JP3423407B2 - Polyalkylene glycol and composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent, an emulsifier, a solubilizer, a dispersant, a wetting agent, a surfactant such as an antifoaming agent, a solvent,
A novel polyalkylene glycol, which is used as a lubricant base, an intermediate raw material, etc. in the cleaning field, paint / adhesive / coating field, textile industry field, rubber / plastic field, food / pharmaceutical / cosmetic industry field, etc. , A surfactant composition and a detergent composition using the same.

[0002]

2. Description of the Related Art Polyalkylene glycols such as polyethylene glycol and polypropylene glycol are industrially produced on a large scale and are used in the cleaning field.
It is used for a wide variety of applications in the fields of paints / adhesives / coatings, textile industry, rubber / plastics, food / pharmaceutical / cosmetics industries.

In particular, as a surfactant, an ethylene oxide adduct of polypropylene glycol is commercially available and used as a pluronic type surfactant (US Pat. No. 2674619). As the pluronic surfactant, a product obtained by adding ethylene oxide to polypropylene glycol having an average molecular weight of about 1000 to 4000 is added so that the content of ethylene oxide in all molecules is 10 to 80%. Therefore, by changing the ratio of the two, products having different properties and physical properties such as HLB can be obtained.

The Pluronic type surfactant is characterized in that it is chemically stable, has excellent detergency, has low toxicity, and has low foaming property. Among them, in particular, the low foaming property is a characteristic property compared to other nonionic surfactants, and industrial applications where foaming is disliked, for example, metal cleaning,
It is used for textile cleaning. However, at present, the suppression of foaming during use under severe conditions such as high pressure spray cleaning is not sufficient. It is known that foaming can be suppressed by reducing the content of ethylene oxide in all molecules, but at the same time, the detergency is reduced.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyalkylene glycol, a surfactant composition having an extremely low foaming property and an excellent detergency, and a detergent composition. .

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found a novel polyalkylene glycol having a specific structure and a specific molecular weight, and a surface active agent using the same. The inventors have found that the agent composition and the detergent composition have excellent performance, and have completed the present invention.

That is, the present invention provides a polyalkyl compound represented by the general formula (I) and having a number average molecular weight of 350 to 30,000.
Ren glycol, which is represented by the general formula (I), is A1 or A2.
Is a polyurea characterized by comprising the general formula (II)
It is ruylene glycol. A1 -B-A2 (I) (wherein, the _{B - (CH 2 CH 2 O} ) -, - (C z H
_2z-2i O)-is composed of n and p bonds, respectively, where i is 0 to 1, 4 when z is 3.
0-6 for ~ 6, 0-3 for 7 and 0 for 8-10
Is an integer of 4 to 4, z is an integer of 3 to 10, n is an integer of 4 to 680, and p is an integer satisfying 0 ≦ p / (n + p) ≦ 0.1. ) Preferably, in the general formula (I), B is-
_{(CH 2 CH 2 O) n} - and, n is an integer from 4 to 680, a polyalkylene glycol.

[0008]

[Chemical 2]

The present invention also contains a surfactant composition characterized by containing 1 to 100% by weight of the above polyalkylene glycol as an essential component, and further 0.001 to 50% by weight of the above polyalkylene glycol. % And water 1-9
The present invention relates to a cleaning composition, which contains 9.999% by weight as an essential component. The polyalkylene glycol of the present invention has a structure in which, as represented by the general formula (I), a hydrophilic portion B portion and a hydrophobic portion A1 or A2 portion are bonded to both ends or one end thereof. is there.

