Technical Field

This invention relates to the art of making polymers and particularly to the manufacture of polymers in Ziegler-Natta and other highly-active polymerization systems wherein the manufactured polymers contain active groups. For example, our invention includes the manufacture of polyolefins such as polypropylene which may be colored or dyed by color-imparting agents chemically bonded directly to the backbone of the polymer. Such a dyeing or coloring technique may be referred to as an integral dyeing technique as distinguished from coloring or dyeing involving a physical mixture of polyolefin and a color-imparting material. The invention contemplates methods of making dyeable polymers, methods of dyeing the dyeable polymers, the dyeable polymers as compositions, and the integrally dyed polymer products. The invention also comprehends a method of protecting a polymerization catalyst system from attack by functional groups in monomers, of protecting the latent functionality of monomers from the catalyst system during the polymerization reaction, polymers including such monomers — both homopolymers and copolymers, the "deprotected" polymers and the "re-functionalized" polymers as end products.

Moreover, this invention relates to methods of imparting to polyolefins properties other than dyeability. It will be seen, that our invention includes a class of copolymers of olefin monomers, particularly propylene, and special ethylenically unsaturated monomers which have polar or other active groups on them capable of further reaction to impart new and other properties to the polyolefin copolymers, such as the ability to absorb moisture and the ability to cross-link and/or form graft-like copolymers with monomers normally unable to graft or cross-link with olefin polymers. These polymers and polymer systems are themselves novel, after modification to remove the protecting group, and after incorporation of the final property-imparting group. The new polymers, protected and modified, are made possible by the use of the protected monomers and method of polymerizing them with a Ziegler-Natta catalyst.

Background Art

Prior to the present invention, a practical, efficient method of integrally dyeing polypropylene and certain other polymers has eluded researchers in the art.

Generally, when we speak herein of dyeable polymers such as dyeable polypropylene, we mean to include polymers receptive to the chemical addition or substitution of modifying groups other than dyes, as will become apparent to those skilled in the art. The fast dyeing of fabrics has long been accomplished through reliance on polar functionalities which are present in the fibers; the dyes are typically designed to react with the polar groups. Polypropylene,

however, whether in the form of synthetic fiber or other more substantial three-dimensional form, must be colored through methods such as physical mixing of colorant or through a relatively expensive and frequently ineffective method of treatment. Pure polypropylene has no reactive groups at all, and of course no polar groups. To our knowledge, attempts to incorporate a monomer having reactive groups such as polar groups into the backbone of polypropylene by copolymerization have been failures. Typically such a monomer will not survive contact with the commonly used Ziegler-Natta catalyst.

By integral dyeing, we mean a dyeing technique which employs "dyesites" as that term is used, for example, in U. S. Patent 3,533,731. In this patent to Schmidl and Jennings, the dyesites are nitrogen-containing and are introduced by way of the monomer N,N-diisopropyl-7-octenylamine. The patent also recites the use of vinyl pyridine to provide nitrogen reactive sites for dyes. Such copolymers of propylene have not found widespread use because the reactivity of the functional nitrogen group makes it too vulnerable to unwanted reactions during the polymerization phase, i.e. in the presence of polymerization catalysts.

More broadly, it may be stated that prior to the present invention a practical method of employing Ziegler-Natta catalysts for the polymerization of monomers containing functional groups has not been develope .

Silicon-containing polymers have been produced by hydrosilation of the unsaturated groups in polybutadiene — see U. S. Patent 4,230,815. Small

amounts of various polymerizable hydrolyzable silanes are employed in U. S. Patent 4,481,322 as part of a filler including various di-unsaturated monomers.

A number of polymerizable silicone esters and silane monomers are disclosed in U. S. Patent 4,454,295, and copolymerized with various acrylates and cellulose esters to make a material for use in manufacturing contact lenses. See also U. S. Patents 3,504,998 and 3,709,656 which also employ various silicon-containing monomers.

A silane compound represented by the formula

RSiR"nY3„-n-wherein R is a member selected from the group consisting of ethylenically unsaturated hydrocarbyl and hydrocarbyloxy groups, R' is an aliphatic saturated hydrocarbyl group, Y is a hydrolyzable organic group, and n is zero, 1, or 2 is employed as a co-monomer with ethylene and made to crosslink through the use of water in the presence of a catalyst to promote condensation linkages, in U. S. Patent 4,297,310. Certain cyclic compounds are polymerized in U. S. Patent 3,920,714 to produce polymers with silyl side groups, and certain polyenes containing silyl groups are shown in U. S. Patent 4,028,483. Alpha-unsaturated compounds containing silyl-protected oxygen have been shown in the prior art; however they are not used for polymerization. See "Reaction of trialkyl (aryl) silanes with unsaturated α-oxides", I. E. Sharikova and V. M. Al'bitskaya, Izv. Vyssh. Ucheb. Zaved. , Khim. Khim. Tekhnol. , 9(4) , 595-599 (1966), In Russian: contains reference to H ₂ C=CH-CH ₂ -CH ₂ -0-SiEt_ . The reaction parameters cited (boiling point = 76-7°C at 11 mm Hg, density = 0.826 g/ml) agree with the present

specification. The compound was prepared from reaction of the -oxide of 1,3-butadiene and triethylsilane, in isopropanol in the presence of chloroplatinic acid (H ₂ PtCl ₆ ) . No use of material was cited in the abstract. See "Reaction of triethylsilane with unsaturated alcohols", E. Lukevics and M. G. Voronkov, Khim. Geterotsikl. Soedin.. Akad. Nauk Latv. SSR, 1965(2), 179-86, In Russian. Primary alcohols (like allyl alcohol) react with triethylsilane in the presence of H _^ P Clg to form triethylsilyl enol ethers (like

H ₂ C=CH-CH ₂ -0-SiEt ₃ ) with evolution of hydrogen. Secondary ethylenic alcohols (eg. l-buten-3-ol =

OH H ₂ C=CH-CH-CH ₃ ) react to give the silyl ether

0-SiEt3 (H ₂ C=CH-CH-CH ₂ ) and products of addition across the double bond [hydrosilation]

O-X Et ₃ Si O-X (Et ₃ Si-CH ₂ -CH ₂ -CH-CH ₃ ) and (H ₃ C-CH-CH-CH ₃ ) .

No uses cited in the abstract. See "Allyloxy carbanions. New synthesis of aldehydes via a β-acyl carbanion equivalent", W. Clark Still and T. L. Macdonald, J. Am. Chem. Soc. 1974, 9_6(17), 5561-3. H ₂ C=CH CH ₂ OSiEt ₃ is used to synthesize 3-alkylated aldehydes. See "Allyloxycarbanions. A synthesis of 3,4-dihydroxy-l-olefins from carbonyl compounds", W. Clark Still and T. L. Macdonald, J. Org. Chem. 1976, 11(22), 3620-2. H ₂ C=CHCH ₂ OSiR ₃ (R = Me, Et) gave stable allyl lithium reagents. See "Conversion of monoalkyl olefins to 1,1-dialkyl olefins by reaction with bis(cyclopentadienyl)titanium

dichloride-trialkylaluminum", James J. Barber, Carl Willis, and George M. Whitesides, J. Org. Chem. , 1979, 4^(20), 3603-4. Synthesis of (5-hexenyloxy) trimethyl silane which is H ₂ C=CH-(CH ₂ ) ₄ -OSiMe ₃ .

