DE1915132A1 - Polybutadiene mixtures - Google Patents

Description

PATENT LAWYERS

DR. M0LLER-BOR6 DIPL-INQ. GRALF8

DR. MANITZ - DR. DEUFEL B MÖNCHEN 22, ROBERT-KOCH-STR. 1 Lo / B - J

TELEPHONE 225110

THJS IMTKKNATIQHAL UlKUUiSXC iUJBÜJSR CUMPAJIY

LIKXXKD ₁

Brunswick Houe ·, Brunswick PXaoe _a ottthaaptou »

"PoXybtttadien-ltiecbaiigen '

Priority : Oro0brit «nnien rom 25 · Kä» 1968 Mr, Η35β / 68

Dl · Jtrfindune concerns the «U« r »ttlX«% * iwd ßi «« iolmften tone Kiechuo ^ wa from] & «a-4tetttephuk« ii, di · · 1ο «η high proportion of B * it «ak« tt «n-> 1fagMll% tlgtkeit beaitMn, bit the "in" ni "dri" "a part of

Εμβ π1 11 erhiaUioh * OiwHEautaolnuc tnthaXttn im

MinM tiMtt Bl «drl4tm portion τοη» #it «Uc» ttMi Ofm greasiness, Xp VaLIt TQH rolybuWdi «n-Iautiohuk« o bttrtift il ·

- 1 909843/1679

BATH ORIGINAL

in general either (a) at least 85 % cie-1 »4-structure or (b) 30 - 45 # cio-1,4 and 50 - 65>» trans-1,4 »where the vinyl (1,2) - Content in both fill 15, - or less, usually 10 r> or less, for example 1-8 >> amounts to _{0. In the} case of the J-oleoprene rubbers, these generally have a carbon content of at least 85 "}" * $ usually over 95 ". '* $ and Bie contain 15 ' e or less, usually below b τη side chain unsaturation (as laopropenyl or 3 ^ structures) In this description, side chain unsaturation is expressed as a percentage of the in the polymer present Geaafflt-U3Rf "? Saturation _f (jemeoeen by I · R." Spectroscopy according to the method van Heap tow - Analytical Chemistry 21. "(1949)" S ₀ 927, printed. Bo are "Cyοίο", ^N cycli "i" rte ⁿ and "lead * r" structures aueaeechloeeeno This koenerziellen Kautechuko be used ale Mehraweckoaterialien and however characterized by a high Bich Rüokprallelaatieität and good Ab "riebfeBtißkeit from" Eb difficulties may arise when they are processed on conventional Pabrikmaechinen, and if x 1 x alone " are used in cheek treads, the "preserved mlechun" adds a "low" ik "it.

I have now been found, so that the men and women are in communication Lautohuk «can be reduced, ind« a di «a · * lt one Rubber or fautaohuken were mixed in, dl · «in n higher Intelligent on side-chain on-line toxicity already.

(IWiMΠ der JtefindUBg «ntkllt A) 5 to 95 (tar · parts »elaiestea» «issβ kautschukartifen Bitni> oly »« rieat ·· old less than 30 Jt ü «ltenkcttsn ~ tlngeaättlgt ~

- 2 -909843/1679

BATH ORIGiWAL

intimately mixed with B) 95 to 5 parts by weight of at least one other chewable diene polymer with more than 30 -ρ rare-chain unsaturation

Such intimately mixed mixtures can through Mixing the solid rubbers together by means of netting Use of conventional rubber processing methods such as an internal mixer or calender or by mixing Hydrocarbons or latices of rubbers »followed are produced by a conventional processing method *

There are several processes but the manufacture of polydienes Rubbers with a large proportion of side chain unsaturation must be particularly effective in working described in German patent application P 1 770 877 ° 9 * This involves the polymerization of the monomers in the presence an organic lithium catalyst and a polyether, in particular Äthyl eriglykoldime thy lather (ölyme) or Mäthylenglykoldimethylather (diglyme), the polyether with the organic lithium compound in the presence of at least one of the monomers is brought into contact with this catalyst it is possible to use rubbery polybutadienes. 4 Polyisoprenes with up to 80 or more vague or higher chain unsaturation can be produced

