DE1720248C2 - Process for making rubbery polymers - Google Patents

Description

(".eichn. ¹ !. d: iP ίΛ.: ϋ die \ 'c> r ^ oi \ rnen ^ iüon i bis ^; - i g. I), w.ir Ja-, ernridiu-i ^ Siiomä !. ⁴ · .; \ e: drive- "i üvru

? Si ::! ■;.!:. ■ η IaPi dürjhfü'ir ·. liaivjiir-genci

[■ -,: ü deslialb edition u; r present in LrHiKi ..! ^. to introduce a new polymerization. mr

2.5 asm it is moeiieh, kiuitschuk-like PoivineriSiiu: in ;:

better Eieenschafien unü oessere "\? rarrie:; har:; c :. ; '. u crhaii £ ü

The process of making rubber

The briindimg iich relates to a method of au, containing polymers by polymerization of kuu-Hersiellen son kauischukartiaen 'branched Pockels 30 tschukbildenden monomers in the presence of a kidney ^ and Mischpols; ^r .ie he stereospecific catalyst at low temperature In recent years, the rubber-like in the first stage and at an elevated temperature in the polymer, which is followed by a second stage with a catalyst that is in accordance with the invention. are characterized for the iroduc'ion of viii by the fact that a conjugated diene is more and more economical or a mixture of a conjugated diene and is important because it has very good physical properties of a monosinyl substituted aromatic compound. Properties in particular with regard to their abrasion resistance at a temperature of -5 to 25 C in counter-resistance, their behavior at low temperatures of a lithium-containing catalyst in a ramr and their resistance to bending cracks. Hydrocarbon diluents, with the addition of an almost completely linear structure to the reaction mixture at 40 to 80 ° C, the reaction mixture has a practically completely linear structure and is merized with an organolithium catalyst. It is advantageous to carry out the prepolymerization Ct. that is, that they do not carry out any branching in their molecule for 1 to 5 hours, "iron (cf. Industrial and Engineering Chemistry, It had to be surprising that with the erindungsge-Johnson BL, Vol. 40 (1948), p. 351, Journal of Polymers, not only prevents cold flow from mer Science, Part C, No. 1, p. 311 (1963) and Part A, but that rather branched chewing No. 2. S. 797 (1964). As a result, they have had disadvantages of chuk-like polymers or copolymers with regard to their flow properties at room temperature, remarkable tensile strength and temperature or their so-called cold-flow values, the tear strength in the non-vulcanized state and extremely high, as well as with regard to their tensile strength - and 50 are characterized by good processability.Tear strength Values that are too low due to the low degree of distortion ad Because of these disadvantages, in the processing of 1,3-butadiene in the presence of n-butyllithium, rubber-like polymers of this type are prior to their at different polymerization periods; Vulcanization often encountered difficulties, so that 55 F i g. 2 shows the relationships between the previous practical application area despite the excellent warming temperature and the Williams-Recovery des neter properties were severely restricted. Polymers at different polymerization periods; In order to avoid the cold flow at room temperature, Fig. 3 shows the relationship between the shear, different methods have already been used, tension and the viscosity of different samples which can be divided into the following three groups: βο from polybutadiene;

Fig. 4 explains the relationships between the

1. crosslinking of the rubber molecules _close by switching M to process oil and Williams recovery work of a crosslinking agent with polyfunk- ^ _m j _t the oil-extended polybutadiene.

tional group (cf. Dutch patent | _{m the} following is the example of polymerization

6 602 265). 6 _{5 of} ^ 3-butadiene in the presence of n-butyllithium as

2. Crosslinking the rubber molecules with the aid of a catalyst the process according to the invention in more detail Radical Generating Agent (British Patent - Illustrated.

1 018.164). In Fig. 1 are the relationships between the poly-

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reftuv. ·; would.

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rim.

