(19)
(11)EP 0 042 572 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
30.12.1981 Bulletin 1981/52

(21)Application number: 81104618.4

(22)Date of filing:  15.06.1981
(51)International Patent Classification (IPC)3C08F 212/12, C08L 25/16, C08L 51/04
// (C08F212/12, 220:44),(C08L25/16, 51:04),(C08L51/04, 25:16)
(84)Designated Contracting States:
BE DE FR GB IT NL

(30)Priority: 16.06.1980 JP 81860/80

(71)Applicant: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
Kita-ku Osaka-shi Osaka-fu 530 (JP)

(72)Inventors:
  • Mathumoto, Sigemi
    Takasago-shi Hyogo-ken (JP)
  • Nagoshi, Fumiya
    Kobe-shi Hyogo-ken (JP)

(74)Representative: VOSSIUS & PARTNER 
Postfach 86 07 67
81634 München
81634 München (DE)


(56)References cited: : 
  
      


    (54)Process for the production of copolymers with a high content of alpha-methylstyrene, thermoplastic resin compositions containing these copolymers and their use for the production of molded articles


    (57) The invention relates to a copolymer with a high content of a-methylstyrene which is characterized in that it is a copolymer comprising 65 to 90 parts by weight of a-methylstyrene with 35 to 10 parts by weight of acrylonitrile and 0 to 5 parts by weight of at least one copolymerizable vinyl monomer and that a component having an a-methylstyrene content of 82% or higher is contained in an amount of 30 parts by weight or more. Such a copolymer may be produced by a process which comprises charging 65 parts by weight or more of a-methylstyrene and 10% by weight or less based on this a-methylstyrene of acrylonitrile and at least one vinyl monomer all in one portion at the initial stage, making the system fully emulsified, gradually adding 35 parts by weight or less of acrylonitrile and the vinyl monomer or monomers, and carrying out emulsion polymerization until the amount of the polymer produced has reached 50 parts by weight or more in such way that the ratio of the a-methylstyrene monomer to the monomers other than a-methylstyrene in the system is always maintained at 90/10 or higher on the weight basis.
    The invention further relates to a thermoplastic resin composition which comprises the above copolymer with high content of a-methylstyrene and a graft copolymer obtained by reacting a diene rubber with monomers comprising an aromatic monovinyl compound and an unsaturated nitrile compound, the diene rubber being present in an amount of 5 to 30 parts by weight.
    Molded products obtained from the composition of this invention have excellent heat resistance and impact resistance.


    Description

    BACKGROUND OF THE INVENTION


    1. Field of the Invention



    [0001] This invention relates to heat resistant copolymers having a high content of cl-methylstyrene, a process for their production and thermoplastic resin compositions which contain these copolymers with a high content of α-methylstyrene and have excellent heat resistance and impact resistance.

    2. Description of the Prior Art



    [0002] Today a great number of thermoplastic resins are being utilized. One representative example thereof is ABS resins which are rubber-modified thermoplastic resins. However, in applications where high resistance to heat distortion is required, ABS resins have proved to be unsuitable. Various methods to improve the heat resistance of ABS resins have been proposed. For example, Japanese Patent Publication No. 18194/1960 describes how a composition having high heat resistance and impact resistance is obtained by mixing a copolymer comprising α-methylstyrene and acrylonitrile with an ABS resin. However, the heat distortion temperature of this composition is as low as slightly above 100°C, and therefore could not be employed where greater heat resistance was required. This is because when α-methylstyrene and acrylonitrile are free-radical polymerizedin the emulsion state, the resulting copolymer is, for the most part, an alternating copolymer even when the ratio of both reactants to be charged is changed. That is, when the amount of α-methylstyrene is 70% by weight or more, the conversion to polymer

    suddenly decreases and α-methylstyrene monomer is thus left unreacted. This tendency is also observed with a terpolymer comprising α-methylstyrene, acrylonitrile and-styrene. Further, Japanese Patent Publication No. 33661/1970 describes.a process which comprises introducing α-methylstyrene into a polymer. According to this process, 75 - 90% by weight of α-methylstyrene and 25 .- 10% by weight of acrylonitrile are copolymerized in a monomer mixture in the first stage, and subsequently in the second stage the polymerization of this gradually remaining α-methylstyrene is completed by adding a monomer chiefly comprising styrene and acrylonitrile. However,

    even when the maximum amount, i.e. 90% by weight, of d-methylstyrene is employed, this process entails a reduction in conversion to polymer and thus it is difficult to make the content of α-methylstyrene in the polymer produced in the first stage 82% by weight or higher. Moreover, when the amount of α-methylstyrene used in the first stage is increased, the amount of the remaining α-methylstyrene is accordingly increased, which in turn requires an increase in the amount of styrene and acrylonitrile to be added to polymerize the above α-methylstyrene in the second stage, so that the α-methylstyrene content in the total polymer eventually results in merely 75% by weight or so.



