JPH0826158B2 - Polyamine-polysiloxane block copolymer - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyamine-polysiloxane block copolymer.

[Technical background of the invention and its problems]

Block copolymers or graft copolymers of polydiorganosiloxane and various linear organic polymers having polarity are well known. For example, block or graft copolymers with polyoxyalkylenes are used as surfactants and foam stabilizers, and block copolymers with polyurethanes are said to be biocompatible.

However, a block copolymer with polyamine is not known. In particular, the above-mentioned copolymer in which the siloxane chains and / or polyamine chains have the same chain length is not known.

A method of reacting a hydroxy group-containing polysiloxane-polyoxyalkylene block copolymer and a polyamine with an organic polyisocyanate to obtain a block copolymer has been disclosed (JP-A-52-57295). Is intended for a polysiloxane-containing polyurethane elastic body, in which a polyoxyalkylene chain and a urethane bond are present between the polysiloxane and the polyamine, and the block copolymer of the present invention has a molecular structure, a purpose and a property. It is different.

The present inventors have previously synthesized a polysiloxane-polyoxazoline block copolymer (Kazama, Tezuka, Imai; Proceedings of the Polymer Society of Japan, Vol. 35, page 336 (1986). This block copolymer is The polyamine-polysiloxane block copolymer of the present invention does not exhibit physiological activity and cannot be emulsified with water, and a method for arranging polyamine chain lengths as in the block copolymer of the present invention has been found. Did not reach

[Object of the Invention]

An object of the present invention is to provide a novel polyamine-polysiloxane block copolymer. In particular, the present invention can provide the above-mentioned copolymer having a uniform length of polysiloxane chain and / or polyamine chain.

[Structure of Invention]

That is, the present invention has the general formula (In the formula, R ¹ represents an alkyl group, a phenyl group, or an alkenyl group, R ² represents the same or different alkyl groups, R ³ represents an alkyl group having 3 or more carbon atoms, and R ⁴ represents an alkyl group. R ⁵ are the same or different alkyl groups, n is 5 to 1,000 on average, m is 5 to 1,000 on average,
p shows the number of 3-10. ) Or general formula (In the formula, R ¹ , R ² , R ³ , n, m and p are as described above and A represents a chain terminating group.) The polyamine-polysiloxane block copolymer represented by the formula:

In the present invention, R ¹ is an alkyl group, a phenyl group, or an alkenyl group. The alkyl group is a methyl group,
Examples are ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group, and examples of alkenyl group include vinyl group and allyl group. Of these, a methyl group or a phenyl group is preferable from the viewpoint of heat resistance, but in the case of obtaining a copolymer having a uniform siloxane chain length, R ¹ is derived from R ¹ Li, and therefore its handling is easy. Therefore, a butyl group is preferable.

R ² is an alkyl group which is the same as or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. The methyl group is preferable because it is easy to perform and the properties of the polysiloxane such as heat resistance, water repellency, and flexibility are best exhibited.

n is an integer of 5 to 1,000 on average, preferably 20 to 200. If n is less than 5 on average, it is difficult to synthesize, and n is 1 on average.
If it exceeds 000, not only is the viscosity too high to handle, but it is also difficult to synthesize with good control.

p is an integer of 3-10. When p is 1, it cannot be synthesized by hydrosilylation reaction, and when p is 2, resistance to hydrolysis reaction is small. On the other hand, when p exceeds 10, the apparent viscosity of the system increases and the heat resistance decreases. Among these, p is preferably 3 because of easy synthesis.

R ³ is an alkyl group having 3 or more carbon atoms, a propyl group,
A butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and the like are exemplified, but the polyamine chain portion has a large molecular weight, and to obtain a block copolymer having a uniform chain length, an isopropyl group, A branched one such as a tert-butyl group or a neopentyl group is preferable, among which,
The tert-butyl group is more preferable because it is easy to handle and obtain the raw materials. The methyl group or the ethyl group cannot extend the polyamine chain to a desired length.

R ⁴ is an alkyl group, and examples thereof include a methyl group, an ethyl group and a propyl group.

