JPH06220200A - N-polyoxyalkyleneaminoalkyl group-containing polyorganosiloxane - Google Patents

Abstract

(57) [Summary] [Structure] General formula (I) Z _a (R ¹ ) _b SiO _{[4- (a + b)] / 2} (I) [In the formula, R ¹ is a substituted or unsubstituted monovalent group. Of the formula (II): Wherein R ² is a divalent hydrocarbon group, R ³ and R ⁴
Is a divalent hydrocarbon group having 1 to 4 carbon atoms, and p and q are 0.
Represents integers satisfying ≦ p ≦ 50, 0 ≦ q ≦ 50 and 2 <(p + q), respectively. a and b are 0 <a ≦ 1, 0 <b <
2 and 1.9 ≦ (a + b) ≦ 2.1]
Composed of a structural unit represented by
10,000 polyorganosiloxanes containing N-polyoxyalkyleneaminoalkyl groups. The present invention provides a novel compound useful as a surfactant having a hydrophobic polysiloxane moiety and a hydrophilic amino group and an oxyalkylene group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel N-polyoxyalkyleneaminoalkyl useful as a silicone-based surfactant which can be used as a treating agent for fibers, a base material for cosmetics, a foam stabilizer, an antifoaming agent and the like. It relates to a group-containing polyorganosiloxane.

[0002]

2. Description of the Related Art A series of compounds known as organically modified silicones are based on polydimethylsiloxane with various organic functional groups introduced therein, and have new properties such as reactivity and compatibility with polydimethylsiloxane. Has been used in a wider field. There are various kinds of such organically modified silicones, and among them, a compound having a hydrophilic structure such as an amino group, a hydroxyl group or a polyether introduced as an organic functional group has a hydrophilic group and a hydrophobic group in one molecule. It has been noted that it can be used as a silicone-based surfactant having a polydimethylsiloxane moiety as a group and has excellent surfactant properties as compared with general organic surfactants. For example, as an example of the use of such a silicone-based surfactant, use of a polyether-modified silicone as a foam stabilizer for urethane foam, a defoaming agent, a cosmetic base, and the like,
Examples include the use of amino-modified silicone as a fiber treatment agent.

However, there are many applications in which conventional organically modified silicones cannot be satisfied, and therefore there has been a demand for the development of a novel silicone-based surfactant which can be easily and stably supplied industrially.

Many investigations and proposals have been made for new silicone surfactants.
Since compounds having an alkylamino group and a polyether or hydroxyalkyl group in the molecule at the same time are expected to have particularly excellent properties, some proposals have been made. For example, Japanese Unexamined Patent Publication (Kokai) No. 3-95228 describes a method for producing a compound containing an amino group and a polyether group, and here, an example in which an amino group and a polyether group are independently introduced is exemplified. In addition, Japanese public Sho 62
-44073, JP-A-2-256689 and 3-
Japanese Patent No. 51375 discloses a method of obtaining a compound useful as, for example, a fiber treating agent or a dentifrice by reacting an amino-modified silicone oil with an organic epoxy compound. These publications describe that a compound partially having a hydroxyalkylaminoalkyl group can be obtained, but do not describe introduction of a polyether at all.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyether-introduced organically modified silicone compound which can be used as a silicone-based surfactant useful in various applications.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors to achieve the above object, a novel N-
It was found that a useful organically modified silicone can be obtained by reacting a polyoxyalkylenealkenylamine with a polyorganohydrogen siloxane, and completed the present invention.

That is, the present invention relates to the general formula (I) Z _a (R ¹ ) _b SiO _{[4- (a + b)] / 2} (I)

[In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and Z represents the formula (II).

[0009]

[Chemical 2]

Where R ² is a divalent hydrocarbon group,
R ³ and R ⁴ are each a divalent hydrocarbon group having 1 to 4 carbon atoms,
p and q are 0 ≦ p ≦ 50, 0 ≦ q ≦ 50 and 2 <(p +
Represents an integer satisfying q).

A and b are numbers satisfying 0 <a ≦ 1, 0 <b <2 and 1.9 ≦ (a + b) ≦ 2.1]

It has a molecular weight of 5
It is a polyorganosiloxane having an N-polyoxyalkyleneaminoalkyl group of 00 to 500,000.

In the above general formula (I) which is a constitutional unit of the compound of the present invention, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and specific examples include methyl, ethyl,
Alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl; aralkyl groups such as 2-phenylethyl, 2-phenylpropyl; phenyl, Aryl groups such as tolyl; chloromethyl, chlorophenyl, 3,3,3-
Substituted hydrocarbon groups such as trifluoropropyl and cyanoethyl may be mentioned.

Of these, an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, is preferred because the raw materials can be easily obtained and synthesized, and the resulting compound has good surface activity.

