DE1720545A1 - Process for the preparation of a hardenable polymeric composition - Google Patents

Description

The invention "relates to mastic compounds, in particular liquid and fluid masses, which are suitable as detergent masses, una a veriahren- to their production.

Distinguish between u.! - basically two kinds of mas tie es, namely one-coriipon giiti ^ e and two-component. Boron aus ■ ± -f ~ -i <: ii a> cüiiiponeriLip uüsa; ti, that the consumer does not have to mi0c.hf; n VVtXJLtLIf and last the mass if they have been encnomrnen to the iser iu-c ,. at the halt aobindet.

yirbom is the i {.onii »ii \, eiiz of the polymer on ω. 'in Ii v / i' -utiif ',, ii. 'tf, s ..iLb'ütijn in the tapriic by the i.orij tyJ.J -'- 1 "ν ^ ^Γ: α; αυίΰ-.ίΐ-'ίχΐ wira in / vvuLkomponon tunsyw üuni..

10 9 8 26/1665

-Z-

Liquid gum is important, because mixing through the Consumer is made on the spot.

The invention provides a method of manufacture liquid rubbers for mas tic.es in which functional groups are attached to ouer near oei the ends of each molecule were introduced. In this way you can always only by setting the type (degree of functionality) and concentration of the curing agents produce an almost perfectly crosslinked product, and maintain any desired spacing between crosslinks.

It's impossible to get a high quality, liquid one Rubber (i.e. having physical properties comparable to those found in high-grade rubber Molecular weight are present) from molecules that have a lower molecular weight and in which the functional groups are waiillos distributed, it is however, it is possible to use a base polymer for the production of. Mastic from iviolecules with randomly arranged functional parts Establish groups, but only with an average one Molecular weight of about 10-20,000 or higher.

Λϊχι high quality liquid rubber, both for one- and two-component Mas i; ices, muli an, each end of the molecule have functional groups.

jjie invention let L see LOi in short describe »l'oiyisobu'üylenc with terminal üarooxy groups, the aicn as mastices, liquid "Diehtun ^ sinit coi and other neatly described / wecice suitable, weraen by a .ureis buf enpro ^ ess in holier yield ana oeiektLvi did ertuilLeru

109826/1 ß65

BAD OBiGINAL

(a) selective splitting of the double bond in butyl rubber with a type II double bond, in particular in butyl rubber, where piperylene or butadiene are the monomers that make up the double bond supply, through ozone in the presence of pyridine, with the formation of carboxylic acid and aldehyde groups.

(b) Oxidation of the aldehyde groups obtained in Acids and peracids and '■

groups

(c) reduction of the peracid groups to GarDonic acid

The luastix masses according to the invention are btoixes which originate from certain monoolefin-diolefin copolymers. In general, these copolymers are made by interpolymerizing a minor proportion of ionoolefin, such as an isoolefin having 4 carbon atoms per molecule, with a minor proportion of a conjugated diolefin in which the 2nd and 3rd carbon grains of the conjugated system The isoolefin used is isobutylene, although other monoolefins such as 3-ethyl-i-butene or 4-diethyl-1-pentene can also be used The other components of the reaction mixture which can be used are 1,3-butadiene, 2,4-hexadiene and piperylene. The conjugated jjioxefins suitable according to the invention are those which, when interpolymerized with isobutylene, yield an unsaturated elastomeric polymer, the predominant proportion of which is double-linuun _L , Gn in "de, r inner iiette 1,2-substituted ethylene groups.

10932G / 16B5

BAD OWGLAL

Generally, the feed will contain between about 60 and 99.5 w / o isoolefin with the remainder being the conjugated diolefin. The polymerization is generally carried out at low temperatures, ie between about -50 and -1o5 ^o c; or below in the presence of a Friedel • Crafts catalyst, such as aluminum tribromide or aluminum trichloride, in a solvent such as a lower alkyl halide, for example methyl chloride or allyl chloride. US Pat. No. 2,356,128 fully describes the process for making such isobutylene-diolefin copolymers. The final rubbery polymer generally has an average molecular weight of about 100,000 to about 1,500,000 and its degree of saturation is characterized by a Wijs iodine number of between about 0.5 and about 50, usually between about 1 and about 20. Low molecular weight gums can be made by increasing the amount of diolefin used to about $ 30 of the total charge and running the reaction at temperatures slightly higher than indicated above.

In the present invention, which uses the rubber copolymers described herein as starting materials, it has been found that not all rubbery isoolefin-diolefin copolymers are suitable. I ¹ For the present process and for the production of the present mastic compounds, only those rubbers are suitable which are composed of isoolefins which have been copolymerized with conjugated diolefins in which the 2nd and 3rd carbon atoms of the linear conjugated system are not substituted, except with hydrogen , have it manufactured. In other words, such substances as isoprene, 2-methyl-1,3-butadiene, myrcene, ocimene, 2,3-dimethyl-1,3-butadiene and the like are not suitable as conjugated diolefins from which the gums or iülastoinoren which can be used as starting materials for the present process are produced.

109826/1665

"To produce rubber that has proven to be successful Use starting materials for the process according to the invention the conjugated diolefins must have the following general formula:

H ₁ - OH = OH - CH = OH - H ₂

in the H, and H _? may be identical or different and a hydrogen atom, a lower alkyl group with 1-Ö carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylpropyl, 2-ethylpropyl groups, a phenyl radical or a simple

alkyl-substituted phenyl radical, such as i'olyl or XyIyI- ä

residues or an O ₁ . to Ou alicyclic reads or alicyisubstituted alicyclic radical, such as cyclopentyl or oyclonexyl or methylcyclopentyl radicals, ". Specific examples of such diolefins which can be used have already been described above and include monomers such as butadiene, piperylene,. 1, j-iiexadiene and 2,4-hexadiene.

j.O "in the example of a method described above produced gummis, using Aluniiniumohloriu as a catalyst and Wiethylchlorid as

mii / tel., yj > j isobutylene and by » piperylene became the ubA-Pateribschriit 2 35o 128 / Weeiti ⁱ ie ^: b-en. The f

rubber-rubber-like nupolymers, have an average Molecular weight of about 42.uOO and about 4.0 / molyii JjoppelDindungen,

