DE1495676A1 - Polystyrene and process for its manufacture - Google Patents

Description

Polystyrene and ancestors of a manufacture The solution relates to a high-impact polystyrene.

Polyners of high fabric strength are currently being used in Inder Rogel in the 'feiae hergeatellt »that Laticea of polystyrene and one Butadiene-styrene-siaatoner can optionally be removed or by Haseenpolymeriaation a solution of styrene and Knutachuk "

According to the present invention, a polymer of improved impact strength is produced by Maaaenpolynerieation of styrene with in it golöotem polybutadiene, which has a highly linear molecular structure. The various polybutadiene, with such a low content of 1 »2 structure, differ in terms of their proportion of organic structure polymers" which are produced in their presence by polymerizing styrene "have different properties and are particularly useful Polymer with high impact strength is obtained when styrene is polymerized in the presence of polybutadiene, the microstructure of which is determined by infrared analysis as follows

1,2 structural component

ice 1,4-8 structural component

drench - 1,4 structural component

5 to 25 to remainder

_BATH

909848/1190

U95676

All · polybutadiene ·, which can be used for firing, ie toi oh ·, dl · nloht »more than 12jl have a 1,2-structural component, have a · linear * structure and have a lower oil content than dl · by Emilslonapoiynerltevtloii he bent polybutadiene ·. Dl · Infrared analysis «In ·· small Bnilelona polybutadiene · shows, for example, 18 * 6 ois- 1.4 structural part and IBfL 1,2-structural part« usaonen old 64 < trane- 1.4 structural part ·

The above-mentioned polybutadiene · low 1,2-structural _{content · and higher £ | £ -1 9} 4 proportions can be reduced by means of Musaenpolyerieation or by means of a hydrocarbon solvent for the monomer. The rerachiedenartier en catalysts can be used in an amount of about 1-30 milllacl (for insoluble catalysts) or about 0.005 sheets (for soluble catalysts) per 100 g de · butadiene -1.3 sur use »for example one Mixture of (a) a halide or another compound of a metal from the group YIII dea P * riodlsohen 8JStSnB sB> cobalt, HiCkSl ₉ palladium, platinum or even iron, oemium, iridium, rhodium or rhodium and (b) an organo-metallic compound of its metal dor group XI or III of the Perlodlsohen Bystens old of the general formula MeR _n ^ X · where Me means for example beryllium, Magnesiusj, zinc, boron or AlualnluB, R o in aryl-l & ylradlkal, X a Rblofen and η the valence of the metal} or an organotallic sol Compound of a metal of Group III of the Periodic Set, aB Bor odsr Aluainiun, jenUß: 1er? _t .naöl MaR _n-2 ^ ^ ^ * ^{dor X "7} ^ ⁿ ^ ^{di #} S-eI have olien meanings" or a mixture of (a) a hydride einsa orgonoaetalllsehen prebinding a · M _e tails, such as aluminum, Ckilllua ₉ IndiuBi, ThalliUM or Olusinlu «ind (b) a Trl- or Tetrahalld of a metal such as titanium, aillzlun, Vhoriun, zircon, tin, lead, Hafnlua» GeraanluB or odsr cerium.

is sin Kntalyaator on Llthiuobaoia 7urv; <indst ₉ with splelsweise uetallisches LlthlUB or an Orjanollthluarerbla diMf0 la which the Lithlua ela · blarelohead krttftlg · reducing Wlrkuag SOStTW ₉ ao iea hydrogen sue «ea vase to remove.

