JPH0116280B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous thickener containing two types of polyether compounds as essential components. Traditionally, water-based thickeners include anions such as sodium alginate, sodium polyacrylate, maleic acid copolymer salts, and polyacrylamide partially hydrolyzed salts; water-soluble aniline resin hydrochloride, polyethyleneimine, and vinylpyridine copolymers. Cationic thickeners such as salts and polythiourea acetates; nonionic thickeners such as water-soluble urea resins, polyethylene oxide, polyvinyl alcohol, and polyacrylamide are known. However, these conventional water-based thickeners have poor stability in the thickened aqueous solution system, causing viscosity changes over time, precipitation due to changes in the pH range of the solution, and mechanical shear stress. Under such conditions of use, it has had various drawbacks such as molecular cleavage and reduced viscosity. The present invention was completed as a result of intensive research in search of a water-based thickener that does not have the above-mentioned drawbacks, and is a water-based thickener that exhibits excellent thickening properties by using a combination of polyether compounds with a specific structure. is intended to provide. The present invention is an aqueous thickener containing a polyether compound represented by the following formula [] and a polyether compound represented by the formula [] in a weight ratio of 1:4 to 4:1. RX [(C ₂ H ₄ O) _a (CpH ₂ pO) _b H] _l ... [] (Here, R is a hydrocarbon group having 5 to 26 carbon atoms,
X is an oxygen atom or a nitrogen atom, p is 3 or 4,
a is the average number of added moles of ethylene oxide, b is the average number of added moles of alkylene oxide having 3 or 4 carbon atoms, a+b is 2 to 200, b/a is 0 to 7/3, and oxyethylene group and 3 or 4 carbon atoms It is added to the oxyalkylene group of 4 in a block form, and either of them may be added first, or they may be added alternately, and l is 1 or 2. ) R′(X′[{C ₂ H ₄ O) _c (CpH ₂ pO) _d }(CqH ₂ qO) _e H
] _n ) _o ... [] (Here, R' is a polyhydric alcohol residue having 2 to 26 carbon atoms, a polyvalent phenol residue, or a polyvalent amine residue, X' is an oxygen atom or a nitrogen atom, p and q is 3 or 4, respectively, c is the average number of added moles of ethylene oxide, d and e are the average number of added moles of alkylene oxide having 3 or 4 carbon atoms, c +
d+e is 10 to 3000, d/c is 0 to 1 and d
When is not 0, the numbers inside { } are added randomly, e/(c+d) is 1/9 to 7/3, and the numbers inside [ ] are added in blocks in the order of the formula,
m is 1 or 2, and n is an integer from 2 to 8. ) In the formula [], the hydrocarbon group represented by R includes aliphatic linear, alicyclic, saturated or unsaturated hydrocarbon groups having a side chain, aromatic hydrocarbon groups, etc. or 26
aliphatic saturated alcohols, aliphatic unsaturated alcohols, alicyclic alcohols, aromatic alcohols, alkyl-substituted phenols, alkenyl-substituted phenols, aliphatic saturated amines, aliphatic unsaturated amines, alicyclic It is expressed as a residue of formula amines, aromatic amines, etc. Alcohols and phenols with R as a residue,
Examples of amines are pentanol, hexanol, heptanol, octanol, nonanol,
Decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, oleyl alcohol, octylphenol, Nonylphenol, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine,
Examples include hexadecylamine, heptadecylamine, octadecylamine, and oleylamine. In the formula [], the alkylene oxide having 3 or 4 carbon atoms represented by CpH ₂ pO includes propylene oxide, butylene oxide, tetrahydrofuran, etc., and these may be added alone or in a mixed state. l indicates the number of polyethylene oxide polyalkylene oxide chains directly bonded to X; if X is an oxygen atom, l = 1; if X is a nitrogen atom, l =
It becomes 2. a and b indicate the average number of added moles of polyethylene oxide and polyalkylene oxide in each polyethylene oxide polyalkylene oxide chain, and b includes the case of 0. When polyethylene oxide and polyalkylene oxide are added alternately, a and b are not the average number of added moles of each block but the average number of added moles of the whole. The polyether compound of the formula [] uses one or more of alcohols, phenols, or amines in which R is a residue as a starting material, and ethylene oxide is added thereto alone, or
