• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU967277A3
    申请号:SU782634046
    申请日:1978-07-12
    公开日:1982-10-15
    发明作者:Делсарт Жак
    申请人:Продюи Шимик Южин Кюльман (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR OBTAINING PRIVATED COPOLYMERS
    The invention relates to the production of graft copolymers by graft polymerization and an emulsion suspension.
    This method allows to obtain a product that has excellent fluidity at high temperatures and a very good surface appearance, including excellent gloss, while maintaining good mechanical properties, including impact strength and tensile strength.
    Among the known methods of grafting polymerization of ethylenically unsaturated monomers on elastomeric grafted skeletons, the so-called water emulsion method can be satisfactory only if 20 used for grafting latexes are polydisperse. If elastomer one-dimensional latexes are used with the same method, then products are obtained whose fluidity at high temperature and the appearance of the surface of which can be satisfactory, and the resistance to impact is mediocre flj,
    The described method makes it possible to obtain products with a high impact strength and good fluidity at high temperatures, but with poor hardness and tensile strength, and the appearance of their surface is particularly mediocre.
    The closest to the proposed technical essence and the achieved result is a method of obtaining graft copolymers by emulsion polymerization of vinyl monomers in the presence of one-dimensional latex, followed by the addition of reactive compound to the obtained product and suspension polymerization of the resulting mixture 2.
    However, the obtained graft copolymers do not have high strength, and the appearance of their surface is unsatisfactory. The purpose of the invention is to increase the strength of the copolymer and improve its surface. The goal is achieved by the fact that according to the method of obtaining graft copolymers by emulsion polymerization of vinyl monomers in the presence of one-dimensional latex, followed by the addition of a reactive compound to the resulting product and suspension polymerization of the resulting mixture as winch monomers a mixture of styrene and acrylonitrile or methyl methacrylate is used; lolybutadIen or co is used as one-dimensional latex polymer styrene with butadiene, emulsion polymerization is carried out to the ratio of ax,. "," 0 - y - 50-112, where X is the degree of conversion of monomers,% in - the amount of latex elastomer, parts by weight dry matter; a is the total amount of monomers, parts by weight, and a mixture of styrene and acrylonitrile or methyl methacrylate and polybutadiene or copolymer of styrene with butadiene is used as a reactive compound. The peculiarity of the “Jlx one-dimensional latexes is extremely narrow. Granulometric Distribution, medium The lower diameter of the fractions is 300–3000 A, and the best is 500–2500 A. The first stage, called the stage of polymerization in the emulsion, takes first 60–90, and better than 70–90% of the total quantity of one-dimensional latex, the composition of the graft copolymer, and the rest The latex, called one 4-sided additional latex, is added at the end of the emulsification prior to the casting stage, and the state of suspension of the reaction medium and after the desired ratio Xt / X is achieved. It is not necessary to use this one-dimensional additional latex, which is used at the beginning of the polymerization in the emulsion, it is only important so that it is a one-dimensional latex grafted elastomer. When using the same latex, it is desirable that the percentage of the gel defined in BNZOLE is 80-95, with a coefficient of swelling of approximately 8-18. In contrast, when using one-dimensional extra latex, different from that used at the beginning of the polymerization in the emulsion, it is desirable that the percent gel be O-OO and even better 60-80% for a factor of 967 to blow up approximately 18-AO. In this latter case, the latex applied at the beginning of the emulsification usually has a gel percentage of 80-95% for a swelling ratio of approximately 8-18. In order for the grafting of the emulsion step to be carried out in good conditions ,. In particular, without occurrence ({shock and without excessive contamination of the reactor, it is recommended to pre-stabilize the latex before the emulsifier is introduced during the polymerization. The most common stabilization systems are used, such as, for example, fatty acid soap, alkyls and alkylarylsulphates, salts of resins, acids, water-soluble polyoxyalkylenes. In these systems, it is better to look for sodium or sodium to use lauric acid, about 0, parts of the suspension are relatively dry latex. All elastomers having an unsaturation of at least 3 wt.% and representing one-dimensional latex are suitable for the proposed method. These elastomers are either homopolymers, such as polyisoprene, polychloroprene, polybutadiene, or copolymers based on ethylene, propylene, for example. , isobutylene, or copolymers of styrene and butadiene, acrylonitrile, and butadiene.Natural rubber is also suitable as an elastomer for the proposed method., mainly elastomers for use in production; e copolymers in this way polybutadienes are used, and styooh and butadiene copolymers are also used. When using styrene and butadiene copolymer, the styrene content is usually less than 20 wt.