DK168446B1 - Styrene / butadiene graft copolymer latex - Google Patents

Styrene / butadiene graft copolymer latex Download PDF

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DK168446B1
DK168446B1 DK598485A DK598485A DK168446B1 DK 168446 B1 DK168446 B1 DK 168446B1 DK 598485 A DK598485 A DK 598485A DK 598485 A DK598485 A DK 598485A DK 168446 B1 DK168446 B1 DK 168446B1
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polymerization
styrene
graft copolymer
mass
butadiene
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DK598485A
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DK598485D0 (en
DK598485A (en
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Herbert Schlueter
Herbert Knipp
Alfred Wieland
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Huels Chemische Werke Ag
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
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Abstract

1. A styrene/butadiene graft copolymer latex obtained by emulsion polymerization in the presence of 1 to 6% by weight of a conventional fat soap and/or resin soap as emulsifier and >= 0.3% by weight of a conventional molecular weight regulator for the polymer, each percentage being based on the total monomers, and characterized by the following features : a) the emulsion polymerization is carried out by a semi-continuous emulsion-feed process ; b) the graft copolymer is composed of 35 to 65% by weight of the graft base (A) which in turn is composed of the graft base (A1) and the grafted-on component (A1), and 35 to 65% by weight of component (B) grafted on in the final step ; c) the graft base (A) is obtained in two polymerization steps ; in the first step, a polystyrene nucleating latex is obtained whose solid (A1) is 1 to 20% by weight, based on the graft copolymer ; the component (A2) of the graft base (A), which is grafted on in the second step, is composed of 86 to 95% by weight of repeating units which are obtained by polymerization of styrene, and 5 to 14% by weight of repeating units which are obtained by polymerization of 1,3-butadiene ; feeding of the emulsifier during grafting being accompanied by intensive stirring in order to avoid the formation of new particles ; d) the component (B) of the graft copolymer, which is grafted on in the final step, is composed of 62 to 70% by weight of repeating units which are obtained by polymerization of styrene, and 30 to 38% by weight of repeating units which are obtained by polymerization of 1,3-butadiene ; feeding of the emulsifier during grafting being accompanied by intensive stirring in order to avoid the formation of new particles : e) the parameters in the preparation of the graft copolymer latex are selected such that the latex particles have an average diameter, determined by surface titration, of 120 to 300 nm.

Description

DK 168446 B1DK 168446 B1

Ifølge den kendte teknik fremstilles latexskum i reglen på den måde, at der ud fra en kautsjuklatex og en forstærkerlatex, dvs. latexen fra et forstærkende polymerisat, ved blanding af latexerne opnås en forstærket kautsjuklatex, den forstærkede 5 kaut s jukkomponent. Ud fra denne samt en virksom mængde af et vulkaniseringsmiddel og sædvanlige tilsætningsstoffer opnås en i varmen vulkaniserbar masse. Denne opskummes med luft eller en anden gas, får tilsat et geleringsmiddel, såsom f.eks. na-triumsilikofluorid, geleres og vulkaniseres så i varmen (DE-10 patent nr. 10 56 364, DE-offentliggørelsesskrift nr. 14 70 810) . Geleringen sker ved stuetemperatur i det infrarøde område eller i opvarmningsfasen til vulkaniseringen. Ved non-gel-fremgangsmåden bortfalder særlige foranstaltninger til geleringen. Det således fremstillede latexskum har en celleagtig 15 struktur.According to the prior art, latex foam is usually produced in such a way that from a rubber latex and an amplifier latex, ie. the latex from a reinforcing polymer, by mixing the latexes a reinforced rubber latex, the reinforced 5 kaut s yoke component, is obtained. From this as well as an effective amount of a vulcanizing agent and usual additives, a heat-vulcanizable mass is obtained. This is foamed with air or another gas, a gelling agent such as e.g. sodium silicofluoride, is then gelled and vulcanized in the heat (DE-10 Patent No. 10 56 364, DE Publication No. 14 70 810). The gelation occurs at room temperature in the infrared region or during the heating phase of the vulcanization. In the non-gel method, special measures for the gelling are voided. The latex foam thus produced has a cellular structure.

Latexskum skal have et godt egenskabsbillede, som kan beskrives med følgende egenskabskombination: a) Høj elasticitet i temperaturområdet fra 20 til 70°C, dvs. at i dette temperaturområde skal efter længere sammentrykning 20 trykdeformeringsresten (compression set) være lavest mulig (DIN 53 572).Latex foam must have a good property image which can be described by the following property combination: a) High elasticity in the temperature range from 20 to 70 ° C, ie. in this temperature range, after longer compression, the 20 compression set residue (compression set) must be the lowest possible (DIN 53 572).

b) Høj trækstyrke og høj forlængelse ved brud (DIN 53 571).b) High tensile strength and high elongation at break (DIN 53 571).

c) Ved forud given indtrykningshårdhed skal rumvægten være mindst mulig (DIN 53 576, økonomi) . Man kan også sige: Ved for- 25 ud given rumvægt skal indt rykningshårdheden (stødhårdheden) være størst mulig.c) For given impression hardness, the room weight must be as small as possible (DIN 53 576, economy). You can also say: At the given room weight, the indentation hardness (shock hardness) must be as high as possible.

