DE1520986A1 - New hardenable urethane elastomers - Google Patents

Description

The present invention relates to new curable urethane elastomers, which, when hardened, have strength properties who have known the pestilence peculiarities so far cured urethane elastomers are substantially superior. In particular, the present invention relates Ethylene-propylene-adipate-polyurethane, which with allyl ether-glycols are extended in the chain. The novel elastomers of the present invention are in use hardenable by sulfur or peroxide hardening substances to to create not only filled, but also unfilled types of rubber, which have unexpected strength properties,

909Ö2S / 1540,

• - 2 - *

BATH ORIGINAL

The advantages that sulfur curable elastomers have are known as such. So far, however, such a polymer curable with sulfur required the introduction of Fillers and reinforcing agents before curing to give the cured elastomer good strength properties to provide. However, there are applications where an unfilled cured elastomer is used which is used by the polyurethanes produced desired properties, such as resistance to abrasion permanent deformation and good tear resistance, prove themselves could if the unfilled elastomer had strength properties that match the strength properties of the previously known unfilled polyurethane elastomers would be significantly superior. These uses include medical and chemical rubber diaphragms Use where, in addition to high strength properties, greater flexibility of the unfilled elastomer is desirable and clear tubes where the Fillers in the elastomer would make fluid flow difficult to visually observe, and those others Article where good mechanical properties, addlion to the better flexibility and transparency, like

they are offered by a non-filled, hardened polyurethane
Elastomer, 'are required.

It is an object of the invention that it creates new polyurethane elastomers that have exceptional strength.

909825/1540

BATH ORIGINAL

have ability properties and a new method for Manufacture of the designated elastomers.

It is a further object of this invention that it creates polyurethanes that have life chains

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aliphatic «-G = O groups and which therefore can be hardened with sulfur or peroxide.

Another object of this invention is that it provides cured elastomers which are filled or unfilled Have strength properties that match the properties previously known sulfur-cured polyurethanes are superior and which ones are used, for example, for diaphragms , Tubes, hoses, etc. can be used.

These and other objects of the present invention are obtained with new polymeric polyurethanes, which essentially consist of the recurring structural unit

... ο ο ο ο

Il It Il Il

- (HN-RMCOR ¹ -Oa) _a -NH-R-NH fO-OR »-0-0-HN-R-NH) ₁ , -wherein -O-R'-O- is a divalent radical consisting of the removal of the terminal hydrogen atoms from a polymeric glycol which has an average molecular weight of at least 2000 and not more than 5000 and which is selected from the group consisting of mixed polyester alkylene glycols of ethylene adipate and

; β Öd β 2 6 / 1SAO _ ₄ "

«4 - '

Propylene adipate ester units are made up of molecular units Main chain recur randomly and in proportions from $ 50 "to $ 95 ethylene adipate to $ 50 to $ 5 Propylene adipate are present and where E is a divalent is an organic radical that is opposite to isocyanate groups is inert and wherein O-R "-0 is a divalent organic radical resulting from the removal of the terminal hydrogen atoms of a non-polymeric glycol derived from is selected from the class consisting of allyl glycols

ι. ι ■ ■

is containing at least one -C = C group, and wherein at least one -C == ö group of the terminal oxygen atoms of the residue by not less than one and no more than 5 atoms is separated and wherein a whole egg ^T ne Number greater than 0 and b is an integer that includes Ό and each of the structural units indicated is linked to the next by a radical selected from the group consisting of -COR ¹ -0-0-

H ti

-ο-O-R '' - O-G-

.11 Il

0 0 residues

is "wherein -OR" -0- and ^ OR "- ©" have the same meaning as described above and wherein at least 80jS dsa Gesamtgewiohts the polymer * .O- "R *" - 0> radicals are and where _they like - oR "-O-residue creates such a satiety that the AHyI-CO = C -) - group at least once approximately in all

90982E / 1ß4Ö "5 -

BATH

7000 molecular weight units of the designated polymer • Polyurethane occurs.

To get the unfilled cured elastomer with good phy-. Sicilian properties, especially with high strength, to create a required balance between the crystalline ones and non-crystalline properties by use of a misoh polyester, which is used as the reaction product of ethylene glycol and propylene glycol with adipic acid is formed «Qbgleioh Molargemisohe of 1ϊ1 up to 9 »50t0.5 ethylene to propylene glycols to get the required To obtain polyester glycols, the preferred range is 7 * 5: 2.5 to 9.0: 1.0 and of these, the most preferred ratio is 8: 2. the Polyester glycols are made through a simple co-esterification the desired molar ratio mixture of ethylene glycol and propylene glycol with enough adipic acid made to create a random misoh polyester of the desired number molecular weight with hydroxy terminated sites. .

The frequency of recurrence of the allyl (- C = C -) groups In the new uncured polyurethanes of the present invention, the molecular weight makes them polymeric Misoh-Polyesterr regulated which ones are used to make this to form new uncured polyurethanes. The ethylene propylene adipate polyester, as far as they are used in the scope of the present invention, have a different

.-β-09826 / ma

- 6 - BATH ORIGINAL

■ - 6 -. ■

Similarly narrow the average molecular weight range from 2000 "to 5000. The preferred average molecular weight for the misoh polyester is approximately 3500. With these misoh polyester materials, which is at least $ 80 of the total weight of the structure of the

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Form polyurethane, AlIyI-C-C = C -) - hardening points, of the non-polymeric allyl glycol constituents of the structure supported, created by at least once for approximately every 7,000 molecular weight units.