    [0003] Thus, in the above-described conventional process the heat resistance of each obtained composition had its limit. Similarly, poly-α-methylstyrene is known as a polymer with a high content of α-methylstyrene, but its thermal decomposition temperature is so low that it cannot be used for practical applications. Also from the aspect of production, it can only be produced by anionic polymerization and cannot be produced by free-radical polymerization.

    [0004] As the result of our extensive study, we have discovered that an α-methylstyrene - acrylonitrile copolymer having a certain range of composition is excellent in heat resistance and that by mixing a graft copolymer with this copolymer satisfactory impact resistance is imparted and, based on this discovery, we have finally accomplished this invention.

    SUMMARY OF THE INVENTION



    [0005] According to this invention, there is provided a copolymer with a high content of α-methylstyrene which is characterized in that it is a copolymer which comprises 65. - 90 parts by weight of α-methylstyrene with 35 - 10 parts by weight of acrylonitrile and 0 - 5 parts by weight of at least one copolymerizable vinyl monomer, and that a component having an α-methylstyrene content of 82% or higher is contained in an amount of 30 parts by weight or more.

    [0006] copolymer with a This invention also provides a process for producing a high content of α-methylstyrene, which process comprises charging 65 parts by weight or more of α-methylstyrene and 10% by weight or less based on this α-methylstyrene of acrylonitrile and at least one vinyl monomer all in one portion at the initial stage, making the system fully emulsified, gradually adding 35 parts by weight or less of acrylonitrile and of vinyl monomer or monomers,and carrying out emulsion polymerization until the amount of polymer produced has reached 50 parts by weight or more in such way that the ratio of the α-methylstyrene monomer to the monomers other than α-methylstyrene in the system is always maintained at 90/10 or higher on'the weight basis.

    [0007] Further, this invention also provides a thermoplastic resin composition which comprises (A) a copolymer with a high content of α-methylstyrene comprising 65 - 90 parts by weight of α-methylstyrene with 35 - 10 parts by weight of acrylonitrile and 0 - 5 parts by weight of at least onecopolymerizable vinyl monomer and containing 30 parts by weight or more of a component having an α-methylstyrene content of 82% by weight or higher, and (B) a graft copolymer which is obtained by reacting a diene rubber with a monomer comprising an aromatic monovinyl compound and an unsaturated nitrile compound, the diene rubber being in an amount of 5 - 30 parts by weight.

    DESCRIPTION OF THE PREFERRED EMBODIMENT



    [0008] What is especially important in this invention is the composition of the copolymer (i.e. the copolymer with a high content of styrene). α-methyl More particularly, it is a copolymer (A), which comprises 65 - 90 parts by weight of α-methylstyrene with 35 to 10 /at least parts by weight of acrylonitrile and 0 - 5 parts by weight of copolymerizable vinyl monomer and contains 30 parts by weight or more of a component having an α-methylstyrene content of 82% by weight or higher, more preferably 10 parts by weight or more of a component having an α-methylstyrene content of 86% by weight or highern. This copolymer has remarkably higher heat resistance as compared with those of the conventional copolymers. By the conventional emulsion polymerization technique, it is difficult to incorporate 30 parts by weight or more of a component containing 82% by weight or more of α-methylstyrene, and thus the resulting heat distortion temperature is 115 - 117°C at best. The copolymer according to this invention can easily have a heat distortion temperature of higher than 117°C. Further, by mixing a graft copolymer (B) with this copolymer (A), there can be obtained a resin composition having high heat resistance and excellent impact resistance. Such a resin composition may be obtained as follows:

    [0009] The copolymer (A) is mixed with a graft copolymer (B) which is obtained by reacting 35 - 85% by weight of a diene rubber and 65 - 15% by weight of a monomer mixture comprising an aromatic monovinyl compound and an unsaturated nitrile compound in a ratio of the aromatic monovinyl compound to the unsaturated nitrile compound of 85 - 60: 15 - 40 so as to give a diene rubber content of 5 - 30% by weight. Thereby a thermoplastic resin composition excellent in both heat resistance and impact resistance

    [0010] is obtained. The copolymer according to the invention is a copolymer with a high content of α-methylstyrene (A). Said copolymer is used /to impart heat resistance to the thermoplastic resin composition which is also a subject of the invention.

