JPS634846B2 - - Google Patents

Description

[Detailed description of the invention]

This invention provides a specific N-substituted maleimide copolymer having an epoxy group or a hydroxyl group,
The present invention relates to a method for producing a novel modified maleimide copolymer by reacting a specific unsaturated compound to introduce an α,β-ethylenically unsaturated group into the copolymer. 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, and a commonly used organic Because it has excellent solubility in solvents, it can be used as a base polymer for various curable compositions, and these curable compositions can be cured at room temperature or by heating in the presence of a curing agent. Furthermore, since it can be cured by energy rays such as radiation and ultraviolet rays, various molded products or cured films can be formed, and furthermore, these molded products or cured films have excellent heat resistance. It exhibits electrical conductivity and electrical insulation properties. That is, this invention has the general formula (However, R is hydrogen or a methyl group, and R ₁
is an alkyl group or aromatic group having 1 to 6 carbon atoms), and a main chain unit represented by the general formula (However, R ₂ is

An N-substituted maleimide copolymer consisting of a main chain unit represented by [Formula] or -CH ₂ -CHR-OH, where R is hydrogen or a methyl group), and an epoxy group or hydroxyl group in the copolymer. An unsaturated compound having an acid group or an acid derivative group capable of reacting with the copolymer is reacted with an unsaturated compound having an α,β-ethylenically unsaturated group in an organic solvent to form an unsaturated group in the copolymer. The present invention relates to a method for producing a modified maleimide copolymer, which is characterized by introducing a modified maleimide copolymer. The N-substituted maleimide copolymer used in the method of this invention has the general formula (However, R and R ₁ are the same as above)
N-substituted maleimide represented by the general formula CH ₂ =CR-CO・O-R ₂ () (However, R and R ₂ are the same as above)
A (meth)acrylate compound represented by is added in an organic polar solvent in the presence of a polymerization initiator at a polymerization temperature of
It is a polymer or oligomer produced by copolymerization at ~150°C, preferably at 20-120°C, in a homogeneous state, a suspension state, or a bulk state. Examples of the organic polar solvent include tetrahydrofuran, cyclohexanone, dimethylformamide, dioxane, benzene, and methanol. The polymerization initiator may be of any type as long as it is a known polymerization initiator capable of addition polymerizing ethylene monomers, such as benzoyl peroxide, lauroyl peroxide, and cumene. Hydroperoxide, organic peroxides such as dicumyl peroxide, azo compounds such as azobisisobutyronitrile, triphenylmethylazobenzene, azodibenzoyl, ethyl azobisisobutyrate, n-butyllithium, ethyllithium, sodium naphthalene, sodium methoxy Examples include polymerization initiators capable of radical polymerization or anionic polymerization such as organic alkali metal compounds such as carbon dioxide, sodium butoxide, and the like. In the above copolymerization reaction, if necessary, a chain transfer agent such as dodecyl mercaptan, thioglycol, butyl mercaptan, carbon tetrabromide or the like may be used to adjust the molecular weight of the copolymer. In the general formula, R ₁ is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, Alternatively, a phenyl group, a phenyl phenyl group, a phenyloxyphenyl group, or at least one hydrogen atom directly bonded to the benzene nucleus of the phenyl group has another substituent, such as a methyl group, ethyl group, or propyl group. , a lower alkyl group such as a butyl group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an aromatic group such as a substituted phenyl group substituted with a halogen atom, etc. R ₁
In particular, alkyl groups having 3 to 5 carbon atoms such as n-propyl group, n-butyl group, n-pentyl group, phenyl group, lower alkylphenyl group, hydroxyphenyl group, lower alkoxyphenyl group, etc. aromatic groups are preferred. Examples of the N-substituted maleimide represented by the above general formula include N-propylmaleimide, N-
Butylmaleimide, N-pentylmaleimide, N
-Phenylmaleimide, N-(P-methylphenyl)maleimide, N-(m-methylphenyl)maleimide, N-(P-methoxyphenyl)maleimide, N-(m-methoxyphenyl)maleimide,
N-(P-hydroxyphenyl)maleimide, N
Examples include -(P-methoxycarbonylphenyl)maleimide, N-(2,4-dimethylphenyl)maleimide, and N-(3,5-dimethoxyphenyl)maleimide. Examples of the (meth)acrylate compound represented by the general formula having the aforementioned group R ₂ (glycidyl or hydroxyalkyl group) include glycidyl acrylate, glycidyl methacrylate, 2-
Specific examples include hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. In the above-mentioned copolymerization reaction, the amounts of the N-substituted maleimide of the general formula and the (meth)acrylate compound of the general formula used are not particularly limited, but the amounts used are based on the amount of the N-substituted maleimide copolymer to be produced. It is preferable to adjust the amount of each monomer used so that the ratio of N-substituted maleimide/(meth)acrylate compound is 0.5 to 5 times the ratio of main chain unit/main chain unit. In this invention, the N-substituted maleimide copolymer is not particularly limited in the ratio of main chain units to main chain units, but the ratio of main chain units to main chain units is
The molar ratio may be 0.1 to 10, preferably 0.2 to 5. Further, in the present invention, the N-substituted maleimide copolymer preferably has an intrinsic viscosity of 0.01 to 3, particularly 0.02 to 2, as measured in tetrahydrofuran at 30°C. In this invention, the unsaturated compound to be reacted with the N-substituted maleimide copolymer has an acid group or an acid derivative group capable of reacting with the epoxy group or hydroxyl group in the copolymer, and α, β
- It is an unsaturated compound having an 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 carboxylic acid halide group (e.g. -COX, where X is a halogen atom such as chlorine, bromine, or iodine). In addition, the α,β-ethylenically unsaturated group of the unsaturated compound has the general formula -CO-CR=
CHR, or

