Polyether-modified organopolysiloxane

Abstract

To provide a polyether-modified organopolysiloxane which has excellent water solubility, without impairing the characteristics of siloxane, while having a polyether chain.SOLUTION: The present invention provides a polyether-modified organopolysiloxane which is represented by formula (1) and has a block copolymer structure comprising a polyblock structure of oxyethylene and a polyblock structure of oxypropylene. (In the formula, each R independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the like, and each R1 independently represents a group represented by formula (2)).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyether-modified organopolysiloxane. [Background technology]

[0002] Water-soluble polyether-modified polyorganosiloxanes are very useful materials that are used in a wide range of fields, such as agricultural spreading agents, paint additives, and cosmetics. In polyether-modified polyorganosiloxanes, the siloxane chain or oxypropylene chain is hydrophobic, so in order to make them water-soluble, methods have been used in the past to increase the proportion of oxyethylene groups in the hydrophilic molecule or to introduce hydroxyl groups to the ends of the polyether chains (Patent Documents 1, 2, and 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2000-327787 A [Patent Document 2] JP 2003-253166 A [Patent Document 3] JP 2018-070794 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the polyether-modified polyorganosiloxane obtained by the method of increasing the ratio of oxyethylene in the molecule or the method of introducing a hydroxyl group to the end of the polyether chain has water solubility, but has the problem that the advantages of siloxane such as surface migration and leveling properties are lost. The present invention has been made in view of the above circumstances, and aims to provide a polyether-modified organopolysiloxane having good water solubility without losing the characteristics of siloxane while having a polyether chain. [Means for solving the problem]

[0005] As a result of extensive research conducted by the present inventors in order to achieve the above object, they discovered that a polyether-modified siloxane having the specific structure shown below can solve the above problems, and thus completed the present invention.

[0006] That is, the present invention provides [1] a polyether-modified organopolysiloxane represented by the following formula (1) and having a block copolymer structure consisting of an oxyethylene polyblock structure and an oxypropylene polyblock structure. [ka] (In the formula, R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; x is an integer of 1 to 100; R 1 are each independently a group represented by the following formula (2): [ka] (In the formula, R 2 is an alkyl group having 1 to 12 carbon atoms or an acetyl group, n is an integer of 2 to 10, a is an integer of 3 to 60, b is an integer of 3 to 60, and b / (a+b) is in the range of 0.3 to 0.8, and the oxypropylene in the parentheses enclosed by a and the oxyethylene in the parentheses enclosed by b each have a polyblock structure in the order shown in the above formula (2).

[0007] The present invention further provides a polyether-modified organopolysiloxane further having at least one of the following structures [2] to [4]: [2] The polyether-modified organopolysiloxane according to the above [1], which has an HLB value of 4 to 7 as determined by the Griffin method. [3] The polyether-modified organopolysiloxane according to [1] or [2] above, wherein a 1% by mass aqueous solution of the polyether-modified organopolysiloxane has a Haze value of 5 or less at 25°C. [4] The polyether-modified organopolysiloxane according to any one of the above [1] to [3], wherein the polyether-modified organopolysiloxane has an HLB value of 4 to 7 as determined by the Griffin method and a Haze value of 5 or less at 25°C of a 1% by mass aqueous solution of the polyether-modified organopolysiloxane. Because the polyether-modified organopolysiloxane of the present invention has the above-mentioned block copolymer structure, it is possible to have high water solubility even if it has a structure in which there are no hydroxyl groups at the terminals of the polyether moieties and the proportion of oxyethylene in the molecule is low.

[0008] The polyether-modified organopolysiloxane of the present invention preferably has an HLB value of 4 to 7 according to the Griffin method and a Haze value of 5 or less in a 1% by mass aqueous solution at 25° C. The polyether-modified organopolysiloxane having the above HLB value and Haze value has high water solubility. In addition, it is expected that the advantages of siloxane such as surface migration and leveling properties are well maintained. Effect of the Invention

[0009] The polyether-modified organopolysiloxane of the present invention is a compound that has good water solubility without impairing the properties of siloxane, and is useful in many applications such as paint additives, resin additives, and cosmetics. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will now be described in further detail.

[0011] The polyether-modified polyorganopolysiloxane of the present invention is represented by the following formula (1) and has a block copolymer structure consisting of an oxyethylene polyblock structure and an oxypropylene polyblock structure. [ka]

[0012] In the above formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a tolyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group. Among them, R is preferably a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, more preferably a methyl group and a phenyl group, and most preferably a methyl group.