Saiicns initial susceptibility at a soLt: ϊμ: ·!;. · ¹ -ren temperature.exceptionally-; / nriiekgeoran- ;! -. ';. and that consequently the continuous, ... ue- unuiuci -.- placed catalyst in the reaction mixture re.jt; ^ is still held and that this is always: L '> e! zie i-viitj: sator not only takes part in the PoiymeriNations-AiiLiiig ^ cM ·.-tion, but also the Viociit ni.ei: ha ;. :.>'■ Methylene or vaesaturated group aes neuernu> ic ·· cool polymers to be added. Ι ·.;, Nai> I thus pointed out that after a long period of contact, the before. Low molecular weight polymers formed for 5 hours at a reaction temperature of 15 ° C. therefore have shorter polymer chains because the rate of polymerisation has been suppressed extremely strongly, but that it has active centers in a relatively high density within the polymer chains.

It has also been shown that a rubber-like polymer obtained by subjecting such a low molecular weight polymer with a number of active centers to conventional polymerization at a temperature, for example from 40 to 80 ^° C., and the polymerization reaction at this temperature completed, shows a very high value of Williams-Recove / y and no flow at room temperature, presumably because the localization reactions at the relevant active centers preceded the polymer chains. are.

For the implementation of the method according to the invention, an important factor is that the density of the active centers can optionally be controlled by the pretreatment at a low temperature and by the pretreatment time, whereby the value for the Williams recovery (in the drawings with »Williams- Recovery "denotes) of the rubber-like polymer in the subsequent process in which the polymerization of the pretreated polymer is terminated under the usual polymerization conditions, also C-jl's optionally by a combination of: --.- ^; Li .--.:. e, .. r. «J. ':.'. i-ae: iüii.k- ⁱ . Ven ': Uire: i is ::: e' τ-

· - ■! ■ • e .- :: n ^ iuiiü>. '. L-: vipir: »:.: R: m * a range of'^; : "- ■; --_ ':'C" je ^ '^' estTi tv ^ enräiik: because oie 'feniper :: -.- a;.; Erna.ivo; >. - ί L a / u long Be.iandiunßMia.i-.v r; .viifr ;. cn-; -, αίϋΓί; ·. · ρ. νom wincnaftlichen St; ¹ "; · now;,!:;:, - .ine ^r v. Uti ^ -Τιϊ r-, ϊ. While a temper. ::, ::

ic; . ■ • her-i.iir- vor. -2 ": d) C Polymerisations-Fortnti.i. · ¹ /Lir.i. ^T 5gL -. Chv> indi: J: .ei ₁ » röber than the polymer. ·. ';":.·> ■ . • ii.ir.gs ^ fichvvin-.iigi. ·. ::: be läßi.

Z ;. the iitriuimna'iiL'en catalysts that are used for the ennuhi. ". g.sgeniäüe V-j-iahren be used, g-e-

.... iiuren before: ' _l icswc!> c rnetaliisciies lithium. Meth ^v '-litnium. Ainvllithiuni. PropvliithiLim. n-Butyllithiiim. • \ myllithium, hiexyliithium, 2-ethylhexyHithium, phenyl lithium, various t'olyllithium compounds. Methylenedilithium, Athyiendilithium. 1,4-dilithiobe

41! / oil and 1,5-diithionaphthalene.

The amount of catalyst required depends on the type of polymer desired a.b. In general is but the amount is practically the same as that used for a reaction at the hitherto customary temperature would.

Conjugated dienes which can be used for the method according to the invention are /. B. 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and 1,3-pentadiene (piperylene).

- '< Diluents which are suitable for the process according to the invention are, for example, paraffinic, cycloparaffinic and aromatic hydrocarbons; typical examples are pentane, hexane, isobutane, isooctane, n-dodecane, cyclopentane,

y _o Cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene. These diluents can be used either alone or in admixture of two or more kinds.
The rubbery polymer built up on the basis of conjugated dienes or the rubbery polymer built up from conjugated dienes and monovinyl-substituted aromatics, which has been obtained in the hydrocarbon diluent by the inventive polymerization process in the presence of these lithium organic catalysts, is treated with an antioxidant such as phenyl-oxidizing agent -Naphthylamine mixed, then separated from the diluent and dried, wherein

i 720 248

one the desired product according to the usual methods receives.

In the case of the polynical reaction according to the invention the polymer, completely free of Cielhe constituents, continuously with a degree of flexibility j of almost ItX) ",,,, based on the conjugated Dien, be received.

in the following, the notable Erl'md'iügs according to he / icltc Fffekt explains, according to which the chew-like Polymers optionally have adjustable, branched structures and, as a result, differ Can be processed excellently and show no flow properties at low temperature, i.e. they do not cold must have.