In general, 'non-polymeric allyl glycols, wel- • ι ι

one contain at least one -G »ö ~ group and the general formula

Σ Χ

W-C-OH W-O-OH

Y-O-OH or, Y

Z T-Ö-OH

• ι.

have to be used. " by hardenable ones, extended in the chain To form polymers of the present invention. In this general structure, T, W, I, and Z can be the same or be different and are selected from the group those of H, a saturated organic best and a organisohen radical consists, which at least one -G = C group contains, where one of the -0 = C groups of each of the Hydroa ^ l groups of the indicated general structure separated by at least 2 and not more than 5 atoms

909826 / 16-40 '' - ⁷ "

8AD ORIGINAL

and T. is selected from the group consisting of saturated organic radicals and an organic radical being

Il

which contains at least one ~ C = C group, one of the designated -G = G groups, if present in T, of each of the designated general hydroxyl groups Structure by at least 1 and not more than 5 atoms is separated. Preferred non-polymeric allyl glycols used in the present invention

I - I.

are those which contain a = C-G group, and those wherein the hydroxyl groups of the designated general structure by 2 to ^4: separated carbon atoms. The most preferred allyl glycols in this regard are grlycerol allyl ethers,

0H _o -GH-GH _o -0-C5H _o -GH = CH _Q

OH OH
OJrimethylolpropane monoallyl ether and 2-butene-1 _f 4-diol

GH ₀ OH. ■■ "■ · ■

I ^ά

OH ^ -Ch ₀ -G-GH ₀ -O-GH ₀ -GH = CH _{0 π} «« π-γττ-πττ GH ₂ OH OH OH

When used in the present invention, the non-polymeric allyl glycols can be used either alone or in conjunction with other non-polymeric allyl glycols. Water can also be used together with the non-polymeric allyl glycol, also as a diluent for the

Allyl glycol with a less expensive chain expander

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terning agents, in which case -the urea bonds can also be formed in the recurring structural units.

The curable polyurethane of the present invention can can usually be prepared by three general methods.

According to the first general process, hereinafter referred to as process A, a polymeric propylene / ethylene adipate polyester glycol of approximately 2000 to 5000 weight percentages is reacted with a molar excess of organic diisocyanate materials in a chain enlargement reaction stage . The diisocyanate excess used in this stage must be sufficient to produce adduct of the type of prepolymer containing isocyanate end groups. The prepolymer adduct is then reacted in a second stage with a suitable non-polymeric allyl glycol in a 1 part or equivalent molar ratio of isoyanate eu active hydrogen - (- ϊΤσο / ΟΗ) to form a polyurethane polymer with theoretically infinite molecular weight to manufacture. The two-stage process of process A proceeds as follows: Stage Ϊ OS (polyester) -OH 4 O = ³ OeETeR = NOO (excess) -— ^

0 * 0

11 Il

0ΑΟ »ϊΓ-Ε-ΪΙΗ-σ-0- (polyester) -O-O-HS-R-ΙίχΌ-Ο

- 9 *

009926/1640

Il

Stage II.

T •

W t

0-

O »

Il

Wp-OH YS-OH

W t

T t

-H

η β the ore ti shall be infinite

Moht-polymeric allyl glycols _t wi · ο "ben the structure fQ ^ OH ^{ηειϋβη",} instead AUOH dtr,

T-O-OE

in the explanation of the reactions use ton, nioint ~ polymeren, Allyl-glycol «in the procedure shown above JL be used"

Haoh the second general incident, continue here Terfahren B fceseiöhnet, which is used to di · replace curable polyurethanes of the present invention, If the non-polymeric allyl glycol is used first a molar excess of organic diisooyanate converted, around an ioyanate terminus Allyl glycol adduct. Equivalent quantities'.-Of Isooyanate-terminated adducts are then used with equivalent Quantities (111 ratio of -HOO / OH) of polymeric

0OS82S / 1S4Ö

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BATH ORIGINAL

Misoh polyester glycol converted to a polyurethane polymer of theoretically infinite molecular weight. The two-step reaction sequence of Method B runs as follows al) i

Level I (excess) χ

Y-G-OH

Il

Tier IX

• fcQmQm

* ti

Z

Il

Z 0

BO (polyester) -OH

zi ο

t ι - ii

ii

H 'O ~ Q-0 »* G - <» O- * H ¥ -R »SH»> 0 »» 0 ~ (Poly t, si ti Il

Tl

theoretizeJx

ο -

xz

ti

ti

WV

■ H

structure

Allyl-glylEoIe, which have the one described above, can andh instead of the

w-C-OH

'. τ. ■

V-O-OH Z

non-polymereii Jp.lyl-glyl: ole used «ground that.in the Explanation of the reactions of Method B used above were shown ·.

90982S71S4 @

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ßAO ORIGINAL

Haoh the third general procedure, here continue all ■ Method G "denotes which is used to obtain the Making curable polyurethanes of the present invention becomes a "one-pull" approach like this is already known, used · the appropriate reactants to implement. In this process the organic diisocyanate, polymeric gopolyester glycol and the non-polymeric allyl glycol all together at the same time Time mixed to the polymer Misöh-Polyester-Glykol and the non-polymeric allyl glycol at the same time to react together with the organic diisocyanate. In this method G, a reaction ratio of 1: 1. Equivalents of isocyanate to active hydrogen - (- NGO / OH) required to be a polymeric molecule by theoretically as well to produce infinite molecular weight. Using this "one pull" technique it is also possible to use a curable one To produce polymeric material which sustains allyl cure at least once for approximately every 7,000 units Molecular weight contains what appears necessary to create the required hardening strength and the desired good physical properties for the unfilled, to impart cured elastomer.

In general, it may be possible to turn to the unfilled, hardened polyurethane has good strength properties to obtain many organic diisocyanates, aromatic as well as aliphatic, either alone or together with

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BAD ORlG ¹ HAL

use another zti. However, are around the described molecular backbone and the maximum separation required for polyurethanes of the present invention Hardening steels, the preferred diisocyanates Aryl, in particular either a Ciemisoh of the 2,4 "and 2 »6 ~ 18ome» fcea * en of (do ^ ylene diisocyanate or ρ, p * -Bipn · - nylene methane diisocyanate. .

