JP3127487B2 - New maleimide polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This onset BACKGROUND OF THE is capable of application to various fields, the polymer having a maleimide derivative unit of the present invention is excellent in heat resistance, can be used molded articles, in films wide range of fields. Further, it can be used as a gas separation membrane, a resist material, or a reactive polymer.

[0002]

2. Description of the Related Art Maleimide derivatives such as phenylmaleimide and cyclohexylmaleimide have been used in ABS and vinyl chloride as heat-resistance imparting agents for resins.
Also, hydroxyphenylmaleimide is being studied as a resist material.

[0003]

An object of the present invention is to provide a is to provide heat resistant modifier resin, and useful novel Ma <br/> Reimi de polymeric resist material.

[0004]

Means for Solving the Problems In view of this problem, the present inventors have conducted intensive studies, and as a result, have found a novel maleimide polymer . That is, the present invention relates to polymer comprising repeating units of maleimide induction having a novel N-Si bonds. Here, the maleimide derivative having an N-Si bond is a compound having a structure represented by the following formula (1), and includes N-trimethylsilylmaleimide, N-ethyldimethylsilylmaleimide, N-butyldimethylsilylmaleimide, -Tert-butyldimethylsilylmaleimide, N-dimethylsexylmaleimide and the like.

[0005]

Embedded image (Where R ₁ , R ₂ , and R ₃ are each hydrogen, and have 1 to 12 carbon atoms.
An alkyl group, an alkoxyl group having 1 to 12 carbon atoms,
The aromatic groups of the formulas 6 to 12 are shown. The maleimide derivative used in the present invention can be used in various fields. In particular, the polymer having the maleimide derivative unit of the present invention has excellent heat resistance and can be used for various molded articles and films. Available,
It can be used as a gas separation membrane, a resist material, a reactive polymer, a precursor of a brominating reagent, and a compatibilizer for various resins.

The polymer of the present invention is a polymer having a repeating unit represented by the following general formula (2), and is composed of a homopolymer of a maleimide derivative and another vinyl monomer copolymerizable therewith. It is a copolymer.

[0007]

Embedded image (Where R ₁ , R ₂ , and R ₃ are each hydrogen, and have 1 to 12 carbon atoms.
An alkyl group, an alkoxyl group having 1 to 12 carbon atoms,
The aromatic groups of the formulas 6 to 12 are shown. If the content of the repeating unit represented by the general formula (2) in the copolymer is less than 5 mol%, heat resistance and gas separation properties are undesirably reduced.

[0008] Other copolymerizable vinyl monomers include styrene, α-methylstyrene, vinyltoluene,
1,3-butadiene, isoprene and halogen-substituted derivatives thereof, methacrylates such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid Acrylic esters such as butyl, cyclohexyl acrylate, phenyl acrylate and benzyl acrylate; vinyl esters such as vinyl acetate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and the like Vinyl ethers, vinyl chloride, vinylidene chloride, maleic anhydride,
N-phenylmaleimide, N-carboxyphenylmaleimide, acrylonitrile, ethylene, propylene,
One or more compounds selected from -butene, 2-butene, isobutene, 1-hexene and the like. The polymerization of these monomers is carried out by a known polymerization method, for example, a bulk polymerization method,
Any of solution polymerization, suspension polymerization and emulsion polymerization can be employed.

Examples of the polymerization initiator include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, tert-butyl peroxy acetate. And organic peroxides such as tert-butyl peroxybenzoate and 2,2′-azobis (2,
4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1 ' Azo initiators such as -azobis (cyclohexane-1-carbonitrile) can be used. Further, as the anionic polymerization initiator, an organic metal compound such as butyllithium and naphthalene sodium can be used.

Solvents usable in the solution polymerization method include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide,
Isopropyl alcohol, butyl alcohol and the like can be mentioned.

[0011] The polymerization temperature in the radical polymerization can be appropriately set according to the decomposition temperature of the initiator, but is generally preferably in the range of 40 ° C to 150 ° C.

The resin obtained in the present invention may contain, if necessary, a heat stabilizer such as hindered phenol or an organic phosphate, a benzotriazole type ultraviolet absorber, a hindered amine type ultraviolet stabilizer, Various lubricants, various fillers and the like may be added .

