JP2716850B2 - Novel organopolysiloxane and method for producing the same - Google Patents

Description

The present invention relates to an organopolysiloxane containing at least one molecular chain of poly (N-acylalkylenimine) in one molecule (hereinafter referred to as poly (N-acyl). Alkyleneimine) and a process for producing the same.

[Problems to be solved by conventional technology and invention]

Conventionally, oil-like polydimethylsiloxane (commonly known as silicone oil) has properties such as water repellency, lubricity, and gloss imparting properties, and is therefore used as a release agent, an antifoaming agent, a polisher, a fabric softener, and cosmetics. And so on. However,
Silicone oil is well soluble in low-polarity n-hexane and the like, but is inherently hardly soluble in other solvents, especially in water and other highly polar solvents. Also, it is difficult to emulsify in water, so there is a limitation on this use. Modifications have been made by introducing long-chain alkyl groups, polyoxyalkylene groups, amino groups, carboxyl groups or epoxy groups, etc., in order to improve such defects and impart new properties to silicone oils. .

Among these modified silicones, the polyoxyalkylene-modified silicone is interesting because it has a nonionic surfactant produced by using a polydimethylsiloxane portion as a hydrophobic group and a polyoxyalkylene portion as a hydrophilic group. However, since the hydrophilicity of the polyoxyalkylene moiety is relatively low, it is necessary to increase the proportion of the polyoxyalkylene moiety to the whole in order to make the polyoxyalkylene-modified silicone water-soluble or to balance hydrophilic and hydrophobic properties. There is. However, in such a case, the properties of the silicone may be canceled by the properties of the polyoxyalkylene.

On the other hand, denaturation by introducing a long-chain alkyl group or the like has been performed for the purpose of making it easily soluble in organic solvents other than those having a considerably low polarity such as n-hexane. However, even in such a case, it has been difficult to improve the solubility without losing the properties as silicone.

Therefore, it has been desired to develop a modified silicone which retains the properties of silicone and has good solubility in various solvents.

On the other hand, a graft or block copolymer having a poly (N-acylalkylenimine) chain formed by ring-opening polymerization of a 2-oxazoline compound and an organopolysiloxane chain is described by Saegusa et al. (The 54th Annual Meeting of the Chemical Society of Japan). Proceedings, I
I, 1557 (1987)), followed by a report by Tezuka et al. (Polymer Journal, 19 , 1091-1100 (1987)), JP-A-63-277247, and U.S. Pat. No. 4,659,777.
Another publication is also described in Japanese Patent Publication No. However,
In the former, an allyl ester is used as an initiator for 2-
It uses the reaction of poly (N-acylethyleneimine) obtained by ring-opening polymerization of oxazolines with polysiloxane having Si-H bond. The reactivity is not so high and the reaction conditions such as solvent can be set. difficult. Further, in the latter, when ring-opening polymerization of the cyclic imino ether compound, an initiator having an organopolysiloxane group prepared in advance is used, and the complexity of the step of preparing these initiators, the purity of the initiator, polymerization, There is a problem in reactivity etc.

The present inventors have also proposed a method for obtaining a graft or block copolymer having a poly (N-acylalkyleneimine) chain and an organopolysiloxane chain as an organopolysiloxane containing a primary amino group or a mercapto group in the molecule. A method for reacting siloxane with poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether compound has been found and a patent application has been filed (see Japanese Patent Application No. 2-4225). This method is easy to produce, the target product is obtained in high purity, and the obtained polymer is used for hair, fiber,
It has the advantage of having high adsorptivity to the skin and the like, but has the disadvantage that the adsorptivity of the obtained polymer decreases under conditions of basic or high salt concentration.

[Means for solving the problem]

In view of the above circumstances, the present inventors have conducted intensive studies and found that water was introduced by introducing a quaternary ammonium group into a polymer composed of a molecular chain of an organopolysiloxane and a molecular chain of poly (N-acylalkylenimine). Poly (N-) which has good solubility in various solvents including the above, retains the excellent properties of silicone, and has high adsorptivity to hair, fiber, skin, etc. even under acidic to basic or high salt concentration. The present inventors have found that an (acylalkyleneimine) -modified silicone can be obtained, and have completed the present invention.

