JPS61252230A - Azo group-containing polysiloxaneamide - Google Patents

Abstract

NEW MATERIAL:An azo group-containing polysiloxaneamide of a MW of 2,000-1,000,000, having repeating units each of which is represented by formula I (wherein R1-R3 may be the same or different from each other, among which R1 and R2 are each H or a lower alkyl group and R3 is H, a (halogen- substituted) alkyl group or a phenyl group, p and q may be the same or different from each other and are each 0 or 1-6 and m is 0 or 1-200). USE:In the production of a vinyl/silicone block copolymer, as a usual radical polymerization initiator, expandable polymers. PREPARATION:A diamine containing a polysiloxane segment of formula II (wherein R2, R3, qand m are the same as defined above) is reacted with an azo group-containing dibasic acid dihalide of formula III (wherein R1 and p are the same as defined above and X is a halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel azo group-containing polysiloxane amide exhibiting radical polymerization activity.

Vinyl-silicone block copolymers have the excellent heat resistance, cold resistance, water repellency, mold releasability, sliding properties, weather resistance, ozone resistance, and electrical properties of vinyl polymers and silicone resins such as organopolysiloxanes. properties, gas permeability, etc., and is suitable for plastics, paints,
It is expected to be used in fields such as mold release agents, adhesives, and gas permeable membranes.

Conventionally, as a method for producing a vinyl-silicone block copolymer, a living anionic polymerization method (for example, M. Morton et al., Journal of Applied Polymer Science (J.

Appl, Polym, Sci, ), 8,
2707 (1964)) and hydrosilylation methods (e.g. P., Chaumont et al., Polymers (
Polymer) #22 [53,668 (198
1)) are known, but both have drawbacks such as requiring fairly strict control of the bonding conditions and being limited in the vinyl monomers that can be applied.

As a result of intensive research into a method for producing a vinyl-silicone block copolymer that does not have the above-mentioned drawbacks, the present inventor succeeded in developing a new compound having radical polymerization activity. We have found that the drawbacks of can be overcome. That is, when a vinyl monomer is polymerized in the presence of a specific compound having a repeating unit in which a dibasic acid containing an azo group and a diamine containing a polysiloxane segment are amide bonded, the compound is decomposed by heat or light. It has been found that the desired vinyl-silicone block copolymer can be efficiently produced by producing a radical having a polysiloxane segment, which acts as a polymerization initiator, and at the same time the segment is introduced into the resulting polymer.

The present invention was completed based on the above findings.

The present invention is based on the general formula [wherein each R1 is the same or different and represents a hydrogen atom, a lower alkyl group, or a nitrile group, and each R2 is the same or different and represents a hydrogen atom or a lower alkyl group. , each R8
are the same or different and represent a hydrogen atom, a halogen atom substituted or unsubstituted alkyl group, or a phenyl group, p and q are the same or black and represent 0 or an integer from 1 to 6, and m is 0 or an integer from 1 to 200, has a repeating unit represented by ], and has a molecular weight of 200ON
It concerns an azo group-containing polysiloxane amide with a molecular weight of 100,000.

In this specification, lower alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, ter
Examples include straight chain or branched alkyl groups having 1 to 6 carbon atoms such as t-butyl, pentyl, and hexyl groups.

Examples of the alkyl group include, in addition to the above lower alkyl groups, linear or branched alkyl groups having 7 to 12 carbon atoms such as heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups.

In addition, examples of the alkyl group substituted with a halogen atom include those in which the above-mentioned alkyl group is halogenated, such as chloromethyl,
Bromomethyl, trifluoromethyl JLI, 2-chloroethyl, 8-chloropropyl, 8-bromopropyl, 8,
8.8-) Lifluoropropyl, 1 *1 +2m2
7 Toyhydroper? Examples include fluorooctyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The compound of the present invention having a repeating unit represented by the general formula (I) has the general formula % Formula % E, where R1 and p are the same as above. ] In the constituent components and general formula represented by, R2, R8, Q and m are the same as above. ] and the constituent components represented by the general formula (%) (5) [In the formula, some of the constituent components represented by the general formula (■), as well as those formed by an amide bond, Y represents a dibasic acid residue.] It also includes those substituted with the constituent represented by the general formula (Tfl). The amount is limited to an amount that does not eliminate the radical polymerization activity of the compound. Examples of dibasic acids include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelain powder, sebacic acid, fumaric acid, itaconic acid,
Terephthalic acid, isophthalic acid, phthalic acid, etc. can be mentioned.