9098A8 / 1190 ^ ₃ ^

BATH ORIGINAL

When such catalysts are used, a polybutadiene is formed

other suitable microstructure. They mentioned catalysts Lithluebftsis include the various Lithiunk;. Hlenwas terstoffe, ie Kohlonwaocorotoffe, in Donen one or nchrere W _(l s η only offatome are replaced with lithium, and adducts of lithium with foiyoyklIschen aromatic compounds Suitable Lithlumkohlenwaonerstoffe oind eB Llthiumalky compounds! such as methyllithium, xthyllithium, butyllithium, amylllthlum, hexyllithium, 2-ethylhexyllithium and n-hexadecyllithium. Aside from the saturated aliphatic lithium compounds, unrelated compounds are also suitable, such as bB AUyllithium, methyl arylalkyl and the like , such as hienyllithium, the various tolyl and ryllithium compounds, alpha and bfttanaphthylthlum, etc., can also be used. Mixtures of the various lithium carbonates are also suitable. A useful catalyst can be obtained, for example, by using a lithium carbonate. rstoff fverblndunc as Auegancsnaterial successively with an alcohol and an olefin, ε.Ω. Propylene (in a similar way as in the "Alfin" technique) is used for the reaction, with a greater or lesser proportion of the lithium from the next daily colloidal substance, a lithium alkoxide, forming a new organolite with the olefin. Further T-IthlumkohlenwnBoeretoffvorblindunien bind the Polylithiumkohl nwasaerfitoffvirbindungen, like in the case of the Rohlenwccoorotcff with from 1 to about 40 carbon atoms, in which the lithium has replaced a number of the Vnocarbonatone. . Examples of suitable Polylithlumkohlommaserotoffvorbindunrren are ge nanntt Dilithiumalkylenv rbiniun ^ s how Mllthiumnethylen, "Di · llthlumftthylen, Hllthlumtrlnethylen, Tlllthiuepcntantthylon, Dilithiumhexaaethylen, Dlllthlumdeoamethylen, Dllithiumootarteoaaethylen and l _t 2 Dlllthiunpropan Other suitable yolyllthlua kohlenwcLSseretorfe are Polylithlum aryl, aralkyl" and - Alkarylvereindungen as sB milthiueibensol 1,4, l _t 5-Sillthiumnaphth · »lln, 1,2-Dllithiun-1,3-Triphenylpropan and the like · AUOH tricycle huhorwertige Llthlumkohlenwaeeeretoffe as * .g. 1,3,5-Trl lithlvapentan or l _f 3 _e 5 ^ rillthiuaibei} aol "ind suitable. Other Terelnunges include the various Llthiumkehleowaeseretoff · Auoh can DilitMii" - ^ lymikliear "si aromtleohes Kohl"

BATH

1k- H

hydrogen adducts sur application o that simply duroh action clay lithium metal with waphthalene, anthrasone and mfcnliohen polynuclear aromatic hydrocarbons are obtained The hydrocarbon receives a negative charge without τοη Ml lose some hydrogen, and serves as an anion dee salves (The lithium loses an electron and serves as a cation). Metallic lithium and the torches can be used independently lithium compounds either for eloh alone or in Any combination as a mixture with each other but use come · to industrial production τοη polybutadiene, there · for since methods are used according to the present invention n-Butyllithium can be used with advantage.

The Konsentration de · catalyst · on · Lithiunbeei amounts to 0.0001 to O ₉ I g · active lithium per 100 g of butadiene-1, Ji is sweokafteeig a Poiynerieationsteraperatur swisohen O ⁰ C and 100 ⁰ O tight turns "The Lithiunpolymer is nioht-krlstallln and has finished egg straps at a low temperature.

In the production of high-quality polymers, the polybutadiene is permanently set in small pieces of commercially available styrene into which it dissolves, for example. distributed. Instead, polybutadiene can also be added to the styrene in a hydrocarbon mixture and the hydrocarbon solvent removed again by means of steam and either dead, during or after the polymerization of the tyrenes. This can also be used in catalytic converters and at a lower temperature. In industrial production, however, the reading in styrofoam is gradually increased and led through a pipe or some other reaction vessel that is under pressure, with the temperature increasing bit more Reaction is increased in order that · reaction · «· never stops liquid this is the jet et generally usual ▼ experienced sun polymerizing τοη styrene. The polymerization can be carried out for example at 50 ⁰ C using ei · nes catalyst or at temperatures up to 250 ° 0 with no Kata lyst.

909848/1 190 ^EAD ORIGINAL

The suspension of the polybutadiene contained in the polymerisation solution can swie.hen 2 to 20 parts of polybutadiene to 98 to Parts of styrene vary. A preferred ratio is 2.5 bia 10 parts of polybutadiene to 97.5 to 90 parts of styrene. Venn not otherwise specified, all information is provided about shares and Progent words on dao Ocwicht. Bi-8 below · Example explains the invention t

Butadiene was used, and all otürendon components (inhi bit or) su remove »and then passed through a clay stool» to dry it «! line 25-proaentiße LHaunc dleooo butadiene in dry witches \ / urde filled in an autoclave, vobel care wrinkled the access of air and moisture was prevented. During the subsequent initial stirring, n ~ butyllithium never became Kvitalyaator cußeoet; i'.t and awar 0.0035 Tiithiua Je luu parts But »· serve. The? Olyuorioation was at for 21 hours