%. The monomers of the proposed method can be introduced completely during the stage of polymerization in the emulsion. They can also be introduced separately. Additional monomer can also be introduced at the end of the emulsion polymerization, when the desired ratios are reached. Among the aromatic vinyl derivatives used as monomers in the process, styrene, o /, methylstyrene, or substituted styrenes, such as o-methylstyrene, u-methylstyrene, I-methylstyrene, dimethylstyrenes, trimethylstyrene and halogenostyrenes, can be mentioned as examples. - such as 2,5-Lichlorostirol. Among acrylic and methacrylic X derivatives used as monomers, acrylic and methacrylic acids, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, methyl methacrylate, ethyl methacrylate, acrylonitryl, - methacrylonitrile can also be mentioned as examples. It is possible to replace part of one or all of the monomers of a mixture consisting of one aromatic vinyl derivative and one acryl or thiacryl derivative, a third monomer, such as vinyl chloride, vinyl ester (i.e., acetate, or propionate, vinyl ether, such as ethyl vinyl ether. Very suitable for use with styrene-acryl and acrylonitrile, in which case the weight ratio of styrene-acrylonitrile is usually between 80/20 and preferably about 70/30, and the resin to be formed has composition close This mixture can be azeotropic. The styrene-methyl methacrylate mixture is also well suited. The proposed method can be carried out in a temperature controlled reactor and mixing device that corresponds to the classical, emulsion and suspension methods. At the stage of emulsion polymerization, they are used in accordance with the known method. in the emulsion phase, the amount of latex and monomers is introduced into a solution containing the amount of water required for the reaction. : Alternatively, the monomers may be injected regularly with emulsion polymerization via, for example, a metering pump. With such an offset, in order to ensure good homogenization of the reaction medium, the temperature is maintained between 20 and 100, and preferably between 40 and 80 ° C. The reaction is continued until the selected C1X / C ratio is reached. In this phase, an additional one-dimensional latex is added and the monomer can be added, then the polymerization is started in the suspension of the second stage of the process by introducing a colloid protective solution into the reaction medium. This polymerization in suspension is carried out by tacloids,
    The initiators are usually of two kinds: water soluble, always more effective under known mixing conditions, temperature and reaction time. The reaction temperature is generally maintained between kO - and, and preferably between 60 and for a time sufficient to completely polymerize the monomers. After the completion of the reaction, the reactor is emptied, and after decanting, centrifuging and drying, the graft copolymer in the form of dragees is obtained. The dry grades contain less than 0.1 residual monomers. The described method may also be performed in other known ways. It is possible, for example, to carry out polymerization in an emulsion suspension continuously in several reactors arranged in steps. All auxiliary agents that can be introduced during classical polymerization in emulsions and suspensions can be used in the proposed method. Thus, at the polymerization stage of in-emulsion, known initiators, chain transfer reagents, catalysts, anti- are used. , Bicants, lubricants. At the same stage, initiators, chain transfer reagents and protective ones are used in the polymerization process In the emulsion, and fat soluble, which are preferable to be used in suspension polymerization. Examples of emulsion polymerization inhibitors include potassium persulphate, ammonium persulphate, sodium peroxide, hydrogen peroxide, azo compounds, such as azo bis, iso-butyronitrile or 2,2-azo-bis (2,4- di-methylvaleronitrile), as well as the following polymerization initiators in suspension: peroxydicarbonates, such as bis (-butylcyclichexyl) peroxydicarbonate; a, decanoyl peroxide, aromatic peroxides, like benzoyl peroxide, perpivalates, like tertiary butyl pergravate, perbenzoates, like tertiary butyl perbenzoate, and peracetates, like tertiary butyl percetate. - tert-butyl perbenzoate, used alone or together in a slurry polymerization step. In addition to these catalysts, all known catalysts for this type of polymerization are suitable for use in the proposed process. The use of chain transfer reagents during the emulsion polymerization step is recommended to improve the flowability of the final graft mix. The most well known are linear and branched mercaptans, thioethers, dimerobol-methylstyrene, some olefinic compounds,. Protective colloids used in the step of polymerization in suspension, are classic, well-known