CA1304394C - Vinyl ether terminated urethane resins - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Vinylether terminated urethane resins may be prepared by reacting the product obtained by the addition of acetylene to an organic polyol with an isocyanate-containing compound at temperatures ranging from about ambient to about 125°C, the resins having the generic formula (CH2=CH-O-R-O-?-NH)n-R'

Description

~3~3~4 VINYL ETHER TERMINATED URETHANE RESINS

.

BACKGROUND OF THE INVENTION

Yarious types of resins w~ll find a wide variety of uses, among which will be printing inks and coatings for the graphic arts and packag~ng industries. Prior res~ns have incluted acrylated urethanes.
These resins are formed by the reaction of a hydroxyacrylate monomer 5 with an isocyanate mono~er or prepolymer and may be based on a wide range of aromatic and aliphatic isocyanates. Multifunctional acrylate monomers such as, for example, trimethylolpropane triacrylate, may be combined w~th the acrylated urethanes in order to reduce the viscosity of the resin and increase the cross-l~nked density of the cured 10 material. The acrylated urethanes may be cured by a free radical polymerization of the acrylate group, th~s be~ng accomplished by ultravlolet ~rradiation in the presence of a photoinit~ator or by electron beam irradiation. The radiation-cured acrylated urethanes may be used in pr~nting inks, floor coatings, automotive coatings, printed lS c~rcuit board coat~ngs, etc. However, the acrylates possess an inherent disadvantage in that the monomers are known to be tox~c whereby a hazard to the general health of either the user or the publ~c at large ~s created.
Vinyl ethers constitute extremely reactlve monomers which are 20 known to polymerize by a cationic mechanism. These compounds may be useful in applications which require a high speed curing of a resin formulat~on. The vinyl ethers react much faster than the epoxy resins and therefore may be used for printing inks, coatings, elastomers, foams, or in other types of materials dependent upon the abil~ty of the 13~3ç~4 resin to cure at a rate which ls contiguous with other processing steps.
One disadvantage which is attendant to the vinyl ethers is that the commercial availability of these ethers is relatively limlted. In general, the vinyl etheIs which are available constitute low molecular 5 weight monofunctional or difunctional monomers. However, in most commercial applications, the use of higher molecular weight polymer resins constitutes the preferred species. This is due to the fact that the higher mole weight materials are non-volatile and will possess more desirable rheological properties, and they permit greater oontrol of the lO properties of the finished product.
As will hereinafter be shown in greater detall, it has now been dlscovered that it is possible to obtain vinyl ether terminated urethane resins which will constitute novel compositions of matter and which will possess characterlstics whlch make them des1rable for use ~n var~ous 15 commerc~al appllcatlons.
The aforesald vlnyl ether term~nated urethane resins whlch are formed by the process hereinafter descrlbed in greater detail may be subjected to a curing treatment to provide tack-free coatings.

BRIEF SUMMARY OF T~E INVENTION

This appllcat10n relates to novel composltlons of matter comprising vlnyl ether terminated urethane resins. More specifically, the lnventlon is concerned with these novel compositions of matter and 25 also to a process for prepar~ng these products. In add~tlon, the lnventlon ls also concerned wlth a process for sub~ectlng these novel composlt~ons of matter to a curlng treatment whereby a flnlshed product comprlslng a tack-free coatlng may be obtalned therefrom.
It ls therefore an ob~ect of thls lnventlon to provlde novel 30 composltl~ns of matter comprlsing certaln reslns whlch may be utlllzed ln varlous commerc~al appllcatlons.
A further object of this inventlon is to prov~de a process for prepar~ng vlnyl ether termlnated urethane resins whlch are utilized for coatings of various and sundry klnds.

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In one aspect, an embodiment of this invention resides in a vinyl ether terminated urethane resin having the generic formula:

~CH2=CH-O-R-O C-NH)n-R' in which R and R' are independently selected from the group consisting Of alkyl, aryl, alkaryl, aralkyl, cyclsalkyl and alkyl oxi~e radicals and n is an integer of from 1 to 4.
Another embodiment of this invention is found in a process for the preparation of a vinyl ether terminated urethane resin which comprises reacting the product obtained by the additlon of acetylene to an organic polyol with an isocyanate-containing compound at reactlon condit~ons, and recovering the resultant vinyl ether terminated urethane resin.
A specific embodiment of this invention resides in a vinyl terminated urethane resin having the generic formula:

o Il (CH2=CH-O-R_O_C_NH)n_R' in which R comprises methylene and R' comprlses dicyclohexylmethyl.
Another specific embodiment of this invention is found in a process for the preparation of a vinyl ether terminated urethane resin wh~ch comprises reacting the product obtained by the add~tion of acetylene to triethylene glycol with 2,4-toluene diisocyanate at a temperature in the range of from about ambient to about 125C and about atmospheric pressure in the presence of a tln-containing catalyst comprising dibutylt~n dilaurate and recover~ng the resultant vlnyl ether terminated urethane resin.