In üer using the OzOnolyseverfahrens described here one is able za änäern the original fluidity and the final crosslinking density in the cured system and thus its hardness and its module, so uieue One division is possible because the maximum Ana aiii of crosslinks per Volumerieinheit

/; .0ϊν _: 0Τ., Lull t

109826/1665

of the mixtures that can be obtained in proportion to the number of those present in a unit of volume of the Hasse functional groups is. Therefore, for a polymer with exclusively terminal functional groups, the Number of vials of functional groups that per unit of volume exist, N, given by the following equation:

N. = 2 P 'P = polymer density

1,-

^Vlr - M _n M number average molecular

weight of the polymer

This results in the following:

In a given polymer in which N is fixed, the maximum number of crosslinks that would be possible would be is, through the use of a tri- or functional hardener, can be achieved while using a really bifunctional agent at all, would not result in any hardening, but only a dough the molecular weight through a linkage of the polymer molecules, each with each other on linked. Therefore, if you scar with a mixture of a bi- and a tri-functional agent the crosslinking density would be adjustable between ü and the maximum.

While the exact chemical nature of the crosslinking is relatively unimportant (provided it provides a stable chemical equilibrium), exercises the present of polar groups in the chain of normally non-polar hydrocarbon polymers is a fundamental one Effect on their physical properties. The dipoles present in polar junctions tend to be to exert mutual reactions Apparent networks are formed where in reality are none at all.

1098 2 6/1665

BATH ORIGINAL

φ "■

Therefore, two cured products can have the same degree of end-to-end linkage of their polymeric Have molecules, have largely different physical properties. For example, if you a polyisobutylene with a terminal arboxy group with a given molecular ratio of tri-: difunctional glycols (through esterification) hardens, its properties were largely increased differ from a product that has the same itlol ratio of tri-: difunctional amines (by Amidization) was hardened. The reason for that is the amide bonds give the hydrogen to one another fairly would bind tightly while the ester linkages would be relatively free of such linkages. That's why the product containing the amide bonds would be harder and be tough. This is the basic theory of urethane technology, in which, for example, polyisocyanates and polyhydroxy and / or polyamino compounds in different Iviengen parts used to make the properties of the hardened products.

The use of this method of adjusting properties is well known and forms the basis of rubber technology. 'The use of pull fabrics and Plasticizers not only allow the physical properties of the hardened product to be adjusted, but also the consistency of the sealant before Hardening.

For example, you may want a connection with a certain thixotropic character, i.e. a compound that works at very low shear forces does not flow, but flows fairly easily with increased high shear forces (e.g. mayonnaise). This attribute can the mastic through the use of lawyers such as silica or soot lent ■, will.

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BAD OftiöiNAL

Since the material that can be produced according to the invention is preferably is liquid and can be easily converted to a high molecular weight vulcanizate spray it onto fabric, wood or concrete to either create a composite or the substrate to make waterproof. In addition, because the substance according to the invention is relatively inert and impermeable to liquids and gases, it can serve as the basis for a flexible, corrosion-resistant protective coating.

In the field of lubricating oil additives and fats, the uses of the substance according to the invention are unlimited.
The importance of the polyisobutylene structure in terms of durability has been demonstrated for many years. With polyisobutylenes that have terminal functional groups, chains with a high molecular weight can be restored via esterification or amidation.

For example, a polyisobutylene with a terminal carboxy group can be converted into the acid chloride will eaea? with ammonia or primary and secondary amines to form a sludge dispersant be reacted or with a difunctional amine to produce a polymer with localized Hydrogen bond moieties are implemented; the the Let the molecular snake become narrow at low temperatures and untangle it at high temperatures and thereby exhibit the properties of a good viscosity index improver.

In addition, the carboxylated polymers can be used in Use fat masses as they form the basis of education of soaps with high molecular weight by reaction with metal hydroxides, oxides or alkoxides.

109826/1665

To put it more precisely, the manufacturing process is running of the polymeric starting compounds for the dicarboxylic acids of the present invention according to the well-known butyl polymerization using ■ AlOl, as a catalyst, club as a solvent. Lie in making the preferred interpolymers used special monomers are isobutylene and piperylene in a ratio by a copolymer with about 3 mol / o piperylene is obtained. Common Miscipolymer Ranges for the production of the diacid are between 0.5 and Iu Mo-L.;> Piperylene. "The average molecular weights can be between 100,000 and over "1,000,000. ™

The piperylene or üutadienisobutylenmischpolpolymer is dissolved in any suitable solvent before ozonolysis, such as an aliphatic hydrocarbon ", like P ent an. ,, iiexan or heptane .. In the Examples were in particular n-hexane. Other solvents such as chlorinated hydrocarbons., are just as suitable.

.uie ozonolysis can be carried out at temperatures between -80 "and -KjU ⁰ U, preferably -2b ° to +50" Ou and in particular 2.7 / iscifxuii -IO and 40 " ⁰ O. J

, Uie ur-.i.Ljß on pyridine or substituted pyridine

deru ■ Jicii'ijurif.smitcej. added üntweder before ozonation or s'bUi-oruwöiEi-a "ffäiirena aer implementation ./ üieser Auraelaan, his ·· so.u eggs expression pyridine extent taken, aa 'ei · aucii Sutuscituierte pyridines uraii.ss c * anchor it we ■ .j. ...; uon iyru aarc ^ i ". xiin'i-rciv / uiüen » To. the üeispiaien. ; ; i. > -.- j.'i ^! ? t..La υ .. "- .. ü.fx3" ^ t; '\ i uuiarts pyridine g, ühirioli IL: ·: .jr ^f Oiiae. -yridiar-ier-ürnolöget :. Oi ^ riü use of

10 9 8 26 / 166-5

C », 2b and 10 iuol or equivalent per iviol of the oil present in the polymeric sealant can be used. Different amounts of pyr'idine were used in the following examples.