Alternatively, it can be produced by block addition polymerization of ethylene oxide and the above-mentioned alkylene oxide. In the case of addition polymerization in blocks, ethylene oxide is added to RX if ethylene oxide is added and polymerized first, but the order of addition polymerization is not limited, and addition polymerization may be performed alternately. The addition polymerization method is not limited, and for example, the reaction can be carried out at 60 to 180°C in the presence of an alkali catalyst. [] If the number of carbon atoms in the hydrocarbon group represented by R in the formula is less than 5, the hydrophobicity of the starting material will be weak, and even if alkylene oxide is added, the balance between the hydrophobic group and the hydrophilic group in the compound obtained will not be balanced, resulting in an increase in the number of carbon atoms. Does not exhibit viscous effects. The reason why the total number of added moles of a+b, ethylene oxide and alkylene oxide, is limited to a range of 2 to 200 is that if it is less than 2 moles, the influence of the hydrophobicity of the starting material is strong, and the water solubility is poor and it cannot be used as an aqueous thickener. First, if it exceeds 200 moles, the proportion of the starting material in the molecule decreases, resulting in too strong water solubility and no thickening effect. The reason why the ratio of b and a is limited to a range of 0 to 7/3 is that if it is larger than 7/3, the water solubility will be poor and it will not exhibit its thickening properties as an aqueous thickener. The reason why a block-shaped addition polymer is used as the compound of formula [] is that it exhibits effective thickening properties due to the balance between hydrophilic and hydrophobic groups. Next, in the formula [], examples of polyhydric alcohols, polyhydric phenols, and polyhydric amines in which R' is a residue include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, and trimethylol. Propane, pentaerythritol, sorbitol, glucose, sucrose, ethyldiethanolamine, butyldiethanolamine, triethanolamine, tripropanolamine,
N,N'-di-naphthyl-p-phenylenediamine, 4,4'-di-aminodiphenylmethane, 4,
4'-di-aminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, bisphenol A, hydrogenated bisphenol A, 4,4'-butylidene bis(6
-tertiary-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-3
-methylphenol), catechol, resorcinol, etc. In the formula [], the alkylene oxide having 3 or 4 carbon atoms represented by CpH ₂ pO and CqH ₂ qO includes the same alkylene oxide as the alkylene oxide in the formula [], and may be the same or different. Good too. m indicates the number of polyethylene oxide polyalkylene oxide chains directly bonded to X'; when X' is an oxygen atom, m=1; when X' is a nitrogen atom, m=2. n indicates the number of chains directly bonded to R' and matches the valence of R'. c, d, and e indicate the average number of added moles of polyethylene oxide and polyalkylene oxide in each chain, and d includes the case of 0. The polyether compound of the formula [] uses one or more polyhydric alcohols, polyhydric phenols, or polyhydric amines as a starting material with R' as a residue, and is prepared by adding ethylene oxide alone to this as a starting material. or after random addition polymerization of ethylene oxide and the above alkylene oxide,
Furthermore, it can be produced by block addition polymerization of the above-mentioned alkylene oxide. In the formula [], c + d + e, that is, the total number of added moles of ethylene oxide and alkylene oxide, is limited to a range of 10 to 3000 because if it is less than 10 moles, the molecular weight is too low and becomes completely water-soluble, which prevents the thickening effect. 3000 again