23 to 43 ⁰ O fortgeeetat · Kaoh Bntfernen dee Lüsunken! Ttola, the polybutadiene had a Hooney age of 77.5 (H3>#) and a bite viscosity of 2.6. The structure of the polymer was determined by infrared analysis

, 4-structure share
trona- 1.4- * itnikturant eil
i, 2-structure!: ture portion

V »!> A ¹ OiIo dos / olybutadiene were made in 92» 5 parts of styrene on FeGlütit and 24 o do. s heated at 115 "C and ansohllcaeend 4 AvuiKlon long to 175 ° C: #ifl govonnene Polynere was treated and then gol'ornt in Kahl factory Dioece Polynere has a aue ^ o ^ elcLhete uciluftfosliigUeit on · In the nuohatehenden label ·.! uind the v / erte the Kcrbsohlng "Tth1 gVeit (in PuÖ-pounds) at the different? listed nperaturen _G and swar in Ve ^ gleioh old Con locate a Itatcriols.dao similarly produced was by polymerizing a butadiene ^ tyrolaischpolyoere in styrene (made from 76.5 ^. butadiene and 23 _t 5? <styrene), These lüech · I'uiyncrlaate contained 7 _t 5 parts of the orundoatorlal · (ontt / eder iclybutadiene or a butndiene- ^ tyrolmiuchpoiyner) as well as 92.5 parts de · Polystyrene superatrat «.

_{0RlQ | NAL}

909848/1190

• 5 ·

Test material specification •
Raw material of the fUaohoolyaerlsat • Zlon temperature
O ⁰ O
-20 ° 0
-4ο ^β σ Polybutadiene Butadiene styrene 3.2 ft. Ib.
1.9 ■ ■
0.8 «"
0.6 »· 2.3 ft.lb.
0.8 ■ ·
0.5 · ·
0.1 «·

The polybutadiene coating was superior to the polybutadiene coating in all 7 applications. The higher impact strength and the higher impact strength and the higher impact strength at low dispersion are retained by polystyrene due to the linear unsupported structure
Polybutadlens

Claimsι

BATH ORIGINAL

909848/1190

Claims (9)

? a t »η t a η β ρ r ί! c h · ι 1. Polymers with high impact strength including styrene as an oil base and Poly butadiene al · Boiaiechunc, thereby {denied that the Polybutadiene has a linear structure and a: Ilkroo structure has, the geoilfl infraredanulyee no more never 12 ji l, 2 ~ structure & ntell cries. 2 · Ltyrolpolyuor according to Anapruch 1 «characterized» theS the polybutadiene forms the smaller part of the polyner 3. Utyrol polyoor according to claims 1 or 2, do.uureh characterized _t that the pulybutodiene component increases the flagon & e Hihroetmktnr :, 2-rtmkturanteU 5 to 12 * '. CLB-1.4- »structural component 25 to 7 (# tranf -I _t 4-structural component neet. 4- Fttyrolpolyocr according to one of the v-up / ^ incencenen ancpr'itibjti thereby nekonnseichnetf that the proportion of roiytutndien 2 - 20) 1 and dor proportion of Folyetyrol 90 at OC ;? amount. 5 × method sur Höretellung eineο tyriljolywere hcher fealgkelt enteprechend one of Toraufße ^ anßenen AncprUohe, characterized in that _t is dieporsiert in styrene linearee polybutadiene having a Mikrcetruktur of not Nohr ale 1,2-otrukturanteil has, and since daae · r> tyr 1 is polymerized with the additives Ten polybutadiene. 6. / meet anepruch b, in that a Lueungeaneat von ^ olybutudien with dom rtyrol (jouiacht and dae Leuncaaittel is removed by Terdeepfen. 7 · ▼ · r. Culu-on after Jen A.nspriiohfm 5 odor C , thereby i; el: ennjieiohnet that one polybutadiene by Polvstoriaieren of butadiene - l _t 3 «1ttele« Ine · Katalyeator · auf Lithiuebeeie -erfei ^ tV win \ rira. 9 0 9 8 4 8/1190 BAD ORIGINAL H95676 0 »Ktyrulhars not advertised hatred at low levels Temperatures, tumbled down in the water <len V-. rfaliron according to one of the Requests 5 - 7. Dipl.-Ing. KlJKT LHNGjyet BATH ORIGINAL 909848/1190