JPS58206692A - Manufacture of polycarbonate type surfactant from ethylene carbonate and monohydric alcohol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 41: Yumei relates to a method for producing a nonionic surfactant 4j, particularly a method for producing a nonionic surfactant consisting of a monohydric alcohol capped with polycarbonate.

In many industrial and domestic greening applications, it is desirable or necessary to use surfactants in cleaning formulations to achieve satisfactory moisture, surface and cleaning properties. be. Additionally, in many of these industrial and domestic applications, maintaining low levels of foam during cleaning operations is essential. For example, surfactants that eliminate foam are of no use in industrial spray metal cleaning operations, and are also used as active ingredients in household dishwashing detergents and rinse aids. is inappropriate.

One of the well-known nonionic surfactants in industry technology (
fatty acid esters of 1-alcohol ethoxylates, which esters are produced by condensing ethylene oxide with detergent-bound alcohols and then reacting such ethoxylated alcohols with fatty acids having 8 to 18 carbon atoms; or It is produced by reacting such an acid with a chloride. The surfactant produced by this method has been awarded the first U.S. patent.
, 970,578, where such surfactants i)S are taught to have excellent wetting, foaming and cleaning properties. However, this surfactant 11 is not satisfactory for applications where suppression of foam is important.

Circle.

A separate nonionic surfactant (
・Japanese Patent Publication No. 919 to 1986-10 teaches a nonionic surfactant produced by a method similar to the method of the present invention. However, the final product is a poor foam suppressant.

In the present invention, ethylene carbonate and alcohol are heated at 180°C to 21°C in the presence of an alkali metal salt catalyst.
This is a method for producing a polycarbonate type surfactant, which is characterized by carrying out the reaction at a temperature of 0°C.

This product contains 3 to 3 mol of surfactant per mole of surfactant.
It also relates to a method for reacting 50 moles of violet with ethylene oxide.

More specifically, the surfactant composition produced by the method of the present invention consists of compounds represented by the following structural formula.

1 R-0--(C112-CH2-0-C-0-CH2-
CH2-0), -HR-(J-(CB2-CHt publication 几-(C#tH foil "Right-C-O-C&-CB2(Jay
ii 1 R(J CCHt(way 20 COC11t CTo(
J), -(Cfb CIi* 0 ] Ni H In each of the above formulas, R is an aliphatic, non-aromatic alicyclic, or aromatic group, y is a number from 1 to 10, and X is 8 ~50. The monohydric alcohol can be capped with ethylene oxide before reacting it with ethylene carbonate, or alternatively the ethylene carbonate/monohydric alcohol reaction product can be further reacted with ethylene oxide to create different The hydroxyethylation reaction of alcohol or polycarbonate reaction products with ethylene oxide is carried out using a basic catalyst, KOH, at temperatures of about 0°C to about 120°C. Can be easily achieved using:

The reaction between alcohol or ethoxylated alcohol and ethylene carbonate is shown by the following reaction formula.

1 R-0-CCH2-CH2-0-C-0-CHt heart
o) y -H The above equation shows that 50% of the available CO7 in the ethylene carbonate is lost as a result of the formation of the carbonate intermediate shown in the first equation V. That is, the theoretical maximum yield of the polycarbonate block portion in the surfactant composition is only 50% of the effective cut during the original ethylene carbonate reaction trial. Moreover, the ethylene carbonate/alcohol reaction is initiated by ethoxy ether groups resulting from the decomposition of ethylene carbonate to ethylene oxide and CO. This ethoxy ether free radical initiation of the polycarbonate/alcohol reaction appears to be accurate. It is co in ethylene carbonate.

This is because only about 88% to 43% of the VC carbonate groups are normally retained as VC carbonate groups in the surface-active grouping acids.

Generally speaking, 1 ton of monohydric alcohol or ethyl alcohol
About 2 to 20 moles and more preferably about 8 to 10 moles of ethylene carbonate per mole of alcohol are reacted together to impart hydrophobic properties to the activator composition. Or polycarbonate 1ml 1l
About 8 to 50 moles, preferably about 8 to 10 moles of ethylene oxide per mole of fi alcohol are reacted together to impart hydrophilicity to the longest surfactant composition.

