JPS58113204A - Manufacture of modified maleimide copolymer - Google Patents

Abstract

PURPOSE:To obtain a novel titled copolymer as a base polymer for curable compositions, by the reaction between an epoxy or hydroxyl group-contg. specific N-substituted maleimide copolymer and a specific unsaturated compound. CONSTITUTION:The objective copolymer can be obtained by the reaction, in a solvent such as dioxane, in the presence of an esterifying catalyst (e.g. triethylbenzylammonium chloride), between (A) an N-substituted maleimide copolymer consisting of two sorts of main chain units of formulaeI(R is H or methyl; R1 is 1-6C alkyl or aromatic) and II (R2 is a group of formula III or -CH2-CHR- OH) respectively, prepared by the copolymerization of an N-substituted maleimide and a (meth)acrylate and (B) an unsaturated compound having an alpha,beta- ethylenic unsaturated group and also an acid or acid derivative group reactive to the epoxy or hydroxyl group in said copolymer (e.g. acrylic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to certain N-substituted maleimide copolymers having epoxy or hydroxyl groups.

By reacting a specific unsaturated compound, the copolymer has α,
The present invention relates to a method for producing a novel modified maleimide copolymer by introducing a β-ethylenically unsaturated group.

The modified maleimide copolymer produced by the method of the present invention has a large number of side chains having α,β-ethylenically unsaturated bonds in the polymer main chain.

It also has excellent solubility in commonly used organic solvents, so it can be used as a base polymer for various curable compositions. It can be cured at room temperature or by heating, and can be cured by energy rays such as radiation and ultraviolet rays, so it is possible to form various molded products or cured films. Alternatively, the cured film exhibits excellent heat resistance and electrical insulation.

(However, R is hydrogen or a methyl group, and R is an alkyl group or aromatic group having 1 to 6 carbon atoms.) 7°, (However, R2 is -〇)I2 0H-OH2 or -(!H2 An N-substituted maleimide copolymer consisting of a main chain unit (2) represented by -(:!HR-OH, υ, R is hydrogen or a methyl group).

An unsaturated group is introduced into the copolymer by reacting the copolymer with an acid group or an acid derivative group capable of reacting with the epoxy group or hydroxyl group in an organic solvent. The present invention relates to a method for producing a modified maleimide copolymer.

The N-substituted maleimide copolymer used in the method of this invention is.

An N-substituted maleimide represented by the general formula (wherein R and R1 are the same as above).

7 General formula OH2= 0R-Co・0-R2(■)(
However, R and R2 are the same as above)) in an organic polar solvent at 9%
It is a polymer or oligomer produced by copolymerizing in the presence of a polymerization initiator at a polymerization temperature of 5 to 150°C, preferably 20 to 120'C, in a homogeneous state, a suspension state, or a bulk state.

Examples of the organic polar solvent include tetrahydrofuran, cyclohexanoyl, dimethylformamide, dioxane, benzene, and methanol.

The polymerization initiator may be any type of polymerization initiator as long as it is capable of addition polymerizing known ethylene monomers.

For example, benzoyl peroxide, lauroyl peroxide.

Organic peroxides such as lame/hydroperoxide, dicumyl peroxide, azo compounds such as azobisisobutyronitrile, triphenylmethylazobenzene, azodibenzoyl, ethyl azobisisobutyrate, n-butyllithium, ethyllithium.

Sodium naphthalene, sodium methoxide.

Examples include polymerization initiators capable of radical polymerization or anionic polymerization such as organic alkali metal compounds such as sodium butoxide.

In the above copolymerization reaction, if necessary, a chain transfer agent such as dodecylmercaptan, thioglycol, butylmercaptan, carbon tetrabromide, etc. may be used to adjust the molecular weight of the copolymer.

In the general formula (2), R1 is a methyl group or an ethyl group.

n-propyl group, isopropyl group, n-butyl group.

Isobutyl group I n-pentyl group, alkyl group having 1 to 6 carbon atoms such as n-hexyl group, or phenyl group, phenylphenyl group, phenyloxyphenyl group,
Or, at least one of the hydrogen atoms directly bonded to the benzene nucleus of the phenyl group is another substituent, such as a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group, hydroxyl group, or alkoxyl group. , an alkoxycarbonyl group, an aromatic group such as a substituted phenyl group substituted with a halogen atom, etc. As R1,
In particular, aromatic compounds such as alkyl groups having 6 to 5 carbon atoms such as n-7" propyl group, n-butyl group, and n-pentyl group, phenyl group, lower alkylphenyl group, hydroxyphenyl group, and lower alkoxyphenyl group, Group groups are preferred.

