CA2203660A1 - Alkoxy silyl capping agents for making terminally functionalized polymers - Google Patents

Abstract

The capping of anionic polymers to make functionalized polymers is improved by using alkoxy silyl compounds having protected functional groups, such as acetal groups, as the capping agent. The protected functional groups are stable under a variety of conditions and then readily convert to more reactive terminal functional groups useful for making adhesives, sealants and coatings.

Description

W O96/13526 PCTnEP~5/04193 ALKOXY SILYL CAPPING AGENTS FOR MAKING
TERMINALLY FUNCTIONALISED POLYMERS

This invention relates to preparation of functionalised polymers used as components in adhesives, sealants and coatings. More specifically, this invention relates to capping of living anionic polymers to add term; n~ 1 functional groups.
Anionic polymerisation of conjugated dienes with lithium initiators, such as sec-butyllithium, and hydrogenation of residual unsaturation has been described in many references. The capping of mono-initiated and di-initiated living anionic polymers to form functional end groups is described in British Patent Application No. GB 2270317.
Anionic polymerisation using protected functional initiators having the structure RlR2R3Si-o-A'-Li is described in US 5,331,058 wherein Rl, R2, and R3 are preferably alkyl, alkoxy, aryl, or alkaryl groups haing from l to l0 carbon atoms, and A' is preferably a branched or straight chain bridging group having at least 2 carbon atoms. Polymerisation with such a protected functional initiator, followed by capp ng to produce a second terminal functional group, p~oduces telechelic polymers which otherwise can be prepared by capping polymers prepared with difunctional initiators such as l,4 dilithiobutane and lithium naphthalide.
The use of a protected functional group avoids the formation of ionic gels which occur when diinitiated polymers are capped with reagents such as ethylene oxide. These gels form even in relatively polar solvent mixtures and hinder subsequent processing steps.

W O96/13526 PCT~EP95/04193 One way to prepare difunctional telechelic polymers without forming a gel is to use a protected functional initiator such as the structure:

CH3-Si-O-CH2-A"-CH2-Li (A) wherein A" is cyclohexyl or -CR'R"-, wherein R' is a linear alkyl having from l to l0 carbon atoms and R" is hydrogen or a linear alkyl having from l to l0 carbon atoms. The compounds of structure (A) initiate polymerisation of anionic polymers at high polymerisation temperatures. The protected functional group survives hydrogenation of conjugated diene polymers and is readily removed by hydrolysis in the presence of methanesulfonic acid. The initiators of structure (A) can be used to make telechelic polymers by capping with ethylene oxide or oxetane. However, oxetane is not readily available on a commercial scale and ethylene oxide can be hazardous due to its reactivity and toxicity.
A recent publication by M.A. Peters and J.M.
DeSimone (Polym. Prepr. (Am. Chem. Soc. Div. Poly-Chem.), 1994,35(2), 484) describes the prepara.lc~ of mono- and di-functional polymers by capping mono-initiated and di-initiated living anionic polymer with a chlorosilane of the following structure:

CH3-1C Si-O-(CH2)3-Si-Cl (B) instead of ethylene oxide or oxetane. In this process, LiCl is eliminated and the protected alcohol group is added to the polymer chain end, avoiding gel formation.

W O96tl3526 PcTAEP95/04193 ~ - G~ ( p ~ - 3 -The present invention is the discovery that mono-initiated or di-initiated anionic polymers are efficiently capped with silyl alkoxy ~ompounds LcR p~e~
possessing acidic alkoxy ~adicals as leaving groups and a variety of protected functional groups, resulting in terminal protected functional groups that are stable under a variety of conditions. The protected functional group is preferably an acetal group, but can be any group that readily converts to more reactive terminal functional groups useful for making adhesives, sealants and coatings.
The anionic polymerisation of unsaturated monomers with mono-lithium initiators such as s-butyllithium or di-lithium initiators such as the diadduct of s-butyllithium and m-diisopropenylben~ene is described in British Patent Application Serial No. 2270317.
Polymerisation results in one or more terminal lithium atoms which readily react with ethylene oxide or oxetane to cap the polymers with one or more terminal hydroxyl groups per molecule. The terminal hydroxyl groups tend to form weak associations between molecules, which has no adverse effects if these chains are mono-initiated. However, the di-alkoxide folymer anions formed by capping di-initiated polymers associate to form an ionic gel w~ch is very~difficult to process.
The use of the protected-functional capping agent of structure (B) avoids gel formation and avoids the problems presented by capping with cyclic ethers.
However, the use of this reagent to cap low molecular weight polymer anions results in the generation of large amounts of lithium chloride, which introduces new difficulties. For example, the preferred method for converting the silyl ether to the alcohol involves contact with aqueous methanesulfonic acid. The presence of high levels of halide in such a mixture f o ~ e~o ~

