JPS63270738A - Polyamine/polysiloxane block copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which can be easily emulsified in water and is chemically stable and physiologically active, by reacting a specified amino-terminated polysiloxane with a polyamine. CONSTITUTION:An amino-terminated polysiloxane of formula I (wherein R<1> is alkyl, phenyl or alkenyl, R<2> and R<5> are each an alkyl, n is 5-1,000 on the average and p is 3-10) is reacted with a polyamine of formula II (wherein R<3> is a 3C or lower alkyl, R<4> is alkyl, and m is 5-1,000 on the average), or an N-alkylaziridine of formula IV is polymerized by ring opening with a sulfonate-terminated polysiloxane of formula III (wherein R<6> is a monovalent hydrocarbon group) to obtain a polyamine/polysiloxane block copolymer represented by formula V or VI (wherein A is a terminal group) and having a ratio of the number-average MW to the weight-average MW of the siloxane chain part of 1.0-1.2.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to polyamine-polysiloxane block copolymers.

[Technical background of the invention and its problems]

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

However, block copolymers with polyamines are not known. In particular, the above-mentioned copolymers in which the chain lengths of siloxane chains and/or polyamine chains are uniform are not known.

Incidentally, a method for obtaining a block copolymer by reacting a hydroxy group-containing polysiloxane-polyoxyalkylene block copolymer and a polyamine with an organic polyisocyanate has been disclosed (Japanese Patent Application Laid-Open No. 57295/1989).
This is intended for a polyurethane elastomer containing polysiloxane, and there are polyoxyalkylene and urethane bonds between polysiloxane and polyamine, and the block copolymer of the present invention has a molecular structure, purpose, and properties. are different.

The present inventors previously synthesized a polysiloxane-polyoxazoline block copolymer (hearsay, procedure, Imai; Proceedings of the Society of Polymer Science, Vol. 35, p. 336 (1986)
). This block copolymer does not exhibit physiological activity like the polyamine-polysiloxane block copolymer of the present invention and cannot be emulsified with water. Furthermore, no method has been found to make the lengths of polyamine chains uniform as in the block copolymer of the present invention.

[Purpose 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 copolymer in which the lengths of polysiloxane chains and/or polyamine chains are uniform.

[Structure of the invention]

That is, the present invention relates to the general formula (wherein R1 represents an alkyl group, phenyl group, or alkenyl group, R2 represents an alkyl group that is the same or different from each other, and R3 represents an alkyl group having 3 or more carbon atoms,
R4 represents an alkyl group, R5 represents an alkyl group that is the same or different from each other, n is 5 to 1,000 on average, r
n represents a number from 5 to 1,000 on average, and p represents a number from 3 to 10.

) or the general formula (wherein R', R'', R3, n, m, p are as described above, and A represents a chain-terminating group).

In the present invention, R1 is an alkyl group, a phenyl group, or an alkenyl group. As an alkyl group, a methyl group,
Examples of the alkenyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and a vinyl group and an allyl group.

Among these, methyl group or phenyl group is preferable from the viewpoint of heat resistance, but when obtaining a copolymer with uniform length of siloxane group, R1 is derived from R'Li, so it is easy to handle. Therefore, a butyl group is preferred.

R2 is an alkyl group that is the same or different from each other, and examples thereof include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, and dodecyl group. A methyl group is preferred because it is easy to use and best exhibits the properties of polysiloxane, such as heat resistance, water repellency, and flexibility.

n is an integer of 5 to 1,000 on average, preferably 20 to 200. Those with n less than 5 on average are difficult to synthesize;
When the average value exceeds 1.000, the viscosity increases so much that not only is it difficult to handle, but also difficult to synthesize in a well-controlled manner.

p is an integer from 3 to 10. A compound with p of 1 cannot be synthesized by a hydrosilylation reaction, and a compound with p of 2 has little resistance to the hydrolysis reaction.

When p exceeds 10, the apparent viscosity of the system increases and the heat resistance decreases. Among these, because it is easy to synthesize,
Preferably, p is 3.

R3 is an alkyl group having 3 or more carbon atoms, a propyl group,
Examples include butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc., but in order to obtain a block copolymer with a large molecular weight and uniform chain length in the polyamine chain portion, isopropyl group, Branched ones such as tert-butyl group and neopentyl group are preferred, and among them, tert
-butyl group is more preferred. Methyl or ethyl groups cannot extend the polyamine chain to the desired length.

R4 is an alkyl group, and examples thereof include a methyl group, an ethyl group, and a propyl group.