An alternative manufacture of poly serving with a high level of side chain unsaturation precludes its use of transition metal compounds with special, cocatalysts

~ 3

909843/1679

a, for example titanium tetrachloride / ftatriuinalkyl, vanadium or chromium acetylacetoiiat / aluminum triethyl in the case of Butadiene and litan ester / aluminum triethyl in the case of isoprene

The polymer (A) can be, for example, a natural rubber or a chewable polymer of butadiene, isoprene, pip arylene or dimethylbutadiene, or a mixture of such rubbers. Mixtures of polybutadiene with natural rubber or ötyrolebutadiene rubbers include homopolymers of both diene polymers Copolymers of two or more dienes and rubber-like copolymers of one or more dienes with one or more monomers, for example styrene or acrylonitrile, understood, the vinyl monomer (s) usually in an amount of 50 percent i · or less of the copolymer _B is present in particular, the polymer (a) a homopolymer of butadiene or a $ loekcopolymerieat of butadiene with styrene, or it may be such a Blookcopolymerisat given by the proportion of Seitonketten-Ungesävtigtkeit of the a-Bloeks is less than 30 J6, generally less than 20 #, and particularly preferably less than 12 '/ *, for example 1 - θ W

The polymer £ B) can for example be a polymer of butadiene, isoprene, piperylene or dimethylbutadiene, a block copolymer of butadiene with styrene or a mixture of such (co) polymers be _0. The percentage of side-chain unsaturation dee polymer (B) is larger than 30 $, usually over '55 'Ar and it can go up to 80 · / »be

'AD ORIGINAL'

909843/1679

wearo

Particularly preferred mixtures are made from a homopolymer of butadiene which has less than 20 P vinyl (1,2) => content and a homopolymer of butadiene which has more than j5ü y-a vinyl (t, 2) <" (rehalt owns *

KautachukmiBchungen according to the invention comprise from 5 to 95 öew, "" l ^l rush dee polymer Δ intimately veiraischt with 95 to 5 Gewo "ropes of the polymer B" In general, 15 to 95 'Üeile polymer Λ 85 to 5 are ieilen polymer B mixed »Particularly preferably 20 to 80 parts of polymer A with 80 to 20 parts of polymer Bo

J) The average side chain infiltration of the rubber mixture, as indicated by idiosyncratic spectroscopy (Hampton method), can be anticipated from the side chain deficiency of the polymeric acid components and the particular chain used. In general, the average side chain infinity should be 25 i * 75 # bia "preferably from 40 to 60 ^ betragene

Polymer Λ and polymer B are normalerweiee feet, they Deho besitsen a molecular weight of more than 15 × 00o ₉ noraalerweiee 10Oo000 to 30O ₀ OOO, however, polymers can old a molecular weight of I ₀ OOO ₀ 000 or even fall even more used becoming in the Kautechukteohnologie is Hooney viscosity (Ml {^ J ⁰⁰ ) is usually used as an index for molecular weight, and it has been found that the best

9843 / 1S79

Sheep, the Mooney viscosity MI falls

each polymer in the range of 20 bia 150, preferably 30 bit 1 O oj liegte Pie rubbers having higher Mooney values are typically stretched with a considerable portion _9, for example, naphthenic or aromatic oils ₈ "to enable its easier processing. The rubber compounds of the invention are mixed and vulcanized in the usual manner and no special ingredients or techniques are required the vulcanized ,, JSrfindung especially for blends for use in Keifenlaufflächen due to the improvement of the physical properties, especially the processing properties and the llaßrutsehfestigkeit _B are given in comparison with the so far obtained from commercially available tire tread rubbers cursing ~ mixtures suitable.,

The following examples illustrate the invention:

example 1

A rubber mixture (rubber λ) was made from a composite

commercially available low vinyl polybutadiene-Han ~ The product Intene 55N? - and a «polybutadiene with high vinyl content by mixing in a Banbury internal mixer accordingly prepared the following Missing batch, wherein the vulcanizing agent and antioxidant are added on a calender: (Xeile Bind always parts by weight).