products: for example, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid, polyacrylamide, karboksimetilmetiltsellyuloza, polyvinyl alcohol, polyglycols, same Latina, water-soluble alginates, and mixtures thereof, wherein , preference is given to hydroxyethyl cellulose and poly vinyl alcohol. Mineral reagents can also be used, such as, for example, calcium triphosphate, B mainly used in an aqueous solution in a range of 0.1 to 3 weight per hour, relative to the weight of the polymer produced. It is desirable, but not necessary, to add lubricants to the reaction mixture prior to the slurry polymerization step. These are classic lubricants such as mixtures of solid paraffin and hydrocarbon oils, refined mineral oils or such esters, kaK butyl stearate, and dioctyl phthalate. They are used in amounts of -C weight, Mi per 100 weight, h, graft copolymer. The proposed method allows to produce graft copolymers containing 10-70%, and preferably kO-6Q% elastomer; Graft copolymers containing kO - (% elastomer have, in general, a very high resistance to impact, which allows to produce commercially available copolymers with different qualities s produced by mixing in different yulichestvah graft copolymer with other polymers or copolymers. Thus, these graft copolymers can be blended with the graft copolymers with polyvinyl chloride to various elastomers with an acrylonitrile-butadiene-styrene, grafted copolymers of acrylonitrile and styrene on elastomers with low percentage of unsaturation, such as copolymers, monomeric ethylene-propylene-diene (MPD) or butyl or acrylic rubbers, as well as with resins, such as, for example, polyvinyl chloride reed, styrene and acrylonitrile resins and their derivatives. Such mixtures typically have a weight content of elastomer between 5 and 60, and preferably between 10 and ku%. . This method of producing graft copolymers reduces agglomeration of graft latex in an emulsion at the time of suspension, which ensures the appearance of a gloss on the final product and due to the additional introduction of latex at the end of the emulsion polymerization, provides a sufficient increase in the number of particles to obtain good mechanical properties product, and good adhesion is provided by polymerization-grafting in suspension of the remaining monomers. The advantage of this method of ejcH is that it is realized by the use of one-dimensional latexes that can be easily manufactured,. Until now, one-dimensional letexes did not allow such an inoculation to take place so that the final product would have good mechanical properties at the same time. nojq external appearance of the surface, In examples lk, mixtures 1-3 are used, while mixture 1 is a graft copolymer mixed with styrene-acrylonitrile | copolymer; 70% by weight, styrene and 30% by weight acrylonitre la and having an internal viscosity measured in dimethylformamide of 0.6 ml / g. The content of the elastomer is 28% by weight, depending on the weight of the final mixture. Mixture 2 corresponds to mixture 1. The only difference is that the content of the elastomer is 13.5 weight, relative to the weight of the final mixture. Mixture 3 is a graft copolymer mixed with o (α-methylstyrene-acrylonitrile copolymer containing b9 weight) methylstyrene and 31 v.s.% acrylonitrile and having an internal viscosity, measured in dimethylformamide and equal to 0.60 dl / g.
    To determine the mechanical properties of the graft, graft copolymers of these examples i are mixed with the copolymer in an internal mixer. Mass renewed in ex,
    covered, then granulated. Pellets are introduced by aiHTOBorofO press. The injection conditions for each example are listed in the table below. 1, T a b e and c a 1. The following qualities are measured: Resistance to Izod impact according to the standard L5TM 25b-5b, expressed in dyul x / meters; Mu Ne Ml viscosity (), measured at 177 ° С; deformation temperature under load (BAT) 18.5 dan, measured in accordance with ASTM D 646-58T and expressed in degrees Celsius; tensile strength at the rate of ASTHD 638-6 T expressed in meg pascals; Rockwell R hardness according to ASTM D 785-65; gloss, gloss measurements are carried out on plates introduced by a press at a pressure of 70 bar and at 25 ° C using a Lange gloss meter (Universal Mesgeret), acting by reflecting at an angle of incidence and calibrated before each measurement so that it is black and the glittery ceramic tile gave a value of 100., Carry out, all the examples in the same reactor, having a thermostatic device with a temperature of 30-140C and with a mixer, the rotation speed of which varies between 60 and 500 rpm. This reactor is designed to have an internal pressure resistance of less than 15 bar, and has several openings allowing various additions to be made. Several metering pumps and several sieves provided for high pressure resistance may be used for this reactor.
    In all examples, the amounts of products used are expressed in weight relative to 100 parts by weight. graft copolymer.
    Examples 1, 2 and 3 are provided for comparison and are intended to clarify the limits and identify their benefits.