The raw polyurethane materials of the present invention can, using either peroxide or sulfur-generating hardeners. If the hardening of the raw elastomers with sulfur or Sulfur-absorbing materials are made to be approximate 1i3 ropes of Sonwef el used per 100 ropes of raw Kauteohuk « When curing raw elastomers with peroxide curing agents takes place, approximately 1: 6 and preferably 1: 3 file peroxide per 100 ropes of raw rubber are used. Activators can also be used together with the hardening agents be used·

The preparation of the roken Eautsolmk-Polyaretliane of the present invention requires a Umwaadlungsoyklus of about 24 hours at about 1ü5Ö ^ö G, or about 40 hours at about ⁰ C 1OQ without Yerwendung of catalysts. A catalyst can also be used where desired to accelerate the conversion cycle. Catalysts, which can be used for this purpose, should be

BATH ORIGINAL

tiary iüßine einj Eetraiae-fcliylMtaii-diamine? Metall-Aoetylaoetoaat ", like MagnesitM ^ beryllium-., Zinc", Lead-, Siean-lIX- "" 2horium- and Cadffiium-aorfcyl-aoetonatej Ootoate, like tin-, lead- and rare earth-octoate j Ieopropyl- titanium-stearatj Di "butyl tin oxide 'and Oirconium-organisohe complexes (Zirco drying catalysts). under Yerwendung of catalysts such as these, it is possible to" to verfcüraen ömwandliangscyklus to about β hours "at 130 ⁰ C, without affecting the properties of the cured rubber .. The catalysts are used to stimulate the isocyanate / hydroxyl reaction

The following examples serve only to explain the present invention and aoll to the scope of the invention in no way incarcerated.

example 1

297t6 δ (4.8 moles) of itylea-glyfcoi. And 91.2 g (1.2 moles) of propylene-glycol were built into tin glass tea cups, that with a RStewerk,! Ehermometer, Stiekstoffeinlassrolsr,

Capacitor ^, *

DajnpfmaateLT 'cold water condenser for the Hiiek river, des water produced during the Eeafction, and a still to remove the water generated during the reaction. Star »To the reaction system, then 800 g (5.5 moles) of adipic acid were added to be insufficient Acid groups create ssu and so sio produce that the

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BATH ORIGINAL

»14 -

see eviegen & exL Mieäh ^ Polyeeter-fflölekQle Hy & roxy-terminal were. Bi © in advance of the molar concentrations were calculated, mn. a Mison- "Polyes-over-Glyl £ ol to give a hydroxyl value of 1 _f $ 13 and, therefore, a theoretical molecular weight of the 3000th

This Gemisoh was heated to 160 ⁰ G and naohdem esterification with Stickstof ^ cleaning and fortsohritt stirring, which was aua the Teresterungareaktion originating water under Rüofcfluss maintained until the temperature of Reaktionssyatems to above. Fell 2 hours at 130 ⁰ G and then the water was removed by distillation from the Eaaktionsgefäss away "Uaohdem the water from the system was removed, was allowed to rise to most of the theoretical amount of water from the Yeresterungsreaktion the reaction temperature to 200 0, about 97 $ from was. Heating was then continued until an acid number of approximately less than 3 was obtained. The reaction was then carried out by cooling the oil. stopped at room temperature. The Misoh polyester glycol produced in this way had an average molecular weight number of approx. 2900, as was determined by end group analysis

Example 2
Stage β X of procedure A »

361.13 g (0.25 equivalent weight) of the misoh polyester glycol, produced as in Example 1, was in a glass re-

90982S / 1S4Ö

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action vascular introduced, aas, Besohiokungstriohter and that was open to the atmosphere through a Iroeknungsröhrohen with a .Rührwerk "Ihermo- ■ meter Xaltwasser-Räckflusskondensator, equipped · The G-efässtemperatur (lernperatur of the reaction system) was allowed to rise to 50 ⁰ O and 47, Qg (0.54 equivant-Sewioh1 # e) of a 4s 1 isomeric Gemisohs of 2 _i 4- / 2 »6-g; o! ^ Rlen-diisoayanaten- was added at an interval of 10 minutes. The reaction was under a nitrogen atmosphere to.ei 3O ⁰ G continued for 4 hours, The Isοcyanat-terminal product had oa "yf> weight / Sew. reactive isocyanate, determined by analysis.

Example g
'Stage II iron procedure A.

702 i Example g 2 hergesljellten adducts were introduced in a glass-Beaktionsgefäss that werkt with a Ruhr "! Ehermometer, MIltrichter equipped by a Srookenröhrohen the atmosphere was open, the £ emperature of the reaction system was heated to 80 ⁰ O and 33 g (of 25 mol) & lycerin-alfa-allyl-ether (dX &) were brewed into the reaction vessel over a period of 10 minutes with vigorous stirring. Meowing was continued for 15 minutes to ensure homogeneity. The 2emperatur of Eeaktionesysteme was maintained at 80 ⁰ O for 4 hours and at the end of this period, the Seftktionsprodukt was 40 hours EIA "a tOO ° O-furnace eingebraöht.

80ößas / is4§ - ig-

BATH

SIn solid, slightly bernsteingefärIster Polyiirethan-Rohkaut- "sehuk was thereby obtained which allows an easy grindability at roll temperatures of 15O ⁰ F showed. Using a feieinen spindle 10 minutes at 212 ⁰ I * he showed a Mooney viscosity of 42. The aging at ambient temperatures (about 75 ⁰ P) afforded slight increase in Shore A hardness values from an initial value of 35 "to 2:39 Weeks and to a final value of. 45 after 16 weeks,

Example 4

The raw material prepared in Example 5 was taken from Use the following sulfur hardening formula vulcanized ί ■

Component parts by weight

Raw polyurethane 100

Sulfur 0 * 75

MBIS. .. 3.00

MBf "'■.. 1.00

RCD 2098 0.55 ^; ; '

Oadmum stearate 0.50

MBiES is a trade name f-ttr Benzothia ^ yl disulfide, ΜΒΐ is a trade name for 2-meroaptobenzothiazole and RGD 2098 is a trade name for a Zinfcciiloride-MBTS-Eomplex. These connections are called A ^ tovators used in this example * The hardening was

"- -if-

BATH ORIGINAL

de effected at 30O ⁰ I ¹ in 30 minutes.3The vulcanized rubber produced in this way exhibited the following physical properties:

Modulus $ 100 (approx. 75 ⁰ I ¹ ), psi 90

200 $ 120

300 $ 213

400 $ 303

$ 500. 800

600 $ 2440 extreme extension (until break), $ 680

Outside tensile strength (to break), psi 4355 Hardness (Shore A Härtemeseer Grade) 45

Example 5

A second approach of raw chews was made, as in example 3 and also showed easy process application to a Kautsohuk mill at 150 F. When cured by the procedure described in Example 4 above, this material had the following physical properties Properties: .