Ozonization is carried out by exposing the piperylene copolymer to ozone-containing building material or jju.it. The concentration of ozone in the air or in the Sauers'Gofi and the rate at which ozone is added can vary widely. It can be 0.1 to ΊΟ wt. >>, preferably 0, b to 5 and in particular 1 to ο wt.

During ozonization, peracid is formed, which must then be reduced to the carboxylic acid group before a usable product is obtained. The production can be carried out either by storage or by heating in the presence of pyrine, or by treating the peracid with alkyl or aryl amines, phosphines, organic bulbs, i'hi'ols or organic phosphonites, or by acid catalyst be carried out with aldehydes. Reduction with pyridine is particularly preferred and is used in most of the examples. Excess reducing agent and its oxidation products are usually, but not always, removed after reduction either by treatment with acidic resins (AmLerlysc, L'owex) caer by washing with water. In iailen in which the oxidized reducing agents form products which in organic LosunfsmiLbain unljüiicu sina, let air i; separate them from the polymeric solution by titration. The latter sea er, ode was iti some of the L ^: ei6pidie ani / örViuidc.

1 09826/1 865

BAD OWGINAL

The polymeric acids are derived from the aliphatic Solvents obtained by stripping off the solvent and subsequent vacuum drying. This separation can also be carried out as thin film evaporation or steam stripping.

Ozonolysis methods for the conversion of 1,2-disubstituted Ethylene in carboxylic acids are known from literature (see P.S. Bailey, Chem. Sev. 58, 925, 1958). However, none of these methods are effective for conversion of unsaturated hydrocarbons of high molecular weight in acids with essentially 2 carboxy end groups suitable in high yield per molecule. "

The reason for this is that all preferred methods use a polar solvent, ie a largely incompatible solvent or reagent, during at least one of the reaction stages indicated. This means, - that the ozonolytic production of acids from olefins has been carried out as follows (a) in jüssigsäure as solvent, (b) in methanol as solvent with subsequent aftertreatment with peracetic acid or performic acid, (c) in an emulsion of aqueous NaOH and 30 yiigem hydrogen peroxide and (d) in a hydrocarbon or chlorinated hydrocarbons * substance solvents followed by treatment with peracid.

However, the previous processes had no selectivity and undesirable by-products were formed reduce the overall yield. In addition, if piperylenebutyl is used, the earlier methods are therefore not feasible as the same with polar solvents Is incompatible. The method according to the invention overcomes all of these disadvantages. ■

109826/1665

First stage of ozonolysis

£ -CH = UH-H + ü -2

[IJ - ^ Ä-tOÜH + Ii-UaI = U + Γ Ij

In order to obtain two moles of acid from one mole of a double bond, the first ozonolysis stage must be followed the conversion of the aldehyde into acid can be carried out. This can be achieved by further ozonolysis of the mixtures be, whereby you get a mixture of peracid and acid .groups, which is probably about the following reaction takes place:

Second stage of ozonolysis

OVo ₂ mixture + HOOOH

R-CH = O - ^ R-O = O

0OH. ■,. · ■, -

H-C = O + H-CE = O ^ 2 It-O = O

• * r

0OH Uli

Although the overall process of ozonolysis has been separated into two stages, it is usually not possible to do that to finish the first ozonolysis test described above without to include a part of the implementation described in the second ozonolysis study, probably the last stage of these two conversions does not take place completely during the second zonoiysis stage. That is why this is at the end of the second uzonolysis stule ite & ctionmixture mainly acid, but contains " also some peracid groups. Since the latter is used as liquid rubber (, mastic) or as prepolymers are not suitable, a judgment stage must be connected to this second stale, in which this

109826/1665

BATH

Peracids Converted into the desired acid groups will. This stage is achieved by reducing the peracid carried out with the pyridine present in the reaction mixture. earlier in the patent application ................

(E 29 72? IVd / 39 c) it was still considered necessary to To remove the pyridine before the reduction, ils is a An important feature of this invention that the pyridine is superior to other reducing agents. acts as an effective reducing agent.

Output stage.

Heat

H-O = O + Uli

The chemical process of each call was in Liodell experiments using trans-4-octene as ι, ιό de 11 sub st rat -explained. From these model studies can be seen that the reactions for / iOzonolysis of polymeric fcLanlich expires.

uie nacii the new misery are made of rubbers using a gas composed entirely of ozone or, more commonly, gases such as air or oxygen, uie contain up to 1 ^. · / 'ozone, a degradation ozonation' subject. In practice, mixtures of oxygen ' or air and ozone are preferred.

.uas from the uesé-level conjugated! »! olefins than the rubber made by one of the reactants y / is dissolved in a suitable solution as described atopieiswöiaü Oil form, irachloride, preferably the straight or branched aliphatic Acmi.3iihydrogen. like n-i: exan, n-hepUan, lüohexan,

109826/1665

BAD ORiGiNAL

Isopentane or any other solvent with which the polymer does not react, and that among those according to the invention Conditions is relatively inert to ozone. In general, the concentration is aes Gums in the solvent expediently from about 1 to about 50 vol.; I, preferably from about 10 to about 20 vol. The pyridine is in one ion concentration in the solvent from about 0.25 to i? ü, preferably 0.5 to IG, in particular from 1 to 5 moles per mole of the ethylene double bond in the rubber molecule. As, as a rule, one can say that pyridine can be used in amounts sufficient to cause the polymer to precipitate will.

An ozone-containing gas is blown into the solution while the temperature is kept at about -10 to about ^0, preferably at about -50 to about +50 0, in particular when the solvent is a hydrocarbon.

In the first stage, the concentration of the ozone in the gas stream is about 0.1 to 100>, preferably 1 to 10 / », and in particular 1 to 6 wt. ^ », in the second stage, which may or may not be required, depending on the ozonization temperature, concentration of the solution and Double bonds of the polymer to be ozonized, the most preferred concentration is 0.5 to} wt / *. The ozone is brought into contact with the polymer until unreacted ozone is detected. To demonstrate breakthrough of unreacted ozone, sodium iodide or potassium iodide is in solution and stretched vulcanized natural rubber is used. The appearance of unconverted oaons indicates termination the first mare. To the remaining aldehyde groups to oxidize, further υζθη

109826/1666

BAD OWGINAL

added. Ozonolysis in the second otuie will performed for a period of time ranging from about 10 to i; (. G, ο of the time required for the first ozonolysis stage was necessary. The Zeii ^ is chosen so that it is sufficient to quantitatively remove the remaining aldehyde groups to oxidize.

under normal factory conditions, the first and second stage often carried out together, but to understand the mechanism of the implementation according to the invention, the concept of levels is important.

