JP2716851B2 - Method for producing novel organopolysiloxane - Google Patents

Description

The present invention relates to an organopolysiloxane having a poly (N-acylalkylenimine) molecular chain at one end (hereinafter referred to as poly (N-acylalkylenimine) -modified silicone and (Hereinafter referred to as the manufacturing method).

[Problems to be solved by conventional technology and invention]

Conventionally, in order to emulsify an oily liquid or wax, various surfactants having a hydrophobic group such as a long-chain alkyl group and a hydrophilic group such as an anion, a cation, and a non-ion have been used as an emulsifier. .

An emulsifier is also required to obtain an oil-in-water (O / W) or water-in-oil (W / O) emulsion mainly composed of various organopolysiloxanes such as dimethylpolysiloxane. However, the combination of the organopolysiloxane and the ordinary surfactant has insufficient affinity between the organopolysiloxane and the hydrophilic oil-based group of the surfactant. Therefore, in order to emulsify the organopolysiloxane, it has been proposed to use a surfactant having an organopolysiloxane moiety as a hydrophobic group.
JP-A-61-212321 and JP-A-61-212324 disclose an organopolysiloxane containing a polyoxyalkylene group on the side chain of a molecular chain, and an ABA type comprising a polyoxyalkylene group bonded to both ends of the molecular chain. Are disclosed. However, although these silicone surfactants can emulsify low molecular weight organopolysiloxanes, their performance is insufficient to emulsify organopolysiloxanes with a high degree of polymerization, and W / O with good stability
Or O / W emulsions have not been obtained.

Further, Japanese Patent Application Laid-Open No. 1-203466 discloses an AB type block copolymer having a polyoxyalkylene group bonded to one end of a molecular chain. However, since the polyoxyalkylene chain has weak hydrophilicity, the organopolysiloxane cannot be emulsified unless the polyoxyalkylene chain is extremely long. In addition, the emulsifying performance is also insufficient, and the organopolysiloxane cannot be emulsified unless a large amount of emulsifier is used. Therefore, the emulsifier content in the emulsion increases, so that the silicone-like performance (slipperiness,
Flexibility) disappears.

Accordingly, there is a need for an emulsifier that can maintain the performance of silicone and that can effectively emulsify organopolysiloxane at a low concentration.

[Means for solving the problem]

In view of the above-mentioned circumstances, the present inventors have conducted intensive studies and, as a result, have found a one-terminal-type amphiphilic silicone capable of emulsifying organopolysiloxane well, and have completed the present invention.

That is, the present invention relates to an organopolysiloxane having a primary, secondary, or tertiary amino group at only one terminal of a molecular chain (hereinafter, simply referred to as one terminal); And a poly (N-acylalkyleneimine) obtained by ring-opening polymerization of the cyclic iminoether compound represented by the formula (1).

 Hereinafter, the present invention will be described in detail.

The cyclic imino ether compound represented by the formula (I) may be a 2-oxazoline or a 2-oxazoline as exemplified below.
-Oxazines. That is, 2-oxazoline, 2-oxazoline
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.

Poly (N-acylalkyleneimine) can be obtained by ring-opening polymerization of the cyclic imino ether compound represented by the formula (I) using these initiators, and this polymer may be a homopolymer. It may be a copolymer,
The copolymer may be a random copolymer or a block copolymer.

The molecular weight of the poly (N-acylalkyleneimine) is
It is preferably from 150 to 50,000, more preferably from 500 to 10,000.

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 comprises a polymerizable species formed by ring-opening polymerization of a cyclic imino ether compound represented by the formula (I) and a primary, secondary or tertiary amino group capable of reacting with the polymer. It can be obtained by reacting with an organopolysiloxane at one end of the chain.

The polymerization active species is represented by the following general formula (IV) or (V) depending on the type of the initiator. (IV) and covalent species (V) represented by the following formulas (Kobayashi, Saegusa, Macromolecular Chemistry Supplement, Vol. 12, p11 (198
Five).