That is, the present invention provides a method for preparing a polyorganosiloxane containing a quaternary ammonium group at both ends and / or side chains of the molecular chain.
Via a valent group, a compound of formula (I) The molecular chain of poly (N-acylalkyleneimine) consisting of a repeating unit represented by
A novel organopolysiloxane characterized in that the weight ratio between the molecular chain of acylalkyleneimine) and the molecular chain of organopolysiloxane is 1/20 to 20/1, and the molecular weight is 500 to 500,000. It is.

The present invention also relates to an organopolysiloxane containing a tertiary amino group at both ends and / or side chains of a molecular chain, and a compound represented by the formula (IV): And a poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether compound represented by the formula (I), and a method for producing a novel organopolysiloxane, and both ends of a molecular chain and / or Or an organopolysiloxane containing a primary or secondary amino group in a side chain,
The cyclic imino ether compound represented by the formula (IV) is reacted with a poly (N-acylalkyleneimine) obtained by ring-opening polymerization, and the resulting secondary or tertiary amino group is further reacted with an alkylating agent. It is intended to provide a novel method for producing an organopolysiloxane characterized by quaternization.

 Hereinafter, the present invention will be described in detail.

The molecular chain of poly (N-acylalkyleneimine) comprising the repeating unit represented by the formula (I) is obtained by ring-opening polymerization of the cyclic imino ether compound represented by the formula (IV).

The cyclic imino ether compound represented by the formula (IV) is a 2-oxazoline or a 2-oxazine as exemplified below. That is, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline,
2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2- Decyl-
2-oxazoline, 2-undecyl-2-oxazoline, 2-dodecyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-tetradecyl-2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2- Oxazoline, 2-heptadecyl-2-
Oxazoline, 2-octadecyl-2-oxazoline,
2-nonadecyl-2-oxazoline, 2-eicosyl-
2-oxazoline, 2-heneicosyl-2-oxazoline, 2-docosyl-2-oxazoline, 2-benzyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-naphthyl-2-oxazoline, 2-anthryl-2- Oxazoline, 2-pyrenyl-2-oxazoline, 2-perylenyl-2-oxazoline, 2-oxazine, 2-methyl-2-oxazine, 2-ethyl-2-oxazine, 2-propyl-2-oxazine, 2-butyl- 2-oxazine, 2-pentyl-2-oxazine, 2
-Hexyl-2-oxazine, 2-heptyl-2-oxazine, 2-octyl-2-oxazine, 2-nonyl-
2-oxazine, 2-decyl-2-oxazine, 2-undecyl-2-oxazine, 2-dodecyl-2-oxazine, 2-tridecyl-2-oxazine, 2-tetradecyl-2-oxazine, 2-pentadecyl-2- Oxazine, 2-hexadecyl-2-oxazine, 2-heptadecyl-2-oxazine, 2-octadecyl-2-oxazine, 2-nonadecyl-2-oxazine, 2-eicosyl-2-oxazine, 2-heneicosyl-2-oxazine, 2-docosyl-2-oxazine, 2-benzyl-2-oxazine, 2-phenyl-2-oxazine, 2
-Naphthyl-2-oxazine, 2-anthryl-2-oxazine, 2-pyrenyl-2-oxazine, 2-perylenyl-2-oxazine and the like.

These cyclic imino ethers are described, for example, in Liebigs Ann. Ch.
em., p996-p1009 (1974).

These compounds may be used alone as a monomer for ring-opening polymerization, or may be used in combination of two or more.

Examples of the polymerization initiator for subjecting the cyclic imino ether to ring-opening polymerization include, but are not limited to, alkyl esters of toluenesulfonic acid, dialkyl sulfates, alkyl esters of trifluoromethanesulfonic acid, and alkyl halides. These initiators can be used alone or in a mixture.

The cyclic imino ether compound represented by the formula (IV) is subjected to ring-opening polymerization using these initiators, whereby a molecule of a poly (N-acylalkyleneimine) comprising a repeating unit represented by the formula (I) is obtained. You can get chains,
This molecular chain may be a homopolymer chain or a copolymer chain, and the copolymer chain may be a random copolymer chain or a block copolymer chain.

