Polyether-modified organopolysiloxane

Abstract

[Problem] The purpose of the present invention is to provide a polyether-modified organopolysiloxane which has good 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 a group selected from among 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 represents an integer of 1 to 100; and each R1 independently represents a group represented by formula (2).) (In the formula, R2 represents an alkyl group having 1 to 12 carbon atoms or an acetyl group; n represents an integer of 2 to 10; a represents an integer of 3 to 60; b represents an integer of 3 to 60; b / (a + b) is within the range of 0.3 to 0.8; and oxypropylene in parentheses with the subscript a and oxyethylene in parentheses with the subscript b respectively have polyblock structures in the sequence shown in formula (2).)

Description

Polyether-modified organopolysiloxane

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

[0002] Water-soluble polyether-modified polyorganosiloxanes are very useful materials that are used in a wide range of fields, such as agricultural spreaders, paint additives, and cosmetics. Because the siloxane chain or oxypropylene chain of polyether-modified polyorganosiloxanes is hydrophobic, conventional methods for making them water-soluble have been to increase the proportion of oxyethylene groups in the hydrophilic molecule or to introduce hydroxyl groups to the ends of the polyether chains (see Patent Documents 1, 2, and 3).

[0003] JP 2000-327787 A JP 2003-253166 A JP 2018-070794 A

[0004] However, polyether-modified polyorganosiloxanes obtained by methods such as increasing the proportion of oxyethylene in the molecule or by introducing hydroxyl groups into the terminals of polyether chains have water solubility, but have the problem that the advantages of siloxanes, such as surface migration and leveling properties, are impaired. The present invention has been made in view of these circumstances, and aims to provide a polyether-modified organopolysiloxane that has good water solubility while having a polyether chain without impairing the characteristics of siloxanes.

[0005] As a result of extensive research into achieving the above object, the present inventors have discovered that a polyether-modified siloxane having the specific structure shown below can solve the above problems, leading to the completion of 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. (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 １are each independently a group represented by the following formula (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 formula (2) above.

[0007] The present invention further provides a polyether-modified organopolysiloxane further having at least one of the following features [2] to [4]. [2] The polyether-modified organopolysiloxane according to [1] above, wherein the polyether-modified organopolysiloxane 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 [1] to [3] above, 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 as determined by a 1% by mass aqueous solution of the polyether-modified organopolysiloxane at 25°C. The polyether-modified organopolysiloxane of the present invention has the above-described block copolymer structure, and therefore has high water solubility even when 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. Polyether-modified organopolysiloxanes having such HLB and haze values ​​are highly water-soluble. They are also expected to maintain the advantages of siloxanes, such as surface migration and leveling properties.

[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.

[0010] The present invention will be described in more detail below.

[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.

[0012] In the above formula (1), R are each independently 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. Of these, R is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, more preferably a methyl group or 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. On the other hand, 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):

[0015] In the above formula (2), R ２is 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 ２ As 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 preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and an acetyl group are more preferred. Among these, a methyl group, an n-butyl group, and an acetyl group are most preferred because of their ease of availability.

[0016] In the above formula (2), n is an integer of 2 to 10, preferably an integer of 3 to 8, with 3 being most preferred 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, 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. On the other hand, 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 above lower limit, the water solubility of the polyether-modified polyorganopolysiloxane is insufficient. On the other hand, if b / (a+b) is larger than the above 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 a and the oxyethylene in the parentheses enclosed by the 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% by 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 using the following formula: HLB = {(oxyethylene group content) x 20} / (total amount of polyether-modified organopolysiloxane)

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

[0023] The haze value at 25°C of a 1% by mass aqueous solution of the polyether-modified polyorganopolysiloxane is 5 or less, more preferably 0 to 4, and even more preferably more than 0 to 2. 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 polyorganosiloxanes can be produced by the addition reaction of organohydrogenpolysiloxanes with alkenyl group-containing polyethers. The addition reaction is preferably carried out in the presence of an addition reaction catalyst. Catalysts commonly used in addition reactions can be used as the addition reaction catalyst. For example, noble metal catalysts such as platinum group metal compounds can be used, including platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Of these, platinum-based catalysts are particularly preferred. Examples of platinum-based catalysts that can be used include chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinylsiloxanes. Among these, a solution of a chloroplatinic acid-sodium bicarbonate-vinylsiloxane complex catalyst (Karstead catalyst) is particularly preferred.

