CA1264392A

CA1264392A - Allyl terminated macromolecular monomers of polyethers

Info

Publication number: CA1264392A
Application number: CA000517080A
Authority: CA
Inventors: Simon H. Yu
Original assignee: BF Goodrich Corp
Current assignee: Goodrich Corp
Priority date: 1985-08-30
Filing date: 1986-08-28
Publication date: 1990-01-09
Also published as: EP0218079A2; US4722978A; EP0218079A3; JPS6259236A

Abstract

ABSTRACT OF THE DISCLOSURE
A cationic ring-opening polymerization of a cyclic ether ("CE") in conjunction with an unsaturated alcohol (propagator) having an allyl double bond, produces a polyether macromer having an allylic group near one end and a hydroxyl group at the other; and prior problems associated with the use of olefinic monomers to produce such macromers are avoided; the macromers may be employed to produce a variety of graft and comb copoly-mers including liquid polymers which are beneficial as dispersants in polymerizations by lowering the viscosity of the reaction mass; in particular the macromers may be quaternized to yield anti-statics, fiber softeners, excipients for drugs and biomimetic drugs; the cationic ring-opening polymerization proceeds by polyaddition of the CE to the OH group which is the propagating species; the CE is an alkylene oxide or an aliphatic or aromatic glycidyl ether; the propagator is a primary or secondary alcohol which, if cyclic may have a single internal double bond in one ring; the catalyst is a Friedel-Crafts acid, strong protic organic or inorganic acid, oxonium salt, or the like; the macromer formed may be homopolymerized to yield a polyvinyl homomacro-mer with pendant chains of polymerized CE; or the CE
may be copolymerized with a wide variety of olefini-cally unsaturated monomers to form a macromer copolymer;
or, plural cyclic ethers may be (a) sequentially poly-merized to form macromer block copolyethers, or, (b) polymerized randomly to form macromer copolyether co-polymers; the cationically ring-opened macromer formed always contains a trace of a cyclic oligomer of the CE.

Description

18SOO'-~G
12643~.~

ALLYL TERMINATED MACROMOLECULAR MONOMERS OF POLYETHERS

BACKGROUND OF THE INVENTION
This invention relates to macromolecular monomers ("macromers" for brevity) of polyethers having a vinyl functional "head" group at one end, through which the macromer is polymerizable with a copolymerizable mono-mer, and a terminal hydroxyl (OH) group at the other end. The polymerization of the macromer generates a polymacromer with a polyvinyl backbone having polyether t0 branches thus resulting in a graft or comb copolymer.
Such polymerization of the macromer of this invention, to form comb copolymers, differs from graft copolymer-ization in the sequence of formation of the backbone relative to the formation of the graft unit.
The macromer is formed by cationic ring-opening polymerization of a cyclic ether ("CE") in conjunction with an alkenyl alcohol which functions as the generator of the propagating species, and a suitable cationic ring-opening catalyst. The alkenyl alcohol (referred to as the "propagator" because it functions as the propaga-ting species (OH group) generator in the presence of a cationic initiator) may be substituted with substituents which do not interfere with the initiation, propagation and transfer reactions which generate the macromer in a polymerization which has the characteristics of a living polymerization. The macromer has substantially uniform molecular weight (mol wt) distribution such that the ratio of the weight average mol wt (Mw1 to the number average mol wt (Mn) is not substantially above about 3, preferably less than 2.
It is to be noted that the macromers of this inven-tion are formed by cationic ring-opening and not carbo-cationic polymerization, though both are classified as cationic polymerizations and often use the same cationic lZ6~39~

initiator. The cationic ring-opening involves the open-ing o~ strained rings of cyclic monomers and the propag-ating species is an oxonium, sulfonium or ammonium ion;
carbocationic polymerization involves substituted ole-finic monomers where the propagating species is a carb-enlum lon.
Numerous macromers of polytetrahydrofuran (polyTHF) have been synthesized by "living" cationic ring-opening polymerization involving an acrylic end group, inter alia, all by end-capping. But acrylic double bonds are ~uite different from allylic double bonds, and acrylic monomers are not cationically polymerizable (see Prin-ciples of Polymeriz~tion by G. Odian, Chap.3, Table 3.1, McGraw Hill, r~ew York 1970). Thus, hydroxyalkyl acryl-ates and methacrylates are unique chain transfer agentswhich are not cationically polymerizable (see U.S.Patent ~lo. Re. 31,468). There was no reason to expect that a monohydroxyl-terminated allyl propagator would remain intact under the conditions suitable for a cationic ring-opening polymerization.
To avoid the side reactions which interfere with the use of olefinic monomers, U.S. Patent No. 4,327,201 to Kennedy and Fritsch teaches the formation of a poly-(isobutylene) macromer with the use of vinyl benzyl halide and an allylic halide in conjunction with a variety of Lewis acid catalysts suited for cationic polymerization. In a later publication, Kennedy h Lo indicate concern over loss of a head group during syn-thesis, and found a specific catalyst which would avoid such loss. ~see "Macromers by Carbocationic Polymeriza-tion II. An Improved Synthesis of Polyisobutenylstyrene and its Copolymerization with Methyl ~ethacrylate and Styrene" Pol~vm.Reprint 23, No.2 Sep.'82).
Much effort has been directed to the preparation of various OE~-terminated difunctional and polyfunctional 12643~2 polyethers by cationic ring-opening polymerization of a CE in conjunction with water or an alcohol or a diol or a polyol as disclosed in U.S. Patents Nos. 3,129,232;
3,305,565; 3,850,856; 4,284,826; 4,077,991; 3,419,532;
3,4n2,169; 3,269,961; inter alia.
U.K. Patent Appln. No. 2,021,606A and U.S Patent No. 4,431,845 teach that OH-terminated poly(chloroalky-lene ethers) have not proven entirely satisfactory when prepared by cationic ring-opening polymerization as disclosed in U.S. Patents Nos. 3,850,856; 3,910,878;
3,3910,879; and, 3,980,579. Thus, the problems inherent in the use of prior art catalysts referred to in the foregoing U.S. patents have been documented. A solution to the problems was provided in the aforementioned U.S.
Patent No. 4,431,845. This solution was to use a cat-alyst comprising (i) a fluorinated acid catalyst having the formula HmXFn+m wherein X is selected from boron, phosphorus, arsenic and antimony, m is 0 or 1, and n is 3 when X is boron and n is 5 when X is phosphorus, arsenic and antimony, and, (ii) a polyvalent tin comp-ound.
This patent reference teaches that only tin fluoro-metallic compounds even among other Group IV metals, has a peculiar catalytic action not attributable to Group V
fluorometallic compounds. With this catalyst, it is suggested that any aliphatic OH-containing material such as a monomeric or polymeric mono- or polyhydric alkanol, haloalkanol or polymeric glycol having up to 6 OH
groups, whether terminal or pendant, may be used in the formation of a polymer with an alkylene oxide, provided at least about 50~ by weight (wt) of the alkylene oxide is a chloroalkylene oxide.
The reaction of a CE with an ethylenically unsaturated alcohol in the presence of a cationic catalyst is disclosed in U.S. Patents Nos. 3,627,022 and ~Z64~Z