    [0011] The process for producing said copolymer is now described. α-Methylstyrene monomer is first charged into a reaction system for emulsion polymerization and, after making the system fully emulsified, acrylonitrile is continuously added dropwise in very small amounts, while in the polymerization system the proportion of the α-methylstyrene monomer and the acrylonitrile monomer is always maintained at great excess of α-methylstyrene as a weight ratio of 90/10 or higher, more preferably 95/5 or higher. Thereby the desired copolymer is obtained. In this case, the amount of the α-methylstyrene to be charged first is at least 65 parts by weight and up to 90 parts by weight.With an amount of less than 65 parts by weight, the heat resistance of the resulting copolymer and resin composition is reduced, while with an amount of more than 90 parts by weight, their mechanical properties are impaired. The amount of the acrylonitrile monomer to be continuously added dropwise is at least 10 parts by weight and up to 35 parts by weight. With an amount of less than 10 parts by weight, the percent conversion by polymerization is reduced, while with an amount of more than 35 parts by weight the resulting copolymer tends discolor on heating and also easily brings about deterioration in physical properties. The α-methylstyrene monomer to be charged first may contain up to 10% by weight based on the α-methystyrene monomer of anunsaturated nitrile compound, lower alkyl esters of methacrylic acid and acrylic acid and the like. The acrylonitrile monomer to be continuously added dropwise may contain up to 15% by weight based on the acrylonitrile monomer of an aromatic monovinyl compound, an α-substitued type aromatic monovinyl compound, lower alkyl esters of methacrylic acid and acrylic acid and the like. As a third component other than α-methylstyrene and acrylonitrile, it is possible to employ up to 5 parts by weight of the above-mentioned vinyl monomer or monomers substantially without adversely affecting heat resistance or impactiresistance.

    [0012] .When it is incorporated in an amount beyond the above range, both physical properties are impaired. This is not desirable..

    [0013] The graft copolymer (B) to be used in the thermoplastic resin composition according to the invention may be obtained by reacting a diene rubber with an unsaturated nitrile compound and an aromatic monovinyl compound represented by acrylonitrile and styrene, respectively. The composition of said graft copolymer is such that the diene rubber comprises 35 - 80% by weight and the unsaturated nitrile compound plus the aromatic monovinyl compound comprise together 65 to 15% by weight. It is preferred that the ratio of the aromatic monovinyl compound to the unsaturated nitrile compound is 85 - 60 : 15 - 40 on the weight basis. In the above- mentioned graft copolymer (B), examples of the diene rubber to be used are polybutadiene, polyisoprene, butadiene - styrene copolymers etc. The invention, however, is not restricted thereto.Also,examples of the aromatic monovinyl compound to be employed include, in addition to styrene, α-methylstyrene, chlorostyrene, tertiary-butylstyrene etc. Examples of the above-mentioned unsaturated nitrile compound are acrylonitrile as well as methacrylonitrile etc.. Further, a part of the above-mentioned aromatic monovinyl compound and unsaturated nitrile compound may be replaced by a lower alkyl ester of methacrylic acid or acrylic acid or the like.

    [0014] the The above-mentioned copolymer (A) and/graft copolymer (B) may be preferably obtained by emulsion polymerization, but the type of polymerization is not limited to emulsion polymerization. Emulsion polymerization may be carried out in a conventional manner. For example, the above-mentioned monomer mixture may be reacted in the presence of a free-radical initiator in an aqueous dispersion. As the free-radical initiator, there may be mentioned peroxides such as potassium persulfate, ammonium persulfate, cumene hydroperoxide etc. In addition, other additives, e.g. a polymerization co-catalyst, a chain transfer agent, an emulsifier etc., which have heretofore been conventionally employed in emulsion polymerization may be appropriately chosen and used.

    [0015] The heat resistance and impact resistance of the thermoplastic resin composition according to this invention can vary depending not only on the compositions or the copolymer (A) and the graft copolymer (B) respectively but also on the mixing ratio thereof. Therefore, the mixing ratio may be selected according to the desired heat resistance and impact resistance, and for the purpose of successfully achieving this invention, it is preferred to mix so that the diene rubber content of the composition after mixing is 5 - 30% by weight. Mixing itself may be effected in a known manner. For example, it is possible to mix respective latexes of the copolymer (A) and the graft copolymer (B) together, saltify the mixture to obtain a coagulated product and, after drying, use it. Alternatively, respective powders or pellets of the copolymer (A) and the graft copolymer (B) are kneaded in a roll mill, an extruder, a Banbury mixer, a kneader etc. and thereafter provided for use. In addition, if necessary, conventional stabilizer, pigments, lubricant, fillers etc. may be added on mixing.

