CN113061242A - 一种聚醚胺化合物、其制备方法及应用 - Google Patents
一种聚醚胺化合物、其制备方法及应用 Download PDFInfo
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- CN113061242A CN113061242A CN202110289422.5A CN202110289422A CN113061242A CN 113061242 A CN113061242 A CN 113061242A CN 202110289422 A CN202110289422 A CN 202110289422A CN 113061242 A CN113061242 A CN 113061242A
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- polyether
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- polyetheramine
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 70
- 229920000570 polyether Polymers 0.000 title claims abstract description 70
- -1 amine compound Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000004185 ester group Chemical group 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 125000001302 tertiary amino group Chemical group 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000010687 lubricating oil Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 210000003918 fraction a Anatomy 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000003141 primary amines Chemical class 0.000 abstract 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical group [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 16
- 239000000391 magnesium silicate Substances 0.000 description 16
- 229910052919 magnesium silicate Inorganic materials 0.000 description 16
- 235000019792 magnesium silicate Nutrition 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005086 pumping Methods 0.000 description 13
- 238000007670 refining Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 3
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- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 3
- 229940073769 methyl oleate Drugs 0.000 description 3
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
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- 239000003729 cation exchange resin Substances 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-ethyl-N-phenylamine Natural products CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QIYDQYBDGDYJKD-UHFFFAOYSA-N methyl 6-methylheptanoate Chemical compound COC(=O)CCCCC(C)C QIYDQYBDGDYJKD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 1
- KEDLMUMBOSGJTL-UHFFFAOYSA-N n-ethylaniline Chemical compound [CH2]CNC1=CC=CC=C1 KEDLMUMBOSGJTL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
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- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
本发明提供一种聚醚胺化合物、其制备方法和应用，其中聚醚胺化合物的分子式为M（OCnH2n)mR，其中M为叔氨基封端的基团，R为酯基，m和n均为正整数。本发明中的聚醚胺化合物与伯胺、仲胺封端的聚醚胺性能相当，可应用于到汽油清净剂中。其具有合成路线相对简单、反应条件相对温和、原料易得、设备要求较低和加工成本较低的优点。
Description
技术领域
本发明属于汽油添加剂的技术领域，具体涉及一种聚醚胺化合物、其制备方法和应用。
背景技术