The molecular weight of the organopolysiloxane having a primary, secondary or tertiary amino group at one end of the molecular chain that can react with the polymerization active species is preferably 300 or more and 300,000 or less, more preferably 800 or more and 80,000 or less. Which may be linear or have a branched chain. If the molecular weight of the organopolysiloxane is less than 300, the properties as silicone are poor, and if it is more than 300,000, it is not preferable because it becomes gel-like and difficult to react.

Examples of these organopolysiloxanes include compounds represented by the following formula (II) or (III).

The organopolysiloxane having a primary, secondary or tertiary amino group at one end of the molecular chain used in the present invention can be synthesized by a known method. For example, it can be synthesized by the following reaction.

(In the formula, R ₂ and m have the above-mentioned meanings.) The compound represented by the general formula (VI) used in this method can be synthesized by a generally known method.

For example, hexaorganocyclotrisiloxane and triorganosilanol, a five-coordinate silicon compound catalyst,
For example, the expression By reacting in the presence of a biscatechol siliconate compound represented by the formula (Wherein R ₂ and m have the above-mentioned meanings), and an organopolysiloxane terminated with a silanol group at one end represented by the formula: is then added to the polymer and diorganochlorosilane [H (R ₉ ) ₂ SiCl] (R ₉ represents an alkyl group or an aryl group having 1 to 18 carbon atoms) and a dehydrochlorination reaction using, for example, trimethylamine as a dehydrochlorination agent (US Pat. No. 3,360,525).

Further, a compound having a -SiH group at one end represented by the general formula (VI) can be synthesized by polymerizing hexaorganocyclotrisiloxane using alkyllithium as a catalyst and terminating with, for example, dimethylchlorosilane.
SP No. 3337497).

Further, as an organopolysiloxane having a primary, secondary or tertiary amino group at one end of a molecular chain used in the present invention, it is disclosed in JP-A-2-91083 and trade name X by Shin-Etsu Chemical Co., Ltd. Those commercially available as -22-178A and X-22-178B can also be used.

In the present invention, the reaction between an organopolysiloxane having a primary, secondary or tertiary amino group at one end of a molecular chain 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 (I) is charged all at once, 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 and an organopolysiloxane containing a primary, secondary or tertiary amino group at one end of the molecular chain are subsequently mixed, and the mixture is mixed at 5 to 100 ° C, preferably 20 to 100 ° C. 60 ℃
The reaction is carried out under the following conditions. The mixing ratio can be appropriately selected as desired, but the reaction is carried out at a ratio of 0.1 to 1.1 mole equivalent of poly (N-acylalkyleneimine) per mole of primary, secondary or tertiary amino groups in the organopolysiloxane. Is preferred. 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 poly (N-acylalkylenimine) having a primary amino group at one end of a molecular chain and a reactive end of poly (N-acylalkylenimine) are described. The reaction is shown below as an example.

The compounds represented by the general formulas (VIII) and (IX) are in the form of an amine salt, and those dissolved in a solvent such as ethanol are anion-exchange resins (for example, Amberlyst A-21; manufactured by Rohm and Haas Company). ) To give a free amine.

By the reaction as described above, a block copolymer having a poly (N-acylalkylenimine) molecular chain at one end of silicone can be obtained.

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 an emulsifier for organopolysiloxane, but also retains the inherent properties of organopolysiloxane, and is used as a raw material for cosmetics and a release agent. It can be used as an antifogging agent, antistatic agent, antifoaming agent, fiber oil agent, plastic modifier, polishing agent, lubricant and the like.

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.