F i g. 3 shows the curves obtained by plotting the viscosity values at different shear forces for three samples. ie polybutadiene, sample A. obtained according to the method according to the invention, polybutadiene-Veigleiclisprobc // with the soft composition like sample I, but produced by a conventional method in which the cold flow has not been improved, and polybutadiene comparative sample C, in the the cold ulcer was removed by the usual procedure, that is, using divinylhenzene.

The preparation of these samples is detailed! in Example I explained in more detail. In order for a polymer kaiitschukarti.'vs little as possible cold lull I shows and excellent Verarbeitbarkeil possesses Nuil ^1, the polymer a sufficient resistance to hold u> I to the left at low shear forces, d. left to withstand an external force, but it must have a sufficiently high flow property so that it can be processed very well under greater shear stress. Fs can not namely Newton-Flieiherhalten besitzcü, if, in which the resistance is exerted on him voltage depending \ o \\ Ciröße the variable.

How to get the F i g. 3 can be seen, it is clear! ill the comparison sample C, in which the cold l-liü.l du; Ji chemical crosslinking has been improved. has an i <high viscosity value at a low shear stress. Further, the viscosity value is maintained even if the shear force applied to the sample is increased. This is clearly the cause of the deterioration in processability of the chewable polymer in which the cold flow has been prevented by chemical crosslinking. A similar tendency can clearly be observed with respect to one (inippe of samples in which the cold flow has been prevented by crosslinking r; _{(with the} aid of free radical formation - .v> the compounds.

In the case of the comparative sample B of polybutadiene prepared by the usual polymerization processes, with a relatively straight-chain structure, with no particular attention paid to the prevention of cold flow, it is found that the viscosity value is sufficiently low to cause the polymer to flow with a small shear stress wild, and that the viscosity value remains unchanged under a large shear force, that is, the workability is not improved.

On the other hand, the polybutadiene sample A, which has been polymerized by the method according to the invention, shows a higher viscosity value than that of the comparative sample C, with a small shear stress, which indicates that the cold flow can be completely prevented while the viscosity value can be kept even lower can than with the

Comparison requirement Ii in the case of a larger Scherspanruinj This clearly expresses the fact that an excellent comparability has been achieved.

It is quite clear that the theological lies shear the trial / its (irimdlage in the Macro structure of the high molecular weight polymer, especially with the fibers that are necessary for this poly mere are characteristic. That means that he Rubber-like poles obtained according to the founding method show no resistance to wear, as is the case Fig. 3 is explained. This is due to the fact / muck supply that the molecule is branched. where dii Branches through the Polymcnsationsbedmgiingei can be precisely controlled.

The method of generating Vcr / wciMingei on a polymer chain according to the invention-based process is completely new and unlearned It differs significantly from the known methods, and finally, for example, chemical fermentation the networking with free radicals forming \ <- out fertilize, mingling various; Poly merer or the addition reaction. With the ilm according to the procedure several \ r part « compared to the known method achieved d.e siel from the commercial point of view as follows silulderi leave:

i Da '.a chemical crosslinking agent o, i.
Kadikalvernet / iingsmittel is used 1.1
continuous working method over a longer period of time,
possible without a goal formation taking place.

2. The cold river can completely lose its power
the. even with rubber stretched with oil ..
Polymers.

3. line 11 he particularly unique Figi-u ■■ ■
the properly manufactured rubber
I olymeren is an excellent salesman > ■
^{<1or XS: | I} ' ^C · ^ ¹ ·> ■ ·' IaH /. B. a lowering d. :
poralur bi-, for achieving strong bears
your roller mill. _cmc improvement in veil ι
^k "''"'II lubricants and vulcanizing agents
a stale proposition:, zcit to note s,

■ * ■ Because of the excellent compatibility which has arisen there are al
more favorable figures. You are special
! »Msite regarding their Abricbhcstämlisk. · ,.
their persistence in the formation of a kiss in the Uiesien

iNcben these particularly important advantages
'""'»" According to the type of rubber received
mensate g, bt there are other cheap bags. :
■ Hanged, such as simplified storage and packaging, storage facilities as well as easier handling and lower transport; Characteristics that are also of great importance.