There are pressures from atmospheric pressure up to 35 »2 kg / cm, preferably from atmospheric pressure up to 7.03 kg / cm applied, with higher pressures applied where the Solvents would normally volatilize when temperatures in the upper range are applied will. British Patent No. 884 44Ö describes the ozonolysis of many polymers, including Natural rubbers and synthetic rubbers such as butyl rubber. jLs is, however, with the present Process not intended to carry out the ozonation without solvents, but only in a solution, or dispersion.

In the proper process, sicji do not form ozonides as intermediates. The implementation proceeds airekt with a ^ ii-aung of aldehyde, peracid and acid functions. the AId eüy cu. unction becomes completely a uarooxy function oxidized.

The Acbr.u has the formation of polymer chains that are a have a lower lüole / gross weight than that of the original Polj ^ meren, i.e. the average

uit.r like the Bale polymers are in ceine inen between about 1,000 and et v / a iiu.ouO, aar / ol ^ e

109826/1665

This is often about 1/20 to about 1 / 2DO of the molecular weight of the starting material before ozonolysis, however the ozonolysis product shows a partial Responsiveness due to the functional end groups mentioned above. There is at least such a functional end group before and usually at each end of the newly formed chains.

For many purposes, the selection of the starting polymers (before ozonization) is carried out in such a way that that the end products (after ozonation, oxidation and reduction) at normal temperatures and pressures ) are semi-liquid.

The new compounds, which have a lower molecular weight than the original polymers and Substantial amounts of aldehyde end groups can also be used using conventional tteagentien such as air, oxygen enriched air, oxygen or by aqueous or non-aqueous solutions of Oxidizing agents, for example peroxides such as hydrogen peroxide, sodium peroxide, solutions of hydrogen peroxide in aqueous sodium hydroxide or carbonate, peracids such as performic acid, peracetic acid or perbenzoic acid, Persulfates such as potassium persulfate, "cerium salts" such as cerium sulfate, potassium permanganate in mineral acids or the like alkaline solutions, potassium ferricyanide, potassium dichromate, rZalium bromate, chlorine or bromine in alkaline solution :, are further oxidized so that the functional end groups are essentially all converted into carboxyl groups will. Non-aqueous systems, such as potassium permanganate in acetone, can also be used use.

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BATH

17205Λ5

optionally, the functional end groups can be reduced to hydroxy radicals. This can be achieved by catalytic hydrogenation or by using chemical iteduktionsmittel, such as complex metal hydrides such as sodium borohydride and Lithiumaluminiumliydrid or Aiuminiumisopropoxyd or by metals such as zinc with an kineralsäure OAER acetic perform vas result of such üeduktion is that the starting polymer is converted into a compound which has a degraded linear chain and a low molecular weight and either hydroxyl end groups or üarooxyl groups or mixtures of these two groups εη each chain.

.When the end groups are a ketone group or function (which, however, cannot be achieved if you have a Type II üleiin used) it is described by simple above Methods not oxidizable to a carboxyl function ion. The reduction of a ketone end group would give a secondary alcohol, and as is known, that is chemical reactivity of a hydroxyl hydrogen in a secondary alcohol less than that of a hyaroxyl hydrogen in a primary alcohol, uie tiedukbion of aldenyd end groups results of course primary alcohol end groups. The chemical activity of active, water-soluble substances at the ends of these degraded polymer chain is important for the final Use for which these products are intended.

i> as ozonoiyse product with subsequent oxidation or jioiuction now lets you see through at barely any temperature
z, U; ',?.'. ue of a polyfunctional agent, dna with the
al: t Lven j.asuoru tu ι \ ua reai'Loren can, like ea t> ci, everyone üt. · Liehen or uyx) Lü (: iien Polyure bharniox ¹ »Lei Lung geticiilant, put forward in order to harden the th lUautix gauge blocks

109826/1665

BAD OPHGlNAL

~ ^4β ~ 17205Α5

produce suitable, for example, üiisocyanatverbindungen such as toluene diisocyanate, hexamethylene diisocyanate, 4 »4'-methylene bis (phenyl isocyanate); bis-giorformate compounds w / fie 'fetramethylene bischloroformate and aeridinyl compounds. In addition, Bpoxyverbindungen use for chain extension and crosslinking. Mixed systems are often also suitable. the The resulting crosslinked products were found to be tough, rubbery and particularly suitable for use as hardened mastic compounds.

The liquid, semi-solid or solid polymers according to the invention can be converted to form crosslinked gourami and plastic products. The substances according to the invention can be used as adhesives, treads for the production of electrical materials and for the production of toys, seals and household items. They can be deformed and can be used to produce foam articles by incorporating a propellant. Ks can be any useful curing process as it is known to be applicable to substances with functional groups that contain active hydrogen (SH, Cl) OH, COH, C-NKH, etc.). For example, the methods described in U.S. Patents 3,209,980 and 3,097,193 are applicable.

The following examples serve to further illustrate the invention.

109826/1665

ν BAD

Example 1;

A reactor equipped with a stirrer and a cooling jacket was charged with 1500 cm ^{J of} a 23% strength by weight ilexane solution of the copolymer of isobutylene and piperylene with an iodine number of 20.4 and an average molecular weight of 191,000. 25 cmr of pyridine were added to this solution and the constituents were cooled to -25.degree. An ozone-containing oxygen stream from a Welsbach Ί-4Ο8 generator with a voltage of 77 V and an acid

1 / Μίπ. , ρ material flow rate of 3 / initiated at 0.42 kg / cm. After 130 tain, ozone appeared in the exhaust gas. At this point, a 175 cm- ⁵ sample was taken, flushed with nitrogen to purge it of oxygen and ozone, warmed to room temperature and treated in the manner described below.