The temperature of the ethylene carbonate/alcohol reaction is approximately 1
80'C to approx. 210℃ The preferred temperature is approx. 40℃ to approx. 170℃
-Ce is kept. Reactions below 180° C. W) are undesirable because the formation of the polycarbonate block portion of the surfactant composition is very slow at such low temperatures. Also, temperatures higher than about 210°C are undesirable. This is because at such high temperatures, ethylene carbonate decomposes into ethylene oxide and co, resulting in a more reactive hydroxyethylation or polyether reaction.

In order to form the polycarbonate block portion of the surfactant, the ethylene carbonate/alcohol reaction must be carried out in the presence of an alkali metal salt catalyst. Examples of useful alkali metal salt catalysts are stannate, potassium stannate, sodium carbonate, potassium carbonate,
They are sodium water monide, potassium hydroxide, the above-mentioned sodium alkoxide of monohydric alcohol, and the above-mentioned potassium alkoxide of monohydric alcohol. Sodium stannate is %ttko4! - It was found to be an effective catalyst. This is because the yield and reaction time of the total acetate used can be changed.

From the above description, it is understood that the polycarbonate-type surfactant product left behind by the present invention is probably constructed by placing some random needle groups within the polycarbonate block portion of the product. Will. It is assumed that 50% of the theoretical αh is retained in the product.
This is because IC4zm is not achieved during the ethylene carbonate/alcohol reaction.

Furthermore, the activator products in this field are each 7L(1) field u
fL is not characterized by a single chemical threat, but rather by the average molecule fL, which depends on the endpoints of the ether and/or carbonate blocks in each molecule.
It will also be understood that it is a mixture of various molecularly detailed compounds.

The following section provides a more detailed explanation of the production of polycarbonate-type surfactants according to the present invention.

-) i: Base L A stirred reaction mixture consisting of ethylene carbonate 264 (1 (80 mol), n-dodecanol 551' (8 mol) and sodium stannate 12, Or (0,056 mol) was reacted under a nitrogen atmosphere. The mixture was heated to 170° C. for 24 hours in a container.

The mixture was then cooled to 180 DEG C. and the mixture was heated to 180 DEG C. by adding 80 V of finely ground magnesium silicate and 6 L of Celite clay.
At this point the reaction product mixture was completely cooled and then filtered to remove the magnesium silicate and celite clay.The reaction product 20001 was a pale yellow clear viscous liquid. This product retained about 40% by mass of the available COt in ethylene carbonate as carbonate groups in the reaction product, as determined by nuclear magnetic resonance spectroscopy.

Example Z Stirred reaction mixture consisting of 44 t (0.5 mol) ethylene carbonate, 18.4 t (0.1 mol) cyclododecanol and 0.2 t (0,001 mol) sodium stannate under a total nitrogen atmosphere in a reactor of 17
Heated to 0°C for 22 hours. Then this mixture is heated to 180℃
Cool to 0.52% magnesium silicate and 1.5% celite clay. otk was added to the mixture. This mixture? Stir continuously for 1 hour at 180°C VC. The reaction product mixture was cooled and then passed through to remove the magnesium silicate and Celite clay. The reaction product is a pale yellow transparent viscous vM liquid35. I got angry.

This solidified when left alone. Approximately 40% by weight of the available CO7 in the ethylene carbonate was retained in the product with carbonate groups.

Example a Ethylene carbonate 44r (0,5 mol), 4-
The reaction conditions of Examples 1 and 2 were repeated, except that the reaction was carried out at 170° C. for 18 hours in a mixed WJ mixture consisting of 2 Or (0,091 r ) of nonylphenol and 0,2 r (0,001 mol) of sodium stannate. The temperature of the mixture was lowered by 180"CV, and the silicate
and celite clay ir', and after stirring and soaking for 1 hour, the reaction product was cooled and filtered.
t. Approximately 83% of the available CO2 in the ethylene carbonate was retained as carbonate groups in the reaction product.

Inuji side raw ethylene carbonate 44 t (0.5 mol), n-
The reaction conditions of Examples 1 and 2 were repeated, except that the reaction was carried out for 400 hours in a mixed 9J gel 150"C consisting of 4.7 y (0,025 mol) of dodecanol and 5 t (0,002 mol) of sodium stannate. +r was rewritten.As in Example 8, a yellow transparent viscous 14fi reaction product 80-3r was obtained using silk and 1F-chest as in Example 8.41% of the immobile CO1 was the reaction product. It was retained as a carbonate group in the material.