example 1
In a Λ11Ι0- equipped with a heating device

mTr'h "" υ ^{l0 C was gCkÜhIt} · ^{wurdc a} l-ösu mimic the given from 25 parts by weight 1,3-Butad.en and 75 Gewichtsteilcn "-hexane consisted; the solution mixture was (previously) also cooled to 10 "C. Solution -, ^{nCr tr} ° P ^fen ^ ise a 5" /, ige n-llesan-η PCnT with ^{a content of} 0.0125 parts by weight of n-butyl chloride, that was sufficiently cooled, admitted.

schenT T ¹ * ^"1 ^ ^{oF Alltok |?} avs was · ^increases in the interim-ReV _1, ^{from 10 to UC} Thereafter, the ReaKtionsgein, _sc h for 5 hours at the lower temperature of 11 C stirred Then the Temaes was Kuhlers. gradually increased. nis the Tcm.DC-

wedge emi

«Ern.rr

iiier -, .-, τ

; ιιΙ i cn-: ml · Ϊ́ ..- | ι ·

Ratiir of the autoclave reached 70 C in the next 4 hours, after this period the reaction rate was 0.25 (weight 2.6-1) in tcrl-hutyl-p-cresol per MX) the weight of the Macile Polybuladi? n pull and the Kcakt .on quit !. The conversion of the 1,1-l) uladien was W.72 ", ' _n . The resulting polyamide solution was dried on a heated Irommel dryer; tr.aη received a polybutadiene (sample A).

For comparison, a solution was continuously introduced into a kettle, which consisted of HX) (icwichlslcilen 1.1 uuladiene, 100 (icwichlteile .i -Hxim and 0.050 (iewiclilstcilcn nhiityllithium). The polymerization was initially continuous dirchgciührt then 2.2 hours at 40 C ₁ 2.2 hours at 45 C. then, 2.2 hours at 50 C, then 2.2 hours at 60 (and sehlieHlich 2.2 hours at 70 C. iewjchlsleilen After the addition of 0.25 (? .6- l) i-lert bulyl-p-crcsol to HX) (iewichtsteilen polybutadiene Auslall on the system, the resulting "o l'olymerlösung a Irockner was fed. dried polybutadiene was obtained as Vergleichsptobe H the conversion of 1,1-Uutadiens wii 9" ) .80 V ₀ .

For a further comparison, cm polymer was produced as comparative sample C, with the same system aj and the same composition of the c lemisehes as in the l'r / cugung of the comparative sample H with the difference that 0.25 (icvichlsleile methylbenzene per KX) (iewichlsteile 1.1 Diitadiene were added. L) The conversion of 1.1 uutadiene and divmylbenzene was W.75 or. '> 5.6 " _r ,

The following lain McI denounces you; Mooncy- \ iskositat, the lial properties and the manageability of the samples A. H um! C.

35 Table I.

Ml.,., (100 C) ')

VI (mm) ² )

HI (mm) ³ ). .

I lielitest (mg / min) ¹ )

I iSpeed ¹ ')
Imm min) Ικι

25 C

60 C

* lowest temperature / um
I get strong streaks
uif the whale (C) ")

l'iohc (II) M. 5 14.0 4.15 1.50 "1.25 0. IK 0.1 7.5 0.06 0.52 0.10 1.20 HO

15.5
1.45 2.2S 0.4

O _- (W 0. ί 1

K) 6

4 pp

In the above table show:

'■ 1 Measured according to JIS-K-nW).

1 Williams p'aslicilate (ASTM l> -92d) Williams-r rholuiig (ASTM 13-> 2 '>>.

'<) Strangpreßgev.hwindfgkeit from a MiindunR of 0.6cm "at 100 C under a pressure v ^<8 cm in 25Og

Deformation speed of a cylindrical specimen with 2cm in diameter and lon height, extending to a 45 ' inclined plane was placed in a thermostat kept at a predetermined temperature.

f'i Minimum surface temperature that is required. so that a sample pulls smoothly onto rollers with a 20J cm diameter handler: Operating conditions: rotation ratio 1: 1.4 and roller spacing 5.0 mm

One can readily see from the table that sample A is far better than comparative sample B in all high-temperature tests, despite the fact that it has the same Mooney viscosity values. Although the comparison sample C shows a satisfactory behavior in comparison to the sample / 1 in the case of the IielKcrsiichen, it is still worse than the comparison sample because of the roller workability, and it turns out that the sample A 111 is excellent in this regard.