• - 6 -909843/1679 ^{BAD Ommt}

Low vinyl polybutadiene 50

High vinyl polybutadiene 50

! SAP kiss (Olruß) 52

Aromatic oil ~ trade mark DUl ¹ ILEX R 12 zinc oxide 4

Stearic acid 1 ₈ 6

Cyclohexylbenzothiazyl-BUlphenamid (CBö) 1 | 0 Sulfur 1.4

4 ~ \ lsopropylamine = diphenylaroin «trade mark NONOX ΖΔ. 1.2

The polybutadiene with a low vinyl content had a Kooney viscosity Mj] V, ^of 55 and a ^ ikr iß-1.4; 40 ^. trano-1,4; ö Jt vinyl (i, 2)

Viscosity tiXii ^ _A of 55 and a microstructure of 44? & »

JDao Polybutadiene K.vö ijc-brn vinyl content beeaß a Mooney «viscosity Mi ^ ₊₄ ^{v (> n} 56 and a microstructure of: 14 S ^ cis-1" 4j 14 # trane-1,4; 72 ft vinyl (1, 2) _Q

JJie Mlßchun ^; became at 144 ° 0 up to 95 # optimal network density vulcanized as shown with Hailaoe-bhawbury-Ourometor

The IiieenBCiiai'ten of the ∆ are in the following with those of a similar smell B, which using the same procedure, using 50 parts of the low vinyl polybutadiene to replace high vinyl polybutadiene (doho a composition based only on polybutadiene with low

909843/1679 ORIGINAL BATHROOM

Viny! Content):

1915152

Property Mixed Reason A Mixture B

Behavior of the mixture on the fast no fur formation,

18 "» Friction 1x1,4) 49 0 (12O ⁰ I?) Walaen «, sen»

Vulcanization time at 144 ⁰ O (95 # optimal vulcanization) 100 # modulus, kg / cm ² (pel) 200 % modulus, kg / cm ² (poi) 300 ⁰ A fiodul, kg / cm ² (psi) tensile strength * kg / om ² (pol) elongation at break, #

Hardness-International degrees of hardness

Tear strength 20 ⁰ G kg (lba) rebound resilience 20 ° 0>

Haßrutachfestlgkeit

Heat build-up (Goodrich)

(from room temperature to 20 C. 30 min)

41 min 24

15 (212) 16 (231)

46 (660) 42 (595)

98 0392) 87 (1240)

(2143) 168 (2380)

440

61 66.5 8 _S 2 (18 _f 2) 11.7 (25.8)

50 56.0

69 42

50 _a O ⁰ C

44.0 ⁰ C

The physical tests above were performed _s where these autrifft _p ent "Bprecheiid the British Hormvoreehrift 903

The seat slip resistance was measured at 20 G using the
Road Research Laboratory-ilaßrutschfeetigkeiteprüferö (Sarbaok "Hallman and lirunot, Rubber Age ^ j} _{r <3} 4 ₈ 76-79 (1965) be"

909843/1679

BADORiGINAL

The table clearly shows that the mixture according to the invention (Mixture A) Advantages in terms of processability and wet slip resistance to polybutadiene coating with a low vinyl content (Mixture B).

Example 2

Using the procedure of Example 1 was a mixture of a commercial, oil extended btyrol-butadiene uopolymerisatkautschuk, trademark IfIlOL 1714p and a polybutadiene with a high vinyl content by mixing in a Banbury Iniienmischer according to the following Mischungsan · »record prepared (parts are by weight _e Parts);

oil-extended btyrene-butadiene rubber with

low vinyl 60

High vinyl polybutadiene 40

IÖAP soot (oil soot) 52

Aromatic oil (J) UTIiEX R) 12

Zinc oxide 4

Stearic acid - 1.6

CBS 1.0

Sulfur 1.4

Antioxidant (NONOX Zk) 1,2

The oil-extended tyrene-butadiene rubber contained 50 parts of aromatic oil for every 100 parts of rubber. It had a styrene / butadiene weight ratio of 24/76 and the butadiene content had the Kicro structure: 20 % cis-1.4; 65 J & trans-1.4 »

909843/1679

1915152

15 # 1 _# 2. Mooney viscosity, MLj + 4 was 40.

