0.82g的二月桂酸二丁基锡催化剂,在85℃下反应1.5h,直至异氰酸根的含量达到5.11%,得到中间产物。
将含有中间产物的反应体系降温到50℃,加入81g的2,2'-[(2-氨基丙基)亚氨基]二乙醇,反应0.5h,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-2)所示,
实施例3
在有氮气保护的条件下,将84g的六亚甲基二异氰酸酯与192g的聚乙二醇单甲醚(n=8)搅拌均匀,加入0.28g的有机铋催化剂,在75℃下反应2h,直至异氰酸根的含量达到7.61%,得到中间产物。
将含有中间产物的反应体系降温到40℃,加入95g的1-[(3-氨基丙基)-(2-羟基丙基)-氨基]-2-丙醇,反应45min,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-3)所示,
实施例4
在有氮气保护的条件下,将111g的异氟尔酮二异氰酸酯与104g的聚乙二醇单甲醚(n=4)搅拌均匀,加入0.56g的辛酸亚锡催化剂,在90℃下反应1h,直至异氰酸根的的含量达到9.77%,得到中间产物。
将含有中间产物的反应体系降温到35℃,加入81g的N-(3-氨基丙基)二乙醇胺,反应1h,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-4)所示,
实施例5
在有氮气保护的条件下,将87g的甲苯二异氰酸酯与236g的聚乙二醇单甲醚(n=10)搅拌均匀,加入0.23g的辛酸亚锡催化剂,在70℃下反应2.5h,直至异氰酸根的含量达到6.50%,得到中间产物。
将含有中间产物的反应体系降温到30℃,加入74g的[(4-氨基丁基)亚氨基]双甲醇,反应1h,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-5)所示,
实施例6
在有氮气保护的条件下,将111g的异氟尔酮二异氰酸酯与148g的聚乙二醇单甲醚(n=6)搅拌均匀,加入0.34g的有机铋催化剂,在80℃下反应2h,直至异氰酸根的含量达到8.11%,得到中间产物。
将含有中间产物的反应体系降温到40℃,加入74g的N,N-双(2-羟乙基)乙二胺,反应45min,直至异氰酸根的含量为0,得到阳离子-非离子型亲水单体,其结构式如下式(1-6)所示,
采用傅立叶红外光谱仪对制备得到的阳离子-非离子型亲水单体进行红外测试,得到如图1所示的红外光谱图。根据图1可知,1105cm-1处的强吸收峰为聚氧乙基链段中醚键(-C-O-C-)的伸缩振动吸收峰;2270cm-1处的异佛尔酮二异氰酸酯中异氰酸酯基(-NCO)的吸收峰消失,在1713cm-1出现羟基与异氰酸酯基反应生成的氨基甲酸酯键(-NHCOO-)的羰基吸收峰,在1660cm-1处出现胺基与异氰酸酯基(-NCO)反应生成的脲基(-NHCONH-)的羰基吸收峰。从上述红外测试结果可知,通过本申请提出的制备方法能够制备得到结构式如式(1-6)所示的阳离子-非离子型亲水单体。
应用实施例1
将50g的聚己二酸丁二醇乙二醇酯二醇(摩尔质量为1000g/mol)在105℃下真空脱水2h。然后通入氮气,降温至70℃,加入20g的六亚甲基二异氰酸酯和10g的异佛尔酮二异氰酸酯,在85℃下反应2h。加入3g实施例1制备得到的阳离子-非离子型亲水单体(其用量为聚氨酯原料总质量的3.2%)、7g的一缩二乙二醇以及5g的丁酮,在80℃下反应3h,得到亲水改性的聚氨酯预聚体。降温至55℃,加入0.52g的冰醋酸中和10min,在2000rpm的高速搅拌下将预聚体分散于192g的去离子水中形成分散液,随后加入26.2g的己二胺溶液(质量分数为10%),于3min内滴加完,然后再反应10min。最后,减压脱去溶剂,得到阳性-非离子型聚氨酯分散体(固含量为30%)。