Part B must be hydrophilic, for which part B is-(CH ₂ CH ₂ O)-,-(C _z H _2z-2i.
O)-, wherein n is 4-68.
An integer of 0, p is an integer satisfying 0 ≦ p / (n + p) ≦ 0.1, and in particular p = 0, that is, B part is-(CH ₂ C
H ₂ O) _n − is preferable. p / (n + p) is 0.
When it is more than 1, the hydrophilicity of the B part is not sufficient, and the detergency and the surfactant effect are lowered, which is not preferable. In addition, n is an integer of 4 to 680. When n is less than 4, hydrophilicity is not sufficient and detergency and surface-active effect are reduced, which is not preferable, and when n is more than 680, the molecular weight is too large and solubility is reduced, which is not preferable. z is an integer of 3 to 10, and z
Is more than 10, the hydrophilicity of the B part is lowered, and therefore the detergency and the surfactant effect are lowered, which is not preferable. In Part B _{- (CH 2 CH 2 O)} - units and _{- (C z H 2z-2i} O) -
The units may be bonded randomly, regularly, or in blocks as long as the above conditions are satisfied.

The A1 and A2 parts must be hydrophobic,
In the general formula (I), A1 and A2 must be a polyalkylene glycol composed of the general formula (II) . Furthermore, polyalkylene glycol in which B is — (CH ₂ CH ₂ O) _n — and n is an integer of 4 to 680 is preferable.

In the general formula (II), 1 of the repeating unit must be an integer of 0 to 10 and m must be an integer of 1 to 10. When l and m exceed 10, the hydrophobicity of the A1 and A2 parts becomes high, and the detergency and surface-active effect of the resulting polyalkylene glycol are reduced, which is not preferable.
Further, in the case where both of them have a structure of 0, since the hydrophobic portion does not exist, the effect of the surface activity is lost, which is not preferable, and it is necessary that at least l = 0 and m = 1. Since the synthetic product is usually obtained as a mixture of polyalkylene glycols having different l and m, it may be used as it is without being separated, or if necessary, it may be further purified to have the above range. It is also possible to separate and use only the l and m components, or only the specific l and m components among them.

The polyalkylene glycol of the present invention is required to have a number average molecular weight of 350 to 30,000, and particularly preferably 350 to 10,000. If the number average molecular weight is less than 350, the molecular weight of the part B is too small, the hydrophilicity is not sufficient, the detergency and the surface-active effect are deteriorated, which is not preferable. It is also not preferable because it is too large and the surfactant effect is reduced.

The polyalkylene glycol of the present invention can be synthesized by various methods. For example, it can be synthesized by the method described below. First, ethylene oxide is polymerized alone or, if necessary, is copolymerized with an alkylene oxide having 3 to 10 carbon atoms to obtain a polymer having a structure of part B. The homopolymer or copolymer obtained here is separated, purified, or continuously without separation, and then cyclohexene oxide is further added to its terminal. This makes it possible to obtain a polyalkylene glycol represented by the general formula (I) having a structure in which the A1 and A2 parts are bonded to both ends of the B part.

Here, the alkylene oxide which can form the part B together with ethylene oxide is, for example,
Propylene oxide, isobutylene oxide, 1-
Examples thereof include butene oxide and cyclopentene oxide. Cyclohexene oxide is used as the alkylene oxide constituting the A1 and A2 parts.
It

Here, the synthesis of the polymer having the structure of part B,
And cyclohexene constituting the polymer and the A1, A2 parts
In the reaction of oxide , various catalysts can be used, and specifically, an acid catalyst, an alkali catalyst, a transition metal catalyst and the like can be used. For example, as an acid catalyst, boron trifluoride, diethyl ether boron trifluoride adduct, boron tetrafluoride, antimony pentachloride, tin tetrachloride, aluminum trichloride, iron trichloride and other metals and half-gold halides, Mineral acids such as hydrogen chloride, hydrogen bromide, sulfuric acid and perchloric acid, organic acids such as acetic acid and paratoluene sulfonic acid, and solid acid catalysts such as zeolite, montmorillonite and cation exchange resins. As the alkali catalyst, sodium hydroxide, potassium hydroxide, lithium hydroxide, an alkali metal such as barium hydroxide, an alkaline earth metal hydroxide, an alkali metal such as sodium and potassium, an alkali metal alcoholate such as sodium and potassium alcoholate, Examples thereof include alkylamines, quaternary ammonium hydroxide salts, and anion exchange resins. Among these, alkali metal hydroxides, alkali metals and alkali metal alcoholates are preferably used, and sodium hydroxide, potassium hydroxide and sodium metal are more preferably used.