The molecular weight of the molecular chain of the poly (N-acylalkyleneimine) is preferably 150 or more and 50,000 or less, and more preferably 500 or more and 10,000 or less.

When the molecular weight is smaller than 150, the properties of poly (N-acylalkylenimine) are lost, and when it is larger than 50,000, production becomes difficult, which is not preferable.

The organopolysiloxane of the present invention is obtained by reacting a polymerization active species formed by ring-opening polymerization of a cyclic imino ether compound represented by the formula (IV) with an organopolysiloxane having a functional group capable of reacting with the polymerization active species. Can be obtained.

The polymerization active species is represented by the following general formula (V) or (VI) depending on the type of the initiator. It is said that it is divided into the types of ion-bonded species (V) and covalently-bonded species (VI) (Kobayashi, Saegusa, Macromolecular Chemistry Supplement, Vol. 12, p11 (198
Five)).

The polymerization active species reacts with an organopolysiloxane containing a tertiary amino group to form a quaternary ammonium salt. The raw material organopolysiloxane containing a tertiary amino group can be obtained by converting a commercially available organopolysiloxane containing a primary or secondary amino group into an alkyl halide such as methyl chloride or propyl bromide; or a dialkyl sulfate such as dimethyl sulfate. A method of tertiaryization with an alkylating agent, And the like, using a silane modifier having a tertiary amine structure such as octamethylcyclotetrasiloxane, and polymerizing a cyclic silicone such as octamethylcyclotetrasiloxane.

On the other hand, the polymerization active species is reacted with an organopolysiloxane containing a primary or secondary amino group, and the resulting secondary or tertiary amino group is converted to an alkylating agent such as an alkyl halide or a dialkyl sulfate as described above. To a quaternary ammonium salt. Further, the counter ion may be exchanged with an ion exchange resin or the like.

The reaction between an organopolysiloxane containing a tertiary amino group, or an organopolysiloxane containing a primary or secondary amino group, and poly (N-acylalkyleneimine) obtained by cationic polymerization of a cyclic imino ether is as follows. You can do it.

Dissolve the initiator in a polar solvent, preferably acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, a single solvent such as ethylene chloride, or a mixed solvent with another solvent if necessary, 40 to 150 ℃, preferably 60 to 100 ℃. Therein, the cyclic imino ether represented by the above general formula (IV) is charged at a time or, if the reaction is severe, dropped to carry out polymerization. The progress of the polymerization can be monitored by quantifying the residual amount of the cyclic imino ether which is a monomer using an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growth terminal maintains the reactivity. Without isolating the polymer, the polymer solution was subsequently mixed with an organopolysiloxane containing a tertiary amino group in the molecule or an organopolysiloxane containing a primary or secondary amino group, and the mixture was mixed with 5 to 100 C., preferably at 20 to 60.degree. The mixing ratio can be appropriately selected as desired, but is 0.1 to 1.1 mole equivalent of poly (N-acylalkyleneimine) to 1 mole of tertiary amino group or primary or secondary amino group in the organopolysiloxane. It is preferred to react. If it is less than 0.1 molar equivalent, it is difficult to impart the properties of the poly (N-acylalkylenimine) intended in the present invention due to a small modification rate, and more than 1.1 molar equivalent is unnecessary.

If water is present in the reaction system, the reactive end of the poly (N-acylalkyleneimine) reacts to produce a corresponding alcohol or the like, which is not preferable. Therefore, it is desirable to remove water almost completely from the reaction system. Therefore, it is desirable that the reaction be performed under an atmosphere of an inert gas such as nitrogen during the reaction.

In order to explain the poly (N-acylalkylenimine) -modified silicone of the present invention more clearly, a reaction between an organopolysiloxane containing a tertiary amino group and a reactive terminal of poly (N-acylalkylenimine) will be described below. Shown in

The counter ion of the quaternary ammonium salt of the compounds represented by formulas (VII) and (VIII) can be ion-exchanged by an ordinary method using an ion-exchange resin or the like.

