JPH0273829A - Maleimide based polymer having peroxy bond in molecule - Google Patents

Abstract

PURPOSE:To obtain the title polymer having excellent heat resistance and suitable as a precursor of block copolymer, modifier of other resin, etc., by copolymerizing a maleimide compound with a polymeric peroxide. CONSTITUTION:The aimed polymer obtained by reacting (A) a maleimide compound consisting of a constitutional unit expressed by formula I (R1 and R2 are H, methyl, etc.) with (B) a polymeric peroxide consisting of a constitutional unit expressed by formula II (R4 is 2-10C alkylene; R5 is 2-10C alkylene, etc.) or a constitutional unit expressed by formula III (R6 is formula IV etc.; R7 is 2-10C alkylene, etc.) or a constitutional unit expressed by formula V (R8 is 2-10C alkylene, etc.; R9 is formula VI) and containing a peroxy bond e.g., at 40-120 deg.C and composed of 90-9.9wt.% component A and 0.1-10wt.% component B and having 1700-530000 viscosity-average molecular weight.

Description

[Detailed Description of the Invention] <Field of Application in Industry> The present invention relates to a maleimide-based polymer having peroxy bonds in the molecule, and more specifically, to a maleimide-based block copolymer precursor having excellent heat resistance. This invention relates to a novel maleimide polymer having a peroxy bond in the molecule, which can be used as a modifier for other resins.

<Prior Art> Vinyl polymers having peroxy bonds in the molecule are described by Sugizai et al., Wangka Shi, Vol. 69, p. 718 (1966).

Polystyrene has peroxy bonds within the molecule.

Furthermore, Japanese Patent Publication No. 14567/1987 discloses polystyrene, polyvinyl acetate, polymethacrylic acid ester, polyvinyl chloride, etc., each having a peroxy bond in the molecule.

However, the above-mentioned publications do not disclose anything about maleimide polymers.

<Problems to be Solved by the Invention> The objects of the present invention are to provide a material that is easy to handle, has excellent heat resistance, and
Another object of the present invention is to provide a maleimide polymer having a peroxy bond in its molecule, which can be used as a 1) precursor of a maleimide block copolymer and as a modifier for other resins.

<Means for Solving the Problems> According to the present invention, the following: or a branched alkyl group, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituted aryl group.)
90 to 99.9% by weight of structural units represented by the following three general formulas (II) to (TV) (wherein R4 represents an alkylene group having 2 to 10 carbon atoms,
<, is an alkylene group having 2 to 10 carbon atoms, -CH2CH□
0C(1□C]12- or -CI, CH20CH2CH
20C1 (indicates 2C11□-).

(In the formula, R5 is -C(CH,)z C1l□CH2C(C
I, )2-1-C(CH3)2-O-C(CH,)2
-1R7 represents an alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, or a phenylene group. ) and (in the formula, R represents an alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, or a phenylene group, and ■<.

is -C(CH2)2 CH2CH2C(CHz )2-
1-C(CH,)2-O-C(CH,, Roux, C(CH
s) z-OC(CH3)2-. ) of the group consisting of
A maleimide polymer having a peroxy bond in the molecule, comprising 0.1 to 10% by weight of a structural unit containing a peroxy bond selected from one species or two or more types, and having a viscosity average molecular weight of 1,700 to 530,000. is provided.

This will be explained in more detail below.

Male-c (c) having a peroxy bond in the molecule of the present invention
x-r,)2-■-c(c■-r,),-, and the imide polymer is a maleimide compound structural unit (hereinafter T:
It is abbreviated as MIC. ) and a specific polymeric peroxide structural unit (hereinafter abbreviated as PMPOC) in a specific ratio.

The above-mentioned MIC used in the present invention can be represented by the following - killing (I), K.

(In the formula, R1 and R2 each represent a hydrogen atom, a halogen atom, or a methyl group, and R3 is a C1-C18 alkyl group, a C3-10 cycloalkyl group, a C6-18 aryl group, or a substituted aryl group) In this case, if R1 is an alkyl group having 19 or more carbon atoms, a cycloalkyl group having 11 or more carbon atoms, a 7-aryl group having 19 or more carbon atoms, or a substituted aryl group, production will be difficult. Cannot be used. Examples of monomers that form the MIC shown in -killing (1) include N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-1-propylmaleimide, N- A group consisting of t-butylmaleimide, N-dodecylmaleimide, N-octadecylmaleimide, N-phenylmaleimide, N-2-methylphenylmaleimide, N-3-isopropylphenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. Preferred examples include compounds or mixtures selected from one or more of the following.