Examples include unsaturated groups represented by the formula: 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, and acid halide compounds thereof, and further include maleic anhydride, succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. A half-ester compound of an acid or an acid anhydride thereof and a hydroxyl group-containing (meth)acrylate compound such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, or a half-ester compound thereof Acid halides and the like can also be mentioned. In the method of this invention, when the N-substituted maleimide copolymer and the unsaturated compound are reacted in an organic solvent, in the presence of a suitable reaction catalyst, such as an esterification catalyst. It is preferable to carry out the above-mentioned reaction. The N-substituted maleimide copolymer used in this invention has _R2 as a substituent.

[Formula] When the main chain unit has a glycidyl group, a quaternary ammunium salt such as triethylamine benzyl chloride, tetraethylammonium chloride, trimethylethylammonium iodide, or triethylamine is used as a reaction catalyst. ,N,
Suitable examples include tertiary amines such as N _- diethylaniline and ethyl N _, N-dimethylaminobenzoate; When the main chain unit has OH (hydroxyalkyl), basic tertiary amines such as triethylamine, tributylamine, dimethylaniline, and pyridine can be suitably used as catalysts for the reaction. In addition, in the method of this invention, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,5-di-tert-butyl-P-cresol, and 2,5-di-tert-butyl hydroquinone is added to the reaction system. It is preferable to carry out the reaction described above. In the method of this invention, the reaction temperature between the N-substituted maleimide copolymer and the unsaturated compound varies depending on the reaction raw materials, catalyst, etc., but generally -30 to
The temperature is 150°C, preferably about -20 to 120°C. The above reaction temperature is determined by using a copolymer containing a main chain unit having a glycidyl group as an N-substituted maleimide copolymer, using the above quaternary ammonium salt as a catalyst, When the maleimide copolymer and the unsaturated compound are reacted, the temperature is preferably 50 to 120°C, particularly preferably 70 to 100°C, and the N-substituted maleimide copolymer has a hydroxyalkyl group When a copolymer containing main chain units is used and a basic compound such as the above-mentioned tertiary amine is used as a catalyst, the temperature is -20 to 40°C, particularly preferably -10 to 20°C. It is preferable that there be. The organic solvent used in the method of this invention is
The same solvents used in the copolymerization reactions described above can be used, for example, tetrahydrofuran, cyclohexanone, N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, dioxane, benzene, xylene, methanol, ethanol and the like. In the method of the present invention, the amount of the unsaturated compound used relative to the amount (Ag) of the N-substituted maleimide copolymer corresponds to all the main chain units in the all N-substituted maleimide copolymer. With respect to 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 the general formula], 1 to 10 times molar, preferably
It is desirable that the amount of the unsaturated compound used is 1.5 to 5 times the mole. X: Amount used (mol) of monomer substitution (monomer represented by the general formula) of the N-substituted maleimide copolymer A: Amount used (g) of the N-substituted maleimide copolymer B: N-substituted maleimide copolymer Content (mol%) of main chain units in the N-substituted maleimide copolymer C: Molecular weight of the monomer represented by the general formula D: Molecular weight of the monomer represented by the general formula According to the method of the present invention, the main chain units in the N-substituted maleimide copolymer Approximately 20% or more of the chain units, especially 30~
99% and then 40 to 95% are denatured to form α and β
- It can be a main chain unit to which a side chain having an ethylenically unsaturated bond is attached. Therefore, the modified maleimide copolymer produced by the method of the present invention is the aforementioned main chain unit, a polymer consisting of a main chain unit and a main chain unit, or a polymer consisting of a main chain unit and a main chain unit. It is. The modified maleimide copolymer produced by the method of the present invention includes: (a) 10 to 80 mol% of main chain units represented by the general formula () (b) General formula or (However, R is hydrogen or a methyl group,
R ₃ is hydrogen, methyl group or phenyl group)
10 to 80 mol% of main chain units represented by (c) 40 mol% of main chain units represented by general formula ()