3,419,621 to yield a monoadduct, the addition of a single cyclic ether (oxirane) unit to the alcohol.
U.S. Patent No. 4,485,211 to Okamoto discloses the use of a hydroxyl-containing material (HCM) having a single OH propagating site to form block copolymers of polyethers. The HCM may be an alkylene glycol such as ethylene glycol, or a prepolymer with plural OH propaga-ting sites, such as poly(glycidyl ether) with 2 sites.
U.S. Patent No. 4,451,618 to Okamoto discloses the use of a hydroxyl~terminated prepolymer (HTP) with one or more OH end groups which also yield polyether block copolymers. With the e~phasis on the essentiality of the OH propagat;ng sites and the routine use of sat-urated end groups, the possibility that a vinyl group, and more specifically, an allylic end group might sur-vive the conditions of cationic ring-opening polymeriza-tion simply escaped notice. In view of the large number of olefinically unsaturated monomers which undergo poly-merization (see the list in Carbocationic Polymerization by Kennedy, J.P. and Marechal, E., Table 3.6, pp 37 et seq., John Wiley & Sons 1982) the fate of the double bond of the propagator seemed speculative.
SUMMARY OF THE INVENTION
It has unexpectedly been found that, under partic-ular conditions, a cationic ring-opening polymerization of a cyclic ether ("CE" ) in conjunction with an ethyl-enically ("allylically") unsaturated alcohol and a cat-ionic ring-opening catalyst, produces a polyether macro-mer having an allylic group near one end and a hydroxyl 30 (OH) group at the other. An allylic group is one which is characterized by having adjacent, optionally substit-uted, carbon atoms neither of which has bonds to an oxygen atom. The allylic group of the alcohol does not undergo carbocationic polymerization under the acidic conditions required for the cationic ring-opening poly-merization of -the CE used. The polymerization proceeds by polyaddition of the CE to the OH group which is the propaga-ting species.
Th:is invention seeks to provide a process for the manufacture of a polyether macromer having an allylic group at or near one end and a hydroxyl group at the other, comprising, polymerizing (A) a ca-tionically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure 1 ~ \ 2 R -CH-(CH2)X- C - R (I) wherein, x is an integer in the range from 0 to about 4, except that when x>l, a second alkylene oxide having x=l or 0 must be present, and, Rl, R2 and R3 are independently selected from the group consisting of hydroven, Cl-C20 alkyl (having from 1 to about 20 carbon atoms) and Cl-C20 haloalkyl, C~-C20 aryl and C7-C20 aralkyl, and, at least one of R , R and R is hydrogen; and (ii) an aliphatic or aromatic glycidyl ether hav-ing the structure Rl-CH - CH -CH2-o-R4 (II) wherein Rl has the same connotation as hereinabove;
and, R4 represents a member selected from the group consisting of a substituted group such as a hydrocarbon group, i.e., Cl-C20 alkyl or substituted alkyl, parti-cularly Cl-C20 haloalkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkoxyalkyl~
C6-C20 aryl (Ar) or substituted C6-C20 aryl (Ar-Q), particularly wherein Q represents Cl-C10 alkyl, lZ6439Z

5a 1 10 Y ~ 2 20 Y 2 20 alkenyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of (i) R5~
C = C -G - OH (III) R6~ C7 and, (ii) ~ G - OH (IV) wherein, G is a valency bond or a spacer selected from the group consisting of branched or linear Cl-C20 alkyl, C7-C20 aralkyl, Cl-C20 haloalkyl, C7-C20 halo-aralkyl, Cl-C20 alkoxy and C7-C20 aralkoxy; and, R5, R and R7 are independently selected from the group consisting of hydrogen, Cl-C20 alkyl (having from 1 to abou-t 20 carbon atoms) and Cl-C20 haloalkyl, C6-C20 aryl and C7-C20 aralkyl; in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel-Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions;

.~ , lZ64392 so as to produce a macromer having the structure R--(M)m--Oil ~V) wherein R represen-ts the residue of said monoolefinic-ally unsaturated alcohol, M rcprcC;ellts the res:iduc .,r at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500, more preferably from 2 to about 100.
It has further been found that a macromer block copolyether may be prepared by polymerizing plural cyclic ethers sequentially, or by using a macromer of this invention as a propagator, so as to have the structure R-(M') -(M") ,-OH (VI) wherein M' and M" represent two ring-opened cyclic 'lB' 126~z ethers, and, m' and m" are integers each in the range from 1 to about 300 such that m' + m" = m.
It has also been found that a macromer random copolymer may be prepared by polymerizing a polyether macromer V or VI with an olefinically unsaturated mono-mer so as to have the structures [R-(M)m-OH]n,[Mo]nll (VIIa) and, [R-(M')ml-(M )ml~-OH]n~[Mo]n~ (VIIb) wherein Mo represents the olefinically unsaturated mono-mer;
n' represents an integer in the range from 1 to about 104,preferably 1 - 103 and refers to the number of pendant OH-terminated polyether chains;
n" represents an integer in the range from 1 to about 105, more preferably 1 - 104; and, R, M, M', M", m, m' and m" have the same connota-tion as before.
It is a specific object of this invention to prov-ide an essentially linear polyether macromer having allylic and OH chain ends, and substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 3.0, and preferably less than 2Ø
It is another specific object of this invention to provide polyurethanes by cross-linking with the terminal OH groups on pendant polyether chains; such pendant chains are present when V or VI are polymerized to yield a polymer (VIIa, b) with a polyvinyl backbone.
It is also a specific object of this invention to provide a macromer with a ring-openable olefinically internally unsaturated alcohol such as 5-norbornene-2-methanol as the propagator so that the ring is the head group for a macromer formed with any first monomer "'':

:, i2643~z identified hereinabove, and thereafter, by metathesis polymerization, polymerizing the macromer with a suit-able ring-openable cyclic olefin (second monomer) to form a copolymer with pendant chains of the first mono-mer. The second monomer preferably has not more thanone double bond~ and not more than one double bond in each ring, such as cyclopentene, dicyclopentadiene, dihydrocyclopentadiene, norbornene (Ns), and-substituted NBs.
Still other specific objects of this invention are to provide (a) a poly(haloepoxide) macromer which may be quaternized to yield antistats, fiber softeners, excip-ients for drugs and biomimetic agents; and, (b) poly-(siloxane-ether) block copolymer surfactants and foam stabilizers.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The cationic ring-opening polymerization disclosed herein occurs because of the specific acid catalysts used with the monoolefinically unsaturated alcohol used to function as a chain propagator for the ring-openable cyclic ether ("CE"). This reaction was not expected to produce the macromer of this invention because it was not realized that the allyl bond of the alcohol would not interfere with the CE to be ring-opened by the catalyst. Macromers of this invention have a Mn in the range from about 200 to about 3000 though even higher mol wts up to about 10,000 may be formed, if desired.
The term "macromer" is used herein to denote at least one of the above-specified ring-opened CE with an "allylic", that is, ethylenically unsaturated as de-fined, head group. If the macromer is formed from a single CE it is referred to as a "homomacromer"; if from more than one comonomer which appears randomly, it is referred to as a "macromer copolymer"; and, if a copoly-mer is specifically formed by sequential copolymeriza-~Z6439Z

tion, it is referred to as a "macromer block copolyether".
To facilitate ~his ring-opening polymerization with living characteristics so that the allylic head group survives the reaction without forming an excessive amount of cyclic oligomers and other undesired byprod-ucts so as to make the reaction uneconomical, it is essential that one use (i) a catalytic amount of a catalyst (initiator) which, though not narrowly crit-ical, is preferably boron trifluoride (BF3) or tin tetrachloride (SnCl4); or borontrifluoride etherate complexes; or, a fluorinated metallic acid catalyst having the formula HMF6 wherein M is selected from P, As or Sb; or, an oxonium salt of the acid; or, oxonium salts of tetrafluoroboron or antimony hexafluoride; and, (ii) an "allylic" alcohol with structure (III) or (IV) which is at least partially soluble, and more preferab-ly, is completely soluble in the reaction mass, with or without a solvent.
If the CE and the alcohol are not mutually soluble, or soluble in a mutual co-solvent, the polymerization will not proceed satisfactorily. The higher the solub-ility, generally the better the polymerization reaction.
The reaction is most preferably carried out in a bulk polymerization in a simple and convenient manner.
Typically, the CE (I) or (II) and the alcohol (III) or (IV), each of which is moisture-free, are charged to a jacketed glass-lined reactor provided with a mech-anical agitator and fitted with a thermoprobe and cond-enser. The reactor is purged with nitrogen and warmed to the polymerization temperature. The catalyst, for example, triethyloxonium hexafluorophosphate (TEOP) dis-solved in methylene chloride is dripped in and the temperatu~re of the reaction mass is controlled to prov-ide a satisfactory rate of polymerization by raising or lowering the temperature of the circulating medium in r .