Den beskrevne egenskabskombination realiseres kun ufuldkomment ved den kendte teknik.The described property combination is realized only imperfectly in the prior art.

I DE patentskrift nr. 24 55 726 foreslås et styren/butadien-30 podecopolymerisat til forstærkning af en syntetisk kautsjuk. Dertil blandes styren/butadien-podecopolymerisatet med den DK 168446 B1 2 syntetiske kautsjuk. De således opnåede blandinger egner sig til fremstilling af skosåler samt elektriske isolationsmaterialer. I modsætning til den ovenfor beskrevne kendte teknik blandes altså ingen latexer. Styren/butadien-podecopolymerisa-5 tet opnås ved emulsionspolymerisation efter en totrins batch-f remgangsmåde.DE Patent Specification No. 24 55726 proposes a styrene / butadiene graft copolymer to enhance a synthetic rubber. In addition, the styrene / butadiene graft copolymer is mixed with the DK 168446 B1 2 synthetic rubber. The mixtures thus obtained are suitable for the production of shoe soles as well as electrical insulation materials. Thus, contrary to the prior art described above, no latexes are mixed. The styrene / butadiene graft copolymer is obtained by emulsion polymerization following a two-step batch process.

Det er den foreliggende opfindelses opgave at tilvejebringe en forstærkerlatex, hvormed den beskrevne egenskabskombination kan realiseres bedre end ifølge den kendte teknik.It is the object of the present invention to provide an amplifier latex by which the described combination of properties can be better realized than in the prior art.

10 Opgaven blev løst på overraskende måde som anført i kravene.10 The task was surprisingly solved as stated in the claims.

Opfindelsen angår en som forstærkerlatex ved fremstillingen af latexskum egnet styren/butadien-podecopolymerisatlatex, som karakteriseres ved struktur- og fremgangsmådeparametre som følger: 15 a) den er opnået ved emulsionspolymerisation efter en grundlæggende kendt, semikontinuerlig emulsionstilløbsfremgangsmåde i nærværelse af 1 til 6, især 3 til 5 masse% af en sædvanlig fedtsæbe og/eller harpikssæbe som emulgator og s 0,3, især s 0,2 masse% af en sædvanlig forbindelse, som regulerer polyme-20 risatets molekylvægt, i hvert tilfælde beregnet på de samlede monomerer; b) podecopolymerisatet består af 35 til 65 masse% podeunderlag (A), som på sin side består af podeunderlag (Al) og påpodet andel (A2), og 35 til 65 masse% af en i det sidste trin påpo- 25 det andel (B) c) podeunderlaget (A) er opnået i to polymerisations trin; i det første trin opnås en polystyrenkimlatex, hvis faststofindhold (Al) andrager 1 til 20, især 5 til 15 masse% beregnet på podecopolymerisatet; den i det andet trin påpodede andel (A2) 30 af podeunderlaget (A) består af 86 til 95 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 5 til 3 DK 168446 B1 14 masse% gentagelsesenheder, som er opnået ved polymerisation af 1,3-butadien; ved tilløb af emulgatoren under podningen omrøres intensivt for at undgå dannelsen af nye partikler; d) den i det sidste trin påpodede andel (B) af podecopolymeri-5 satet består af 62 til 70 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 30 til 38 masse% gentagelsesenheder, som er opnået ved polymerisation af 1,3-butadien; ved tilløb af emulgatoren under podningen omrøres intensivt for at undgå dannelsen af nye partikler; 10 e) parametrene ved fremstillingen af podecopolymerisatlatexen udvælges grundlæggende på kendt måde således, at latexpartik-lerne har en ved overfladetitrering (sæbetitrering) bestemt middeldiameter i intervallet fra 120 til 300 nm.This invention relates to an styrene / butadiene pod copolymer latex suitable as an amplifier latex which is characterized by structural and process parameters as follows: a) obtained by emulsion polymerization following a basic known, semi-continuous emulsion process method in the presence of 3, to 5 mass% of an ordinary fat soap and / or resin soap as an emulsifier and s 0.3, in particular s 0.2 mass% of an ordinary compound which regulates the molecular weight of the polymerate, in each case based on the total monomers; b) the graft copolymer is comprised of 35 to 65% by weight graft (A), which in turn consists of graft (A1) and grafted portion (A2), and 35 to 65% by weight of a grafted portion (A) in the final step ( B) c) the graft substrate (A) is obtained in two polymerization steps; in the first step, a polystyrene chimlatex whose solids content (Al) is 1 to 20 is obtained, in particular 5 to 15% by weight, calculated on the graft copolymer; the proportion (A2) of the graft substrate (A2), which is grafted in the second step, consists of 86 to 95 mass% repeating units obtained by polymerization of styrene and 5 to 3 mass% repeating units obtained by polymerization of 1,3-butadiene; at the inlet of the emulsifier during grafting, it is stirred intensively to avoid the formation of new particles; d) the proportion (B) of the graft copolymer polymer grafted in the last step consists of 62 to 70 wt% repeating units obtained by polymerization of styrene and 30 to 38 wt% repeating units obtained by polymerization of 1, 3-butadiene; at the inlet of the emulsifier during grafting, it is stirred intensively to avoid the formation of new particles; E) the parameters in the preparation of the graft copolymer latex are basically selected in a known manner such that the latex particles have a mean diameter (soap titration) in the range of 120 to 300 nm.