According to the present invention, a poly (N-acylalkyleneimine) molecular chain is attached to a terminal and / or a side chain of a molecular chain of an organopolysiloxane via a divalent group containing a quaternary ammonium group by the above reaction. The poly (N-acylalkyleneimine) -modified silicone can be obtained.

In the present invention, the divalent group containing a quaternary ammonium group is represented by the formula (II) or (III) And the group represented by

The novel organopolysiloxane of the present invention can be prepared from a viscous oil to a solid resin by the difference in the kind of the molecular chain of the organopolysiloxane, the kind of the molecular chain of the poly (N-acylalkylenimine) and the combination of both molecular chains. To various states. The weight ratio of the molecular chain of the poly (N-acylalkyleneimine) to the molecular chain of the organopolysiloxane can exhibit the characteristics of the present invention in the range of 1/20 to 20/1, and more preferably 1/10 to 5 /. It is in the range of 1. The molecular weight is practically in the range of 500 to 500,000, and more preferably in the range of 1,000 to 100,000. The molecular weight is
It can be determined by GPC (gel permeation chromatography).

Further, the organopolysiloxane of the present invention exhibits various properties from hydrophilicity to lipophilicity by changing the chemical structure of the acyl group. For example, when R _{1 of} the acyl group has a hydrogen atom or a carbon number of 3 or less and the molecular chain of poly (N-acylalkylenimine) is hydrophilic, the molecular chain of poly (N-acylalkylenimine) It has both hydrophilicity and strong hydrophobicity due to the molecular chain of organopolysiloxane, and is not only useful as a surfactant,
Retains the original properties of organopolysiloxane, and is used for cosmetic raw materials, release agents, antifogging agents, antistatic agents, defoamers, fiber oil agents, plastic modifiers, polishes, lubricants, etc. Can be.

Further, R _{1 of} the acyl group has 4 or more carbon atoms, and poly (N
When the molecular chain of (acylalkyleneimine) is oil-soluble, not only the solubility in an organic solvent is increased, but also the original properties of organopolysiloxane are retained, and cosmetic raw materials, plastic modifiers, It can be used as a dispensing agent, lubricant or compatibilizer for polymer blends.

In addition, since the organopolysiloxane of the present invention has a quaternary ammonium group, it has good adsorptivity even under conditions of basic or high salt concentration, has little irritation, and has high safety.

〔Example〕

Next, the present invention will be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples.

Synthesis of Amino-Modified Silicone Containing Tertiary Amino Group as Raw Material Synthesis Example 1 3.73 g (0.012 mol) of bis (N, N-dimethyl-3-aminopropyl) tetramethyldisiloxane, 120 g (0.405 mol) of octamethylcyclotetrasiloxane Polymerization catalyst
0.90 g (tetramethyl hydroxide 0.12 g (1.32 x
10 ^-3 mol) contained; a polymerization catalyst was prepared by dissolving tetramethyl hydroxide pentahydrate in octamethylcyclotetrasiloxane and toluene, reacting at 80 ° C. for 12 hours, and drying under vacuum at 80 ° C./2 mmHg. . The tetramethyl hydroxide content was determined by a hydrochloric acid titration method. ) And heat for 72 hours. Amino-modified silicone containing tertiary amino groups at both ends was synthesized by removing the oligomer at 120 ° C. under a vacuum of 2 to 5 mmHg. The product was a clear and colorless oil. The molecular weight was determined by GPC method, and the weight average molecular weight was 11000 (in terms of polystyrene / solvent chloroform). The amine equivalent was determined to be 5,300 by a hydrochloric acid titration method.