Samples A, Ii and C were processed according to the information in the table. The tolerability, the lielk'igenschaflcn I, the (xlrusionseigeiisehafien 'and the Uohfestigkeit the uncured compositions are reported in the following IaIx ¹ IIe III

Table Il
/ usiimmenscl / iing

Polybutadiene

KuIl (high-quality furnace soot)

Aromatic process oil

Stearic acid

Zinc oxide

Antioxidant phenyl / i-naph-

thylamine

sulfur

Vulcanization components N- (yclo-

hexylbcn7Othia / ylstilfarnid

Table III

(ir \ vi (hlslcilc

HX)

50

IO

.1

Mischds'.iicr P'nuiien) ')

1 rental speed wedge *)

(mm / min), 70 C.

rupture characteristics ⁸ )

A) Amount of extrusion (ml / min)

U) swelling at the nozzle ( ¹ Vo)

C) Appearance of the I xtrudal.
Strength of mass (kg / cm ² ) ⁴ )

Prorvn M) <«) I. 27 40 0.07 1.25 8.1 7.4 .18
4th
1.6 .12

62 0.14 6.1

50 I 2.2

the working temperature

11 fs an open whale was used!

was XO (
2) Defoim.ilionsgeschwmdigkeil of a /> Lindrischen l'rohe with

2 cm in diameter and 1 cm in height, on a 4S ge

I tended to put in a thermostat which was at

a predetermined temperature was kept 1) I s became a hearing aid of the following I iKcnscluftrn

used:

Schiaubenahmessiingcn: H mm diameter ¹ H) mm

Screw rotation: 20 rpm

Extruded mouth size 2.0 mm

The extrusion temperature was WT. The appearance of the l ^: \

trudats was judged to have a satisfactory appearance

the value 4 was given

⁴⁾ "! F ^ ^We in ^e, _f ^{WU riien Crha! Th} ^ ^{in 'lem} the method of measurement according ^{nI <vulkanisierlcn l> robes} was applied

It can be seen from Table JII that sample A obtained according to the invention requires a very short mixing time and that, moreover, the flow property, the extrusion property, in particular the appearance of the extrusion, and the rolling resistance are better than in comparison samples B and C.

The he following Table IV shows the physical properties of these three different samples measured after they have been for 30 minutes vulkanisert in a hot press at 140 ⁰ C.

309 686/281

Table IV

l'rolicn (C) (A) (/)) 133 146 130 72 70 66 420 480 490 3 "i 42 35 64 63 62 61 60 60 0.0 « 0.04 0.06 2250 2630 2010

Tensile strength (kg / cm ² ) *). .
3 (K) "/ ₀ -Ziign> dul (kg / cm ² ) *)

Extensibility. ("/") *)

Tear strength (kg / cm) *)

Jlärt (Hs JIS) *)

lip ring plasticity
RÜPKL-Llasti / itätslester

Akron Abricb

(ml / IO (K) times) **)

hicgerißhildting, measured with

the demattiatester

(just)***)

* (icmcsscn according to JlS-ftJOI. ·· Uimlrthung 2M) rpm, angle 15, llel.iMiin «

♦ ·· (iemev> en according to AS I'M-IJ-III.1-59.

From the results in Table IV, it can be readily seen that the sample A obtained by the process of the invention has excellent physical properties including fundamental properties such as tear strength and tensile strength.

Example 2

The rehearsals AI, AI. / (- 3 and AA were after the

The same procedure as for the preparation of sample A in Example 1, with the difference that the preheating temperature and the preheating temperature have been changed. Sample A-7 in this example is the same as sample A in Example 1.

The Mooney Viscosity and Leak Property Values these four samples are given in Table V below.