.
AMENDE~ SHEET

W O 96/13526 PCT~EP95/04193 ~ v~c~l ~c ~ _ 4 _ presents severe corrosion problems. Also, the polymers are preferably hydrogenated with a Ni/Al catalyst (to be described in detail below) that is poisoned by high levels of halide. In order to hydrogenate polymers capped with structure (B), an aqueous acid wash would likely be required to remove the LiCl. A drying step would probably also be required, since the catalyst is also deactivated by water.
The advantages gained by using a protected-lo functional capping agent are realized without introducing halide ions by capping mono-initiated or di initiated polymers with silyl alkoxides ~aving acidic alkoxy ~eaving groups and stable protecting groups as shown by the following structure:
CH3 ~ p~ cl~
I

Y-(CH2)3-Si-Z (1) ~v I o ~ e~c,c, 15 wherein Y is a protected functional group, preferably an acetal group, which is stable during the polymerisation step and converts to more reactive terminal functionality as described below, and Z is an acidic alkoxy ~roup, preferably phenoxy radicals or trifluoroethoxy radicals. The acetal group is preferred as the protecting group since it is easily introduced and cleaved, and has more favorable raw material costs than the t-butyl dimethylsilyl ether group of structure (B) or the trimethylsilyl ether 25 group of structure (A).
The alkoxy ~ilyl capping agents of equation (1) are prepared by hydrosilation of the appropriate dimethylsilane (Z-Si(CH3)2H) with an allyl species containing the protected functional group (CH2=CH-CH2-Y). Hydrosilation was accomplished using a Pt catalyst, as is generally described by M. A. Peters ~E\IDEI~ SH~Er WO96/13526 PCT~5/04193 and J. M. DeSimone (Polym. Prepr. (Am. Chem. Soc.Div.
Polym. Chem.), 1994,35(2), 484). After capping of the polymer, the protecting group is removed by reaction with methanesulfonic acid, as described in U.S. Patent 5,391,663.
A variety of processes for removal of the protecting groups are known; for a review, see T. W.
Greene, "Protective Groups in Organic Synthesis", J.
Wiley and Sons, New York, 1981. A preferable process would involve easily handled, relatively low toxicity, and inexpensive reagents. In a preferred process, the acetal group is removed by reaction of the polymer solution with 1 - 10 equivalents (basis acetal end groups) of a strong organic acid, preferably methanesulfonic acid (MSA), in the presence of 0.1% -2% by weight of water and 5% - 50% by volume of isopropanol (IPA) at about 50C.
Mono-initiation is preferentially performed using s-butyllithium. Di-initiation is preferentially performed using the diadduct of s-butyllithium and m-diisopropenylbenzene, as described in British Patent Application Serial No. GB 2270317. Polymerisation is preferably initiated at a temperature from 20C to 60C, most preferably from 30C to 40C. It is generally advisable to keep the polymerisation temperature below about 100C; above this temperature, side reactions that change microstructure and limit capping efficiency may become important. Polymerisations can be carried out over a range of solids, preferably from 5% to 80%, most preferably from 10% to 40%. For high solids polymerisations, it is preferable to add the monomer in increments to avoid exceeding the desired polymerisation temperature. If the initiator is to be added to the full monomer charge, it is preferable to run the polymerisation between 10% and 20~ solids.