126~

the jacket.
The polymerization is generally carried out at a temperature in the range from about 25-50C but this range is not critical, some polymerizations proceeding satisfactorily at as low as 0C, or lower, and others at as high as 90C, or higher. The progress of the reaction is monitored by measuring total solids. Upon completion, the polymerization is terminated with aqueous sodium bicarbonate solution, and an antioxidant such as GoodriteR3114 is added, and the temperature of the mixture raised to about 60C and maintained for about an hour. The liquid macromer is separated from the aqueous phase and washed with distilled water at room temperature. Unreacted monomer, if any, may be removed by distillation under vacuum.
The conversion to the macromer and its mol wt are controlled by the ratio of the monomer to the alcohol, according to the following equation:
Monomer, g Mn= [ + l] x mol wt of alcohol x % total solids Alcohol, g About 0.1-0.5g of TEOP is used per kg of monomer when allyl alcohol is the alcohol used. The amount of sodium bicarbonate used as a short-stop is about three times the amount of TEOP. The amount of antioxidant added is about 0.2% by wt of the macromer. It is essential that all reactants be moisture-free because each molecule of water, if present, will initiate a polymer terminated with OH groups at both ends of the chain.
The macromer is characterized by gel permeation chromatography (GPC) analysis at 40 C using a Water's 200 with columns packed with Styraqel. THF is used as carrier solvent. All mol wts are calibrated relative to polystyrene. Cyclic oligomers, if present, and they usually are in a small amount in the range from a trace, ~6g392 that is about 10 ppm to about 10% by wt or more, are excluded from the calculation of mol wts. The presence of cyclic oligomers provides a "fingerprint" of a macro-mer formed by cationic ring-opening; a macromer of iden-tical structure, if prepared by anionic polymerizationwill be free of cyclic oligomers. Examples of macromers of polyethers prepared by anionic polymerizations are found in Japan 70 28,786 (Chem.Absts. 74, 14138r (1971);
Japapn 74, 15,480; and U.S.Patent No. 3,875,202.
FT infrared spectra were recorded with a Nicolet 7199 spectrometer. Samples were prepared by applying a thin coat of macromer on a KBr crystal.
Carbon-13 NMR spectra were obtained at 20.1 MHz using a Bruker WP-80 spectrometer. Macromers were exam-ined as a 20 wt% solution in benzene-d or chloroform-d with internal tetramethylsilane reference at 30 C.
Proton NMR spectra were obtained at 200.13 MHz in chloroform-d at 30 C using a Bruker WH-200 spectrometer.
Trichloroacetylisocyanate was used as a derivatizing agent for the OH group analysis.
Mass spectra were obtained with a Varian MAT 311A
mass spectrometer in the field desorption mode. Samples were dissolved in either methanol or THF. The solution was then saturated with solid LiBr so that the lithiated molecular ions [MLi] were produced during analysis.
Glass transition temperature (T ) is determined by a Perkin-Elmer DSC-2 differential scanning calorimeter at a 40 C/min heating rate under helium.
Hydroxyl number (OH No.) was determined by acetyl-- 30 ation with an acetyl anhydride-pyridine mixture accord-ing to a standard procedure and the end point is deter-mined by automatic titration. The OH No. is defined as the milligram equivalent of KOH per gram of the macro-mer, where a mole of KOH is equivalent to one mole of OH
group.

, .

-~264392 Iodine number was determined based on the addition of iodine monochloride to the olefinic double bond. The excess iodine monochloride was then determined by titra-tion with thiosulfate. I No. is defined as the grams of I absorbed per lO0 g of macromer.
The halogen, for example, chlorine content is measured by a modified Shoniger method and used to calculate the number of epichlorohydrin ("ECH") units in the macromer.
Among the alkylene oxides having structure (I) which may be used are (i) 1,2-epoxides such as ethylene oxide, propylene oxide, cis- and trans- but preferably cis-butene-2-oxide, cis- and trans-pentene-2-oxide, cis- and trans-hexene-2-oxide, cis- and trans-hexene-3-oxide, and the like; (ii) 1,3-epoxides such as oxetane;
and (ii) haloalkyl epoxides (epihalohydrinsj such as l-chloro-2,3,epoxypropane (ECH), l-bromo-2,3-expoxy-propane (epibromodydrin), l-chloro-2,3-epoxybutane, 1-iodo-2,3-epoxyhexane, 3-chloro-4,5-epoxyoctane, 1-chloro-2,3-epoxycyclohexane, l-bromo-2,3-epoxymethyl-butane, 2-chloro-2-methyl-3,4-epoxypentane, and the like.
1,4-epoxides such as tetrahydrofuran ("THF"), 1,5-epoxides such as tetrahydropyran ("THP"), and 1,6-epox-ides such as oxepane ("OXP") do not form homomacromers with allylic head groups. THP does not even form co-polymers with 1,2-or 1,3-epoxides, but THF and OXP do.
The copolymers of THF or OXP with 1,2- or 1,3-epoxides are random.
Among the aliphatic or aromatic glycidyl ethers having structure (II) which may be used, are methyl glycidyl ether, ethyl glycidyl ether, methylethyl glyci-dyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and the like.
Among the monoolefinically unsaturated acyclic ~' ., ,, , ~