Synthesis Example 2 A mixture of 6.00 g (0.031 mol) of N, N-dimethylaminopropylmethyldimethoxysilane and 1.46 g (0.081 mol) of water was heated at 60 ° C. for 5 hours.
Remove under reduced pressure at 2 ° C. and 2-5 mmHg. After heating to 80 ° C, 120 g (0.405 mol) of octamethylcyclotetrasiloxane,
Hexamethyldisiloxane 1.01 g (6.2 × 10 ^-3 mol) and polymerization catalyst 0.90 g (tetramethyl hydroxide 0.1
2 g (1.32 × 10 ⁻³ mol) contained; prepared in the same manner as in Synthesis Example 1. ) And heat for 72 hours. An amino-modified silicone containing a tertiary amino group in the side chain was synthesized by removing the oligomer at 120 ° C. under a vacuum of 2 to 5 mmHg. The product was a clear and colorless oil. The molecular weight was determined by GPC, and the weight average molecular weight was 22000 (in terms of polystyrene / solvent chloroform). The amine equivalent was determined to be 3900 by a hydrochloric acid titration method.

Synthesis of poly (N-acylethyleneimine) -modified silicone Example 1 Mixture of 1.64 g (0.01 mol) of methyl trifluoromethanesulfonate (methyl triflate), 10.2 g (0.12 mol) of 2-methyl-2-oxazoline, and 10 ml of chloroform Was refluxed for 5 hours to synthesize a terminally reactive polymer of poly (N-acylethyleneimine) (molecular weight: 1,000). Amino-modified silicone containing a tertiary amino group at both ends synthesized in Synthesis Example 1 in another container (molecular weight 11,000, amine equivalent 5300) 5
2.8 g (0.0048 mol) are dissolved in 70 ml of chloroform. A solution of the terminal reactive polymer of poly (N-acylethyleneimine) was placed in a solution of an amino-modified silicone containing a tertiary amino group, and reacted at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight 13000) having poly (N-acylethyleneimine) chains at both ends of polydimethylsiloxane was obtained. This copolymer was a pale yellow rubber.

Example 2 3.28 g (0.02 mol) of methyl triflate, 20.0 g (0.24 mol) of 2-methyl-2-oxazoline, chloroform 4
After refluxing 0 ml of the mixture for 3 hours, 20.0 g (0.12 mol) of 2-heptyl-2-oxazoline was added and refluxed for 5 hours to obtain poly (N-acetylethyleneimine) and poly (N-caprylylethyleneimine). Terminal-reactive polymer composed of block oligomer (C ₁ / C ₇ = 50/50 (wt
%) And a molecular weight of 2000). In another container, 105.6 g of an amino-modified silicone (molecular weight: 11,000, amine equivalent: 5300) containing tertiary amino groups at both ends synthesized in Synthesis Example 1 (9.6 × 10
^-3 mol) in 150 ml of chloroform. Poly (N-
A solution of the terminal reactive polymer of acylethyleneimine) was placed in a solution of an amino-modified silicone containing a tertiary amino group, and reacted at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight 15,000) having poly (N-acylethyleneimine) chains at both ends of polydimethylsiloxane was obtained. This copolymer was a pale yellow rubber.

Example 3 Methyl triflate 3.28 g (0.02 mol), 2-methyl-2-oxazoline 20.0 g (0.24 mol), 2-heptyl-2-oxazoline 20.0 g (0.12 mol), chloroform 4
By refluxing 0 ml of the mixture for 5 hours, the poly (N-
Terminally reactive polymer (C ₁ / C ₇ = 50/50 (wt%)) composed of a random polymerization type oligomer of acetylethyleneimine) and poly (N-caprylylethyleneimine), molecular weight 200
0) was synthesized. In another container, an amino-modified silicone containing a tertiary amino group in the side chain synthesized in Synthesis Example 2 (molecular weight: 2200
Dissolve 78.1 g (3.55 × 10 ^-3 mol) of 0, amine equivalent 3900) in 150 ml of chloroform. A solution of the terminal reactive polymer of poly (N-acylethyleneimine) was placed in a solution of an amino-modified silicone containing a tertiary amino group, and reacted at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, poly (N-acylethyleneimine) is added to the side chain of polydimethylsiloxane.
A graft copolymer having a chain (molecular weight: 33,000) was obtained. This copolymer was a pale yellow rubber.