    Example 1. Suspension of the reaction medium is carried out without performing preliminary emulsion polymerization. The characteristics of the latex used are shown below. Nature One-dimensional polybutadiene Dry extract,% Pz (average diameter in quantity), A J) p (average diametr in weight), A 2.050 Mooney viscosity 220 Percent gel,% 87.9 Blister index. Stabilization, Laurat potassium, 1 with Mooney: AL 1 + 4 / ZKbjdiLV / t The produced graft copolymer contains 50% polybutadiene 381 styrene and 12 acrylonitrile. The reactor is filled with 50 parts of latex 8, calculated on the dry extract. The solution is diluted so that the total water content, including tex water, is 1bO h. Then, 0.5 parts of potassium persulfate is dissolved in 5 parts of water, the mixture contains 38 parts of styrene, 12 hours of acrylonitrile , 0.4 parts of tridodecyl mercaptan, 1.5 parts of trinonylphenyl phosphite, 0.2 parts of tributyl perpivalate. Then 1.5 m. Of polyvinyl alcohol is added to the solution in 50 parts of water. Close the reactor. Stir at 250 rpm and heat to 10 hours. After cooling, fine powder is obtained, which is washed, centrifuged and dried. As a result, the properties shown below are Izod, J / m Stretching, BDT hardness, C 51 (type of surface 22 (Surface type surface is uneven and even and dull) dull) This experience shows that bringing to suspension of the reaction medium from the very beginning of the reaction, i.e. without an emulsion rolling stage, leads to graft copolymers that produce Products with an uneven and mat surface appearance, Rokuell low hardness, weak tensile strength, Mooney satisfactory viscosity and relatively high impact strength From medium enriched graft copolymers, and low grades, for grains depleted of graft copolymers. Example 2 (comparison). The reduction of the reaction medium to the state occurs at the moment when the grafting of emulsion polymerization is still insufficient. The characteristics of the latex used are shown below. Latex designation O One-dimensional Nature of polybutadiene 32 Dry extract,% Viscosity Mooney Index Blow,% Gel percentage,% Stabilization,% Sodium Laurate, 1.3 A graft copolymer containing 50 polybutadiene, 38 styrene and 12% acrylonitrile was manufactured. The reactor is filled with 50 parts of polybutadiene in terms of dry (extract. The solution is diluted with 150 parts of water, including latex. Mixed at 80 rpm and heated to 60 ° C. With a solution of 0.5 parts of persulfate water for 10 parts of water, then include a standing feed with a mixture consisting of 1., 7 parts of styrene and t parts of acrylonitol, which is fully introduced into the reactor for one hour at. A sample that is taken in this moment, gives a dry extract of 27.9. A mixture consisting of 25.3 parts of styrene and parts of acrylonitrile, 0.3 parts of tridodecylmercaptan, 1 part three is added using a sieve. nonylphenylphosphite, 0.2 parts of tributyl perpivalate. Mixed at 250 rpm, Add 2 parts of polyvinyl alcohol polyviol () in a solution of 1PO parts of water using a sieve. Keep the medium temperature for 10 hours. Then under normal conditions a copolymer is obtained. The measured mechanical qualities are given below. Izod, J / m Stretch, Hardness 56. BAT, “with 94 41 (dull gloss surface type) 27.9% dry extract, measured at the end of the emulsion grafting, corresponds to the conversion The content of monomers present, introduced by n emulsion. The ratio ah /, previously defined, is 127.7 - “- 4 26.8%. . 50 The emulsion graft is insufficient, the product has an increased impact strength, but it is clearly insufficient. Example 3 (comparison). The graft copolymer is made only by emulsion polymerization. The used latex is identical to latex in example 1, but it is not stabilized. The copolymer produced contains 50 polybutadiene, 38 styrene, 12% acrylonitrile. The reactor is filled with 50 parts of polybutadiene, calculated on the dry extract. The solution is diluted with 180 parts of water. Heat to 62C, mixing at 80 jub / min. At this temperature, a solution of 0.5 parts of potassium persulfate is added to 10 parts of water and immediately begin to make constant additions of monomers and a constant addition of 2.5 parts of rosin to 35 parts of water, while maintaining the temperature. These two constant additives are continued for 4 hours. The added mixture of monomers consists of P-967 38 parts of styrene, 12 parts of acrylnitrile and 0.35 parts of tridodecyl mercaptan. Next, the reaction proceeds at 6 hours. The graft copolymer is then flocculated with scoop and magnesium sulfate solution, which is further dried and mixed with resin to obtain mixture 1. The following mechanical properties are achieved. Izod, J / m Rast MPa Hardness ndt, h 93 (outer gloss surface is smooth and glossy) 5
    Table 2 7714 The resulting product has a clearly insufficient impact strength (Izod). In addition, the cTHpojri remaining at the end of the reaction is 0.7 and the residual moisture before drying is 3. The following examples (, 5) are within the scope of the proposed polymerization method. In these examples, for a product with 50 elastomers, the percentage of moisture content before drying is about 22%, and the amount of residual monomers is less than O, P. An example. Acrylonitrile-butadiene-styrene (ABC) type copolymers are made. The characteristics of the latex used are given in table. 2
    1596727716
    In accordance with the table. 3, the reaction of calculating the ratio of ax /. The mediator is then filled in. And parts of the latex are injected into the sieve system.