The reader may be interested in the following patents which disclose various methods of making dyeable polypropylene, none of which is similar to ours: 3,419,638, 3,779,703, and 3,131,990.

Special interest may be directed to U. S. Patents 3,655,633, 3,857,825, 3,929,850, and 3,920,715 which disclose polymers having silyl end groups. In addition, it should be observed that the compounds O-trimethylsilylallyl alcohol (CH ₃ ) ₃ Si-OCH ₂ CH=CH ₂ and N-trimethyl-silylallylamine are known compounds offered for experimentation by Petrarch Systems of Bristol, Pennsylvania. The compound 2-[(trimethylsilyl)oxy] ethyl methacrylate has been polymerized by Hirao, Kato, Yamaguchi and Nakahama as reported in Macromolecules 1986, 19., 1294-1299. The polymerization of certain monomers protected with silyl groups, specifically 4-vinyl phenol, 2-(4 vinylphenyl) ethanol, and 4-vinylaniline, are reported in the same article; however, none of the polymerizations is with a Ziegler-Natta catalyst. A series of hydrogenalkenyloxysilanes is reported in U. S. Patent 4,294,975.

Disclosure of Invention

We have invented a method of making polymers having functional groups. The invention involves the introduction to the polymer chain of reactive sites which may be employed for other purposes as well as the fixation of dyes, by the use of specially made

monomers blocked with silyl groups more fully described elsewhere herein, and the polymerization of the monomers, either alone or in the presence of other copolymerizable monomers in a polymerization system comprising a transition metal containing salt, a base metal alkyl, and optionally an external donor, i.e. any of the commonly used or classically described Ziegler-Natta catalyst systems.

Within the term "Ziegler-Natta catalysts" we mean to include all the catalysts and/or catalyst systems discussed by John Boor, Jr., in his book ZIEGLER-NATTA CATALYSTS AND POLYMERIZATIONS (Academic Press, 1979) particularly pages 33-35 under the subheading "Definition of Ziegler-Natta Catalysts", incorporated by reference herein. Generally, the term "Ziegler-Natta catalysts" includes all metal alkyls (or hydrides) of Groups I to III base metals together with transition metal salts of Groups IV to VIII transition metals. As discussed by Dr. Boor, this broad definition includes some combinations which are not commercially practical or even effective enough for laboratory study with certain monomers. As long as they are effective to some degree, under polymerization conditions, they are within the scope of our definition as used herein; the term "Ziegler-Natta catalyst" is also intended to include the possible presence of third or fourth substances such as electron donors, support materials, and the like. It should be observed also that an important feature of our invention is the protection of the Ziegler-Natta catalyst from attack by an active group which it is desired to insert in a polymer. Thus the term "Ziegler-Natta catalyst" assumes a polymerization

system which is operable and effective to make a polymer so long as the catalyst is not rendered ineffective by an extrinsic substance such as a monomer containing an active group.

Effective polymerization conditions, i.e. pressure, temperature, solvent and the like for Ziegler-Natta catalyst systems are well known; our invention is applicable to effect blocking of the monomer reactive sites at least to some degree under any such polymerization conditions.

The blocking of the reactive sites on the monomers, which our technique accomplishes, prevents them from attacking and/or destroying the Ziegler-Natta catalyst. After polymerization, and removal of the blocking groups, the reactive sites may find use to improve the compatibility of otherwise hydrophobic polymers such as polypropylene, polyethylene, and copolymers of propylene, ethylene and other olefins, with more hydrophilic polymers such as nylon, polyesters and cellulosics. Such hydrophobic and hydrophilic polymers often are miscible in the molten state, but solidify into separate phases. But with a hydrophilic moiety integrated in the polyolefin, they will tend to blend in a much more intimate fashion even in the solid state. Our monomers and new polymers may also be used to form covalent linkages to various other functional groups, hydrocarbyl fragments, functionalized hydrocarbyl fragments, and other organic and inorganic moieties. Similarly they may function as graft sites for other polymeric chains. The introduction of such functional, organic and inorganic groups to a predominantly polyolefin chain imparts properties to

them hitherto unknown such as, for example, dyeability particularly by basic and reactive dyes, crosslinkability, adhesivity, wetability, and resistance to oxidative degradation.

As discussed and claimed herein, the term

"polymer" includes both homopolymers and copolymers. That is to say, the phrase "a polymer of a compound" having a general or specific formula or "a polymer including a compound" of a certain description "as a monomer" means that the mer units in the polymer may be derived from that compound or group of compounds only, or alternatively only some of the mer units are to be derived therefrom, in which case the balance of the mer units in the polymer may be derived from any one or more comonomers copolymerizable therewith. The term "alpha-olefin" is intended to include ethylene as well as other polymerizable olefins such as propylene and higher olefins with an unsaturated group in the alpha position, preferably having up to about ten (10) carbon atoms.

A paradigm of our technique is as follows:

CH ₂ =CH(CH ₂ ) _n OH + ClSiR ₃ >

'YYYYVYYY..

KCH2-)nOSiR,3

' YYVYYYY.

i—(CH2,)nOSiR,3

+ H ₂ 0 —>

...YYYVYYYY...

I

(CH ₂ ) _n + HOSiR ₃

OH where n is a whole number from 1 to about 50 or more, although we prefer from about 2 to about 21; more particularly, we prefer about 3 to about 10. In this preferred version, each R is independently selected from alkyl, aryl, aralkyl, alicyclic and oxyalkyl groups having from about 1 to about 20 carbon atoms;

Y represents -CH-.-CH-; and V represents CH--CH-.