R ^{5 s} are alkyl groups that are the same or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. However, a methyl group is preferable because of its high reactivity.

m is an integer of 5 to 1,000 on average, preferably 20 to 200. Those having an average m of less than 5 do not sufficiently exhibit the characteristics of the block copolymer. On the other hand, when m exceeds 1,000 on average, the viscosity becomes too high, which makes it difficult to handle and makes it difficult to synthesize the composition with good control.

A is a group introduced into the copolymer by a chain termination reaction, or a group generated during the post-treatment thereof, which varies depending on the reaction conditions and the washing method after the reaction, but is a cyclic polyamine group, a hydroxyl group, a methoxy group. Examples thereof include a group and an ethoxy group.

The block copolymer represented by the formula (I) can be obtained, for example, as follows. That is, the general formula (Wherein R ¹ , R ² , R ⁵ , n and p are as described above), and a terminal amine type polysiloxane represented by the general formula (In the formula, R ³ , R ⁴ and m are as described above).

The terminal amine type polysiloxane (III) can be synthesized as follows. That is, the general formula [R ² ₂ Si
O] ₃ (where R ² is as described above) in the presence of an organolithium compound represented by the general formula R ¹ Li (where R ¹ is as described above) in tetrahydrofuran. Polymerize and then the general formula R ² ₂ H
A general formula R ¹ [R ² ₂ SiO] is obtained by performing a desalting reaction with diorganochlorosilane represented by SiCl (where R ² is as described above).
A polysiloxane containing a hydrosilyl bond at one end represented by _n R ² ₂ SiH (where R ¹ , R ² and n are as described above) is obtained (Kazama, Tezuka, Imai; Proc.
Volume 35, page 1684 (1986)). In addition to this, in the presence of platinum catalyst, dimethylallylamine, diethylallylamine,
The terminal amine type polysiloxane (III) can be obtained by hydrosilylating a dialkylalkenylamine such as diisopropylallylamine or dimethylbutenylamine.

In this case, the ratio of the weight average molecular weight to the number average molecular weight (dispersion degree) in the first step reaction is 1.0 to 1.2
Since a polysiloxane with a siloxane chain length equal to or less than 1.1 can be obtained, the terminal amine type polysiloxane (III)
In the same manner, a product having a uniform siloxane chain length can be obtained.

In addition, such terminal amine type polysiloxane (II
I) is, for example, R ¹ R ² ₂ SiCl and [R ² ₂ SiO] _q (where R ¹ ,
R ² is as described above, q is an integer of 3 or 4, and R ^{1 is formed} by telomerization or ring-opening equilibrium reaction.
[R ² ₂ SiO] _n R ² ₂ SiCl (provided that R ¹ , R ² and n are as described above) is obtained, and the terminal chlorine atom is hydrogenated with LiAlH ₄ or the like, and then similarly dialkylalkenylamine is formed. It can also be obtained by reacting. However, this method cannot make the lengths of the siloxane chains uniform.

Polyamine (IV) is prepared by ring-opening polymerization of N-alkylaziridine using alkyl trifluoromethanesulfonate such as methyl trifluoromethanesulfonate as a reaction initiator in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran. It can be obtained in the form of a solution. According to this method, the obtained polyamine (IV) has a dispersity of 1.0 to 1.2, and 1.1 or less depending on the conditions.
A polyamine having a uniform amine chain length is obtained. As the N-alkylaziridine, those having a branched alkyl group such as N-isopropylazirindine, N-tert-butylaziridine and N-neopentylaziridine give a high polymer in good yield.

Terminal amine type polysiloxane (III) and polyamine (I
The reaction of V) can be carried out at room temperature by adding the tetrahydrofuran solution of (IV) to a solution of (III) in a mixed solvent of aprotic polar solvent such as hexamethylphosphotriamide and tetrahydrofuran. it can. Further, an organic solvent such as tetrahydrofuran may coexist in order to uniformly dissolve the terminal amine type polysiloxane (III) and allow the reaction to proceed smoothly.