    in dry extract (latex designation (latex designation is given in
    Sa is given in brackets in Table. 3. Rast-brackets in table 3, the solution of which
    the thief is diluted so that the $ is prepared in advance in such a way
    the total amount of water, including the water content to be the total water represented by the latex, was represented as B parts.
    At 80 rpm, J parts are styroted and agitated in a sieve production aid reactor, heated re, K parts acrylonitrile, b parts
    stock Wednesday to. 0TDM, M parts of an antioxidant like phos C parts of potassium persulphate, dissolved phyte, N parts of tributyl perpivalate,
    foot in 10 hours of water. Regulate tempe-P parts of lauroyl peroxide, 0 parts
    hold up to and begin to constant tributyl perbenzoate. nutrition with the following mixture: styrene C
    parts, acrylonitrile E parts, three 15300 rpm, and with the help of another sieve
    dodecyl mercaptan (TDM) p. parts. This is introduced into 1 parts of polyvinyl.
    the constant food, carried out SPVS alcohol dissolved in 5 h,
    using a metering pump, regul-water. When stirring, the mixes are produced in such a way that the suspension cycle is complete, the indicated
    the mixture was introduced into the reaction table-20b. 3. Then empty and cool for 6 hours. When the reactor is continuously fed. The dragee is washed with water,
    Completion is complete, the dry extract is centrifuged, and then dried, it is tested on the grafted sample. Mechanical properties of mixtures
    tex. This dry extract serves for the table below. C.
    - T a b l and c a 3
    17
    38, i
    Dry extract, 35.9
    Conversion
    967277
    18 Continued table. 3
    37,8
    36.5 36.6
    31.2, 2, 7.7 Stretch, IPa 7.5. EXAMPLE 5. A graft copolymer of the type methacrylate methyl butadiene styrene (IBS |) was made. For this, the reactor was filled with kOh, the latexar of example k was calculated dry extract. Mix at 80 rev / min and dilute the solution so that the total amount of water is 120 hours. Heat up. When a solution is introduced from a part of potassium persulfate and 8 parts of water, constant nutrition is started for a total duration of 3 m. Of a mixture consisting of 28 parts of methyl methacrylate, 12 hours of styrene and 0.2 parts of tridodecylmercaptan. dry extract is made, which is equal to 3B, which corresponds to a conversion content of 88%, and the ratio / is 88 88%. With the help of a sieve, 10 parts of latex are used, for example, dissolved in such a way that the total water content is 30 hours , then - a mixture of 7 parts of methyl methacrylate, 3 parts of styrene, (G, 3 parts of lauroyl peroxide and 1 hour of antioxidant of the type (Bosphite. The temperature is brought to, the reaction medium is mixed at 350, and then the solution is introduced 1.1 h polyvinyl alcohol dissolved in 100 parts of water. The temperature is regulated for 5 hours.
    权利要求:
    Claims (2)
    [1]
    Continued table. , 7, 2, 3,0 Dragee grafted copolymer, washed with warm water, centrifuged, and then dried This graft copolymer is mixed so that the final mixture contains 2Q% polybutadiene, with methylstyrene copolymer containing 70. wt.% Methyl methacrylate and 30 wt. % styrene, and with an internal viscosity, measured in dimethylformamide 0.5 ll / g. This mixture, sprayed at 175 under a pressure of 120 bar, has the mechanical qualities shown below. Izod, j / m250 Muni 5 GlavtVZ Thus, the invention makes it possible to obtain grafted copolymers with high strength and good surface. The invention method of obtaining graft copolymers by emulsion polymerization of vinyl monomers in the presence of one-dimensional latex followed by the addition of a reactive compound to the resulting product and suspension polymerization of the resulting mixture, different
    21Ch6727722
    By the fact that, in order to increase the strength, a is the total amount of monomers, ti of the copolymer and the improvement of its surface by weight.h.