Examples & Ethylene carbonate 44 f (0.5 mol), 2.
4.6゜8-tetramethyl-1-nonanol 5t (
0,025 mol) and sodium stannate 0.29 (
0,001 mol) at 150°C.
Except for the time reaction, IJI and reaction conditions of 2'
repeated again. The main reaction product 26. I got jH'. Effective C0
1% of the 40% of 2 was retained as carbonate groups in the reaction product.

Example 6 Ethylene carbonate 44 t (0.5 mol), n-
Dodecanol 6.8? (0,084 mol) and potassium carbonate 0. Example 1 except that a mixture of Olt (0,001 mol) was reacted at 185°C for 24 hours.
The reaction conditions of and 2 were repeated again. After preparation and treatment as in Example 8, 26.99 k of the reaction product was obtained as a dark brown clear viscous liquid. 19 of effective COz
% of the weight was retained as carbonate groups in the reaction product.

Example 7 - 87.8 r (L2 mol) of rhodecanol and 0.05 f (0,0027 mol) of metallic sodium are mixed in a reactor at ioOoC until the sodium dissolves. - Bonate 88.1 t (1
The reactor was heated to 0°C and the stirred mixture was heated to 200°C and kept at this temperature for 2 hours.

After purification and treatment as in Example 8, 88.2 f of a pale yellow clear viscous liquid was obtained.

゛Example & Ethylene carbonate 22t (0.25 mol), π
- Todo 1' diltriethoxylate mixture with n-tetradecyltriethoxylate (approx. 50150 mol% mixture) consisting of 16.62 (0.05 mol) and sodium stannate 0.2 f (0.001 mol) The stirred reaction mixture was heated to 150° C. for 17 hours in a reactor under nitrogen atmosphere. After making n4 and filtering as in Example 8, the reaction product is a pale yellow clear viscous liquid 24.1 t
I got it.

Example a Ethylene carpone ~) 44 f (0.5 mol), n
-Mixture of dodecyl hexaethoxylate and n-tetradecyl hexaethoxylate (phantom 50150%
) 28.6 f (0.05 mol) and sodium stannate 1
The stirred reaction mixture consisting of 1 um and 0.2 f (0,001 mol) was heated to 150° C. for 24 hours. Example 8
After purification and treatment as described above, the reaction product 48.11 was obtained as a pale yellow clear viscous liquid.

Example 1α Ethylene carbonate 27 t (0.81 mol), 2
, 4゜6.8-natramenal-1-nonyloccuethoxylate 58-Or (0.10 mol) and 0.2 f (0.001 mol) of stannic acid in a stirred reactor as in Example 8. Heated to 150°C for 20 hours. Purification and filtration as in Example 31. After that, 64.2 tk of the reaction product was obtained as a pale yellow transparent viscous liquid.

Example IL Ethylene carbonate) 44 (1 (5 mol), 2.4, 6
゜8-tetramethyl-1-nonyl ocume ethoxylate 53゜t (0,96 mol) and sodium stannate 2
F (0.01 mol) was reacted in a stirred reactor under nitrogen atmosphere at 161 J°C vc for 24 hours. The mixture was then heated to 100° C., magnesium silicate 10F and celite clay 109 k) JIJ, and the mixture was stirred for 1 hour. After filtration, 708 tk of the reaction product was obtained as a pale yellow, clear viscous liquid.

Example 12゜Ethylene carbonate 15.1? (0-17 mol)
, tertiary octylphenol sealed with 40 moles of ethylene oxide per mole of alcohol 17.1? (0,
0087 mol) and sodium stannate 0.2 t (
0,001 mol) was heated at 160° C. for 12 hours in a stirred reactor as in Example 8.

After purification and filtration as in Example 8, 10.79 of the reaction product was obtained as a tan solid.