126~39z "allylic" alcohols having the structure (III) which may be used, are relatively short chain alcohols having from 3 to about 6 carbon atoms such as allyl alcohol, 2-methyl-2-propene-1-ol (2-methallyl alcohol), 2-buten-1-ol ~crotyl alcohol), 1-buten-3-ol (l-methallyl alcohol), 3-buten-1-ol, 4-penten-1-ol, 2-pentene-1-ol, 3-penten-2-ol, 4-penten-2-ol, 2-methyl-1-buten-3-ol, 2-methyl-1-buten-4-ol, 3-methyl-2-buten-1-ol, 2-ethyl-1-propen-3-ol, 2-ethyl-1-penten-3-ol, 5-hexen-1-ol, 4-hexen-1-ol, 5-hexene-1-ol, 2-methyl-1-penten-3-ol, 2-methyl-4-pent-en-3-ol, 4-methyl-3-penten-1-ol, and the like; rela-tively long chain alcohols having from 7 to about 20 carbon atoms such as 9-decen-1-ol, 10-undecen-1-ol (10-undecylenyl alcohol), and naturally occurring citronel-lol or oleyl alcohol; arylalcohols in which the OH groupis on the sidechain such as cinnamyl alcohol, and those in which the OH group is a phenolic OH group such as 2-allyl phenol; and, monoadducts of a single CE unit to the above mentioned "allylic" alcohols, such as 2-hyd-roxyethyl allyl ether, 2-hydroxy-1-methylethyl allyl ether, 2-hydroxy-2-methylethyl allyl ether, 4-hydroxy-butyl allyl ether, diethylene glycol monoallyl ether, 2-hydroxy-2-chloromethyl ethyl allyl ether, and the like.
Among the allylic cyclic alcohols having the struc-ture (IV) which may be used are those in which theolefinic bond is in the ring which may be a single or fused ring structure having from 5 to 10 carbon atoms, such as for example, 2-cyclohexene-1-ol, 3-cyclohexen-1-methanol, 6,6-dimethyl bicyclo[3.3.1]hept-2-ene-2-ethanol[(lS)-(-)-Nopol], 5-norbornene-2-methanol, and bicyclo(2.2.2)oct-5-ene-2-methanol.
In the more preferred embodiments of this invention the macromer is formed with a head group derived from any desired "allylic" alcohol and an oligomer which may be (i) a homopolymer of a 1,2-epoxide, or 1,3-epoxide; or (ii) a copolymer of a 1,2-epoxide and/or 1,3-epoxide (OXT) and/or 1,4-epoxide (THF) and/or 1,6-epoxide (OXP);
or (iii) a homopolymer of a glycidyl ether (II); or (iv) a copolymer of (II) and a 1,2-, 1,3-, 1,4- or 1,6-epoxide. Random copolymers are formed by simply mixingthe monomers, while block copolymers are formed by the sequential addition of the monomers.
The macromer is formed by the action of a cationic ring-opening catalyst identified hereinabove with the "allylic" alcohol (III) or (IV) and the alkylene oxide (I) or (II), under mild reaction conditions, namely a temperature in the range from about 0 C to about 150 C, and more preferably from about 25-80 C, at ambient or slightly elevated pressure.
The catalyst is used in an amount sufficient to initiate the polymerization. It is most prefered to use a cyclic or acyclic oxonium salt which may be primary, secondary or tertiary. The cyclic oxonium salt may be prepared by reaction of an acyclic oxonium salt with THF. It is most preferred to use a trialkyloxonium or other oxonium salt of the HMF6 acid prepared as described in U.S.Patent No. 3,585,227. The amount of catalyst used is not critical, from about 0.001 part to about 1 part per 100 parts by wt of oxirane reactants, and more preferably from about 0.01 to about 0.1 part, being generally sufficient. It is desirable, both for economic reasons and for control of the reaction, to keep the amount of catalyst used as low as possible.
The amount of catalyst used has very little effect on the mol wt of the macromer formed, but affects the rate, which in turn affects the temperature of the reaction. Most polymerizations proceed satisfactorily with about 0.05 parts of catalyst per 100 parts of CE.
The mol wt is controlled by the ratio of alkylene oxide or glycidyl ether to allylic alcohol. Because the poly-lZ6439Z

merization proceeds via polyaddition a designed (desir-ed) mol wt may be obtained. If the mol wt of a macromer is kept relatively low by including from about 2 to about 8 repeating units, the linear macromer is formed substantially free of cyclic oligomers, but at least a trace of cyclic oligomers is always found in practice.
Most preferred linear macromers have a Mn in the range from about 200 to about 3000.
A homomacromer of polyepichlorohydrin (PECH) with an allylic head group is conveniently prepared using allyl-ic alcohol and ECH and conducting the polymerization reaction in bulk at about 30 C. Infrared, nmr and FD
mass spectroscopy, GPC, liquid chromatography (LC), and chemical analyses for chlorine and OH number confirmed lS the structure of the macromer as being representedby CH2=CHCH2-(OCH2CH) -OH (VIII) CH Cl wherein n is in the range from 2 to about 100.
As is well known, reactive liquid polymers ( RLPs) referred to hereinbelow, are used as tougheners for unsaturated polyester resin systems because they co-cure with the polyester in addition to contributing to the ease with which it can be handled; the macromers of this invention are used in an analogous manner, as tough-eners, to provide further options for tailoring the properties of the system. The macromers are also used as a base for the formulation of perfumes.
The homomacromer (VIII) and other macromers having the general structure (V) are particularly useful as non-aqueous dispersants for sterically stabilized disper-sion polymerizations because the terminally unsaturatedhead group serves to anchor the dispersant by copolymer-ization with the monomer (for example, acrylic acid) which is to be polymerized. In such polymerizations, zhortly zfter initiation of polymerizatio~, polymer ~., ~, ., 16 lZ6439z begins to precipitate from the solution and forms aggre-gates which interfere with the reaction by retarding access of monomer to free radicals. This contributes to poor removal of heat and several related problems. The macromer interferes with formation of the aggregates and the viscosity of the reaction mass is substantially reduced. The effectiveness of the macromer (VIII) as a dispersant in a dispersion polymerization of acrylic acid in benzene is illustrated in Example 20 herein-below.
Macromers of this invention may be homopolymerized by conventional methods such as by free radical polymer-ization effected with a lower alkyl peroxide and the like, so as to form a polyvinyl polymer with pendant polyether chains; and, they are also used as comonomers in a variety of polymerization reactions with conven-tional vinyl, acrylic, or diene monomer in which the allylic head group is copolymerizable.
For example, the monomer (I) is copolymerizable with (a) a C2-C12 vinyl monomer such as vinyl chloride, vinyl acetate, acrylonitrile, ethylene, propylene, 4-vinylpyridine, vinylpyrrolidone, styrene, 4-chlorosty-ene, and the like; (b) a C -C monomer such as an unsaturated carboxylic acid or its ester, such as acry-lic acid! methacrylic acid, acrylic amide, butyl acryl-ate, ethyl acrylate, 2-ethylhexyl acrylate, and the like, (a) and (b) each being free radical polymerizable;
(c) a C -C acyclic or cyclic alkadiene monomer such as butadiene, isoprene, cyclopentadiene, or dicyclopenta-, and (d) a C5-C20 cycloalkene like cyclopentene cycloheptene, bicyclo(2.2.1)-hept-2-ene, namely NB, which may have acyclic or cyclic (spiro) substituents such as alkyl NB, cycloalkyl NB, phenyl NB, and the like.
When the macromer (VIII) is copolymerized with ethyl acrylate the random copolymer is represented by 17 ~;~6~392 the structure ~C~I CH ) --~CH CHt-- ( IX) 21 n" 21 n' COC H CH ~OCH CH~OH

2 5 2 21 n When macromer (VIII) is copolymerized with styrene the random copolymer is represented by the structure -~CH Cllt - -~CH CH~- (X) 2~ n" 21 n' ~ CH -(OCH CHt--OH

S By varying the ratio of conventional vinyl, acrylic, or diene to ECH monomer, and the number of ECH
units in the macromer, each of the copolymers may be obtained with a wide range of properties ranging from hard plastic to soft elastomeric.
The macromer is also copolymerizable with reactive liquid polymers (RLPs) such as those having the structure Y O
H C-C-X-C-O-(G')-OH (RLPl) wherein Y is H or alkyl, X is zero, alkylene or arylene, and G' is a polymeric backbone comprising units of at least one epihalohydrin, optionally together with at least one other epoxide; or, the structure Y O
H C=C-C-O(CH ~- O-(G')-O(CH ) OH (RLP2) wherein x' and x" are each in the range from 2 to l0, and, Y and G' have the same connotation as that given hereinbove. Preparation of the RLPs is set forth in detail in U.S. patents Re. 31,469 and 3l,468 respective-1~ .