R5 is an alkyl group that is the same or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a methyl group is preferred because of its high reactivity.

m is an integer of 5 to 1,000 on average, preferably 20 to 200. If m is less than 5 on average, the characteristics of a block copolymer will not be fully exhibited. Moreover, when m exceeds 1.000 on average, the viscosity increases so much that it is not only difficult to handle, but also difficult to synthesize in a well-controlled manner.

A is a group introduced into the copolymer by a chain termination reaction,
Alternatively, it is a group generated during post-treatment, and examples thereof include a cyclic polyamine group, a hydroxyl group, a methoxy group, a nidoxy group, etc., depending on the reaction conditions and the method of washing after the reaction is completed.

The block copolymer represented by formula (I) can be obtained, for example, as follows. That is, a terminal amine type polysiloxane represented by the general formula (wherein R1, R2, R8, n and p are as described above) and a terminal amine type polysiloxane represented by the general formula (wherein R3, R4 and m are as described above). It can be obtained by reacting with the represented polyamine.

The terminal amine type polysiloxane (I) can be synthesized as follows. That is, the general formula (R2□5i
n) Polymerizing hexaorganotrisiloxane represented by s (where R2 is as described above) in tetrahydrofuran in the presence of an organolithium compound represented by the general formula R'Li (wherein R1 is as described above), Then, a desalting reaction is performed with a diorganochlorosilane represented by the general formula R2□H3iC1 (wherein R2 is as described above) to form the general formula R'(R'2SIO)-R'2SIH (wherein R', R ' and n are as described above) to obtain a polysiloxane containing a hydrosilyl bond at one end (Fubon, Hiratsuka, Imai; Proceedings of the 35th Polymer Symposium, No. 35
Volume No. 1684 (1986)). This is subjected to a hydrosilylation reaction with a dialkylalkenylamine such as dimethylallylamine, diethylallylamine, diisopropylarylamine, or dimethylbutenylamine in the presence of a platinum-based catalyst to form a terminal amine type polysiloxane (I[I). Obtainable.

In this case, the first stage reaction yields a polysiloxane with uniform siloxane chain lengths, with a ratio of weight average molecular weight to number average molecular weight (dispersity) of 1.0 to 1.2, depending on the conditions, 1.1 or less. terminal amine type polysiloxane (
In III), it is also possible to obtain products with uniform siloxane chain lengths.

In addition, such terminal amine type polysiloxane (III
) is, for example, RIR2□5iC1 and [R22SiO
].

(However, as mentioned above, R' and R2 are telomerization or ring-opening equilibration reaction during which q is an integer of 3 or 4).
It can also be obtained by obtaining 2,5iC1 (wherein R1, R2 and n are as described above), hydrogenating the terminal chlorine atom with LIAI84 or the like, and then reacting it with a dialkylalkenylamine in the same manner. However, with this method, it is not possible to make the lengths of the siloxane blocks the same.

Polyamine (EV) can be produced by ring-opening polymerization of N-alkylaziridine in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran using an alkyl trifluoromethanesulfonate such as methyl trifluoromethanesulfonate as a reaction initiator. It can be obtained in solution form. According to this method, the polyamine (TV) obtained has a dispersity of 1.0 to 1.2, depending on the conditions, 1.
．． Polyamines with uniform amine chain lengths of 1 or less can be obtained. Examples of N-alkylaziridine include N-isopropylaziridine, N-tert-butylaziridine, N-
Products with branched alkyl groups, such as neopentylaziridine, give high polymers in good yields.

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

The block copolymer represented by formula (II) can be obtained, for example, as follows. That is, by using the terminal sulfonic acid ester type polysiloxane represented by the general formula (wherein R', R'', n and p are as described above, and R8 represents a monovalent hydrocarbon group), the general formula ( An N-alkylaziridine represented by the formula (wherein R3 is as described above) can be obtained by open polymerization in the presence of tetrahydrofuran and an aprotic polar solvent.

In formula (V), R6 is a methyl group, an ethyl group,
Examples include phenyl group and p-)'J group, but due to their high reactivity, p-)! A J group is preferred.

The terminal sulfonic acid ester type polysiloxane (V) is (
After hydrosilylating polysiloxane containing a hydrosilyl bond at one end, which is an intermediate raw material for I[I], with an alkenyl alcohol such as allyl alcohol or 3-butenyl alcohol in the presence of a platinum catalyst, the general formula R'SO is obtained. □C
It can be obtained by reacting a chlorosulfuryl compound represented by 1 (where R6 is as described above).

In this case, as in (III), depending on the method for producing the polysiloxane containing a hydrosilyl bond at one terminal end, it is possible to obtain a polysiloxane having a uniform chain length.