汽油清净剂是一种具有清净、分散、抗氧和防锈性能的复合汽油添加剂，加入车用汽油中既能抑制燃油系统内部沉积物的生成，又能将已生成的氧化沉积物迅速分散、清除，进而确保汽车发动机动力性正常发挥，使燃油的燃烧性能得到改善。一般高品质的汽油清净剂以聚醚胺为最主要成分，聚醚胺又称端氨基聚醚，是一类以聚氧化烷基结构为主链，以末端的胺基为活性官能团的化合物。
聚醚胺为一种油溶性表面活性剂，传统的汽油聚醚胺的合成方法是聚醚胺化还原法，实质是将聚醚、氨和氢气的混合物在一定温度、压力及催化剂存在下直接进行临氢催化还原胺化生产聚醚胺。这种方法虽然产物转化率高，杂质少，活性高，生产中需要使用氨气、氢气，属于危险工艺。而且反应的压力温度较高，增加了设备投资。合成过程中使用了昂贵的催化剂，又增加了生产成本。聚醚胺合成的主要方法还有离去基团法、水解法和硝基封端法，这三种方法都是先用活泼基团与聚醚多元醇羟基上的氢进行反应得到中间体，再后处理得到聚醚胺产品。但它们都存在着所添加的试剂有毒、污染环境且不易购置的缺点，尤其是副反应较多，产生的副产物也较多，降低了聚醚的转化率；而且，在后处理过程中需要加入大量的酸或碱进行中和，生成大量的无机盐。鉴于目标产物聚醚胺与无机盐的相容性，为产物的分离带来不便。
为了解决上述问题，我们一直在寻求一种理想的技术解决方案。
发明内容
本发明的目的是针对现有技术的不足，从而提供一种与氨基封端的聚醚胺性能相当，有望应用于实际的汽油清净剂中。其合成路线相对简单，反应条件相对温和，原料相对易得、设备要求相对较低、加工成本也相对较低。
本申请的技术方案为：一种聚醚胺化合物，其分子式为M（OCnH2n)mR，其中M为叔氨基封端的基团，R为酯基，m和n均为正整数。该聚醚胺与伯氨基或者仲氨封端的聚醚胺性能相当，可作为汽油清洁剂或者润滑油添加剂使用。
作为技术方案的进一步改进，聚醚胺化合物的分子量为500-1500，清洁效果好，更优选聚醚胺化合物的分子量为800-1200。
作为技术方案的进一步改进，M中叔氨基个数为i,1≤i≤3,,i为正整数。叔氨基数量增加后清洁效果更好，但是氨基过多的话会增加乳化的可能性，反而清洁效果降低
作为技术方案的进一步改进，所述M中封端的氨基为叔氨基、芳叔氨基和杂环叔氨基中的其中之一。
作为技术方案的进一步改进，为了提高清洁效果，3≤n≤7。
作为技术方案的进一步改进，为了提高清洁效果，12≤m≤20。
作为技术方案的进一步改进，R为C6～C26的长链酯基，更优选R为C8～C18的酯基，相关化合物更为常见、易得。
上述聚醚胺化合物的制备方法，包括：
步骤一、以具有一个活性基团的叔氨基封端化合物为起始剂，进行烷氧基化反应合成初步聚醚，所述活性基团为-OH或者-NH。该步反应中催化剂是碱金属氢氧化物，如氢氧化钠、氢氧化钾、氢氧化铯、氢氧化钡或其组合。催化剂的使用量是第一步合成聚醚总质量的0.1%至0.5%。烷氧基化的温度为100～130℃。反应的压力为0.1～0.5Mpa。向聚醚中加入占聚醚1～10wt%的去离子水和1～5wt%的中性精制剂，中性精制剂如硅酸镁，搅拌后升温脱水至水分小于1000ppm，得到初步聚醚。
步骤二、将初步聚醚进行酯交换反应，将初步聚醚分子末端的-OH转化酯基，得到末端改性后的聚醚化合物。酯交换反应所用催化剂为非均相酯交换催化剂，包括固体酸和固体碱，固体酸是沸石分子筛、杂多酸、阳离子交换树脂、固体超强酸之一；固体碱是以氧化铝为载体的固体碱，也可以是非水溶性的金属氧化物，如氧化镁、氧化锌或者稀土氧化物。酯化后需要对聚醚进行精制，向其中加入占聚醚1～10wt%的水，70～80℃搅拌1小时，加入其质量1～5wt%的中性精制剂，中性精制剂如硅酸镁，升温脱水至水分含量降低至300ppm，抽滤得到最终聚醚产物。
作为技术方案的进一步改进，步骤二采用的酯类化合物为高级脂肪酸酸的甲酯或乙酯，酯交换后后生成的甲醇或者乙醇更易除去。
作为技术方案的进一步改进，步骤二中酯类化合物与聚醚的摩尔比为1～1.5，反应的温度为60～150℃，反应压力为0.1～0.8atm，反应时间为3～15小时。
上述聚醚胺化合物的应用为：所述聚醚胺化合物作为汽柴油清净剂主剂，其质量分数a为1≤a≤40%，或者所述聚醚胺化合物作为润滑油的添加剂，其质量分数b为0＜b≤1%。
本发明相对现有技术具有突出的实质性特点和显著的进步，具体的说，本发明提供一种叔氨基封端的聚醚胺，与伯氨基或者仲氨封端的聚醚胺性能相当，可作为汽油清洁剂或者润滑油添加剂使用；进一步说，该聚醚胺是以胺或者醇胺为起始剂，原料相对易得，加工成本也相对较低；再一步说，该聚醚胺经过两步反应制得，合成路线相对简单，反应条件相对温和，对设备要求相对较低。本发明的聚醚胺及其制备方法具有合成路线相对简单、反应条件温和、原料易得和加工成本较低的优点。
具体实施方式
下面通过具体实施方式，对本发明的技术方案做进一步的详细描述。
各实施例中的所用原料均来自于市售。
实施例1
以85g N,N二甲基乙醇胺为起始剂，以3g氢氧化钾为催化剂，在105~115℃下，搅拌30min，压力为-0.01Mpa。然后再缓慢通入900g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为950。
中间体加入沸石负载磺酸基催化剂0.95g，等摩尔量1.1倍的异辛酸甲酯，通氮置换两次，后在110℃下抽负压至-0.09Mpa，持续6小时，得到酯化封端产物。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，化验水分小于300ppm后，过滤得到产品。
实施例2
以97g N,N二甲基异丙醇胺为起始剂，以3g氢氧化铯为催化剂，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入750g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为823。
初步聚醚中加入分子筛负载磺酸基催化剂4.2g，等摩尔量1.3倍的异辛酸乙酯，通氮置换两次，后在150℃下抽负压至-0.02Mpa，持续6小时。得到酯化封端产物。
向烷基化改性后的产物中加入60g去离子水和硅酸镁15g，加热至80℃，抽负压至-0.03Mpa，直至化验水分小于300ppm后，过滤得到产品。
实施例3
以102g N,N,N三甲基乙二胺为起始剂，以3g氢氧化钡为催化剂，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入800g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为850。
