CN102962005A - Ethoxylated trimester-group quaternary ammonium salt and preparation method thereof - Google Patents
Ethoxylated trimester-group quaternary ammonium salt and preparation method thereof Download PDFInfo
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- ethoxylated
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 14
- -1 triester group quaternary ammonium salt Chemical class 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 61
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- 125000004185 ester group Chemical group 0.000 claims description 18
- 150000002148 esters Chemical group 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229940100198 alkylating agent Drugs 0.000 claims description 9
- 239000002168 alkylating agent Substances 0.000 claims description 9
- 230000008676 import Effects 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 5
- 229930195729 fatty acid Natural products 0.000 claims 5
- 239000000194 fatty acid Substances 0.000 claims 5
- 150000004665 fatty acids Chemical class 0.000 claims 5
- 150000004671 saturated fatty acids Chemical class 0.000 claims 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims 1
- 229940008406 diethyl sulfate Drugs 0.000 claims 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000003780 insertion Methods 0.000 claims 1
- 230000037431 insertion Effects 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 150000005691 triesters Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 24
- 229960004418 trolamine Drugs 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004902 Softening Agent Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 3
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical compound OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 description 3
- 229940029614 triethanolamine stearate Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 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 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 229940067592 ethyl palmitate Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229940098695 palmitic acid Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种乙氧基化三酯基季铵盐及的化学特征结构式如下:式中：R为C6-C22的饱和或不饱和的直链烷基，饱和或不饱和的支链烷基； X-代表烷基化阴离子；a、b、c相同或不同，为乙氧基的个数，平均值为3-20。本发明具有能耗低，转化率高，选择性好，产品纯度高的优点。
A kind of ethoxylated triester group quaternary ammonium salt and the chemical characteristic structural formula are as follows: In the formula: R is a C 6 -C 22 saturated or unsaturated straight-chain alkyl group, a saturated or unsaturated branched-chain alkyl group; X - represents an alkylated anion; a, b, and c are the same or different, and are ethyl The number of oxygen groups, the average value is 3-20. The invention has the advantages of low energy consumption, high conversion rate, good selectivity and high product purity.
Description
Technical field
The invention belongs to a kind of ethoxylation three ester based quaternary ammonium salts and preparation method thereof.
Background technology
Ester based quaternary ammonium salt is the emerging green cationic surfactant of a class, very easily biodegradation, not only have good biological degradability, compatibility, antistatic behaviour, flexibility, and cost of material is low, can not cause the rear yellowing of fabric, but the product of production high concentration is the Typical Representative in " green " softening agent.The later stage eighties 20th century, ester based quaternary ammonium salt obtained development at full speed along with the attention of people to environmental protection, and the ester based quaternary ammonium salt for preparing take triethanolamine as raw material on the international market has at present become the main product of fabric softener.
The key component of ester based quaternary ammonium salt is single, double, three ester amine quaternary ammonium salts, and what wherein soft effect, antistatic effect effect were best is the quaternary ammonium salt of diester amine, and monoesters amine quaternary ammonium salt takes second place, and three ester amine quaternary ammonium salts are relatively poor as the softening agent practical effect.Present research mainly concentrates on the content that how to improve diester amine quaternary ammonium salt, and reaction condition is wayward.The at present research for preparation high-purity ethoxylation three ester based quaternary ammonium salts has no report.
Summary of the invention
The purpose of this invention is to provide a kind of highly purified ethoxylation three ester based quaternary ammonium salts and preparation method thereof.
Ethoxylation three ester based quaternary ammonium salts of the present invention, its chemical feature structural formula is as follows:
X
-Represent the alkylation anion;
A, b, c are identical or different, are the number of ethyoxyl, and mean value is 3-20.