Examples of the N-substituted maleimide represented by the general formula (1) include N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, N-phenylmaleimide IN (P-methylphenyl)male'fmide, N (m -methylphenyl)maleimide, N-(P
-methoxyphenyl)maleimide F's N-(m-methoxyphenyl)maleimide.

N-(P-hydroxyphenyl)maleimi)", N-(
P-methoxycarbonylphenyl)maleimide, N
-(2,4-dimethylphenyl)maleimide.

Examples include N (315-dimethoxyphenyl)maleimitona.

Examples of the (meth)acrylate compound represented by the general formula (3) having the above-mentioned group Rz (glycidyl or hydroxyalkyl group) include glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Specific examples include propyl acrylate and 2-hydroxypropyl methacrylate.

In the above-mentioned copolymerization reaction, the amounts of the N-substituted maleimide of general formula (1) and the (meth)acrylate compound of general formula (2) to be used are not particularly limited; The amount of each 7mer used is adjusted so that the ratio of N-substituted maleimide/(meth)acrylate compound is 0.5 to 5 times the ratio of main chain unit I/main chain unit ■ of the coalescence. Adjustment is preferred.

In the present invention, the N-substituted maleimide copolymer is not particularly limited in the ratio of main chain units (2) to (2), but the ratio of main chain units (2) to main chain units (2) is.

0.1-10. Preferably, the molar ratio is 0.2 to 5.

Further, in the present invention, the N-substituted maleimide copolymer has an intrinsic viscosity of 0.01 to 3.0 as measured in tetrahydrofuran at 30°C. In particular, it is preferably 0.02 to 2.

In this invention, the unsaturated compound to be reacted with the above-mentioned N-substituted maleimide copolymer has an acid group or acid derivative group capable of reacting with the epoxy group or hydroxyl group in the copolymer, and α, It is an unsaturated compound having a β-ethylenically unsaturated group.

Preferred examples of the acid group of the unsaturated compound include at least one carboxyl group, dicarboxylic anhydride group, etc., and examples of the acid derivative group of the unsaturated compound include a carbo/acid halide group (e.g. , -aoX,
X is a halogen atom such as chlorine, bromine, iodine i)
can be mentioned.

In addition, as the α,β-ethylenically unsaturated group of the unsaturated compound, specifically, an unsaturated group represented by the general formula -00-(!R=OHR, or -Co-CR=OH-C) can be mentioned. In the above general formula, R is hydrogen or a methyl group.

Preferably, the unsaturated compound has a molecular weight of about 500 or less, particularly 400 or less.

Preferred examples of the unsaturated compounds include acrylic acid, methacrylic acid, cinnamic acid, or acid halide compounds thereof, and maleic anhydride, succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Acids or their acid anhydrides and 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Also included are half-ester compounds with hydroxyl group-containing (meth)acrylate compounds such as acrylates, and acid halides of these half-ester compounds.

In the method of this invention, when the above-mentioned N-substituted maleimide copolymer and the above-mentioned unsaturated compound are subjected to two reactions in an organic solvent, an appropriate reaction catalyst 2, for example, an esterification catalyst, is used in the presence of the reaction catalyst. It is preferable to carry out the above-mentioned reaction.

When the main chain unit (■) has a cydyl group).

Catalysts for the above reaction include quaternary ammonium salts such as triethylamine benzyl chloride, tetraethylammonium chloride, trimethylethylammonium iodide, or triethylamine, N,N-diethylaniline, N,N-)ethyl methylaminobenzoate. Preferable examples include 6th-class amines such as -
When the main chain unit (2) has CH2-CHR-OH (hydroxyalkyl), a basic 6th class amine such as triethylamine, tributylamine, dimethylaniline, or pyridine is preferably used as the catalyst for the above reaction. Can be used.

In addition, in the method of this invention, hydroquinone, hydroquinone monomethyl ether, 2.5
-di-tert-butyl-P-cresol, 2,5-
It is preferable to carry out the above reaction by adding a polymerization inhibitor such as di-tertiary-butylhydroquinone.

