CN101469510B - Fatty acid compositions of methyl ester for esterquats production suitable for fabric softener - Google Patents
Fatty acid compositions of methyl ester for esterquats production suitable for fabric softener Download PDFInfo
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- CN101469510B CN101469510B CN 200810184780 CN200810184780A CN101469510B CN 101469510 B CN101469510 B CN 101469510B CN 200810184780 CN200810184780 CN 200810184780 CN 200810184780 A CN200810184780 A CN 200810184780A CN 101469510 B CN101469510 B CN 101469510B
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- quaternary ammonium
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- ammonium salt
- ester
- methyl esters
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Abstract
The present invention discloses a fatty acid compound which is used for the methyl ester that is suitable for the ester quaternary ammonium salt production of fabric softener, and relates to the ester quaternary ammonium salt compound which comprises methyl ester compound. The invention is characterized by comprising 40%-95% of saturated fatty acid and 5%-60% of unsaturated fatty acid. Furthermore the ester quaternary ammonium salt compound executes ester exchange reaction with triethanolamine and executes quaterisation reaction with dimethyl sulfate.
Description
Technical field
The present invention relates to the composition of a kind of saturated fatty acid and unrighted acid methyl esters, for the production of ester based quaternary ammonium salt.Especially, the present invention relates to a kind of methyl esters composition, for the production of having good fabric-softening and the ester based quaternary ammonium salt of wettability again.Therefore, these ester based quaternary ammonium salts are applicable to produce fabric softener.
Background technology
Ester based quaternary ammonium salt is cationic surfactant, usually is called quaternary fatty acid triethanolamine ester salts by those skilled in the art.Ester based quaternary ammonium salt typically is used to softening fibre or preparation cosmetics owing to having good fabric softening effect and high ecological toxicity compatibility.
Ester based quaternary ammonium salt is made by two step process usually, wherein methyl esters and triethanolamine carry out ester exchange, the triethanolamine ester that makes subsequently under the condition that the catalyst such as isopropyl alcohol exists, by dimethyl suflfate by alkylation or quaternized, make the ester based quaternary ammonium salt as the biodegradation cationic surfactant.
Have in the prior art some patented technologies, these patented technologies relate to the ester based quaternary ammonium salt with fabric-softening performance.These patented technologies comprise production and the application of far-ranging ester based quaternary ammonium salt.Wherein, U.S. Patent No. US2004097395 is interesting, and this patent relates to a kind of fabric softening compositions that contains ester based quaternary ammonium salt, and these ester based quaternary ammonium salts have certain ester distribution and chelating agent.The invention discloses a kind of water-based clean cycle fabric softening compositions that contains certain compound, it is stable that the physical property of said composition can keep, and the characteristics of said composition are to have stable viscosity at wide ambient temperature range with for a long time.Said composition contains 1% to 25% quaternary ammonium compound and 0.001% to 2% chelating agent.
Disclose a kind of ester based quaternary ammonium salt in European patent No.EP1160238, this ester based quaternary ammonium salt is by using binary acid and aliphatic acid, being made by methyl diethanolamine.The ester based quaternary ammonium salt of inventing has the performance of improvement, the pliability and dispersibility and the high biodegradability that for example improve; Therefore, this ester based quaternary ammonium salt is suitable as at the clean cycle fabric softener, a kind of composition in destaticing paper, hair conditioner, paper remover, and is used for other and requires the application of high-flexibility.
A kind of ester based quaternary ammonium salt that is made by unrighted acid is disclosed in U.S. Patent No. 5296622, the two keys or the ester that carried out being shaped exchange (trans-configured) with alkanolamine that this ester based quaternary ammonium salt contains at least 40% (molar percentage).These product are quaternized by alkylating agent subsequently, make the end product as fabric softener.Also described in European patent No.DE1619058 and No.DE179468 as the saturated fatty acid of fabric softener and the ester based quaternary ammonium salt of alkanolamine.The product that is particularly importantly obtained by following mode in this respect is namely by the reaction between the triethanolamine of the saturated fatty acid of 2mol and 1mol and the quaternization by using dimethyl suflfate or chloromethanes to carry out subsequently.Although the fabric of being processed by such quaternized ester demonstrates good pliability, these fabrics usually demonstrate nonconforming hydrophobicity, and this is embodied in processed fabric and has poor wettability again or water absorption.