Example 4 2.16 g (0.014 mol) of diethyl sulfuric acid, 2-methyl-2-
A mixture of 7.0 g (0.082 mol) of oxazoline and 10 ml of chloroform was refluxed for 5 hours to synthesize a poly (N-acylethyleneimine) terminal-reactive polymer (molecular weight: 500).
In another container, an amino-modified silicone containing a tertiary amino group at both ends synthesized in Synthesis Example 1 (molecular weight 11,000, amine equivalent 5
300) 73.7 g (6.7 × 10 ^-3 mol) is dissolved in 100 ml of chloroform. A solution of the terminal reactive polymer of poly (N-acylethyleneimine) was placed in a solution of an amino-modified silicone containing a tertiary amino group, and reacted at 55 ° C. for 5 hours. The solvent was distilled off under reduced pressure to obtain a block copolymer having a poly (N-acylethyleneimine) chain at both ends of polydimethylsiloxane (molecular weight: 12,000). This copolymer was a pale yellow rubber.

Example 5 6.16 g (0.04 mol) of diethyl sulfuric acid, 2-methyl-2-
Oxazoline 28.0 g (0.33 mol), 2-heptyl-2-
By refluxing a mixture of 12.0 g (0.071 mol) of oxazoline and 50 ml of chloroform for 5 hours, a terminal-reactive polymer comprising a random polymerization type oligomer of poly (N-acetylethyleneimine) and poly (N-caprylylethyleneimine) ( C ₁ / C ₇ = 30/70 (wt%), molecular weight 1000). In another container, 156.2 g (7.1 × 10 ⁻³ mol) of an amino-modified silicone (molecular weight: 22,000, amine equivalent: 3900) containing a tertiary amino group in the side chain synthesized in Synthesis Example 2 was added to chloroform 2
Dissolve in 00 ml. A solution of the terminal reactive polymer of poly (N-acylethyleneimine) was placed in a solution of an amino-modified silicone containing a tertiary amino group, and reacted at 55 ° C. for 5 hours.
The solvent was distilled off under reduced pressure to obtain a graft copolymer having a poly (N-acylethyleneimine) chain on the side chain of polydimethylsiloxane (molecular weight: 27,000). This copolymer was a pale yellow rubber.

Example 6 Amberlite IRA400 (ROHM) obtained by dissolving a block copolymer having poly (N-acylethyleneimine) chains at both ends of the polydimethylsiloxane obtained in Example 1 in ethanol, regenerating the solvent, and replacing the solvent with ethanol. ·and·
(An anion exchange resin manufactured by Haas Co.). The mixture was neutralized with hydrochloric acid, and the solvent was distilled off under reduced pressure to obtain a pale yellow rubbery resin. Confirmation that trifluoromethanesulfonic acid as an initiator fragment was removed was performed by measuring the content of sulfur element (100 ppm or less).

Example 7 A graft copolymer having a poly (N-acylethyleneimine) chain attached to the side chain of the polydimethylsiloxane obtained in Example 5 was dissolved in ethanol, regenerated, and the solvent was replaced with ethanol. Amberlite IRA400 (ROHM)・ And Haas Co. anion exchange resin).
The mixture was neutralized with hydrochloric acid, and the solvent was distilled off under reduced pressure to obtain a pale yellow rubbery resin. Confirmation of the removal of the ethyl sulfate as the initiator fragment was performed by measuring the content of the sulfur element (100 ppm or less).

Comparative Example 1 15.42 g (0.100 mol) of diethyl sulfuric acid, 2-methyl-2
-Oxazoline 140 g (1.645 mol), 2-heptyl-2
-Oxazoline 60.0 g (0.354 mol), chloroform 300 m
By refluxing the mixture of l for 5 hours, a terminal reactive polymer (C ₁ / C ₇ = 30/70) composed of a random polymerization type oligomer of poly (N-acetylethyleneimine) and poly (N-caprylylethyleneimine). (Wt%), molecular weight 2000)
Was synthesized. In a separate container, 500 g (0.05 mol) of 3-aminopropyl-substituted polydimethylsiloxane at both ends (manufactured by Chisso Corporation, FM3325, amine equivalent 5000, molecular weight 10,000) is dissolved in chloroform 1500 ml. The solution of the terminal reactive polymer of poly (N-acylethyleneimine) was placed in a solution of an amino-modified silicone containing a primary amino group, and reacted at 55 ° C. for 5 hours. The solvent was distilled off under reduced pressure to obtain a block copolymer having a poly (N-acylethyleneimine) chain at both ends of polydimethylsiloxane (molecular weight: 14,000). This copolymer was a pale yellow rubber.