[0013] In the above formula (1), x is an integer of 1 to 100, preferably an integer of 3 to 80, more preferably an integer of 5 to 60, even more preferably an integer of 10 to 50, and most preferably an integer of 15 to 40. If x is smaller than the above lower limit, the characteristics of the siloxane are not fully exhibited. If x is larger than the above upper limit, the water solubility of the polyether-modified polyorganopolysiloxane may be impaired.

[0014] In the above formula (1), R 1 are each independently a group represented by the following formula (2): [ka]

[0015] In the above formula (2), R 2 is an alkyl group having 1 to 12 carbon atoms, or an acetyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, and a dodecyl group. Among these, R 2As the alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, an octyl group, a dodecyl group, and an acetyl group are preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and an acetyl group are more preferable. Among these, a methyl group, an n-butyl group, and an acetyl group are most preferable because of their easy availability.

[0016] In the above formula (2), n is an integer of 2 to 10, preferably an integer of 3 to 8, and most preferably 3 in terms of availability.

[0017] In the above formula (2), a is an integer of 3 to 60, preferably an integer of 3 to 50, more preferably an integer of 4 to 40, even more preferably an integer of 5 to 30, and most preferably an integer of 10 to 20. If a is smaller than the above lower limit, the compatibility with other materials may be affected. On the other hand, if a is larger than the above upper limit, the water solubility of the polyether-modified polyorganopolysiloxane may be impaired.

[0018] In the above formula (2), b is an integer of 3 to 60, preferably an integer of 3 to 50, more preferably an integer of 4 to 40, even more preferably an integer of 5 to 30, and most preferably an integer of 10 to 20. If b is smaller than the above lower limit, the water solubility of the polyether-modified polyorganopolysiloxane is insufficient. If b is larger than the above upper limit, the characteristics of the siloxane are not fully exhibited.

[0019] In the above formula (2), b / (a+b) is in the range of 0.3 to 0.8, preferably 0.32 to 0.7, more preferably 0.32 to 0.6, even more preferably 0.35 to 0.55, and most preferably 0.4 to 0.5. If b / (a+b) is smaller than the lower limit, the water solubility of the polyether-modified polyorganopolysiloxane is insufficient. If b / (a+b) is larger than the upper limit, the characteristics of the siloxane are not fully exhibited.

[0020] In the above formula (2), the oxypropylene in the parentheses enclosed by the above a and the oxyethylene in the parentheses enclosed by the above b each have a polyblock structure in the order shown in the above formula (2). By having the oxypropylene and oxyethylene in the polyblock structure in the above order, it is possible to provide a polyether-modified polyorganopolysiloxane that has high water solubility while better maintaining the properties of the siloxane.

[0021] The polyether-modified polyorganopolysiloxane represented by the above formula (1) preferably has an HLB value of 4 to 7 according to the Griffin method, and a 1 mass % aqueous solution of the polyether-modified polyorganopolysiloxane has a Haze value of 5 or less at 25° C. The HLB value can be calculated by the following formula. HLB = {(oxyethylene group content) × 20} / (total amount of polyether-modified organopolysiloxane)

[0022] The polyether-modified polyorganopolysiloxane more preferably has an HLB value of 4.1 to 6.8, further preferably has an HLB value of 4.2 to 6.6, and most preferably has an HLB value of 4.2 to 6.0. If the HLB value of the polyether-modified polyorganopolysiloxane is equal to or higher than the lower limit, the polyether-modified polyorganopolysiloxane can have sufficient water solubility. If the HLB value is equal to or lower than the upper limit, the characteristics of the siloxane can be fully exhibited.

[0023] The Haze value of a 1% by mass aqueous solution of the polyether-modified polyorganopolysiloxane at 25° C. is 5 or less, more preferably 0 or more and 4 or less, and even more preferably more than 0 and 2 or less. If the Haze value is equal to or less than the upper limit, the polyether-modified polyorganopolysiloxane of the present invention has extremely high water solubility.

[0024] Polyether-modified polyorganosiloxane can be produced by the addition reaction of organohydrogenpolysiloxane and alkenyl group-containing polyether. The addition reaction is preferably carried out in the presence of an addition reaction catalyst. The addition reaction catalyst can be a catalyst generally used in addition reactions. For example, a noble metal catalyst such as a platinum group metal compound can be used, and examples of catalysts include platinum, palladium, rhodium, and ruthenium. Among these, platinum catalysts are particularly preferably used. In addition, the platinum catalyst may be, for example, chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, or a complex of chloroplatinic acid with various olefins or vinylsiloxanes. Among them, a solution of chloroplatinic acid neutralized with sodium bicarbonate-vinylsiloxane complex catalyst (Karstead catalyst) can be preferably used.