W O 96/13526 PCTnEP95/04193 The protected group is introduced by reacting l.05 - 2 equivalents of the capping agent of structure (1) per lithium site (2 per chain in the case of di-initiated polymers) at a temperature of 40C - 80C
for at least 30 minutes. If no polar microstructure modifier was present during the polymerisation, it may be desireable to add a non-reactive coordinating agent, such as diethyl ether or glyme, during this step.
The polymers of the present invention preferably comprise a polymerised unsaturated monomer selected from the groups consisting of styrene, l,3-butadiene, and isoprene. When the anionic polymer comprises polymerised l,3-butadiene which contains residual monomer unsaturation which is to be saturated by hydrogenation, the anionic polymerisation of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethyl ether or glyme (l,2-diethoxyethane) to obtain the desired amount of l,4-addition. As described in Re 27,145, the level of l,2-addition of a butadiene polymer or copolymer can greatly affect elastomeric properties after hydrogenation. The hydrogenated polymers exhibit improved heat stability and weatherability in the final, adhesive, sealant or coating.
The l,2-addition of l,3-butadiene polymers having terminal functional groups influences the viscosity of the polymers as described in more detail below. A
l,2-addition of about 40% is achieved during polymerisation at 50C with 6% by volume of diethyl ether or lO00 ppm of glyme. Generally, vinyl contents in this range are desirable if the product is to be hydrogenated, while low vinyl contents are preferred if the polymer is to be used in its unsaturated form.
Hydrogenation of at least 90%, preferably at least 95%, of the unsaturation in low molecular weight butadiene polymers is achieved with nickel catalysts as WO96/13526 PCT~5/04193 described in U.S. Patents Re. 27,145 and 4,970,254 and U.S. No. 5,166,277. The preferred nickel catalyst is a mixture of nickel 2-ethylhexanoate and triethylaluminum described in more detail in the examples. It is preferable to extract the nickel catalyst after hydrogenation by stirring the polymer solution with aqueous phosphoric acid ~20 - 30 percent by weight), at a volume ratio of about 0.5 parts aqueous acid to 1 part polymer solution, at about 50C for 30 - 60 minutes while sparging with a mixture of oxygen in nitrogen.
This step is also described in more detail in the examples.
Sufficient IPA must be present during deprotection to prevent the formation of a discrete aqueous phase.
Excess acid is then removed by washing with dilute aqueous base, preferably O.lN - 0.5N sodium hydroxide, followed by water. For some applications, such as coatings prepared by baked cures of the polymer with amino resins in the presence of a strong organic acid catalyst, it may be preferable to use the polymer in its "protected" form. The viscosity of the protected polymer is lower and conditions such as those described above should accomplish the deprotection (generate the alcohol) during the cure.
` The conjugated diene polymers produced as described above have the conventional utilities for terminally functionalized polymers of such as forming adhesives, coatings, and sealants. Additionally. the polymers may be used to modify polyurethanes, polyesters, polyamides, polycarbonates, and epoxy resins.
A composition of the instant invention may contain plasticizers, such as rubber extending plasticizers, or compounding oils or organic or inorganic pigments and dyes. Rubber compounding oils are well-known in the art and include both high saturates content oils and high aromatics content oils. Preferred plasticizers CA 02203660 l997-04-24 W O96/13526 PCTi~5'01193 are highly saturated oils, e.g. TUFFLO 6056 and 6204 oil made by ARCO and process oils, e.g. SHELLFLEX 371 oil made by SHELL. The amounts of rubber compounding oil employed in the invention composition can vary from s 0 to 500 phr, preferably between 0 to 100 phr, and most preferably between 0 and 60 phr.
Optional components of the present invention are stabilizers which inhibit or retard heat degradation, oxidation, skin formation and color formation.
Stabilizers are typically added to the commercially available compounds in order to protect the polymers against heat degradation and oxidation during the preparation, use and high temperature storage of the composition.
Various types of fillers and pigments can be included in the coating or sealant formulation. This is especially true for exterior coatings or sealants in which fillers are added not only to create the desired appeal but also to improve the performance of the coatings or sealant such as its weather-ability. A
wide variety of fillers can be used. Suitable fillers include calcium carbonate, clays, talcs, silica, zinc oxide, titanium dioxide and the like. The amount of filler usually is in the range of 0 to about 65%w based 2s on the solvent free portion of the formulation depending on the type of filler used and the application for which the coating or sealant is intended. An especially preferred filler is titanium dioxide.
The dihydroxylated conjugated diene polymers of the present invention may also be blended with other polymers to improve their impact strength and/or flexibility. Such polymers are generally condensation polymers including polyamides, polyurethanes, vinyl alcohol polymers, vinyl ester polymers, polysulfones, polycarbonates and polyesters, including those, like W O96/13526 PCT~EP95/04193 .