〔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 One-End Amino-Modified Silicone as Raw Material Synthesis Example 1 25.6 ml of a 10% hexane solution of n-butyllithium (n-butyllithium)
Butyllithium (0.040 mol) diluted with 100 ml of THF
Keep at ° C. 200 g of hexamethylcyclotrisiloxane (0.
(90 mol) in 50% THF solution is added dropwise in 30 minutes, and the reaction is carried out at 0 ° C. for further 16 hours. Cool to -78 ° C and terminate the polymerization by adding 4.16 g (0.044 mol / 10% excess) of dimethylchlorosilane. The solvent is distilled off under reduced pressure, and the precipitate of lithium chloride is separated by filtration. The oily substance was dissolved in THF, purified by reprecipitation with a mixed solvent of methanol / water, and dried under reduced pressure at 100 ° C./2 mmHg. One end of the colorless and transparent oil was hydrosilyl group, and the other end was butyl group. 180 g of polydimethylsiloxane plugged with the above were obtained. When the molecular weight was determined by the GPC method, the weight average molecular weight was 4,800 (in terms of polystyrene / solvent chloroform). A reaction vessel was charged with 100 g (0.021 mol) of a silicone having a hydrosilyl group at one end and 50 ml of toluene synthesized as described above, and heated to 60 ° C. After addition of 10 ml of a 0.1% solution of chloroplatinic acid in isopropyl alcohol (2.44 × 10 ⁻⁶ mol of chloroplatinic acid), 29.9 g (0.23 mol) of 3- (trimethylsilylamino) propene was added dropwise. After completion of the dropwise addition, the mixture was aged for 20 hours while maintaining the reaction temperature at 110 ° C., and then demethylated with silylation using 50 ml of methanol. The low boiling point of the reaction product
Evaporation was carried out over 2 hours at 0 ° C./10 mmHg to obtain a colorless and transparent oily silicone having a primary amino group at one end. The amine equivalent was determined to be 5,300 by a hydrochloric acid titration method. When the molecular weight of the amino group acetylated with acetic anhydride was determined by GPC method, the weight average molecular weight was 470.
0 (in terms of polystyrene / solvent chloroform).

Synthesis Example 2 64 ml of a 10% hexane solution of n-butyllithium (0.10 mol of n-butyllithium) was diluted with 100 ml of THF and kept at 0 ° C. A 50% THF solution of 200 g (0.90 mol) of hexamethylcyclotrisiloxane was added dropwise in 30 minutes, and the temperature was further reduced to 0 ° C. for 16 hours.
React with. Cool to -78 ° C and add dimethylchlorosilane
The polymerization is stopped by adding 10.40 g (0.11 mol / 10% excess). The solvent is distilled off under reduced pressure, and the precipitate of lithium chloride is separated by filtration. The oily substance was dissolved in THF, purified by reprecipitation with a mixed solvent of methanol / water, and dried under reduced pressure at 100 ° C./2 mmHg. 170 g of blocked polydimethylsiloxane were obtained. When the molecular weight was determined by GPC method, the weight average molecular weight was 2,200 (in terms of polystyrene / solvent chloroform). A reaction vessel was charged with 100 g (0.045 mol) of a silicone having a hydrosilyl group at one end and 50 ml of toluene synthesized as described above, and heated to 60 ° C. 10 ml of a 0.1% isopropyl alcohol solution of chloroplatinic acid (chloroplatinic acid
(2.44 × 10 ⁻⁶ mol), and then 42.5 g (0.5 mol) of dimethylallylamine was added dropwise. After completion of the dropwise addition, the mixture was aged for 20 hours while maintaining the reaction temperature at 110 ° C. Washing the product with water to remove excess dimethylallylamine,
Drying was performed at 100 ° C./10 mmHg for 2 hours to obtain a colorless and transparent oily silicone having a tertiary amino group at one end. The amine equivalent was found to be 1900 by a hydrochloric acid titration method. When the molecular weight was determined by GPC method, the weight average molecular weight was 2,200 (in terms of polystyrene / solvent chloroform).

Example 1 Synthesis of Poly (N-acylethyleneimine) -Modified Silicon at One Terminal Example 1 2.16 g (0.014 mol) of diethylsulfuric 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).
Amino-modified silicone having a primary amino group at one end synthesized in Synthesis Example 1 in another container (molecular weight 4700, amine equivalent
54.2) 74.2 g (0.014 mol) is dissolved in chloroform 100 ml. A solution of the terminal reactive polymer of poly (N-acylethyleneimine) is placed in a solution of the amino-modified silicone,
The reaction was performed at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight 5500) having a poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane was obtained. This copolymer was a pale yellow rubber.

