DE1770332A1 - Process for the production of styrene polymers - Google Patents

Description

Process »» for the production of styrene polymers

The present invention relates to a process for the production of styrene polymers with high impact strengths and to the polymers produced in this way. The term "Styrolpolymerieat" in the present application relates to all solid homopolymers or copolymers of styrene or nuclear ^ methylaubatituierteiStyroleiinit a Erweichungepunkt below 70 ⁰ O., geaie * ate gemäfl British Standard 2762, cable 1, Method 1Ö20 · Hisohpolymeriaste can be obtained by • Mi3chpolyÄeriaatiOA Tön styrene with other, vinylaromatic compounds, such as «o-», a- or> -methylstyrene, 2% - Diohlorstyrol and ei.-Methylatyröl, or with biopolymerizable conomers, which are not aromatic vinyl compounds, like a.3 . Acrylonitrile, ethyl methacrylate and dinethyl itaconate. Excellent preparations can also be derived from copolymers of o-, m- or p-methylatyrene with polymerizable monomers that are not aromatic vinyl compounds, such as acrylonitrile, methyl methacrylate and dimethyl itaconate *

109842 / 13Ö7

BATH ORIGINAL

Here production τοη ait Kauat achuk reinforced bsw. Styrolpolyaerisaten saw made by polymerizing a Lbeung a rubber in a styrene-containing or made from styrene monomer solution is known existing _f · Furthermore, it is known to significantly door Brzielung desirable products. Subject the solution to stirring under the action of shear forces during the initial stages of the polymerization.This movement accelerates the phase inversion, so that the chewing content of the polymerizing solution is distributed throughout the entire mixture in the form of discrete particles.If the phase inversion has taken place once, it needs to be Stirring does not necessarily have to continue; however, the QrQB * of the rubber parts in the end product can be regulated by further stirring, so that further stirring can be used to regulate the exact nature of the end product »

The known processes have led to difficulties when they are used for the production of styrene polymers with more than about 10 oew. -jt reinforcing rubber were applied

T ι

The aim of the present invention is to create a method which can be carried out in a manner which can be carried out in a manner that can Another object is to provide a method for making products with good gloss and smooth texture.

bath

109842/1397 ° ° * «* na

Dae erfindungsgeiiäiie process for producing a otyrolpolyrr.tirieate3 Rait high impact resistance is characterized "jekonnseiclmot, da3 a solution" nit at least 10 wt. -I * a high-cis polybutadiene or a high-cis butadiene / styrene I.-ischpolymerisates in the The following described type in a monoueren material forming a styrene- ■ Colyiaerisat such conditions, whereby a polymer is effected with phase inversion, the iiohe cis-polybutadiene or the high cis-butaciien / Svvrol-IIiachpolyiaerisat a viscosity of 10-45 cps. or 20-45 cps., measured with a 5-weight ^c / aigen solution in styrene at 25 ⁰ C, has. ' *

The present invention relates in particular to a process for producing a styrene polymer with high impact strength, which is characterized in that a solution containing at least 10% by weight of a high cis-polybutadiene or a high cis-butadiene / styrene copolymer is used of the type described below in an other material forming a styrene polymer, subjected to such conditions that a polymerization with Phaeninvorsion is brought about, the high cis-polybutadiene or high cis-butadiene / styrene copolymer having a viscosity - measured in% of a 5 -We .-> jigen solution of the same in styrene at 25 ⁰ O. between 10-45 cpe. and a "Mooney Viakosität" - determined under conditions of KL1 + 4 at 100 ⁰ C. - not having under (10 0.4S 4), v / obei S is the weight percentage of bound styrene Id high cis-polybutadiene or butadiene / S -cyrol-Iiischpolymarisat is.

109842/1397

BATH

The type and viscosity of the reinforcing rubber used l3t decisive for the method according to the invention. Under a "high egg polybutadiene" or a "high oic butadiene / Small styrene polymer becomes a homopolymer of butadiene or a copolymer of styrene and butadiene with one The main part by weight of polymerized butadiene units is understood in which at least 30% of the polymerized butadiene units have the cis -! »* 4 structure» i.e. duroh the following can be shown / grounded "

CH

CH

CH

and not more than 10 % of the polymer! alartÄ butadiene units have the 1: 2 structure, ie by which the following formula can be represented «. .