Comparative Example 2 Amberlist A-21 obtained by dissolving a block copolymer having poly (N-acylethyleneimine) chains at both ends of the polydimethylsiloxane obtained in Comparative Example 1 in ethanol, regenerating, and replacing the solvent with ethanol. (Anion exchange resin manufactured by Rohm and Haas Co.) was passed through the column, and then the solvent was distilled off under reduced pressure to obtain a pale yellow rubbery resin. The confirmation that the ethyl sulfate, which is an initiator fragment, was removed was confirmed by measuring the sulfur element content (10%).
0 ppm or less).

Example 8 50 g of a block copolymer having poly (N-acylethyleneimine) chains at both ends of the polydimethylsiloxane obtained in Comparative Example 2 was dissolved in 70 ml of isopropyl alcohol, and an excess amount of 8.82 g (0.07 mol) of dimethyl sulfate was dissolved. ) And reacted at 70 ° C. for 8 hours. By removing volatile components, a block copolymer in which a hetero atom between poly (N-acylethyleneimine) and polydimethylsiloxane became a quaternary ammonium salt was obtained.

Comparative Example 3 9.24 g (0.06 mol) of diethyl sulfuric acid, 2-methyl-2-
Oxazoline 50.0 g (0.588 mol), 2-heptyl-2-
Oxazoline 99.37 g (0.588 mol), chloroform 200 ml
Is refluxed for 6 hours to obtain a terminal reactive polymer (C ₁ / C ₇ = 33/67 (C ₁ / C ₇ = 33/67) comprising a random polymerization type oligomer of poly (N-acetylethyleneimine) and poly (N-caprylylethyleneimine). wt%) and a molecular weight of 2500). In another container, polydimethylsiloxane having a 3-aminopropyl group in the side chain (Shin-Etsu Silicone Co., Ltd.)
Manufactured, KF864, amine equivalent 3800, molecular weight 18000) 228.6 g (0.
Is dissolved in 500 ml of chloroform. Poly (N
-Acylethyleneimine) was placed in a solution of an amino-modified silicone containing a primary amino group, and reacted at 55 ° C for 5 hours. The solvent was distilled off under reduced pressure to obtain a graft copolymer having a poly (N-acylethyleneimine) chain on the side chain of polydimethylsiloxane (molecular weight: 30,000). This copolymer was a pale yellow rubber.

Comparative Example 4 Amberlyst A-21 in which a graft copolymer having a poly (N-acylethyleneimine) chain attached to a side chain of the polydimethylsiloxane obtained in Comparative Example 3 was dissolved in ethanol, regenerated, and solvent-replaced with ethanol. (Anion exchange resin manufactured by Rohm and Haas Co.) was passed through the column, and then the solvent was distilled off under reduced pressure to obtain a pale yellow rubbery resin. Confirmation that the ethyl sulfate, which is the initiator fragment, has been removed can be confirmed by measuring the sulfur element content (100p
pm or less).

Example 9 100 g of the graft copolymer having a poly (N-acylethyleneimine) chain in the side chain of the polydimethylsiloxane obtained in Comparative Example 4 was dissolved in 100 ml of isopropyl alcohol, and 3.69 g (0.03 g) of an excessive amount of propyl bromide was dissolved. Mol) and reacted at 70 ° C. for 8 hours. By removing volatile components, a graft copolymer in which a hetero atom between poly (N-acylethyleneimine) and polydimethylsiloxane became a quaternary ammonium salt was obtained.

Solubility and dispersibility test of poly (N-acylethyleneimine) -modified silicone Example 10 The solubility and dispersibility of poly (N-acylethyleneimine) -modified silicone obtained in Examples 1 to 9 in various solvents were evaluated. . Table 1 shows the results.