Synthetic method of the present invention is that stearic acid and triethanolamine carry out the ester aminating reaction with certain proportion, uses ester group plug-in type ethoxylation catalyst again, finishes the ethoxylation modification of three ester amine.Ethoxylation three ester amine and alkylating agent carry out quaterisation and obtain ethoxylation three ester based quaternary ammonium salts, and concrete preparation method comprises the steps:
(1) aliphatic acid is added in the reactor, stir and be warmed up to 70-120 ℃, after it all melts, add acidic catalyst and triethanolamine, be warming up to 200-220 ℃, reacted 6-10 hour, when the product acid value was lower than 5mgKOH/g, cessation reaction obtained three ester amine;
(2) with after three ester amine and the mixing of ester group plug-in type ethoxylation catalyst, under agitation add reactor, use N
2Displace the air in the reactor, be warming up to reaction temperature 160-220 ℃, operating pressure is 0.1-2.0MPa, is keeping importing oxirane under the reaction pressure condition, and aging 30-120min is cooled to 50-80 ℃ of discharging, obtains ethoxylation three ester amine;
(3) ethoxylation three ester amine are warming up to 40-50 ℃, treat that ethoxylation three ester amine melt fully, stopped heating, add isopropyl alcohol and alkylating agent, continue to be heated to 60-80 ℃, carry out quaterisation, reaction 5-8h, unhindered amina quality percentage composition is lower than 2% in recording product, can stop reaction.
Each component addition is: the mol ratio of aliphatic acid and triethanolamine is 3.0-3.3:1, and the acidic catalyst consumption is 0.5 ‰-5 ‰ of aliphatic acid and triethanolamine gross weight, is preferably 1 ‰-5 ‰.Three ester amine: the mol ratio of oxirane is 1:9-18; The consumption of ester group plug-in type ethoxylation catalyst is 0.5 ‰-10.0 ‰ of three ester amine and oxirane gross weight; The mol ratio of ethoxylation three ester amine and alkylating agent is 1.0:0.9-1.1.The isopropyl alcohol consumption is the 10%-20% of ethoxylation three ester amine and alkylating agent gross weight.
Described aliphatic acid is C
6-C
22Saturated and unrighted acid, such as stearic acid, palmitic acid, oleic acid, laurate or behenic acid etc.
Described alkylating agent is halogen methane, dimethyl suflfate, dithyl sulfate, dimethyl carbonate, diethyl carbonate or trimethyl phosphate.
Aforesaid ester group plug-in type ethoxylation catalyst is that alkaline earth oxide is 30-90wt%, and the III family metal oxide is 1-40wt%, and carrier is 1-30wt%.Concrete preparation method has a detailed description in Chinese patent CN 1190265C.
Aforesaid acidic catalyst is sulfuric acid, phosphorous acid, p-methyl benzenesulfonic acid, alkyl benzene sulphonate.
Ethoxylation three ester based quaternary ammonium salts of the present invention are positive non-ionic surface active agent, have both had the character of cationic surfactant, can be used on fabric softener, the leather softening agent, the many-sides such as bactericide also have non-ionic characteristic simultaneously, can also be used for emulsifying agent, washing agent etc.
The present invention compares with traditional ester based quaternary ammonium salt and has the following advantages:
1. this product has the detergency that traditional ester based quaternary ammonium salt does not possess, and can play certain clean result in the time of as softening agent.
2. this product is as a kind of novel positive non-ionic surface active agent, with cation and non-ionic characteristic.
3. the adding of polyoxyethylene groups, can improve the problems such as quaternary ammonium salt cationic and the composite difficulty of anion surfactant greatly.
4. adopt this synthetic method, energy consumption is low, and conversion ratio is high, and is selectively good, and product purity is high.
Following examples are to further specify of the present invention, but do not limit in any form the present invention.
Description of drawings
Fig. 1 is the intermediate product of example 1 and the IR Characterization figure of end product;
Fig. 2 is the intermediate product of example 1 and the nuclear-magnetism phenogram of end product.
Specific implementation method
Embodiment 1:
With being dissolved with the aqueous solution 300mL of aluminum nitrate 90g and diatomite 29g, being added dropwise among the dispersion liquid 150mL that contains 60g CaO, stir 1hr under the room temperature, get a mixed catalyst slip, this slip is removed NO through strong-base anion-exchange resin
3 -, after ion-exchange is finished, catalyst is separated from ion exchange resin, drying, at 500 ℃ of lower calcining 1hr, grinding is sieved, and obtaining consisting of CaO is 36wt%, and aluminium oxide is 34wt%, and diatomite is the Ca-Al ester group plug-in type ethoxylation catalyst of 30wt%.
Take by weighing in the four-hole boiling flask that the 300g stearic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 120 ℃, after it all melts, add 0.9g sulfuric acid and 99g triethanolamine, be warming up to 210 ℃, react after 8 hours, recording the product acid value is 3.5mgKOH/g, and stopped reaction obtains three ester amine.