polyacetones, which have a'recurring ester linkage in - the molecule, and those, like polyalkylene arylates, including polyalkylene terephthalates, having a structure formed by polycondensation of a dicarboxylic acid with a glycol. The blends may be made in the reactor or in a post compounding step.
The preferred process of the present invention caps di-initiated 1,3-butadiene polymers with alkoxy silyl capping agents having acetal protecting groups represented by the structure:
~ IL ~Q~Q

F~3 ICH3 CH3-CH2-O-C~-O-CH2-CH2-CH2-Si-Z (2) wherein Z is a phenoxy group or a trifluoroethoxy group. The alkoxy ~ilyl capping agents of equation (2) are prepared by hydrosilation of the appropriate dimethylsilane (Z-Si(CH3)2X) with the vinyl acetal resulting from the reaction of ethyl vinyl ether and allyl alcohol in the presence of an acid catalyst.
Hydrosilation was accomplished using a Pt catalyst, as is generally described by M. A. Peters and J. M.
D DeSimone (Polym. Prepr. (Am. Chem. Soc.Div. Polym.
Chem.), 1994,35(2), 484). After capping of the polymer,~
the protecting group is removed by reaction with methanesulfonic acid, as described in U.S. Patent No.
5,391,663.
The preferred process ultimately produces dihydroxylated, saturated 1,3-butadiene polymers having a peak molecular weight from 500 to 200,000, most preferably from 500 to 20,000. The dihydroxylated polymers can be unsaturated with 1,2-addition from 5%
to 95% or hydrogenated with 1,2-addition from 30% to 70%. The polymers preferably have from 1.75 to 2.0, ~MENDE!)SHEE~

WO96/13526 PCT~5/04193 most preferably from 1.95 to 2.0, terminal hydroxyl groups per molecule.
The preferred process initially makes a novel intermediate polymer which has a protected acetal functional group on each end of a linear 1,3-butadiene polymer. The intermediate polymer can be sold in a saturated or unsaturated version for making adhesives, sealants, and coatings wherein either the supplier or the customer deprotects the functional groups by a reaction that converts the protected functional groups to hydroxyl groups. L~ P~ ~7 The preferred process comprises di-initiation with the diadduct of s-butyllithium and m-diOisopropenyl-benzene, polymerisation of 1,3-butadiene, and capping with an .acidic alkoxy ~ilyl acetal having structure (2). The reaction results in exclusion of lithium alkoxide and the silyl acetal protecting group replaces the lithium at both ends of the living anionic polymer molecule.
The intermediate polymers of the present.invention are useful for making adhesives (including pressure sensitive adhesives, contact adhesives, laminating adhesives and assembly adhesives), sealants (such as J urethane architectural sealants, etc.), coatings (such as topcoats for automotive, epo~-primers for metal, polyester coil coatings, alkyd maintenance coatings, etc.), films (such as those requiring heat and solvent resistance), molded and extruded thermoplastic and thermoset parts (for example thermoplastic injection molded polyurethane rollers or reaction injection molded thermoset auto bumper, facie, étc.).
The present invention is further described by the following examples which include the best mode known to Applicant for making a saturated, linear polybutadiene polymer having one or two terminal silyl acetal groups.
The examples are not intended to limit the present Al~1ENDED ~HEET

W O96/13526 PCT~EPgS/04193 ~ c~d~ ~
The examples are not intended to limit the present invention to specific embodiments.
Examples The peak molecular weights were measured using gel permeation chromatography (GPC) calibrated with polybutadiene standards having known peak molecular weights. The solvent for the GPC analyses was tetrahydrofuran.
The 1,2-additions of polybutadiene were measured by 13C NMR in chloroform solution.
Three protected-functional capping agents, ethyl(dimethylethoxysilylpropyl) formaldehyde acetal (CAl), ethyl(dimethylphenoxysilylpropyl) formaldehyde acetal (CA2), and ethyl(dimethyl-3,3,3-trifluoroethoxy-~
silylpropyl) formaldehyde acetal (CA3), were preparedby hydrosilation of the appropriate dimethylsilane (dimethylethoxysilane, dimethylphenoxysilane, and dimethyl-3,3,3-trifluoroethoxysilane, respectively) as described previously. Reaction conditions are summarized in Table 1 for these agents.
Example 1 Poly(butadiene) "mono-ols" were prepared by initiation with s-butyllithium while poly(butadiene) "diols" were prepared by initiation with the product of diisopropenyl benzene and 2 equ-i~alents of s-butyl-lithium. Unless otherwise specified, polymer examples 1-1 through 3-2 were prepared in cyclohexane/diethyl ether(10%) and methanol was added to terminate any uncapped ch~; nS . For the alkoxy~silyl acetal capping agents of structure (2) (i.e. CAl, CA2, and CA3), the characteristic yellow color of the polymer anion faded considerably after adding the capping agent. Samples were deprotected using methanesulfonic acid, dried (rotary evaporator), and analyzed by GPC, 13C NMR, and HPLC. Samples taken prior to deprotection were contacted with concentrated phosphoric acid to remove La~ ~47 ~ ENDED ~HEET