1 /

CH„

Normally the reaction of the silyl monomer with propylene will be in a relatively high ratio of propylene to silyl monomer, since many properties can be imparted to the polypropylene with less than about 5% of the silyl co-monomer polymerized with the propylene while maintaining a high molecular weight; however, copolymers with very high percentages of silyl monomer can readily be made and are useful within our invention. For example, copolymers of 99% or more silyl monomer and 1% or less ethylene or propylene are within our invention, as are copolymers of as little as .05 percent silyl monomer and the balance olefin monomers. Particularly useful copolymers are copolymers of about 0.5 to about 25 mole percent silyl-containing monomers and the balance alpha-olefins containing from 2 to 10 carbon atoms, preferably propylene. Homopolymers of the silyl monomers, and their activated derivatives, are also within our invention. All such homopolymers and copolymers exhibit stereoregularity. Stereoregularity in this context is intended to include copolymers of the silyl monomers with ethylene, in that the silyl mer units tend to be stereoregularly oriented and the ethylene groups polymerized in a Ziegler-Natta system tend to be entirely linearly oriented, i.e. without any branches. Of course, stereoregularity in silyl-ethylene copolymers is more discernable in the higher ratios of silyl to ethylene mer units. Alpha-olefin/silyl copolymers of this invention where the alpha-olefin has three carbon atoms or more are generally at least about 40% stereoregular; when a donor such as DPMS is used, they may be 90% or more

stereoregular. For our purposes a polymer which is about 40% stereoregular may be considered substantially stereoregular. Copolymers will typically exhibit random distribution of mer units but block or sequential distributions may be effected by alternately varying concentrations of the monomers as known in the art.

Monomers containing silyl groups, such as those of the above paradigm formula CH ₂ =CH(CH ₂ ) OSiR.., and others within the scope of the present disclosure tend to be neutral or beneficial in controlling stereoregu-lar polymerization, and are incorporated in the polymer chain at a more or less predictable rate dependent on concentration and reactivity ratios; they are incorporated by way of olefin insertion onto metal-carbon single bonds.

However, certain types of polymerization cataysts should be avoided. Even though the silyl group (SiR_) protects the ultimately desired polar function, there are some catalysts which cannot tolerate the polarity of the alkoxy silyl functionality, such as some non-Ziegler-Natta catalysts e .g . those which produce H ₂ 0 or ROH during polymerization in acidic or basic media where R'OSiR- is not stable. So long as the alkoxy silyl group does not attack the catalysts, however, such polymerization systems are within the contemplation of our invention.

Our invention includes the polymerization of compounds of the formula CH ₂ =CH(CH_) OSiR ₃ where n is an integer from 1 to about 50 and each R is independently selected from alkyl, alkaryl, oxyalkyl, alicyclic and aryl groups having from 1 to 10 carbon

atoms. More generally, our invention includes the use to make polymers of compounds (monomers) of the general formula

[CH ₂ =CH(CH ₂ ) _a ] _y (X)(0 ₄ _ _w SiR _w ) _z where each a is independently either zero or one, y is an integer from 1 to 4, X is an alkyl, aryl or alkaryl group having from 1 to about 50 carbon atoms and a number of hydrogen atoms reduced by the total of y + z, z is an integer from 1 to about 6, each R is independently selected from alkyl, oxyalkyl, alkaryl, aryl, alicyclic and aryloxy groups having from 1 to about 20 carbon atoms, and w is an integer from 1 to 3, and the use of such monomers to make polymers as described elsewhere herein.

When z is 1 and y is 1, and where X is an alkyl group, X may be expressed as (C H„ ) where m is an integer from 1 to about 50, preferably 1 to 20.

Our invention will be further described with reference to the following examples.

Three general synthesis procedures were followed in the work described herein. We do not intend to be limited to these methods of synthesis.

Method I, a general procedure for the synthesis of alkenoxy silanes and aralkenoxy silanes was as follows:

CH ₂ =CH-CH ₂ [X]OH + ClSiR ₃ + B >

CH ₂ =CH-CH ₂ [X]OSiR ₃ + HC1 • Bl

where X and R are as defined as above, B is a hydrogen halide acceptor such as pyridine, and other halides may be substituted for the chlorine. Generally the same procedure applies to the "paradigm" described above.

All operations were performed under inert gas, usually argon, by standard Schlenk tecnhiques or in a glove box/bag. All liquid reagents not supplied under inert atmosphere were purged with inert gas for at least 5 minutes prior to use; otherwise they were used as received, as were solid reagents.

A round bottom flask with side arm was fitted with, magnetic stirring bar and a gas inletted addition funnel. The apparatus was assembled hot (from a drying oven), evacuated and refilled with inert gas. The evacuation/refill cycle was repeated between three and six times.

The flask was charged with a given amount of aralkenol [an organic compound containing at least one hydroxy group (HO-) and at least one terminal olefinic bond (H_C=CH-) connected by an organic fragment described as X above, composed mainly of carbon and hydrogen and minimally being the methylene moiety (-CH--)], one, or slightly more than one, mole of a hydrogen halide acceptor (typically pyridine) , per mole of -OH and enough inert solvent to allow facile stirring even in the presence of the hydrogen halide acceptor salt which will precipitate from s'olution. The solvent was chosen for convenience of removal later. Generally low boiling solvents were used, such as ether. The addition funnel was charged with one mole halide (as halo silane—typically chloro tri-aralkyl silane) per mole of hydroxyl and a small to moderate amount of solvent. With stirring, the solution in the flask was cooled to about 0°C and a slow addition of the halo silane was performed. After the addition was completed, the mixture was stirred for at least a half hour at 0°C and then allowed to

warm to room temperature, generally overnight. At this stage the reaction mixture can be left for extended periods of time provided moisture is excluded,

The solid hydrogen halide acceptor complex was filtered off and washed with a volume of the inert solvent at least equal to about one-third the amount used during the reaction. Failure to thoroughly wash the solid tended to lower the isolated yield and resulted in yield estimations based on the weight of the recovered solid of more than 100%.

If the inert solvent were low boiling, it was next distilled from the filtrate. Otherwise it would subsequently be separated from the product by vacuum distillation.

The usual method of product purification consisted of an atmospheric pressure distillation followed by a vacuum distillation from a mixture of the once distilled product and triethyl aluminum (TEA) . TEA addition was used to facilitate distillation by combining with reactive compounds which were expected to boil near the boiling point of the desired monomer. Elimination of TEA addition may easily be effected, for example, by careful distillation. The addition of TEA was a convenience rather than a necessity. If the product was expected to boil near the temperature at which TEA boils the addition of TEA was avoided. Similarly if the product was expected, or found, to boil at a very high temperature the atmospheric pressure distillation was not performed, in which case TEA was added or not to the reduced pressure distillation. And finally if a poly-test indicated satisfactory performance with a once distilled (or non-TEA containing) distillation,

the second (or TEA containing) distillation could be eliminated. Purification with TEA is not related to the use of the Ziegler-Natta systems except with respect to the generally improved polymerization results; however, even impure materials have polymerized to some degree. Boiling point information was obtained from these distillations. Atmospheric pressure boiling points were uncorrected for actual atmospheric pressure at time of distillation.

For convenience in handling, a rough estimate of the density of each product was made by weighing an empty calibrated syringe and the same syringe containing a known volume of the product. The weight difference and indicated volume were used to calculate a density estimate. This procedure was used for the first few times a product was transferred and, when convenient to obtain accurate weight information, afterwards.