The reaction conditions include, for example, a reaction temperature of 50.
˜200 ° C. The reaction pressure can be atmospheric pressure or under pressure. Further, a reaction solvent can be used if necessary.
The polyalkylene glycol of the present invention can be used in the various applications described above, and can be preferably used as a surfactant, for example. In that case, in addition to the product of the present invention, other surfactants, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc., solvents, additives, etc. Etc. can also be added. When adding other components, the content of the polyalkylene glycol of the present invention in the surfactant composition needs to be 1% by weight or more, and if it is less than that, the low foaming characteristic of the product of the present invention, and The feature of being excellent in detergency is not enough. The polyalkylene glycol of the present invention can be preferably used as a detergent composition by mixing with water.
At that time, the content of the polyalkylene glycol of the present invention in the detergent composition needs to be 0.001 to 50% by weight. If the content is less than 0.001% by weight, the detergency is insufficient, and if it exceeds 50% by weight, it is not sufficiently mixed with water, which is not preferable. This detergent composition may contain other surfactants, solvents, additives, etc., if necessary.

[0018]

EXAMPLES The tests in the examples were carried out according to the following methods. (1) Foaming test Using a 0.1 wt% aqueous solution as a test liquid, JIS
According to K 3362, Los Miles method, temperature 20 ℃
The foamability of the test solution was indicated by the height of the foam immediately after the test droplet was dropped. The smaller the value, the lower the foaming property.

(2) Detergency test As a test liquid, 0.02, 0.2 wt% aqueous solution was used, and cutting oil (30 mesh, 30 mesh, 45 × 85 mm) attached to a wire net under the following conditions ( Unipet GH35, made by Nippon Oil Co., Ltd., is washed to obtain a test piece (Ag)
It was created. Preparation of test piece: After immersing the wire net in a liquid prepared by dissolving 25% of cutting oil in 1,1,1-trichloroethane,
Pull up. Then, it is dried at 100 ° C. to obtain 1,1,1-
The weight of the product obtained by evaporating trichloroethane was measured and used as a test piece (Bg). Washing conditions: Washing temperature of the above test piece was 5
At 0 ° C, wash for 30 seconds in an ultrasonic cleaner, 3 in running water
Rinse for minutes. Then, after drying at 100 degreeC and evaporating water, the weight of the test piece was measured and it was set as the test piece (Cg). The cleaning rate was obtained by the following formula, and the cleaning power of the test solution was expressed. The larger the value of the cleaning rate, the better the cleaning power. Cleaning rate (%) = (B−C) / (B−A) × 100

[0020]

Example 1 Polyethylene glycol # 60 was added to a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
0 (average molecular weight 600) 142.7 g, tetraglyme 120 g, sodium hydroxide 23.8 g were charged, 16
The mixture was heated and stirred at 0 ° C. After 93.6 g of cyclohexene oxide was charged in the dropping funnel, the mixture was gradually dropped into the flask over 1 hour. Then, the mixture was further heated and stirred at 160 ° C. for 1 hour. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. After allowing to cool, 1N sulfuric acid aqueous solution and methylene chloride were added to the reaction solution, and the mixture was shaken and separated. Further, water was added to the methylene chloride phase and shaken and separated. By this operation, the sodium hydroxide of the catalyst was neutralized, and the produced inorganic salt was removed. The methylene chloride phase was heated under reduced pressure to remove methylene chloride and the reaction solvent, tetraglyme, to obtain 83.4 g of the target polyalkylene glycol.

