JPH0721036B2 - Method for producing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention uses a polyfunctional polymerization initiator having one azo group in the molecule to produce a block copolymer having polyamide as a unit. On how to do.

[Conventional technology and its problems]

It is already well known that a vinyl monomer can be polymerized with a compound containing an easily decomposable azo group.
However, there are few reports on a method for producing a block copolymer of a polyamide-vinyl polymer using this.

The collection of high molecular weight polymers (vol.33 (3), 131 (1976)) describes a method for producing a block copolymer of a polyamide-vinyl polymer, but it is necessary to introduce an azo group into the polyamide chain. Therefore, diamine and acid chloride must be used as raw material monomers. The present inventors have conducted intensive studies in view of such problems, as a result, found a method for producing a block copolymer of a polyamide-vinyl polymer using dicarboxylic acid and diisocyanate that are industrially easily available as raw material monomers, The invention was reached.

[Means for solving problems]

That is, the gist of the present invention is to provide an azo compound having a dicarboxylic acid and a diisocyanate containing at least two functional groups which have one azo group which is not directly bonded to an aromatic ring in the molecule and which is reactive with the isocyanate and / or the carboxylic acid. Compound,
And a heating method in an organic solvent in the presence of a radically polymerizable vinyl monomer.

1 not directly bonded to an aromatic ring in the molecule used in the present invention
The azo compound having one azo group is one having at least two functional groups reactive with isocyanate and / or carboxylic acid, and the functional group is preferably a carboxyl group, a hydroxyl group, an imidazolyl group or an imino group. Groups or amino groups. Specifically, A-N = NA-A '(A and A'represent a residue containing a functional group having a reaction activity with isocyanate and / or carboxylic acid, and the bonding portion with the azo group is not an aromatic ring. , A and A ′ may be the same or different), and the following can be mentioned.

General formula (Here, R ¹ and R ² are hydrogen, a lower alkyl group, a nitrile group,
Alternatively, an aromatic group and x represents an integer of 0 to 10.

X represents a functional group having a reactive activity with an isocyanate and / or a carboxyl group such as a hydroxyl group, a carboxyl group and an amino group. ), Such as Also the general formula (Wherein R ¹ , R ² , x, and X are as defined above), for example Also the general formula (Here, R ¹ and R ² are the same as above, and R ³ represents a divalent aliphatic group.) Also the general formula (Where R ¹ , R ² , R ³ and X are the same as above) Also the general formula (R ¹ , R ² , R ³ , x and X are the same as above) Also the general formula (Here, R ¹ and R ² are the same as above, and Y represents a functional group having a reaction activity with an isocyanate and / or a carboxyl group, or a hydrogen atom or a halogen atom.) , Etc. (Here, R ¹ , R ² , and X are the same as above) For example, Etc. further, Are also useful.

The azo compound of the present invention is, of course, not limited to these, and also includes derivatives such as hydrochlorides and hydrates of these azo group-containing polyfunctional compounds.

The amount of these azo group-containing polyfunctional compounds used is 0.01 to 20 mol%, preferably 0.1 to 10 mol%, based on the radically polymerizable vinyl monomer used in the reaction. If the amount of this azo group-containing compound is less than 0.01 mol%, the polymerization conversion rate of the vinyl monomer will decrease, and if it is more than 20 mol%, the molecular weight of the vinyl polymer will decrease too much, which is not preferable.

The radically polymerizable vinyl monomer used in the present invention is a monomer that gives a linear polymer, and CH ₂ ═C
Compounds having a vinyl group represented by are preferred, but are not particularly limited as long as they are radically polymerizable.

Specifically, butadiene, isoprene, diene-based monomers such as 2-chloro-1,3-budadiene, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, furfuryl (meth) acrylate, fluoromethyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, (meth) acrylate-based monomers such as glycidyl (meth) acrylate, (meth) acrylamide, butyl (meth) acrylamide, octyl (meth) acrylamide, N, N-dimethylmethyl (meth) acrylamide , (Meth) acrylamide monomers such as morpholyl (meth) acrylamide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl monochloroacetate, vinyl benzoate, vinyl cinnamate, etc. Styrene-based monomers such as carboxylic acid vinyl ester-based monomers, styrene, α-methylstyrene, 4-acetoxystyrene, 4-benzoylstyrene, 4-bromostyrene, 4-chlorostyrene, 4-cyanostyrene and 2-hydroxymethylstyrene, Vinyl ether type monomers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, and halogenated vinyl type monomers such as vinyl chloride, vinylidene chloride and 2-chloropropene. Mer, methyl vinyl ketone, methyl isopropenyl ketone, vinyl ketone monomers, such as phenyl vinyl ketone, and the like.