The block copolymer represented by the formula (II) can be obtained, for example, as follows. That is, the general formula (In the formula, R ¹ , R ² , n and p are as described above, and R ⁶ is a monovalent hydrocarbon group.) N-alkylaziridine represented by the formula (in the formula, R ³ is as described above) can be obtained by ring-opening polymerization in the presence of tetrahydrofuran and an aprotic polar solvent.

In formula (V), R ⁶ is a methyl group, an ethyl group,
Examples thereof include a phenyl group and a p-tolyl group, but the p-tolyl group is preferable because of its high reactivity.

The terminal sulfonate ester type polysiloxane (V) is
After hydrosilylating an alkenyl alcohol such as allylacol or 3-butenyl alcohol to a polysiloxane containing a hydrosilyl bond at one end, which is an intermediate raw material of (III), in the presence of a platinum catalyst, the compound represented by the general formula R ⁶ SO ₂ It can be obtained by reacting a chlorosulfuryl compound represented by Cl (wherein R ⁶ is as described above). Also in this case (II
As in the case of I), a product having a uniform siloxane chain length can be obtained depending on the method for producing the polysiloxane containing a hydrosilyl bond at one end.

The reaction of ring-opening polymerization of N-alkylaziridine (VI) with a terminal sulfonic acid ester type polysiloxane (V) to obtain the copolymer of the present invention is carried out, for example, by converting the above polysiloxane (V) into hexamethylphosphotriamide. Such as an aprotic polar solvent or a mixed solvent obtained by adding a good solvent for the above polysiloxane (V) such as tetrahydrofuran, if necessary, and then adding N-alkylaziridine (VI) to 80-120 ° C. Can proceed at temperatures of. Also in this case, as the N-alkylaziridine, one having a branched alkyl group as described above is preferable in terms of obtaining a high polymer. After completion of the reaction, the solvent and unreacted materials are removed from the obtained mixture, the copolymer is dissolved in a solvent such as a hydrocarbon solvent, and freeze-dried to obtain a purified copolymer (II).

During this ring-opening polymerization, A is formed by a chain termination reaction. The content of A is not essential to the invention. For example, growing polyamine chains may terminate by forming a polyamine ring, such as a piperazine ring. In addition, a hydroxyl group or an alkoxy group such as a methoxy group, an ethoxy group or an isopropoxy group may be formed due to water present in the system, water used for the post-treatment, alcohol or the like.

The polyamine-polysiloxane block copolymer of the present invention can be represented by the structural formula (I) or (II) depending on its synthetic method, and in both cases, the polysiloxane chain and the polyamine chain are bonded via a polymethylene bond. Things
Essentially the same. However, the compound represented by the formula (I) can be obtained with a polyamine chain portion having a uniform polydispersity of 1.0 to 1.2. In addition, those represented by any of the structural formulas can be obtained in which the degree of dispersion of the siloxane chain portion has a uniform chain length of 1.0 to 1.2, depending on the method for producing the polysiloxane containing a hydrosilyl group at one end.

〔The invention's effect〕

The diblock polyamine provided by the present invention
Polysiloxane block copolymers can be easily emulsified in water, are chemically stable, have physiological activity, interact with negatively charged substances, have coordination with metals, and have unique orientation. Has surface forming ability. In particular, a block copolymer in which one or both segments have the same chain length exhibits various interesting properties. For example, this can control the phase separation structure. By adjusting the chain length of the polyamine chain, it is possible to control the responsiveness to biological proteins, and by adjusting the chain length of the polysiloxane chain, the surface properties of the copolymer such as surface tension and contact angle with water can be controlled. Further, when the chain lengths of both segments are the same, those having stable characteristics as a surfactant can be obtained.

Therefore, the polyamine-polysiloxane block copolymer of the present invention is useful as a surfactant, an antibacterial / antifungal agent, a component of an antifouling paint, a dyeability improving agent, and a fiber treating agent.

〔Example〕

Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples and Comparative Examples. In these examples, parts represent parts by weight.