The molecular weight of the obtained polyalkylene glycol determined by measuring the hydroxyl value was 829, and the number of moles of cyclohexene oxide added to 2.4 moles of polyethylene glycol was 2.4 moles. That is, the obtained polyalkylene glycol is represented by the formula (I) in which A1, A2
Is represented by the general formula (II), and B is-(CH ₂ CH ₂
O) _n −, (the average value of 1 is 1.2, and the average value of m is 1.
It is a mixture of the polyalkylene glycol of the present invention represented by the average value of 2 and n of 13.2). The infrared absorption spectrum and proton nuclear magnetic resonance spectrum of the obtained polyalkylene glycol are shown in FIGS. 1 and 2.

This polyalkylene glycol was dissolved in water and a foaming test and a detergency test were conducted. The results are shown in Table 1.

[0023]

Example 2 Polyethylene glycol # 10 was added to a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
00 (average molecular weight 1000) 100.0 g, tetraglyme 59 g, sodium hydroxide 10.1 g were charged, and 1
The mixture was heated and stirred at 60 ° C. After charging 24.6 g of cyclohexene oxide into the dropping funnel, the mixture was gradually dropped into the flask over 1 hour. Then, the mixture was further heated and stirred at 160 ° C. for 1 hour. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. Then, the same treatment as in Example 1 was carried out to obtain 41.6 g of the intended polyalkylene glycol.

The polyalkylene glycol thus obtained had a molecular weight of 1271 as determined by measuring the hydroxyl value, and the number of moles of cyclohexene oxide added to 1 mole of polyethylene glycol was 2.8 moles. That is, the obtained polyalkylene glycol has the general formula (I)
2 is represented by the general formula (II), and B is-(CH ₂ C
H ₂ O) _n - is a mixture of (polyalkylene glycol average value of l is 1.4, the average value of m is 1.4, the average value of n is represented by 22.3). The infrared absorption spectrum and proton nuclear magnetic resonance spectrum of the obtained polyalkylene glycol are shown in FIGS. 3 and 4.

This polyalkylene glycol was dissolved in water and a foaming test and a detergency test were conducted. The results are shown in Table 1.

[0026]

Comparative Example 1 Known as a low-foaming surfactant,
Pluronic L31 (Asahi Denka Kogyo, average molecular weight 110
0, the structural formula is HO (CH ₂ CH ₂ O) _a (CH ₂ CH (C
H ₃ ) O) _b (CH ₂ CH ₂ O) _c H, the proportion of ethylene oxide part in all molecules being 10% by weight) was dissolved in water, and a foaming test and a detergency test were conducted. . The results are shown in Table 1.

[0027]

Comparative Example 2 Known as a low-foaming surfactant,
Pluronic L61 (Asahi Denka Kogyo, average molecular weight 200
0, the structural formula is HO (CH ₂ CH ₂ O) _a (CH ₂ CH (CH
₃ ) O) _b (CH ₂ CH ₂ O) _c H, the proportion of the ethylene oxide portion in all molecules being 10% by weight) is dissolved in water,
A foamability test and a detergency test were conducted. The results are shown in Table 1.

[0028]

Example 3 20.1 g of tetraethylene glycol (molecular weight 194) and 10.4 g of sodium hydroxide were placed in a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
Was charged and heated and stirred at 180 ° C. After charging 40.4 g of cyclohexene oxide into the dropping funnel, the mixture was gradually dropped into the flask over 1 hour. Then 18 more
The mixture was heated and stirred at 0 ° C. for 1 hour. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. The same treatment as in Example 1 was performed to obtain the target polyalkylene glycol.

The molecular weight of the obtained polyalkylene glycol determined by measuring the hydroxyl value was 532, and the number of moles of cyclohexene oxide added to 3.4 moles of tetraethylene glycol was 3.4 moles. That is, the obtained polyalkylene glycol has the general formula (I)
2 is represented by the general formula (II), and B is-(CH ₂ C
H ₂ O) _n - is a mixture of (polyalkylene glycol of the present invention the average value of l is 1.7, the average value of m is 1.7, the value of n is represented by 4).