The quaternized ester of the mixture of saturated and unrighted acid has also been described in another U.S. Patent No. US3915867, the type that is for example obtained easily by natural fat and oily hydrolysis, this quaternized ester demonstrate the good softening power of using triethanolamine to have.Yet, do not demonstrate the fabric-softening performance based on the quaternized ester of unrighted acid and alkanolamine.Therefore, obviously demonstrate than by the worse performance of those quaternized esters of only using saturated fatty acid to make based on the mixture of the quaternized ester of saturated and unrighted acid.
At present, in fabric softener market, the vegetables based raw material is winning higher acceptance than animal based raw material.Vegetables base feed can be obtained by various seeds, for example soybean, sunflower seeds, coconut oil fruit, coconut and rapeseed.Yet most vegetables base oil and fat contain the LCFA of low saturation, therefore are not suitable for the formula Design of fabric softener.For most vegetables oil, compare from those of the aliphatic acid of animal tallow with those, due to its high degree of unsaturation, C16 and C18 that especially many unsaturates and saturation degree are lower, need to carry out hydrogenation treatment partially or completely, to obtain acceptable fabric-softening performance.Although it is found that long and fully the saturated ester based quaternary ammonium salt based on hydrocarbon have higher softening power, the raising of saturation degree will tend to strengthen the hydrophobic effect on fabric, thereby cause poor wettability again.
The major defect of disclosed ester based quaternary ammonium salt is in the prior art, although the ester based quaternary ammonium salt of inventing has good fabric softening effect, does not have good wettability again.Due to this shortcoming of prior art, the present invention wishes to develop the ester based quaternary ammonium salt composition of a kind of innovation and improvement, thereby overcome above-mentioned shortcoming by introduce the unsaturated hydrocarbons of some in the ester based quaternary ammonium salt composition.
Summary of the invention
Main purpose of the present invention is to develop a kind ofly to have good softening and the ester based quaternary ammonium salt composition of wettability again, so that it can be used in the formula Design of fabric softener.
Another object of the present invention is to utilize the raw material with suitable aliphatic acid composition, and this raw material contains the saturated and unrighted acid methyl esters that proportional suitable ester based quaternary ammonium salt is produced.
Another purpose of the present invention is that the production for ester based quaternary ammonium salt provides saturated and unsaturated fatty-acid compositions, and said composition has best wetting characteristics again, has hydrophobicity and demonstrate simultaneously good fabric-softening power.
The present invention has realized at least one in aforementioned purpose whole or in part, wherein one of embodiments of the invention have been described a kind of ester based quaternary ammonium salt composition, said composition contains mixtures of methyl esters, be characterized in containing 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters, and carry out ester exchange reaction and carry out quaterisation with dimethyl suflfate with triethanolamine.
Another embodiment of the present invention is the fabric softener that contains the ester based quaternary ammonium salt composition, said composition contains mixtures of methyl esters, be characterized in containing 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters, and carry out ester exchange reaction and carry out quaterisation with dimethyl suflfate with triethanolamine.
What the person skilled in the art will easily understand is, the present invention can realize these purposes well, and obtains described end product and advantage and those intrinsic advantage therein.Embodiment described here is not intended to limit the scope of the invention.
The specific embodiment
The present invention relates to a kind of saturated fatty acid for ester based quaternary ammonium salt production and the composition of unrighted acid methyl esters.Especially, the present invention relates to a kind of methyl esters composition, said composition can be used for producing and has good fabric-softening performance and the ester based quaternary ammonium salt of wettability again.Therefore, these ester based quaternary ammonium salts are applicable to produce fabric softener.