The PMPOC used in the present invention has the following - killing (If)
, (I[I) or (IV), in which R
4 represents an alkylene group having 2 to 10 carbon atoms.

R9 is an alkylene group having 2 to 10 carbon atoms, C)I, CIl
, 0CR2CH, - or -CH2CH20CH2CH2
Indicates 0cH2CH,-. Also, R6 is -C(CI(i)
zCH2CH2C(CHa)z-1-c(cH,>z-
O-c<crr3)2-1C(CR3)z @C(C
H3) represents z-, and R7 represents an alkylene group, a cyclohexylene group, or a phenylene group in which m has a prime number of 2 to 10. Further, in the formula, R, C represents an alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, or a phenylene group, and R9 represents C(CI,
), CH2Cl1□c(CI3')2-1c(cr
r,)2-O-c(cHJ)2-1 has good polymerizability with the drying agent, and the peroxy group can exist thermally stably in the resulting maleimide polymer. . Furthermore, since it also plays a role as a polymerization initiator,
It also has excellent polymerization initiation efficiency.

I] MPO used in the present invention, denoted by the above-denoted (n)
C is diacyl type, for example, Japanese Patent Publication No. 62-14567
It can be manufactured by the method described in the above publication. Examples of the diacyl polymeric peroxide include c(cr(,)z-■-c(cIia)z-.

Said - Extermination (IT) - (IV) PMP expressed by Te
The monomer forming ○C is the maleimide compound (n=
Indicates a positive number from 2 to 20. ) etc. can be preferably mentioned.

In addition, P represented by the above-mentioned -killing (I[r)] used in the present invention
MPOC is an ester type and can be produced, for example, by a method in which dibasic acid dichloride and alkylene dihydroperoxide are reacted in the presence of an aqueous sodium hydroxide solution. Preferred examples of the M ester type polymeric peroxide include (n = a positive number of 2 to 20).

Further, the PM represented by -killing (IV) used in the present invention
POC is a carbonate type and can be produced by, for example, reacting a dihydric alcohol with phosgene, and specifically, by reacting an alkylene dichloroformate with a dihydroperoxide in the presence of an aqueous sodium hydroxide solution. It can be obtained by a method etc. Preferred examples of the carbonate 1-type polymeric peroxide include the following.

The maleimide polymer having a peroxy bond in the molecule of the present invention has the above-mentioned MIC, PMPOC shown by the above-mentioned -Sakatsu HI), and PMPO shown by the above-mentioned -Sakatsu (III).
C and PMPOC selected from one or more of the group consisting of PMPOC represented by -killing (IV), wherein the selection of the PMPOC is based on the 10-hour half-life temperature of the peroxy bond ( This is carried out at a temperature at which the concentration of peroxy groups becomes half after 10 hours, based on the index of thermal decomposition rate of peroxy groups), solubility, etc.

In addition, when producing a block polymer by polymerizing other vinyl monomers using the maleimide polymer having a peroxy bond in the molecule of the present invention, the preferable peroxy bond, that is, the 10-hour half-life temperature and polymerization initiation efficiency are also taken into consideration. selected. The respective gold content ratios of the MIC and PMPOC are C90-99,9 by weight, and PMPOC0,1
The proportion is ~10% by weight. At this time, if the MIC content exceeds 99.9% by weight, that is, if the PMPOC content is less than 0.1% by weight, the PMPOC content is too small.

Cannot be used as a precursor or modifier for block copolymers. Further, when the content of MIC is less than 90% by weight, that is, when the content of PMPOC exceeds 10% by weight, the concentration of PMPOC becomes high, creating a handling hazard and reducing storage stability.

In order to investigate the content of MIC and PMPOC, the total nitrogen content in the obtained maleimide polymer having peroxy bonds in the molecule is measured by the Kerbourg method, etc., and the content of MIC and activity The content of PMPOC can be determined by measuring the amount of oxygen by iodometry or the like.

The viscosity average molecular weight of the maleimide polymer having peroxy bonds in the molecule of the present invention is in the range of 1,700 to 530,000. In this case, if the viscosity average molecular weight is less than 1,700, the molecular weight per molecular weight will decrease and it will not be a precursor for producing a block copolymer with excellent heat resistance, which is not preferable, and if it exceeds 530,000, This is not preferred because the solubility in the solvent decreases and it becomes difficult to remove impurities. The viscosity average molecular weight defined in the present invention is the viscosity average molecular weight in terms of polystyrene determined from the intrinsic viscosity.