Den s emikon tinuer lige emulsionstilløbsfremgangsmåde til frem-15 stilling af styren/butadien-podecopolymerisatlatexen er grundlæggende kendt (se f.eks. US-PS 4.134.872).The emicon tinous straight emulsion process for preparing the styrene / butadiene graft copolymer latex is basically known (see, for example, U.S. Pat. No. 4,134,872).

Styrol/butadien-podecopolymerisat-partiklerne i forstærkerla-texen ifølge opfindelsen udviser som følge af trækkene b) til d) forholdsvis hårde og bløde områder med forholdsvis høj, hen-20 holdsvis lav glasovergangstemperatur. Partiklerne kan på forenklet måde beskrives som følger:The styrene / butadiene graft copolymer particles in the amplifier latex according to the invention exhibit relatively hard and soft regions with relatively high, relatively low glass transition temperature, due to features b) to d). The particles can be described in a simplified manner as follows:

De består af en forholdsvis hård kerne (podeunderlag) og en forholdsvis blød skal med forholdsvis høj, henholdsvis lav Tg.They consist of a relatively hard core (graft substrate) and a relatively soft shell with relatively high and low Tg, respectively.

Overfladetitreringen til bestemmelse af middeldiameteren af 25 styren/butadien-podecopolymerisat-partiklerne sker som beskrevet i J. Paint Techn. 47 (1975) 41, højre spalte, sidste afsnit ff.The surface titration to determine the mean diameter of the styrene / butadiene graft copolymer particles occurs as described in J. Paint Techn. 47 (1975) 41, right column, last paragraph et seq.

Styren/butadien-podecopolymerisatlatexen ifølge opfindelsen anvendes alment som forstærkerlatex til fremstilling af den 30 forstærkede kaut s jukkomponent. Denne har sædvanligvis følgende 4 DK 168446 B1 kendetegn: 1. den opnås gennem følgende foranstaltninger: 1.1 en kautsjuklatex blandes med en forstærkerlatex (latex af et forstærket polymerisat: faste stoffer: 2 til 30, især 5 til 5 25 massedele per time): 1.2 blandingen af latexer inddampes til et faststofindhold på a 55, især s 60 masse%; 2. kautsjuklatexen er en NR-latex eller en SBR-latex, der blev underkastet foranstaltninger, som bevirker agglomerering af 10 kaut s jukpartiklerne, eller en blanding af en NR-latex og en SBR-latex, der blev underkastet foranstaltninger, som bevirker agglomerering af kautsjukpartiklerne; 3. SBR-latexen er ikke carboxyleret; den er opnået ved emulsionspolymerisation i nærværelse af en sædvanlig fedtsæbe og/el- 15 ler harpikssæbe som emulgator, SBR indeholder 15 til 35, især 20 til 30 masse% gentagelsesenheder, som er opnået ved polymerisation af styren; 4. den forstærkede kaut s jukkomponent udviser ved et faststof-indhold på 68 masse% en viskositet på a 2.500, især a 2.000 20 mPas, bestemt i Brookfield-viskosimeteret (spindel III, 30 omdr./min., 20°C) .The styrene / butadiene graft copolymer latex of the invention is generally used as an amplifier latex for the manufacture of the 30-reinforced kaut s yoke component. It usually has the following characteristics: 1. it is obtained through the following measures: 1.1 a rubber latex is mixed with an amplifier latex (latex of a reinforced polymer: solids: 2 to 30, in particular 5 to 5 25 parts per hour): 1.2 the mixture of latexes is evaporated to a solids content of α 55, especially s 60 mass%; 2. The rubber latex is an NR latex or an SBR latex subjected to measures causing agglomeration of the 10 kaute yoke particles, or a mixture of an NR latex and an SBR latex subjected to measures causing agglomeration. of the rubber particles; 3. The SBR latex is not carboxylated; it is obtained by emulsion polymerization in the presence of a conventional fatty soap and / or resin soap as an emulsifier, SBR contains 15 to 35, in particular 20 to 30 mass% repeating units obtained by polymerization of styrene; 4. The reinforced kaut s yoke component at a solid content of 68 mass% exhibits a viscosity of α 2,500, in particular α 2,000 20 mPas, determined in the Brookfield viscometer (spindle III, 30 rpm, 20 ° C).