A second method applies to the synthesis of aralkenoxy silanes:

+ p ^r Na + (R'O)'4.-wSiRw >

[CH ₂ =CH-CH ₂ (X)0] _m (R-0) ₄ _ _w _ _m Si _w + (m-p)R'OHT-

+ pR'ONa

where m is an integer from 1 to (4-w), R' is an alkyl group chosen so that R'OH has a low boiling point (preferably less than about 125°C), w is an integer from 0 to 3, and p is a small number less than 1.

The general apparatus set up was as for Method 1 except no addition funnel was required. The aralkenol and aralkoxy aralkyl silane in a 1:1 molar ratio were combined in a flask to which was then added approximately 0.01 mole of sodium per mole of aralkenol. Alternately the aralkenol and the sodium were reacted together before the silane was added. In either case the mixture was stirred at room temperature till the sodium dissolved. This was done under a static head of inert gas. Upon dissolution of the sodium, the reaction flask was fitted with a distillation head, condenser and collection flask. The temperature of the reaction mixture was raised to 10-20°C above the boiling point of the alcohol to be distilled away as a very slow inert gas purge was established into the reaction flask, up through the distillation head and condenser and out through the collection flask, which may have been cooled to facilitate collection of the alcohol. Alternately, or in conjunction with this method of alcohol removal, an inert solvent which formed an azeotrope with the alcohol, or which boiled slightly above the alcohol, could have been added to the reaction mixture and then distilled away.

Final product purification was as for Method 1. Except when ω-undecenyl alcohol was reacted with diphenyl dimethoxy silane the only purification was to distill away all low boiling compounds. R'ONa remained in the product.

A third general method was as follows:

m CH- =CH-CH- (X) OH + Y SiR , , * 2 2 n ( 4-n)

[CH ₂ =CH-CH ₂ (X) 0] _m Y _n _ _m SiR ₄ _ _n -HllYHT

where n is an integer from 1 to 4, m is an integer, less than or equal to n, and from 1 to 3 and YH is a compound which boils at less than about 70°F.

Method 3 is very similar to Method 2; the main differences are that in Method 3 no catalytic sodium is required and YH is very volatile at room temperature and so heating is not required. Reaction mixtures were nevertheless generally heated in order to increase reaction rate and decrease solubility of YH. Heating was for 18 hours to a few days.

Y can be Cl ^~ provided that the hydroxyl group in R ^~ OH (where R ^~ corresponds to CH_=CH-X- with X defined as above) is attached to an aromatic ring (otherwise yield will be low) . In this case HC1 is given off.

If Y is NR" , where R" is a small alkyl group (1-3 carbons), YH is a low boiling amine.

Product purification was as for Method 1 but good results can be obtained without further purification.

Paradiσm of Method 1 Synthesis 3-Butenoxy Triethylsilane

H ₂ C=CH-CH ₂ CH ₂ -0-Si(CH ₂ CH ₃ )

All operations were conducted under inert atmosphere using standard Schlenk and/or glove box techniques.

Into a 1.0 liter round bottom flask fitted with gas inlet, magnetic stirring bar and 125 ml gas inletted addition funnel, which apparatus had been assembled hot, evacuated and refilled with argon five times, were charged 24.88 g of 3-butenol (Aldrich, 0.34 mol), 27.01 g of pyridine (Aldrich, 0.34 mol) and 150 ml anhydrous, Argon purged, ether (Aldrich). To the addition funnel were added 50 g of chloro triethyl silane (Alfa, 0.34 mol) and 50 ml of anhydrous ether.

The 1.0 liter flask was cooled to 0°C in an ice/water bath with magnetic stirring of its contents. After a short time slow addition of the chlorotriethylsilane solution was begun. White precipitate formed immediately. After addition was completed, the mixture was stirred an additional two hours at 0°C. It was then allowed to warm to room temperature overnight.

The solid pyridinium hydrochloride was separated from the solution by filtration. It was washed with about 100 ml of anhydrous ether.

The ether was removed from the filtrate by atmospheric pressure distillation. A purification was also effected by atmospheric pressure distillation. The materials which distilled below 186°C were discarded as well as the first few ml of product that distilled at 186°C. Product was collected between 186°C and 189°C with the several ml of material remaining in distillation flask being discarded. Isolated yield was 37.03 g or 58% based on starting alcohol.

A second purification was effected by a vacuum distillation from triethylaluminum (TEA) : A 100 ml round bottom gas inletted flask fitted with a

short path distillation head and 50 ml collection flask was charged with 32.60 g of the product (3-butenoxy triethyl silane) and 5.0 ml of a TEA solution in heptane (Texas alkyls, 25.1 wt.%, density = 0.715 g/ml) . All product that was collected at a pressure of 5.0 ± 0.25 mm Hg up to about 61°C was discarded. Product was collected into a new collection flask at 63.0°C at a pressure of 5.0 + 0.2 mm Hg. The total collected product weighed 23.59 g.

For the product expected to be 3-butenoxy triethyl s.ilane, the following properties were obtained:

Boiling point: 186-188°C; P = 1 atm. (uncorrected)

63.0°C; P = 5.0 ± 0.2 mm Hg Density (3 determinations): 0.86 ± 0.02 g/ml.

13 Cnmr analysis subsequently confirmed the product as 3-butenoxy triethyl silane.

1, 2 , 4, 5, 9, and 11

Monomer Examples

Method 1 was used to react 2-propenol, 3-butenol (detailed synthesis described above) , 5-hexenol, and 7-octen-l,2-diol with various halo silanes. The solvent was ether. Specifics of the reactions are described in Tables 1 and 3.

Monomer Examples 6 and 8.

Hepta-1,6 dien-4-ol, and 10-undecenol were reacted with alkoxy silanes according to Method 2. Details are shown in Tables 2 and 3.

Monomer Examples 7 and 10.

2-Allylphenol and 2-methyl-3-buten-2-ol were silylated according to method 3. See Tables 2 and 3 for further elucidation.

Monomer Example 3.

Using standard inert atmosphere techniques 31.5 ml (0.15 mol) of dichloro diphenyl silane and 50 ml anhydrous ether were charged to a 500 ml round bottom, gas inletted, flask fitted with magnetic stirring bar and 125 ml addition funnel.

The addition funnel was charged with 15.5 ml of 4-pentenol (0.15 mol), 12.1 ml pyridine (0.15 mol) and about 97 ml of anhydrous ether. Dropwise addition of the alcohol/pyridine solution was begun to the vigorously stirred chloro s _. ilane solution. The temperature of the reaction flask was kept between 20 and 24°C by a water bath. The reaction mixture was stirred for an additional three hours after the completion of the addition and then allowed to rest undisturbed.

The pyridinium hydrochloride was filtered off and washed with 100 ml and then 50 ml of ether. About 50 ml of the filtrate was removed via argon purge.

