Process for producing vinyl polymers

Abstract

The present invention provides a process for producing a vinyl polymer characterized in that, in a radical polymerization of a vinyl monomer, a substituted hydroxylamine represented by a general formula: 1

Description

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a method of radical polymerization of a vinyl monomer in the presence of a specific substance, and particularly, to a process for efficiently producing a vinyl polymer which has a high molecular weight desirable for practical properties such as mechanical properties, heat resistance and the like, and which has controlled molecular weight distribution.

[0003] 2. Description of the Prior Art

[0004] In conventional radical polymerization, the molecular weight of the produced polymer strongly depends on the polymerization temperature, that is, the molecular weight of the polymer obtained is restricted by the polymerization temperature. Although the polymerization temperature is typically lowered in order to achieve a high molecular weight, decrease in polymerization temperature will elongate the polymerization time and increase the amount of remaining monomer. It becomes, therefore, difficult to effect an efficient production. Similarly, although the polymerization temperature is typically elevated in order to achieve a low molecular weight, increase in polymerization temperature so accelerate the polymerization rate that it becomes difficult to control the reaction. For these reasons, there is a wide need for a polymerization method of freely onto the molecular weight in a radical polymerization.

[0005] As an attempt to control the molecular weight in a radical polymerization, Tatemoto et al. have reported that radical polymerization of a fluorine-containing monomer such as tetrafluoroethylene proceeds in a manner like living polymerization in the presence of an iodine compound such as (CF3)2CF-I (Sozo Tatemoto, Koubunshi-Ronbun-Shu 49, 765 (1992)). Likewise, Otsu et al. have found that, when certain sulfur compounds were used, radical polymerization of styrene or the like occurred under light irradiation and that the extent of conversion and the molecular weight of the produced polymer with the time (J. Polym sci; part A; polym. chem., 32, 2911 (1994)). According to these methods, it is possible to control the molecular weight in a considerably wide range. However, these methods lack universality because they require a special polymerization initiator or a use of limited kinds of monomer.

[0006] In anionic polymerization, a precise control of the molecular weight is possible by a polymerization on method called living polymerization. Recently, it has also become popular to research a polymerization system which enables living polymerization in radical polymerization For example, it has been shown in Japanese Patent Publication No. 94-199916 A that, by using a radical polymerization initiator such as benzoyl peroxide together wait a stable free radical agent such as 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO), a living-like polymerization of styrene can be achieved. According to this method, by selecting a polymerization condition, the molecular weight of the polymer obtained will depend not only on the polymerization temperature but also on the amounts of the initiator and the stable free radical agent used, so that one can control the molecular weight by those amounts to a certain extent.

[0007] Thus, when the above method is used, one can obtain a resin having a controlled molecular weight. However, this method has a drawback that the reaction rate in this method is so slow that it takes considerably more time compared with the usual radical polymerization to reach a high extent of conversion. In addition, coloration of the obtained polymer may sometimes occur depending on few reaction condition. Furthermore, TEMPO requires special attention in its handling and storage because it exists in radical state, and it is also very expensive. This method has thus some shortcomings that for example, it requires more production costs compared with conventional methods.

[0008] In view of such a situation, the present inventors have concentrated their efforts on controlling the radical reaction of vinyl monomer with the aim of increasing productivity and improving practical physical properties of radically polymerized vinyl polymers. In result, we have found by chance a method for obtaining a vinyl polymer having a high molecular weight and a restrained molecular weight distribution while retaining a high polymerization rate by including a specific substituted alkylhydroxylamine in the polymerization system, and thus completed the present invention.