OH-CH

CH Il

CH ₂

Preferably not more than 2 parts of the polymerized Butadiene units have the 1i2 structure,

The reinforcing polybuadiene rubber that is most preferred according to the invention is one in which at least 90% of the polymerized butadiene units have the 1: 4-3 structure and less p.ls 2 i "have the 1" 2 structure ""

109842/1387

bath

-P-

ϋΐε can each nononere iiaterial, the £ e. üäß the '' ior given definition provides a styrene polymer, uerdor used .. The particularly orfindun-'ß ^ emäße check process is suitable for the production of rubber-reinforced wit copolymers of styrene and .Acrylnitril with , 10-U0 G «w.-Jtf polyntritltrtta aorylnitril. The process according to the invention is also particularly suitable for the production of terpolymers reinforced with rubber from styrene, cC -ethylstyrene and acrylonitrile with 10-30 wt. These rubber-reinforced copolymers are characterized by high heat resistance.

Do.3 monomeric material must contain at least 10% by weight of reinforcing ■ high cis-polybutadiene or high cis-butadiene / styrene chewing bulk. Be should "weckmäßig nioht more than 15 wt .- # of ^s rubber included. 12r founding sgeLiäS has been found that by using more than 20 Sew. - No significant advantage is obtained from the rubber

The reinforcing rubber must be selected so daj3 its "viscosity -measured as 5 - / '. * Solution in styrene at 25 ⁰ C, within the stated range is, the larger the concentration of the rubber in the monomeric material is less uraso' _t Kautccruk July should suitably the viscosity of the selected rubber in. If, therefore, a 10-Jeige solution are polymerized in the rubber inonouorer "material, it should expediently Eire viscosity zwinchen 40-45 cpa. ben hr \. a 1 5-Zevi" -7 * ic ^Q Lö3un,? The rubber polymerizes \ ;? rden, then the rubber should voraucuv / eiae a vialtonite '- ;. t between 20-25 cps. H .-. Ben.

1098A2 / 1397 _ba d ^u

Should 2UR achieve einco kautochukverstärkten Styrolpolyr.orisates Lit Aehr ijuten 2i enschnften? The I! Ooney-dee ViGko3ität Hohkautschuks, beuiimmt under conditions I! L1 + 4 boi 10O ⁰ O., are not / ert under the specified V ι what the 3u3P .rjr _; en- • otzung dt «fu using ·« Kautsohuk · depends. For a · a · polybutadier.kautachuka, the Kboney viscosity should not be below 10, preferably not below 20. In the case of a rubber containing a butadiene / styrene copolymer with 25% by weight of bound styrene, the tlooney viscosity should not be

below 20, preferably not below 35 ». In particular should not affect the Ilooney viscosity below (10 + 0.43), whereby 3 for the total percentage of bound styrene im Rubber stands.

Process for the production of higher and higher cis-polybutadienes cio-Mischpolyaeriaate from styrene and butadiene and known. Through a known setting or modification of the processes used, I know cis-Kautachuke with the desired viscosity getting produced.

. '. Also the processes for the polymerization of solutions reinforcing, Kutschuk-like! materials in styrene polyacrylate forming, r: onoueren materials under conditions that a Phase inversion bev / irkon are known. Practically all require the solution during the initial polymerization stages is subjected to a shear movement. In the process according to the invention at a concentration of the high cis-Kautsci.uko. between 10-15 Ggw .- ^ j there is a phasoninver jion, if about 15-30> ί of the non egg; er en material polyraerized h.nben.

109842/1397 construction original

The process is carried out erfindungsgenäße zweckuuSig Urhitzen by the solution of the reinforcing rubber in the monomeric Liaterlal or a rope of the same at a temperature between 60-110 ⁰ C. in the presence of a Polymerisationekatalysators or at 110-135 ⁰ C in the absence of a polymerization catalyst ", wherein the Löuung Ldttels a stirrer of a shear water jet

subjecting "The shear movement is maintained until the" phase inversion ended. After that Schcrbevegung is not critical, but can be used to iiinstelluns of! _t particle gröfle of the reinforcing rubber in the poiyraerisei-end '<■ ·

Illumination be applied,

* - ■

Achieving phase inversion is the method of implementation the subsequent polymerization is not decisive «The partially polymerized mixture can either statically or by passing eie through a polymerization zone in a suitable Device can be heated through. The · partially polymerized The mixture can also be dispersed as a suspension in water and continuing the polymerization under suspension conditions so that the product is obtained in the form of beads. Such Procedure for the condition of the polymerization styrene polymer% forming, ionotizing materials after their partial polymerization and phase inversion are known. According to the invention can any of these methods can be used. · ■

V *. V.