The collection flask was fitted with an additional flask which was purged with argon and then charged with 51 ml of a 3.0 molar ethyl magnesium bromide solution in ether (0.15 mol). This solution was added incrementally over about two hours to the vigorously stirred filtrate solution. Stirring was maintained for two hours more and then the reaction mixture was allowed to remain undisturbed overnight.

The resultant slurry was filtered. The solid on the frit was washed with about 75 ml of ether. Then the ether was vacuum stripped from the filtrate to leave an oily liquid in which a white solid was suspended. This product was slurried in about 100 ml of n-pentane and the resultant slurry was filtered. The pentane was vacuum stripped again leaving an oil in which there was a small amount of white solid suspended. This solid settled out in a few days.

Total isolated yield was 22 g which is about 49%. lHnmr spectra confirmed the nature of the product as 4-pentenoxy diphenyl ethyl silane.

Table 3 lists available rough density estimations.

Table 1 Method 1 Syntheses

Molar

Reactants Ratio Solvent Yield (%)

Distillation #

Silane Ratio of Wash Vol. Total Example

Aralkenol Silane Aralkenol to Rxn Vol . ^' Isolated #1 #2 Compound Name #

2-Propenoxy

Ally!alcohol Chloro diphenyl TEA diphenyl methyl (2-Propenol) methyl silane 0.92 0.3 82 VAC. silane

3-Butenol Chloro triethyl TEA 3-Butenoxy tri¬ silane 1.00 0.5 58 760mm VAC . ethyl silane

5-Hexenoxy tri¬

1.01 0.5 80 760mm methyl silane

5-Hexenol Chloro trimethyl silane TEA 5-Hexenoxy tri-

1.00 0.5 66 760mm VAC. methyl silane

5-Hexenol Chloro dimethyl TEA 5-Hexenoxy di¬ ethyl silane 0.95 73 VAC. methyl ethyl silane

7-0cten-l , Chloro trimethyl 1, 2-Di (tri- 2-diol silane 2.03 0.7 760mm ethylsiloxy) 7-octene

5-Hexenol Chloro dimethyl 0.99 65 VAC; 5-Hexenoxy di¬ 11 isopropyl silane TEA methyl isopropyl silane

Table 2 Methods 2 & 3 Syntheses

Molar

Hepta-1,6- Ethoxy dimethyl 4-(Dimethyl dien-4-ol phenyl silane 0.98 None 0.01 N.A. 80 vacuum phenyl si loxy)-

1 ,6-heptadiene

U-Undecenyl Dimethoxy Not 10-Undecenoxy alcohol (or diphenyl silane 1.00 n-Heptane 0.01 N.A. 85 able ethoxy diphenyl 10-Undecenol) silane

Tr s-(2-Methyl-3-

2-Methyl-3- Tris (dimethyl 0.31 None N.A. Dimethyl buteπ-2-oxy) 10 buten-2-ol ami no) phenyl Amine phenyl silane silane

2-A11ylphenol Chloro tribenzyl Estimated 2-Allylphenoxy silane 0.99 Toluene N.A. HC1 as 70% tri benzyl silane Reaction Incomplete

Table 3

Aralkyl (and Aralkoxy) Siloxyaralkene Characteristics

Approximate Number of Compound Boiling Point Pressure density density (Example') CO CmmHg') (g/ml') determinations

224-232 91+1 1.07+.03

156+1 6.3±0.9

157+1 6+1

186-188 760 0.86+0.02

63.0 5.0+0.2

0.97+.07

.65 760 0.854 ;0.02

79 45

74 39

5 93.0+0.9 29.9+0.6 0.855+0.019 10

6 130+1 8.7

7 solid

8 214 2.7 solid

9 242-244 760 0.851+0.003 3

10 1.02 1

11 82 9.8 0.804

Thus it may be seen that we have prepared a class of compounds which are useful in making polymers for various purposes as recited elsewhere herein. Our invention includes the use to form polymers of compounds of the general formula

(CH ₂ =CH-CH ₂ ) _y (X) (0 ₄ _ _w SiR _w ) _z

where y is an integer from 1 to 4, X is an alkyl, aryl, alicyclic, or alkaryl group having about 1 to about 50 carbon atoms, z is an integer from 1 to about 6, each R is independently selected from alkyl, oxyalkyl, alkaryl and aryl groups having from 1 to about 20 carbon atoms, and w is an integer from 1 to 3. More specifically, our invention includes the polymerization of compounds of the general formula

where n is an integer from 1 to about 50 and each R is independently selected from alkyl, oxyalkyl, alkaryl and aryl groups having from 1 to about 10 carbon atoms. Examples of compounds which may be polymerized in our invention include 2-propenoxy dimethyl phenyl silane, 2-ρropenoxy-diphenyl methyl silane, 2-propenoxy triisopropyl silane, and other compounds of the general formula

wherein R is an isopropyl group and R' and R" are independently selected from alkyl, oxyalkyl, alkaryl and aryl groups having from 1 to about 20 carbon atoms,

General Copolymerization Procedure

Case 1 - One comonomer being gaseous Standard inert atmosphere techniques were used to exclude moisture and oxygen throughout the manipulations recited below.

A round bottom flask fitted with a side arm, magnetic stirring bar and a stopper, which apparatus had been assembled hot from a drying oven and was then either evacuated and refilled with inert gas several times or (and) purged with the inert gas for at least 15 minutes, was charged with a given amount of solvent, heptane or toluene, usually 125 ml. The solvents were freshly distilled from sodium and triethyl aluminum (TEA) over which they had been refluxing for at least 18 hours under an inert atmosphere. Immediately after the solvent had been charged to the flask a given amount (see Tables A and B) of alkyl aluminum co-catalyst, which was in the form of a heptane solution of about 25 wt.% (0.715 g/ml in heptane), was also added to the flask which was then lowered into a thermostated oil bath and magnetic stirring was begun.

At this point the inert gas atmosphere in the flask was replaced with the gaseous comonomer by a minimum of 3 cycles of evacuation and refilling back to atmospheric pressure with the comonomer. After the third cycle the solution was stirred for at least 10 minutes (usually longer) to allow the solvent to become saturated with the comonomer. Pressure was maintained at about one atmosphere via a bubbler.

Next were added an "external donor", which usually was diphenyl dimethoxy silane or phenyl

triethoxy silane, if one was being used, and the other comonomer. The polymerization was initiated by the addition of the transition metal containing co-catalyst.

As the gaseous comonomer was consumed it was replaced by maintaining the pressure constant at one atmosphere via a bubbler.

After a specified period of time (see "run time" in Tables A and B) the reaction was quenched by the addition of acidified alcohol (HC1 in iso-propanol, ethanol, and/or methanol) . The quenched reaction s-lurry was combined with the alcohol solution of volume at least twice the original volume of the inert reaction solvent. The resultant slurry was stirred for at least 45 minutes and then filtered. This treatment not only stopped the reaction, it dissolved catalyst residues and removed the silyl groups and thus regenerated the hydroxyl groups.