The above-mentioned ester group plug-in type of 2.4g ethoxylation catalyst is joined in the three ester amine, stir in the lower 1L of the input autoclave, open and stir, N
2Displaced air is warming up to 160 ℃, imports oxirane, keeps system pressure 0.1MPa, when being 50g to the oxirane addition, and closed loop oxidative ethane inlet valve, aging 30min is cooled to 50 ℃, and discharging obtains ethoxylation three ester amine, and 148g weighs.
Ethoxylation three ester amine are joined in the 250mL four-hole bottle, be heated to 50 ℃, stopped heating adds 13g isopropyl alcohol and dimethyl suflfate 8.8g, is warming up to 70 ℃, reaction 6h, and the product unhindered amina content of survey is 1.36%, stops reaction.
Obtaining that average ethyoxyl adds and count is 3.0 ethoxylation three ethyl stearte ylmethyl sulfate methyl ammoniums (3EQDMS-3EO).Wherein, average EO adduction number adopts the method for perchloric acid-glacial acetic acid nonaquepous tration to be defined as 3.0, and IR Characterization figure and nuclear-magnetism phenogram are as shown in Figure 1 and Figure 2.As can be seen from Figure 1, the infrared signature absworption peak of triethanolamine stearate three esters is 2940～2840 cm
-1(C-H), 1740 cm
-1(C=O), 1649 cm
-1(C-N), 1170 cm
-1(C-O), and greater than 3 000 cm
-1The place illustrates the content of single, double ester amine in the intermediate product seldom without obvious hydroxyl characteristic absorption peak; 3EQDMS-3EO and ethoxylation triethanolamine stearate three esters are at 1110 cm
-1The place has very strong characteristic absorption peak to occur, and showing has-existence of C-O-C-group.This shows, inserted polyoxyethylene chain in the product.As can be known from Fig. 2, the chemical shift of each proton of end product 3EQDMS-3EO is attributed to: 0.88 (3H, 1), 1.26 (26H, 2), 1.61 (2H, 3), (2.32 3H, 4), 3.32 (3H, 8), 3.68～3.80 (21H, 6), (3.82 2H, 7), 3.98 (2H, 9), 4.17 (3H, 5).Compare with intermediate product ethoxylation triethanolamine stearate three esters, 3EQDMS-3EO's
1The proton peak that 3.32 (3H, 8) and 3.98 (2H, 9) are located in the HNMR spectrogram can show quaterisation has occured.Comprehensive above IR with
1The analysis result of HNMR can confirm that end product is 3EQDMS-3EO.The analysis of following examples is identical.
MgO 33g and diatomite 12g are mixed, add among the aqueous solution 190mL of chloride containing aluminium 10.5g, stir 1hr, washing, drying at 500 ℃ of lower calcining 1hr, are ground, sieve, obtaining consisting of MgO is 60wt%, and aluminium oxide is 14.4wt%, and diatomite is the Mg-Al ester group plug-in type ethoxylation catalyst of 25.6wt%.
Take by weighing in the four-hole boiling flask that the 300g laurate joins 500mL, at N
2Stir under the condition of protection and be warmed up to 90 ℃, after it all melts, add 3.5g phosphorous acid and 55.8g triethanolamine, be warming up to 200 ℃, react after 7 hours, recording the product acid value is 4.5mgKOH/g, and stopped reaction obtains three ester amine.
The above-mentioned ester group plug-in type of 3.5g ethoxylation catalyst is joined in the three ester amine, stir in the lower 1L of the input autoclave, open and stir, N
2Displaced air is warming up to 180 ℃, imports oxirane, keeps system pressure 1.0MPa, when being 96g to the oxirane addition, and closed loop oxidative ethane inlet valve, aging 70min is cooled to 75 ℃, and discharging obtains ethoxylation three ester amine, and 194g weighs.
Ethoxylation three ester amine are joined in the 250mL four-hole bottle, be heated to 40 ℃, stopped heating adds 15g isopropyl alcohol and chloromethanes 9.2g, is warming up to 80 ℃, reaction 5h, and the product unhindered amina content of survey is 1.37%, stops reaction.Obtaining that average ethyoxyl adds and count is 6.0 ethoxylation three ethyl laurate ylmethyl ammonium chlorides.