This is because when the molecular weight is exceeded, the viscosity decreases significantly due to molecular breakage under conditions where mechanical shear stress is applied, which poses a practical problem. The reason why the ratio e/(c+d) is limited to the range of 1/9 to 7/3 is that if it exceeds 7/3, the water solubility will be poor and it will not exhibit thickening properties as an aqueous thickener; If it is less than 9, the hydrophobic group derived from the alkylene oxide is too small and the balance between the hydrophobic group and the hydrophilic group is not balanced, resulting in no thickening effect. In the formula [], the reason why the random addition polymerization moiety in { } or polyethylene oxide and the alkylene oxide represented by CqH ₂ qO are block-wise addition-polymerized in that order is that when randomly added, the hydrophobic group This is because there is no balance between the hydrophilic groups and the viscosity increasing effect, and even if the order of addition is reversed, the viscosity increasing effect will not be exhibited at all. The polyether compounds of the above formulas [ ] and [ ] are blended in the above proportions to form an aqueous thickener. Of course, each compound may be added to water separately and blended in a state dissolved in water. The aqueous thickener of the present invention is used as an aqueous solution of 0.1 to 60% by weight, but if a particularly small change in viscosity is required, a water-soluble compound with a number average molecular weight of 500 to 100,000 may be added to the aqueous solution. When it is contained in an amount of 0.1 to 30% by weight, an aqueous solution with a small change in viscosity due to temperature can be obtained, and the lubricity is also improved. A particularly preferred composition in this case is []
1 to 15% by weight of a polyether compound of the formula;
It is an aqueous solution containing 1 to 15% by weight of a polyether compound of the formula [] and 1 to 5% by weight of a water-soluble compound. Furthermore, if necessary, various additives such as a polar agent, a lubricity improver, an antifoaming agent, and an antioxidant may be added. Examples of the water-soluble compounds having a number average molecular weight of 500 to 100,000 include polyacrylates, maleic acid copolymer salts, water-soluble urea resins, polyvinyl alcohol, polyacrylamide, polyethyleneimine,
Although there are polyether derivatives, polyether derivatives having a strong affinity with the polyether compounds of the formula [] and [], particularly polyoxyalkylene glycol, are preferred. It is known that the polyether compound of the formula [] exhibits a thickening effect by itself in a very narrow range where the number of added moles of the hydrophobic group of the starting material and the alkylene oxide are balanced. "Surfactant" by Yoshiro Ishii, published by Seibundo Shinkosha) has the disadvantage that the thickening property in this case is highly temperature dependent. In other words, the thickening effect in this case is only near the cloud point temperature of the aqueous solution, and the thickening effect is extremely weak at temperatures below the cloud point temperature, and furthermore, the cloud point temperature in this case is usually around 30°C. , it is difficult to use as an aqueous thickener. On the other hand, the composition of the present invention, which is a combination of the polyether compound of the formula [] and the polyether compound of the formula [], exhibits a synergistic effect, eliminates the above drawbacks, and is effective against water of any pH value. It exhibits excellent solubility and thickening properties, and is chemically and physically stable in aqueous solutions, making it useful as an aqueous thickener. As described above, the water-based thickener of the present invention exhibits excellent thickening properties even when added in small amounts, and is stable against chemical and mechanical shear stress, so it is particularly suitable as a water-based lubricant base. It exhibits excellent effects as a base for high water content hydraulic fluids, a base for water-glycol flame-retardant hydraulic fluids, a base for water-soluble metal working fluids, etc. Furthermore, the water-based thickener of the present invention uses existing natural polymer compounds such as gum tragacanth, pectin, sodium alginate, methyl cellulose, carboxymethyl cellulose, and starch, or synthetic polymers such as polyacrylamide, sodium polyacrylate, and polyvinyl alcohol. It can also be used in the fields of paper processing agents, adhesives, dispersants, cosmetics, gelling agents, latexes, thickeners for water-based paints, etc. Hereinafter, production examples and examples of the present invention will be described. Production example 1 Production of compound of formula [] Oleyl alcohol at 5.36℃ in a 30-volume airtight container.
Kg (20 moles), 40 g of potassium hydroxide as a catalyst, and 8.8 g of ethylene oxide under nitrogen gas atmosphere.