    In particular, as a vinyl monomer, a mixture of styrene and acrylonite compounds is used as a reactive mixture; a mixture of styrene and
    or methyl methacrylate as s-acrylonitrile or methyl methacrylate
    ae one-dimensional latex - polybutadiene polybutadiene or styrene copolymer
    or copolymer of styrene with butadiene, with butadiene.
    emulsion polymerization is carried out by sources of information. before attitude
    50-112%, 1. US Patent ",
    where X is the degree of conversion of monomers, cl. 260-880, published. T9b9. .
    ;
    [2]
    2. US patent N3 50796,
    B - the amount of latex-elastomer el. 260-885, published. 19b9 (protos, parts by weight of dry matter; 15type).
    Taken into account during the examination
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    同族专利:
    公开号 | 公开日
    IE781369L|1979-01-12|
    DE2861665D1|1982-04-15|
    NO149547C|1984-05-09|
    CS207637B2|1981-08-31|
    DK149433B|1986-06-09|
    IT1108113B|1985-12-02|
    DK149433C|1986-11-24|
    JPS5418893A|1979-02-13|
    FR2397431A1|1979-02-09|
    PL111070B1|1980-08-30|
    EP0000462B1|1982-03-17|
    NO149547B|1984-01-30|
    DK310478A|1979-01-13|
    NO782417L|1979-01-15|
    IE47114B1|1983-12-28|
    IT7868637D0|1978-07-11|
    FR2397431B1|1981-02-13|
    CA1099842A|1981-04-21|
    ES471638A1|1979-10-01|
    EP0000462A1|1979-01-24|
    US4186155A|1980-01-29|
    JPS6223766B2|1987-05-25|
    PL208319A1|1979-03-12|
    DD136844A5|1979-08-01|
    引用文献:
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    RU2588139C1|2013-06-28|2016-06-27|ЭлДжи КЕМ, ЛТД.|Method of producing thermoplastic resin, characterised by excellent surface and lustre|US3370105A|1963-05-07|1968-02-20|Bell & Richardson Inc De|Process for manufacture of impact polymers|
    US3436440A|1964-05-14|1969-04-01|Hitachi Chemical Co Ltd|Method of graft-copolymerization of monomers onto diene-type polymer|
    US4011283A|1970-02-06|1977-03-08|Bp Chemicals Limited|Polymerization process|
    US3887652A|1970-11-09|1975-06-03|Dart Ind Inc|Process for producing transparent graft polymer compositions|
    CA1026038A|1973-06-14|1978-02-07|Foster Grant Co.|Styrene-acrylonitrile grafted polybutadiene polymeric composition having high impact at low rubber levels|
    US4042647A|1975-03-21|1977-08-16|Uniroyal, Inc.|Latex suspension process and graft polyblend composition using small particle size spine|
    JPS5533768B2|1975-07-31|1980-09-02|JPS58145716A|1982-02-25|1983-08-30|Kazuo Saotome|Graft polymer composition|
    DE3304544A1|1983-02-10|1984-08-16|Bayer Ag, 5090 Leverkusen|ABS MOLDS|
    FR2619569B1|1987-08-20|1990-09-07|Charbonnages Ste Chimique|METHOD FOR MANUFACTURING AN IMPACT RESISTANT THERMOPLASTIC RESIN COMPRISING A STEP OF TRANSFER OF PARTICLES OF A REINFORCEMENT LATEX IN THE MATRIX MONOMERS, USING IONIC AGENTS|
    JPH0230764U|1988-08-20|1990-02-27|
    JPH0285629U|1988-12-22|1990-07-05|
    US5380785A|1993-04-05|1995-01-10|The Goodyear Tire & Rubber Company|Rubbery polymer|
    WO2000077009A1|1999-06-14|2000-12-21|Ortho-Mcneil Pharmaceutical, Inc.|DITHIEPINO[6,5-b]PYRIDINES, AND RELATED COMPOSITIONS AND METHODS|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7721435A|FR2397431B1|1977-07-12|1977-07-12|
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