SUMMARY OF THE INVENTION

[0009] The present invention provides a process for producing a vinyl polymer characterized in that, in a radical polymerization of a vinyl monomer, a substituted hydroxylamine represented by a general formula: 3 (in which R1 and R2 represent hydrogen, a (substituted) aliphatic hydrocarbon group having one or more carbon atom(s) or an aromatic hydrocarbon group) and/or a general formula. 4

[0010] (in which and R3 and R4 represent a (substituted) aliphatic hydrocarbon group having one or more carbon atom(s)) is added.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention is described below in more detail

[0012] In each of R1 and R2 of the general formula (I) of the present invention, the aliphatic hydrocarbon group may include, for example, methyl, ethyl, isopropyl, t-butyl, butyl and the like group, and the aromatic hydrocarbon group may include, for example, phenyl, bensyl and the like group.

[0013] Similarly, —R3—R4 in the general formula (2) may include a divalent (substituted) aliphatic hydrocarbon group corresponding to those groups in the general formula (1) such as —CH3CH2—, —CH2CH2CH2CH2—, —CH(CH2)CH2—CH(CH2)CH2——C(CH2)2CH2—C(CH2)3CH2—, —CH2CH2CH2CH2—CH2CH2CH2CH2—, or the like.

[0014] Furthermore, the hydrocarbon groups i the above general formulas (1) and (2) may optionally be substituted, and the substitutent may include, for example, an aliphatic hydrocarbon such as a methyl or ethyl group, an aromatic hydrocarbon such as a phenyl group, halogen a halogenated hydrocarbon, a carbonyl group, a hydroxy group, an amino group, and the like.

[0015] In the present invention, the substance presented by the general formula (1) (substituted hydroxylamine) may include dimethylhydroxylamine, dimethylhydroxylamine, isopropylhydroxylamine, dimethylhydroxylamine, and the like.

[0016] In the present invention, the substance represented by the general formula (2) may include N-hydroxylamine N-hydroxylsuccinimide, N-hydroxylphthalimide and the like.

[0017] In the present invention, although the radical polymerization may be initiated by any of the known methods, for example, using an initiator, heat, light or radioactive rays, it is preferable to use an initiator. Although there is no special restriction on the ratio of the substance represented by the above general formulas(1) and (2) (substituted hydroxylamine) used to the radical polymerization initiator, it is preferable to use a mole ratio between the substance represented by the above general formulas(1) and (2) and the radical polymerization initiator at 0.01/1-100/1 (substance represented by the above general formulas(l) and (2)[substituted hydroxylamine]/radical polymerization initiator), more preferably at 0.1/1-10/1, and particularly preferably at 0.1/1-1.0/1. At a mole ratio of the substance represented by the above general formula (1) and (2) to the radical polymerization initiator below 0.01/1, it will be difficult to control the molecular weight and molecular weight distribution, while at a mole ratio above 100/1, he polymerization rate will decrease.

[0018] There is no special restriction on the vinyl monomer used in the present invention, and it may be exemplified by aromatic vinyl compounds, &agr;, &bgr;-unsaturated carboxylic acids, &agr;, &bgr;-unsaturated carboxylic acid esters, &agr;, &bgr;-unsaturated carboxylic amides, &agr;, &bgr;-unsaturated nitrites, vinyl carboxylates, vinyl halides, vinylidene halides, conjugated dienes and the like compounds capable of radically polymer.

[0019] As an aromatic vinyl compound, although styrene is typically used, other aromatic vinyl compounds, for example, an alkyl-substituted styrene such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, p-ethylstyrene, p-t-butylstyrene, &agr;-methylstyrene or &agr;-methyl-methylstyrene, and an halogenated styrene such as o-chlorostyrene or p-chlorostyrene may also be used. A preferable aromatic vinyl compound includes, for example, styrene, &agr;-methylstyrene and p-methylstyrene; and styrene is especially preferable.