Comparative Example 5 The solubility and dispersibility of each of the poly (N-acylethyleneimine) -modified silicones obtained in Comparative Examples 1 to 4 in each solvent were evaluated in the same manner as in Example 10. Table 1 shows the results.

Comparative Examples 6 to 8 Unmodified silicones commercially available (Comparative Example 6; PS041, manufactured by Chisso Corporation, molecular weight 4970), amino-modified silicones having tertiary amino groups at both ends obtained in Synthesis Example 1 (Comparative Example) 7) With respect to the amino-modified silicone having a tertiary amino group in the side chain obtained in Synthesis Example 2 (Comparative Example 8), the solubility and dispersibility in each solvent were evaluated in the same manner as in Example 10. Table 1 shows the results.

As is clear from Table 1, the organopolysiloxane having a quaternary ammonium group of the present invention is easily soluble in various solvents from hexane to water. This is because oil-soluble polydimethylsiloxane and water-soluble N-acyl polyethyleneimine are blocked or grafted. Also,
The organopolysiloxanes of Comparative Examples 1 to 4 having secondary or tertiary amino groups also have good solubility in various solvents. On the other hand, polydimethylsiloxane and amino-modified silicone are hardly soluble in polar solvents and hard to disperse in activators.

Adsorption test of poly (N-acylethyleneimine) -modified silicone Example 11 Adsorption of the poly (N-acylethyleneimine) -modified silicone obtained in Examples 1 to 9 on hair was evaluated.
Each solution was prepared as shown in Table 2. Human hair was immersed in each of the solutions in Table 2 for 3 minutes, sufficiently washed with ion-exchanged water, and then dried with a dryer. The adsorptivity of the poly (N-acylethyleneimine) -modified silicone to hair depends on the hair after adsorption.
From the ATR method FT-IR spectrum, the "difference spectrum" was obtained by subtracting that before adsorption, and the characteristic absorption of silicone (1260 cm ^-1 )
From the area of the silicone was estimated. The amount of adsorption is
It will be expressed as a percentage of the area of characteristic absorption of silicone relative to the area of amide I absorption of the hair.

 Table 3 shows the results.

Comparative Example 9 The adsorptivity of the poly (N-acylethyleneimine) -modified silicone obtained in Comparative Examples 1 to 4 to hair was evaluated.
The preparation of each solution and the method of evaluating the amount of adsorption were performed in the same manner as in Example 11.

 Table 3 shows the results.

As is clear from Table 3, those using the organopolysiloxane of the present invention of Examples 1 to 9 adsorb to hair even in the entire pH range and in the presence of a high concentration of salt. When these are adsorbed on the hair, the slip becomes better and the feel becomes smoother. It also gives the hair softness.

Those using the organopolysiloxanes of Comparative Examples 1 to 4 adsorb well when neutral to acidic, but hardly adsorb when becoming basic. Also, it is difficult to adsorb even in the presence of salt.

Claims (4)

(57) [Claims] 1. A compound of the formula (I) which is linked via a divalent group containing a quaternary ammonium group to both ends and / or side chains of the molecular chain of the organopolysiloxane. The molecular chain of poly (N-acylalkyleneimine) consisting of a repeating unit represented by
A novel organopolysiloxane, wherein the weight ratio of the molecular chain of acylalkyleneimine) to the molecular chain of the organopolysiloxane is 1/20 to 20/1, and the molecular weight is 500 to 500,000. 2. A divalent group containing a quaternary ammonium group represented by the formula (II) or (III): The novel organopolysiloxane according to claim 1, which is a group represented by the following formula: 3. An organopolysiloxane having tertiary amino groups at both ends and / or side chains of a molecular chain, and a compound represented by the formula (IV): A method for producing a novel organopolysiloxane, comprising reacting a cyclic imino ether compound represented by the formula (I) with a poly (N-acylalkyleneimine) obtained by ring-opening polymerization. 4. An organopolysiloxane containing a primary or secondary amino group at both ends and / or side chains of a molecular chain, and a compound represented by the formula (IV): Reacting with a poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether compound represented by the following formula, and further quaternizing the resulting secondary or tertiary amino group with an alkylating agent. A method for producing a novel organopolysiloxane characterized by the following.