When the macromer (VIII) is copolymerized with the RLPl the copolymer is represented by the structure (CH -CY ) (CH2-ClH-t--, (XI) X-C-O-(G')-OH CH-~OCH CIHt--OH
CH2Cl lZ64~}~Z

with the ~ackbone terminated conventionally.
In an analogous manner macromer (VIII) may be co-polymerized with RLP2 to yield a macromer copolymer having the structure ~CH -CY ) - - (CH -CH ) (XII) 2 I n" 2 t n' ~-0(CH2t--,O-(G') 2 2I n 2 x CH2Cl and by varying the ratio of vinyl or acrylic monomer units to the number of PECH units, each of the copoly-mers may be obtained with a wide range of properties ranging from from hard plastic to soft elastomeric.
t0 Such macromer copolymers are formed by conventional methods, for example, the aforementioned free radical polymerization process. These macromer copolymers with a profusion of pendant OH groups connected to a poly-vinyl backbone, are useful in the production of tailored polyurethanes by reaction with organic isocyanates.
Where only two homomacromers or macromer block copolyethers are connected by a diisocyanate so as to have terminal allylic groups, the urethane macromer may be used for crosslinking a wide variety of olefinically unsaturated monomers. Quite unexpectedly, the macromer of this invention behaves in a manner analogous to one with an acrylic head group as disclosed in U.S.Patents Nos. 3,850,770; 3,960,572; 4,367,302; and 4,377,679.

After the macromer (VIII) is quaternized (aminated), it is particularly useful in the preparation of quater-nized oligomers for water treatment and other applica-tions such as antistats and dispersants. Amination of the chloromethyl groups in PECH with a wide variety of aliphatic and aromatic amines is known to produce the corresponding ammonium salt which provides cationic charges and imparts hydrophilicity to the polymer.
~' .

lg 1264392 Thus, the normally hydrophobic PECH oligomer is convert-ed to a hydrophilic polymer, but a polymer with both hydrophilic and hydrophobic characteristics is difficult to obtain. The ability to control these properties allows one to 'fabricate' water-treatment chemicals.
The aminated macromer has the structure CH =CHCH - ( OCH CH ) -OH ( XI I I ) 2 2 2t n+ 8 CH N R .X' wherein X' represents a halogen, n is an integer in the range from 2 to 100, and R represents the residue of an amine used to aminate the macromer.
Because high mol wt quaternized polymers are most preferred for water treatment, and such polymers are aminated only with difficulty, it is particularly con-lS venient to prepare the macromer in a mol wt which issufficently high to be easily and essentially complete-ly aminated, then homopolymerize the macromer (XIII) to produce a polyvinyl polymer with a profusion of substan-tially fully aminated pendant chains. Such polymers 20 having a Mw in the range from about 100,000 to about 200,000 are effective coagulants, and those in the range from about 500,000 to about 1,000,000 are effective flocculants. It is well known that commercially avail-able Hydrin and Herchlor PECH elastomers in such de-25 sirably high mol wt ranges are aminated with difficulty,and then only to an unsatisfactory extent.
The macromer (VIII) in which the OH group is end-capped with an end-capping unit, for example, acrylo-nitrile, may be block-polymerized with a silyl hydride-30 terminated polysiloxane to provide an especially effect-ive superwetting agent. The end-capping group is not critical and a variety of esterification and etherifica-tion reactions can be used to cap the terminal OH
groups, as for example disclosed in U.S.Patents Nos.

2 o 1Z643~2 2,998,409 and 33,507,927; British Patents Nos. 748,856;
848,660; 869,323; 877,256i 911,959; inter alia; or, by reacting with an alkylisocyanate as in sritish 924,259;
or, by reacting with diaæomethane as in sritish 894,439.
The end-capped macromer is represented by CH =CHCH -(OCH CH) -O-Z (XIV) 2 2 2I n CH2Cl wherein Z is the residue of an end-capping unit.
In the particular instance when the end-capping unit is an acrylonitrile residue, the structure of the end-capped homomacromer is represented by CH =CHCH -(OCH2CIH) -O-CH2CH2CN (XV) CH2Cl The organohydrosiloxane reactant may be a mono-, di-, or polyhydrosiloxane containing more than two Si-bonded H atoms, wherein any valences of Si not bonded to H or to O in a Si to O to Si bond are bonded to a monovalent hydrocarbon or halaohydrocarbon group, such as those disclosed in greater detail in U.S.Patent No.
4,150,048 to Schilling et al.

Particularly preferred organohydrosiloxanes 20 have a Si-bonded H at each end as shown by the formula HR" SiO[R" SiO] SiR" H (XVI) 2 2 z 2 in which R" is an unsubstituted or halogen-substituted monovalent hydrocarbon group and z is an integer in the range from 0 to about 300, more preferably 5 to 50.
The block copolymer is formed under addition reac-tion conditions, preferabaly at elevated temperature from about 50-100 C in the presence of a non-reactive solvent, and catalyzed by a neutral Pt-containing hydro-silation catalyst such as that described in U.S.Patent No. 3,220,972, or Pt metal deposited on charcoal, used 30 in concentrations disclosed in U.S.Patent No. 3,507,815, namely from 0.001 to about 5 % by wt of the reactants.

~1 The macromer block copolymer formed may be repres-ented by the formula A'A"2 (XVII) wherein A' represents the residue of a polysiloxane block (XVI) and A" represents the residue of a polyether block of end-capped macromer (XV) after it has been aminated.
. Examples 1-4 In the following 4 illustrative examples the macro-mer (VIII) was made as described hereinbefore, in a nitrogen atmosphere, with moisture-free reactants charg-ed to a glass-lined reactor, and TEOP catalyst in CH Cl is dripped into the reactor. The amount of catalyst is varied in Exs. 1 and 2, all other reaction conditions being kept the same; in Exs. 3 and 4 the ratio of ECH to allyl alcohol (AA) is varied to obtain a targeted mol wt Mn. The polymerization temperature was controlled at 30-35 C with an ice-bath and overnight reactions were carried out at room temperature (20 C).
TABLE I
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Targeted Mn 550 550 1000 2000 ECH, wt., kg 1.0 1.0 0.496 0.340 moles 10.8 10.8 5.4 3.7 AA, wt., kg 0.125 0.125 0.029 0.0097 moles 2.2 2.2 0.50 0.17 Ratio ECH/AA, mole 5.0 5.0 10.7 22.
wt. 8.0 8.0 17.1 35.1 TEOP, wt., g 0.6 0.9 0.25 0.20 wt.% 0.053 0.080 0.048 0.057 30 Time of rxn, hr 24 24 S 24 Conversion, ~ 97 100 >97 98 The resulting macromer from each of the 4 runs set forth as Exs. 1-4 in the Table I hereinabove was analyz-ecl. The results are set orth in Table II hereinbelow:

J1264;3~Z

TABLE II
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Mn from GPC 615 614 977 1830 from OH No. 559 534 1025 2200 from I No. 554 558 llO0 ---from stoich 505 510 1040 2010 GPC Mw 792 797 1528 3330 Ratio Mw/Mn 1.29 1.30 1.6 1.8 OH No. titration 100. 105. 54. 25.
Iodine No. 45.8 45.5 23 ___ Visc.*, cps @ 25 775 846 10460 22000 T , by DSC, C -59 -57 -42 -39 %gcyclic oligomers <1 <1 <1 10 *viscosity herein, and in all following illustrative examples is Brookfield viscosity measured @ 25 C.
In the following examples 5-8 a homomacromer (V) wherein M is a repeating unit of a single CE, was made in an analogous manner by bulk polymerization of each of the following 1,2-epoxides: propylene oxide (PO), n-butyl glycidyl ether (BGE), dodecylene oxide (DO) andtrifluoroethyl glycidyl ether (TFEGE), respectively. In each case, allyl alcohol is used as the unsaturated alcohol which provides the OH group as the propagating species. The polymerization conditions are set forth in Table III herebelow. The targeted Mn is calculated on the basis of 90% total solids.
TABLE III
Ex. 5 Ex. 6 Ex. 7 Ex. 8 Monomer PO BGE DO TFEGE
wt., g 101. 537.55.2 35.
moles 1.74 4.12 0.30 0.22 AA, wt., g 12. 63.2.9 2.0 moles 0.21 1.08 0.05 0.03 TEOP, g 0.13 1.10 0.25 0.01 wt.% 0.12 0.18 0.43 0.03 126~

TABLE III (contd) Ex. 5Ex. 6 Ex. 7 Ex. 8 Targeted Mn 492 498 1047 967 Rxn temp. C, 30 35 35 30 5 Time of rxn, hr 4 2 6 8 6 Total solids, ~73 92 83 77 The resulting homomacromer from each of the 4 runs set forth as Exs. 5-8 in Table III hereinabove was analyzed. The results are set forth in Table IV
hereinbelow. All homomacromers are low viscosity li~uids having a Brookfield visc @ 25 C of <100 cps.
Each is insoluble in water but soluble in toluene, heptane and methanol.
TABLE IV
Ex. 5Ex. 6 Ex. 7 Ex. 8 Homomacromer of PO BGE DO TFEGE
Mn from GPC 639 521 1510 757 from OH No. 524 555 1508 657 from I No. 469 754 1204 907 Mw/Mn 1.43 1.41 1.41 3.29 T , by DSC, C -87. -93. -52. -70.
O~ No. 107 101 37 85 Iodine No. 54 34 21 28 % cyclic oligomers 5.6 <1 1.9 <1 In a manner generally analogous to that described hereinabove, a homomacromer of oxetane (Mn = 400) is prepared with allyl alcohol providing the OH group as the propagating species.
In the following illustrative examples 9-12, a macromer copolymer (V) wherein M represents a repeating unit of at least two randomly connected CEs M' and M , o is made by bulk polymerization of a mixture of the monomers under conditions analogous to those described hereinabove. Each of the copolymers includes ECH as a comonomer and any one of ethylene oxide (EO), propylene r 126~3~3z 2~

oxide (PO), tetrahydrofuran (THF) and oxepane (OXP); and the copolymers are identified as follows: (EO/ECH);
(PO/ECH); (THE/ECH); and, (OXP/ECH) in Exs. 9-13 respec-tively, the latter being oxirane comonomers. The condit-ions of polymerization are set forth in Table v herebelow.
TABLE V
Ex. 9 Ex. 10 Ex. 11 Ex. 12 Macromer co'mer EO/ECH PO/ECH THF/ECH OXP/ECH
Monomer EO PO THFOXP
wt., g 35. 35. 100.50.
moles 0.79 0.69 1.39 0.50 Comonomer ECH ECH ECHECH
wt., g 65. 64. 50.25.
moles 0.70 0.69 0.540.27 15 Comonomer/monomer 1.13 0.87 2.57 1.85 AA, wt., g 11.6 11.6 6.23.1 moles 0.2 0.2 0.110.05 TEOP, g 0.15 0.13 0.6 1.0 wt.% 0.13 0.12 0.38 1.28 20 Targeted Mn 503 498 13171317 Rxn temp. C, 0 30 20 35 Time of rxn, hr 7 30 7 72 Total solids, % 55 55 56 87 The resulting macromer copolymer from each of the 4 runs set forth as Exs. 9-12 in Table V hereinabove was analyzed. The results are set forth in Table VI herein-below.
TABLE VI
Ex. 9 Ex. 10 Ex. 11 Ex. 12 Macromer co'mer EO/ECH PO/ECH THF/ECH OXP/ECH
Mn from GPC 463 441 13401230 from OH No. 392 379 872722 from I No. 446 403 10041716 Mw/Mn 1.30 1.35 3.4 2.6 35 Brookfield visc. <100 <100 1200 2000 ~Z643~Z

TABLE VI (contd) Ex. 9 Ex. 10 Ex. 11 Ex. 12 Macromer co'mer EO/ECH PO/ECH THF/ECH OXP/ECH
T , by DSC, C -79. -83. -25. -78.
O~ No. 143 148 64 78 Iodine No. 57 63 25 15 % cyclic oligomers 3.4 <1 1.4 1.9 In the following illustrative examples 13-15, a macromer copolymer (V) wherein M represents a repeating unit of at least two randomly connected CEs M' and M , is made by bulk polymerization of a mixture of the monomers under conditions analogous to those described hereinabove. The following macromer copolymers of THF
and OXP with EO and PO, specifically identified as THF/EO, THF/PO and OXP/PO respectively are prepared under the specific conditions of polymerization which are set forth in the following Table VII.
TABLE VII
Ex. 13 Ex. 14 Ex. 15 Macromer co'mer THF/EO THF/PO OXP/PO
Monomer THF l'HF OXP
wt., g 28. 55. 50.
moles 0.39 0.77 0.50 Comonomer EO PO PO
wt., g 50. 44.6 43.5 moles 1.14 0.77 0.75 Comonomer/monomer 0.34 1.0 0.67 AA, wt., g 12. 6.5 4.35 moles 0.21 0.11 0.07 30 TEOP, g 1.5 0.9 1.1 Macromer co'mer THF/EO THF/PO OXP/PO
wt.% 1.67 0.85 1.12 Targeted Mn 392 856 1176 Rxn temp. C, 5 5 10 35 Time of rxn, hr 7 5 25 :;, 26 ~26439Z

TABLE VII (contd) Ex. 13 Ex. 14 Ex. 15 Macromer co'mer THF/EO THF/PO OXP/Po Total solids, % 69 76 51 The resulting macromer copolymer from each of the 3 runs set forth as Exs. 1-15 in Table VII hereinabove was analyzed. The results are set forth in Table VIII
hereinbelow.
TABLE VIII
Ex. 13 Ex. 14 Ex. 15 Macromer co'mer THF/EO THF/PO OXP/PO
Mn from GPC 705 1260 863 from OH No. 456 1029 526 from I No. 488 958 969 Mw/Mn 1.7 2.3 1.7 Brookfield visc. <100 140 120 T , by DSC, C -95. -91. --O~ No. 123 55 107 Iodine No. 52 27 26 20 % cyclic oligomers 96 6 In a manner analogous to that described herein-above,~the following macromer copolymers are prepared with allyl alcohol providing the head group and OH
; propagating species:
ECH/THF; ECH/OXP; ECH/n-BGE; ECH/THF/OXP; and ECH/OXP/n-BGE.
Homomacromers and macromer copolymers prepared as ~-~ illustrated in the foregoing examples show character--~ istic absorption at about 3450 cm (broad) assigned to ~;~ 30 the terminal hydroxyl group and at 1650 and 3080 cm to the C=C stretching of the terminal allyl group by FT
' infrared spectroscopic analysis. The terminal allyl group of the macromers is also detected by proton and ~, .
carbon-13 nmr:

,: ., . ~ ~
~ ~ .