Kg (200 mol) at 90 to 130℃, 0.5 to 5.0
Addition polymerization was carried out under a pressure of Kg/cm ² to obtain 13.9 Kg of polyoxyethylene (10) oleyl ether (crude product). After neutralizing the potassium hydroxide in this crude product with an aqueous hydrochloric acid solution, it was dehydrated at 80 to 120°C under reduced pressure of 50 mmHg or less for 2 hours, and the precipitated salt was separated to obtain 13.6 kg of purified reaction product. Production example 2 Production of compound of formula [] In a 30-meter airtight container, put 1.3 kg (10 mol) of octanol and 60 g of potassium hydroxide as a catalyst, and add 11.6 kg of propylene oxide under a nitrogen gas atmosphere.
(200 mol) at 90 to 130℃, 0.5 to 5.0 kg/
After addition polymerization under a pressure of cm ² , 6.6 kg (150 mol) of ethylene oxide was further added under the same conditions to form polyoxypropylene (20), oxyethylene (15), and octyl ether (block polymer).
19.4Kg (crude total product) was obtained. This crude product was purified in the same manner as in Production Example 1 to obtain 18.7 kg of purified reaction product. Production example 3 Production of compound of formula 310g of ethylene glycol in a 60 volume airtight container
(5 mol) and 60 g of potassium hydroxide, and 22 kg (500 mol) of ethylene oxide in a nitrogen gas atmosphere.
was subjected to addition polymerization at 90 to 130°C under pressure of 0.5 to 5.0 Kg/cm ² , and then 11.6 kg (200 mol) of propylene oxide was added under the same conditions to obtain polyoxyethylene (101) and oxypropylene (40). 33.5 kg (crude product) of glycol (block polymer) was obtained. This crude product was purified in the same manner as in Production Example 1 to obtain 32 kg of purified reaction product. Various samples used in the following examples were manufactured in the same manner. Example 1 The kinematic viscosity and cloud point of the aqueous solutions of the present invention and comparative products prepared by blending the compounds of formulas [] and [] with the compositions shown in Table 1 were measured, and the appearance was observed. The results are shown in Table 1. The compounds used in Table 1 are shown by formulas that do not correspond to the formulas [] and [] to make the structures easier to understand, but [] is a polyether compound of the formula [], and [] is a polyether compound of the formula []. The polyale compound of the formula [ ] represents another water-soluble compound.
In addition, the compounds in { } of sample No. 13 and the compounds labeled (random polymer) in No. 16 and No. 18 were added in a random manner, but the others were added in a block manner. show. As is clear from the results in Table 1, when only the polyether compound of the formula [] was used, it did not thicken (No. 4, No. 5), did not dissolve,
(No. 7), and even if the viscosity increases to some extent, it may not become a completely transparent solution (No. 8). The polyether compound of the formula [] does not show any thickening effect when used alone (No. 6). However, the product of the present invention, which is a combination of both compounds, exhibits excellent thickening properties, is completely transparent in appearance, and has a high clouding point, indicating that it has excellent performance as a water-based thickener. (No.1
~ No. 3, No. 9 ~ No. 13). Also, [] expression and []
Compounds outside the formula range do not exhibit thickening properties (No. 14 to No. 18).

【table】

【table】

[Table] Next, Table 2 shows the results of a comparative test of thickening properties, storage stability, and shear stability between the present invention and existing thickeners. In Table 2, the compositions of the products of the present invention are as follows, and [], [] and [] indicate the same as above.

[Table] Also, sodium polyacrylate has a polymerization degree of 340.