If the filtration proceeded very slowly, the slurry was combined with enough water to make the filtration proceed at a convenient rate.

The polymer was resuspended in alcohol, stirred, filtered and vacuum dried overnight. Boiling heptane soluble content was determined by standard methods.

Some variations in the procedure were possible.

If the second comonomer was a solid, it was added as a solid or as a solution in the inert solvent,

If no solvent was used, the second comonomer was combined with the alkyl aluminum co-catalyst, and possibly other components excluding the transition metal containing co-catalyst, and this solution was saturated with the gaseous comonomer.

Case 2 - Neither comonomer being gaseous These polymerizations were run in essentially the same manner as the previous polymerizations. Since the comonomer was not a gas however the evacuation and refilling of the polymerization vessel with comonomer was unnecessary. The monomer was syringed (if it was a liquid or in solution) into the inert solvent prior to.the alkyl aluminum addition. From this point on Case 2 polymerizations were identical to Case 1 polymerizations.

General Homopolymerization Procedure In general these procedures were very similar to the copolymerization procedures except that the problem of introducing the comonomer was obviated. The general sequence of combination of the catalytic system components was as follows (with all the apertaining restrictions required by the exclusion of air from the reactor as in the copolymerizations) : solvent (if used); monomer; alkyl aluminum co-catalyst; external donor (if used); transition metal co-catalyst. Occasionally, the external donor was combined with the reaction mixture prior to the alkyl aluminum compound.

The workup of these polymers was somewhat more difficult than that of the copolymers. There was a marked tendency for the homopolymers to dissolve in acidified alcohol, so much more water was required. If a product dissolved, it was reprecipitated by the addition of large amounts of water. If this treatment was required, often the plain alcohol wash step was eliminated. Boiling heptane extractions usually were not performed.

Details of all polymerizations are indicated in Table A. Compound numbers refer to the compounds made in the respective monomer syntheses examples 1-11; compound 12 is a commercial sample of O-trimethylsilylallyl alcohol. Table A-l lists parameters of copolymerizations with propylene at a pressure of one (1) atmosphere. Table A-2 lists copolymerization parameters used with comonomers other than propylene. Gaseous monomers were held at 1 atmosphere; liquid monomers were employed at the indicated concentrations. Table A-3 presents details of the homopolymerizations of the designated aralkenoxysilanes. Solvent volumes (in ml) are listed only when they differ from 125 ml. Yields and characteristics of the desilylated polymers are shown in Tables C and D. All NMR results of homopolymers and copolymers indicated stereoregularity of the desilylated polymers.

Comparison Polymerizations

That the parent alkenols do not copolymerize under conditions comparable to those in which the finished protected monomers polymerize is demonstrated by attempted co-polymerizations of propylene and unsilylated alcohols. Various copolymerizations were run to show the polymerization capabilities of this class of compounds. Details of the polymerizations are shown in Table B; results and polymer characteristics are shown in Table E. Allyl phenyl ether is employed in one attempt; its inability to polymerize demonstrates that the presence of an ether group alone is not sufficient to permit polymerization.

Table A-l

Polymerization Parameters - Copolymerizations w th Propylene

Trans Metal Temp.

Aral kenoxysi lane Solvent Ext. Donor Al . Cocat. Cocat. Run Time CO

# Cone. Cone. Cone. Wght Cmpd. Run (M) Name Name !_M) Name (M) Name (mq) (hrs)

1 198 2.13 — DPMS 0.019 TEA 0.75 FT-l-SS 1063 6days 20

213 .4 nC DPMS .003 TEA .06 FT-l-SS 513 4 55

215 0.85 nC ₇ (17) DPMS 0.009 TEA 0.46 FT-l-SS 1033 25 60

2 160 3.43 — — — TEA 0.40 FT-l-SS 298 2 55 2.72 0.64 879 2

226 0.20 nC ₇ — — DEAC 0.11 TiCl ₃ 472 4 50

3 162 2.58 — — — TEA 0.39 FT-l-SS 667 3 60

218 0.13 nC DPMS 0.006 TEA 0.11 FT-l-SS 271 2 50

4 125 0.05 nC ₇ (300) — — TEA 0.26 FT-l-SS 1080 "24" 20

126 0.29 — TEA 1.50 FT-l-SS 294 "24" 20

Table A-l (Continued)

Polymerization Parameters - Copolymqrilotions with Propylene

trans Hetal Temp.

Aral titmmvi, lane Spl ^* " ^*"" t tltt P.ff ^" >r A . CM»1, Cocat. Run Tl-tt re.) Cone . Cone . Cone . Wght

C«φd, Rgη _, (H) _N ^* unc. M<> ^*** - _____ ________ _____ wt Jaa ______

4 120 __flfi nC ₇ TEA α_a FT-l-SS 510 0-5 20 1.32 10 0.57 1

144 0.40 tol (100) — — TEA 0.069 FT-l-SS 500 3 50

145 0.40 tol (100) PES .0034 TEA 0.069 FT-l-SS 950 3 50

146 0.73 tol (100) PES .0124 TEA 0.063 FT-l-SS 850 3 70

245 0.117 nC ₇ DPMS .0030 TEA 0.059 FT-l-SS 258 2 50

246 0.324 nC ₇ DPMS .0080 TEA 0.156 FT-l-SS 185 2 55

251 0.314 nC ₇ 'DPMS .0079 TEA 0.155 FT-l-SS 287 2 50

Et ₂ M- -S«He ₃ .0157

(

253 0.368 nC ₇ (50) OPHS .0167 TEA 0.311 FT-l-SS 254 55

5 247 0.117 nC ₇ DPMS .0030 TEA 0.058 FT-l-SS 266 2 55

248 0.317 nC ₇ DPMS .0079 TEA 0.155 FT-l-SS 253 2 55

252 0.318 nC ₇

254 0.635 nC ₇ (50)

Table A-l (Continued)

Polymeri iation Parameters - Copol ymeri <τat ion5 wi th Propylene

Trans Hetal Temp.