[0013]

The maleimide derivative used in the present invention can be used in various fields, and the polymer having the maleimide derivative unit of the present invention has excellent heat resistance and can be used in a wide range of fields such as molded articles and films. . Further, it can be used as a compatibilizer for gas separation membranes, resist materials and various resins.

[0014]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[0015] The glass transition temperature (T
g) is obtained by using Seiko-Electronics DSC200.
20 ° C./min. The temperature was measured at a rate of temperature rise.

The decomposition temperature (Td) of the produced polymer is
Using TG / DTA200 manufactured by Seiko Denshi Co., Ltd., in nitrogen at 10 ° C./min. The temperature was measured at a rate of temperature rise.

Example 1 (Synthesis of N-trimethylsilylmaleimide) 25.0 g (0.2%) of maleimide was placed in a 1-liter eggplant-shaped flask.
6 mol), 65.3 ml of trimethylsilyl chloride (2
(6.1 g; 0.26 mol) and 300 ml of benzene, and the mixture was heated under reflux for 6 hours. After filtering out the precipitated salt, the pale yellow solution was concentrated at room temperature under a nitrogen stream. After vacuum distillation once, the mixture was passed through an alumina-benzene column and vacuum distillation was repeated again to obtain N-trimethylsilylmaleimide. Colorless liquid, yield 33.6 g (77.1%), boiling point (bp) 75 ° C / 5 mmHg.

Example 2 (Synthesis of N-tert-butyldimethylsilylmaleimide) 2-1 25.0 g of maleimide was placed in a 1-liter eggplant-shaped flask.
(0.26 mol), 46.7 g (0.31 mol) of tert-butyldimethylsilyl chloride, 50.0 ml (36.6 g, 0.36 mol) of triethylamine and 300 ml of benzene were added, and the mixture was heated under reflux for 6 hours. After the precipitated salt was separated by filtration, the pale orange solution was concentrated at room temperature under a nitrogen stream to obtain a pale orange solid. After passing through an alumina-benzene column, recrystallization from benzene gave colorless crystals. Yield 22.3 g (40.9%), mp (mp) 72 ° C.

2-2 Literature in 100 ml eggplant-shaped flask; Journal of Organic Chemistry
(JOC), 39, 21 (1974) 6.76 g of N-silver-maleimide synthesized by the method described in
(0.033 mol), tert-butyldimethylsilyl chloride 5.00 g (0.033 mol), benzene 50
Then, the mixture was heated and refluxed for 3 hours in a dark place. After the precipitated silver chloride was filtered off, the pale yellow solution was passed through an alumina-benzene column to remove benzene to obtain a white solid. Recrystallization from benzene gave colorless crystals. 4.80 g yield
(68.7%), mp 72 ° C.

[0020] EXAMPLE 3 (N-dimethyl cough synthesis sill silyl <br/> maleimide) N- Silva - maleimide 28.5 g (0.14 g), dimethyl Seki sill silyl chloride 25.0 g (0.14 mol), 300 ml of benzene was added, and the mixture was heated and refluxed for 3 hours in a dark place. After the precipitated silver chloride was filtered off, it was passed through an alumina-benzene column and recrystallized from benzene to obtain a white solid. Yield 20.1 g (61.1%), mp 42 ° C.

Table 1 ──────────────────────────────────── Sample mp (° C) bp (° C)イ ミ ド maleimide 92-94 trimethylsilyl chloride -40 57 N-trimethylsilyl 75 / 5 mmHg maleimide tert-butyldimethyl 86-89 silyl chloride N-tert-butyldimethyl72 silylmaleimide dimethylsexylsilyl 55-56 / chloride 10 mmHg N-dimethylsexylsilyl 42 maleimide ４ Example 4 (Radical polymerization of N-trimethylsilylmaleimide) N-trimethylsilylmaleide during glass sealing A benzene solution of a mide (1 mol / l) and 2,2′-azobisisobutyronitrile (0.005 mol / l) was added, and the flask was purged with nitrogen, degassed, and then sealed. After polymerization at 60 ° C. for 5 hours, polyN-trimethylsilylmaleimide was precipitated in a large amount of anhydrous hexane. The polymer was isolated by filtration. Yield 62.
1%. After quantitatively converting into a polymaleimide by the method shown in Reference Example 1, the intrinsic viscosity measured at 30 ° C. in a DMF solvent was 0.40 dl / g.