In other words, the viscosity average molecular weight is determined from the intrinsic viscosity ('1.) by the following formula (1), and the intrinsic viscosity number is 0.02 to 1.6.
is polystyrene equivalent viscosity average molecular weight 1700-530
Corresponds to 000.

(n)=K・(-Mv)'...(1
) (is a constant in the formula, K X 10103 (100
/g)=0.0716. Further, α=9.76 is the numerical value of polystyrene in a chloroform solution at 25°C. ) ("Polymer Handbook" 2nd edition IV-17, published by Wiley Interscience).

In the present invention, the viscosity average molecular weight of the obtained maleimide polymer can be determined by gel permeation chromatography (
GPC) and the like.

The maleimide polymer having peroxy bonds in the molecule of the present invention can be produced by known polymerization methods such as solution polymerization, suspension polymerization, and bulk polymerization. Specifically, the MIC monomer and the PMPOC
Monomers, preferably at a polymerization temperature of 40 to 120°C and a polymerization time of 3 to 20 hours. The amounts of the MIC monomer and PMPOC monomer at this time are based on 100 parts by weight of the MIC monomer.

Preferably, the amount of PMPOC monomer is from 0.2 to 30 parts by weight, particularly preferably from 0.5 to 20 parts by weight. Said PM
If the amount of POC monomer charged is less than 0.2 parts by weight, the polymerization rate will drop significantly and the concentration of peroxy groups in the maleimide polymer having peroxy bonds in the produced molecules will be low, which is not preferable. If it exceeds 30 parts by weight, the peroxy group concentration will be too high and the monopolymerization reaction may run out of control, which is not preferable.

<Effects of the Invention> The maleimide polymer having a peroxy bond in the molecule of the present invention is composed of MIC with high heat resistance and PMPOC with radical polymerization initiating ability, so it has excellent safety, storage stability, and ease of handling. It has excellent properties and can be used as a precursor for maleimide block copolymers and as a modifier for other resins.

<Examples> The present invention will be explained in more detail below using reference examples and examples, but the present invention is not limited thereto.

A fourth flask equipped with a thermometer and a stirrer was charged with 183 parts of adipic acid chloride and 75 parts of triethylene glycol. The mixture was then stirred at 20° C. for 60 minutes under a nitrogen gas stream to obtain 210 parts of triethylene glycol bis(adipoyl chloride) as a viscous colorless liquid.

Next, 50% hydrogen peroxide solution and 420 parts of 10% sodium hydroxide solution were placed in a four-bottle flask equipped with a thermometer, a stirrer, and a dropping funnel, and 11 parts of the sodium peroxide solution was added.
Manufactured. Thereafter, while stirring vigorously and keeping the reaction temperature at 5° C., 176 parts of the previously prepared triethylene glycol bis(adipoyl chloride) was added dropwise over 20 minutes.

When stirring was continued for 30 minutes, a white solid was produced.

This was filtered, washed twice with IQ cold water, and then vacuum dried to obtain 140 parts of a white powder. The molecular weight of the obtained white powder was measured using a vapor pressure equilibrium molecular weight measuring device (manufactured by Hitachi, Ltd.).
2340 (n
The valve was 5.8). The amount of active oxygen measured by iodometry was 2.19%. Therefore, the purity is 99.5%
Met. In addition, the infrared absorption spectrum is 1725 cm-”
The absorption of the carbonyl group of the ester group is 1.780.

Absorption of the carbonyl group of the diacyl group was observed at 1805as-'', and absorption of the peroxy group was further observed at 875ai-''.

111 A fourth flask equipped with a thermometer, a stirrer, and a Dimroth condenser was charged with 250 parts of a 0.5% by weight aqueous polyvinyl alcohol solution. Next, cyclohexylmaleimide 8
0 parts and 10 parts synthesized in Reference Example 1 were dispersed and charged in 20 parts of methyl ethyl ketone. Next, polymerization was carried out at 75° C. for 3 hours while stirring while purging the inside of the reactor with nitrogen gas.

The produced polymer was taken from house to house, washed with water, dissolved in chloroform, and then poured into lower leaves of methanol to precipitate the polymer. This was delivered to each house and dried under vacuum to obtain 76 parts of a white powder polymer.