[0020] The &agr;-unsaturated carboxylic acid may include acrylic acid, methacrylic acid and the like. The &agr;, &bgr;-unsaturated carboxylic acid ester may include, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate, alkyl methacrylates such as methyl methecrylate, ethyl methacrylate and butyl methacrylate, and derivatives thereof. The &agr;,&bgr;-unsaturated carboxylic amide may include, for example, acrylamide, methacrylamide, and derivatives thereof. The &agr;, &bgr;-unsaturated nitrile may include acrylonitrile, methacrylonitrile, &agr;-chloroacrylonitrile and the like. The vinyl carboxylates may include vinyl acetate, vinyl propionate and the like. The vinyl halide may include vinyl fluoride, vinyl chloride, vinyl bromide, vinyl iodide and the like. The vinylidene halide may include vinylidene fluoride, vinylidene chloride, vinylidene bromide, vinylidene iodide and the like. The conjugated diene compound may include butadiene, isoprene, chloroprene, piperidene, chlorobutadiene and the like.

[0021] There is no special restriction on the radical polymerization initiator used in the present invention so far as it is capable of initiating radical polymerization, and the following compounds may be used, for example: organic peroxides, for example, peroxyketals such as 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane and n-butyl-4,4bis(t-butylperoxy)valerate, hydroperoxides such as cumene hydroperoxide and diisopropylbenzene peroxide peroxide, dialkyl hydroperoxides such as t-butylcumyl peroxide and di-t-butyl peroxide, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, peroxydicarbonates such as bis(t-butylcyclohexyl) peroxydicarbonate, and peroxyesters such as t-butyl peroxybenzoate, t-butyl peroxyacetate and 2,5-dimethyl-2,5-dibenzoylperoxy)hexane; azo compounds such as azoisobutyronitrile, 2,2-iazobis(2methylbutyronitrile), and 1,1-azobis(cyclohexaril-carbonitrile); and peroxide such as benzoyl peroxide.

[0022] The radical polymerization initiator is preferably used at a mole ratio to vinyl monomer of 0.001/100-10/100 (radical polymerization initiator/vinyl monomer), and more preferably at a mole ratio of 0.01/100-1/100. This is because, at a ratio of radical imitator to vinyl monomer below 0.001/100, it will be difficult to control the molecular weight, and at a mole ratio above 10/100, the polymerization will proceed so quickly that it becomes difficult to control the reaction.

[0023] There is no special restriction on the process of carrying out the polymerization of the present invention, and any of the usual polymerization modes such as bulk polymerization, suspension polymerization, bulk-suspension polymerization and solution polymerization may be used In the case of solution polymerization, no more than 20 parts by weight of solvent may be included in the process with 100 parts by weight of vinyl monomer, if necessary. Solvent more than 20 parts by weight is disadvantageous because it will decrease the polymerization rate and productivity.

[0024] There is no special restriction on the solvent included in tee process so far as the monomer and the produced polymer as soluble in the solvent. An example of solvent may be toluene, ethylbenzene, methyl ethyl ketone, benzene or the like, and toluene or ethylbenzene is especially preferred because the boiling points are close to the polymerization temperature. The above solvents may be used alone or in combination.

[0025] Furthermore, according to the process of the present invention, the molecular weight can be controlled by the amounts of the initiator and the monomer as well as the extent of conversion, so that the polymerization can be conducted in a very simple mode. Furthermore, according to the process of the present invention the molecular weight can be controlled by the amounts of the initiator and substance represented by the above general form (1) or (2). It is, therefore, very easy to industrialize the present invention. The process according to the present invention may be carried out in a continuous mode or in batch.

[0026] The polymerization temperature at which the present invention operates is typically 60° C.-160° C., and preferably 90° C.-150° C. At a temperature below 60° C., the reaction rate will be too low for an industrial production process, while at a temperature above 160° C. side reactions during the polymerization will occur to a extent not negligible, rendering the reaction control difficult.

[0027] When a stricter control is required in carrying out the present invention, a compound which has a function controlling heat polymerization may be used, if necessary. Among the compounds having such a function are, for example, phenylphosphonic acid, D, L-camphor-10-sulfonic acid, p-toluenesulfonic acid, 2-fluoro-1-methylpyridininium and the like.