Foranstaltningerne til agglomerering af kautsjukpartikleme i SBR-latexen er kendte (se f.eks. DE-PS nr. 12 13 984 og nr. 26 45 082) . 1The measures for agglomerating the rubbery particles in the SBR latex are known (see, for example, DE-PS Nos. 12 13 984 and Nos. 26 45 082). 1

Ved vulkaniseringsmidler til fremstilling af den i varmen vul-kaniserbare masse forstås de kendte vulkaniserings sys terner. Et foretrukket vulkaniseringssystem indeholder svovl i kombination med de sædvanlige fremskyndere. Mængden af vulkaniserings-midlet retter sig efter de øvrige blandingskomponenter og kan 5 DK 168446 B1 let fastlægges ved simple orienterende forsøg.By vulcanizing agents for preparing the heat vulcanizable mass is understood the systems of known vulcanization systems. A preferred vulcanization system contains sulfur in combination with the usual accelerators. The amount of the vulcanizing agent is directed to the other blending components and can be easily determined by simple orienting experiments.

Sædvanlige tilsætningsstoffer til fremstilling af den i varmen vulkaniserbare masse er f.eks. fedtsæber og harpikssæber (de kan allerede foreligge i den forstærkede kautsjukkomponent i 5 en mængde, som er tilstrækkelig til videreforarbejdningen af den vulkaniserbare masse), ældningsbeskyttelsesmidler og lysbeskyttelsesmidler, fortykkelsesmidler, f.eks. carboxymethyl-cellulose, og fyldstoffer, f.eks. kridt, kaolin og stivelse.Conventional additives for preparing the heat-vulcanizable mass are e.g. fatty soaps and resin soaps (they may already be present in the reinforced chewing gum component in an amount sufficient for the further processing of the vulcanizable mass), aging and light preservatives, thickeners, e.g. carboxymethyl cellulose, and fillers, e.g. chalk, kaolin and starch.

Opfindelsen belyses af følgende eksempler. I disse betyder de-10 le (T) massedele og procent (%) masseprocent.The invention is illustrated by the following examples. In these, part (T) means mass parts and percent (%) mass percent.

Sammenligningsekseraplerne, der ikke er ifølge opfindelsen, betegnes med store bogstaver.The comparative excerpts, which are not according to the invention, are denoted by uppercase letters.

Den gennemsnitlige partikeldiameter af de i det følgende beskrevne latexer blev bestemt som ovenfor anført.The average particle diameter of the latexes described below was determined as indicated above.

15 Viskositeterne af de forstærkede kautsjukkomponenter blev bestemt i Brookfield viskosimeter (spindel III, 30 omdrejninger pr. minut, 20°C).The viscosities of the reinforced chewing gum components were determined in Brookfield viscometer (spindle III, 30 rpm, 20 ° C).

Fremstilling af forstærkerlatexerne 1 og A - C: 1 2 3 4 5 6 EKSEMPEL 1.Preparation of the amplifier latexes 1 and A - C: 1 2 3 4 5 6 EXAMPLE 1.

2 (styren/butadien-podecopolymerisat-latex ifølge opfindelsen): 3 I en polymerisationsreaktor blev en emulsion af 84 T fuldt af- 4 saltet vand, 0,2 T kaliumoleat (fast stof, foreliggende som 5 17%ig vandig opløsning), 0,1 T kaliumcarbonat, 0,015 T af te- 6 tranatriumsaltet af ethylendiamintetraeddikesyre, 10 T styren og 0,15 T ammoniumperoxodisulfat opvarmet i 1 - 2 timer til 70°C. Derved fremkom en polystyren-kimlatex med en gennemsnitlig partikeldiameter på 40 nm.2 (styrene / butadiene graft copolymer latex according to the invention): 3 In a polymerization reactor, an emulsion of 84 T was fully de-salted water, 0.2 T potassium oleate (solid, present as 5 17% aqueous solution), 0 , 1 T potassium carbonate, 0.015 T of the tetrasodium salt of ethylene diamine tetraacetic acid, 10 T styrene and 0.15 T ammonium peroxodisulfate heated for 1-2 hours to 70 ° C. Thereby a polystyrene seed latex with an average particle diameter of 40 nm was obtained.