向初步聚醚中加入1.5倍摩尔量的硬脂酸甲酯，8g强酸型阳离子交换树脂催化剂，通氮置换两次，后在抽负压至-0.01Mpa，80℃反应下，持续8小时。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，直至化验水分小于300ppm后，过滤得到产品。
实施例4
以121g N乙基苯胺为起始剂，以3g氢氧化铯为催化剂，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入730g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为830。
向初步聚醚中加入1.4倍摩尔量的软脂酸甲酯，5g催化剂杂多酸，通氮置换两次，后在抽负压至-0.01Mpa，80℃反应下，持续15小时。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，化验水分小于300ppm后，过滤得到产品。
实施例5
以85g N,N二甲基乙醇胺为起始剂，3g催化剂氢氧化钠，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入700g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为755。
向初步聚醚中加入1.4倍摩尔量的油酸甲酯，3.5g氧化铝负载氢氧化钠载体催化剂，通氮置换两次，后在抽负压至-0.01Mpa，80℃反应下，持续10小时。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，化验水分小于300ppm后，过滤得到产品。
实施例6
以85g N,N二甲基乙醇胺为起始剂，3g氢氧化钠催化剂，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入700g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为503。
向初步聚醚中加入1.05倍摩尔量的油酸甲酯，3.5g催化剂氧化镁，通氮置换两次，后在抽负压至-0.01Mpa，170℃反应下，持续10小时。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，化验水分小于300ppm后，过滤得到产品。
实施例7
以84.1g 2-甲基咪唑啉为起始剂，3g催化剂氢氧化钠，在105~115℃下，搅拌30min，压力为-0.05Mpa。再通入700g环氧丙烷进行烷氧基化反应。使用硅酸镁精制得到初步聚醚，测定分子量为760。
向初步聚醚中加入1.05倍摩尔量的油酸甲酯，3.5g催化剂氧化锌，通氮置换两次，后在抽负压至-0.01Mpa，170℃反应下，持续10小时。
向烷基化改性后的产物中加入60g去离子水，加入硅酸镁15g。加热至80℃，抽负压至-0.03Mpa，化验水分小于300ppm后，过滤得到产品。
性能评价：
1、依据GB19592-2004进行清净性评价。采用汽油机进气阀沉积物的模拟实验方法，在规定的实验条件下，将定量的的基础汽油或实验汽油经过喷嘴与空气混合并喷射到一个已经称重并加热到试验温度条件下的沉积物收集器上，模拟汽油机进气阀沉积物生成。模拟汽油中加入聚醚胺的量为150ppm，然后将生成的沉积物称量，结果见表一。
2、依据GB/T19230.2-2003进行破乳性评价，结果见表一。
表一 各实施例聚醚胺性能测试结果
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | FL-1000 | |
| 沉积物（mg） | 0.5 | 0.3 | 0.4 | 0.1 | 0.6 | 0.6 | 0.6 | 0.3 |
| 破乳性界面 | 1b | 1b | 1b | 1b | 1b | 1b | 1b | 1b |
| 破乳相分离 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 1 |
从以上数据可知，该聚醚胺的阻垢性能与亨斯曼FL-1000类似，可以作为汽柴油清净剂主剂使用，也可以作为润滑油添加剂使用，达到了市面上优质汽油清洁剂的品质。
最后应当说明的是:以上实施例仅用以说明本发明的技术方案而非对其限制；尽管参照较佳实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解，依然可以对本发明的具体实施方式进行修改或者对部分技术特征进行等同替换；而不脱离本发明技术方案的精神，其均应涵盖在本发明请求保护的技术方案范围当中。
Claims (10)
1.一种聚醚胺化合物，其特征在于，其分子式为M（OCnH2n)mR，其中M为叔氨基封端的基团，R为酯基，m和n均为正整数。
2.根据权利要求1所述的聚醚胺化合物，其特征在于，聚醚胺化合物的分子量为500-1500。
3.根据权利要求1或2所述的聚醚胺化合物，其特征在于，M中叔氨基个数为i,1≤i≤3,i为正整数。
4.根据权利要求3所述的聚醚胺化合物，其特征在于，所述M中封端的氨基为叔氨基、芳叔氨基和杂环叔氨基中的其中之一。
5.根据权利要求1或2所述的聚醚胺化合物，其特征在于，3≤n≤7。
6.根据权利要求1或2所述的聚醚胺化合物，其特征在于，12≤m≤20。
7.根据权利要求1或2所述的聚醚胺化合物，其特征在于，R为C6～C26的长链酯基。
8.如权利要求1-7任一项所述聚醚胺化合物的制备方法，包括：
步骤一、以具有一个活性基团的叔氨基封端化合物为起始剂，进行烷氧基化反应合成初步聚醚，所述活性基团为-OH或者-NH；
步骤二、将初步聚醚进行酯交换反应，将初步聚醚分子末端的-OH转化酯基，得到末端改性后的聚醚化合物。
9.根据权利要求8所述的聚醚胺化合物的制备方法，其特征在于，步骤二采用的酯类化合物为高级脂肪酸酸的甲酯或乙酯。
10.如权利要求1-7任一项所述聚醚胺化合物的应用，其特征在于，所述聚醚胺化合物作为汽柴油清净剂主剂，其质量分数a为1≤a≤40%，或者所述聚醚胺化合物作为润滑油的添加剂，其质量分数b为0＜b≤1%。
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