The ozonation was stopped, and 1 1/2, 3 and 5 btd. later samples taken. That in the reactor remaining material was flushed well with nitrogen and allowed to stand overnight, gradually and after the temperature rose to room temperature. At the the next day the ingredients were back to -25 ° C cooled and for a further 2 and 5 hours a stream of ozone exposed.

The individual Prouen were processed as follows. After being warmed to room temperature, they were placed in a 500 cm- ³ glass flask which was sealed, and 100 cm- ^{5 of} fresh jiexan was added. <. "Edem flask, 25 'iJulionsäureaustauscherharz (Dowes 5OVV-Xd) was added and k'die ingredients 15 ois 2u Kin. Vigorously agitated. At this point, could no longer be detected pyridine smell.

109826/1665

BATH

The solution was then poured into another 500 cm square stopper bottle filtered, the resin with 50 crar fresh hexane washed out and the washing liquids added to the filtrate. Then 3 »5 cm ^ trimethyl phosphite added to the flask, and the mixture was left to stand for 24 hours at ambient temperature, whereby the reduction of the peroxide compounds was effected.

In order to effect the oxidation of the excess phosphite and then to remove the oxidized product, 20 chH of distilled water and 30 cm " ³ 3 / aiges hydrogen peroxide were added to each flask and the constituents were shaken well. Then 10 g of the exchange resin were added and the Reduction and extraction were allowed to continue for 24 hours, with frequent agitation during the first 8 hours.

The liquid components of the flask were then placed in a separatory funnel, the aqueous layer separated and the exan solution placed in closed flasks and dried over anhydrous sodium sulfate. The solutions were then filtered in Petri dishes, and the hexane was evaporated off and finally dried ^{by heating at 105 0 O for 16 hours in a vacuum oven.}

The amount of polymer recovered in [each experiment was 23-26 g. A carboxylic acid analysis was carried out on a sample. Tris- ^ T- (2-methyl) aziridinyl7phosphine oxide was added to another sample so that 1,3-aziridinyl groups were present for each carboxylic acid group in the polymer. The mixture was then heated for 24 h. In a forced air oven at 90 ⁰ C. A periodic test determined the gel point, with a lower number indicating the more complete carboxylation of the polymer. The data obtained in this way are shown below.

109826/1665

sample Post-zonization
Time, £ 3td. * 1 0 2 1.5 .1 3.0 4th 5.0 5 7.0 ο 10.0

, 9 Gel time
■ hours 5 1720545 ,1 9 , 75 acid
mg Küfl / fi »7 6.2 , 5 3ö to 5.5 -5 , 0 4ö , 3 4.25-4 , 5 49: , 9 3.75-4 53: 3.0 -3 5O ₁ OJ ₁

* The time after, the ozone was detected in the exhaust gas for the first time became.

The above data clearly shows the need for the so-called second ozonolysis stage under certain reaction conditions, when a product is to be developed which has a uonen carboxylic acid content.

■ Example 2:

Ϊ5 k {i piperylenebutyl with an iodine number of 21.4 was dissolved in purified hexane and formed a solution of 23 wt /) polymers. To the resulting adhesive, 1,455 pounds of pyridine was added to give a mixture of 9.82 g of pyridine per 100 g of the polymer. 55 kg of this mixture of pyridine, polymers and i-iexane were added to a 114 l glass-lined keaictor, and the mixture was cooled to -20 0 and oxygen containing 2.6 % by weight O ^ was passed through the mixture at a rate of 0.1 L / 4'liri. blow through.

, / ahrrma der er ^ uen OzonLüierungsa., ufe eased the ^ aeti irilQbs toi Tu from a u \ It Laren «maser ^ .he Li to an opalescent XiLir ... L) Io Um: ietüunt ·; was persecuted by the fact that one wlihreriu. den Vüraucheu i 1 üua to; i'proüun entnalnn. l) Le-3e Pi'Oben v / 'jrdi-jn after aifujor VoraruuLUmg nac-ti dei · in example 4 oe- »ciiriebenen iAe uhode ml.'goar'bü L te t. üie L'irji'eunisue of linborüuciiimf. this i'robon were ln rifu ho parting 'L'abolLo 1 again u ^ eDen. 109826/1685

ORIGlNAL BATHROOM

Attempt Moles of O3 / Total weight iabell I MIBil
acid Carboxyl Time,
Sxunde Mole dop
pelbind. Weight 70 Op
as COOn groups/
Mole Ent taken
sample Oarooxylated polyisobutylene ^{# & /} "° 2 gel time at 9C ° C
btd. M.

9.75

0.43

O> 8

23

20.9 0.92 30.1 1.33 39.5 (a) 1.74 40.1 1.77 41.1 Ί, 02 41, c 42, o ι, βϊ 43.2 1.S2

1 ^ 22 2.61

17ÖT, 24

18th

ö »5 4.0

4.5 4.5 4.5 4.0 4.0

6679

3418 2141 1879 1910

7.57

21.4
42.9
52.6
52.6

52.2
52.9

0.93

1.31
1.65.
1.75
1.78

1.75
1.75

Properties of the hardened product

J » unsolvable. Swellable polymer content

ΊΟ0 '/ 3 soluble

100 % soluble

60.3

79.6
80.0
60.3

79.0

51.9 1/3 60.0
■ I84ü (b) 5o, 2 (b) 1.65 (b) x 62.5

(a) üzona breakthrough after 39 bcunaen

(b) Vi

Vurae kept for a long time before analysis via sulionic acid exchanger.

9.71

4.60 4.70 4.66 5.19

4.60 4.56

On beating these solutions became semi-milky and cLunois-colored, and on standing still a substance insoluble in hexane deposited on the bottom of the container. After 39 hours of ozone-oxygen addition, uzon was detected for the first time in a gas released from the low-level reactor, "to ensure that the conversion is complete, the ozone addition was continued for another 4.2 LyM of 43.2 hours. The mixture was stored for 13 days at room temperature and then ^{heated for 24 btd. to Db 0} O. After heating for 9 hours, 100 g of pyridine were added to ensure that all reactive groups (such as peracid ) have been reduced.