6 DK 168446 B16 DK 168446 B1

Til dette materiale blev sat følgende strømme ved 75°C: 1) Blanding af 19 T fuldt af saltet vand og 4 T kaliumoleat (fast stof, foreliggende som 17%ig vandig opløsning), tilsætningstid 5 timer (konstant strømningshastighed) .To this material were added the following streams at 75 ° C: 1) Mixture of 19 T full of salted water and 4 T potassium oleate (solid, present as 17% in aqueous solution), addition time 5 hours (constant flow rate).

5 2) Opløsning af 1,35 T ammoniumperoxodisulfat i 5 T helt af- saltet vand, tilsætningstid 6 timer (konstant strømningshastighed) .2) Dissolve 1.35T ammonium peroxodisulfate in 5T fully salted water, addition time 6 hours (constant flow rate).

3) Blanding af 45 T styren/l,3-butadien (masseforhold 89/11) og 0,06 T tert.-dodecylmercaptan, til sætnings tid 2,5 time 10 (konstant strømningshastighed) .3) Mixture of 45 T styrene / l, 3-butadiene (mass ratio 89/11) and 0.06 T tert-dodecyl mercaptan, to set time 2.5 hours 10 (constant flow rate).

4) Blanding af 45 T styren/l,3-butadien (masseforhold 67/33) og 0,09 T tert.-dodecylmercaptan, tilsætningstid 2,5 time (konstant strømningshastighed) .4) Mixture of 45 T styrene / 1,3-butadiene (mass ratio 67/33) and 0.09 T tert-dodecyl mercaptan, addition time 2.5 hours (constant flow rate).

Tilsætningen af strømmene 1-3 blev påbegyndt samtidig. Efter 15 2,5 time (afslutning af første podetrin) blev der begyndt med strøm 4.The addition of streams 1-3 was started simultaneously. After 15 2.5 hours (completion of the first inoculation stage), stream 4 was started.

Den efter afslutning af andet podetrin fremkomne styren/buta-dienpodecopolymerisat-latex havde et indhold af fast stof på ca. 501 og en gennemsnitlig partikeldiameter på 220 nm.The styrene / buta-diene graft copolymer latex obtained after completion of the second stage step had a solids content of approx. 501 and an average particle diameter of 220 nm.

20 EKSEMPEL AEXAMPLE A

(styren/butadien-podecopolymerisat-latex) :(styrene / butadiene graft copolymer latex):

Eksemplet svarer til eksempel 1 i masseforholdet mellem de i alt anvendte monomerer (styren/l,3-butadien = 80/20) og i de øvrige fremstillingsparametre, men strømmene 3 og 4 blev er-25 stattet med følgende strøm: 3) Blanding af 90 T styren/l,3-butadien (masseforhold 70/20) og 0,15 T tert.-dodecylmercaptan, tilsætningstid 5 timer (kon- 7 DK 168446 B1 stant strømningshastighed) .The example corresponds to Example 1 in the mass ratio of the total monomers used (styrene / 1,3-butadiene = 80/20) to the other manufacturing parameters, but streams 3 and 4 were replaced with the following stream: 3) 90 T styrene / 1,3-butadiene (mass ratio 70/20) and 0.15 T tert-dodecylmercaptan, addition time 5 hours (constant flow rate).

Tilsætning af strømmene 1-3 blev påbegyndt samtidig.Addition of streams 1-3 was started simultaneously.

Den efter endt podningstrin fremkomne styren/butadien-podeco-polymerisat-latex havde et indhold af fast stof på ca. 50% og 5 en gennemsnitlig partikeldiameter på 200 'nm.The styrene / butadiene-podeco-polymerized latex obtained after the inoculation step had a solids content of approx. 50% and 5 an average particle diameter of 200 µm.

EKSEMPEL BEXAMPLE B

(styren/butadien-podecopolymerisat-latex) :(styrene / butadiene graft copolymer latex):

Eksemplet svarer til eksempel 1, men strømmen 4 blev erstattet med følgende strøm: 10 4) Blanding af 45 T styren/1,3-butadien (masseforhold 72/28) og 0,09 T tert.-dodecylmercaptan, tilsætningstid 2,5 time (konstant strømningshastighed).The example is similar to Example 1, but stream 4 was replaced with the following stream: 4) Mixture of 45 T styrene / 1,3-butadiene (mass ratio 72/28) and 0.09 T tert-dodecylmercaptan, addition time 2.5 hours (constant flow rate).

Den efter afslutning af det andet podetrin fremkomne styren/-butadien-podecopolymerisat-latex havde et indhold af fast stof 15 på ca. 50% og en gennemsnitlig partikeldiameter på 210 nm.The styrene / butadiene graft copolymerate latex obtained after the second graft stage had a solids content of approx. 50% and an average particle diameter of 210 nm.