[0028] When a thermoplastic resin is produced by the process of the present invention, admixes, stabilizers or the like agents usually used may be added. For example, in the case of styrene-based thermoplastic resins, a lubricant such as mineral oil, silicone oil, zinc stearate, calcium stearate, or ethylenebisstearylamide, an oxidation inhibitor such as a phenolic or phosphorus antioxidant, a UV absorbent, and a colorant may be added during or after the polymerization.

[0029] The present invention will be further illustrated by the following Examples to which the present invention is not restricted.

EXAMPLES

[0030] As described below, the polymers of Examples 1-7 and References 1-2 were subjected to the follow measurements (1) and (2), and the results are summarized in Table 1.

[0031] (1) Measurement of conversion

[0032] The extent of conversion was calculated by gas-chromatographically quantifying the amount of remaining monomer in the reaction solution sampled at a given interval during the reaction.

[0033] (2) Measurement of the molecular weight

[0034] For the polymer in the reaction solution sampled at a given interval during the reaction, the molecular weight was measured according to a GPC method using a GPC (LC-10A) manufactured by SHIMADZU CORPORATION and GPC columns (three KF-806L columns in tandem) manufactured by Showa Denko K.K.

[0035] Unless otherwise indicated, the polymerization reaction was earned out under nitrogen stern in a polymerization apparatus in which a reactor having 20 L inner volume equipped with an agitator was connected to a biaxial extender equipped with a vent line. The stat time of the reaction was defined as the point when the temperature reached 95° C.

EXAMPLE 1

[0036] A stock solution consisting of 150 mol of styrene, 0.3 mol of benzoyl peroxide and 0.15 mol of dimethylhydroxylamine was introduced into the reaction, and heated with stirring at 95° C. for 3.5 hours. After raising the temperature to 130° C., stirring was continued for additional 4.5 hours to synthesize the polymer. After removing remaining monomer polystyrene was recovered from the biaxial eider to obtain the polymer of Example 1.

EXAMPLE 2

[0037] A stock solution consisting of 150 mol of styrene, 0.3 mol of benzyl peroxide and 0.09 mol of diethylhydroxylamine was introduced into the reactor, and polymerized at 95° C. for 3 hours. Then, the polymer of Example 2 was obtained by following the same procedures as those in Example 1.

EXAMPLE 3

[0038] A stock solution consisting of 150 mol of styrene, 0.3 mol of benzoyl peroxide and 0.21 mol of diethylhydroxylamine was introduced into the reactor, and the polymer of Example 3 was then obtained by following the same procedures as those in Example 1.

EXAMPLE 4

[0039] A stock solution consisting of 150 mol of styrene, 0.3 mol of benzoyl peroxide, 0.15 mol of diethylhydroxylamine and 0.3 mol of camphorsulfonic acid was introduced into the reactor, and the polymer of Example 4. Was obtained by following the same procedures as those in Example 1.

EXAMPLE 5

[0040] A stock solution consisting of 150 mol of styrene, 0.3 mol of benzoyl peroxide and 0.15 mol of diethylhydroxylamine was introduced into the rector, and polymerized at 130° C. for 6 hours. Then, the polymer of Example 5 was obtained by following the same procedures as those in Example 1.

EXAMPLE 6

[0041] A stock solution consisting of 150 mol of styrene, 0.15 mol of benzoyl peroxide and 0.075 mol of diethylhydroxylamine was introduced into the reactor, and the polymer of Example 6 was the obtained by following the same procedures as those in Example 1.

EXAMPLE 7

[0042] A stock solution consisting of 150 mol of styrene, 0.15 mol of benzoyl peroxide and 0.075 mol of diethylhydroxylamine was introduced into the reactor, and the polymer of Example 6 was then obtained by following the same procedures as those in Example 1.