CA 02203660 l997-04-24 W O 96/13526 PCT~EP95/04193 ~ p ~ - '2 -or neutralize lithium salts prior to drying; except in one case, described below, this did not result in significant hydrolysis of the acetal groups.
To simplify the analysis, screening studies were carried out using "mono-initiated" polymers although di-initiated polymers are preferred. The results are summarized in Table 2. HPLC could not unambiguously resolve acetal-capped polymer from proton-terminated polymer, so only NMR data was used to assess the io capping efficiency prior to deprotection. The results of the analysis of the deprotected products are also summarized in Table 2; 13C NMR results are consistent with quantitative hydrolysis of the acetal group. The more acidic alkoxy ~ apping agents were much more ~ p ~e~
reactive than the ethoxy analog, yielding capping efficiencies on the order of 90% without adding THF or any other reaction promoter.
GPC analysis indicated that a small fraction of the polymer anions were coupled (twice original MW). This may be due to oxygen coupling or the presence of a small amount of silane impurity with two "active"
ligands; the capping agents were added without further purification. These experiments also suggest that both capping agents react readily at moderate temperatures.
Analysis by NMR could detect no~ignificant improvement-in capping efficiency between samples capped for 30 minutes at 40C and samples taken after heating to 80C
and holding at 80C for an hour.
Example 2 In order to assess the utility of this approach for preparing diols, a diinitiated butadiene polymer (Example 2-1) was capped with the phenoxy silyl acetal compound (CA2) at 40C, and an aliquot of the same cement was reacted with excess ethylene oxide (Example 2-2). The analytical results are summarized in Table 3. The silyl acetal capped product remained a viscous ~`E~DF~H~ET

W O96/13526 PCTAEPg5/04193 G,~ p~ ~ - 13 -liquid while the ethylene oxide capped product formed a gel. After deprotection, the silyl acetal capped product was analyzed by HP~C as well as 13C NMR. The NMR results indicate slightly higher capping efficiency with the phenoxy silyl acetal than with ethylene oxide.
The HPLC chromatograms are consistent with this conclusion. The ethylene oxide capped product contains substantially more unfunctionalized and mono-functionalized material and less diol. A
substantial amount of material, tentatively identified as tri-ol (resulting form initiation by trifunctional lithium species), was also observed. The relatively high levels of both mono-ol and tri-ol in this polymerisation suggest that the optimum yield of diinitiator may not have been achieved, but it is clear that products comparable to those obtained by EO
capping were produced without the complications of the gel using the alkoxy~ ilyl approach. ~ p ~G~
~xam~le 3 A sample (3-1) prepared by capping a monoinitiated polymer with the phenoxy silyl acetal compound (CA2), followed by methanol termination was hydroge~ated tsing 300 ppm of a 2.5:1 Al:Ni catalyst, added in three 100 ppm aliquots over 3 hours. About 95.6% o' the ~_ vmer double bonds were hydrogenated~ sample c' ~ s cement was isolated without methanol additio~ (3-2).
Surprisingly, the acetal seems to have been hydrolyzed by the phosphoric acid neutralization; an unusually high level of suspended salts was also noted in the dry sample. On standing, a significant amount of precipitate, presumably lithium phenoxide, settled out of the solution. After decanting from the precipitate, the sample was hydrogenated as described above; the extent of hydrogenation achieved was quite low, only about 56%. The reason for the decreased yield is unclear, but it seems safe to conclude that it is A~END~r;~HE~