Synthesis Examples 1 to 3 Hexamethylcyclotrisiloxane was polymerized with butyllithium in tetrahydrofuran and further reacted with dimethylchlorosilane to obtain a siloxane chain having a number average degree of polymerization of 30 and a ratio of the weight average molecular weight to the number average molecular weight. Is 1.
08, one end hydrosilyl group, the other end was charged with 25.1 parts of polydimethylsiloxane blocked with a butyl group into the reaction vessel, after replacing the inside of the vessel with nitrogen, 38.6 parts of dimethylallylamine was added, and 0.34 part of Add platinum on carbon containing 5% platinum and stir evenly while keeping the temperature at 90
The hydrosilylation reaction was carried out while maintaining the temperature at ℃. The reaction was continued for 8 hours, and ¹ H-NMR was measured. As a result, it was confirmed that the Si—H bond disappeared completely and the reaction proceeded completely. The product was washed with water to remove excess dimethylallylamine, dehydrated and filtered by a conventional method to obtain polysiloxane S-1 having a terminal dimethylamino group.

Similarly, the number average degree of polymerization of siloxane chains is 50 and
Polysiloxane S having a dimethylamino group at the end was prepared from 100 polysiloxanes containing a hydrosilyl bond at one end and having the same chain length at the same mixing ratio and reaction conditions.
-2 and S-3 were obtained. Table 1 shows the number average degree of polymerization and the degree of dispersion of the raw material siloxane, and the weight average and number average molecular weights of S-1 to S-3. Further, the ¹ H-NMR chart of S-2 is shown in FIG.

Synthetic Examples 4 to 6 20.0 parts of each of the same three kinds of hydrosilyl group-containing polysiloxanes used in Synthetic Examples 1 to 3 were dissolved in 69.4 parts of toluene, and 0.34 parts of 5% platinum was added in a nitrogen stream. Carbon-containing platinum containing carbon and 25.2 parts of allyl alcohol were added, and the hydrosilylation reaction was carried out with stirring under the conditions shown in Table 2. Then, the carbon-supported platinum was filtered off using a membrane filter, after removing toluene and unreacted allyl alcohol by vacuum distillation, washed several times with methanol, freeze-dried from benzene,
A hydroxypropyl group-containing polysiloxane was obtained.

Dissolve 10.0 parts of this hydroxypropyl group-containing polysiloxane in the amount of methylene chloride shown in Table 2, add the amounts of tosyl chloride, triethylamine and 4-dimethylaminopyridine shown in Table 2 and stir at 20 ° C for 22 hours. Then, the reaction was carried out. The reaction product was extracted with 39.5 parts of n-hexane, repeatedly precipitated in methanol for purification, and lyophilized from benzene to give tosyl group-containing polysiloxanes T-1 to T-.
-3 was obtained.

Number average degree of polymerization and dispersity of raw material siloxane, conditions of hydrosilylation reaction, yield of hydroxypropyl group-containing polysiloxane, yield of tosyl group-containing polysiloxane,
In addition, Table 2 shows the weight average and number average molecular weight thereof. The ¹ H-NMR chart of T-2 is shown in FIG.

Examples 1 to 4 N-tert-butylaziridine was dissolved in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran, methyl trifluoromethanesulfonate was added thereto, and ring-opening polymerization was carried out at 15 ° C. for 20 minutes while stirring. went. The amount of each charge is as shown in Table 3. A part of the obtained reaction solution was extracted and the weight average and number average molecular weight of the produced polyamine were determined.
The dispersity was 1.1 or less in all cases.

The tetrahydrofuran solutions of the dimethylamino group-containing polysiloxanes S-1 to S-3 obtained in Synthesis Examples 1 to 3 were added to the obtained reaction solutions. The added amount is shown in Table 3. The mixture was stirred at 30 ° C. for 2 hours to carry out a coupling reaction. The reaction product was poured into methanol to be isolated, further washed repeatedly with isopropanol, dissolved in benzene and freeze-dried to obtain a polyamine-polysiloxane block copolymer. Table 3 shows the yield, weight average and number average molecular weights, and the proportion of the polyamine segment in the copolymer obtained as the integral ratio from NMR.

In addition, ¹ H-NMR of the block copolymer obtained in Example 4
And IR charts are shown in Figs. 3 and 4, respectively.
The attribution is shown in Table 5.