Modulus, $ 100 approx 75 ⁰ I ¹ , psi 87

$ 200 173

$ 300 ■ 230

400 $ 370

500 $ 993

600 $ 3040

extreme extensibility (Me break), $ 646 Ultimate Tensile Strength ("), psi 4440 Hardness (Shore A hardness meter grade) '45

- 18 -

ßAD

le

• Example 6

A third approach from miseh polyester polyurethane raw rubber was prepared as described in Example 3 above and using at 287 ° F for 45 minutes hardened of the following mixture:

component

raw mixed polyester-polyurethane sulfur

MBTS

RCD 2098

Parts by weight 7th 100 1 25th 4th 2 O, 1 Q ₉

Stearic acid (lubricant)

The following properties were obtained:

Crack Strength lb / linear in 141

Abrasion resistance. 4.6

(Taber Abreiber, 2000 revolutions H - 18 disc, 500 g load) Modulus at low temperature

^G 10 000 -17 ⁰ P

Bayehore rebound 28

When testing the abrasion resistance, the lower one shows Appreciate the better resilience. Of course, smoked eau-de-sac skins, such as those used for tire treads used under the same conditions those used above were tested and had • an abrasion resistance value of 50. -

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■ - ^{ri ;} Ui0986

Example 7 ■

The sulfur-curable, crude mixed polyester-polyureiihane which are produced by the process according to the invention can, as already stated above, also be cured by a peroxide curing process. The so-sucked rubbers show no reversal at high temperatures, which is characteristic of sulfur-cured elastomers. are superior to those shown by & n peroxide-cured _r previously known, unfilled polyether-polyurethanes expanded in the allyl chain.

In order to explain the new properties ^v of the peroxide-cured polyester polyurethanes of the present invention, a crude polyester-polyurethane was prepared as follows: 707 ^ 1 g of mixed polyester-isocyanate terminated adduct (0.5 Iq.uivälentsgewicht) was prepared as described in Example 2 above ^ and then in this order according to the procedure described in Example 3 above with an aemisoh of 26.1 g (0.3 Aq ₁ UiVaIentgewicht) monoallylates of trimethylol propate (MAE) and 11.0 g (0.25 Å ^r equivalent weight) of 2-butene-1 * 4-aiol (B = D) implemented. This made bin solid, slightly amber-colored Köhsiiraff.

BATH ORIGINAL

This raw mixed polyester polyurethane was then made with compared to a raw polyether-polyurethane that is commercially available and known as Adiprene C. is after the two raw materials using the following unfilled peroxide hardening mixture have been hardened:

Part of G-emisoh

1 2 3 Misoh polyester polyurethane raw material 100 100 '100' Polyether-polyurethane raw material *

Di-Cup -40C ^ 1 2. 4 2.5

wherein (1) the ingredients are present in parts by weight per hundred raw rubber and (2) Di-Cup -40 0 is a trade name for a mixture of dioumyl peroxide, supported by calcium carbonate, which is 40% active. The curing was effected in 15 minutes at 300 ^° F for the mixed polyester preparations and in 30 minutes at 307 ^° I ¹ for the polyether preparation. The resulting rubbers exhibited the following properties:

Self-preparation

1 2 '3 4 looser extensibility, $ 573 376 230 210

Ultimate tensile strength psi 1077 2013 1107 331

Modulus $ 100 approx. 75 ⁰ F, psi 33 150 250 190

$ 200 70 286 530 295

300 $ 80 563 - -

400 $ 160 - -

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■: · ■ "■ BAD ORIGINAL

Example 8

In Part A of this example, a useful monomeric Allyl glycol isooyanate adduct formed using an approximately 400% excess of diiaooyanate to produce a low viscosity solution of monomeric adduct in excess diisooyanate. To the raw material To prepare as described in Part B of this example, the adduct and the excess diisooyanate were put together with the mixed polyester glycol of Example 1, reacted to form an isocyanate-terminated prepolymer which contained some allyl glycol in the main molecular chain. This prepolymer was then used in Part 0 of this example in a 1: 1 ratio of isocyanate to active Hydrogen reacted with more allyl glycol to form the crude elastomer. This raw elastomer generally had a greater density of the corresponding allyl groups than that of the elastomer prepared in Example 3, im The procedure of Part B of this example was used, with each mixed polyester-glycol molecule being most commonly performed the excess diisocyanate was replaced and only occasionally by the allyl glycol isocyanate adduct.

In the procedure used in Part C of this example ^ wuufedas isocyanate-occupied or loaded Misohpolyesteroo glycol is then reacted with more allyl glycol to get on top of this

^OT way to replace the occasional allyl glycol isoöi cyanate adduct-occupied mixed polyether glycol molecules ο two allyl glycol molecules connected to one another and only separated by a diisooyanate molecular unit.

INSPECTED

-.22 -

Part Ai .