It varies depending on the material, catalyst, etc., but generally -30 to 150
°C2 is preferably within the range of -20 to 120 °C.

The above reaction temperature was determined by using a copolymer containing a main chain unit (1) having a glycidyl group as the N-substituted maleimide copolymer, using the above-mentioned quaternary ammonium salt as a catalyst, When the substituted maleimide copolymer and the unsaturated compound are reacted, the temperature is preferably 50 to 120°C, particularly preferably 70 to 100°C, and
As the N-substituted maleimide copolymer, a copolymer containing a main chain unit (■) having a hydroxyalkyl group is used,
When a basic compound such as the above-mentioned 6th class amine is used as a catalyst, the temperature is preferably -20 to 40°C, particularly preferably -10 to 20°C.

The organic solvent used in the method of this invention is the same as that used in the copolymerization reaction described above.
, N-diethylacetamide + N-methyl-2-pyrrolidone, dioxane, benzene.

Examples include xylene, methanol, and ethanol.

In the method of this invention, the amount of the unsaturated compound used relative to the amount (A2) of the N-substituted maleimide copolymer corresponds to all the main chain units in the all N-substituted maleimide copolymer. 1 per the amount of N-substituted maleimide copolymer used (X moles) calculated by the following formula to the number of moles (X moles) of the monomer component [(meth)acrylate compound represented by general formula (■)]. It is desirable to use the unsaturated compound in an amount of 10 to 10 times the amount, preferably 1.5 to 5 times the amount.

X: Amount used (mol) of monomer substitution (monomer represented by the general formula (■)) of the N-substituted maleimide copolymer Amount used of the AiN-substituted maleimide copolymer (f) BiN
- Content of the main chain unit (■) in the substituted maleimide copolymer (molti) C: Molecular weight of the monomer represented by the general formula (■) D: Molecular weight of the monomer represented by the general formula (2) According to the method of the present invention,
About 20 units or more of the main chain units (■) in the N-substituted maleimide copolymer, especially about 30 to 99 units, and further about 40 to 95 units,
Degenerate.

It can be a main chain unit (2) to which a side chain having an α,β-ethylenically unsaturated bond is bonded.

Therefore, the modified maleimide copolymer produced by the method of the present invention has the above-mentioned main chain unit "1", main chain unit "1",
and a polymer consisting of main chain units ■.

Alternatively, it is a polymer consisting of main chain unit I and main chain unit ■.

The modified maleimide copolymer produced by the method of this invention includes:

(a) A main chain unit represented by 110 to 80 mos of the main chain unit represented by the general formula (1) (wherein R is hydrogen or a methyl group, and R3 is hydrogen, a methyl group, or a phenyl group) [ [[10 to 80 molar ratio, and (C) general formula (I
A modified maleimide copolymer having a main chain unit of less than 40 moles represented by I) can be suitably shown.

The modified maleimide copolymer obtained by the method of this invention is t
Using a solution of the polymer in tetrahydrofuran, 30°
Determine the specific viscosity η8p when the viscosity measured at C is
The intrinsic viscosity obtained by extrapolating the value of /C (C'; concentration) up to 0% concentration is 0.01 to 4. In particular, Q is about 02 to self.

Furthermore, the modified maleimide copolymer obtained by the method of the present invention has a softening point of 30 to 200°C2, especially 50 to 180°C.
It has high solubility in solvents with a decomposition point of 250 °C or higher.

Are there any examples of this invention below? show.

Synthesis Example 1 [Synthesis of N-substituted maleimide copolymer] Phenylmaleimide 5, O, Of (289 mmot
) 1.1 ooy (6,70 mmot) of 77' Hisia 7'' Tyronitrile (hereinafter abbreviated as AIBN) was added, and after purging the inside of the flask with nitrogen gas, 482 t of tetrahydrofuran (hereinafter abbreviated as THF) was added. A homogeneous solution was obtained.Next, 41. of glycidyl methacrylate (2 sq mmot) was added, and the temperature of the two reaction systems was raised to 60°C, maintained at 60°C, and left in a nitrogen gas atmosphere for 3 hours. 9. Continue stirring the anti-core liquid to perform copolymerization.

A copolymer was produced. Thereafter, the two reaction solutions were cooled to room temperature, and 2.5 liters of ethyl ether was added to the reaction solution to precipitate a copolymer. This copolymer was used to obtain 48.5 y (yield: 53.3% by weight) of an N-substituted maleimide copolymer. This N-substituted maleimide copolymer is calculated based on two-element analysis values, and the content of the main chain unit I is expressed in moles relative to the main chain units (I + I [') in the total polymer (hereinafter referred to as maleimide content). It was +28.6 molti.