It is also possible to use two or more of these in combination.

Further, maleic anhydride or its derivative can be used as a comonomer.

Furthermore, if necessary, a polyfunctional vinyl monomer such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, or trimethylpropane tri (meth) acrylate may be used in combination.

Diisocyanate used in the present invention have the general formula ONC-R ⁴ -NCO (R ⁴ is _{-C 6 H 4 -, - C} 6 H 4 -X'-C 6 H 4 - divalent aromatic residue represented by Group or a divalent aliphatic residue having 2 to 20 carbon atoms, and X'is CH ₂ or O or S.) is one or more diisocyanates. For example, diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate and the like. .

Dicarboxylic acid used in the present invention have the general formula HOOC-R ⁵ -COOH (R ⁵ is a divalent aromatic residue, or a divalent carbon atoms 2 to 20,
Shows the aliphatic residue of. ) One or more dicarboxylic acids represented by Examples thereof include isophthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanenic acid, dodecanenic acid, tridecanenic acid, and tetradecanenic acid.

The amount ratio of the diisocyanate, the azo compound and the dicarboxylic acid used in the present invention is preferably such that the total amount of the azo compound and the dicarboxylic acid is 0.8 to 1.2 mol with respect to 1 mol of the diisocyanate, Depending on the purpose, it is possible to react even at a molar ratio exceeding this range.

The organic solvent used in the present invention is preferably an organic solvent that does not react with any of the reactants dicarboxylic acid and diisocyanate. Specific examples thereof include dimethyl sulfone, diphenyl sulfone and tetramethylene sulfone, and further N-methyl-2-pyrrolidone, N, N-dimethylformamide, N-acetyl-2-pyrrolidone, hexamethylphosphoramide, N. , N-dimethylacetamide, dimethyl sulfoxide, etc. can also be used.

Each of the above solvents may be used alone, or two or more kinds of solvents may be used in combination. Furthermore, it can be used in combination with other solvents such as benzene, dioxane, xylene, toluene, cyclohexane.

In the present invention, the reaction is preferably carried out in the temperature range of 40 to 240 ° C, more preferably 60 to 200 ° C. The reaction at a temperature lower than 40 ° C. requires a long reaction time because the decomposition rate of the azo group is not sufficient, and the reaction at a temperature higher than 240 ° C. is angry to cause a side reaction of isocyanate, which is preferable. Absent.

The reaction time is usually 1 to 15 hours. If necessary, a tertiary amine, alcoholate, phenolate,
An organometallic compound or the like can be used as a catalyst. Specific examples thereof include alkali metal alcoholates such as sodium methylate and potassium methylate, tin octoate, namarioctoate, dibutyl-tin-octoate, dibutyl-tin-laurate, triethylamine and the like. These catalysts are preferably added in the range of 0.01 to 5 mol% with respect to the diisocyanate.

Separation and purification of the polymer obtained after completion of the reaction are generally carried out by the method used for this type of polymer. For example, the obtained polymer solution is isolated by a method of pouring the polymer solution into a large amount of a non-solvent such as water, alcohol, acetone or the like to precipitate the polymer.

The polyamide-vinyl polymer block copolymer obtained by the present invention can be molded into various articles by a known molding method.

The polymer of the present invention can also be used as a mixture with various plastics as an impact resistance modifier for various plastics, a modifier for polymer alloys or a compatibilizer.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples without departing from the gist thereof.

In addition, the value of ηinh (intrinsic viscosity) in the examples is a value measured at 30 ° C. in N-methylpyrrolidone at 0.5% by weight.

Example 1 Tetramethylene sulfone 120 g styrene 34 g in a 300 ml three-necked flask. 0.5 g 4,4'-diphenylmethane diisocyanate 11.0 g adipic acid 5.0 g isophthalic acid 1.0 g were charged, and the whole system was replaced with nitrogen. All reactions were performed under a nitrogen atmosphere.

The reaction was carried out at a reaction temperature of 70 ° C. for 4 hours, then 0.07 g of sodium methylate was added as a catalyst to raise the reaction temperature to 130 ° C., and the reaction was carried out for 3 hours. During that time, generation of carbon dioxide was observed, and the viscosity of the solution gradually increased.