In the general formula (I), Z is

[0016]

[Chemical 3]

It is a polyoxyalkylene group-containing aminoalkyl group represented by: Wherein R ² is a divalent hydrocarbon radical, in particular _{- (CH 2) 3 -,} - (CH 2) 4
_{-, - (CH 2) 5} -, - (CH 2) 2 -CH (CH 3) - , etc. are exemplified. R ³ and R ⁴ are the same or different divalent hydrocarbon groups having 1 to 4 carbon atoms, and specifically, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) _{4
-, - CH 2 CH (CH} 3) -, - CH 2 CH (C 2 H 5)
-, Etc. are illustrated. Because of the good properties of inter alia resulting _{compound, - (CH 2) 2 -} , - CH 2 CH (CH 3)
− Is preferable. p and q represent the number of oxyalkylene groups, and are integers that satisfy 0 ≦ p <50, 0 ≦ q <50, and 2 <(p + q). As Z, for example,

[0018]

[Chemical 4]

And the like.

In the general formula (I), a and b are 0 <a.
≦ 1, 0 <b <2, 1.9 ≦ (a + b) ≦ 2.1. If a is larger than 1, the lipophilicity of the obtained compound is insufficient, and if b is 2 or more, Insufficient hydrophilicity. Further, the compound of the present invention is substantially linear or partially branched, and a + b is 1.9 to 2.
The range is 1.

The compound of the present invention has a molecular weight of 500-500.
500,000, preferably 1,000-
It is 50,000. If it is less than 500, it is difficult to achieve both lipophilicity and hydrophilicity, and if it is more than 500,000, handling becomes inconvenient.

The compounds of the present invention have the general formula (III) H _a (R ¹ ) _b SiO _{[4- (a + b)] / 2} (III)

(Wherein R ¹ , a and b are the same as above)

A polyalkyl hydrogen siloxane comprising a structural unit represented by the general formula (IV)

[0025]

[Chemical 5]

(In the formula, R ⁵ represents a divalent hydrocarbon group,
(R ³ , R ⁴ , p and q are the same as above)

N-polyoxyalkylenealkenylamine represented by can be synthesized by hydrosilylation using an addition reaction catalyst such as platinum or a platinum compound.

The polyalkylhydrogensiloxane having the structural unit of the above formula (III) is a silicone containing a Si--H group in the molecule, and the skeleton of the polysiloxane may be linear, branched or cyclic. , Si-H
The position of the group may be at the end of the molecular chain or at the side chain.

Examples of the polyalkyl hydrogen siloxane used in the present invention are as follows.

[0030]

[Chemical 6]

(Where, c and d are 0 ≦ c ≦ 1,000,
0 ≦ d ≦ 1,000 and 20 ≦ (c + d) ≦ 1,000
Is an integer that satisfies. The above formula is a random copolymer and does not necessarily mean a block copolymer)

[0032]

[Chemical 7]

(Where e and f are 1≤e≤1,000,
0 ≦ f ≦ 1,000 and 20 ≦ (e + f) ≦ 1,000
Is an integer that satisfies. The above formula is a random copolymer and does not necessarily mean a block copolymer)

[0034]

[Chemical 8]

(In the formula, g is an integer satisfying 6 ≦ g ≦ 1,000)

[0036]

[Chemical 9]

(In the formula, h is an integer satisfying 2 ≦ h ≦ 1,000)

And

[0039]

[Chemical 10]

(Where i and j are 1≤i≤10, 0≤j
An integer that satisfies ≦ 10 and 3 ≦ (i + j) ≦ 10.
The above formula is a random copolymer and does not necessarily mean a block copolymer)

These polyalkyl hydrogen siloxanes can be synthesized according to known methods. For example, it can be obtained by cohydrolyzing chlorosilanes such as methyldichlorosilane, dimethylchlorosilane, trimethylchlorosilane, diethylchlorosilane and phenyltrichlorosilane, or corresponding alkoxysilanes depending on the composition. Alternatively, a cyclic siloxane compound such as octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane, and a disiloxane such as tetramethyldisiloxane or hexamethyldisiloxane may be polymerized and equilibrated in the presence of an acid catalyst. You can also get

In N-polyoxyalkylenealkenylamine (IV), R ⁵ represents a divalent hydrocarbon group, but CH
₂ = CH-R ⁴ - is a divalent hydrocarbon radical similar to R ² by an addition reaction with poly alkyl hydrogen siloxane.

The above compound (IV) can be synthesized by a known method. For example, it can be easily obtained by carrying out a ring-opening addition polymerization reaction of a predetermined amount of alkylene oxide using alkenylamine as a reaction initiator. Examples of the alkenylamine include allylamine, propenylamine, octenylamine and the like. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran. These alkylene oxides may be used alone or in combination of two or more to form a copolymer. The copolymer may be a random copolymer or a block copolymer. The compound thus obtained is mostly composed of a tertiary amine, and in some cases it may contain a secondary amine and a primary amine as a raw material, but the primary amine is a factor that inhibits the subsequent hydrosilylation. Therefore, it is preferable to reduce the amount as much as possible by controlling the reaction conditions and the separation operation.