The high vinyl polybutadiene was the same material used in Example 1 _{and the like}

J) Ie blends were vulcanized at 144 Q to 95 / Siger optimal crosslink density, as shown previously on the Wallacs-Uhawbury Ourometer

The properties of this mixture determined as in Example 1 (hiech '' G) are compared with those of a similar extinguishing (mixture D) prepared using the same procedure, a polybutadiene with a low vinyl content (UrElSNiS 55Ny) being the polybutadiene with a high vinyl content replaced, compared in the following table;

characteristic Behavior on the courtship

Vulcanization time at 144 C. (95? *. Optimum)

100 yi module kg / cm ² (psi) 200 w module kg / a x ² (psi) 300% fcodul, kg / cm ² (psi) Zerrei ^ feetigkeit, kg / cm ² (psi) Elongation at break 'Ji hardness, Into rubber hardness degrees

Miechum; C mixture 33

Formation of formation of very smooth, smooth fur on the pellet the roller ο roller (slight bag formation),

42.5 * 27.5 ¹

15.2 (216) 14.4 (205)

53 (750) 44 (622)

99 (1400) 96 (1360)

(2350) 246 (3490)

500

60.5 65.0

-

909843/1679

19IbI32

λλ

M is c hung Q mix. I) Relief capacity kg (lbs) 11.3 (2 ^c j _g i) 12 ₈ 8 (28.2)

Rebound resilience * 20% $ 39 ,8th ⁰ C 49 ₈ 8th Wet slip resistance 68 »Ο 53, O Heat dew (Goodrich) 40 p8 47, 3 ⁰ C

Example!

1 OO ^ G Bin polybutadiene with a Mooney ^ viscosity ML ₁ " _Δ of 61 and a steric structure of 11? $ Cis-1 _g 4j 19 $> trano-1i4 and 70 ⁰ U Vir, yl (i _? 2) vmrdö under Use of an organic lithographic bluing / polyether catalog produced _Q J) ate polymer was not removed from the carbon waBoerato ff solvent: c © rintp ddi = remained as package ₀

Another polybutadiene with a Moonay quality IiL. of 50 and an ateriochen iütrulctur νοη 42 $ cis «1 _f 4? 50? & Trans- = 1 j, 4 and 8 yo Vinyl (i _f 2) was produced using a lithium alkyl catalyst. This was also not separated from the carbon fiber

The 7Λ: α ± polybutacliene pairs. it was agreed that the same ropes of each (based on solid rubber) were available and the polymer mixture was then iaoliert · (idischun ^ Ji) _n The sterile structure of this mixture was 24 ^ cis-i _t 4j 35 ί »trans-1,4; 4t $ vinyl (i _E 2) and ilire Kooney 'viscosity was

In a similar way - rare an isi-disparity of a polybutadiene old of a MpoR'3y == Viökoältiit ^ - _{ϊ +} α ^V0I i 50 and one

9098A3 / 1679

eteric structure of 13 & cis-1,4; 23 i » trans-1,4 and 64 £ vinyl (1,2) prepared with the above-described polybutadiene with a low vinyl content (mixture F). The steric structure of this mixture was 26 i »cie 1.4; 37 % trana-1.4; 37 % vinyl (1,2) and its Mooney viscosity was 44 "

These mixtures were mixed separately according to the following formula (in parts by weight):