The obtained polyalkylene glycol was dissolved in water and subjected to a foaming property test and a detergency test in the same manner as in Examples 1 and 2, as a result, the foaming property was 0 mm and the cleaning rate was 99%.
It was (washing liquid concentration 0.2%).

[0031]

Example 4 Polyethylene glycol # 60 was added to a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
0 (average molecular weight 600) 1204 g, sodium metal 2
3.0 g was charged and the mixture was heated and stirred at 165 ° C. After charging 433 g of cyclohexene oxide into the dropping funnel,
The solution was gradually dropped into the flask over 1 hour. Then, the mixture was further heated and stirred at 165 ° C. for 1 hour. GPC of reaction liquid
From the analysis, the conversion of cyclohexene oxide is 100.
%Met. The same treatment as in Example 1 was carried out to obtain 830 g of a target polyalkylene glycol.

The molecular weight of the obtained polyalkylene glycol determined by measuring the hydroxyl value was 795, and the number of moles of cyclohexene oxide added to 1 mole of polyethylene glycol was 2.0 moles. That is, the obtained polyalkylene glycol is represented by the formula (I) in which A1, A2
Is represented by the general formula (II), and B is-(CH ₂ CH ₂
O) _n- , wherein the average value of 1 is 1, the average value of m is 1, and the average value of n is 13.2).

The obtained polyalkylene glycol was dissolved in water and subjected to a foaming test and a detergency test in the same manner as in Examples 1 and 2, and as a result, the foaming property was 0 mm and the cleaning rate was 100%.
It was (washing liquid concentration 0.2%).

[0034]

Example 5 A flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel was charged with 240 g of ethylene oxide propylene oxide random copolymer (average molecular weight 1200, ethylene oxide content 95 mol%) and 2.5 g of sodium metal. After charging, the mixture was heated and stirred at 165 ° C.
After 39.2 g of cyclohexene oxide was charged in the dropping funnel, the mixture was gradually dropped into the flask over 1 hour.
Then, the mixture was further heated and stirred at 165 ° C. for 1 hour. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. Perform the same processing as in Example 1,
220 g of the target polyalkylene glycol was obtained.

The polyalkylene glycol obtained had a molecular weight of 1386 as determined by measuring a hydroxyl value, and the number of moles of cyclohexene oxide added to 1 mole of the ethylene oxide propylene oxide random copolymer was 1.
It was 9 mol. That is, the obtained polyalkylene glycol has the same general formula (I) as A1 and A2 in the general formula (II).
Is a polyalkylene glycol composed of
3, i = 0, the average value of l is 0.95, and the average value of m is 0.
95, the average value of n is 25.5, the average value of p is 1.3, p
/(N+p)=0.05), which is a mixture of the polyalkylene glycol of the present invention.

The obtained polyalkylene glycol was dissolved in water and subjected to a foaming test and a detergency test in the same manner as in Examples 1 and 2, and as a result, the foaming property was 0 mm and the cleaning rate was 99%.
It was (washing liquid concentration 0.2%).

[0037]

Example 6 Polyethylene glycol # 40 was added to a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
00 (average molecular weight 4000) 100.0 g, tetraglyme 50 g, sodium hydroxide 1.5 g
The mixture was heated and stirred at 0 ° C. After charging 36.8 g of cyclohexene oxide to the dropping funnel, the mixture was gradually dropped into the flask over 2 hours. Furthermore, the mixture was heated and stirred at 180 ° C. for 3 hours. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. The same treatment as in Example 1 was performed to obtain the desired polyalkylene glycol 104.
g was obtained.

The polyalkylene glycol thus obtained had a molecular weight of 5215 as determined by measuring a hydroxyl value, and the number of moles of cyclohexene oxide added to 1 mole of polyethylene glycol was 12.4 moles. That is, the obtained polyalkylene glycol has the following formula (1) in the general formula (I):
A2 is represented by formula (II), and the B - (CH ₂
CH ₂ O) _n- , wherein the average value of 1 is 6.2, the average value of m is 6.2, and the average value of n is 90.5. .