Examples 5 to 7 Tosyl group-containing polysiloxanes T-1 to T-3 obtained in Synthesis Examples 4 to 6 were charged into a reaction vessel, deaerated and replaced with nitrogen, and hexamethylphosphotriamide was added to tetrahydrofuran. Further, N-tert-butylaziridine was added and heated with stirring to carry out ring-opening polymerization of tert-butylaziridine using a tosyl group-containing polysiloxane as an initiator. The charged amounts and reaction conditions are shown in Table 4.

After completion of the reaction, unreacted N-tert-butylaziridine,
Hexamethylphosphotriamide and tetrahydrofuran were distilled off under reduced pressure, and a 1: 1 mixture of ethanol and water was added to precipitate a polymer. Further, washing with a 1: 1 mixture of ethanol and water was repeated to remove the by-produced cyclic polyamine oligomer. Then, benzene was added and freeze-dried to obtain a purified polyamine-polysiloxane block copolymer.

The obtained block copolymer is a colorless viscous solid,
It was soluble in hexane, benzene, tetrahydrofuran, chloroform and carbon tetrachloride and insoluble in acetone, methanol, dimethyl sulfoxide and water. Further, this block copolymer exhibited an emulsifying action in dilute hydrochloric acid.

Table 4 shows the yield of the block copolymer, the average molecular weight, the ratio of the polyamine segment in the copolymer, the reaction rate of tert-butylaziridine, and the efficiency of the initiator. The ¹ H-NMR and IR charts of the block copolymer obtained in Example 7 showed the same characteristic absorptions as in FIGS. 3 and 4, respectively.

Comparative Example 1 The same experiment as in Example 5 was conducted except that hexamethylphosphotriamide was not used, 700 parts of methylene chloride was used as a solvent instead of tetrahydrofuran, and the reaction conditions were 0 ° C. and 48 hours. No reaction was carried out, and the target polyamine-polysiloxane copolymer was not obtained.

Comparative Example 2 The same experiment as in Example 7 was carried out except that hexamethylphosphotriamide was not used, the amount of tetrahydrofuran was 466 parts, and the reaction conditions were 60 ° C. and 26 hours. The target polyamine-polysiloxane copolymer was not obtained.

[Brief description of drawings]

Figure 1 is ¹ H-NMR chart of the dimethylamino group-containing polysiloxane obtained in Synthesis Example 2, FIG. 2 ¹ H-NMR chart of the tosyl group-containing polysiloxane obtained in Synthesis Example 5, the 3 and 4 show ¹ H-NMR and IR of the polyamine-polysiloxane block copolymer obtained in Example 4.
A chart is shown.

Claims (7)

[Claims] 1. A general formula (In the formula, R ¹ represents an alkyl group, a phenyl group, or an alkenyl group, R ² represents the same or different alkyl groups, R ³ represents an alkyl group having 3 or more carbon atoms, and R ⁴ represents an alkyl group. R ⁵ are the same or different alkyl groups, n is 5 to 1,000 on average, m is 5 to 1,000 on average,
p shows the number of 3-10. ) Or general formula (In the formula, R ¹ , R ² , R ³ , n, m, and p are as described above, and A represents a chain-terminating group.) A polyamine-polysiloxane block copolymer represented by the formula: 2. The polyamine-polysiloxane block copolymer according to claim 1, wherein R ¹ is a butyl group. 3. The polyamine-polysiloxane block copolymer according to claim 1, wherein R ² is a methyl group. 4. The polyamine-polysiloxane block copolymer according to claim 1, wherein the ratio of the weight average molecular weight of the siloxane chain portion to the number average molecular weight is 1.0 to 1.2. 5. The polyamine-polysiloxane block copolymer according to claim 1, wherein p is 3. 6. The polyamine-polysiloxane block copolymer according to claim 1, wherein R ³ is a tert-butyl group. 7. The polyamine-polyamine according to claim 1, wherein in the copolymer represented by the general formula (I), the ratio of the weight average molecular weight of the amine chain portion to the number average molecular weight is 1.0 to 1.2. Siloxane block copolymer.