P representing the number of moles of alkylene oxide added
And q are 0 ≦ p <50, 0 ≦ q <50, 2 <(p +
q), preferably 2 <(p + q) <
50, and more preferably an integer satisfying 2 <(p + q) <20. If p + q is 2 or less, hydrophilicity is not sufficient,
Further, when p + q increases, the amine content decreases, but the amine content is set to be less than 50 in order to maintain a sufficient effect.

The above reaction is carried out under pressure or at normal pressure depending on the properties of the alkylene oxide. The reaction proceeds without a catalyst, but a catalyst may be used to accelerate the reaction. As the reaction catalyst, an alkali catalyst such as sodium hydroxide or potassium hydroxide can be used. When a catalyst is used, an acid is used as a neutralizing agent. In this case, it is preferable to neutralize with a weak acid such as phosphoric acid or acetic acid.

By a hydrosilylation reaction of a polyalkyl hydrogen siloxane having a structural unit of formula (III) and N-polyoxyalkylenealkenylamine (IV),
The method for synthesizing the compound of the present invention will be described below.

As a catalyst for the hydrosilylation reaction, platinum group compounds such as platinum, palladium and rhodium are used, and among them, platinum compounds are generally used. As the platinum catalyst, platinum-supported catalyst such as platinum black, platinum carbon or platinum alumina; chloroplatinic acid in isopropanol,
Examples thereof include platinum complex compounds such as platinum octanol complex and platinum-vinyl siloxane complexes; or platinum colloid. The amount of catalyst is 0.1 to 0.1 in terms of the amount of platinum element.
It is 1,000 ppm, and preferably used in the range of 1 to 500 ppm. If it is less than 0.1 ppm, the reaction is slow and industrially disadvantageous, and if it is more than 1,000 ppm, no such effect is obtained, and the platinum compound is expensive, which is economically disadvantageous.

Although this reaction can be carried out without a solvent,
A suitable solvent may be used to improve the reactivity.
Examples of such a solvent include hydrocarbons such as toluene and xylene; alcohols such as isopropanol. The reaction is carried out under appropriate heating conditions, but the temperature is preferably set in the range of 60 to 120 ° C.
If the temperature is lower than 60 ° C., the reaction proceeds slowly, which is disadvantageous, and if the temperature is higher than 120 ° C., a side reaction such as thermal deterioration of the polyether portion may occur, which is not preferable.
Usually, a method of dropping N-polyoxyalkylenealkenylamine or polyalkylhydrogensiloxane is used because of easy control of the reaction, but the reaction is performed in a state where all materials are mixed from the beginning with a catalyst having weak activity. You can also start. The reaction is carried out by stirring under heating for 3 to 20 hours. Generally, it is preferable that no Si—H group remains from the viewpoint of storage stability of the obtained compound,
Therefore, if necessary, a treatment step of reacting the remaining Si—H group with alcohols, unsaturated hydrocarbons, or the like may be included. Further, in order to prevent the Si—H group from remaining, it is preferable to carry out the reaction in a state in which the alkenyl group is about 1.3 times more moles than the Si—H group.

Isolation and purification of the compound of the present invention can be carried out by a generally known method. For example, after completion of the reaction, the solvent, low boiling components, unreacted substances and the like are removed by distillation, and then a purification step such as filtration is performed for the purpose of removing the catalyst.

[0050]

The compound of the present invention is used as a surfactant having a hydrophilic amino group containing a polyoxyalkylene group and a hydrophobic polysiloxane skeleton, as a fiber treatment agent, a cosmetic, a foam stabilizer, and a paint. It is useful as an additive such as a lubricant.

[0051]

EXAMPLES The present invention will be specifically described with reference to the following examples. In addition, "%" in an Example represents "weight%." Moreover, the measured value shows a value at 25 ° C.

The following four types of polyalkyl hydrogen siloxane were used. Here, as a siloxane unit, M is (CH ₃ ) ₃ SiO _1/2 and M ^H is H (CH ₃ ) ₂ S
io _1/2 , D is (CH ₃ ) ₂ SiO, ^DH is H (CH ₃ ) S
iO and Q represent SiO ₂ , respectively. S-1: Composition formula: MD ^H ₁₀ M, viscosity: 8 cSt S-2: Composition formula: MD ^H ₈ D ₄₀ M, viscosity: 45 cSt S-3: Composition formula: MD ^H ₂₂ D ₇₈ M, viscosity: 90 cSt S -4: Composition formula: ( ^MH ₂ Q) ₄ , viscosity: 20 cSt

As the N-polyoxyalkylenealkenylamine, the following compound P-1 was used, in which allylamine was used as an initiator and propylene oxide was added in an amount of 5 mol per mol of allylamine.