The reaction of ring-opening polymerizing N-alkylaziridine (VI) with terminal sulfonic acid ester type polysiloxane (V) to obtain the copolymer of the present invention can be carried out, for example, by converting the above-mentioned polysiloxane (V) into hexamethylphosphotriamide. The above polysiloxane (V) is dissolved in an aprotic polar solvent such as or a mixed solvent containing a good solvent such as tetrahydrofuran if necessary, and N-alkylaziridine (■) is added thereto and heated at 80 to 120°C. The process can be carried out at a temperature of In this case, the N-alkyl aziridine is preferably one having a branched alkyl group as described above in terms of obtaining a high polymer. After the reaction is completed, the solvent and unreacted materials are removed from the resulting mixture, the copolymer is dissolved in a solvent such as a hydrocarbon solvent, and the purified copolymer (I[) is obtained by freeze-drying. .

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, a growing polyamine chain may terminate by forming a polyamine ring such as a piperazine ring. Furthermore, depending on the water present in the system or the water or alcohol used in post-treatment, a hydroxyl group or an alkoxy group such as a methoxy group, an ethoxy group, or an isopropoxy group may be formed.

The polyamine-polysiloxane block copolymer of the present invention can be represented by the structural formula (I) or (n) depending on the synthesis method, and both have a polysiloxane chain and a polyamine chain bonded via a polymethylene bond. They are essentially the same thing. However, in the case of formula (I), the degree of dispersion of the polyamine chain portion is 1.0 to 1.2.
It is possible to obtain products with the same chain length. Also,
Regardless of the structural formula, it is possible to obtain a polysiloxane having a uniform chain length with a degree of dispersion of 1.0 to 1.2 in the siloxane chain portion, depending on the method of manufacturing the polysiloxane containing a hydrosilyl group at one end.

〔Effect of the invention〕

The diblock type polyamine-polysiloxane block copolymer provided by the present invention can be easily emulsified with water, is chemically stable, has physiological activity, and is resistant to interactions with negatively charged substances and metals. It has coordinating properties and the ability to form surfaces with unique orientation. In particular, block copolymers in which one or the other segment have the same chain length exhibit various interesting properties. For example, this allows the phase separation structure to be controlled. By matching the chain lengths of polyamine chains, it is possible to control the responsiveness of living organisms to proteins, and by matching the chain lengths of polysiloxane chains, it is possible to control the surface properties of copolymers, such as surface tension and contact angle with water. Furthermore, when the chain lengths of both segments are made the same, a surfactant with stable properties 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 improver, and a fiber treatment agent.

〔Example〕

The present invention will be explained below using 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, and the number average degree of polymerization of the siloxane chain was 30, and the ratio of weight average molecular weight to number average molecular weight. is 1
．． 25.1 parts of polydimethylsiloxane of No. 08 in which one end was blocked with a hydrosilyl group and the other end was blocked with a butyl group was charged into a reaction vessel, and after purging the inside of the vessel with nitrogen, 38.6
0.34 parts of carbon-supported platinum containing 5% platinum were added, and the hydrosilylation reaction was carried out while stirring uniformly and maintaining the temperature at 90°C. The reaction was continued for 8 hours, and as a result of measuring 'H-NMR, it was confirmed that the 5i-H bond completely disappeared, and the reaction proceeded completely.

The product was washed with water to remove excess dimethylallylamine, followed by dehydration and filtration in a conventional manner to obtain polysiloxane S-1 having dimethylapeno groups at the ends.

Similarly, from polysiloxanes containing a hydrosilyl bond at one end and having a number average degree of polymerization of 50 and 100 and having the same chain length, polysiloxanes having a dimethylamino group at the end were prepared using the same compounding ratio and reaction conditions. Siloxanes S-2 and S-3 were obtained. Table 1 shows the number average degree of polymerization and dispersion of the raw material siloxane, as well as the weight average and number average molecular weight of S-1 to S-3. Also, S-2' H-
An NMR chart is shown in FIG.

Table 1 Synthesis Examples 4 to 6 20.0 parts of each of the three types of hydrosilyl group-containing polysiloxanes used in Synthesis Examples 1 to 3 were dissolved in 69.4 parts of toluene, and in a nitrogen stream, .34 parts of carbon-supported platinum containing 5% platinum and 25.2 parts of allyl alcohol were added, and a hydrosilylation reaction was carried out under the conditions shown in Table 2 while stirring. Next, carbon-supported platinum was filtered out using a membrane filter, toluene and unreacted allyl alcohol were removed by vacuum distillation, and then washed several times with methanol and freeze-dried in benzene to obtain a hydroxypropyl group-containing product. A polysiloxane was obtained.