Aralkenoxvsllane Solvent Ext. Donor Al. Cocat. Cocat. Run Time CO

Cone. Cone. Cone. Wght

C pd. Run (H) Name Name (H) Name (H) Name (mα) (hrs)

6 243 0.123 nC ₇ PES .0031 TEA 0.060 FT-l-SS 234 2 50

244 0.232 nC PES .0058 TEA 0.112 FT-l-SS 238 2 50

7 236 0.17 tol (90) DPHS .01 TEA 0.12 FT-l-SS 1117 2 50

237 0.13 tol (175) OPHS .01 TEA 0.13 FT-l-SS 1070 2 50

8 220 0.35 tol — — TEA 0.13 FT-l-SS 216 2 50

227 fi-22 tol — — DEAC J D5 TlCl _j 606 I 55 0.27 0.12 2 )

228 1.01 tol (40) — — TEA 0.41 FT-l-SS 1425 2 55

9 169 0.389 tol (100) DPHS .0069 TEA 0.065 GF2A 456 3 70

175 2.46 — DPHS .0269 TEA 0.253 FT-l-SS 813 3 60

223 0.109 nC ₇ PES .0030 TEA 0.059 FT-l-SS 305 2 55

10 250 0.116 nC ₇ DPHS .0031 TEA 0.060 FT-l-SS 270 2 55

11 277 0.125 nC ₇ DPHS .0030 TEA 0.058 FT-l-SS 323 2 50

278 0.344 nC _j OPHS .0028 TEA 0.055 FT-l-SS 366 2 50

279 0.694 nC; (50) OPHS .0061 TEA 0.119 FT-l-SS 360 2 50

280 0.359 nC ₇

12 241 0.118 nC

Table A-2

Polymer zation Parameters (M2 ^C3~) Copolymerizations with Comonomers other than Propylene

Trans Metal Temp.

Aralkenoxvsilane Comonomer Solvent Ext. Donor Al. Cocat. Cocat. Run Time CO

# Cone. Cone. Cone. Cone. Wght C pd. Run (M) Name (M) Name Name (M) Name (M) Name (mq) (hrs)

5 274 0.384 Z-~ 1 at . nC ₇ (100) — TEA 0,13 FT-l-SS 1271 2 55

9 233 0.240 C ₆ " 1.42 nC ₇ (100) DPMS .0029 TEA 0.056 FT-l-SS 282 2 50 11 281 0.303 C ₆ 0.290 nC ₇ DPMS .0028 TEA 0.054 FT-l-SS 261 4 50

5 270 0.124 C ₈ ~ 2.29 nC ₇ (75) PES .0031 TEA 0.060 FT-l-SS 254 50

None 273 C-- 1 atm. nC ₇ (100) — TEA 0.141 FT-l-SS 1952 2 60 None 219 C ₆ ~ 1,67 nC ₇ (100) DPMS .0032 TEA 0.062 FT-l-SS 594 2 55 None 269 C~- 2.35 nC ₇ (75) PES .0031 TEA 0.061 FT-l-SS 254 3 50

Table A-3 Homopolvmerization Parameters

Trans Metal Temp.

Aralkenoxysilane Solvent Ext. Donor Al . Cocat. Cocat. Run Time (°C ⁾

# Cone. Cone. Cone. Wght

Oπpd. Run (M) Name Name (M) Name (M) Name (m ) (hrs)

197 208 DPMS 0.019 TEA 0.73 FT-l-SS 1024 4days 26 214 1.91 TEA 0.88 FT-l-SS 1481 15days 60

159 1.58 TEA 1.05 FT-l-SS 1469 3days 20

11153-027 TEA FT-l-SS 373 3.5 75

3 11153-022 1.09 TEA 1.05 FT-l-SS 327 20

117 0.42 — TEA 1.45 FT-l-SS 989 6days 20

118 0.42 — TEA 1.45 FT-l-SS 893 7days 20

134 2.88 TEA 1.20 FT-l-SS 156 1 20 1.64 ^■ *<- -) 0.69 3

135 0.71 nC ₇ (40) TEA 0.15 FT-l-SS 150 5days 20

Table A-3 (Continued)

Homopol vmeri zati on Parameters

Trans Metal Temp.

Aralkenoxvsilane Solvent Ext. Donor Al. Cocat. Cocat. ' Run Time CO

# Cone. Cone. Cone. Wght C pd. Run (M) Name Name (M) Name (M) Name (mq) (hrs)

4 136 2.43 — — TEA 0.81 FT-l-SS 101 2 20 1.61 1.07 16 1.20 1.20 8 0,96 1.28 18

8 229 0.54 tol (85) — — TEA 0.24 FT-l-SS 1936 3days 55

9 170 0.725 tol (25) — — TEA 0.198 FT-l-SS 1108 18 20

238 0.31 to! (25) DPMS .03 TEA 0.53 FT-l-SS 1406 5days 85

Tabl e B

Polymerization Parameters

Trans Metal

Monomer Solvent Ext. Donor Al. Cocat. Coc at. Run Time Temp.

Cone. Cone. Cone. Wght

Run # Name (M) Name Name (M) Name (M) Name .(mg) (hrs) CO

310 ally! alcohol 0.123 nC ₇ DPMS .0030 TEA 0.059 FT-l-SS 436 2 50

234 2-Allyl phenol 0.268 nC ₇ (50) DPMS .007 TEA 0.137 FT-l-SS 262 2 50

232 Allyl phenyl ether 0.656 nC ₇ (100) DPMS .0035 TEA 0.068 FT-l-SS 376 2 50

239 4-Pentenol 0.114 nC DPMS .0030 TEA 0.059 FT-l-SS 234 2 50

Tifc C (Part 1)

KSULTS OF comncmMTims mm morncnE (H, • ¹ franil ne)

CMVMIMM

Holt fraction ... fraction Nelho- VLH loll 1* fan •s "• "l 9/9 cat HcptlM 1 Intel. ^l - ^f c _ _Λ- ".

(I) Cc> CO XlOOO xlOOO ".

19) 1 Run

III • 0.020 0.0-8 |I.AM1 7.S βl.» ri- 44.2 4.01

OS « «.0I EA 2.0 rn I6J ».to

160 l 0.04$ o.«ι IM

O.OJO •.051 EA I.S 7i.a 150.5 11 I.S • m •.011 o.oss EA 20.5 H.t IM S.ll 5.01

162 J Mt fully NNR lβ •I

4* r*t» 4 •.2 14.4 144 65 113 24.2 til 0.OM S.4I

O.Ott EA IM ♦4.1 IM ' 44.6 ».22

241 • •.OH •.221 EA 71.« 43.2 142.3 104.4 244 a «.0I

•••N •.147 EA 47.1 l tt.l 141.1 117.2

2-2 • •.0O*-t.«t •.025-0.0B EA M Ϊ5.6

IS*.* 113,4

Table C (Part 1)

(continued)

RESULTS OF COPOLYIIERIZATIONS WITH PROPYLENE (H, » Propylene)

Composition

Hole fraction Wt. fraction Method Yield Boiling

Run g/g cat Heptane

^H l ^M l ^H l ^T c w I Insol .

(X) ( ^β c) (°c) 1000 1000

169 9 <.01 NHR

0.015 0.050 EA 14.9 84.8 157 112.7 323 58.5 5.54

175 0.046 0.142 NHR

0.049 0.151 EA 3.8 91.2 152.4 113.6

223 0.011 0.037 EA 52.2 93.1 154.8 110.6 177 16.3 10.8

250" 10 <.01 NHR

0.031 0.062 EA 146 96.2 162.1 117.7

277 11 0.014 0.032 EA 114 96.7

278 0.052 0.116 EA 62.4 93.0

279 — — — 17.5 95.8

280 — *— — 77.3 95.3

241 12 0.046 0.062 EA 1.5

*Incrιrporation of the silylated πcnαπer was apparently minute.