[0025] In the above addition reaction, the ratio of the organohydrogenpolysiloxane to the alkenyl group-containing polyether, that is, the ratio of the number of moles of alkenyl groups in the alkenyl group-containing polyether to the number of moles of Si-H groups in the organohydrogenpolysiloxane, is preferably 1.00 to 2.00, more preferably 1.05 to 1.50, and even more preferably 1.02 to 1.30.

[0026] The amount of the addition reaction catalyst may be any amount that is sufficient as long as it is a catalytic amount. In particular, the amount of the addition reaction catalyst is preferably 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, and most preferably 1 to 20 ppm, calculated as a metal relative to the total amount of the organohydrogenpolysiloxane and the alkenyl group-containing polyether. By using the addition reaction catalyst in an amount within the above preferred range, a sufficient reaction speed can be achieved while suppressing side reactions.

[0027] The reaction temperature of the above addition reaction is not particularly limited, but is preferably 0 to 150° C., and more preferably 20 to 100° C. If the reaction temperature is 0 to 150° C., a sufficient reaction speed can be achieved while preventing side reactions.

[0028] In addition, the above addition reaction may use a reaction solvent as necessary, for example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, methylcyclohexane and ethylcyclohexane, ether solvents such as dioxane, dibutyl ether and dimethoxyethane, ester solvents such as ethyl acetate and butyl acetate, nitrile solvents such as acetonitrile and benzonitrile, and alcohol solvents such as ethanol, propanol, isopropyl alcohol and butanol. EXAMPLES

[0029] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0030] [Haze value] In the following, the haze value of a 1% by mass aqueous solution of polyether-modified polyorganosiloxane at 25°C was measured using a cell with a cell length of 1 cm with the following device, and the haze value of each material was measured at 25°C after a blank (air) measurement. Device name: Nippon Denshoku Industries Co., Ltd. Haze Meter NDH-4000

[0031] [Synthesis Example 1] 100g of n-butanol and 3.86g of sodium methoxide were charged into a 5-liter autoclave equipped with a stirring device, a nitrogen inlet tube, and a thermocouple. After nitrogen replacement, the temperature was raised to 120°C, and 622g of ethylene oxide was dropped under conditions of 0.3MPa (gauge pressure) or less, and the mixture was stirred for 1 hour. Then, 821g of propylene oxide was dropped at 120°C and 0.2 to 0.5MPa (gauge pressure), and the mixture was stirred for 2 hours. The mixture was subjected to reduced pressure treatment at 75 to 85°C and 50 to 100Torr for 1 hour to remove the remaining ethylene oxide and propylene oxide. Then, 139g of potassium hydroxide and 86g of allyl chloride were charged. After nitrogen replacement, the mixture was reacted at 120°C for 3 hours, and 560g of water was added and stirred for 10 minutes. After standing for 1 hour, the lower layer that separated into phases was discharged, and the upper layer was recovered. The pH was adjusted to 6 to 7 with hydrochloric acid, and the solution was dried under reduced pressure at 100°C for 1 hour (gauge pressure: 0.095 MPa) to remove the contained moisture. After that, filtration was performed to remove the generated salt, and about 1,400 g of polyoxyalkylene monoallyl ether represented by the following formula (3) was obtained. [ka] (In formula (3), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.)

[0032] [Example 1] 692 g of the polyoxyalkylene monoallyl ether represented by the above formula (3) and 220 g of the siloxane represented by the following formula (4) were placed in a reaction vessel, and then 76 mg of a 3% by mass solution of chloroplatinic acid in isopropyl alcohol was added and reacted at 90°C for 2 hours. [ka] After the reaction, the volatile matter was removed at 100° C. / 3 torr for 1 hour, yielding 862 g of the target polyether-modified siloxane represented by the following formula (A). [ka] (In formula (A), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane (A) obtained above had an HLB value of 5.6, and a Haze value of a 1% by mass aqueous solution at 25° C. was 0.28.

[0033] [Example 2] The above-mentioned Example 1 was repeated, except that 440 g of the siloxane represented by the following formula (6) was used instead of 220 g of the siloxane represented by the above formula (4), to obtain 1,072 g of a polyether-modified siloxane represented by the following formula (B). [ka] [ka] (In formula (B), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane (B) obtained above had an HLB value of 4.2, and a Haze value of a 1% by mass aqueous solution at 25° C. was 2.0.

[0034] [Example 3] The above Example 1 was repeated, except that 687 g of polyoxyalkylene monoallyl ether represented by the following formula (7) was used instead of 692 g of polyoxyalkylene monoallyl ether represented by the above formula (3), to obtain 859 g of polyether-modified siloxane represented by the following formula (C). [ka] (In formula (7), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) [ka] (In formula (C), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane (C) obtained above had an HLB value of 5.7, and a Haze value of a 1% by mass aqueous solution at 25° C. was 0.25.