The compound of the present invention has, for example, the general formula [where %R2, R8, q and m are the same as 1 above]. ] A diamine containing a polysiloxane (including disiloxane) segment represented by the general formula % Formula % 1 In the formula, R1 and p are the same as above, and 1x represents a halogen atom. ] It can be produced with high yield by reacting with a dibasic acid cybaride containing an azo group represented by the following.

In addition, when producing a compound of the present invention having a component represented by the above general formula (5), the above general formula (
A mixture in which part of the dibasic acid cybaride containing an azo group is replaced with the corresponding dibasic acid cybaride may be used.

The above reaction is preferably carried out in the presence of a base melting medium. Examples of the base catalyst include triethylamine, N,N-dimethylaniline, piperidine, pyridine, 1,5-diazabicyclo(41,(Nnonene-5(DBN), 1.8
-diazabicyclo[5,4,0]undecene-7 (DB
U), tri-n-butylamine, sodium hydride, n-butyllithium, etc., and can be appropriately selected and used from these.

Moreover, the reaction is usually carried out in a solvent. Examples of solvents include hydrochloric compounds such as tetrahydrofuran, diethyl ether, dimethoxyethane, and dioxane, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and trichlene, n-hexane, petroleum ether, petroleum benzine, and toluene. , hydrocarbons such as benzene and xylene, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, and one or more of these may be used.

The ratio of the cyanide represented by the general formula (M) to the cybaride represented by the general formula (2) is not particularly limited and is appropriately determined. Normally, it is preferable to keep the two in approximately equimolar proportions. When using a base catalyst, the amount used is based on the raw material compound (ma).
It is usually preferable to use about 0.5 to 8.0 times the mole of the solvent based on the raw material compound (Ma).Although the amount of the solvent to be used is appropriately increased or decreased depending on the viscosity of the reaction solution, etc., it is usually 1
It is preferable to use about 00 to 4000% by weight.

The reaction temperature is not particularly limited, but is usually -20 to 50°C.
The temperature is appropriate, preferably -10 to 80°C in order to prevent decomposition of the azo group and to make the product high molecular weight. The standing time is not particularly limited, but is usually 0.1 to 4
The reaction temperature for about 8 hours, preferably 0.5 to 6 hours, may be raised stepwise from low temperature to room temperature.

Preparation of the target product may be carried out as appropriate depending on the type of raw materials, base catalyst, solvent, etc. used. This can be easily carried out by removing the base, etc., then drying and removing the solvent. If necessary, operations such as extraction and solvent washing may be further performed and fractionated.

As mentioned above, the compound of the present invention thus obtained is composed of the constituent components (m and (2) or I), (to) and (5), and is an oligomer or primer with a molecular weight of usually about 2,000 to 100,000. be. Its properties vary depending on its molecular weight and polysiloxane segment content, but it is usually a colorless to pale yellow powder, viscous oily, or rubber-like substance. Although its solubility similarly varies, it is usually dissolved in methyl ethyl ketone, tetrahydrofuran, chloroform, etc.

The compound of the present invention can be easily converted into N2 by heating or light irradiation.
It generates and decomposes, producing radical species.

At that time, if various vinyl monomers are present, polymerization occurs rapidly and has a unique property of producing a block copolymer containing polysiloxane segments.

Therefore, by heating or irradiating with light in the coexistence of the compound of the present invention and a vinyl monomer, the compound of the present invention acts as a polymerization initiator, and at the same time, radical fragments having polysiloxane segments are introduced into the resulting polymer, resulting in polysiloxane. (AB) type or ABA type vinyl consisting of a segment prisoner and a vinyl primer segment (8)
Silicone block copolymers can be efficiently produced.

As the vinyl monomer in the method for producing a vinyl-silicone block copolymer, any monomer that can be polymerized by a radical reaction can be used, such as styrene, methacrylic acid or its ester, acrylic acid or its ester, itacon, etc. Examples include acids or esters thereof, vinyl chloride, acrylonitrile, vinyl acetate, ethylene, propylene, butadiene, vinylidene chloride, tetrafluoroethylene, chlorotrifluoroethylene, etc., and at least iai of these are used.