Example 2 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, 212 g (0.04 mol) of an amino-modified silicone (molecular weight: 4700, amine equivalent: 5300) having a primary amino group at one end synthesized in Synthesis Example 1 was mixed with 250 ml of chloroform.
Dissolve in The solution of the terminal reactive polymer of poly (N-acylethyleneimine) was added to the solution of the amino-modified silicone and reacted at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, poly (N-
As a result, a block copolymer (molecular weight: 6000) having an acylethyleneimine) chain was obtained. This copolymer was a pale yellow rubber.

Example 3 Amberlyst A-21 obtained by dissolving a block copolymer having a poly (N-acylethyleneimine) chain at one end of the polydimethylsiloxane obtained in Example 2 in ethanol, regenerating, and replacing the solvent with ethanol. (ROHM &
Through a column packed with Haas anion exchange resin)
Thereafter, 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).

Example 4 A 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 obtain poly (N-acylethylene). An imine) terminal reactive polymer (molecular weight 1000) was synthesized. Amino-modified silicone having a tertiary amino group at one end synthesized in Synthesis Example 2 in another container (molecular weight 2200, amine equivalent 1900)
19.0 g (0.01 mol) is dissolved in 30 ml of chloroform. The solution of the terminal reactive polymer of poly (N-acylethyleneimine) is added to the solution of the amino-modified silicone,
Reacted for hours. By distilling off the solvent under reduced pressure, a block copolymer having a poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane (molecular weight 3000) was obtained. This copolymer was a pale yellow resin.

Example 5 Methyl triflate 3.28 g (0.02 mol), 2-methyl-2-oxazoline 20.0 g (0.24 mol), 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, 44.0 g (0.02 mol) of an amino-modified silicone (molecular weight: 2200, amine equivalent: 1900) having a tertiary amino group at one end synthesized in Synthesis Example 2 is dissolved in 100 ml of chloroform. The solution of the terminal reactive polymer of poly (N-acylethyleneimine) was added to the solution of the amino-modified silicone and reacted at 55 ° C. for 5 hours. The solvent was distilled off under reduced pressure to obtain a block copolymer (molecular weight 4000) having a poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane.
This copolymer was a pale yellow rubber.

Example 6 Amberlite IRA400 (ROHM) obtained by dissolving a block copolymer having a poly (N-acylethyleneimine) chain at one end of the polydimethylsiloxane obtained in Example 5 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 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).
Amino-modified silicone X-22 having a secondary amino group at one end marketed by Shin-Etsu Chemical Co., Ltd. in another container
Dissolve 37.0 g (0.014 mol) of -178A (amine equivalent 2640) in 70 ml of chloroform. The solution of the terminal reactive polymer of poly (N-acylethyleneimine) was added to the solution of the amino-modified silicone and reacted at 55 ° C. for 5 hours. By distilling off the solvent under reduced pressure, a block copolymer having a poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane (molecular weight: 3200) was obtained. This copolymer is
It was a pale yellow rubber.

Example 8 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, the same amino-modified silicone having a secondary amino group at one end as in Example 7 (amine equivalent 2640) 10
5.6 g (0.04 mol) is dissolved in 200 ml of chloroform. The solution of the terminal reactive polymer of poly (N-acylethyleneimine) is added to the solution of the amino-modified silicone,
Reacted for hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight 3700) having a poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane was obtained. This copolymer was a pale yellow rubber.

Example 9 Amberlist A-21 obtained by dissolving a block copolymer having a poly (N-acylethyleneimine) chain at one end of the polydimethylsiloxane obtained in Example 8 in ethanol, regenerating the solvent, and replacing the solvent with ethanol. (ROHM &
Through a column packed with Haas anion exchange resin)
Thereafter, the solvent was distilled off under reduced pressure to obtain a pale yellow rubbery resin. Confirmation of removal of the ethyl sulfate as the initiator fragment was performed by measuring the content of the sulfur element (100 ppm or less).