MgO 79.3g and diatomite 30g are mixed, add among the aqueous solution 500mL of chloride containing aluminium 25g and zinc chloride 1.2g, stir 1hr, washing, drying at 500 times calcining 1hr, are ground, and sieve, and get Mg-Al-Zn ester group plug-in type ethoxylation catalyst.Obtaining consisting of magnesia is 65.3wt%, and aluminium oxide is 9.7wt%, and diatomite is 24.4wt%, and zinc oxide is 0.6% the Mg-Al-Zn ester group plug-in type ethoxylation catalyst that contains gallium ion.
Take by weighing in the four-hole boiling flask that 276g oleic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 100 ℃, after it all melts, add 1g p-methyl benzenesulfonic acid and 120g triethanolamine, be warming up to 210 ℃, react after 10 hours, recording the product acid value is 3.5mgKOH/g, and stopped reaction obtains three ester amine.
The above-mentioned ester group plug-in type of 3.4g ethoxylation catalyst is joined in the three ester amine, stir in the lower 2L of the input autoclave, open and stir, N
2Displaced air is warming up to 200 ℃, imports oxirane, keeps system pressure 0.5MPa, when being 414g to the oxirane addition, closes the EO inlet valve, and aging 50min is cooled to 70 ℃, and discharging obtains ethoxylation three ester amine, and 569g weighs.
Ethoxylation three ester amine are joined in the 500mL four-hole bottle, be heated to 40 ℃ of stopped heatings, add 46g isopropyl alcohol and 20g dimethyl suflfate, be warming up to 65 ℃, reaction 8h, the product unhindered amina content of survey is 1.46%, stops reaction.Obtaining that average EO adds and count is 9.0 ethoxylation three ethyl oleate ylmethyl sulfate methyl ammoniums.
Embodiment 4
The 15gMgO powder is mixed with the 7.5g4A zeolite, add contain 1.9% gallium nitrate aqueous solution 400mL in, strong stirring 1hr, at 120 ℃ of lower dry 2hr, 500 ℃ of lower calcining 1hr grind, and sieve, and must contain the MgO ester group plug-in type ethoxylation catalyst of gallium ion.Obtaining consisting of magnesia is 63.2wt%, and gallium oxide is 11.4wt%, and the 4A zeolite is the MgO ester group plug-in type ethoxylation catalyst that contains gallium ion of 25.4wt%.
Take by weighing in the four-hole boiling flask that the 278g palmitic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 70 ℃, after it all melts, add 0.68g sulfuric acid and 80g triethanolamine, be warming up to 220 ℃, react after 6 hours, recording the product acid value is 4.1mgKOH/g, and stopped reaction obtains three ester amine.
The above-mentioned ester group plug-in type of 4.1g ethoxylation catalyst is joined in the three ester amine, stir in the lower 1L of the input autoclave, open and stir, N
2Displaced air is warming up to 220 ℃, imports oxirane, keeps system pressure 2.0MPa, when being 200g to the oxirane addition, closes the EO inlet valve, and aging 120min is cooled to 80 ℃, and discharging obtains ethoxylation three ester amine, and 386g weighs.
Ethoxylation three ester amine are joined in the 500mL four-hole bottle, be heated to 45 ℃, stopped heating adds 50g isopropyl alcohol and Celfume 34g, is warming up to 60 ℃, reaction 7h, and the product unhindered amina content of survey is 1.56%, stops reaction.Obtaining that average EO adds and count is 10.0 ethoxylation three ethyl palmitate ylmethyl ammonium bromides.
Take by weighing in the four-hole boiling flask that the 210g stearic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 110 ℃, after it all melts, add 1.3g hydrochloric acid and 112g triethanolamine, be warming up to 220 ℃, react after 6 hours, recording the product acid value is 3.5mgKOH/g, and stopped reaction obtains three ester amine.
Take by weighing that ester group plug-in type ethoxylation catalyst joins in the three ester amine in the 5.0g example 1, stir in the lower 2L of the input autoclave N
2Displaced air is warming up to 190 ℃, imports oxirane, keeps system pressure 1.5MPa, when being 520g to the oxirane addition, closes the EO inlet valve, and aging 60min is cooled to 60 ℃, and discharging obtains ethoxylation three ester amine, and 746g weighs.