Reference 1

[0043] The polymer of Reference 1 was obtained by following the same procedures as those in Example 1 with the exceptions that a stock solution consisting of 150 mol of styrene and 0.3 mol of benzoyl peroxide was introduced into the reactor and that the reaction was stopped a 2 hours at 130° C.

Reference 2

[0044] The polymer of Reference 2 was obtained by following same procedures as those in Example 1 with the exceptions that a stock solution consisting of 150 mol of styrene, 0.3 mol of benzoyl peroxide and 0.36 mol of 2,2,6,6tetraethyl-1-piperidinyloxy was introduced into the reactor and that the polymerization time was 80 hours.

EFFECTS OF THE INVENTION

[0045] As described above, a radically polymerized vinyl polymer having a high molecular weight and a controlled molecular weight distribution can be obtained by the process of the present invention, even under a polymerization condition at a high temperature. The present invention provides, therefore, a process enabling to produce vinyl polymers which promise to have practical properties such as appearance, mechanical properties and heat resistance useful as materials for various moldings and coatings. Thus, the industrial and technical value of the present invention is extremely high. 1 TABLE 1 Reaction Con- Time version Example (h) (%) Mn × 10−4 Mw × 10−4 Mw/Mn Example 1 2 21.0 4.06 6.62 1.53 4 40.4 5.34 7.58 1.36 8 74.6 7.80 10.45 1.30 Example 2 1 31.2 3.36 5.21 1.52 2 54.6 4.23 6.55 1.55 3 70.2 5.33 8.04 1.51 Example 3 2 11.7 4.87 7.89 1.62 4 18.2 5.86 9.02 1.54 6 42.5 7.08 10.55 1.49 8 80.3 8.81 12.51 1.42 Example 4 2 31.6 4.13 7.31 1.77 4 68.1 5.69 9.39 1.65 8 87.9 6.74 9.77 1.45 Example 5 1 12.4 2.40 4.82 2.01 3 45.3 5.22 8.87 1.70 6 88.6 7.68 12.60 1.64 Example 6 2 18.5 6.21 10.43 1.68 4 42.7 12.77 19.66 1.54 8 79.9 17.20 29.58 1.42 Example 7 2 10.1 5.61 10.22 1.82 4 20.4 8.94 15.65 1.75 8 55.7 15.26 26.09 1.71 Reference 1 0.5 54.3 4.75 15.44 3.25 1 70.2 4.44 13.01 2.93 2 89.4 5.26 13.26 2.52 Reference 2 20 22.1 0.22 10.50 1.33 40 43.6 0.51 9.77 1.28 80 70.5 0.80 11.30 1.27

Claims

1. A process for producing a vinyl polymer characterized in that, in a radical polymerization of a vinyl monomer, a substituted hydroxylamine represented by a general formula:

5

(in which R1 and R2 represent hydrogen, a (substituted) aliphatic hydrocarbon group having one or more carbon atom(s) or an aromatic hydrocarbon group) and/or a general formula:

6

(in which R3 and R4 represent a (substituted) aliphatic hydrocarbon group having one or more carbon atom(s)) is added.

2. A process for producing a vinyl polymer set forth in claim 1 characterized in that the radical polymerization is carried out a radical polymerization initiator.

3. A process for producing a vinyl polymer set forth in claim 2 characterized in that the radical polymer initiator is used at a mole ratio between said radical polymerization initiator and the vinyl monomer of 0.001/100-101100 (radical polymerization initiator/vinyl monomer).

4. A process for producing a vinyl polymer set forth in claim 2 or 3 characterized in that the substituted hydroxylamine set forth in claim 1 and the radical polymerization initiator are used at a mole ratio between said substituted hydroxylamine and said radical polymerization initiator of 0.01/1-100/1 (substituted hydroxylamine/radical polymerization initiator).

5. A process for producing a vinyl polymer set forth in any one of claims 1-4 characterized that the vinyl monomer is an aromatic compound.