Polymer 1 00
ISAF-Rufl (oil soot) '50

Aromatic oil (DUXRKX R) 10

Antioxidant (HONOX ZA) 1,2

Zinc oxide 4

Stearic acid. 1.5

C.BoS _c '1.0

Diphenylguanidine (DoPoOo) O ₉ 4

Sulfur 2.0

Using the same niche working method and approach three control blends were made using the low vinyl poly butadiene (blend 0), the polybutadiene with 70 '; » Vinyl (blend U) and polybutadiene with 64 Vinyl (Mixture 1) alone also made

These five mixtures would be up to 95 times more optimal at 144 ° C Network density, as with the Wallace-Showbury Curometer was shown vulcanized, and the physical properties of each mixture determined as previously. “The results are in listed in the table

12th

909843/1679

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Ψ » O <P »«
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I. τ > ^ «» 4I α T ^^ CO • Η KN U.N. (D
H Ct "a 0} Sp- CO β P "
pa 8th ν5 OO T (Ρ · CM Φ St. if a
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• Η S. • Η

909843/1679

Example 4

Four liaison lines J ₉ K, I »and M were made according to the following approaches:

Styrene ^ butaäien copolymer with

low Viny! content. 37t5 pro

100 hooharoaatiachea 01 (XHTQL 1712)

containing 68.75 68.75 68.75 68.75

Low vinyl polybutadiene " salary (IHSBRB 45H?)

High vinyl polybutadiene - 50 Polybutadlene mixture χ = 62.5 ~ Polybutadiene mixture Y

fiuß, V285

Aroaatieches oil (BUTRüX. R)

Zinc oxide

Stearic acid Antioxidant (HOSQX ZA)

CB ₉ S ₉

sulfur

Average vinyl coat

The polybutadiene compound X had a Hooney viscosity of 73 and a vinyl content of 41%. It was made by mixing two polymer components (by weight of solid rubber) according to Example 3 and adding 25 liters of oil (DUTRKX H) per 100 ropes obtained before the mixture was worked up. The two pastes were (1) a polybutadiene with a Hooney viscosity ^{of 12} ° ^{and an} ethereal structure of 42 '/ * cia-1.4;

- 14

909843/1679

- 5 - , 5 - »5 50 75 25th 75 , 25 75 75 40 40 23 36 5 5 5 , 5 5 • 5 5 2 2 2 »4 2 1" 1 1 1.5 1" 1 1 1.25 2 2 2 2 11 42 27 27

50 £ trana-1,4 and 8 # vinyl (1,2) and (2) a polybutadiene with a Mooney viscosity MLj ^ J of 69 with a steric structure of 11 % cis-1,4i 19 t trans-1, 4 and 70 # VinyX- (1,2) ο Before use, the oil content was increased to 57.5 per 100 by adding more oil (DOIREX R) to the internal mixer

You Polybutadienmischung Y had a Mooney ViBkosität of 75 and a vinyl content of 41 she was in a similar manner · aue the two above-mentioned polymer? Get asten "and · before working up the mixture wurde'2,5 parts PoIyisobutylen-Wclchmacher ( HYVIü) added per 100 ropes «. Before use, the oil content was increased to 27.5 parts per 100 by adding oil (DITIRSX H) to the internal mixer

Bieee mixes J through M were segmented into test tires built in, which were driven 6 "400 km (4000 miles)" The physical properties of every rubber compound are required with the abrasion index are shown in the table «.