EKSEMPEL CEXAMPLE C

(polystyren-latex) :(polystyrene latex):

Eksemplet svarer til eksempel l, men strømmene 3 og 4 blev erstattet med følgende strøm: 1 3) Blanding af 90 T styren og 0,15 T tert.-dodecylmercaptan, tilsætningstid 5 timer (konstant strømningshastighed).The example is similar to Example 1, but streams 3 and 4 were replaced with the following stream: 1 3) Mixture of 90 T styrene and 0.15 T tert-dodecyl mercaptan, addition time 5 hours (constant flow rate).

Tilsætningen af strømmene 1-3 blev påbegyndt samtidig.The addition of streams 1-3 was started simultaneously.

Den efter endt polymerisation fremkomne polystyren-latex havde et indhold af fast stof på ca. 50% og en gennemsnitlig parti- 8 DK 168446 B1 keldiameter på 200 nm.The polystyrene latex obtained after polymerization had a solids content of approx. 50% and an average particle diameter of 200 nm.

Frems til liner af SBR-latexen:For the SBR latex liners:

Latexen blev fremstillet på kendt måde ved Redox-polymerisati-on efter følgende recept: 5 120 T helt afsaltet vand, 2,7 T kaliumoleat (beregnet som 100%-ig), 0,5 T af et kondensationsprodukt af formaldehyd og naphtha-1ensulfonsyre, 0,29 T kaliumchlorid, 10 31 T styren, 69 T 1,3-butadien.The latex was prepared in a known manner by Redox polymerization following the following recipe: 5 120 T of completely desalted water, 2.7 T of potassium oleate (calculated as 100% yeast), 0.5 T of a condensation product of formaldehyde and naphtha-1 -sulfonic acid , 0.29 T potassium chloride, 10 31 T styrene, 69 T 1,3-butadiene.

Efter 65% omsætning af monomererne blev polymerisationen afbrudt. Den fremkomne SBR-latex blev underkastet de i DE-PS 12 13 984 anførte foranstaltninger til agglomerering af kautsjuk-15 partiklerne. Den gennemsnitlige partikeldiameter var så 240 nm. Res tmonomer eme blev fraskilt på kendt måde. Polymerisatet indeholdt 26% gentagelsesenheder, der var fremkommet ved polymerisation af styren (IR-analyse) .After 65% reaction of the monomers, polymerization was discontinued. The resulting SBR latex was subjected to the measures specified in DE-PS 12 13 984 for agglomeration of the rubber particles. The average particle diameter was then 240 nm. Res tmonomer eme was separated in known manner. The polymerization contained 26% repeating units produced by polymerization of styrene (IR analysis).

Fremstilling af de forstærkede kautsiukkomponenter 1 og A - C: 20 SBR-latexen blev i hvert enkelt tilfælde blandet med en af forstærker-latexeme 1 og A - C (faste stoffer: 20 T phr). Den fremkomne blanding af latexerne blev inddampet til et indhold af fast stof på 70%.Preparation of the Reinforced Rubber Components 1 and A - C: The 20 SBR latex was in each case mixed with one of the amplifier latexes 1 and A - C (solids: 20 T phr). The resulting mixture of the latexes was evaporated to a solids content of 70%.

Med et indhold af fast stof på 68% udviste de forstærkede kaut-25 s jukkomponenter følgende viskositeter: 1: 1.400 mPa’S. A: 1.200 mPa*s. B: 1.300 mPa*s.With a 68% solids content, the reinforced Kaut-25's yoke components exhibited the following viscosities: 1: 1,400 mPa's. A: 1,200 mPa * s. B: 1,300 mPa * s.

C: 1.350 mPa’S.C: 1,350 mPa'S.

9 DK 168446 B19 DK 168446 B1

Fremstilling af de vulkaniserbare masser l og A - C og latex-skummene (prøveleaemer) 1 og A - C:_Preparation of the vulcanizable masses 1 and A - C and the latex foams (sample layers) 1 and A - C:

De vulkaniserbare masser blev fremstillet efter følgende recept (faste stoffer): 5 100 T af en af de forstærkede kautsjukkomponenter 1 og A - C, 0,5 T kaliumoleat (tilsætning som 17%ig vandig opløsning), 0,25 T carboxymethylcellulose (tilsætning som 2,5%ig vandig opløsning).The vulcanizable masses were prepared according to the following recipe (solids): 5 100 T of one of the reinforced chewing gum components 1 and A - C, 0.5 T potassium oleate (addition as 17% aqueous solution), 0.25 T carboxymethyl cellulose (addition as 2.5% aqueous solution).