The following examples illustrate the present Invention without limiting it.

1Ö9842 / 1397

BATH

38l 3 P 1 e 1 1

120 2 polybutadione rubber were in a ϊ.Ίβοηυη, ϊ aua 044 ß monomeric styrene and 240 pounds of acrylonitrile. The Polybuttria rubber hp.tte the following properties ι

i'microstructure; ois 1., 4 98.8 Jf

trans 1.4 0.4 #. .

1,2 OjBji

Mooney viscosity ML1 + 4 at 100 ⁰ O. 12

Viscosity at 25 ⁰ C. a

5-gev * .- i & Lg. Solution 'in styrene 36 ops

10 ig mineral oil and 2.5 g were added to the solution thus prepared Lauroyl peroxide added. The solution was in an asylindrical Gl.T.s £ öfr.3 with an inner diameter of 10 cn and one Given a height of 20 cm. The vessel was not provided with a stirrer, there also 4 three-bladed propellers made of rustproof Steel (Gescr.tdurchmesser 8 on) consisted of a shaft

made of stainless steel (diameter 1.1 cm). The stirrer was operated at 100 rpm. A slow stream of nitrogen was passed over the surface of the solution. The glass vessel was heated in an oil bath which was kept at such a temperature was that the! temperature of polymerieierenden Ilischung was 64 ⁰ C.. After 4-7 hours, 18.3 # of the monomeric mixture had polymerized and phase inversion had occurred.

The following was now used to partially polymerize the mixture Solution added:

"••"/AROUND

16 g styrene, 4 g acrylonitrile, 2 e "O- ^ Iethylstyrolcliiaeree, 2 β " Antioxidant 2246 "(the company Cyanamid of UK Limited) and 0.6 g di-tert-butyl peroxide · ·

The mixture obtained was poured into a cylindrical stainless steel polymerisation vessel with a capacity of about 4.5 liters, a diameter of 15.2 cn and a depth of. 25.7 cm given. The vessel was set to music with a non-dented stirrer shaft which extended into the vessel to a depth of 24.1 tons. A three-winged, upward court- · | The third propeller was attached to the bottom of the shaft, and a similar, downward-facing propeller was 6.9 cm above the lower propeller. Each prdpdlar moved a cylinder q cm! In diameter. Before the partially polymerized oil solution was added, a solution of 4.5 g of polyvinyl alcohol ("Iloviol N 70-88", manufactured by Farbwerke Hoechst), 0.2 g of dihexyl natriurasulfoauccinate ("i: ar.o :: al IIA", manufactured by Hardman & Holden ltd.) in 20Oi) yeast. Vaaser was placed in the rustproof storage polymerization vessel. The Gofüß λ was 3 shells under pressure with nitrogen by /? eo; .Ult, to be removed with oxygen j then was a . pressure of 1.4 kg / om set The polymerization was terminated by _the% following scheme:

Time; std 1 110 1 , 5 1 1 1 0 , 5 0 * 5 2 Ter.p .; ⁰ O. 105 1 15th 120 .125 130 1 35 145 155 Stirrer speed 300
age? Rev./min Cf \ n

109842/1397 bad original

The after cooling and filtering of the 2o action37; iir.chun5 obtained pearls of the rubber-diffused styrene / acrylonitrile "fish-olynerisatcs v / urdon not washed and dried" DiO pearls were used to remove a small amount of unreacted ilonomor "50 * heated minutes at 4 on Hg Druok to 155 ⁰ O. Then freed from volatile Katerial beads were press by successive passage through a strand and Stran ^ scjiuidevorrichtung tableted · had nterinlien the prepared from the tablets, druokverfonaten !! the following jäigonschafton *
Tensile strenght; BS2782-301JJ kg / en ² . 310.1

«Inheritance 19

For comparison purposes, a similar experiment was carried out under oil conditions, but using "iakt ^ ne 1202" Polybutpdienkauxacauk (manufactured by the Polyiaer Corporation of Sarnia, Canada). The viscosity of this rubber as a 5% strength by weight styrene solution at 25 ° 0. was 62 cps. The Uooney viscosity (HH + 4 at 100 ⁰ C.) of Hohkautschuks was 38. The microstructure was as follows ι ice 1.4 97 </ »; trans 1.4 1.5 ti 1.2 1.5 i ^%