During this period of time, the rarity of the changed Adhesive from chamois in dark brown and it formed a considerable amount of hexane-insoluble sludge. jiin χ eil of this sludge settled when you saw the left untouched.

The ozonized and heated adhesive was removed from the reactor and treated with a strongly acidic ion exchange resin treated to remove the pyridine and its oxidation products. The distance was recorded as complete- viewed when all the pyridine odor had disappeared, which after the addition of i3> t> kg, of the resin and stirring of the mixture 45 iviin. long entered.

During the treatment of the adhesive with the resin was its color lighter, but so much color remained, that a dark brown product was obtained after the hexane had been stripped off.

The resin was / was filtered off from the adhesive through filter paper, jas iiexan was made from the carboxylated polymer

109826/1665

BAD OWGLAL

stripped by thin film evaporation. The analyzes of the polymer are given in Table II below.

Table II Analyzes of the carboxylated polyisobutylene

Acid (mg KüH / g. Polym.) '= 53.5 M _n (VPO) = 1875

Wt.> O ₂ = 3.13

) COOH groups / mole of polymer M 1.78

(calculated)

£ Solids (at 90 ° C 3 days with = 99.0 Vacuum pump pumped out)

The product was dark brown and free of any insoluble substances.

The carboxylated polymers of this example were also evaluated by curing them with tris / T- (2-methyl) aziridinyl7phosphine oxide (MAPO) in the following manner: To 5 g of the polymer, 0.5 g of MAPO was added and mixed thoroughly. The mixture was poured into an open aluminum weighing that one hineintat oven in a fan "and kept there at 90 ⁰ C. The sample was tested from time to time on their progressive hardening and was tough and elastic after 4 1/2 hours, has been displayed thus the growth of the polymer either by chain extension or chain extension and crosslinking. the sample was 24 h. gehär- at 90 ⁰ C tet '. the forming cross-linking of the cured sample was measured by that a weighted with a weight piece Immersed in cyclohexane for 48 hours at room temperature

109826/1665

Gum was determined as Ö1, ö, where b, '(t> g cyclohexane per g of insoluble polymer was taken up by the gelled (insoluble) polymer. The samples taken during the test were treated in the same way and the results are reproduced in rabello 1.

xi example .5;

ü g piperylenebutyl polymer with an iodine number (ΙΗυΡυ)

of 30, o and an M of 1YI uuU were dissolved in 23 g of purified iiexan and gave an adhesive with a content of 2..i G-j '.; ./- »i / oiymerem. The adhesive was placed in a glass reactor surrounded by a wanted r; a _t ^r : even. Your own 2 * 3 τ pyriaine were added and αι, Μ (iemiscxi was abbreviated to ^ oruur ^ and aiii "-iu υ. Then üauerstofi was abbreviated to aiu Genal g from Z ^ m ^ ü / λ. With Giner Goschv / indigkai c from .5 l / U in. durcxi the mixture through ge ulasen. \\) ϊ min. after aie Oaon-oauerstofisu, ^r, Aüe υegönnen "had been, was first detected in the gas escaping from the liet'ktor ozone. At this point in time the i'lieio ^ eschv / inaigkeit was on 2 l / ldln. and ergao reduces an uzon concentration of 35? ü ^ mg per 1 üaa ozone-Bauer toifgemisch three more u Gunden was added with the reduced KLieiägescuiwinüifekeit, jährend dieüer Zeitupanne were sucked all younges minute samples from the lieaküor and CLAL

l'rooen were worked up dadurcu that you can get so much ,, exan as mügiicu stripped off a uampLuad and

the residual aexane in a vacuum oven

t V abairippoe. υ La Pi'obü became dunacii in t ^J entan i'sl ^ .uid man lieU diü Lüaanf, üLer liacht stand untouched, uicf unloü L LotiiiS ui &lui'ini ubse could do. the

109826/1665

Solution was filtered through a paper filter, the pentane stripped off on a steam bath and then Finally dried overnight in a vacuum oven at 90 °. The samples were then analyzed and cured. the Results are shown in Table III.

109826/1665

ORIGlNAL BATHROOM

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109826/1865

P ") Γ-Τ

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BATH ORIGINAL

Example 4:

In this example the ozonization was at -2b ° ö while the remainder of the procedure was followed exactly as in Example 3. After 149 minutes of testing, ozone was found in the reactor exhaust gas for the first time proven. The flow rate was increased to 2 l / ivin. and the experiment continued for another 4 hours. During this period, every 40 min. Samples taken from the reactor, processed, analyzed and cured as in example three. The results are given in Table IV.

109826 / 166S

■ F-i rf M. H Φ 0) • Η • Η • Η .ρ ω Alles Sh τ-Ι φ, ■ 0) si Ct? -P σ ¹ ! χ; approx Φ φ φ M. « U O H H φ H • Η CQ O Φ : ο I ^ ε H O ο H -ρ • • Η φ CO ΐ H φ

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■ ο ί-1 ί = Ί Ή OH O

LA

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LfA

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- 29 -

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LT \

C-

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109 828 A166S BAD ORiGiHAL

Example 5:

Example 5 is the same as Example 3 with the difference that the ozonization was carried out ^{at +4 0 O.} After 142 minutes, ozone was detected for the first time in the exhaust gas from the heater. The piling speed was set to 2lAiin. and the attempt another 60 Hin. continued. During this period, samples were taken from the reactor every 15 minutes, processed, analyzed and cured as in Example 3. The results are shown in Table 5.