Før opskumningen blev de vulkaniserbare masser gjort færdige 10 ved tilsætning af en 50%ig dispersion af følgende vulkaniseringssystem (faste stoffer): 2 T svovl, 1 T zinkdiethyldithiocarbamat, 1 T zink-2-mercaptobenzothiazol, 15 1 T diphenylguanidin, 3 T zinkoxid, 0,5 T kaliumoleat (tilsætning som l7%ig vandig opløsning), 1 T antioxidant.Prior to foaming, the vulcanizable masses were completed by adding a 50% dispersion of the following vulcanization system (solids): 2 T sulfur, 1 T zinc diethyl dithiocarbamate, 1 T zinc-2-mercaptobenzothiazole, 1 T diphenylguanidine, 3 T zinc oxide, 0.5 T potassium oleate (addition as 17% aqueous solution), 1 T antioxidant.

Luft blev pisket ind i de vulkaniserbare masser med en skumpi-20 skemaskine. Til de fremkomne våde skum (rumvægt ca. 130 g/i) blev der sat 2 T natriumsilikofluorid, der forelå som 25%ig vandig opløsning, og de blev hældt i opvarmelige forme, ved gelering i opvarmningsfasen og påfølgende vulkanisering ved 100°C/30 minutter fremkom latexskummene 1 og A - C. De blev 25 vasket med vand, tørret ved 75°C/16 timer(rumvægt 100 g/1) Qg karakteriseret som anført i følgende tabel.Air was whipped into the vulcanizable masses with a foamy machine. To the resulting wet foams (about 130 g / l) were added 2 T sodium silicofluoride, which was present as 25% aqueous solution, and poured into heating molds, by gelling in the heating phase and subsequent vulcanization at 100 ° C / For 30 minutes, latex foams 1 and A - C. were obtained. They were washed with water, dried at 75 ° C / 16 h (room weight 100 g / l) Qg characterized as shown in the following table.

DK 168446 B1 xDK 168446 B1 x

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Claims (4)

1. Styren/butadien-podecopolymerisatlatex, opnået ved emulsionspolymerisation i nærværelse af 1 til 6 masse% af en konventionel fedt sæbe og/eller harpikssæbe som emulgator og s 0,3 masse% af en konventionel forbindelse, som regulerer polymeri-10 satets molekylvægt, idet hver masse% er baseret på de totale monomerer, kendetegnet ved, at: a) emulsionspolymerisationen udføres efter en semikontinuerlig emulsionstilløbsfremgangsmåde, b) podecopolymerisatet består af 35 til 65 masse% podeunderlag 15 (A), som på sin side består af podeunderlag (Al) og påpodet andel (A2), og 35 til 65 masse% af en i det sidste trin påpodet andel (B), c) podeunderlaget (A) er opnået i to polymerisationstrin; i det første trin opnås en polystyrenkimlatex, hvis faststofind- 20 hold (Al) andrager 1 til 20 masse%, baseret på podecopolymerisatet; den i det andet trin påpodede andel (A2) af podeunderlaget (A) består af 86 til 95 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 5 til 14 masse% gentagelsesenheder, som er opnået ved polymerisation af 1,3-25 butadien; ved tilløb af emulgatoren under podningen omrøres intensivt for at undgå dannelsen af nye partikler; d) den i det sidste trin påpodede andel (B) af podecopolymerisatet består af 62 til 70 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 30 til 38 masse% gen- 30 tagelsesenheder, som er opnået ved polymerisation af 1,3-butadien; ved fødning af emulgatoren under podning omrøres inten- DK 168446 B1 sivt for at undgå dannelsen af nye partikler; e) parametrene ved fremstillingen af podecopolymerisatlatexen vælges således, at latexpartikleme har en middeldiameter, bestemt ved overfladetitrering, på 120 til 300 nm.1. The styrene / butadiene graft copolymer latex obtained by emulsion polymerization in the presence of 1 to 6 mass% of a conventional fat soap and / or resin soap as emulsifier and s 0.3 mass% of a conventional compound which regulates the molecular weight of the polymerate. each mass% being based on the total monomers, characterized in that: a) the emulsion polymerization is carried out following a semi-continuous emulsion flow process; b) the graft copolymer consists of 35 to 65 mass% graft substrate 15 (A), which in turn consists of graft substrate ) and grafted portion (A2), and 35 to 65% by mass of a grafted portion (B) in the last step, c) the graft substrate (A) is obtained in two polymerization steps; in the first step, a polystyrene germ latex whose solids content (A1) is 1 to 20 mass% is obtained, based on the graft copolymer; the proportion (A2) of the graft substrate (A2) grafted in the second step consists of 86 to 95 mass% repeating units obtained by polymerization of styrene and 5 to 14 mass% repeating units obtained by polymerization of 1.3 Butadiene; at the inlet of the emulsifier during grafting, it is stirred intensively to avoid the formation of new particles; (d) the proportion (B) of the graft copolymer polymer grafted in the last step consists of 62 to 70 wt% repeating units obtained by polymerization of styrene and 30 to 38 wt% repeating units obtained by polymerization of 1, 3-butadiene; upon feeding the emulsifier during grafting, intensively stirred to prevent the formation of new particles; e) the parameters for the preparation of the graft copolymer latex are selected such that the latex particles have a mean diameter, as determined by surface titration, of 120 to 300 nm. 2. Styren/butadien-podecopolymerisatlatex ifølge krav l, kendetegnet ved, at: f) podecopolymerisatet består af 45 til 60 masse% podeunderlaget (A) og 40 til 55 masse% af den i det sidste trin påpodede andel (B) .The styrene / butadiene graft copolymer latex according to claim 1, characterized in that: (f) the graft copolymer consists of 45 to 60 weight percent graft (A) and 40 to 55 weight% of the proportion (B) grafted in the last step. 3. Styren/butadien-podecopolymerisatlatex ifølge krav 1 eller 2, kendetegnet ved, at: g) den påpodede andel (A2) af podeunderlaget (A) består af 87 til 93 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 7 til 13 masse% gentagelsesenheder, som 15 er opnået ved polymerisation af 1,3-butadien? h) den i det sidste trin påpodede andel (B) af podecopolymerisatet består af 65 til 69 masse% gentagelsesenheder, som er opnået ved polymerisation af styren, og 31 til 35 masse% gentagelsesenheder, som er opnået ved polymerisation af 1,3-buta- 20 dien.The styrene / butadiene graft copolymer latex according to claim 1 or 2, characterized in that: g) the grafted portion (A2) of the graft substrate (A) consists of 87 to 93 wt% repeating units obtained by polymerization of styrene, and 7 to 13 mass% repeating units 15 obtained by polymerization of 1,3-butadiene? (h) the proportion (B) of the graft copolymer which is grafted in the last step consists of 65 to 69 mass% repeating units obtained by polymerization of styrene and 31 to 35 mass% repeating units obtained by polymerization of 1,3-buta - 20 done. 4. Styren/butadien-podecopolymerisatlatex ifølge ethvert af kravene 1 til 3, kendetegnet ved, at i) latexpartikleme har en middeldiameter på 150 til 250 nm. 25The styrene / butadiene graft copolymer latex according to any one of claims 1 to 3, characterized in that i) the latex particles have an average diameter of 150 to 250 nm. 25
DK598485A 1984-12-28 1985-12-20 Styrene / butadiene graft copolymer latex DK168446B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843447585 DE3447585A1 (en) 1984-12-28 1984-12-28 STYROL / BUTADIENE-GROPFCOPOLYMERISATE LATEX AND THIS CONTAINING AS A REINFORCING LATEX, WHICH CAN BE VULCANIZED IN THE HEAT FOR THE PRODUCTION OF LATEX FOAM
DE3447585 1984-12-28