PEO is polyethylene oxide (molecular weight 250,000), which is obtained by saponifying polymethyl acrylate with sodium hydroxide. Storage stability was determined by taking the viscosity immediately after dissolution as 100 and showing the change in viscosity over time as an index. Shear stability was measured using an ultrasonic shear stability tester (output
Ultrasonic waves were irradiated at 30° C. for 60 minutes using a power of 150 W and a frequency of 10 KC, and measurements were made using the following formula. Shear stability = Kinematic viscosity at 25°C after ultrasound irradiation/Kinematic viscosity at 25°C before ultrasound irradiation

[Table] From the results in Table 2, the product of the present invention exhibits thickening properties comparable to those of existing thickeners, and also exhibits superior storage stability and shear stability. It can be seen that it is excellent. Example 2 A lubrication performance test was conducted using the product of the present invention as a base for water-based lubricating oil compositions, particularly high water content hydraulic oils that require excellent thickening properties even when added in small amounts. A composition in which the following additives were added to the 5% aqueous solution of the product of the present invention prepared in Example 1, and a 5% aqueous solution of the existing thickener PEO (polyethylene oxide) used in Example 1 as a comparative product were added as shown below. A foaming test according to JIS K-2518, a test using a Soda four-ball tester and a Chimken oil tester, and a pump test under the following conditions were conducted on the composition containing the following additives. The results are shown in Table 3. (Additives) Oleic acid 1.0% by weight Potassium hydroxide 0.2 〃 Morpholine 0.2 〃 Benzotriazole 0.1 〃 Antifoaming agent (Shin-Etsu Chemical Co., Ltd. KM-83) 0.01% by weight (Pump test) Hydraulic pump: V- manufactured by Bitsukas Co., Ltd. 104C vane pump oil amount: 80 Set pressure: 70Kg/cm ² rotation speed: 1200rpm Oil temperature: 50℃ Test time: 100 hours Viscosity ratio = Kinematic viscosity at 40℃ after pump test / Kinematic viscosity at 40℃ before pump test As is clear from the results in Table 3, the water-based lubricating oil composition based on the thickener of the present invention has better lubricity than the comparative product, and in the pump test, the amount of pump wear was small. It can be seen that it is excellent as a water-based hydraulic oil because it does not generate sludge and the change in viscosity ratio is small.

【table】

Claims (1)

[Scope of Claims] 1. An aqueous thickener containing a polyether compound represented by the following formula [] and a polyether compound represented by the formula [] in a weight ratio of 1:4 to 4:1. RX [(C ₂ H ₄ O) _a (CpH ₂ pO) _b H] _l ... [] (Here, R is a hydrocarbon group having 5 to 26 carbon atoms,
X is an oxygen atom or a nitrogen atom, p is 3 or 4,
a is the average number of added moles of ethylene oxide, b is the average number of added moles of alkylene oxide having 3 or 4 carbon atoms, a+b is 2 to 200, b/a is 0 to 7/3, and oxyethylene group and 3 or 4 carbon atoms It is added to the oxyalkylene group of 4 in a block form, and either of them may be added first, or they may be added alternately, and l is 1 or 2. ) R′(X′[{(C ₂ H ₄ O) _c (CpH ₂ pO) _d }(CqH ₂ qO) _e
H] _n ) _o ... [] (Here, R' is a polyhydric alcohol residue having 2 to 26 carbon atoms, a polyvalent phenol residue, or a polyvalent amine residue, X' is an oxygen atom or a nitrogen atom, p and q are respectively 3 or 4, c is the average number of added moles of ethylene oxide, d and e are the average number of added moles of alkylene oxide having 3 or 4 carbon atoms, c+
d+e is 10 to 3000, d/c is 0 to 1,
When d is not 0, it is added randomly within { }, and e/(c+d) is 1/9 to 7/3
The numbers in [ ] are added in block form in the order of the formula, m is 1 or 2, and n is an integer from 2 to 8. ) 2 [R in the formula] is pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, cyclo Pentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, oleyl alcohol, octylphenol, nonylphenol, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine,
The aqueous thickener according to claim 1, which is a residue of one or more compounds selected from octadecylamine and oleylamine. 3 R′ in the formula [] is ethylene glycol,
Propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, glucose, sucrose, ethyldiethanolamine, butyldiethanolamine, triethanolamine, tripropanolamine, N,N'-diethanolamine, -Naphthyl-p-phenylenediamine, 4,4'-di-aminodiphenylmethane, 4,4'-di-aminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, bis Phenol A, hydrogenated bisphenol A, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), catechol and resorcinol Claim 1, which is a residue of one or more compounds selected from
The aqueous thickener according to item 1 or 2. 4 In [] and [], CpH ₂ pO
and CqH ₂ qO are propylene oxide, respectively
The aqueous thickener according to any one of claims 1 to 3, which is one or more alkylene oxides selected from butylene oxide and tetrahydrofuran.