109826/1665

Ozonization of Tiperylenbut.yl at + 4 ° C

. "be

OO PO CD

26th

Ve I'v.uclis permanent
, in; "in. after
the Oy in the exhaust ■
was evacuated 2050 acid
mg / EOIl /
g »polyine. ■ (Jew.f /
° 2 Hol Breakdown 2077 50.5 .3.51 1.85 15th 2022 51.5 3-44 1.92 30th 2068 51.5 3.45 1 .85 A 5 2017 55.0 3.53 2.00 60 51.7 3.45 1.87

In Cycloliexan 'bei eiiiei " dwell time ν jttz do the gel side ■; ■> vualösl. Q. \ J.elirälaiger .Std. Polymers s share

84.7

4-0

86.0

91.4

4.86

4.74

cn cn

Example 6: ..,: ... ''. V:

233 g of a piperylene butyl polymer with an iodine number (INOPO) of 19.6 and Mv of 328,000 were purified in 765 Dissolved hexane and resulted in an adhesive concentration of 23 wt. / <> of the polymer. This adhesive was placed in a glass reactor equipped with a cooling jacket given. To this adhesive was also added 25 grams of pyridine and the mixture was stirred and set to + cooled down. The mixture was at a speed of 2.0b standard liters / lVlin. Oxygen with a content of 25 mg, Ο -, / ΐ (2 wt. ^ o) blown through. After 175 min., After the addition of ozone oxygen had begun, ozone was detected for the first time in the exhaust gas of the reactor. At this time the flow rate was reduced to 1.3 l / min and the experiment was continued for an additional hour. The ozone concentration during this part of the experiment was 3-1 mg O ^ / l. The product was worked up according to Example 3, analyzed and hardened. The results of this experiment are given in Table VI.

Example 7 t

This experiment was the same as in Example 6 except that 250 g of the polymer were used and that the ozonization was carried out at +24 ⁰ C. After a few minutes, ozone was detected for the first time in the exhaust gas of the reactor and the flow rate was reduced exactly as in example ο. The ozone-oxygen mixture was added for an additional hour. The ozonated polymer was worked up as in Example 6. The results are given in Table VI.

109826/1665

Example 8:

This example was the same as Example 7 with the difference that the ozonization was carried out at +45 G. became. After 204 minutes, ozone was detected for the first time in the exhaust gas of the reactor, and the flow rate as in Example υ reduced. The ozone oxygen noise became added another hour. The ozonized polymer was worked up as in example t>. The results . are reproduced in Table VI.

10 9 8 2 6/1665

Table VI

Influence of temperature on the ozonization of piperylene butyl

Taken
sample Implementation
temperature Moles of O /
Mol ^J
Double COOH
■ it ». ^M n ties 29 + 4 ^ 55.8 ^ 1744 30th + 24 .1.65 54.6 1784 31 + 45 1.73 56.1 1695

COOH
Group/
Mole Weight
ok
O 2 • Gel-
Time
Hours. 5 / v 1.77 3. 42 4, O 1.74 3. 64 4, O 1.72 3. 59 4,

Properties of the hardened product

yes unl7bsl.
Polymer

81.0
85.6
90.0

more swellable proportion of

5.94
3.86
4.25

CD (Jl

-> ■ cn

Example 9-:

A series of experiments were carried out in the following manner: A piper butyl polymer with an iodine number of 2U.7 and Mv of 2,000 was dissolved in hexane and gave a 23% strength by weight solution. Then partial quantities of 2 μg of the polymer (.600 «η ^{0 of} the adhesive) were ozonized with different amounts of pyridine, which are given in the table. The ozonization was ^{carried out at + 4 0} O, with 2 liters of oxygen containing 25 mg of 0- / (2 G-ew. ^ O 0-) being blown into the adhesive with stirring. The time at which ozone was detected in the exhaust gas for the first time is given in Table VII. From this point on, the l 'flow rate was set to 2 l / min and the ozonation continued for a further hour. The ozone concentration during this test section was 31; · mg C -, / 1. After the experiment was terminated, samples of the ozonated adhesive were processed according to the following procedure.

ü; A sample was prepared according to the procedure Ä, as follows Descurieoen is won.

(1) Additional pyridine was added to bring the pyridine concentration to 0 % by weight of the polymer. In external experiments which were carried out with pyridine concentrates over

No additional pyridine was added if the weight was carried out.

(2) The hexane was partially stripped from the samples on a steam bath. ■

(3) The iiexan that cannot be removed from the steam bath could be, was by heating the sample to 9u ° l ίο ötd. heated under a vacuum of 0.1 / u for a long time.

109826/1665

BATH ORIGINAL

(4) The sample was then dissolved in pentane and left untouched until it turned black Pentane-insoluble matter had settled on the bottom of the container.

The pentane solution of the sample was filtered to remove the insolubles and

(b) the pentane was stripped in the same way like the hexane in stages 2 and 3

The dry polymer was analyzed, cured, and post-processed The swelling properties were determined in cyclohexane at skin temperature for 48 hours. The results of these experiments are given in Table VI.

A second sample of the ozonated adhesive, taken on Final ^ e.that was taken from the ozonization process, was worked up according to procedure B below.

(1) To a 200 cnr ⁵ sample was around the active oxygen to reduce containing groups added 3.5 g 'Primethylphosphit.

(2) The trimethyl phosphite was allowed to react for 16 hours.

(3) The unreacted trimethyl phosphite was then oxidized by blowing oxygen with a content of 2b, 0 mg oVl into the reduced sample for 109 minutes. During this stage, a white, hexane-insoluble layer formed at the bottom of the jar.

(4) The trimethyl phosphite was washed three times Wash away the sample with water.

109826/1665

BATH

(5) 'Me, the sample containing solution was over Ha _? bü, dried and the hexane stripped off in the same manner as in Steps 2 and 3 of Method A of Example 9

The dry polymer was then analyzed, cured and the swelling properties in cyclohexane were determined. The results are given in Section VII . -

109826/16 65

Table_VII Results of ozonization with different pyridine concentrations.

ggr pyridine Obtained by method:

g.Polymer gel time, hours

i ° insoluble polymer swellable fraction

Test duration after the first 0 in the exhaust gas was detected, in minutes

A. B. A. 33 B. 5 0 34 k .0 B. 104 2 A. 35 1671 1 B. 17th 4th 36 A. B. 145 3 ^r L. 4th B. 54 5 32 1800 2046 1' 1 19th 1635 .0 181 8th 25th 50. 5 75 35 1668 1671 1 1568 75 1834 .25 1.0 44.5 35.8 72 49 .7 48. 5 5. 3 0 54.5 52.7 50 58 .6 66. .8th 11.0 14.25 6th - 4th 6th .58 3. 0 83. 84 86 4.5 4.0 3- .26 3 .65 soluble 80. - 76. 89 77. 84 3. 1 1690 82.8 76.5 87 1 74 soluble 5. 75 3. 2 3. 51. 3.58 4.31 3 1 9 3. 94 10 50. 9 3.