CH = CH - CH O-H nmr, ppm 5.3~d) 5.9(m) 4.0(d) 13 5.2(d) C nmr, ppm 116 136 72 FD mass spectra of these macromers also show a series of species with their molecular weight corres-pondinq to polymers possessing one unit of the al'yl group and a terminal OH group. For homomacromers, their mol wts correspond to [allyl alcohol + (monomer) ] in structure (V); for macromer copolymers, their mol wts correspond to [allyl alcohol + (monomer) + (monomer) ]
corresponding to structure (VI).
In the following examples 16-19 a PECH homomacromer (VIII) wherein M is a repeating unit of ECH, is made in a manner analogous to that described hereinbefore with the following allylically unsaturated alcohols, 2-methyl-2-propene-l-ol (2MP); undecenyl alcohol (UA); cinnamyl alcohol (CA); and, allyl phenol (AP), respectively, which provide the head group for each homomacromer. The poly-merization conditions are set forth in Table IX herein-below. The targeted Mn is calculated on the basis of 90% total solids.
TABLE IX
Ex. 16 Ex. 17 Ex. 18 Ex. 19 Unsatd. alcohol 2MP UA CA AP
wt., g 10.71 22.1 18.2 6.2 moles 0.15 0.13 0.14 0.05 ECH, wt., g 89.3 78. 81.7 27.9 moles 0.97 0.84 0.88 0.3 TEOP, g 0.075 0.125 0.075 0.026 wt.% 0.07 0.12 0.08 0.08 Targeted Mn 606 694 663 664 Rxn temp. C, 32 35 35 33 Time of rxn, hr 7 7 8 6 ~2643g2 TABLE IX (contd) Ex. 16 Ex. 17 Ex. 18 Ex. 19 Unsatd. alcohol 2MP UA CA AP
Total solids, % 9393 87 67 The resulting homomacromer from each of the 4 runs set forth as Exs. 16-19 in Table IX hereinabove was analyzed. The results are set forth in Table X herein-below. All the foregoing homomacromers are relatively low viscosity liquids. The Brookfield visc @ 25 C of some of the homomacromers is stated.
TABLE X
Ex. 16 Ex. 17 Ex. 18 Ex. 19 Unsatd. alcohol 2MP UA CA ~P
Mn from GPC 790 903 806 529 from OH No. 671 834 559 528 from I No. 730 --- 937 416 Mw/Mn 1.4 1.3 1.5 7.5 Brookfield visc. 1000 500 1140 ---T , by DSC, C -58. -71. -57. -50.
~H No. 84 67 100 106 Iodine No. 35 -- 27 61 FT infrared spectra and proton nmr spectra of PECH
homomacromers in Exs 16-19 show characteristic absorption and chemical shifts corresponding to the allylic unsaturated group of the starting alcohol. FD
mass spectra of these macromers also show a series species with their mol wts corresponding to [alcohol +
(ECH) ] as shown in structure (V).
It is to be noted that only primary and secondary alcohols provide the desired macromers, and tertiary alcohols do not. For example, when 2-methyl-3-butene-2-ol is used under polymerization conditions analogous to those used hereinabove, no allylic unsaturation is detected in the polymer obtained.

f '' f ,, 12~439z Example 20 PECH homomacromer (VIII) as a dispersant in the precip-itation polymerization of acrylic acid in benzene:
To a 2 liter jacketed glass reactor equipped with a reflux condenser and a stirrer, are charged 230 g of acrylic acid, 25.5 g of (VIII) prepared as in Ex. 2 hereinabove, 1.73 g of allyl pentaerythritol as a cross-linking agent, and 1245 g of benzene as solvent. The reactor is gradually heated from room temperature while agitating and bubbling nitrogen through the reaction mass. 0.28 g of lauroyl peroxide are added to serve as the free radical initiator when the reaction mass o o reached 70 C, and the reactor was allowed to reach 80 C.
After 4.5 hr the reactor was commenced and it was cooled to room temperature.
The foregoing reaction was repeated under identical conditions except that no homomacromer was added.
The Brookfield viscosity of the reaction mass at 25 C, without the macromer, was 400 cps; for the reaction mass in which the macromer was added the viscosity was 150 cps.
The reaction mass was dried at 100 C under 26"
vcuum for 16 hr with a rotary evaporator. A total of 209 g of fine powder polymer was obtained. 50 g of the powder was washed with benzene three times. Analysis shows the powder has a 2.2 wt % Cl content corresponding to incorporation of 6.4 wt% of the homomacromer.
The small homomacromer content of the poly(acrylic acid) does not vitiate the effectiveness of the polymer as a thickener in aqueous solutions. Only 1% by wt of the polymer in water produces a Brookfield viscosity @
25 C of 128,000 cps and a pH of 7.6. The polymer pro-duced without the macromer, used at the same 1% by wt, has a viscosity of 129,000 and a pH of 7.5. It is evident that there is no loss in effectiveness of the 12~4392 polymer, but there is a highly desirable improvement in the polymerization conducted as described.

.:
'

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the manufacture of a polyether macromer having an allylic group at one end and a hydroxyl group at the other, comprises, polymerizing (A) a cationically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure (I) wherein, x is an integer in the range from O to about 4, except that when X71, a second alkylene oxide hav-ing x=l or O must be present, and, R1, R3 and R3 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C6-C20 aryl and C7-C20 aralkyl, and, at least one of R1, R2 and R3 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether hav-ing the structure (II) wherein R1 has the same connotation as hereinabove;
and, R4 represents a member selected from the group consisting of hydrogen, C1-C20 alkyl or substituted alkyl, C1-C20 haloalkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkoxy-alkyl, C6-C20 aryl (Ar), substituted C6-C20 aryl (Ar-Q), wherein Q represents C1-C10 alkyl or haloalkyl C2-C20 alkenyl ox C2-C20 haloalkenyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of (i) (III) and, (ii) (IV) wherein, G is a valency bond or a spacer selected from the group consisting of branched or linear C1-C20 alkyl, C7-C20 aralkyl, C1-C20 haloalkyl, C7-C20 halo-aralkyl, C1-C20 alkoxy and C7-C20 aralkoxyl; and R5, R and R7 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C6-C20 aryl and C7-C20aralkoxyl;
in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel-Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions;
so as to produce a macromer having the structure R-(M)m-OH (V) wherein R represents the residue of said monoole-finically unsaturated alcohol, M represents the residue of at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500.

2. The process of claim 1, wherein said macro-mer is selected from the group consisting of a homomacromer of said alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, haloalkyl-1,2-epoxide, aliphatic glycidyl ether, aromatic glycidyl ether and oxetane;
a macromer copolyether copolymer of tetrahydro-furan or oxepane with a comonomer selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide, oxetane, an aliphatic glycidyl ether, and an aromatic glycidyl ether;
a macromer block copolyether of an alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide, oxetane, an aliphatic glycidyl ether and an aromatic glycidyl ether; and, a macromer copolymer of an olefinically unsatu-rated monomer with a comonomer selected from the group consisting of said alkylene oxide (I), said homomacro-mer, said macromer copolyether copolymer and said macromer block copolyether.

3. The process of claim 2, wherein said mono-olefinically unsaturated alcohol is selected from the group consisting of (i) a monoolefinically unsaturated acyclic "allylic" alcohol having the structure (III) selected from the group consisting of (a) a relatively short chain alcohol having from 3 to about 6 carbon atoms, (b) a relatively long chain alcohol having from 7 to about 20 carbon atoms, and, (c) arylalcohols in which the OH group is on the side-chain;

(ii) allylic cyclic alcohols having the structure (IV) wherein the olefinic bond is in a single or fused ring structure having from 5 to 10 carbon atoms, and, (iii) monoadducts of a single cyclic ether with the foregoing "allylic" alcohols.