The following modified maleimide copolymers can be suitably shown. For the modified maleimide copolymer obtained by the method of this invention, the specific viscosity η _sp is determined from the viscosity measured at 30°C using a tetrahydrofuran solution of the polymer, and the value of η _sp /C (C; concentration) is calculated. , the intrinsic viscosity obtained by extrapolating to a concentration of 0% is 0.01 to 4, especially,
It is about 0.02 to 3. Furthermore, the modified maleimide copolymer obtained by the method of this invention has a softening point of 30 to 200°C, particularly 50 to 200°C.
The temperature is about 180℃, and the decomposition point is 250 to 350℃, especially
It has a temperature of about 260 to 340°C, is powdery at normal room temperature (20°C), and has high solubility in various solvents. Examples of the present invention will be shown below. Synthesis Example 1 [Synthesis of N-substituted maleimide copolymer] Capacity 1 equipped with a reflux condenser, stirrer, and thermometer
Phenylmaleimide in a three-necked round-bottomed flask.
50.5g (289mmol) and 1.100g (6.70mmol) of azobisisobutyronitrile (hereinafter abbreviated as AIBN)
After replacing the inside of the flask with nitrogen gas,
Furthermore, tetrahydrofuran (hereinafter abbreviated as THF)
482 ml was added to make a homogeneous solution, then 41.0 g (289 mmol) of glycidyl methacrylate was added, and the temperature of the reaction system was raised to 60°C and maintained at 60°C for 3 hours in a nitrogen gas atmosphere. While stirring the reaction solution, copolymerization was carried out to produce a copolymer. Thereafter, the reaction solution was cooled to room temperature, and the reaction solution was added to 2.5 ml of ethyl ether to precipitate a copolymer. This copolymer was dissolved again in tetrahydrofuran, poured into ethyl ether again, and purified by reprecipitation to obtain 48.5 g (yield: 53.3% by weight) of an N-substituted maleimide copolymer as a white powder. This N-
For the substituted maleimide copolymer, the content of the main chain unit (hereinafter referred to as maleimide content) in mol% relative to the main chain unit (+) in the total polymer calculated from the elemental analysis value was 28.6 mol%. . Example 1 [Synthesis of modified maleimide copolymer] 8.0 gr of the copolymer obtained in Synthesis Example 1 (37.9 mmol when the content of all main chain units is expressed as the concentration of the compound represented by the general formula) was A 200 ml four-necked round bottom flask equipped with a reflux condenser, a stirrer and an air blowing tube was charged with 156 g of dioxane as a solvent.
7.64 g (106 mmol) of acrylic acid, 1.72 g of triethylbenzyl ammonium chloride (hereinafter abbreviated as TEBAC), and 0.172 g of hydroquinone monomethyl ether (hereinafter abbreviated as MEHQ) were added to make a homogeneous solution, and the mixture was heated to 90% while blowing air.
The reaction was carried out at ℃ for 5 hours. The acid value of the reaction solution at the start of the reaction was 34.4, but at the end it was 23.5. 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 three times for purification. The obtained polymer was dehydrated as an acetone solution, precipitated with ether, and then dried. 7.15g of pale yellow crystals
I got it. The softening point, decomposition point and intrinsic viscosity of this modified maleimide copolymer are shown in Table 2. Further, the results of nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and high performance liquid chromatography analysis of this modified maleimide copolymer are shown in chart diagrams in FIGS. 1 to 3, respectively. The softening point of the polymer is the value determined by the capillary method, and the decomposition point of the polymer is the value determined by the DSC-
Using a TGA (Differential Scanning Calorimeter Thermogravimetric Analysis) device, the temperature at which weight loss began during heating was indicated. The intrinsic viscosity [η] is a value determined by determining the specific viscosity η _sp from the viscosity measured at 30° C. using a tetrahydrofuran solution of the polymer, and extrapolating η _sp /C to a concentration of 0%. In the nuclear magnetic resonance spectrum (NMR) chart shown in Figure 1, the peak at 7 to 8 ppm is related to the phenyl group of the phenylmaleimide group,
The peak around 6 ppm is related to acryloyl groups. Infrared absorption spectrum (IR) in Figure 2
In CHART, the peak at 810 cm ^-1 is related to an acryloyl group, and the peak at 1780 cm ^-1 is related to an imide group. In the liquid chromatography chart in Figure 3, 1 on the horizontal axis