It was not possible to bring about polymerization in the glass vessel at a controlled, uniform rate. After 3.0 hours, 27.6 % of the monomeric mixture had polymerized. The product from the suspension polymerization la; ·; in unsuitable form ^ rofer, bean-like particles and not as globular spherical pearls *

109842/1397. Bad _Of , _laNAL

BB ₁ j. 9 PI β 3, 2

120 g of polybutadiene rubber were dissolved in 864 g of monomeric styrene. The older polybutadiene rubber was identical to that described in Example 1. To the solution prepared in this way, 15 g of linoral oil, 3 g of dC -Ilethylstyrene diner and 0.3 g of di-tert-butyl peroxide are added. The solution was placed in a cylindrical glass vessel with an internal diameter of 10 cm and a height of 20%. The vessel 'was XAIT a stirrer provided AUA 7 horizontal bars AU3 stainless Stthl (Durchmeaser 0.6 ca | length 7.6 cn) existed in the cinoia λ ex atand of 2.0 cn on a vertical shaft of stainless chair "(Diameter 0.6 cm) were not mounted, with a stirrer v / urds" o5i 40 Ü!.: Dr./min operated. B's slow stream of nitrogen was passed over the surface of the solution. Da3 Glasgefriß vurde in an oil bath erhitgt was maintained at such a Tenperatur da3, since the 3 'Teuperatur the polymerisic-Tenden Mischuni;!. Was 112 G. After ⁰ 5, V 2 hours hctten 33. _f> ί of Iloror.eren polymerized, and the phase inversion had taken place. For the partially polymerized mixture, a solution of 2 g of 2,6-di-tert-butyl-p-cresol in 16 g of styrene was now added.

Polymerization was carried out in v / aesar suspension according to Böicv, iol 1 finished according to the following scheme

Zeiti Btd 0.5 0.5 1.5 0.5 0.5 4 Temp.ι ⁰ O. "'115 125 130 135 H5 155

guide speed 500 'f

digkeitj Ümdr / oin

The obtained after cooling and filtering the reaction mixture, KriUtachuk-reinforced polyetyrene beads are treated with water washed and dried · Then the painters were cleaned by

108842/1387

BATH

successive passage through a "volatile" material removing extruder and a strandsohneidinaaohlne tablot tiort. The form made from the tablet shade üurcli Druclr »« rfornung I.'ntörlalien had the folcomlen property ent

Tensile strength JJ.3.27Ö2-301J | ' lcg / oo ² - 180.6

B.S.2782-1O2D 95.5 ° O.

The method described in the examples using other reinforcing rubbers of the kind described above, v / ie 2.3. a random _p high cis-I'ischpolymorioat of styrene and butadiene with a major proportion by weight of polymerized butadione units, in the at least 3 & 7 »of the polymerized butadiene 3 units the cia-14 structure and not more than 10 ji of the polymerized butadiene units 1: 2-3 structure, can be varied

109842/1397 ^

Claims (5)

.- 13 Claims 1 1, - Process * for the production of a styrene polymer with high impact resistance, in which a solution of at least 10% by weight of a reinforcing rubber from the group of high polybutadiene and. Hisctipolymers in which at least 30 % of the polymerized butadiene units have the cio-14 structure and more than 10% of the polymerized butadiene units have the 1: 2 structure *, in a monomeric material that forms a composite polymer and forms this solution Subject to conditions by which a polymerisation with phase inversion is effected, characterized in that the rubber is selected so that it has a viscosity of 10-45 cps measured as 5 to% by weight Solution .in styrene at 25 ⁰ O. has. 2.- Method according to claim 1, characterized in that the vest & rlcende rubber has a viscosity of 20-45 cps. measured as a 5-gev .- # i £ e solution in styrene at 25 ⁰ C, has. 3.- The method according to claim 1 and 2, characterized in that the rubber has a Mooney viscosity, measured under the conditions ML1 + 4 at 100 ⁰ C, of not less than (10 + 0.4S), where S for the Percentage by weight of bound styrene in the rubber. 4.- The method according to claim 3, characterized in that man a high cis polybutadiene with a Mooney viscosity used by not less than 20. 109842/1397 BATH ORIGINAL 5.- ancestors according to claim 3, characterized in that nan ein holies ci3-3ux & dier / 3tyrol-Hi3chjx> lyiAQri3at: r.it 25 öe; w, -; i {jebunäoner. 'Jtyvol nit a liooney viscosity of Not WQnlser ala * 35 Patent attorney ι 109842/1397