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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Abstract
The invention relates to ethoxylated trimester-group quaternary ammonium salt and a preparation method thereof. The chemical feature structural formula of the ethoxylated trimester-group quaternary ammonium salt is shown in the specification, wherein in the formula, R represents a saturated or unsaturated straight-chain alkyl group and a saturated or unsaturated branched-chain alkyl group of C6-C22; X<-> represents an alkylated negative ion; a, b and c are same or different and represent the number of oxethyl; and the average value of a, b and c is 3-20. The preparation method disclosed by 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)
1. ethoxylation three ester based quaternary ammonium salts reach, and it is characterized in that the chemical feature structural formula of ethoxylation three ester based quaternary ammonium salts is as follows:
In the formula: R is C
6-C
22Saturated or undersaturated straight chained alkyl, saturated or undersaturated branched alkyl;
X
-Represent the alkylation anion;
A, b, c are identical or different, are the number of ethyoxyl, and mean value is 3-20.
2. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 1 is characterized in that comprising 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 ‰, three ester amine of aliphatic acid and triethanolamine gross weight: 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.
3. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 2 is characterized in that described acidic catalyst consumption is 1 ‰-5 ‰ of aliphatic acid and triethanolamine gross weight.
4. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 2 is characterized in that described aliphatic acid is C
6-C
22Saturated and unrighted acid.
5. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 4 is characterized in that described C
6-C
22Saturated and unrighted acid be stearic acid, palmitic acid, oleic acid, laurate or behenic acid.
6. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 2 is characterized in that described alkylating agent is halogen methane, dimethyl suflfate, dithyl sulfate, dimethyl carbonate, diethyl carbonate or trimethyl phosphate.
7. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 2, it is characterized in that described ester group plug-in type ethoxylation catalyst is that alkaline earth oxide is 30-90wt%, the III family metal oxide is 1-40wt%, and carrier is 1-30wt%.
8. the preparation method of a kind of ethoxylation three ester based quaternary ammonium salts as claimed in claim 2 is characterized in that described acidic catalyst is sulfuric acid, phosphorous acid, p-methyl benzenesulfonic acid or alkyl benzene sulphonate.
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| CN105771789A (en) * | 2015-12-22 | 2016-07-20 | 广东椰氏实业股份有限公司 | Phosphate-based quaternary ammonium salt cationic surfactant and synthesizing method thereof |
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