The vinyl-silicone block copolymer using the compound of the present invention is produced in the presence or absence of a solvent or dispersant. Examples of solvents or dispersants include tetrahydrofuran, diethyl ether, dimethoxyethane,
Ny-chill exclusively for dioxane, n-hexane, octane,
Petroleum benzene, benzene, toluene, hydrocarbons such as xylene, methanol, ethanol, impropatul,
Examples include alcohols such as t-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexamonocarbon ketones, acetonitrile, water, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. If necessary, a degree of polymerization regulator such as n-dodecyl mercaptan can be appropriately added to a reaction system in which one or more of these can be used.

The proportion of the azo group-containing polysiloxane amide of the present invention and the vinyl monomer used in the above production varies depending on the molecular weight of the compound of the present invention used, the azo group content, etc., but can generally be selected from a wide range. Generally, it is appropriate to adjust the amount of the latter to 111 parts by weight of the former to about 0.5 to 1000 parts by weight. Further, when a solvent or a dispersant is used, the amount used is usually about 1 to 2000 parts by weight per 1 part by weight of the azo group-containing polysiloxane electrode of the present invention.

When the above production is carried out by heating, the reaction temperature is:
Usually about 80-180°C, preferably 50-100°C
It is appropriate to set it as follows, and it may be changed as the polymerization progresses. The reaction time is usually about 1 to 48 hours, preferably 1 to 24 hours.

Further, when the above production is carried out by light irradiation, the heating temperature is usually about 0 to 60'C, preferably about 20 to 60'C.
The reaction time is usually 1 minute to 12 degrees Celsius.
The time period is preferably 80 minutes to 5 hours. As a light source used for light irradiation, for example, a high pressure mercury lamp can be used. The irradiation light is preferably UV light in order to rapidly photodecompose the compound of the present invention and polymerize the vinyl monomer.

Thus, by using the compound of the present invention, vinyl-
Silicone block copolymers are produced very efficiently. The content of polysiloxane segments in the resulting vinyl-silicone block copolymer-ζ can be arbitrarily varied by changing the ratio of the compound of the present invention to the vinyl monomer. It is within the range that each characteristic is imparted and the properties inherent to the vinyl polymer are not impaired, and the specific amount of ζ is usually about 0.1 to 60% by weight in the co-polymerized molecule.

The compound of the present invention can be used very suitably in the production of vinyl-silicone block copolymers as described above, and can also be used as a common radical initiator, I? j It can also be used as a foamable polymer, etc.

Hereinafter, the present invention will be explained in more detail by referring to production examples of the compounds of the present invention as Examples and production examples of various vinyl-silicone block copolymers using the compounds of the present invention as Reference Examples.

9! Example 1 VPO (Vapor Pressure Osmo)
Ql, t with an average molecular weight of 2100 according to
m-cyaelectronopropylboridimethylsiloxane (in the general formula (ma), R2 and R8 are methyl groups, q is &
, m is 26 on average) 21.87F (10,0mM
), triethylamine 2.02F (20.0 mM), and 40 ml of chloroform were placed in a 200 ml four-loop flask equipped with a reflux condenser, a stirrer, a calcium chloride tube, and a thermometer, and thoroughly stirred. While cooling the flask with ice water, 4.4'-azobiscyanopentanoic acid chloride 8.17. f (10,0mM)
A solution consisting of form 4011111 was added dropwise over 40 minutes. After stirring for 2 hours at N temperature, chloroform 800, m
It was diluted by adding Il, transferred to a separating container, added with water, and washed for imitation.

Next, the Sζ chloroform layer was separated, dried with FiL#l sodium, and then dried to dryness at room temperature to give the product 20
．． 98F (yield 87%) was obtained. This product is 1B
-NMR spectrum and infrared absorption spectrum,
It was confirmed that the compound was an azo group-containing polysiloxane amide having the desired polysiloxane segment. The IH-NMR spectrum is shown in FIG. 1, and the infrared absorption spectrum is shown in FIG. 2.

The average molecular weight of the compound of the present invention obtained above was 2.29 based on GPC (gel permeation chromatography). The properties and solubility are shown in Table 8 below.