Example 1 [Synthesis of modified maleimide copolymer] The copolymer obtained in Synthesis Example 1 was 8.0 pr (the content of all main chain units (■) is expressed as the concentration of the compound represented by the general formula (■): 37 .9 mmot) thermometer, reflux condenser.

Transfer acrylic acid to a 200-proof four-hole round bottom flask equipped with a stirrer and an air blowing tube, dioxane 156f as a solvent, and acrylic acid 7. b4f (106mmot), triethylbenzylammonium chloride (hereinafter referred to as

The acid value of the reaction solution at the start of the test was 34.4, which was 23.5 at the end of the test. Water was slowly added to the reaction solution to precipitate the polymer, and then the polymer was further dissolved in acetone and precipitated with water. This procedure was repeated six times for purification. The obtained polymer was dehydrated as an acetone solution, precipitated with ether, and then dried. 7.15 f of pale yellow crystals were obtained.

The softening point, decomposition point, and intrinsic viscosity of this modified maleimide copolymer are shown in Table 2. Also.

The results of nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and high performance liquid chromatography analysis of this modified maleimide copolymer are shown as charts in FIGS. 1 to 2, respectively.

The softening point of the polymer is a value determined by the capillary method, and the decomposition point of the polymer is determined using a DSC-TGA (differential scanning calorimeter thermogravimetric analysis) device.
It is expressed as the temperature at which weight loss begins during heating.

The intrinsic viscosity [η] is calculated from the viscosity measured at 30°C using a tetrahydrofuran solution of the polymer, and the specific viscosity ηsp
This is the value obtained by extrapolating ηsp/C to the concentration 0eII.

In the nuclear magnetic resonance spectrum (NMR) chart of FIG. 1, the peak at 7 to 8 ppm is related to the phenyl group of the phenylmaleimide group, and the peak around 6 ppm is related to the acryloyl group.

In the infrared absorption spectrum (R) chart in Figure 2, the peak at +810 (WL) is related to the acryloyl group, and the peak at +1780i1 is related to the imide group.The liquid chromatography chart in Figure 3 ( liquid chromatography)
In the chart, one scale on the horizontal axis indicates 2 minutes, R work indicates the oil wetting rate, and UVX indicates the ultraviolet absorbance.

Examples 2 and 3 Using the copolymer obtained in Synthesis Example 1, the reaction was carried out in the same manner as in Example 1, except that methacrylic acid or cinnamic acid was used, under the conditions shown in Table 2. I did it.

, the reaction rate written is based on the epoxy group of the copolymer.

It was calculated from the amount of decrease in alcohol.

Table 2 shows the properties of this modified maleimide copolymer.

In addition, the modified product using methacrylic acid is shown in Figure 4, and the modified product using cinnamic acid is shown in Figure 6.
and Fig. 7, respectively.

Synthesis Examples 2 to 7 Maleimide compounds and unsaturated compounds having the types and amounts shown in Table 1 were copolymerized in the same manner as in Synthesis Example 1 under the conditions shown in Table 1.

The maleimide content of the obtained copolymer is shown in Table 1.

Example 4 Using the copolymer obtained in Synthesis Example 2, a reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 2. The reaction rate and the properties of the obtained modified maleimide copolymer were
Shown in the table. Further, an IR chart is shown in FIG.

Example 5 Using the copolymer obtained in Synthesis Example 6, the properties of the Example 1 copolymer are shown in Table 2. Further, an IR chart is shown in FIG.

Example 6 Using the copolymer obtained in Synthesis Example 4, a reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 2. The reaction rate and the properties of the obtained modified maleimide copolymer were
It is shown in the table. Moreover, the engineering R chart is shown in FIG.