应用对比例1
应用对比例2
应用对比例3
应用对比例4
应用对比例5
实验结果测试及分析:
实验测试方法:
1.粒径测试:将样品用去离子水稀释至含固量为0.5%,吸取适量样品稀释液至样品池中,并将样品池中气泡赶出,采用纳米粒度分析仪测定其粒径。
2.配伍稳定性:在10ml带有刻度的试管中,用滴管加入5ml乳液,然后缓慢加入1ml1%的NaCl溶液或0.1%的CaCl2溶液,充分摇匀后放置试管架上,于24h后观察,是否发生破乳、沉淀、絮凝等现象。
实验结果分析:将应用实施例1和应用对比例1-5制备得到的水性聚氨酯分散体进行性能测试,测试结果如表1所示。
表1
从表1中可以看出,与其他应用对比例相比,应用实施例1得到的水性聚氨酯分散体粒径小、与钠盐和钙盐溶液配伍稳定性好,即该聚氨酯分散体具有更好的耐电解质性能。这说明新型的阳离子-非离子型亲水单体作为亲水扩链剂使用时,能赋予聚氨酯分子链更强的自乳化分散能力,同时明显改善了聚氨酯分散体的耐电解质性能和配伍性。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
2.根据权利要求1所述的阳离子-非离子型亲水单体,其特征在于,R1选自碳原子数为4-14的烷基、环烷基或者芳烷基中的至少一种。
3.一种如权利要求1或权利要求2所述的阳离子-非离子型亲水单体的制备方法,其特征在于,包括如下步骤:
在保护气氛下,将二异氰酸酯、聚乙二醇单甲醚以及催化剂混合得到第一混合物,将所述第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%,得到中间产物;以及
在保护气氛下,将所述中间产物与双羟基二元胺混合得到第二混合物,将所述第二混合物反应至异氰酸根在所述第二混合物中的含量为0,得到阳离子-非离子型亲水单体。
4.根据权利要求3所述的阳离子-非离子型亲水单体的制备方法,其特征在于,所述二异氰酸酯、所述聚乙二醇单甲醚与所述双羟基二元胺的摩尔比为1:(0.98-1.05):(0.95-1.02)。
5.根据权利要求3所述的阳离子-非离子型亲水单体的制备方法,其特征在于,所述二异氰酸酯选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯中的至少一种。
6.根据权利要求3所述的阳离子-非离子型亲水单体的制备方法,其特征在于,所述双羟基二元胺选自N,N-双(2-羟乙基)乙二胺、[(4-氨基丁基)亚氨基]双甲醇、N-(3-氨基丙基)二乙醇胺、2,2'-[(2-氨基丙基)亚氨基]二乙醇、[(3-氨基丙基)亚氨基]双甲醇、1-[(3-氨基丙基)-(2-羟基丙基)-氨基]-2-丙醇中的至少一种。
7.根据权利要求3所述的阳离子-非离子型亲水单体的制备方法,其特征在于,所述聚乙二醇单甲醚的聚合度为3-20。
8.根据权利要求3所述的阳离子-非离子型亲水单体的制备方法,其特征在于,所述将第一混合物反应至异氰酸根在所述第一混合物中的含量为异氰酸根初始摩尔含量的50%的步骤中,反应温度为60℃-90℃;
及/或,所述将第二混合物反应至异氰酸根在所述第二混合物中的含量为0的步骤中,反应温度为30℃-50℃。
9.一种如权利要求1或权利要求2所述的阳离子-非离子型亲水单体在制备聚氨酯中的应用。
10.根据权利要求9所述的阳离子-非离子型亲水单体在制备聚氨酯中的应用,其特征在于,所述阳离子-非离子型亲水单体的质量为所述聚氨酯原料总质量的1%-6%。
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