Examples 2 to 6 The compounds of the present invention shown in Table 2 were obtained in the same manner as in Example 1 using the raw materials and basic catalysts shown in Table 1.

Table 2 Example 7 α,#-diaminopropylpolydimethylsiloxane used in Example 1 7.0Of (8.88mM), triethylamine 0.67F (6.62mM) and RIO.

The form solution was placed in a 100 ml four-flask equipped with a reflux condenser, a stirrer, a calcium chloride tube, and a thermometer, and thoroughly stirred. Cool this flask on ice and add 4#4-azobiscyanopentanoic acid chloride 0.5
8jl (1,67mM) and sebacic acid dichloride 0.
A solution consisting of 4ON (1.67 mM) and chloroform 101F11 was added dropwise over 25 minutes. After stirring at room temperature for 2 hours, 100 ml of chloroform was added, the mixture was transferred to a separating container, water was added thereto, and the mixture was washed by shaking. Next, the chloroform layer was separated, dried over sodium sulfate, and concentrated to dryness at room temperature to obtain product 6.14F (80% yield). This product was confirmed by IH-NMR spectrum and infrared absorption spectrum to be an azo group-containing polysiloxane amide, which is the compound of the present invention having the desired polysiloxane segment.

The average molecular weight of the compound of the present invention obtained above was determined by GPC analysis: Mn = 18000, Mw -42000, Mv'Mn-
It was 2.28. The properties and solubility are shown in Table 8.

Next, Table 8 shows the properties of each of the compounds of the present invention obtained in Examples 1 to 77 and their solubility in various solvents at 111m.・× indicates that it does not dissolve.

Reference Example 1 91 Compound of the present invention obtained in Example 1 4.82fC azo group content 2.0 mM), methyl methacrylate 20.0
f (200F#M) and toluene BOml were placed in four flasks and stirred at 80° for 0.5 hours while blowing dry nitrogen gas. After stirring, a large excess of methanol is added, the resin is separated, and the mixed low molecular weight polysiloxane is removed by Soxhlet extraction with petroleum ether for 24 hours to obtain the desired methyl methacrylate-silicone block copolymer 16. 58F was obtained. The desired product was confirmed by IH-NMR spectrum and GPC.

The polysiloxane segment content of this block copolymer according to IH-NMR spectrum was 4.4% by weight. The polymerization rate of methyl methacrylate calculated from this polysiloxane segment content was 79%. Also,
GPC curve shows a single peak, Mn=47000,
My = 151jυυ, My/Mn = 1.77
Met. The intrinsic viscosity at 80°C is 0 for a benzene solution.
．． It was 88 di/fl. In order to evaluate the water repellency of this block copolymer, the water contact angle (θ) of a cast film prepared from a methylene chloride solution was measured, and it was 67° for the methyl methacrylate homopolymer, whereas this block copolymer The polymer had a remarkable improvement in water repellency of 96°.

Reference Examples 2 to 4 Using the raw materials shown in the fourth table, in the same manner as Reference Example 1,
A block coelectric composite shown in Table 5 was obtained.

Table 4

[Brief explanation of the drawing]

Figure 1 shows 1H-NMR of the compound of the present invention obtained in Example 1.
Spectrum (solvent CDC18, concentration 125”flo,
Figure 2 shows the infrared absorption spectrum of the same sample (measured by applying a methylene chloride solution to a CKBr plate and drying it under reduced pressure). C or higher)

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, each R_1 is the same or different and represents a hydrogen atom, a lower alkyl group, or a nitrile group, and each R_2 are the same or different and represent a hydrogen atom or a lower alkyl group, and each R is the same or different and represents a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group, or a phenyl group. p
and q are the same or different and represent 0 or an integer of 1 to 6, and m represents 0 or an integer of 1 to 200. ] It has a repeating unit represented by
100,000 azo group-containing polysiloxane amide. 2. The azo group-containing polysiloxane amide according to claim 1, which comprises a repeating unit represented by the above general formula (I). 3. The repeating unit represented by the general formula (I) above, and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Y indicates a dibasic acid residue. R_2, R_3, q
and m are the same as above. ] Claim 1 consisting of a repeating unit represented by
The azo group-containing polysiloxane amide described in 2.