ο
co
co
to
cn

Example 10:

Three zonization experiments 3, 39 and 40 were carried out, 250 g of piperylenebutyl polymer having an iodine number of 19.7 and an Mv of 233 × 302 dissolved in iiexan to form a 23% by weight polymer were used in each of these experiments. The experiments were carried out in a jacketed glass reactor and the ozonations were carried out at + 4 ⁰ O. Experiment A was carried out with 25 cm pyridine / 250 g of the polymer, experiment B with 54.5 cm pyridine and experiment with 154.5 cm * pyridine. The rest of the procedure was the same for all experiments. The mixture was stirred and cooled to + 4 ⁰ C. Oxygen with a content of 25 mg Ο -, / ΐ was then bubbled through the mixture at a rate of 3 l / min. Ozone was detected in the exhaust gas from the heater at a point in time as shown in each case in Table VIII. The flow rate at this point was reduced to 2 1 / kin. and you used 35 mg Ο -, / ΐ and continued the experiment for another hour. The work-up was the same as in Example 4. The results of these experiments are summarized in Table VIII.

attempt Table VIII 3b 14th -3 9 ,8th '40 , 9 Influence of • η 19 ' , 7 1851 1905 , 76 Carboxyl 52, 5ü , 87 58 , 99 Weight ρ O ₂ Pyridine concentration , 73 ,1 2 , 0 OuOii / lüol .1·, , 7 I. , 20 y \ , 12 ρ insol. Polyine. 95 ■ 91 90 , 25 95 , 0 swellable part 4, 25th 4th 4th oil time, btd., uei 90 ° U. 4th 4th ü / ίΰΑΡΟ

cm- ^J pyriain 2? <J r polymeres

Try your new. η ae-r era

υ was detected in the exhaust gas, in

Min.

14--

ü?

BAD ORiGSNAl

Danajich can be according to the method according to the invention Copolymers which contain olefin structures with J? Yp II double bonds in the main chain, with Convert and break down ozone, with saturated hydrocarbon chains with lower molecular weight arise, either primary OH groups or at each end Have carboxyl groups or a mixture of terminal OH and carboxyl groups. The exact type of product depends on the ozonization conditions and the subsequent treatments.

fc The versatility of the procedure is evident in the attached Drawing in which the preferred üaonojyiise- and reduction stages are shown in process sections 1 and 2. In addition, there is the direct reduction of the original reaction mixture, the acid, peracid and contains aldehyde functions, the preferred method to make polyols as outlined by Process Section 3 is played. The same reaction mixture can be reduced in such a way that one Mixture of acid and alcohol obtained as shown by process section 4. These are preferred Implementation sections.

P It can also be seen from the flow chart of the drawing that the reduction and oxidation are controlled to obtain various individual reaction products consisting of (a) acid and aldehyde mixtures and (b) consist of diacids. You also have a choice between different process stages in order to arrive at different reaction mixtures.

So can molecules with methyl ketone end groups by applying converted to CarDonic acids by the haloforra reaction to increase the carboxyl content if necessary raise.

109826/1665

Claims (1)

Claims t a) Rubber-like copolymers obtained by interpolymerization from oC to 99.5% by weight of a (J ^ to O ₇ isoolefin with 40 to "0.5 Dew, ¹ /» of a conjugated diolefin of the general formula K ₁ - OH = Uli - OH = CH - H ₂ in which R ₁ and R _{0 are} a hydrogen atom, a C ₁ to C _Q \ d 'ΊΟ jm Alkyl, a phenyl or a CV to Co cycloalkyl M radical has been prepared in the presence of about 0.5 to 10 moles of pyridine per mole of double bond, ozonized and b) the peracid groups of the ozonolysis products which consist of polymeric fractions, the molecular weight of which is lower than that of the rubber-like copolymers and the at least peracid functions and carboxyl and have aldehyde functions or combinations of the aforementioned imnktions, by reaction ^ eden Idol's peracid with 1 to iu'oine reducing agent for Peracid reduced to carboxylic acid groups. 2. "The method according to claim I, characterized in that a pyridine is used as a reducing agent for peracid. 5. The method according to claim i or 2, characterized in that piperylene is used as the conjugated diolefin. 4. The method according to claim 1 or 2, characterized in that butadiene is used as the conjugated diolefin. 109826/1665 ij. Method according to one of Claims 1 to 4, characterized in that that an unsubstituted pyridine is used as pyridine. ο. Method according to one of the preceding claims 1 to 5, characterized in that the ozonization is carried out until an ozone breakthrough is observed will. '/. Method according to claim 1, characterized in that the ozonization is continued after the ozone breakthrough has occurred until essentially all of the aldehyde functions have been oxidized to acid functions. 8. The method according to claim 1, characterized in that reduction by catalytic hydrogenation and treatment with reducing agents which form hydroxyl groups is carried out. 9. The method according to any one of the preceding claims, characterized in that isoprene is used as the isoolefin will. 10. curable polymeric composition, characterized in that it is produced by the process of claims I to 9 became. . 11. Composition according to claim 10, characterized in that it was produced according to claim ο and a) acid and hydroxyl functions, b) acid and aldehyde functions or c) contains polyol functions, 109826/1665 12. Lias se according to claim 10, characterized in that it according to claim 7 was produced and a) diacid function or υ) contains polyol function. 13. Mass characterized in that it is implemented by
the carboxylic acid prepared according to claim 1 was obtained with a polyfunctional substance. H. mass according to claim 13 »characterized in that as polyfunctional substance an aziridinyl compound was used. V ^. Hasse according to claim 13 »characterized in that an epoxy compound is used as the polyfunctional substance
became. 16. Hasse according to claim 13 »characterized in that a misocyanate compound is used as a polyfunctional substance became. i'ür Esso Hesearch and Engineering Company f 109826/1665 Blank page