Example 7 Copolymer obtained in Synthesis Example 5 7.0fr (total main chain unit
When the content of is expressed as the concentration of the compound represented by the general formula ■, it is 3
2.4 mmot) was placed in a 1001 four-eye flask equipped with a thermometer, two dropping funnels, a calcium chloride tube, and a stirrer, dissolved in 60 d of tetrahydrofuran, and then cooled to 0°C in a water bath. While continuing to stir, 3.6 y of triethylamine (s5bmmot) was slowly added dropwise thereto, and then 2.93 f of acrylic acid chloride (
32,4 mmot) of tetrahydro 79 years old 30 tnl
j solution was slowly added dropwise over 40 minutes. Stirring was continued in this state for 30 minutes, the temperature was brought to room temperature, and stirring was further continued for 2 hours. After filtering the precipitate, solution F was added to 300 d of 2% HCt aqueous solution to precipitate the polymer. The polymer was further dissolved in acetone and reprecipitated with water, then dehydrated as an acetone solution, and precipitated with ether.

The precipitated polymer was dried to obtain modified maleimide copolymer 1.51 in the form of a white powder.

Table 3 shows the properties of this modified maleimide copolymer.

Moreover, the engineering R chart is shown in FIG.

Note that the reaction rate was determined based on the hydroxyl value of the N-substituted maleimide copolymer and the hydroxyl value of the modified maleimide copolymer.

Example 8 Using the copolymer obtained in Synthesis Example 5 and methacrylic acid chloride, a reaction was carried out in the same manner as in Example 7 under the conditions shown in Table 3.

The properties of the obtained modified maleimide copolymer are shown in Table 3, and the NMR, IR, and liquid chromatograms are shown in Figures #12, 13, and 14, respectively.

Example 9 Using the copolymer obtained in Synthesis Example 6 and methacrylic acid chloride, a reaction was carried out in the same manner as in Example 7 under the conditions shown in Table 3.

The properties of the obtained modified maleimide copolymer are shown in Table 6, and the engineering chart is shown in FIG. 15.

Example 10 Using the copolymer obtained in Synthesis Example 7 and methacrylic acid chloride, a reaction was carried out in the same manner as in Example 7 under the conditions shown in Table 3.

The properties of the obtained modified maleimide copolymer are shown in Table 6, and the NMR and engineering R charts are shown in FIGS. 16 and 17, respectively.

Example 11 Half-esterified mixed solution 2 of phthalic anhydride (1 mol) and 2-hydroxyethyl methacrylate (1.1 mol)
9.2 f (acid compound 106 mmot) and Synthesis Example 1
Copolymer 8f obtained in dioxane 372f, TK
It was reacted in the same manner as in Example 1 with BAC4,09fl MKHQ, 0.4092.

The reaction rate based on the acid value was a'5% + yield 9.02.

It has a softening point of 142-148°C and a decomposition point of 29B'C.

The intrinsic viscosity was 0.132. The engineering R chart of the modified maleimide copolymer obtained is shown in FIG.

Reference Example 1 A photocurable composition consisting of 100 parts by weight of the modified maleimide copolymer obtained in Example 1, 100 parts by weight of trimethylolpropane triacrylate, and 5 parts by weight of benzoin isopropyl ether was prepared. It was applied to a thickness of 30μ on a copper plate. Mercury lamp (sow/cm
) The film that was cured by irradiation with light did not change at all even after being immersed in a 260°C solder bath for 10 seconds, and the temperature at which the amount of electricity began to decrease in TGA (same as above) was 310"C. .

[Brief explanation of drawings]

Figures 1, 12, and 16 show Example 1゜8.1.
FIG. 2 is an NMR chart of a modified maleimide copolymer obtained in Example 0. Figure 2, Figure 4, Figure 6, Figure 8, Figure 9, Figure 10,
11, 13, 15, 17, and 18 are R charts of the modified maleimide copolymers obtained in Examples 1 to 10. Also, FIGS. 3, 5, 7, and 14. 1 is a liquid chromatogram of modified maleimide copolymers obtained in Examples 1 to 6 and Example 8. Patent applicant: Ube Industries, Ltd.

Claims (1)

[Scope of Claims] (However, R is hydrogen or a methyl group, and R1 is an alkyl group or aromatic group having 1 to 6 carbon atoms)6 (However, R2 is 10H2-OH-cHz or =C
An N-substituted maleimide copolymer consisting of a main chain unit (2) represented by H2-0HR-OH, where R is hydrogen or a methyl group. An unsaturated compound having an acid group or acid derivative group capable of reacting with the epoxy group or hydroxyl group in the copolymer and having an α,β-ethylenically unsaturated group is reacted in an organic solvent. A method for producing a modified maleimide copolymer, which comprises introducing an unsaturated group into the copolymer.