The scale indicates 2 minutes, RI indicates refractive index, and UV indicates 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. In addition, the reaction rate was determined from the amount of acid decreased relative to the epoxy groups of the copolymer. The properties of this modified maleimide copolymer are shown in Table 2, and the IR and liquid clots are shown in Figures 4 and 5 for the modified product using methacrylic acid, and Figures 6 and 7 for the modified product using cinnamic acid. Each is shown in the figure. 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, Example 1
The reaction was carried out in the same manner as in Table 2 under the conditions shown in Table 2. Table 2 shows the reaction rate and the properties of the modified maleimide copolymer obtained. The IR chart is shown in Figure 8. Example 5 Using the copolymer obtained in Synthesis Example 3, Example 1
The reaction was carried out in the same manner as in Table 2 under the conditions shown in Table 2. Table 2 shows the reaction rate and the properties of the modified maleimide copolymer obtained. The IR chart is shown in Figure 9. Example 6 Using the copolymer obtained in Synthesis Example 4, Example 1
The reaction was carried out in the same manner as in Table 2 under the conditions shown in Table 2. Table 2 shows the reaction rate and the properties of the modified maleimide copolymer obtained. The IR chart is shown in Figure 10. Example 7 7.0 gr of the copolymer obtained in Synthesis Example 5 (32.4 mmol when the content of all main chain units is expressed as the concentration of the compound represented by the general formula) was placed in a thermometer, dropping funnel, calcium chloride tube, and stirring. The mixture was placed in a 100 ml four-necked flask equipped with a vacuum cleaner, dissolved in 60 ml of tetrahydrofuran, and then cooled to 0°C in an ice bath. While continuing to stir, add 3.6 g (35.6 mmol) of triethylamine.
Slowly dropwise add 2.93 g (32.4 mmol) of acrylic acid chloride and 30 g of tetrahydrofuran.
ml solution was slowly added dropwise over 40 minutes. Stirring was continued for 30 minutes in this state, the temperature was brought to room temperature, and stirring was further continued for 2 hours. After filtering out the precipitate, reduce the liquid to 2%
It was added to 300 ml of HCl aqueous solution to precipitate the polymer. The polymer is further dissolved in acetone and reprecipitated with water, and then dehydrated as an acetone solution.
Precipitation was carried out with ether. The precipitated polymer was dried to obtain 1.5 g of a modified maleimide copolymer in the form of a white powder. The properties of this modified maleimide copolymer are shown in Table 3, and the IR chart is shown in FIG. The reaction rate was determined from 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, the third
The reaction was carried out under the conditions shown in the table. The properties of the obtained modified maleimide copolymer were
In addition, NMR, IR, and liquid chromatograms are shown in the table and in FIGS. 12, 13, and 14, respectively. Example 9 Using the copolymer obtained in Synthesis Example 6 and methacrylic acid chloride, the third
The reaction was carried out under the conditions shown in the table. The properties of the obtained modified maleimide copolymer were
The table and IR chart are shown in Figure 15. Example 10 Using the copolymer obtained in Synthesis Example 7 and methacrylic acid chloride, the third
The reaction was carried out under the conditions shown in the table. The properties of the obtained modified maleimide copolymer were
The table also includes NMR and IR charts.
and Fig. 17, respectively. Example 11 29.2 g (106 mmol of acid compound) of a mixed solution of a half-esterified product of phthalic anhydride (1 mol) and 2-hydroxyethyl methacrylate (1.1 mol) and 8 g of the copolymer obtained in Synthesis Example 1 were added to 372 g of dioxane. ,
A reaction was carried out in the same manner as in Example 1 with 4.09 g of TEBAC and 0.409 g of MEHQ. The reaction rate based on the acid value was 83%, the yield was 9.0g, the softening point was 142-148℃,
It had a decomposition point of 298°C and an intrinsic viscosity of 0.132.
An IR chart of the obtained modified maleimide copolymer is shown in FIG. Reference example 1 Modified maleimide copolymer obtained in Example 1
A photocurable composition consisting of 100 parts by weight, 100 parts by weight of trimethylolpropane triacrylate, and 5 parts by weight of benzoin isopropyl ether was prepared, and this composition was coated on a copper plate to a thickness of 30 μm. The film cured by irradiation with light from a mercury lamp (80W/cm) did not change at all even when immersed in a solder bath at 260°C for 10 seconds, and the temperature at which weight loss started at TGA (same as above) was 310°C. It was warm at ℃.