Ethoxylation three ester amine are joined in the 250mL four-hole bottle, be heated to 50 ℃, stopped heating adds, and 13g isopropyl alcohol and dithyl sulfate 22g dropwise and be warming up to 75 ℃, reaction 6h, and the product unhindered amina content of survey is 1.74%, stops reaction.Obtaining that average EO adds and count is 12.0 ethoxylation three ethyl stearte ylmethyl ethyl-sulfate ammoniums.
Embodiment 6
Take by weighing in the four-hole boiling flask that the 265g stearic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 80 ℃, after it all melts, add 1.6g sulfuric acid and 116g triethanolamine, be warming up to 200 ℃, react after 9 hours, recording the product acid value is 3.1mgKOH/g, and stopped reaction obtains three ester amine.
Take by weighing that ester group plug-in type ethoxylation catalyst joins in the three ester amine in the 4.9g example 2, stir in the lower 2L of the input autoclave N
2Displaced air is warming up to 170 ℃, imports oxirane, keeps system pressure 0.6MPa, when being 615g to the oxirane addition, closes the EO inlet valve, and aging 90min is cooled to 70 ℃, and discharging obtains ethoxylation three ester amine, and 832g weighs.
Ethoxylation three ester amine are joined in the 500mL four-hole bottle, be heated to 40 ℃, stopped heating adds 34g isopropyl alcohol and trimethyl phosphate 10.1g, and dropwise and be warming up to 75 ℃, reaction 5h, the product unhindered amina content of survey is 1.27%, stops reaction.Obtaining that average EO adds and count is 15.0 ethoxylation three ethyl stearte ylmethyl dimethyl phosphate ammoniums.
Embodiment 7
Take by weighing in the four-hole boiling flask that the 300g stearic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 90 ℃, after it all melts, add 2.0g phosphorous acid and 119g triethanolamine, be warming up to 220 ℃, react after 7 hours, recording the product acid value is 3.6mgKOH/g, and stopped reaction obtains three ester amine.
Take by weighing that ester group plug-in type ethoxylation catalyst joins in the three ester amine in the 6.7g example 3, stir in the lower 2L of the input autoclave,, N
2Displaced air is warming up to 180 ℃, imports oxirane, keeps system pressure 1.0MPa, when being 1173g to the oxirane addition, closes the EO inlet valve, and aging 95min is cooled to 75 ℃, and discharging obtains ethoxylation three ester amine, and 1546g weighs.
Ethoxylation three ester amine are joined in the 1000mL four-hole bottle, be heated to 45 ℃, stopped heating adds 53g isopropyl alcohol and dimethyl carbonate 25g, and dropwise and be warming up to 80 ℃, reaction 5h, the product unhindered amina content of survey is 1.27%, stops reaction.Obtaining that average EO adds and count is 17.0 ethoxylation three ethyl stearte ylmethyl methyl carbonate ammoniums.
Take by weighing in the four-hole boiling flask that the 375g behenic acid joins 500mL, at N
2Stir under the condition of protection and be warmed up to 100 ℃, after it all melts, add 2.0g sulfuric acid and 134g triethanolamine, be warming up to 210 ℃, react after 7 hours, recording the product acid value is 3.9mgKOH/g, and stopped reaction obtains three ester amine.
Take by weighing that ester group plug-in type ethoxylation catalyst joins in the three ester amine in the 4.6g example 4, stir in the lower 2L of the input autoclave N
2Displaced air is warming up to 185 ℃, imports oxirane, keeps system pressure 2.0MPa, when being 630g to the oxirane addition, closes the EO inlet valve, and aging 90min is cooled to 80 ℃, and discharging obtains ethoxylation three ester amine, and 1089g weighs.
Ethoxylation three ester amine are joined in the 2000mL four-hole bottle, be heated to 40 ℃, stopped heating adds 115g isopropyl alcohol and diethyl carbonate 48g, and dropwise and be warming up to 80 ℃, reaction 6h, the product unhindered amina content of survey is 1.59%, stops reaction.Obtaining that average EO adds and count is 20.0 ethoxylation three behenic acid ethoxycarbonyl methyl carbonic acid ethyl ester ammoniums.
Claims (8)
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