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DK598485D0 DK598485D0 (en) 1985-12-20
DK598485A DK598485A (en) 1986-06-29
DK168446B1 true DK168446B1 (en) 1994-03-28

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DE10063160A1 (en) 2000-12-18 2002-06-20 Basf Ag Aqueous polymer dispersion, used for production of latex foam and foam articles e.g. carpet backing, contains styrene-butadiene rubber particles and reinforcing polymer with hard and soft phases based on the same monomers
US20060052513A1 (en) 2004-09-09 2006-03-09 Soren Butz Polymer latex suitable for the preparation of dip-molded articles
US8158691B2 (en) 2005-04-04 2012-04-17 Polymer Latex Gmbh & Co. Kg Aqueous reinforced rubber dispersions and their use for making latex foams
US8222362B2 (en) 2006-08-10 2012-07-17 Polymerlatex Gmbh Latex with reduced odor

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DE1056364B (en) * 1956-06-09 1959-04-30 Huels Chemische Werke Ag Process for the production of articles from foam rubber
US3917749A (en) * 1973-12-14 1975-11-04 Goodyear Tire & Rubber Resinous butadiene/styrene reinforcing copolymers
DE2607220C3 (en) * 1976-02-23 1980-08-14 Chemische Werke Huels Ag, 4370 Marl Process for the preparation of aqueous copolymer dispersions
US4307134A (en) * 1980-12-22 1981-12-22 Atlantic Richfield Company Process for producing plasticized elastomer-styrene coated beads
US4333969A (en) * 1980-12-23 1982-06-08 Atlantic Richfield Company Process for producing styrenic polymer beads of preferred bead size

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DK598485D0 (en) 1985-12-20
EP0187905A3 (en) 1987-07-29
EP0187905A2 (en) 1986-07-23
DE3447585A1 (en) 1986-07-10
DK598485A (en) 1986-06-29
DE3578565D1 (en) 1990-08-09
CA1266934A (en) 1990-03-20
EP0187905B1 (en) 1990-07-04

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