1524 g (17.5 g equivalent weight) of a 4: 1 Gemisohs of 214- and 2,6-tolylene-diisooyanate isomers was placed in a resin reaction vessel with a funnel ^ stirrer, thermometer and a reflux condenser, the Atmosphere was opened through a trooken tube. 231 g (3.5 equivalent weight) of glyoerin-alfa-allyl ether were then added to the isocyanate mixture over a period of 5 minutes while stirring and charging with dry nitrogen gas, during which time the temperature of the plant rose from 35 to 42 ⁰ C rise. Within 10 minutes after the addition of glycerol-alfa-allyl ether was Reaktionsgemisoh exotherm to 7Q ⁰ O. This temperature was 1 hour maintained with the aid of externally supplied heat and at the end of this time, the mixture was cooled to room temperature, ca 23 ⁰ O, brewed. The reaction product, a thin yellow liquid, was analyzed to have an active -NCO w / w content of $ 32.9.

Part bi

314.3 g (2.46 equivalent weight of active -NOO, based on 32.9 $ -NGO w / w) of the reaction product from Part A were placed in a resin reaction vessel equipped as in Part A..1242 g a 4: 1 ^{ÄthyleniPro-:} pylene adipate mixing polyester prepared as in example 1,

90 9825 / 15Λ0 - 23 -

which had a molecular weight of approximately 2484 was then added to the resin reaction vessel over a period of 15 minutes. The resulting mixture was ^{heated to 8O 0} O and left for 4 hours. A yellow viscous liquid which had a viscosity of 1560 poises (at 80 ⁰ F) and a -ETCO content of 3.15 $ wt / wt., Was prepared by.,

Jell G:

776 g of the product from Part B, which was determined by analysis immediately before the intended use reactive -NCO content of $ 2.7 weight / Wt. Was placed in a reaction vessel, which, with a stirrer and a filling funnel, to the atmosphere opened by a drying tube, equipped was. The contents of the kettle were then heated to 120.degree

and 33 g of glycerol alfa allyl ether were then added all at once to the vessel. The mass was then continuously stirred and heated for 15 minutes. The resulting product was eingebrächt for 24 hours in an oven at 120 ⁰ O.

Part D;

The product from Part 0 was a light amber colored raw solid elastomer with a Mooney viscosity of 32. It was light on a rubber mill with rolling temperatures

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of 200 F and had an initial hardness of 35 Shore A grades.

This raw material was prepared using the preparation and procedure as described in Example 3 above cured and produced an elastomer with the following propertiesj

Ultimate tensile strength, psi 2475

Extreme stretch ability, $ 6-1-0

Modulus, $ 100 87

$ 200

300 $ 183

400 $ 283

500 $ 617

$ 600. 1825

Shore hardness A 42

Example 9

In this example, the Misohpolyester isocyanate-terminated adduct is in the chain extended with a mixture of two different allyl glycols in two proportions to θ £ η non-filled Rohelastomere to manufacture, which have good after Sohwefelhärtung tensile ligenschaf- showed ^xo th. .

to part A:

ü 703.5 g (0.5 g equivalent weight) of a misoh polyester

*** isocyanate-terminated adducts, which have a molecular

had a weight of about 3000 and which was 3 $ weight / weight reactive-liCO-groups and as in Example 2

- 25 -

Above mentioned, was produced, was placed in a covered resin vessel, which was equipped with a stirrer. The temperature of the contents of the vessel was then allowed to rise ^{to TOO 0 C.} A homogeneous mixture of 24.75 g (0.575 equivalent weight) of glycerol alfa-allyl ether and 5.5 g (0.125 equivalent weight) of 2-butene-1 _f 4-diol were then added to the heated product.

The contents of the jar were mixed to create a uniform mixture and then heated to 150 ° C and Leave it there for 24 hours

A sulfur hardening of the resulting raw material was using the preparation and method of Example 5 above. The following physical properties were obtained with the cured elastomer:

Mooney Viscosity 97

Modulus, $ 200, about 75 ⁰ I ¹ , psi 160

275

. 710

'■ ■ »· extreme tensile strength, psi 3810

extreme elasticity, fi ■ 680 hardness, Shore A. ⁴⁵

horny Bt '

705.5 g (0.5 equivalent weight) of an isocyanate-terminated copolymer prepared as in the above example 2, was 16.5 g (0.25 equivalent weight)

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Glycerine alfa allyl ether and 11.0 g (0.25 equivalent weight) 2-butene ~ 1,4-diol implemented. He knew the raw material sioh was cured as described in Part A of this example. The cured elastomer made from it has-./■te the following properties:

Mooney viscosity Example 10 20e Modulus, $ 200, approx. 75 ° ?, psi 115 .30.0Ji. 185 $ 500 450 ultimate tensile strength, psi ' 3820 extreme elasticity, fi 645 Hardness, Shore A 45

707.1 g (0.5 equivalent weight) of an isocyanate-terminated misoh polyester, prepared as in Example 2, was placed in a reaction vessel which was equipped with a stirrer and a lid. 21.7 g (0.25 equivalent weight) of monoallyl ether of trimethylol propane (MAE) was then added to the mixed polyester with stirring and the resulting exothermic reaction caused the temperature of the mixture to rise from room temperature to 85 ⁰ O. Then an additional 21, 8 g of MAE are added to the material with mixing. The rise in temperature to 85 ^e C and the addition of the two portions MAEJ carried out in a period of 10 minutes. The temperature of the reaction tube

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Systems increased gut to 11O ⁰ C. The Reaktionsmaßse was then brought efäss 6 to another and then for 40 hours leaving the transferred reaction mass at 100 0 in an oven. This produced a solid, amber-colored raw material which, when hardened with sulfur as in Example 4, had the following physical properties. '·

Mooney Yiscosity 55 Modulus, 200? £ about 75 ⁰ F, psi 110 $ 300 190 500fo 595 ultimate tensile strength, psi 4095 extreme extensibility, fo 695 Hardness, Shore A 42 Example 11

In this example an isocyanate terminated Mixed polyester in the chain with a mixture of allyl glycol and water expanded to create an unfilled sulfur cured polyurethane-polyurea, that had unexpected physical properties.