The obtained polyalkylene glycol was dissolved in water and subjected to a foaming test and a detergency test in the same manner as in Examples 1 and 2, and as a result, the foaming property was 0 mm and the cleaning rate was 99%.
It was (washing liquid concentration 0.2%).

[0040]

Example 7 Polyethylene glycol # 60 was added to a flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel.
0 (average molecular weight 600) 50.0 g, Y-type zeolite (manufactured by Tosoh Corporation, HS-USY, HSZ-360U)
2.5 g of (A, H type) was charged, and the mixture was heated and stirred at 170 ° C. Cyclohexene oxide 18.0 was added to the dropping funnel.
After charging g, the solution was gradually added dropwise to the flask over 1 hour. Then, heating and stirring was further performed at 170 ° C. for 4 hours. From the GPC analysis of the reaction solution, the conversion rate of cyclohexene oxide was 100%. Zeolite is filtered off from the reaction solution to obtain the desired polyalkylene glycol 830
g was obtained.

The molecular weight of the obtained polyalkylene glycol determined by measuring the hydroxyl value was 795, and the number of moles of cyclohexene oxide added to 2.0 moles of polyethylene glycol was 2.0 moles. That is, the obtained polyalkylene glycol is represented by the formula (I) in which A1, A2
Is represented by the general formula (II), and B is-(CH ₂ CH ₂
O) _n- , wherein the average value of 1 is 1, the average value of m is 1, and the average value of n is 13.2).

The obtained polyalkylene glycol was dissolved in water and subjected to a foaming test and a detergency test in the same manner as in Examples 1 and 2, and as a result, the foaming property was 0 mm and the cleaning rate was 100%.
It was (washing liquid concentration 0.2%).

[0043]

[Table 1]

[0044]

INDUSTRIAL APPLICABILITY The novel polyalkylene glycol of the present invention can be used as a surfactant composition or a detergent composition having extremely low foaming property and excellent detergency, and its industrial value is extremely high.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of polyalkylene glycol of Example 1.

FIG. 2 is a proton nuclear magnetic resonance spectrum of the polyalkylene glycol of Example 1.

FIG. 3 is an infrared absorption spectrum diagram of the polyalkylene glycol of Example 2.

FIG. 4 is a proton nuclear magnetic resonance spectrum of the polyalkylene glycol of Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-206001 (JP, A) JP-A-4-21647 (JP, A) JP-A-57-94018 (JP, A) JP-A-54- 151138 (JP, A) JP-A-2-142748 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 65/28 B01F 17/42 C11D 1/722 CA (STN)

Claims (4)

(57) [Claims] 1. A polyalkylene glycol represented by the general formula (I) and having a number average molecular weight of 350 to 30,000 , wherein A1 in the general formula (I) is
, A2 is composed of the general formula (II).
Polyalkylene glycol. A1 -B-A2 (I) (wherein, the _{B - (CH 2 CH 2 O} ) -, - (C z H
_2z-2i O) _-is composed of n and p bonds, respectively, wherein i is 0 to 1 when z is 3, and
When it is 4 to 6, it is 0 to 2, when it is 7, it is 0 to 3, when it is 8 to 10, it is an integer of 0 to 4, z is an integer of 3 to 10, n is an integer of 4 to 680, and p is 0 ≦ p / ( n + p) represents an integer satisfying 0.1. ) [Chemical 1] 2. In the general formula (I), B is-(CH ₂ CH
₂ O) _n- , where n is an integer from 4 to 680, The polyalkylene glycol according to claim 1. Wherein 1 to 100% by weight as essential components a polyalkylene glycol according to any one of claims 1-2
A surfactant composition characterized by containing the same. Wherein the polyalkylene glycol 0.001% by weight of any of claims 1-2 and water 1-9
A cleaning agent composition containing 9.999% by weight as an essential component.