Table C (Part 2)

RESULTS OF COPOLYMERIZATIONS WITH COMONOMERS OTHER THAN PROPYLENE (M, ≠ C*)

Composition Boiling

Mole fraction Wt. fraction Method Yield Heptane

Run g/g cat Insol.

"l ^M 2 ^M l ^M l f or I % ] (*)

274 s .005-.024 .017-0.082 El.Anal. 16 98.1

^C 2*

273 None n NA NA NA 11 94.0

233 9 0.103 0.164 El.Anal. [28]

^C 6 ⁼ —

281 11 n 0.369-0.426 0. 410-0.494 El.Analj 157] 0.40 \. NMR 219 None 1ι NA NA [55] —

270 5 0.025-0.200

^C 8 ^* 0. 022-0.182 El.Anal. [76] —

269 None n NA NA NA [91] —

Table D

HOMOPOLYMERIZATION YIELDS

Unoptimized Isolated

Run Monomer Yield # (%)

197 1 10 n

214 10

159 2 22

11153 « -027 -

11153 -022 3 90

117 4 5

118 n 2

134 n 13

135 n 10

136 n 17

238 7 -

229 8 20

170 9 6

Table E CCMPAKISCN CC-OL-MagZATICKS WITH PRCPYIΣNE

(^ = Propylene)

Run Unprotected Yield Mole Wgt.

♦ aramer ( ^) g/g cat Εra . F∑a .

310 allylalσohol

234 2-allyl phenol 0 232 allyl phenyl 0 ether

239 4-Pentenol 0

Key for Tables

M - molar = moles/liter cmpd # - correspond to example #'s in previous section

DPMS - diphenyl dimethoxy silane

<Z- ^~ - ethylene

C3 ^~ - propylene or -C3 olefin

Cs ⁼ - 1-hexene or -C olefin

Cs ⁼ - octene-1 nC - n-heptane or C7 alkane (normal isomer) tol - toluene

M]_ - comonomer #1

M2 - comonomer #2

T _m - melting temp.

T _c - crystallization temp.

^M w ^M n ~ weight, number average mol. weights, respectively.

FT1-SS - A titanium catalyst supported on magnesium choride, available commercially from Himont Inc.

GF2A - A titanium catalyst supported on magnesium choride, available commercially from Himont Inc.

* - not soluble

DEAC - diethyl aluminum chloride

PES - phenyltriethoxy silane

TEA - triethyl aluminum

Et2NSi β3 - diethylaminotrimethyl silane

Thus it may be seen that our invention includes methods of making polymers comprising polymerizing, in the presence of a Ziegler-Natta catalyst, monomers including a monomer containing at least one group of the formula — OSiR- wherein each R is independently selected from alkyl, alicyclic, oxyalkyl, alkaryl and aryl groups having from 1 to 30 carbon atoms. It also includes the hydrolysis or alcoholysis of such polymers to obtain functional polymers. The polymers may be homopolymers derived from the -OSiR_ containing monomers, or may have a ratio of copolymerizable monomers to such monomers as high as 10,000 or higher.

Adhesion to Metals About 0.5 g of copolyhexenol/propene (Run #128) was placed between two pieces of aluminum foil. This sandwich was placed between the heated platens (about 380°F) of a hydraulic press. The press was closed with a few pounds of pressure for about 0.5 minute. The pressure was increased to 30,000 psig for about 2.5 minutes at 380°F. Pressure was released; the sandwich was recovered and cooled to room temperature. The aluminum foil could not mechanically be removed from the film of copolymer except with much damage to the copolymer film. In order to remove the metal, it had to be digested away with caustic solution.

Homopolypropylene when pressed in this manner easily separated intact from the metal foil.

Oxidation of Polymer Films Films were made from (1) hexenol/propene copolymer (Run #128) and (2) homopolypropylene

produced under conditions of Run #128 except in the absence of comonomer. The films were made by compression of the polymer materials between Mylar sheets. While the resulting copolymer film adhered to the Mylar, it separated relatively easily after return to room temperature. These films were flexible and transparent.

The films were suspended in toluene saturated with Jones reagent (8N chromic acid - H-CrO.) at about 50°C for 16 hours. They were then washed with fresh toluene. The copolymer film was slightly discolored (brownish) and was slightly less transparent than it was originally. Its flexibility and ease of tearing were unchanged by the Jones reagent. The homopolymer film was definitely more discolored (brownish) . It was more translucent than transparent. But the most noticeable change was a complete loss of flexibility. It had become very brittle.

Apparently, the presence of the alcohol had an antioxidant effect at least with regards to the mechanical properties of the polymer film. While we do not intend to be bound by any theories, we believe the presence of the hydroxyl groups at the ends of the short branches tends to dissipate the ability of an oxidizing agent to attack the "backbone" structure of the polymer.

IR of the polypropylene film showed three peaks in the carbonyl stretch region: about 1628 cm- medium, broad; about 1720 cm- medium, sharp; about 1775 weak shoulder. The most prominent feature of the carbonyl stretch region of the copolymer IR was a strong sharp band at about 1735 cm- . A weak

broad band at about 1635 cm~ and two weak shoulders at about 1710 and about 1775 cm ^" correspond to the similar bands in the polypropylene spectrum. Both spectra have bands in the O-H stretch region but the copolymer displays a stronger sharper band. Not all of the alcohol groups were oxidized as is shown by absorption in the 1050 cm- region of the copolymei IR:this is the CH ₂ -OH stretch region.

Dyeing of Polymer Powders

Hexenol/propene copolymer - Basic Red 1

To a dye bath composed of 0.18 g of Rhodamine 6G (Basic Red 1 - C.I. 45160), 6.52 g n-butanol, 57.4 g water was added, a sample of polymer resulting from Run #128 (alcohol monomer content about 5% mole) which weighed 0.56 g. The mixture was refluxed for 4 hours, after which time the solid was collected by filtration and it wa ^' exhaustively sequentially washed with the following: warm water/butanol with detergent; warm water with detergent; warm water; and warm water. The solid was air dried on a frit for about 10 minutes and then vacuum dried overnight. A deep pink colored solid resulted.

Polypropylene - Basic Red 1

An identical treatment of a sample of a homopolypropylene was made. The polymer was made under conditions identical to Run #128 except no comonomer was used. A distinctly less colored polymer powder resulted. The pickup of any color at all was attributed to the high ash content resulting from

acidic catalyst residues. In a later preparation, pre-washing the homopolymer sequentially with acidic, neutral, basic and neutral water solutions resulted in a much' less intensely colored pinkish solid. Similar pre-washing of the copolymer only slightly reduced the coloration of the resulting solid. The copolymer was presumed to have been intrinsically dyed.