【table】

【table】

【table】 [Brief explanation of the drawing]

Figures 1, 12 and 16 show the modified maleimide copolymers obtained in Examples 1, 8 and 10.
It is an NMR chart. Figure 2, Figure 4, Figure 6
Fig. 8, Fig. 9, Fig. 10, Fig. 11, Fig. 1
Figure 3, Figure 15, Figure 17, and Figure 18 show the IR of the modified maleimide copolymers obtained in Examples 1 to 10.
It's a chat. Also, Figure 3, Figure 5, Figure 7
14 are liquid charts of the modified maleimide copolymers obtained in Examples 1 to 3 and Example 8.

Claims (1)

[Claims] 1. General formula (However, R is hydrogen or a methyl group, and R ₁
is an alkyl group or aromatic group having 1 to 6 carbon atoms), and a main chain unit represented by the general formula (However, R ₂ is [Formula] or -CH ₂ -CHR-OH, and R is hydrogen or a methyl group.) An N-substituted maleimide copolymer consisting of a main chain unit represented by: An unsaturated compound having an acid group or an acid derivative group capable of reacting with the epoxy group or hydroxyl group in the compound and having an α,β-ethylenically unsaturated group is reacted with the unsaturated compound in an organic solvent. A method for producing a modified maleimide copolymer, which comprises introducing an unsaturated group into the polymer.