[0054]

[Chemical 11]

Molecular weight: 347, total amine value: 162, tertiary amine value: 163

Example 1 500 ml equipped with a reflux condenser, stirrer and dropping funnel
Into a four-necked flask of No. 1, 90.2 g (0.26 mol) of P-1, toluene 100 g, isopropanol solution of chloroplatinic acid 0.2 g (platinum content 1%) and sodium acetate 1% methanol solution 3 g, 100 under nitrogen flow
The temperature was raised to ° C. Then from the dropping funnel, S-115.2 g (0.
02 mol) was added dropwise over 1 hour. Exotherm was observed with dropping, and the liquid temperature rose to 105 ° C. 5 as it is
Stirring is continued for a while, and infrared absorption spectrum analysis shows Si-H.
It was confirmed that the absorption of binding (2,140 cm ^-1 ) had disappeared. Next, it was kept at 120 ° C. and 50 mmHg for 1 hour to completely remove toluene and other low-boiling components. After cooling, the mixture was filtered to obtain the compound A-1 of the present invention as a pale yellow transparent viscous liquid. Table 1 shows the measured values of viscosity, specific gravity, refractive index, amine equivalent, hydroxyl value, surface tension, number average molecular weight, and infrared absorption spectrum of A-1. From these results, it was confirmed that A-1 is represented by the following structural formula (V).

MD ^Z ₁₀ M (V)

Here, D ^Z represents a Z (CH ₃ ) SiO unit, and Z is a group represented by the following formula.

[0059]

[Chemical 12]

[0060]

[Table 1]

Here, the amine equivalent, the hydroxyl value, the surface tension and the number average molecular weight were measured as follows. Amine equivalent: A sample is dissolved in isopropanol, tetrabromophenolphthalein ethyl ester potassium is used as an indicator, and the amine equivalent is measured by titration with perchloric acid. Hydroxyl value: Measured by titration by acetic anhydride-pyridine method. Surface tension: Measured using a Wilhelmy type (CBVP type) surface tensiometer (manufactured by Kyowa Interface Science Co., Ltd.). Number average molecular weight: measured by high performance liquid chromatography (GPC).

Example 2 Compound A-2 was obtained in the same manner as in Example 1 except that 72.0 g (0.02 mol) of S-2 was used instead of S-1. A-2 was evaluated in the same manner as in Example 1, and the results are shown in Table 1. From these results, it was confirmed that A-2 is represented by the following structural formula (VI).

MD ^Z ₈ D ₄₀ M (VI)

Example 3 145.1 g (0.02 mol) of S-3 instead of S-1
Compound A-3 was obtained in the same manner as in Example 1 except that was used. A-3 was evaluated in the same manner as in Example 1, and the results are shown in Table 1. From these results, it was confirmed that A-3 is represented by the following structural formula (VII).

MD ^Z ₂₂ D ₇₈ M (VII)

Example 4 Compound A-4 was obtained in the same manner as in Example 1 except that 15.5 g (0.02 mol) of S-4 was used instead of S-1. A-4 was evaluated in the same manner as in Example 1, and the results are shown in Table 1. From these results, it was confirmed that A-4 is represented by the following structural formula (VIII).

(M ^Z ₂ Q) ₄ (VIII)

Here, M ^Z represents a Z (CH ₃ ) ₂ SiO _1/2 unit.

Thus, a novel copolymer compound containing a hydrophobic polysiloxane moiety, a hydrophilic amino group and a polyoxyalkylene group in one molecule was obtained, and this compound was compared with the corresponding polyalkylene oxide. It has a low surface tension and is useful as a novel silicone surfactant and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 71/02 LQE 9167-4J 83/05 LRY 8319-4J D06M 15/647 // A61K 7/00 J 9164-4C

Claims (1)

[Claims] 1. A compound represented by the general formula (I) Z _a (R ¹ ) _b SiO _{[4- (a + b)] / 2} (I) [wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group]. And Z is of the formula (II) Wherein R ² is a divalent hydrocarbon group, R ³ and R ⁴
Is a divalent hydrocarbon group having 1 to 4 carbon atoms, and p and q are 0.
Represents integers satisfying ≦ p ≦ 50, 0 ≦ q ≦ 50 and 2 <(p + q), respectively. a and b are 0 <a ≦ 1, 0 <b <
2 and 1.9 ≦ (a + b) ≦ 2.1]
Composed of a structural unit represented by
10,000 polyorganosiloxanes containing N-polyoxyalkyleneaminoalkyl groups.