Table V

Pretreatment temperature

Pretreatment time

(Hours)

ML _IM (100 ^; C)

Y-3 (mm)

R-I (mm)

Hot test (mg / min)

Hot quantity (mm / min)

25 C

60 C

l'mhc

.1-1

K)

34.0 3.00 1.88 0.75

0.13 0.18

Al ΛΛ 10 20th 5 3 34.5 33.5 4.15 2.30 3.25 1.05 0.30 1.60 0.06 0.16 0.10 0.19

V.

H c i s ρ i e I 3

An autoclave was charged with a solution which contained 3.1 parts by weight of 1,3-butadiene, 18 parts by weight of styrene, 87.2 parts by weight of n-llexane and 0.068 (parts by weight of M-Uiityllilhium; the Vorbehaiullungsreaktioti was 5 hours at a temperature of 5 C. I. A sample U was obtained by adding the resulting reaction mixture to a polymer

in under the same conditions as with the Hersiel ment of the comparative sample / ·. ' below threw winds.

Hei tier production of the sample / ·. ' became the .Poly merization reaction started by introducing a solution into an autoclave, the 3.8 (parts by weight 1,3-Dutadicn, 18 weight, styrene, 87.2 weight parts η-hexane and 0.068 parts by weight s-butyllithium contained. The reaction was initially 2 hours long) at 60 ° C., then at 70 ° C. for 6 hours and finally at 75 ° C. for 1 hour.

Since 1,3-butadiene, which has a higher reaction rate than styrene, was consumed faster than styrene in the case of a rapid reaction, a solution was added intermittently to the reaction mixture, which contained 78.2 (parts by weight 1,3-llutadiene by 312, 8 Gewichisteile n-llcxan contained to the concen tration of 1,3-butadiene in the Rcaktionsgemiscl · br keep a certain level. 30 minutes ι ^»1 completion of the Zugabc was Rcaktionsgenmi I with 0.25 (icwichtstcilen 2,6- l) i-tert-butyl-p-cresol pt,

jo IUi parts by weight of polymer are added and the ration is terminated. The conversion of 1,3-butadiene mi <styrene was 99, SO and 99.72 ¹ V ₀ , respectively. The resulting solution was gelrock net on a heated drum dryer. a polymer, sample / ·., was obtained

; 15 I ine sample / 'was prepared by the above beschricbeni'i process for the preparation of the sample /-.'erzeugt m except that 0.25 Gewichtslcile Divinylhenze were added "of the starting solution / The I'm uaiulltmgsgradc 1.3 -Butadicn-Styrene and Diviini benzol were in this lall 99.88, 99, / 0 and 9 ^c .d <) "

The physical properties and the hot properties of these samples I), 1. and / ■ 'are given in Table VI below.

45

Table Vl

20th

34.5 3.50 2.40 0.50

0.08 0.12 ML ₁₁₁ (KX) C)

55

60

The measurements were carried out using the same methods as those in Table I under the footnotes 1 to 5 are explained.

Table V clearly shows that polymers with the desired degree of branching, ti. H. the desired flow property by controlling the pretreatment temperature and the pretreatment time can be produced.

Amount of bound styrene *) (percent by weight)

Amount of styrene blocks **)
(Weight percent)

Y-3 (mm)

R-I (mm)

Flow test (mg / min)

Flow rate (mm / min)

at 25'-C

6O ⁰ C

! • raw I / II

46.0 18.0

0.05 4.30 3.75 0.30

0.11 0.28

46.5 18.0

0.06 1.90 0.38 8.5

0.88 2.05

♦ Measured with an Abbe refractometer. ** Determined by oxidative decomposition with the aid of vi Di tert-butyl hydroperoxide and osmium hydroxide.

The other measurements were carried out according to the method in Table [.

It can be seen from Tahelle VI that sample D was used in all flow tests

is better than the comparative sample /. ', despite / the fact that they have the same Mooney viscosity values. If, moreover, a comparison is made with the sample obtained with the aid of a chemical coupling agent, the robe I) is superior to the sample in terms of the speed of flow at high temperature.