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 Examples 1 to 4 Unmodified silicones commercially available (Comparative Example 1; PS041, manufactured by Chisso Corporation, molecular weight 4970), amino-modified silicones having a primary amino group at one end obtained in Synthesis Example 1 (Comparative Example 2) ), An amino-modified silicone having a tertiary amino group at one end obtained in Synthesis Example 2 (Comparative Example 3), a commercially available modified silicone having a secondary amino group at one end (Comparative Example 4;
(Shin-Etsu Chemical Co., Ltd.) was evaluated for solubility and dispersibility in the same manner as in Example 10. Table 1 shows the results.

Comparative Example 5 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 another container, 3-aminopropyl-substituted polydimethylsiloxane (manufactured by Chisso Corporation, FM3325,
500 g (0.05 mol) of an amine equivalent of 5000 and a molecular weight of 10,000 are dissolved in 1500 ml of chloroform. The solution of the terminally reactive polymer of poly (N-acylethyleneimine) was placed in a solution of polydimethylsiloxane substituted at both ends with 3-aminopropyl, 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 6 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 polydimethylsiloxane having a side chain 3-aminopropyl 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.

Emulsion stability test Example 11 (Preparation of W / O emulsion) Block copolymer 5 having poly (N-acylethyleneimine) chain at one end of polydimethylsiloxane obtained in Examples 1 to 3 Parts by weight are dissolved in 65 parts by weight of 50 cSt dimethylpolysiloxane and heated to 70 ° C. 30 parts by weight of water to 30
In a minute, the mixture was slowly cooled and a W / O emulsion was obtained. Table 2 shows the results of evaluating the stability of the emulsion.

Comparative Example 7 (Preparation of W / O Emulsion) A block copolymer having poly (N-acylethyleneimine) chains at both ends of the polydimethylsiloxane obtained in Comparative Example 5 and Comparative Example 6 A W / O emulsion was obtained in the same manner as in Example 11 for the graft copolymer having a poly (N-acylethyleneimine) chain on the side chain of the obtained polydimethylsiloxane, and the stability was evaluated. Table 2 shows the results.

Example 12 (Preparation of O / W emulsion) 3 parts by weight of a block copolymer having a poly (N-acylethyleneimine) chain at one end of the polydimethylsiloxane obtained in Examples 4 to 9 was added to water 67. Dissolve in parts by weight, 50 cSt
Was added and emulsified with a homomixer to obtain an O / W emulsion. The stability of the emulsion was evaluated. The average particle size 24 hours after emulsification was measured. Table 3 shows the results.

Comparative Example 8 (Preparation of O / W Type Emulsion) A block copolymer having poly (N-acylethyleneimine) chains at both ends of the polydimethylsiloxane obtained in Comparative Example 5, and Comparative Example 6 With respect to the graft copolymer having a poly (N-acylethyleneimine) chain on the side chain of polydimethylsiloxane, an O / W emulsion was obtained in the same manner as in Example 12, and the stability was evaluated. The results are shown in Table 3, and the stability of the emulsion was poor.

Adsorption test of poly (N-acylethyleneimine) -modified silicone Example 13 The adsorption of the poly (N-acylethyleneimine) -modified silicone obtained in Examples 1 to 9 to hair was evaluated.
Each solution was prepared as shown in Table 4. Human hair was immersed in each of the solutions in Table 4 for 3 minutes, sufficiently washed with ion-exchanged water, and 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 5 shows the results.

Example 14 The adsorptivity of the O / W type silicone emulsion obtained in Example 12 to hair was evaluated. The silicone emulsion was diluted to 0.1 wt% with water, and the adsorptivity to hair was determined in Example 13.
The evaluation was performed in the same manner as described above. Table 6 shows the results.

Claims (3)

(57) [Claims] An organopolysiloxane having a primary, secondary or tertiary amino group at only one end of a molecular chain, and a compound represented by the formula (I): 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. 2. An organopolysiloxane having a primary, secondary or tertiary amino group at only one terminal of a molecular chain is represented by the formula (II): The method for producing a novel organopolysiloxane according to claim 1, which is represented by the following formula: 3. An organopolysiloxane having a primary, secondary or tertiary amino group at only one end of the molecular chain is represented by the formula (II)
I) The method for producing a novel organopolysiloxane according to claim 1, which is represented by the following formula: