JPH04320408A - Polymer having thiuram disulfide functional group, manufacture of the polymer, and manufacture of graft copolymer by using the polymer - Google Patents

Abstract

PURPOSE: To provide a polymer which has a thiurum disulfide functional group as a pendant group and functions as an initiator, a chain transfer agent, and a terminating agent when a graft copolymer is produced by the free radical polymerization of a vinyl monomer and a diene monomer.

CONSTITUTION: This polymer is composed of a chain unit exhibited by formula I, where, R₁ is H, alkyl, cycloalkyl, aryl or the like; R₂, R₃, R₄ are each alkyl, cycloalkyl or aryl. In the production of the polymer, first a monomer shown by formula II or formula III (x is counter ion) and as required a vinyl comonomer are polymerized. Next, a polymer obtained from a unit exhibited by formula IV or formula V and possibly at least one kind of aforementioned comonomer is reacted with carbon disulfide and a compound given by formula VI or formula VII in the presence of an oxidizing agent to obtain the objective polymer.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

The present invention provides homopolymers and copolymers having thiuram disulfide functional groups as pendant groups,
Methods of making the polymers, as well as agents with the triple function of initiator, chain transfer agent, and terminator (abbreviated as "iniferter") useful in producing graft copolymers by free radical polymerization of vinyl monomers and diene monomers. (representing the polymer).

[0002] The present invention first provides the formula:

0003

[C6]

[In the formula, R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups; alkyl group, aryl group, or a combination of at least two of these groups), or an alkyl group, cycloalkyl group, aryl group substituted with at least one halogen atom, or a group represented by A combination of at least two of the groups, for example a monovalent organic group selected from 3,3,3-trifluoropropyl groups, where A is a single bond, an alkylene group, a cycloalkylene group, an arylene group, or A combination of at least two of these groups, a group represented by the formula: (B represents an alkylene group, cycloalkylene group, arylene group, or a combination of at least two of these groups) , R2 , R3 , R
4 individually represents an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups, and at least one of R3 and R4 further contains at least one hydroxyl group or carboxylic acid group. or may represent a polyoxyethylene or polyester sequence derived from a polyoxyethylene or polyester terminated with a hydroxyl functional group, respectively;
The present invention also relates to polymers whose chain bonds may randomly contain other units obtained from at least one vinyl monomer. Alkyl groups, cycloalkyl groups, aryl groups, or combinations of these groups included in the above definitions, or alkylene groups, cycloalkylene groups, arylene groups, or combinations of these groups are O
or at least one heteroatom such as S and/or at least one formula: (wherein R represents an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups. ).

Other suitable vinyl units have the formula:

0006
]

[C7]

[wherein R5 and R6 are hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups; an alkyl group substituted with at least one halogen atom;
A cycloalkyl group, an aryl group, or a combination of at least two of these groups; a group represented by -CN; (wherein D is an alkylene group, a cycloalkylene group, an arylene group, or a combination of these groups a combination of at least two of them); (wherein, R1
6, R17, R18 are alkyl groups, cycloalkyl groups,
a group represented by an aryl group or a combination of at least two of these groups; or a unit represented by a pyridine group (provided that R5 and R6 never represent hydrogen at the same time); It is.

Maleic anhydride, and nitrogen is an alkyl group,
Units derived from maleimides substituted by cycloalkyl or aryl groups are also suitable.

The molecular weight of these random copolymers and homopolymers is preferably between 500 and 2,000,000. The proportion of units (I) can vary within a wide range. This is because at least one unit (I) can be present per copolymer chain.

Alkyl groups included in the above definition are especially C1-C12, especially C1-C6 alkyl groups, cycloalkyl groups are especially C3-C12,
In particular C1-C7 cycloalkyl groups, the aryl group being for example phenyl or naphthyl. Furthermore, the definition of groups such as alkyl groups, cycloalkyl groups or aryl groups, or alkylene groups, cycloalkylene groups or arylene groups includes combinations of at least two of these groups, such as aralkyl groups, Alkaryl groups and the like are included.

The polyalkylene sequences included in the definition of R3 or R4 have the following formula: (wherein R8 is an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups) Yes, a is 1 to 1,000, preferably 1 to
200) by removing the terminal functional group OH from polyoxyalkylene.

Polyester sequences encompassed by the definition of R5 have the following formula: where R9 is as defined for R8;
R10 and R11 each independently represent an alkylene group, a cycloalkylene group, an arylene group, an alkenylene group, an arylene group substituted with an alkenyl group, and these groups have at least one heteroatom and/or at least one group of the formula : (wherein R12 is selected from an alkyl group, a cycloalkyl group, and an aryl group and may contain a substituent), and b is 1 to 300, preferably 1 to
50] from the polyester represented by the terminal functional group O
It may be obtained by removing H.

Examples of suitable R10 and R11 groups containing at least one unsaturation include the following formulas:
-CH=CH- ・-CH2 -CH=CH-CH2 -

[0014]

[Chemical formula 8]

(In the formula, c is a value of 1 to 12, and R13
and R15 each independently represent a single bond, an alkylene group, a cycloalkylene group, an arylene group, or a combination of at least two of these groups, and R14 represents hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or a combination of these groups. (Indicates a combination of at least two of the groups)

[0016]

[Chemical formula 9]

Examples include groups represented by the following.

The invention further provides: - in a first step, the formula:

[
0019

[Chemical formula 10]

carrying out the polymerization of at least one monomer of the formula (wherein X represents a counterion such as a halide or an acid group, for example HSO3 -) and optionally at least one vinyl comonomer, - in the second stage, the formula:

[0021]

[Chemical formula 11]

The polymer obtained in the previous step containing units of the formula ##STR1## optionally obtained from comonomers is treated in the presence of at least one oxidizing agent with carbon disulfide and of the formula:

[0023]

[Chemical formula 12]

The present invention relates to a method for producing the above-mentioned polymer, which is characterized by reacting it with a compound represented by:

Suitable monomers of formula (III) are, inter alia, N-t-butylaminoethyl methacrylate, N-1-butylaminoethyl methacrylate, N-butylaminoethyl methacrylate,
-ethylaminoethyl methacrylate, N-methylaminoethyl methacrylate and the corresponding acrylates.

Suitable comonomers are, inter alia, alkyl methacrylates and alkyl acrylates in which the alkyl group contains, for example, from 1 to 8 carbon atoms, vinyl aromatic hydrocarbons, unsaturated nitriles, cyanoethyl acrylate, acrylamide, lower hydroxyalkyl acrylates. , lower hydroxyalkyl methacrylates, acrylic acid, methacrylic acid, maleic anhydride and maleimides substituted with alkyl or aryl groups. Particularly suitable comonomers are methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, styrene, α-methylstyrene, monochlorostyrene, t-butyl These include styrene, vinyltoluene, 2-vinylpyridine, and 4-vinylpyridine.

Non-limiting examples of amines of formula (V) include, inter alia, diethylamine, dimethylamine, N-ethyl-N
-Methylamine, N-methyl-N-propylamine, N
-Ethyl-N-propylamine, dipropylmine, diisopropylamine and cyclopentylamine.

A preferred embodiment of the two-stage method will now be described.

First stage The polymerization is carried out as bulk, suspension, emulsion or solution polymerization, for example at temperatures of about 30 to 150°C. Substances capable of solubilizing the polymer chains, such as tetrahydrofuran,
Select the solvent among toluene, ethanol and mixtures thereof.

The initiator is selected from free radical generating compounds such as peroxides, azo compounds, peracids, redox systems. Polymerization can be carried out photochemically or radiochemically.

In a preferred embodiment of the second stage, the total number of secondary amine groups, ie, the secondary amine groups contained in the units (IV) and (IV') of the polymer of the previous stage, has the formula (V) or (V' ) A secondary amine group contained in the compound represented by (IV) or (
An equimolar amount of CS2 is used with respect to IV'), which is used in large molar excess. Compound(
III) Approximately 1 mol per 1 mol of compound (II)
I') tertiary amine in an amount of approximately 2 mol per mol (
For example, the reaction can be carried out in the presence of triethylamine or pyridine). For example, about 1 mole of oxidizing agent is added to 1 mole of CS2. The oxidizing agent may be selected from among iodine, hydrogen peroxide, alkali metal hypochlorites, alkyl and aryl hydroperoxides, and potassium hexacyanoferrate, among others.

The reaction can be carried out in a solvent, for example water, alcohol or a water/alcohol mixture. CS2 or tertiary amines may also function as solvents. The reaction is generally about −
It is carried out at 20°C to room temperature.

The invention further provides that the graft contains a vinyl or diene sequence and the copolymer has the formula:

[0034]

[Chemical formula 13]

The present invention relates to a graft copolymer consisting of a chain bond of units represented by the formula (wherein Po represents a vinyl or diene polymer sequence). This chain linkage may include randomly distributed units derived from at least one other vinyl monomer.

The molecular weight of the Po sequence is generally about 100-1
,000,000, preferably about 1,000-10
It is 0,000.

The invention further relates to a process for the preparation of said graft copolymers, characterized in that the polymerization of the vinyl or diene monomers is carried out in the presence of an "iniferter" polymer as described above at a temperature of about 50 to 160°C. The "iniferter" polymer is preferably introduced together with the monomers at the beginning of the polymerization.

The amount of "iniferter" polymer introduced is generally 10-5 to vinyl or diene monomer.
~0.5 mole/l.

Suitable vinyl monomers are as described above.

Suitable diene monomers are inter alia butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-methylene-2- norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadiene, 5-ethylidene-2
- norbornene, 5-(2-propenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 1,5-cyclooctadiene, bicyclo[2.2
．． 2] Octa-2,5-diene, cyclopentadiene, 4,7,8,9-tetrahydroindene and isopropylidenyltetrahydroindene.

These graft copolymers can serve to make mixtures of homopolymers PA, PB compatible with each other. In this case, the chemical nature of the Po sequence is e.g.
The chemical properties of A and the properties of monomer B are the same as those of the comonomers used in the synthesis of the polymers of the invention.

The following examples illustrate the invention in a non-limiting manner.

Examples 1 to 6 Free radical copolymerization of methyl methacrylate (MMA) and Nt-butylaminoethyl methacrylate (BaeM) (Examples 1 to 3) and n-butyl methacrylate (MM)
B) Free radical copolymerization of BaeM with BaeM (Examples 4-6).

Overall process Monomer concentration is approximately 2 mol/l, initiator (azo or peroxide compound) concentration is approximately 2×10-3 mol/l.
as, benzene, tetrahydrofuran (THF)
Alternatively, copolymerization was carried out as bulk or solution polymerization in dimethylformamide (DMF). The copolymerization was carried out in a stirred flask, sealed under vacuum or kept under inert gas (N2, argon) after introduction of the reactants, protected from light. Polymerization was carried out by immersing the flask in an oil bath adjusted to the required temperature for the desired time. After copolymerization, the flask was removed and cooled in an isopropanol/dry ice mixture. Polymer toluene, THF
or any other solvent and then precipitated dropwise into heptane or methanol. The resulting precipitate or resin product was collected in a molten glass crucible, washed with heptane or methanol, and dried at 45° C. under vacuum until constant weight was obtained (12-24 hours).

[0045] Polymerization temperature: 60°C±5°C, polymerization time: 45~
Polymerization reaction carried out in toluene solution in 90 minutes

0
046]

[Table 1]

Examples 7a and 7b Synthesis of “polyiniferter” with thiuram side groups

[
0048

[Chemical formula 14]

Example 7a) 15 g of the copolymer of Example 1 in 150 ml of toluene
(contains 1.56 x 10-4 mole, 1.56 x 10-5 mole of secondary amine) and 1 ml (1.56 x 10-4 mole, containing 1.56 x 10-5 mole of secondary amine)
56 x 10-2 mole) of CS2, then 1.14
g (1.56 x 10-2 mole) of diethylamine was added. Then 2 g (
1.56×10 −2 mole) of iodine was added to the reaction mixture maintained at 20° C. with stirring.

The mixture was stirred until the iodine completely disappeared. This mixture was then poured into a methanol/water mixture. The precipitate was redissolved in toluene, dried and collected by evaporation of the solvent under partial vacuum.

Example 7b) 4.34 g (6.78×10 −5 m ) of the copolymer of Example 6 containing (1.56×10 −5 mole) of secondary amine
ole) was treated as in Example 7a.

Examples 8-15 Synthesis of Graft Copolymers Graft "polyiniferters" of Examples 7a and 7b
Vinyl monomer starting from: styrene (Examples 8-1
1) and hydroxyethyl methacrylate (HEMA)
Free radical polymerization of Examples 12-15.

General procedure After introduction of the reactants, vacuum sealing or inert gas (N2
Polymerizations were carried out in stirred flasks (or tubes) maintained under argon). (The grafted "polyiniferters" obtained in Examples 7a and 7b were dissolved in toluene). Polymerization was carried out by immersing the flask in an oil bath adjusted to the required temperature for the desired time. After the end of the polymerization, the flask was removed from the oil bath, cooled in an isopropanol/dry ice mixture, and the graft copolymer was added dropwise into heptane or methanol, depending on the graft comonomer. The soluble fraction was redissolved in toluene (or methanol when using HEMA as the grafting comonomer) and precipitated again in a suitable non-solvent.

The graft copolymer was then dried at 45° C. (24-48 hours) until a constant weight was obtained.

Styrene (Examples 8 to 11) was prepared using the compounds obtained in Examples 7a and 7b by varying the concentration (g/l) of "grafted polyiniferter" relative to monomer, polymerization temperature and polymerization time. and HEMA (Example 1
Various polymerizations of 2 to 15) were carried out.

The graft copolymer is characterized by its weight average molecular weight (Mw) and the weight percent of graft comonomer.

[0057]

[Table 2]

Claims (1)

[Scope of Claims] [Claim 1] A polymer composed of the following chain units. [Formula 1] [Here, R1 is a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups, or the formula: (in the formula,
R7 represents hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or a combination of at least two of these groups, or an alkyl group or a cycloalkyl group substituted with at least one halogen atom; ,
A monovalent organic group selected from an aryl group or a combination of at least two of these groups;
is a single bond, or an alkylene group, a cycloalkylene group, an arylene group, or a combination of at least two of these groups, or a formula: (wherein B is an alkylene group, a cycloalkylene group, an arylene group, or one of these groups) R2, R3 and R4 each individually represent an alkyl group, a cycloalkyl group, an aryl group or a combination of at least two of these groups, and R3 and At least one of R4 may furthermore contain at least one hydroxyl or carboxylic acid group or may represent a polyoxyethylene chain or a polyester chain obtained from polyoxyethylene or polyester, respectively, terminated with a hydroxyl function. . However, this polymer chain may randomly contain other chain units obtained from at least one type of vinyl monomer, and may also include an alkyl group, a cycloalkyl group, an aryl group included in the above definition, or any of these groups. A combination of groups or an alkylene group, a cycloalkylene group, an arylene group or a combination of these groups has at least one heteroatom and/or at least one of the formula: (wherein R is an alkyl group, a cycloalkyl group, an aryl group, group or a combination of at least two of these groups). ] [Claim 2
A polymer according to claim 1, having a molecular weight of 500 to 2,000,000. 3. A method for producing a polymer according to claim 1, characterized in that - in the first step, at least one polymer of the formula:
carrying out the polymerization of a species monomer and optionally at least one vinylic comonomer, - in a second step units of the formula: optionally obtained from said at least one comonomer; The polymer obtained in the previous step containing units is treated in the presence of at least one oxidizing agent,
A method characterized by reacting carbon disulfide and a compound represented by the formula: [Chemical formula 4]. 4. The monomer of formula (III) used is N-t-butylaminoethyl methacrylate, N-1
-butylaminoethyl methacrylate, N-ethylaminoethyl methacrylate, N-methylaminoethyl methacrylate and the corresponding acrylates. 5. In the second stage, at least 1 mol of CS2 is used per secondary amine residue contained in the unit (IV) or (IV') of the polymer obtained in the first stage, and 5. Process according to claim 3, characterized in that the compound represented by ) or (V') is used in a large molar excess. 6. A tertiary amine or compound (III') in an amount of about 1 mole per mole of compound (III).
6. Process according to any one of claims 3 to 5, characterized in that the second stage reaction is carried out in the presence of an amount of tertiary amine in an amount of about 2 mol per mol of ). 7. A graft copolymer containing a vinyl or diene polymer chain in the graft portion and consisting of the following chain units. embedded image (Here, Po represents a vinyl or diene polymer chain. However, this copolymer chain may randomly contain other chain units obtained from at least one vinyl monomer.) [Claim 8] The molecular weight of the polymer chain Po is 100~
Claim 7 characterized in that: 1,000,000
Copolymers described in. 9. The polymerization according to claim 7 or 8, characterized in that the polymerization of vinylic or diene monomers is carried out at a temperature of 50 to 160° C. in the presence of an “iniferter” polymer as defined in claim 1. Method for producing the described graft copolymer.