- 15 ~

9098A3 / 1679 BAD ORIGINAL

co

co

co

cn - »α

OD

J K L. M. Mixture viscosity MI ₄ at 100 ° 0 42 ₉ 5 42 57 78 Hooney vulcanieation at 145 ⁰ C Die to 5 "sparked impulse min t2 ^u 0 ^w 12 ⁹ 32 » 10 ^a i5 ^w 8 ^e 55 " VulkaniaatioB - min at 145 ° C 30th 30th .30 30th 300 i * module kg / cm ² (lba / in ² ) 94 _e 6 95 _e 3 98.7 98.8 (1345) (1355) (1404) (1406) Tensile strength kg / en ² (lbe / in ² ) 191 177 179 172 (2718) (2520) (2542) (2448} Elongation at break %
1 bat ' 550 530 520 480. Tear strength Tusf 2Q ⁰ G kg (Ibβ) 15A 12.6 *. ' (34.5) ί33.3) (31.7) (27.9) Tear strength at 100 ⁰ G kg (lbe)
. · ■ ' '(». * (IW) into Kauteciiuk degrees of hardness 60 61 60 63 Kick impact elasticity at 20 ° 0 - ^ 42.6 38.6 39.5 37 »3 Rebound resilience at 50 ⁰ G - * 46.4 41 _ff 7 50.4 5Ö _b 1 Rebound elasticity at 7O ⁰ C ~ f> 48 »2 44 ₉ 9 53 _B 2 52.6 Naßrutschfestigceit ⁺ 6658 72 »5 68.5 73, i Goodrißh-Wänneötau ⁰ C 49p5 50p 5 43 45, Sperberg-Yeraciaissus pain 109 ₉ 7 103 ₉ 6 99.1 tOÖ ₅ 9 Haeh 7 days aging at 70 ° C: ₂ V Tensile strength kg / cm ² (lbf / in) 177
(2523) 174
(2467) 168
(2392) 158,.
(2250) Elongation at break % 380 410 380 340 '^; (

CD _i.

* At 2O ⁰ C using the apparatus described in Example 1

Rubber Age <&, Mr. 4 »582-3 (1964)

17 -

909843/1679

Claims (1)

1. Rubber mixture, characterized in that this ▼ on 5 to 95 wt. «Ropes of at least one chewing diene polymer * old less than £ 30 side label unsaturation, intimately Termiacht ait (B) 95 to 5 parts by weight at least one other chewing gauze-like diene polymers with more than 30 J * Contains side chain unsaturation 2 · Lautachukaiechung according to claim I ₁ characterized in that it contains at least 15 parts by weight of polymer (A) and up to 85 parts by weight of polymer (B) · 3e rubber mixture according to claim 1 or 2, characterized in that the polymer (A) is or contains a rubber-like polymer of butadiene » 4o rubber mixture according to one of the preceding claims, characterized in that the polymer (A) has a Mixture of clay polybutadiene with natural rubber or styrene-butadiene rubber 1st 5 · Rubber mixture according to one of Claims 1 to 3 » characterized in that the polymer (A) is natural rubber »polyisoprene, polypiperylene or polydimethylbutadiene or this contains. 6o rubber mixture according to one of the preceding claims, characterized in that the polymer (B) is a Is or contains a polymer of butadiene " - 18 - 909843/1679 7o rubber mixture according to one of the preceding claims, characterized in that the polymer (B) is polyisoprene, polypiperyltn or Folydlmethyrbutadiene or these contains « 8. Rubber mixture according to Claim 1 or 2, characterized in that components (A) and (B) are homopolymers of butadiene sindo 9o rubber mixture according to one of the preceding claims, characterized in that the polymer (A) has less than 20 ¹ A side chain unsaturation ο 10ο rubber mixture according to claim 9 »characterized in that the polymer (A) has less than 12 S» side chain unsaturation. 11 β rubber mixture according to claim 10, characterized in that the polymer (A) is a polymer of butadiene and a butadiene content with a microstructure of 30 - 45% ciB-1,4 and 50 to 65 £ trans-1,4 possesses 12 ₀ Rubber mixture according to one of the preceding claims, characterized in that the polymer (B) has at least 35 % side chain unsaturation * 13ο rubber mixture according to one of the preceding-Bpriiche, characterized in that the polymer (B) up to 80 i "side-chain unsaturation besitzto - 19 ~ 909843/1679 14o rubber mixture according to one of the preceding claims, characterized in that the average öeitenketten-Üngeeättigtkeit 25 * amounts to 75. 15 · Rubber mixture according to claim 14 »characterized in that the average side chain unsaturation is 40 to 60 % . 16. Vulcanized tire tread made from a rubber mixture according to one of the preceding claims ₀ 909843/1679