To 696.5 g (0.5 equivalent weight) of an isocyanate terminated Mixed polyester prepared as in Example 2 and having a molecular weight of about 2786 were 28.05 g glycerine alfa allyl ether (approx. 0.426 equivalent weight) and 0.675g water (approx. O0f4 equivalent weight)

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added with stirring. The temperature of this reaction mixtures rose by exotherm to 90 ⁰ C, and was taken after 15 minutes at 9O ⁰ C to 10O ⁰ C and left for 40 hours at this temperature. Sulfur curing was effected on this raw material as described in Example 4, whereby an elastomer was produced which had the following properties.

Mooney viscosity Example 12 90 Modulus ,. $ 200, about 75 ° F, psi 100 $ 300 165 $ 400 690 ultimate tensile strength, psi 3585 extreme extensibility, $ 700 Hardness, Shore A • 45

To illustrate process C described above, a homogeneous mixture of 66 g (1 equivalent weight) of glycerol alfa-allyl ether and 1415 g (1 equivalent weight) of misoh polyester glycol of ethylene propylene adipate, which has a molecular weight of 2830 and was prepared as in Example 1, placed in a 5 l resin container equipped with a stirrer. The temperature of the container contents was increased to 80 ^° C. and left there. 174.2 g of a 4: 1 isomeric mixture of 2,4-: 2,6-tolylenediisooy-

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anaten added over a period of 10 minutes.

The reaction mixture was continuously stirred for 1 hour at .80 ⁰ C and brought to this time in a container which was placed in an oven at 150 ⁰ C and left there for 24 hours. Sulfur hardening as described in Example 4 was effected on the resulting crude product. This cure produced a firm, slightly amber colored elastomer that had the following properties:

ultimate tensile strength, psi 4010

extreme extensibility, fi 710

Hardness, Shore A 44

Example 13

Another batch of cured elastomer was prepared as described in Example 12 above. This hardened Elastomer had three physical properties:

ultimate tensile strength, psi 4047

extreme extensibility, i> 683

Hardness, Shore A ^- 45

which have the properties of that produced according to Example 12

Materials are to be compared.

-χ Example 14

o Another approach of raw material was made, as in example

• ■. "■ - 30 -

described, produced, except that the temperature of the reaction mixture was ^{heated to 85 ° C. for 2 hours and then left at 130 °} C. for 24 hours in order to produce the raw material. After the raw material, as described in B _e ispiel 4 was cured, the cured elastomer had the following properties:

ultimate tensile strength, psi 4120

extreme extensibility, $> 737

Example 15

Another approach of raw materials was performed as described, prepared except that performed in this case, the reaction for 1 hour at 12O ⁰ C and then the temperature of the reaction mass was maintained at 130 C for 24 hours to prepare the raw material in Example 12 . Curing on the resulting raw material was effected as described in Example 4, resulting in an elastomer having the following properties:

ultimate tensile strength ^ psi 4752

extreme elasticity, # 720

Hardness, Shore A 80.

Example 16

In this example a 1: 1 (based on the -OH content) Mixture of mixed polyester glycol product from Example 1

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and also using glycerol alfa allyl ether a one-step reaction technology (process 0) with p, p'-diphenylene methane diisοcyanate implemented. The resulting raw material was then as described in Example 4 "at approx. 75 3? cured to give an elastomer having a Mooney viscosity from 144, the 200? s, 300? and $ 500 - igen modulus of 150, 240 and 1125 psi, an ultimate tensile strength of 3955 psi, an ultimate extensibility from $ 545 and a hardness of 47 Shore A durometer grades would have.

The process used in this example to make the raw material the result of first blending 707 g (0.5 equivalent weight) of an ethylene / propylene adipate mixed polyester which had a molecular weight of about 2830 with 33 g (0.5 equivalent weight) of an ethylene / propylene adipate mixed polyester Equivalent weighted) G-lycerin-alfaallyl-ether (GAE). 125 g (1 equivalent weighted) ρ, ρ · -diphenylene methane diisocyanate (MDI) was introduced into a 5 l resin vessel which was provided with a stirrer. The MDI was melted at about 50 ⁰ G, and the mixture of mixed polyester glycol and GAE was then added to the MDI and the temperature of the reaction mass increases with stirring to 120 ⁰ C. This temperature was left with stirring for 5 minutes. The contents of the vessel were then placed in a 130 ^° C. oven for 24 hours. A solid, amber colored elastomer raw material was obtained by this process.

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Example 17

Many elastomers require reinforcement duroh fillers in order to develop their best physical properties for curing. In the previous examples unfilled elastomers were produced which have excellent strength properties. These unfilled elastomers can be reinforced with fillers to substantially increase these properties beyond what was achievable using the prior art reinforced sulfur cured polyether-polyurethanes. The literature (Development Products Report, No. 11, November 1958, Elastomer Chemicals Department, EI du Pont de Nemours & Oo (Inc.) describes the properties obtained using
a sulfur curing process including a filler with a polyalkylene ether-polyurethane, which was called Adiprene 0.

component 1 3 , 75 preparation 2 3 100 1 , 75 100 100 rubber O , 5 30th Soot (HAFr ¹ ) - O 20th 20th Oumar W 2 1/2 * "/ O 3 3 MBTS 1 1 MBT 0.75 0.75 sulfur '0.55 0.35 ROD 2098 0.5 0.5 Cadmium stearate - 33 , 90982 5/1540

in which »iek. (1) HAI "means a furnace black with high abrasion resistance (high abrasion furnace carbon black) and (2) Cumar W 2 i / 2 is a trade name for _: a cumeron-indene resin. The properties of the cured, filled polyalkylene ether-polyurethane are the following:

characteristic

Extreme elongation in 5 extreme tensile strength, psi, hardness, Shore A
Crack Strength lbs / in

Modulus, 100 $ psi 300 $ psi 50C # psi

These properties were achieved by hardening the polyalkylene ether raw material at 287 °! ' and reached a duration of 60 minutes.