[0025] In the addition reaction, the ratio of the organohydrogenpolysiloxane to the alkenyl group-containing polyether is preferably such that 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 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 catalytic amount. In particular, the amount is preferably 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, and most preferably 1 to 20 ppm, calculated as metal relative to the total amount of the organohydrogenpolysiloxane and the alkenyl group-containing polyether. By using an amount of the addition reaction catalyst within this preferred range, a sufficient reaction speed can be achieved while suppressing side reactions.

[0027] The reaction temperature for the addition reaction is not particularly limited, but is preferably 0 to 150° C., 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] Furthermore, the addition reaction may be carried out in the presence of a reaction solvent, if necessary. Examples of such solvents include 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.

[0029] EXAMPLES 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] 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 after blank (air) measurement at 25°C. Device name: Haze Meter NDH-4000 manufactured by Nippon Denshoku Industries Co., Ltd.

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

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

[0033] Example 2 The procedure of Example 1 was repeated, except that 440 g of a 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). (In formula (B), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy the relationship 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 1% by mass aqueous solution had a haze value of 2.0 at 25°C.

[0034] [Example 3] 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). (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.) (In formula (C), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy the relationship 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 1% by mass aqueous solution had a haze value of 0.25 at 25°C.

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

[0036] [Example 5] 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 polyether-modified siloxane represented by the following formula (E). (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.) (In the above, oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy the above-mentioned formula (1) of b / (a+b)=0.4.) The polyether-modified siloxane obtained above had an HLB value of 4.2, and a 1% by mass aqueous solution had a haze value of 1.0 at 25°C.

[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), to obtain 858 g of a polyether-modified siloxane represented by the following formula (F). (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.) (In formula (F), oxypropylene and oxyethylene form block structures in the order shown above, respectively, and satisfy the relationship b / (a+b)=0.5 in formula (1) above.) The polyether-modified siloxane obtained above had an HLB value of 5.7, and a 1% by mass aqueous solution had a haze value of 0.27 at 25°C.

[0038] Comparative Example 1 Example 1 was repeated, except that 692 g of the polyoxyalkylene monoallyl ether represented by the above formula (3) was replaced with 856 g of a polyoxyalkylene monoallyl ether represented by the following formula (11), in which oxyethylene and oxypropylene are bonded randomly without regard to the order shown below and oxypropylene is bonded to the terminal acetyl group, to obtain 1,018 g of a polyether-modified siloxane represented by the following formula (G). (In the above formula (11), the oxypropylene and oxyethylene are bonded randomly, regardless of the above order, and the oxypropylene is bonded to the acetyl group at the polyether terminal.) (In the above formula (G), the oxypropylene and oxyethylene are bonded randomly, regardless of the above order, and satisfy the relationship b / (a+b)=0.5 in the above formula (1).) The HLB value of the polyether-modified siloxane obtained above was 6.0, and a 1% by mass aqueous solution was cloudy, with 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 are summarized in Table 1 below.

[0040]

[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 such HLB values ​​and haze values ​​have high water solubility. Because the polyether-modified organopolysiloxane of the present invention can have good water solubility without impairing the properties of the siloxane, it is useful for many applications such as paint additives, resin additives, and cosmetics.

[0042] The present invention is not limited to the above-described embodiments, which are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that provides similar effects is included within 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. (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): (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. The polyether-modified organopolysiloxane according to claim 1, wherein the polyether-modified organopolysiloxane has an HLB value of 4 to 7 as determined by the Griffin method.

3. The polyether-modified organopolysiloxane according to claim 1, wherein a 1% by weight 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 as determined by the Griffin method and a haze value of 5 or less at 25°C of a 1% by weight aqueous solution of the polyether-modified organopolysiloxane.

Images