The obtained polymer solution was poured into a large amount of methanol to precipitate the polymer, which was then washed with a large amount of methanol repeatedly and then dried to obtain 29 g of a polymer.

Ηinh of the obtained polymer was 0.62 dl / g.

The polymer obtained was subjected to Soxhlet extraction with cyclohexane to extract a polystyrene homopolymer, and the ratio of the block-copolymerized styrene to the styrene subjected to the polymerization was determined (block efficiency).
%Met.

In addition, the IR of the polymer after extraction was measured. In addition to the absorption characteristic of polystyrene, absorptions derived from amide bonds at 1645 cm ^-1 and 1587 cm ^-1 were observed.

Examples 2 to 5 The same operations as in Example 1 were carried out except that the azo group-containing compound was changed as shown in Table 1, to obtain polymers as shown in Table 1.

Example 6 In a 300 ml three-necked flask, N-methyl-2-pyrrolidone 120 ml Methyl methacrylate 30 g 0.5 g 4,4'-diphenylmethane diisocyanate 11.0 g adipic acid 5.0 g isophthalic acid 1.0 g were charged, and the whole system was replaced with nitrogen. After that, the same operation as in Example 1 was performed to obtain 25 g of a polymer. When IR of this polymer was measured, absorption derived from an amide bond was observed at 1640 cm ⁻¹ and 1587 cm ⁻¹ .

Examples 7 to 9 Polymers shown in Table 2 were obtained in the same manner as in Example 6 except that the vinyl monomer was changed as shown in Table 2.

Example 10 In a 300 ml three-necked flask, N-methyl-2-pyrrolidone 120 ml styrene 30 ml 0.5 g 1,6-hexamethylene diisocyanate 7.4 g adipic acid 5.0 g isophthalic acid 1.0 g were charged, and the whole system was replaced with nitrogen.

After the reaction temperature was kept at 70 ° C and the reaction was carried out for 4 hours, 0.08 g of sodium methylate was added as a catalyst to raise the reaction temperature to 130 ° C and the reaction was carried out for 5 hours. During that time, generation of carbon dioxide was observed, and the viscosity of the solution gradually increased.

The obtained polymer solution was poured into a large amount of acetone to precipitate the polymer, which was then washed with a further large amount of acetone and then dried, whereby 31 g of a polymer was obtained.

When the IR of the obtained polymer was measured, it was 1680 cm ^-1 , 1533
Absorption derived from an amide bond was observed at cm ^-1 .

In addition, ηinh of the obtained polymer was 0.47 dlg ⁻¹ .

Further, the polymer obtained was subjected to Soxhlet extraction with cyclohexane to determine the block efficiency.
%Met.

Comparative Example 1 A 300 ml three-necked flask was charged with N-methyl-2-pyrrolidone 120 ml styrene 30 g 2,2'-azoisobutyronitrile 0.5 g 4,4'-diphenylmethane diisocyanate 11.0 g adipic acid 5.0 g isophthalic acid 1.0 g. The whole system was replaced with nitrogen.

After reacting at a reaction temperature of 70 ° C. for 4 hours, 0.07 g of sodium methylate was added as a catalyst to raise the reaction temperature to 130 ° C., and the reaction was further performed for 3 hours. The polymer solution thus obtained was treated in the same manner as in Example 1 to obtain 31 g.
Was obtained.

The polymer was subjected to Soxhlet extraction with cyclohexane, and the IR of the extraction residue was measured to be 1644 cm ^-1 , 15
Absorption due to the amide bond at 85 cm ⁻¹ was observed, but absorption due to polystyrene was not observed.

〔The invention's effect〕

According to the method of the present invention, a block copolymer of polyamide-vinyl polymer can be industrially advantageously produced. The copolymer is not only used for the production of various molded products, but also useful as a modifier and compatibilizer for various plastics.

Claims (2)

[Claims] 1. An azo compound containing a dicarboxylic acid and a diisocyanate, each molecule having one azo group not directly bonded to an aromatic ring and having at least two functional groups reactive with an isocyanate and / or a carboxylic acid, And a method for producing a polymer, which comprises reacting by heating in an organic solvent in the presence of a radically polymerizable vinyl monomer. 2. The functional group having a reactive activity with isocyanate and / or carboxylic acid is a carboxyl group, a hydroxyl group, an imidazolyl group, an imino group or an amino group, according to claim 1. Production method.