[0035] [Example 4] The above Example 1 was repeated, except that 738 g of the polyoxyalkylene monoallyl ether represented by the following formula (8) was used instead of 692 g of the polyoxyalkylene monoallyl ether represented by the above formula (3), to obtain 907 g of a polyether-modified siloxane represented by the following formula (D). [ka] (In formula (8), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) [ka] (In formula (D), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane (D) obtained above had an HLB value of 5.3, and a Haze value of a 1% by mass aqueous solution at 25° C. was 3.4.

[0036] [Example 5] The above Example 1 was repeated, except that 578 g of polyoxyalkylene monoallyl ether represented by the following formula (9) was used instead of 692 g of polyoxyalkylene monoallyl ether represented by the above formula (3), to obtain 751 g of a polyether-modified siloxane represented by the following formula (E). [ka] (In formula (9), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.4 in formula (1) above.) [ka] (In the above, oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.4 in the above formula (1).) The polyether-modified siloxane obtained above had an HLB value of 4.2, and a Haze value of a 1% by mass aqueous solution at 25° C. was 1.0.

[0037] [Example 6] Example 1 was repeated except that 691 g of the polyether represented by the following formula (10) was used instead of 692 g of the polyether represented by the above formula (3) in Example 1, to obtain 858 g of a polyether-modified siloxane represented by the following formula (F). [ka] (In formula (10), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) [ka] (In formula (F), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane obtained above had an HLB value of 5.7, and a Haze value of a 1% by mass aqueous solution at 25° C. was 0.27.

[0038] [Comparative Example 1] Example 1 was repeated except that 856 g of polyoxyalkylene monoallyl ether represented by the following formula (11), in which oxyethylene and oxypropylene are bonded randomly regardless of the order shown below and oxypropylene is bonded to the acetyl group at the end, was used instead of 692 g of polyoxyalkylene monoallyl ether represented by the above formula (3), to obtain 1,018 g of polyether-modified siloxane represented by the following formula (G). [ka] (In the above formula (11), oxypropylene and oxyethylene are bonded randomly, regardless of the above order, and oxypropylene is bonded to the acetyl group at the polyether end.) [ka] (In the above formula (G), oxypropylene and oxyethylene are bonded randomly, regardless of the above order, and satisfy b / (a+b)=0.5 in the above formula (1).) The polyether-modified siloxane obtained above had an HLB value of 6.0, a 1% by mass aqueous solution was cloudy and had a Haze value of 98 at 25°C.

[0039] The HLB values ​​and the Haze values ​​of 1% by mass aqueous solutions at 25° C. of the polyether-modified siloxanes obtained in Examples 1 to 6 and Comparative Example 1 above are summarized in Table 1 below.

[0040] [Table 1]

[0041] As shown in Table 1 above, the polyether-modified organopolysiloxane of the present invention has an HLB value of 4 to 7 according to the Griffin method and a Haze value of 5 or less in a 1% by mass aqueous solution at 25°C. Polyether-modified organopolysiloxanes having the above HLB and Haze values ​​have high water solubility. The polyether-modified organopolysiloxane of the present invention can have good water solubility without impairing the properties of the siloxane, and is therefore useful for many applications such as paint additives, resin additives, and cosmetics.

[0042] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A polyether-modified organopolysiloxane represented by the following formula (1) and having a block copolymer structure consisting of an oxyethylene polyblock structure and an oxypropylene polyblock structure: 【Chemistry 1】 (In the formula, R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; x is an integer of 1 to 100; R １ are each independently a group represented by the following formula (2): 【Chemistry 2】 (In the formula, R ２ is an alkyl group having 1 to 12 carbon atoms or an acetyl group, n is an integer of 2 to 10, a is an integer of 3 to 60, b is an integer of 3 to 60, and b / (a+b) is in the range of 0.3 to 0.8, and the oxypropylene in the parentheses enclosed by a and the oxyethylene in the parentheses enclosed by b each have a polyblock structure in the order shown in the above formula (2).

2. 2. The polyether-modified organopolysiloxane according to claim 1, wherein the polyether-modified organopolysiloxane has an HLB value of 4 to 7 according to the Griffin method.

3. 2. The polyether-modified organopolysiloxane according to claim 1, wherein a 1% by mass aqueous solution of the polyether-modified organopolysiloxane has a haze value of 5 or less at 25°C.

4. The polyether-modified organopolysiloxane according to claim 1, wherein the polyether-modified organopolysiloxane has an HLB value of 4 to 7 according to the Griffin method and a Haze value of 5 or less at 25°C of a 1% by mass aqueous solution of the polyether-modified organopolysiloxane.

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