Other polyether-polyure'thane hardened with sulfur, which in U.S. Patent 2,808,891 and welehe are also reinforced with 30 parts of HAP soot, resulted in the following properties at best:

ultimate tensile strength, psi 5100

ultimate extensibility, $ 520

Modulus, $ 300, psi 1980

Hardness, Shore A 67

For comparison, the following hardening preparation was made with 909 825/1540 - 34 -

preparation CM 3 1 - 630 615 530 4200 4850 2100 50 60 58 165 256 180 140 320 130 340 1750 320 1030 3400 800

Ib / Uuöb

the polyester-polyurethane raw rubber of the present Invention, which as described in Example 3, produced was used. ■

Component parts by weight

Rubber 100 stearic acid 0.25

MBTS 4

MBT 2

Cadmium stearate 1

RCD 20 98 0.7

Russ' (HAP) ^^ 30

Various cures were effected in (A) 10 minutes, (B) 15 minutes, and (C) 30 minutes at 30O ⁰ F. The following physical properties were obtained for (I) aging without heat, (IX) aging with heat, 70 minutes at 212 ^° F, and (III) aging with heat, 70 hours at 250 Ft

characteristic

ultimate tensile strength, psi modulus, 3OO? 6

extreme elasticity? δ A 740 470

B 610 470

C 510 460

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Hardening A. Aging i II • III Time B. 5900 5900 4240 C. 5600 5300 4400 A. 5540 5450 4300 B. 1700 3420 3150 C. 2200 3540 3400 2710 3300 3300

Hard, - Shore A A. 70 75 73 B. 71 74 74 0 70 76 74 Crack resistance, Ib / linear in A. 340 B. 385 C. 350

Ί / SL SO

(1) SAF is a corresponding furnace black with low abrasion resistance. Comparing the properties of these reinforced polyester-polyurethane with the unfilled preparations, as they were produced in example 4, so one generally notices approximately 20 to 25 percent Improvement in the ultimate tensile strength with an insignificant difference in the ultimate extensibility and a 200 ^ ige improvement in the tensile strength.

Comparing the properties of the previously known Materials with the properties of the products of the present invention shows that the properties of the the latter show a substantial improvement over the properties of the preceding.

Example 18

A comparison was made according to the curing conditions of (A) 30 minutes, or (B) 60 minutes and (Q) 90 minutes at 287 ^° I "between the polyester-polyurethane raw material, which was prepared as described in Example 3, and the polyether polyurethane raw material

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Known as Adiprene O for resilience compared to abrasion with the Taber Abrader at 1000 revolutions and 2000 revolutions and when using the Disc ITr. 42 and a weight of 500 g. The following sulfur hardening formulation was used to make the to cure both polyurethanes:

component Weight parts A. 6.2 2000 rev Raw rubber
Russ (SAF) ..
Gumeron-indene resin
MBTS
MBT
sulfur
RCD 2098 100
50
15th
4th
1
0.75
0.55 A. 7.5 4.6 Hardened rubber hardness condition 1000 rev. B. 5.6 5.8 Polyester-polyurethane B. 11.6 1 5.4 Polyether-polyurethane C. 15.1 0.4 Polyester-polyurethane C. 22.5 1 8.5 Polyether-polyurethane 8.6 Polyester-polyurethane Polyether-polyurethane , Example 19

The physical properties of peroxide cured Polyester-polyurethanes according to the invention Processes were produced can be provided by reinforcing the cured polyurethane with suitable pill

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to be improved. The following peroxide preparation for hardening of a polyester-polyurethane raw chew as described in Example 3 consists of:

Component . Part by weight

Raw rubber 100

Tue Cup-40 0 3

Titanox - AMö ' ¹ ' .10

Hi SiI 233 ^ 2

wherein (1) litanox-AMO is a trade name for one finely divided litanium dioxide filler and (2) Hi SiI 233 is the trade name for a powdered hydrated silicon dioxide filler which provides curing of the raw rubber in 30 minutes at 300 F.

The elastomer produced has the following physical properties:

Extreme extensibility, $> .420

ultimate tensile strength, psi 3050

Hardness, Shore A. ⁶ 2

Modulus, 100 ^, psi. 212

■ ":. 200? Δ 475

1075

The ITCO / OH ratio required to achieve the Raw rubber in stage II of procedure A and B and in method 0 as stated above, should are as close as possible to the stoichiometric value, i.e.

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in a 1: 1 molar ratio. If NCO is used in excess, is made, a softer raw material, welohes considerably hardened. If an excess of OH is used, extremely soft materials are obtained. Under a 1: 1 molar ratio is within the requirements of the present invention a molar ratio the limits of approximately 0.95: 1 »05 NCO / OH to understand * In order to improve and / or modify the properties of the polyester-polyurethane polymers of the present invention, the polymers can be filled with different fillers, ' Dyes, Weiohmaohern, etc., which are known, are processed.

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Claims (1)