Hereinafter, will be according to a preferred embodiment of the invention, and with reference to appended specification and accompanying drawing, the present invention is described.Yet, it should be understood that according to a preferred embodiment of the invention to describe just in order to help to discuss the present invention with accompanying drawing; In addition, what can expect is, those skilled in the art can in the situation that need not to depart from appended claims scope, design various amendment schemes.
The invention discloses a kind of ester based quaternary ammonium salt composition, said composition contains mixtures of methyl esters, be characterized in containing 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters, and carry out ester exchange reaction and carry out quaterisation with dimethyl suflfate subsequently with triethanolamine.
Characteristics of the present invention are, introduce the unrighted acid methyl esters of some in saturated fatty acid methyl ester, with for the production of ester based quaternary ammonium salt.According to a preferred embodiment of the invention, mixtures of methyl esters contains 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters.With the methyl esters weighing scale, the quantity that exists of saturated fatty acid is preferably 60% to 90%, and the quantity that exists of unsaturated acids is preferably 5% to 26%.
According to a preferred embodiment of the invention, methyl esters comes from vegetable oil or animal tallow.Methyl esters preferably comes from palm oil, soybean oil, corn oil, cottonseed oil, peanut oil, olive oil, rapeseed oil, sunflower oil, coconut oil, palmitic stearin, palm-kernel oil, lard, tallow or derivatives thereof or wherein multiple combination.The fact that it will be understood by those skilled in the art that is if having suitable saturated fatty acid with respect to the ratio of unrighted acid from the oil in other sources, also can use these oil.
Can produce for the starting material of ester based quaternary ammonium salt production and have good pliability and the good fabric of wettability again, this starting material is methyl esters, and this methyl esters has a certain proportion of palm property, tristearin and oily matter and other a small amount of fatty acid materials.Described as most preferred embodiment of the present invention, suitable saturated fatty acid is palmitic acid, stearic acid or its combination, and suitable unrighted acid is oleic acid.In most preferred embodiment of the present invention, contain 68% palmitic acid and stearic acid in mixtures of methyl esters, as its saturated fatty acid composition; Also contain 26% oleic acid in mixtures of methyl esters, as its unrighted acid composition.
Another embodiment of the present invention is the fabric softener that contains the ester based quaternary ammonium salt composition, said composition contains mixtures of methyl esters, be characterized in containing 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters, and carry out ester exchange reaction and carry out quaterisation with dimethyl suflfate with triethanolamine.The fabric softener of inventing can have best wetting characteristics again, have hydrophobicity and demonstrate good fabric-softening power.
The aliphatic acid that is applicable to the methyl esters of fabric softener formula Design is that the premixed by following material obtains: hydrogenation methyl esters (fully saturated) and 98.7% palmitic acid and the premixed of stearic mixture, and the palmitic acid of non-hydrogenation methyl esters and 36.4% and stearic mixture, 53.2% oleic acid and the premixed of other a small amount of fatty acid materials.Compare, demonstrate better softening performance although come from the ester based quaternary ammonium salt of fully saturated palmityl methyl esters with the ester based quaternary ammonium salt that comes from non-hydrogenated palm base methyl esters, due to the hydrophobicity effect, its wettability ability reduction again; This hydrophobicity effect is to be caused by the chain length of complete saturated fatty acid in oil or fatty feed.Degree of unsaturation will affect wetting power again, and this effect can be observed from curve map, and can be observed wetting power by this figure increases with introduce unrighted acid in ester based quaternary ammonium salt production again.
According to a preferred embodiment of the invention, the ester based quaternary ammonium salt that comes from the methyl esters of palmitic acid, stearic acid and oleic acid with some is compared with tallow base commodity ester based quaternary ammonium salt with palmitic stearin is fatty acid-based, demonstrate close softening performance, and do not reduce wettability again.