The three different samples /). /. ' and / ■ '«.irden in a corresponding manner according to the sowing / tier IabelleVIl further processed, the corresponding samples of unvulcanized masses being obtained. The results of experiments carried out with these masses with regard to their I xtrusioiiseigeiischafien are given in Table VIII.

Table VII

Zusanimcnset / ιιημ

Butalien / styrene copolymer

Soot (see table II)

Aromatic process oil

Stearic acid

Zinc oxide

Antioxidants ο Table II)
Vulcanization equipment iiiuger

(see table II)

sulfur

(icuit-htstoik-

100
60
20th

Table VIII Mooney viscosity ill) rehearse 57.0 (ML _IU 100 C) 7.0 txtrusionsmence (ml well) 50 Swelling at the nozzle ("/") 54.0 2 Appearance of the extrudate *) 36 7.6 In a Bunbury mixer 4th 30th S, 2 required mixing time (min) .. 4th 6.5 7.3

• A satisfactory appearance was hired at 4.

In the above experiments the mixing was carried out on a Bunbury mixer at 120 ° C; that Extrusion was done at 90 C with a Brahender extruder having the following properties:

Screw wear measurements: 15 mm diameter · 90 mm screw rotation: 20 rpm
Extrusion mouth

size: 2.0 mm

Extrusion temperature: 90 ^{c C.}

It can be seen from Table VIII that Sample D obtained by the process of the present invention requires only a very short mixing time in the Banbury mixer, indicating that it has excellent processability. It has also been shown that Sample D has far better extrusion properties, ie, extrusion rate and extrudate appearance, than Sample F.

The following Table IX shows the physical properties of these three different samples, measured after vulcanizing at 140 ° C. for 30 minutes.

Table IX

Tensile strength (kgcm-)

300 ° "- / iigir.odiil (kg / cm ³ ). .
κ extensibility ( ¹ V _n )

Rcil.lfestineit (kg'cm)

Hardness (tfsJIS). '

Jump clasti / itut after

RLIPKf: Elasticity tester
'5 Co)

Akron Abricb

happy U>) tl.) 2M) 205 95 93 4SS 485 40 38 60 60 58 5S 0.04 0.04

460 38 63

The measurements were made according to ile methods Table IV performed.

In the results of Table IX / own it is clear that in the case of the sample / "by preventing the flow properties with the help of a chemical crosslinking agent a considerable breakdown of most of the fundamental physical properties, d. H. the Z'igfestigkcit is observed. In contrast to this, sample D excellent tensile strength and tear resistance.

Example 4

A solution with a content of 25 parts by weight of 1,3-butadiene, 75 parts by weight η-hexane, 0.0055 parts by weight of n-uutyllithium and 0.2 parts by weight Diinylhenzene was subjected to a preliminary reaction at 10 ° C. for 5 hours.

Then, the pretreated mixture was fed to a kontiinnerlich Polynierisationsanlagc and f continuously first 2.2 hours at 40 Γ, then 2.2 hours at 45. Then 2.2 hours at 60 C and finally 2.2 hours polymerized hei ¹ 70 C. There; Reaction mixture was mixed with 0.5 (iewichtstcilen 2.6-di-tert-butyl-p-eresol and 50 parts by weight of an aromatic process oil with a specific gravity of 1.0035 and VGC (viscosity constant) of 0.933Γ per 100 parts by weight of polybutadiene at the outlet of the plant, and after thorough η mixing the resultant mixture was fed to a Trommelnockner, where it was considered an oil extended polymer sample al · (i ei.

For comparison, a Polytnerisationsanl.igc was continuously charged with a solution the " ¹ SGe-

όο parts by weight of 1,3-butadiene, 75 parts by weight of n - '. exan contained 0.0055 parts by weight of n-bulyllithium and 0.2 parts by weight of divinylben / ol. The Polymerisationsreak tion was continuously be first 2.2 hours 40 ⁼ C, then 2.2 hours at 45 ^C C, then 4.4 Stunder at 6O ⁰ C and then 2.2 hours at 70'C performed. The reaction mixture was then admixed with 0.5 part by weight of 2,6-di-tert-butyl-p-cresol and 50 parts by weight of an aromatic process oil per 100 parts by weight of polybutadiene at the outlet from the plant.