    [0016] This invention is more particularly described by the following examples, in which all the "parts" mean "parts by weight".

    Examples and Comparative Examples


    1) Production of Copolymer (A)



    [0017] The following materials were charged into a reactor equipped with a stirrer:



    [0018] After flushing with purified nitrogen and subsequent heating with stirring at 60°C in a nitrogen stream, the monomer mixture (I) indicated in Table 1 was charged. After fully emulsifying and mixing the system, the monomer mixture (II) indicated in Table 1 was continuously added dropwise. On completion of this addition, stirring was further continued at 60°C and then the polymerization was terminated. The copolymer latex formed was coagulated with calcium chloride, then washed with water, separated by filtration and dried to obtain a powder-polymer, which was then pelletized and measured for heat resistance. In addition, the latex in the course of the reaction was taken as samples, and the composition was anaylzed and the conversion to polymer measured. The conversion, composition and heat resistance of the thus obtained copolymer are given in Table 1.

    [0019] Further, using the same monomers as those for A-10 in Table 1 [the monomer mixtures (I) and (II)], the monomer mixture (I) was continuously added dropwise together with 0.5 part of cumene hydroperoxide and subsequently the monomer mixture (II) was continuously added dropwise together with 0.1 part of cumene hydroperoxide, after which stirring was continued at 60°C. The heat distortion temperature of the obtained copolymer was 113°C.



    [0020] From the results shown in Table 1 and those described above, it is evident that the heat resistance of the copolymers of this invention is superior to those of the copolymers obtained in the prior art. That is, the α-methylstyrene - acrylonitrile copolymers obtained in the prior art had a limited heat resistance because most of each such copolymer was composed of an alternating copolymer of α-methylstyrene and acrylonitrile. Conversely,

    as shown as A-1 to 6 in Table 1, the copolymers of this invention contain components containing 82% by weight or. more of α-methylstyrene and thus exhibit excellent heat resistances which have not heretofore been achieved.


    2) Production of Graft Copolymers (B)



    [0021] The following materials were charged into a reactor equipped with a stirrer.



    [0022] After flushing with purified nitrogen and subsequent heating with stirring at 60°C in a nitrogen stream, 12 parts of acrylonitrile and 28 parts of styrene were continuously added dropwise together with 0.3 part of cumene hydroperoxide. On completion of this addition, stirring was continued at 60°C and then the polymerization was terminated.

    3) Production of Thermoplastic Resin Compositions



    [0023] The copolymer (A) and graft copolymer (B) produced as described above were mixed together in the latex form at a proportion of 75 : 25, and this mixed latex was, after adding an antioxidant, coagulated with calcium chloride, washed with filtration water, separated by / and dried to obtain a powder copolymer mixture which was then pelletized and provided for measurement of physical properties. The results are shown in Table 2.

    [0024] As evident from the results of Table 2, the compositions C-1 to 6 according to this invention exhibit remarkably superior heat resistance as compared with the prior art compositions and afford thermoplastic resins having a combination of the desired excellent heat and impact resistance.




    Claims

    1. A copolymer with a high content of α-methylstyrene which is characterized in that it is a copolymer comprising 65 - 90 parts by weight of α-methylstyrene with 35 - 10 parts by weight of acrylonitrile and 0 - 5 parts by weight of at least one copolymerizable vinyl monomer and that a component having an α-methylstyrene content of 82% or higher is contained in an amount of 30 parts by weight or more.
     
    2. A process for producing a copolymer with a high content of α-methylstyrene which is characterized by charging 65 parts by weight or more of α-methylstyrene and 10% by weight or .one less, based on this α-methylstyrene, of acrylonitrile and at least / vinyl monomer all in one portion at the initial stage, making the system fully emulsified, gradually adding 35 parts by weight or less of acrylonitrile and of the vinyl monomer or monomers, and /carrying out emulsion polymerization until the amount of polymer produced has reached 50 parts by weight or more in such way that the ratio of the α-methylstyrene monomer to the monomers other than α-methylstyrene in the system is always maintained at 90/10 or higher on the weight basis.
     
    3. A thermoplastic resin composition which is characterized in that it comprises (A) a copolymer with a high content of α-methyl styrene comprising 65 - 90 parts by weight of α-methylstyrene with 35 -.10 parts by weight of acrylonitrile and 0 -5 parts by weight of at least one copolymerizable vinyl monomer and containing 30 parts by weight or more of a component having an α-methylstyrene content of 82% by weight or higher, and (B) a graft copolymer which is obtained by reacting a diene rubber with a monomer comprising an aromatic monovinyl compound-and an unsaturated nitrile compound and that the diene rubber is in an amount of 5 to 30 parts by weight.
     





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