Content disclosed by the invention comprises appended claims and previously described content.Although the present invention has carried out specific descriptions to a certain degree in its preferred form, but be understood that, preferred form disclosed by the invention just provides by way of example, aspect implementation detail, a lot of changes can also be arranged, these changes can be passed through to change the combination of each several part and arrange to realize, and need not to depart from scope of the present invention.
For example
Provide the aliphatic acid composition of methyl esters in table 1 and table 2, for the production of the ester based quaternary ammonium salt that is applicable to the fabric softener formula Design; Give ester based quaternary ammonium salt in table 1 and table 2, this ester based quaternary ammonium salt comes from the methyl esters with these aliphatic acid compositions.
Example 1
Use methyl esters as the production of the quaternized triethanolamine ester of palmityl of starting material, and this methyl esters contain following composition, i.e. the oily matter of 68% palm property and tristearin material and 26%.
A. ester exchange reaction.The 3kg methyl esters has following composition, i.e. 68% palmitic acid and stearic acid and 26% oleic acid; 0.890kg triethanolamine and 0.15kg sodium methoxide; Their aqueous solution forms take percentage by weight as 1% are incorporated in the reactor that is equipped with mechanical agitator.Reactant mixture is being heated to 100 ℃ under the 200mbar vacuum pressure, in 30 minutes.It is stirred reaction mixture under the condition of 540rpm in stir speed (S.S.).These conditions are kept reached 1 to 1.5 hour, or until the amine value of reactant mixture reaches maximum fixed value.Then in continuous stirring and under the 200mbar vacuum pressure condition, the palmitic stearin triethanolamine ester is cooled to 60 ℃.
B. quaterisation.Subsequently, above-mentioned reactant mixture 3.54kg is mixed with isopropyl alcohol, and be heated to 45 ℃ under atmospheric pressure.Then dropwise join dimethyl suflfate 0.715kg in reactant mixture; This dropping is carried out between 45 ℃ to 50 ℃ temperature, and stir speed (S.S.) is 77rpm.After dripping dimethyl suflfate, be under the 540rpm condition, further be heated to 60 ℃ in mixing intensity with being about to reactant mixture.Keep these conditions, until the amine value reaches below the 5mgKOH/g sample.Then, for removing unreacted dimethyl suflfate, the 0.022kg glycine is joined in reactant mixture, stirred again 1 hour at 60 ℃ subsequently.
Example 2
Application examples
The towel that uses ester based quaternary ammonium salt to process is assessed, this ester based quaternary ammonium salt comes from and contains aliphatic acid composition A, B as shown in table 1 and the methyl esters of C, and this assessment be based on their softening performance and again wettability carry out, wherein softening performance carries out according to ASTM D 5237-92, AATCC EP5 with indoor, then wettability carries out according to ASTM D 5237-92.
Softening assessment is undertaken by 20 trained group members, they assess the towel that uses ester based quaternary ammonium salt to process, this ester based quaternary ammonium salt comes from and contains aliphatic acid composition A, B as shown in table 1 and the methyl esters of C, and test result is shown in Table 3.Result shows, come from the ester based quaternary ammonium salt of the methyl esters that contains aliphatic acid composition A, B and C, contain 66.2% palm property and compare with the ester based quaternary ammonium salt of the palmitic stearin aliphatic acid of tristearin material and 25.8% oily matter with coming from, demonstrate close softening performance.Equally, come from the ester based quaternary ammonium salt of the methyl esters that contains aliphatic acid composition A, B and C, contain 48.4% palm property and compare with the ester based quaternary ammonium salt of the tallow of 42.8% oily matter with the tristearin material with coming from, demonstrate close softening performance.
The wettability again of processed towel is determined by the rising horizontal checkout; In this test, the rising level to the dye solution that measures with millimeter 10 minutes after is assessed.Test result is as shown in table 4.
* PSFA: palmitic stearin aliphatic acid
Claims (5)
1. ester based quaternary ammonium salt production method, ester based quaternary ammonium salt is carried out ester exchange reaction and carries out quaterisation with dimethyl suflfate obtaining by methyl esters composition and triethanolamine, and described methyl esters composition contains 40% to 95% saturated fatty acid methyl ester and 5% to 60% unrighted acid methyl esters.