The intrinsic viscosity [1] of the obtained cyclohexylmaleimide polymer was measured at 25° C. in chloroform and found to be 0.374, and the viscosity average molecular weight in terms of polystyrene was 78,000. The amount of active oxygen determined by iodometry was 0.23%. Therefore, the content ratio of the constituents containing peroxy groups introduced into the molecule is:
It was found to be 5.9%. In addition, as a result of measuring the infrared absorption spectrum, 1805■-1 and 1780an-'
In 17QQan-', absorption of the carbonyl group by the diacylperoxy group of the polymeric peroxide was observed, and absorption of the carbonyl group of the maleimide group was observed in 17QQan-'. From the above, it was found that this polymer was polycyclohexylmaleimide having a peroxy bond in the molecule. FIG. 1 shows the I chart of the obtained product, and Table 1 shows the reaction conditions and measurement results.

1. Type and amount of maleimide compound and polymeric peroxide 1 A maleimide polymer was prepared in the same manner as in Example 1, except that the polymerization temperature and time were changed. Table 1 shows the conditions and measurement results.

40 parts of benzylmaleimide in 4 flasks equipped with a loss thermometer, a stirrer, and a reflux condenser.

10 parts and 300 parts of tetrahydrofuran were charged, and the reaction was carried out at 60° C. for 3 hours while stirring and purging the system with nitrogen gas. The polymerization solution was poured into methanol in a large pot to precipitate a polymer. The mixture was then separated in a furnace and dried under vacuum to obtain 32 parts of white powder.

The intrinsic viscosity (female) of the obtained benzylmaleimide polymer was measured in chloroform at 25°C and found to be 0.22.
5, and the polystyrene equivalent viscosity average molecular weight is 4000
It was 0. The amount of active oxygen determined by iodometry was 0.44%.

As a result of measuring the infrared absorption spectrum, 1805.178
Absorption of the carbonyl group of the diacyl group of the polymeric peroxide was observed at 0(ff-') and absorption of the carbonyl group of the imide ring at 1700an-'. From the above, this white polymer is a benzylmaleimide having a peroxy bond in the molecule. It turned out to be a polymer.

Table 2 shows the reaction conditions and each measurement result.

A maleimide polymer was prepared in the same manner as in Example 4, except that the types and amounts of the maleimide compound, polymeric peroxide, and solvent, polymerization temperature, and polymerization time were changed.

Conditions and measurement results are shown in Table 2-2q. Yutaka 11-kuni [Production of cyclohexylmaleimide-styrene block copolymer] 0.5% polyvinyl alcohol was placed in a fourth flask equipped with a thermometer, stirrer, and reflux condenser. 300 parts of an aqueous solution was charged, and then a solution in which 20 parts of the polycyclohexylmaleimide produced in Example 1 and having a peroxy bond in the molecule was dissolved in 80 parts of styrene monomer was charged. The polymerization reaction was carried out at 570° C. for 8 hours while stirring while purging the inside of the reactor with nitrogen gas. The produced white powder was delivered to each house, washed with water, and then vacuum dried. The weight of the obtained polymer was 88 parts.

Next, the resulting hot cyclohexane was extracted for 12 hours to separate the styrene homopolymer, and the infrared absorption spectrum was measured. As a result, the absorption of the carbonyl group of the imide ring was at 1700Ql-'1450(!l). −
” absorption of carbon-hydrogen vibration of phenyl group was observed.

Therefore, it was found that the obtained polymer was a cyclohexylmaleimide-styrene block copolymer, and its blocking efficiency was 678% of the extraction residue.

[Brief explanation of the drawing]

FIG. 1 is a chart showing the JR of the maleimide polymer having peroxy bonds in the molecule produced in Example 1.

Claims (1)

[Claims] The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼... (I) (In the formula, R_1 and R_2 each represent a hydrogen atom, a halogen atom, or a methyl group, and R_3 is a carbon 90 to 99.9 weight structural units represented by a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituted aryl group. % and the following three general formulas (II) to (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R_4 represents an alkylene group having 2 to 10 carbon atoms,
R_5 is an alkylene group having 2 to 10 carbon atoms, -CH_2C
H_2OCH_2CH_2- or -CH_2CH_2O
CH_2CH_2OCH_2CH_2- is shown. ), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_6 is -C(CH_3)_2CH_2CH_2
C(CH_3)_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_7 is a carbon number of 2 to 10 Indicates an alkylene group, a cyclohexylene group, or a phenylene group. ) and ▲Mathematical formulas, chemical formulas, tables, etc.▼...(IV) (In the formula, R_8 represents an alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, or a phenyl group, and R_9 represents -C
(CH_3)_2CH_2CH_2C(CH_3)_2
−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. 0.1 to 10% by weight of a structural unit containing a peroxy bond selected from one or more of the group consisting of
A maleimide polymer having a peroxy bond in the molecule, characterized by having a viscosity average molecular weight of 1,700 to 530,000.