4. The process of claim 2, wherein said cationic initiator is selected from the group con-sisting of boron trifluoride (BF), boron trifluoride etherate complexes, tin tetrachloride (SnC14), a fluorinated metallic acid catalyst having the formula HMF6 wherein M is selected from P, As or Sb; an oxonium salt of said acid, and oxonium salts of tetra-fluoroboron.

5. The process of claim 4, wherein said mono-olefinically unsaturated alcohol is at least partially soluble in the reaction mass subjected to polymerization.

6. The process of claim 5, wherein polymerization is effected in the range from about 0°C to about 150°C
and ambient pressure.

7. The process of claim 6, wherein said cationic initiator is present in an amount in the range from 0.001 part to about 1 part by wt. per 100 parts by wt. of said cyclic ether.

8. The process of claim 7, wherein said macromer is a macromer block copolyether having the structure R-(M')m'-(M")m"-OH (VI) wherein M' and M" represent two ring-opened cyclic ethers, and, m' and m" are integers each in the range from 1 to about 300 such that m' + m" = m.

9. The process of claim 7 wherein said macromer is a macromer copolymer having a structure selected from [R-(M)m-OH]n'[Mo]n" (VIIa) and, [R-(M')m'-(M")m"-OH]n'[Mo]n" (VIIb) wherein, n' represents an integer in the range from 1 to about 104;
n" represents an integer in the range from 1 to about 105; and, M' and M" may be present in said macromer as a block copolyether or as a random copolyether copolymer, Mo represents an olefinically unsaturated monomer selected from the group consisting of (a) a C2-C12 vinyl monomer, (b) a C3-C10 unsaturated carboxylic acid or its ester, (c) a C4-C20 acyclic alkadiene or cycloalkadiene, and, (d) a C5-C20 cycloalkene.

10. The process of claim 9 wherein said vinyl monomer (a) is selected from the group consisting of vinyl chloride, vinyl acetate, acrylo-nitrile, ethylene, propylene, 4-vinylpyridine, vinyl-pyrrolidone, styrene, and 4-chlorostyrene;
said carboxylic acid or carboxylic acid ester (b) is selected from the group consisting of acrylic acid, methacrylic acid, vinyl benzoic acid, vinyl naphthoic acid, acrylic amide, butyl acrylate, ethyl acrylate, and, 2-ethylhexyl acrylate;
said alkadiene (c) is selected from the group consisting of butadiene, and isoprene; and, said cycloalkane (d) is selected from the group consisting of cyclopentene, cycloheptene, norbornenes and dicyclopentadiene.

11. A polyether macromer having an allylic group at one end and a hydroxyl group at the other, formed by polymerizing (A) a cationically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure (I) wherein, x is an integer in the range from 0 to about 4, except that when x>1, a second alkylene oxide having x=1 or 0 must be present, and, R1, R2 and R3 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C6-C20 aryl and C7-C20 aralkyl, and, at least one of R1, R2 and R3 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether having the structure (II) wherein R1 has the same connotation as hereinabove;
and, R4 represents a member selected from the group consisting of hydrogen, C1-C20 alkyl or substituted alkyl, C1-C20 haloalkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkoxyalkyl, C6-C20 aryl (Ar), substituted C6-C20 aryl (Ar-Q), wherein Q is selected from the group consisting of C1-C10 alkyl, C1-C10 haloalkyl, C2-C10 alkenyl or C2-C20 haloalkenyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of (i) (III) and, (ii) ( IV) wherein G is a valency bond or a spacer selected from the group consisting of branched or linear Cl-C20 alkyl, C7-C20 aralkyl, C1-C20 haloalkyl, C7-C20 haloaralkyl, CC1-C20 alkoxyl and C7-C20 aralkoxyl; and R1, R2 and R3 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C6-C20 aryl and C7-C20 aralkyl;
in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel-Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions;
so as to produce a macromer having the. structure R-(M)m-OH (V) wherein R represents the residue of said monoole-finically unsaturated alcohol, M represents the residue of at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500;
whereby said macromer is produced in conjunction with at least a trace quantity of cyclic oligomer of said cyclic ether.

12. The polyether macromer of claim 11, repre-sen?ed by a homomacromer having the structure (VIII) wherein n is in the range from 2 to about 100.

13. The polyether macromer of claim 11, repre-sented by a macromer copolymer having the structure (XI) wherein, n' represents an integer in the range from 1 to about 104;
n" represents an integer in the range from 1 to about 105; and the backbone is terminated conventionally.

14. The polyether macromer of claim 11, after it has been aminated so that it is represented by the structure (XIII) wherein X' represents a halogen, n is an integer in the range from 2 to 100, and R8 represents the residue of an amine used to aminate the macromer.

15. A macromer block copolymer represented by the formula A'A"2 wherein A' represents the residue of a polysiloxane block having the structure HR"2SiO[R"2SiO]zSiR"2H (XV) in which R" is an unsubstituted or halogen-substituted monovalent hydrocarbon group and z is an integer in the range from 0 to about 300, and A" represents the residue of a macromer having the structure (XIV) wherein Z is the residue of an end-capping unit.

16. A macromer block copolymer according to claim 15, wherein z is an integer of 5 to 50.

17. A process according to claim 1, wherein said macromer (V) has an Mn of 200 to 10,000.

18. A polyether macromer according to claim 11, wherein said macromer (V) has an Mn of 200 to 10,000.

19. The process of claim 3, wherein said relatively short chain alcohol in i) a) is selected from the group consisting of allyl alcohol, 2-methyl-2-propene-l-ol, 2-buten-1-ol, 1-buten-3-ol (l-methallyl alcohol), 3-buten-1-ol, 4-penten-1-ol, 2-pentene-1-ol, 3-penten-2-ol, 4-penten-2-ol, 2-methyl-1-buten-3-ol, 2-methyl-1-buten-4-ol, 3-methyl-2-buten-1-ol, 2-ethyl-l-propen-3-ol, 2-ethyl-1-penten-3-ol, 5-hexen-1-ol, 4-hexen-l-ol, 5-hexene-1-ol, 2-methyl-1-penten-3-ol, 2-methyl-4-penten-3-ol and 4-methyl-3-penten-1-ol;
said relatively long chain alcohol in i) b) is selected from the group consisting of 9-decen-1-ol, 10-undecen-1-ol, citronellol and oleyl alcohol;
said aryl alcohols in i) c) are selected from the group consisting of cinnamyl alcohol, and those in which the OH group is a phenolic OH group including 2-allyl phenol;
said allylic cyclic alcohols in ii) are selected from the group consisting of penten-l-ol, 2-cyclohexen-l-ol, 3-cyclohexen-1-methanol, 6,6-dimethyl bicyclo[3.3.1]hept-2-ene-2-ethanol[(IS)-(-)-Nopol], 5-norbornene-2-methanol, and bicyclo(2.2.2)oct-5-ene-2-methanol; and said monoadducts in iii) are selected from the group consisting of a monoadduct with an alcohol selected from the group consisting of 2-hydroxyethyl allyl ether, 2-hydroxy-1-methylethyl allyl ether, 2-hydroxy-2-methylethyl allyl ether, 4-hydroxy-butyl allyl ether, diethylene glycol monoallyl ether and 2-hydroxy-2-chloromethyl ethyl allyl ether.