2. method according to claim 1, it is characterized in that: methyl esters comes from vegetable oil or animal tallow.
3. method according to claim 1 and 2 is characterized in that: methyl esters comes from palm oil, soybean oil, corn oil, cottonseed oil, peanut oil, olive oil, rapeseed oil, sunflower oil, coconut oil, palmitic stearin, palm-kernel oil, lard, tallow or wherein multiple combination.
4. method according to claim 1 and 2, it is characterized in that: saturated fatty acid is palmitic acid, stearic acid or its combination.
5. method according to claim 1 and 2, it is characterized in that: unrighted acid is oleic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MYPI20072344 MY151001A (en) | 2007-12-28 | 2007-12-28 | Fatty acid compositions of methyl ester for esterquats production suitable for fabric softener |
| MYPI20072344 | 2007-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101469510A CN101469510A (en) | 2009-07-01 |
| CN101469510B true CN101469510B (en) | 2013-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810184780 Expired - Fee Related CN101469510B (en) | 2007-12-28 | 2008-12-26 | Fatty acid compositions of methyl ester for esterquats production suitable for fabric softener |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101469510B (en) |
| MY (1) | MY151001A (en) |
| SG (1) | SG153794A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586029A (en) * | 2012-01-05 | 2012-07-18 | 上虞市精细化工厂 | Preparation method of easily-degraded esterquat softening agent |
| CN103835132B (en) * | 2012-11-26 | 2017-09-29 | 五邑大学 | A kind of biodegradable antistatic finishing agent and preparation method thereof |
| BR102014025172B1 (en) * | 2013-11-05 | 2020-03-03 | Evonik Degussa Gmbh | METHOD FOR MANUFACTURING A TRIS- (2-HYDROXYETHYL) -METHYLMETHYL ESTER OF FATTY ACID AND ACTIVE COMPOSITION OF SOFTENING CLOTHES |
| CN106400483A (en) * | 2016-09-08 | 2017-02-15 | 济宁锦祥化工科技有限公司 | Green edible grade softening agent for textile printing and dyeing and preparing method thereof |
| CN107129882B (en) * | 2017-03-30 | 2020-04-21 | 纳爱斯集团有限公司 | Transparent laundry detergent composition with washing and softening effects and preparation method thereof |
| CN115745814A (en) * | 2022-11-10 | 2023-03-07 | 如皋市万利化工有限责任公司 | Preparation method of soybean oil ester-based quaternary ammonium salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637743A (en) * | 1991-12-31 | 1997-06-10 | Stepan Europe | Quaternary ammonium surfactants derived from tertiary amines and fabric softeners containing quaternary ammonium surfactants |
| JP2001181244A (en) * | 1999-12-27 | 2001-07-03 | Lion Corp | Cationic surfactant composition containing ester bond and method for preparing the same |
-
2007
- 2007-12-28 MY MYPI20072344 patent/MY151001A/en unknown
-
2008
- 2008-12-26 CN CN 200810184780 patent/CN101469510B/en not_active Expired - Fee Related
- 2008-12-26 SG SG200809637-2A patent/SG153794A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637743A (en) * | 1991-12-31 | 1997-06-10 | Stepan Europe | Quaternary ammonium surfactants derived from tertiary amines and fabric softeners containing quaternary ammonium surfactants |
| JP2001181244A (en) * | 1999-12-27 | 2001-07-03 | Lion Corp | Cationic surfactant composition containing ester bond and method for preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001－181244A 2001.07.03 |
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| Publication number | Publication date |
|---|---|
| SG153794A1 (en) | 2009-07-29 |
| MY151001A (en) | 2014-03-31 |
| CN101469510A (en) | 2009-07-01 |
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Granted publication date: 20130626 Termination date: 20181226 |