Claims J ^ / Polymers polyester-polyurethane characterized in that they consist essentially of the repeating Structural unit O O 0 0 Il. Ti H ti (HH-R-HH-GOR ^1-0 -G) -HH-R-HH- (GOR "-OG-HN-R-HH). a, D. R is a divalent organic radical inert to is ο cyanate groups is; -O-R'-O- is a divalent radical obtained from a distance the terminal water st off atoms from a polymeric glycol which has an average molecular weight of at least 2000 and not more than 5000, where da »denotes polymeric glycol a mixed polyester-alkylene-glycol which is randomly distributed ethylene adipate and propylene adipate ester units in the skeleton of the contains designated polymeric glycol, wherein the random distribution of the designated ester units is such that the designated ester units in the skeleton of the designated polymeric glycol in the ratio of approximately $ 50 to $ 95 Ethylene adipate units: 50 to 5 # propylene adipate units available; a is an integer greater than 0; 909825/1540 ~ 4 ° ~ 0-R "-0 is a divalent organic residue derived from the Removal of terminal hydrogen atoms from one non-polymeric allyl glycol, where the -C = G- ' Group in the designated allyl glycol from the terminal ones Oxygen atoms of the 0-R "-0 radical are separated by not less than one and not more than 5 atoms; b is an integer including 0; each of the designated structural units with the next linked by a residue selected from the group 0 0 0 0 the from ^ ^f ■ "and""residues be -GO-R'-0-C -COR" -0-0- stands, in which O-R'-O and 0-R ⁿ -0 have the same meaning as explained above and at least 80 $ of the total molecular weight of the polymer O-R'-O are residues with the proviso that the O-R "- 0 remainder appears in such a frequency that an allyl group occurs at least once approximately every 7000 molecular weight units of the polymeric polyester-polyurethanes mentioned. 2. Polymeric polyester-polyurethane as in claim 1 characterized in that the designated non-polymer Glycol is at least one allyl glycol which contains at least one -G == C group and is selected from the group consisting of glycols having the structures XX 1 " W-C-OH W-C-OH ¹ and '
VC-OH Y «09825 / 1S40 , _ ' ₀ _ _m -.- C ζ - 41 - where V ₁ W, X and Z can be the same or different radicals, selected from the group consisting of H, saturated organic radicals and organic radicals, Il which contain at least one -C = G- group, with little- ■ »■» '■ at least one of the designated -C = O- groups from each of the hydroxyl groups of the structures indicated is separated by at least 2 and not more than 5 atoms and Y is separated from the Group is selected which consists of saturated organic radicals and organic radicals, the at least one -G = C- group, at least one of the bezeioli- I I neten -C = C- groups in Y of each of the hydroxyl groups of the designated structure is separated by at least 1 and not more than 5 atoms. 3. Polymeric polyester-polyurethane according to claim 2, characterized in that the designated non-polymer Il Glycol contains a -C = C- group and in which the hydroxyl groups of the structures indicated are separated by 2 to 4 carbon atoms. 4. Polymeric polyester-polyurethane according to claim 5 characterized in that the designated non-polymeric glycol is glycerol-aifa-allyl-ether. 5. Polymeric polyether-polyurethane according to claim 5 characterized in that the designated non-polymeric glycol is trimethylol propane monoallyl ether. 909825/1540 - 42 - 6. Polymeric polyester-polyurethane according to claim 3, characterized in that the designated non-polymeric glycol is 2-butene-1 _f 4-diol. 7. Polymeric polyester-polyurethane according to claim 2, characterized in that the non-polymeric glycol a mixture of at least two of the designated allyl glycols is. 8. Polymeric polyester-polyurethane according to claim 2 daduroh characterized in that the designated non-polymeric glycol is a mixture of at least one of the designated Allyl glycols and water is. 9 · Polymeric polyester-polyurethane according to claim 1 characterized in that R has at least one aryl group contains. 10. Cured elastomer, obtained by treating the polymeric polyester-polyurethane, according to claim 1 with a vulcanizing agent selected from the group which consists of peroxides and sulfur-yielding materials under tulcanization conditions. 11- Process for the production of polymeric polyester-polyurethanes, characterized in that it involves the conversion of a · polymeric propylene / ethylene adipate polyester glycol with a consistency molecular weight of approximately 2G00 to 909825/1540 . ■■■■ - 43 -. 5OOQ and a non-polymeric allyl glycol with at least an organic diisocyanate, the proportions of the reactants being selected so that the allyl hardness parts at least once approximately every 7,000 units of molecular weight of the polymeric polyester / ply urethanes indicated. be created. 12. The method according to objection 11, characterized in that that the designated polyester glycol causes the reaction from. Adipic acid, .with a mixture of Athjien-glyko.l and propylene glycol is formed, the designated -Gemically a molar ratio of ethylene glycol: propylene glycol contains from 1: 1 to 9.5: 0.5. 13 * The method according to claim 12, characterized in that that the designated molar ratio of ethylene glycol: propylene glycol 7.5: 2.5 to 9.0: 1.0. 1r4, method according to claim 12, characterized in that that this. designated molar ratio of ethylene glycol: propylene ^ glycpl 8: 2 is. ^x 15. The method according to claim 11 characterized in that the designated non-polymeric glycol, at least one allyl & lyko is l, which contains at least one -G = C- group and. is selected from the group consisting of glycols that form the structures 909825/1540 - 44 - X X- f ι W-O-OH. W-O-OH * and " T-C-OH Y ι ι ζ. τ-σ-ΟΗ where V, W, X and Z have the same different radicals eein, selected from the group consisting of H, saturated organic residues and organic residues, which contain at least one -0 = 0- group, where at least one of the designated -O = G- groups of; each of the Hydroxyl groups of the structures indicated, by at least 2 and no more than 5 atoms is separated and X is off The group selected is »welohe from saturated organic Rests and organic radicals consists, which contain at least one -0 = 0- group, with at least one of the designated -G = O- G groups in T of; j6 that of the hydroxyl groups of the structure indicated is separated by at least 1 and not more than 5 atoms. 16. The method according to claim 15, characterized in that that means © allyl glycol glycerine alfa allyl ether is. . _ω 17. Verfaliren according to claim 15, characterized in that ο ■■■ -.- "" to that the designated allyl glycol trimetholpropane monoallyl • ° is ether.
cn oi · 18. The method according to claim 15, characterized in that ^ ³ that the designated ■ allyl glycol is used together with water. _ 45 _ 19. The method according to claim 11, characterized in that the organic DiiwQoyanat denied consists of little 8 least one »Iiomer γοη tolylene diisocyanate. 20. The method painted claim 11 dadnxeh gekennatlohnet that the bezelolmete Dlisooyanat ρ _t p * -Diphenylen- 21. The method according to one of the earlier mentioned sprays, characterized in that vulcanization especially using peroxide or sulfur supplying vulcanizing agent is carried out. - · ■ · ■. ■■ ■ - ■. . ; Söiiai / tiii * bad