After thorough mixing, the reaction mixture was fed to a drum dryer dried, using an oil-stretched polymer as a sample /. ' received.

F i g. 4 shows the comparison of the lowering of the flow resistance in the case of the mate extended with oil lial with the sample G extended with oil, which after the process according to the invention has been obtained

after

as well as with the sample stretched with oil // that
known method was generated.

In Fig. 4 the values are the Williams-Rectnery applied to the flow resistance.

One can see the F i g. 4 that the effect of preventing the cold flow is achieved by calling branches according to the method of the invention, this property being maintained even when stretching with a C ' , which is in contrast to known methods.

The physical properties of these Samples G and H were measured before and after stretching with the converting oil: the values are given in Table X below.

Table X
Before stretching with the process oil The following Table XlI shows the physical ·! Properties of the non-vulcanized, processed samples including the raw strength, processability and, in particular, the ability to extrude.

Table Xl!

rehearse

(C)

ΙΗΪ

ML, _M ((KXTC)

R-I (mm)

Y-3 (mm)

Gel content (%) *)

After stretching with the process oil

ML _1n (100 C)

R-I (mm)

Y-3 (mm)

Flow test (mg / min)

* Weight percent of the residue obtained by dissolving the samples in toluene and filter the resulting solution through a 200 mesh sieve (mesh size 0.074 mm). Other Experiments and measured values were carried out according to the methods in Table I.

94.0 93.0 4.2 4.1 4.6 4.8 0
rfnhreeg 5.3
tsöI 1 ML * 111 ν '
36.0 30.5 3.5 1.6 3.6 3.0 0.7 1.6

It can be seen from Table X that Sample G is superior to Sample H in this regard. that the gel content can be reduced to practically zero and that this is characteristic of the cold flow prevention and that this property is not influenced by the stretching with oil.

The oil-extended samples G and // were then processed further in a Bunbury mixer according to the instructions in Table XI below, and their compatibility was measured.

Table XI

composition

Polybutadiene

HAF soot

Zinc oxide

Stearic acid

Antioxidant aldol - ((\ - naph-

thylamine)

Antioxidants (as in Table II)
Vulcanization accelerator (as in

Table II)

sulfur

Weight

100
60
5.0
2.0

1.0
1.0

1.0
1.6

55 sample (CPi I (//)

58 9 61 5 4, 3, 110 38 120 20th 1, 1, S. 6th

Mixing time in the Bunbury mixer

(Minutes)?> 3 9.5

Mooney viscosity ML ₁ ,,

(100 "'θ

Raw strength (kg / cm -) *)

Extrusion properties * *)
Extrusion pressure (kg / cm ² ) ... extrudability (g / min). Appearance of the extrudate ***) | • Values obtained by applying the measuring method according to

JIS-K-6301 on the unvulcanized samples. * · Exirusion attempts were made with a Garvey-Die-

Tester carried out.
··· Satisfactory extrusion was rated 12.

Table XII clearly indicates that Sample G has better mixing properties in a Banbury mixer, a lower Mooney viscosity

ML _{1 + 4} (100 "C) in the processed state, a greater raw strength and a better extrudability than the comparative sample H. The raw strength in particular represents a considerable improvement in processability in the manufacture of vehicle tires.

These two unvulcanized samples were then vulcanized at 140 ° C. for 50 minutes. The physical Properties of the vulcanized samples were measured. The results are in the following Table XIII shown.

Table XIII

Tensile strength (kg / cm ² )

300% tensile modulus (kg / cm ² )

Extensibility (° / ₀ )

Tear strength (kg / cm)

Hardness (HsJIS)

Spring elasticity according to RÜPKE

Elasticity Tester (7 ₀ )

Akron abrasion (ml / 10000 times) ... Flexural crack formation, measured with the Demattiatester (mal) *) ..

♦ According to ASTM-D-8U-59.

sample

(G)

(ff)

162

84 455

44

58

57 0.04

2660

118

82 412

37

54

53 0.08

2210

The results in Table XIII show that Sample G is apparently superior to Comparative Sample H in fundamental physical properties such as tensile strength, tear strength and Akron abrasion.

For this purpose 2 sheets of drawings

Claims (1)

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