This hydroxypropyl group-containing polysiloxane 10.0
Tosinopetriethylamine chloride and 4-dimethylaminopyridine were added in the amounts shown in Table 2, and the mixture was stirred at 20° C. for 22 hours to carry out a reaction. The reaction product was extracted with 39.5 parts of n-hexane, purified by repeated precipitation in methanol, and freeze-dried in benzene to obtain tosyl group-containing polysiloxanes T-1 to T-3.

Table 2 shows the number average degree of polymerization and dispersion of the raw material siloxane, the conditions for the hydrosilylation reaction, the yield of hydroxypropyl group-containing polysiloxane, the yield of tosyl group-containing polysiloxane, and the weight average and number average molecular weight thereof. . Further, the 'H-NMR chart of T-2 is shown in FIG.

Table 2 Examples 1 to 4 Dissolving N-tert-butylaziridine in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran,
Add methyl trifluoromethanesulfonate to this,
Open polymerization was carried out at 15° C. for 20 minutes while stirring. The amount of each preparation is shown in Table 3. When a portion was extracted from the obtained reaction solution and the weight average and number average molecular weights of the produced polyamine were determined, as shown in Table 3, the degree of dispersion was 1.1 or less in all cases.

Tetrahydrofuran solutions of dimethylamino group-containing polysiloxanes S-1 to S-3 obtained in Synthesis Examples 1 to 3 were added to the obtained reaction solution. The amounts added are shown in Table 3. This mixture was stirred at 30° C. for 2 hours to perform a coupling reaction.

The reaction product was isolated by pouring it into methanol, washed repeatedly with isopropanol, dissolved in benzene, and freeze-dried to obtain a polyamine-polysiloxane block copolymer. Yield, weight average and number average molecular weight,
Table 3 shows the proportion of polyamine segments in the copolymer determined as an integral ratio from NMR.

In addition, ' H- of the block copolymer obtained in Example 4
NMR and IR charts are shown in FIGS. 3 and 4, respectively, and their attributions are shown in Table 5.

Examples 5-7 Tosyl group-containing polysiloxane T obtained in Synthesis Examples 4-6
-1-T-3 was charged into a reaction vessel, degassed and nitrogen-substituted, then hexamethylphosphotriamide was added with tetrahydrofuran, and further N-tert-butylaziridine was added and heated with stirring. Ring-opening polymerization of tert-butylaziridine was carried out using a group-containing polysiloxane as an initiator. The amounts charged and reaction conditions for each are shown in Table 4.

After completion of the reaction, unreacted N-tert-butylaziridine, hexamethylphosphotriamide, and tetrahydrofuran were distilled off under reduced pressure, and 1=1 of ethanol and water was distilled off.
1 mixture was added to precipitate the polymer. Furthermore, washing was repeated with a 1:1 mixture of ethanol and water to remove by-product cyclic polyamine oligomers. Then, a purified polyamine-polysiloxane block copolymer was obtained by adding benzene and freeze-drying.

The obtained block copolymer was a colorless viscous solid, soluble in hexane, benzene, tetrahydrofuran, chloroform, and carbon tetrachloride, and insoluble in acetone, methanol, dimethyl sulfoxide, and water. Moreover, this block copolymer showed emulsifying effect in dilute hydrochloric acid.

The yield of the block copolymer, the average molecular weight, the proportion of polyamine segments in the copolymer, the reaction rate of tert-butylaziridine, and the efficiency of the initiator are shown in Table 4. The 'H-NMR and IR charts of the block copolymer obtained in Example 7 showed the same characteristic absorption as in FIGS. 3 and 4, respectively.

Table 5 Comparative Example 1 The same experiment as Example 5 was carried out 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 for 48 hours. However, no reaction occurred at all, and the desired polyamine-polysiloxane copolymer could not be obtained.

Comparative Example 2 An experiment similar to Example 7 was conducted, except that hexamethylphosphotriamide was not used, the amount of tetrahydrofuran was 466 parts, and the reaction conditions were 60 ° C. for 26 hours.
No reaction took place and the desired polyamine-polysiloxane copolymer was not obtained.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R^1 represents an alkyl group, phenyl group, or alkenyl group, and R^2 is Represents an alkyl group that is the same or different from each other, R^3 represents an alkyl group having 3 or more carbon atoms, R^4 represents an alkyl group, R^5 represents an alkyl group that is the same or different from each other, and n is the average 5-1,0
00, m indicates an average of 5 to 1,000, and p indicates a number of 3 to 10. ) or general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, R^1, R^2, R^3, n, m, p are as mentioned above, A is chain termination A polyamine-polysiloxane block copolymer represented by: 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. Claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight of the siloxane chain portion is 1.0 to 1.2.
The polyamine-polysiloxane block copolymer described in 1. 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 according to claim 1, wherein in the copolymer represented by 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. Polysiloxane block copolymer.