W O 96113526 PCT~Pg5/04193 p ~ - 14 -preferable to terminate with met~anol prior to - hydrogenation.
Table 1 Summary of Alkoxy ~ilyl Capping Reaction Conditions Sample Initiator CA# CA:Li Rxn Time Txn Temp 1-1 s-BuLi CAl 1.5:1 60 min.l 80 1-2 s-BuLi CA12 1.5:160 min. 1 80 1-3 s-BuL CA13 1.5:160 min. 1 80 1-4 - s-BuLi CA2 1.5:130 min. 40C
1-5 s-BuLi CA2 1.5:160 min.4 80C
1-6 s-BuLi CA3 1.5:130 min. 40C
1-7 s-BuLi CA3 1.5:1 , 60 min.4 80C
2-1 DiLi5 CA2 1.05:1 80 min. 40C
3-1,3-26 s-BuLi CA3 l:l60 min. 40C

1 CA added at 40C, then heated to 80C for 60 min.
2 100 ppm glyme added with CAl.
3 Tetrahydrofuran added until 5% by volume, prior to CAl.

4 Prepared by heating preceding 30 min/40C sa~.ple to 80C and holding for 60 min. ~

5 Product of 2 moles s-butylithium and 1 mole diisopropenyl benzene (DIPB).

6 Sample 3-2 was not terminated with methanol.

[ ~ r ~--WO96/13526 PCT~P95/04193 Table 2 Summary of Analytical Data for Mono-ols Prepared by Capping with CA1 and CA2 SampleMW Capping % hydro- % mono-(GPC) Effic'y carb(1) ol(1) (NMR) (NMR(2)/ (NMR(3) HPLC) HPLC) 1-1 2,000 65% 40/34 60/66 1-2 5,000 70% ---- ----1-3 4,800 83% 28/15 72/85 94% ____ 1-5 4,100(4) 99% 22/8 78/92 1-6 4,160(4) 89% ---- ----1-7 4,160(4) 90% 25/15 75/85 3-1 4,320(4) 80%205/1o(5,6) 80/go(5,6) 3-2 4,320(4) 79%21(5~7)/10(5)79(5,7)/90(5) (1) Unless otherwise specified, after deprotection.
(2) No acetal resonances detected by 13C NMR, consistent with quantitative hydrolysis of all capped chains.
(3) Lower value relative to HPLC and theoretical (complete conversion of capped chains) may be due to error in backing out the contribution of interefering resonances.
(4) 2%-3% polymer of twice this MW (coupled product).
(5) Hydrogenated sample.
(6) Sample deprotected during isolation; did not require treatment with MSA/IPA to effect deprotection.

(7) Capping efficiency prior to deprotection;
hydrogenation obscures s-bu resonance so that the s-bu:C-OH ratio cannot be determined.

.~

W O96/13526 PCT/~7~/0~l93 Table 3 Analytical Data for Diols Prepared by Capping with Phenoxy Silyl Acetal (CA2) or Ethylene Oxide (EO) Sam- Cap- MW NMR % % % %
ple ping (GPC) C.E.HC M-ol Diol Triol Agent (1)(HPLC) (HPLC) (HPLC) (HPLC) 2-1 CA2 4,700 96%0.5 18 50 31.5 2-2 EO 4,500 86~5 23.5 44.5 27 (1) MW of 4,400 prior to adding capping agent (MeOH
termin.).

Claims (10)

C L A I M S

1. A process for making functionalized polymers, comprising the steps of:
anionically polymerizing an unsaturated monomer with a mono-lithium or di-lithium initiator; and terminating the polymerizing step by addition of an alkoxy silyl compound having the structure:

wherein Y is a protected functional group which converts to more reactive terminal functionality, and Z
is an acidic alkoxy or phenoxy group, optionally followed by selective hydrogenation of any ethylenic unsaturation of the obtained compound.

2. A process of claim 1, wherein Y is an acetal group.

3. The process of claims 1-2, wherein the unsaturated monomer is 1,3 butadiene.

4. A process of claims 1-3, wherein as alkoxysilyl compound is added wherein Z is an acidic alkoxy group.

5. The process of claims 1-4, wherein the polymerizing step is initiated with a di-lithium initiator at a temperature from 20°C to 60°C.

6. The process of claims 1-5, wherein Z is a trifluoroethoxy group.

7. The process of claims 1-5 wherein Z is a phenoxy group.

8. The process of claims 1-7, further comprising the step of hydrogenating residual unsaturation in the functionalized polymer.

9. A functionalized polymer, comprising:
a saturated or unsaturated polymer of 1,3-butadiene or isoprene; and one or more terminal silyl acetal groups.

10. The polymer of claim 9, wherein the silyl acetal groups have the structure:

and the polymer is saturated.