Example 1a Ethylene carbonate 44f (05 mol), 2,4,6
゜8-tetramethyl-1-nonanol 20 t (0,
1 mol) and sodium stannate 0.2 F ((10
The reaction conditions of Example 5 were repeated except that the reaction was carried out for 20 hours using a mixture k150'c consisting of 0.01 mol). The reaction product was purified and filtered as in Example 8. 2 Of ((to 88 mol)) of this reaction product and 0.1 r ((10018 mol) of potassium hydroxide) were charged into the entire reactor and heated to 110°C. Ethylene oxide 7
．． 5 t (0.17 mol) Of course tst reactor VC7JO
The mixture was then continuously stirred for 16 hours. After purification and purification as in Example 3, 235t2 of the reaction product was obtained as a pale yellow clear viscous liquid.

Example 1 ethylene carbonate) 44 t (0.5 mol), 2
, 4.6° 8-tetramethyl-1-nonanol 10 t
(0.05 mol) and sodium stannate 0.29
(0,001 mol)'e at 150°C 2
The reaction conditions of Example 5 were repeated again, except that the reaction was carried out for 0 hours. This reaction product ZUt ((to 28 mol), ethylene oxide 5 f (0,114 mol) and potassium hydroxide 0.1 f (0,0018 mol)
was stirred continuously in a reactor at 110° C. for 16 hours.

After purification and filtration as in Example 3, 25.59% of the reaction product was obtained as a pale yellow clear viscous liquid.

Table M1 below lists the molar ratios of ethylene carbonate and ethylene oxide reacted with 61 moles of alcohol and the catalysts used in the above examples.

However, the following second example shows the full potential of the reaction product of the above example as an interfacial agent.

(1) 0.1% yield by weight in deionized water. The number with a tatami mark is 1.0 in deionized water! 11 gongs in case of normal % inertia.

(2) 1 according to ASi'M No. 1881 test method, (8) according to ASTM D-1881 test method.

(4) The sieveness of the foam is O1 - % interfacial viscosity τ water αi liquid 2
Blend for 1 minute at low speed in a 50-inch blender to measure E5/ζ-1, and the 4 liquids and foam will be measured directly in a standard 500d, rounded cylinder with round opening. Ta. The height of the bubbles was determined to be 5 rana≠kl +iji immediately after 2 steps.

(In 5J [w phrase test thread Vζ, 1 9 inch (21 cm) strip of non-mercerized natural cloth Tezo
1 was attached to the hook of No. 1, and then this was determined by C-thread. Creation 0.1 car ψ
Vine with %/ζ. This array? 1 serving! The mixture was dropped into 500 ml of the same world 1'1 lrtIl liquid moefu liquid in a J-under. When the tape became wet, it fell to the bottom of the cylinder. This indicates the humidity and temperature time.

(6) According to ASTM D-2024 Test 1c o 1.
A 0.1% concentration was used instead of 0'10a ItL.

Patent applicant: The Dow Chemical Company
Attorney Patent Attorney Ai Kawase
Patent Attorney Takehiko Saito Continued from page 1 0 Inventor Poppy Burks State of Louisiana, United States of America 70 127 Parlis of Orleans New Orleans RI 1 Nosti Lane 41 Department of Procedural Corrections C Method) % Formula % 1, Display of the case 1982' Blfh No. 82530 2, Title of the invention 3, Relationship with the Ministry case to be amended % Applicant name The Dow Chemical Company/, Name Patent attorney (6323) Ken Aiji 1. ．． 5. Subject of amendment '＼'', -1-2' (1) Special Fit of Kei 1: Applicant's column and certificate of attorney's authority (2) In 11, write the details , the content of the S stop is high, and there is no inertia stop.

Claims (1)

[Claims] 1. A method for producing a polycarbonate surfactant, which comprises reacting ethylene carbonate and a monohydric alcohol at a temperature of 130°C to 210°C in the presence of an alkali metal salt catalyst. 2. The method according to claim 1, wherein 2 to 20 moles of ethylene carbonate are reacted per mole of monohydric alcohol. 8. Monohydric alcohol has the formula RC) CCHt Ca
Claim 1 having t 03 -H (wherein R1d is an aliphatic, non-aromatic fat, - or aromatic group, and 2 is a number from 3 to 50) The method described in section. 4. The valley is 3 to 1 mole per mole.
A process according to claim 1, characterized in that the reaction is carried out with 50 moles of 1 ethylene oxide. −