Example 5 (Synthesis of high molecular weight poly N-trimethylsilylmaleimide) N-trimethylsilylmaleimide was converted to 2,2'-azobisisobutyronitrile (0.005) in the same manner as in Example 4.
(Mol / l) at 370 hours for bulk polymerization. The yield was 18.1%, and the intrinsic viscosity of the polymaleimide measured in the same manner as in Example 4 was 1.67 dl / g.

Example 6 (Photopolymerization of N-trimethylsilylmaleimide) In the same manner as in Example 4, N-trimethylsilylmaleimide (1 mol / l), 2,2'-azobisisobutyronitrile (0.05 mol / l) The benzene solution of 1) was irradiated with light from a distance of 10 cm using a 100 W high-pressure mercury lamp, and polymerized at 30 ° C. for 20 hours. The yield was 64.3%, and the intrinsic viscosity of the polymaleimide measured in the same manner as in Example 4 was 0.58 d.
1 / g.

Example 7 (Radical polymerization of N-tert-butyldimethylsilylmaleimide) N-tert-butyldimethylsilylmaleimide was polymerized in the same manner as in Example 4, and a large amount of
-Tert-butyldimethylsilylmaleimide was precipitated. The polymer was isolated by filtration. The yield is 60.5
%Met. Poly N- measured in a DMF solvent at 30 ° C
The intrinsic viscosity of tert-butyldimethylsilylmaleimide was 0.35 dl / g.

Example 8 (Anionic polymerization of N-tert-butyldimethylsilylmaleimide) N-tert-butyldimethylsilylmaleimide (0.
17 mol / l) with sec-butyl lithium (0.016
(Mol / l) in tetrahydrofuran at −78 ° C. for 1 hour. After terminating the polymerization with methanol containing hydrochloric acid, the mixture was poured into a large amount of methanol, and hydrochloric acid was further added. Yield 34.7%, isolated poly N-te
The intrinsic viscosity of rt-butyldimethylsilylmaleimide was 0.35 dl / l (in DMF solvent, 30 ° C.).

Example 9 (Radical polymerization of N-dimethylsexylsilylmaleimide) N-dimethylsexylsilylmaleimide was polymerized in the same manner as in Example 4, and a large amount of methanol was converted to polyN-dimethylsexylsilylmaleimide. Was precipitated. The polymer was isolated by filtration. The yield was 56.0%. DM
The intrinsic viscosity of poly N-dimethylsexylsilylmaleimide measured at 30 ° C. in the F solvent was 0.32 dl / g.

Table 2 {Polymer Tg (° C) Td (° C)}ポ リ Poly-N-trimethyl 261 380 silylmaleimide Poly-N-tert-butyl 216 396 Dimethyl Silylmaleimide Poly-N-dimethylsexyl 204 386 Silylmaleimide ───────────────────────────────── Reference Example 1 ( Hydrolysis of polymer) Poly-N-trimethylsilylmaleimide was converted to hydrochloric acid (0.2
The mixture was left at room temperature for 30 minutes in dioxane containing N) to quantitatively obtain polymaleimide.

Continuation of the front page (56) References JP-A-2-132106 (JP, A) NUCLEOSIDES & NUC LEOTIDES, 7 [5-6] (1988) (USA) p. 577-580J. Org. Chem. , 40 [1] (1975) (US) p. 24-28 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 30/08 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A maleimide polymer comprising 5 mol% or more of a repeating unit represented by the following general formula (2) and having an intrinsic viscosity of 0.01 to 10 dl / g measured in a DMF solvent at 30 ° C. Coalescing. Embedded image (Where R ₁ , R ₂ , and R ₃ are each hydrogen, and have 1 to 12 carbon atoms.
An alkyl group, an alkoxyl group having 1 to 12 carbon atoms,
The aromatic groups of the formulas 6 to 12 are shown. )