~3~43~?4 In addition, another embodiment of this invention is found in a polymeric material that results from curing a vinyl ether terminated resin having the generic formula:

1l (CH2=CH-O-R-O-C NH)n R' in which R and R' are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals and n is an integer of from 1 to 4 which has been polymerized by a curing treatment at curing conditions.
Yet another embodiment of this invention resides in a method for obtaining a tack-free coating which comprises subjecting a vinyl ether terminated urethane resin havlng the generic formula:

( CH2=cH-o-R-o-c-NH)n-R ' in which R and R' are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals and n is an integer of from 1 to 4 to a curing treatment at curing 25 conditions, and recoverlng the resultant tack-free coatlng.
Other objects and embodlments wlll be found ln the following further deta~led descriptlon of the inventlon.

DETAILED DESCRIPTION OF THE INVENTION

As hereinbefore set forth, the present invention is concerned with novel compositions of matter comprising vinyl ether terminated urethane resins and to a process for the preparation thereof. In addition, the novel compositions of matter may be subiected to a curing 35 reaction or treatment whereby the resins will polymer~ze to produce a 13~43~

coating which is solid and tack-free. The desired resins may be prepared by the reaction of a hydroxy vinyl ether with a multifunctional isocyanate monomer or prepolymer. The hydroxy vinyl ether which is utilized as one c~?onent to form the novel composition of matter of the 5 present invention may be prepared by the base catalyzed reaction of acetylene with polyols. The process may be exemplified by the following equation in which a diol is reacted with acetylene at an elevated temperature and pressure in the presence of a basic catalyst which, in the reaction, ~s represented by potass~um hydroxide:

KOH
HO-R-OH+C2H2 ~ _` CH2~CH-O-R-O-CH-CH2+CH2-CH-O-R-OH
~,press.

In the above equation, R may be selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals. The reaction conditions which may be employed to effect this acetylene reaction will include temperatures in the range of from about 120C to 20 about 300C and a pressure in the range of from about atmospheric up to about 100 atmospheres. Other basic catalysts which may be employed to effect th~s react~on wlll ~nclude such compounds as sodlum hydroxide, l~th~um hydrox~de, calc~um hydrox~de, magnesium hydrox~de, stront~um hydroxide, etc. The react~on product wh~ch ~s obta~ned by th~s process 25will compr~se a d~v~nyl ether and a hydroxy v~nyl ether. If so des~red, the product may be separated by fract10nal d~st~llat~on ~nasmuch as the d~v~nyl ether product possesses a bo~l~ng po~nt lower than the start~ng polyol and the hydroxy v~nyl ether. In add~t~on, the bas~c catalyst is also separated from the product ~nasmuch as the presence of such a 30compound ~n the f~n1shed res~n would ~nh1b~t the subsequent polymer~zation.
Examples of polyols wh~ch may be sub~ected to acetylation will ~nclude 1,2-ethanediol, 1,3-propanediol, 1,4-butaned~ol, 1,5-pentanedlol, 1,6-hexaned~ol, d~ethylene glycol, triethylene glycol, 35d~propylene glycol, tripropylene glycol, 1,3-cyclopentanediol, 13~4394 1,4-cyclohexanediol, trimethylol propane, pentaerythritol, 1,4-cyclohexane dimethanol, tris(2-hydroxyethyl) trimethylol propane, 1,4-bis(2-hydroxyethyl) phenyl ether, 1,2-bis(2-hydroxyethyl) phenyl ether, 1,3-bis(2-~ ~roxyethyl) phenyl ether, bis(2-5 hydroxyethyl)bisphenol-A, etc.
It is to be understood that the abovementioned polyols are only representative of the class of compounds which may be employed in the present invention and that the invention is not necessarily limited thereto.
The product obtained by the reaction of acetylene with the polyol will subsequently be reacted with an isocyanate-containing compound which may comprise either an isocyanate monomer or an isocyanate prepolymer. The reaction between the product obtained by the add1tion of acetylene to an organic polyol ind the isocyanate-containing lS compound may be effected at react10n conditions which will 1nclude a temperature in the range of from about ambient to about 125C and preferably at atmospheric pressure, although it is also contemplated within the scope of this invention that superatmospheric pressures ranging up to about 50 atmospheres may be employed, if so desired. When 20 ut11izing temperatures at the lower range hereinbefore set forth, that is, temperatures of about ambient, it is preferred to effect the reaction in the presence of a catalyst. A particularly preferred type of catalyst is one which conta1ns tin and which may be exemplified by dibutyltin dilaurate. Other process variables which may be employed to 25 effect the des1red reaction and thus form the vinyl ether term~nated urethane resin will ~nclude the use of an ~nert solvent such as methylene chloride which may be removed in a subsequent step in a vacuum.
The reaction between the acetylene addition product and the 30 isocyanate-conta1n1ng compound may be exemplif~ed by the following reaction:

2CH2=CH-O-R-OH + OCN-R'-NCO
O Q
CH2=CH-0-R-0-e-NH-R'-NH-e-0-R-0-CH=CH2 l~U4394 in which R' may be selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals. In addition, R' may be monomeric or polymeric in nature. Some examples of monomeric isocyanates which may be employed in the process of the present invention will include 2,4-toluene diisocyanate, mixtures of 2,4-and 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenylpropane diisocyanate, dicyclohexylmethane diisocyanate, etc.
While the hereinbefore equation discloses the reaction between a hydroxy vinyl ether and an isocyanate-containing compound, it is also contemplated within the scope of this invention that the reaction may be effected utilizing the entire reaction product which is obtained by the reaction of acetylene with the polyol. This acetylene reaction produces a mixture of the divinyl ether, the hydroxy vinyl ether and the unreacted polyol.
It is, of course, possible by utilizing fractional distillation to separate the hydroxy vinyl ether from the reaction product mixture and thus utilize only this compound in the subsequent reaction. However, it is also contemplated within the scope of this invention that the other components of the reaction product mixture, after separation of the catalyst, may be utilized and thus incorporate the divinyl ether and the unreacted polyol into the vinyl ether terminated urethane resin. The unreacted polyol such as a diol will serve to chain extend the resin inasmuch as each hydroxy group on the polyol will react with the isocyanate group and thus form a higher molecular weight material. Therefore, if the total concentration of the hydroxy group from the polyol and the hydroxy vinyl ether are known, they then may be combined with an equivalent concentration of isocyanate.
Conversely, the divinyl ether will not possess any free hydroxy groups and therefore will not react with the isocyanate. However, the divinyl ether may serve as a ~`

13~43~?4 diluent which will lower the viscosity of the mixture during the resin synthesis. Additional divinyl ethers may also be added after the synthesis of the resin has been completed in order to further adjust the viscosity of the formulation. Thus, when the resin is finally cured by means hereinafter set forth in greater detail, the additional divinyl ether which is present y _~ G~

13~3~4 copolymerizes with the vinyl ether term;nated urethane resin and effectively increases the cross-link density of the final product.
The process for preparing the v~nyl ether terminated urethane resin may be effected in any suitable manner and may compr~se either a batch or continuous type operation. For example, when a batch type operation is to be employed, the isocyanate-containing compound is placed in an appropriate apparatus and, if so desired, in the presence of an inert solvent. The hydroxy vinyl ether e1ther in a pure state or in the presence of a divinyl ether and a polyol may be added to the isocyanate-containing compound. In the event that the reaction is to be effected at ambient or room temperatures, a catalyst of the type hereinbefore set forth may then be added. Conversely, if the reaction is to be effected a~ elevated temperatures, the reaction apparatus is then heated to a predetermined temperature and maintained thereat for a period of t~me sufflcient to permit the reaction to come to its completion. Following the end of the reactlon period, the deslred vinyl ether terminated urethane resln is then recovered.
It is also contemplated within the scope of this invention that the reaction may be effected in a continuous manner of operation. When this type of operation is employed, the starting components of the res~n are continuously charged to a reaction zone which is maintained at the proper operating conditions prev~ously selected. After passage through the reaction zone for a predetermined time, either in the presence or absence of a cata1yst and/or a solvent, the reactor effluent is 25 cont~nuously discharged and recovered.
In the preferred embodlment of the lnventlon, the reactants are present ln a 1:1 stoich~ometry of hydroxy and lsocyanate groups.
However, it is also contemplated that in some lnstances it may be desirable to use a slight excess of hydroxy vinyl ether ln order to 30 ensure the complete reaction of the isocyanate. Conversely, it is also contemplated that an excess of isocyanate may be used to give additional cross-linking through the formation of allophanate llnkages. Therefore, the ratio of hydroxy and isocyanate may vary through a range of from about 0.8:1 to about 1.2:1 moles of hydroxy vinyl ether per mole of 35 isocyanate.

~3~43~4 g The vinyl ether terminated urethane resins which are obtained may be cured by any method known in the art to obtain the desired product. For example, the resins may be subjected to an electron beam induced curing by subjecting the resin to irradiation from an energy source such as an electron beam in which the energy dosage which is applied to the mixture is relatively low, that is, ln a range of from about 0.1 to abou~ 10.0 Mrads. The exposure to this energy may take place in the presence of an onium salt. Examples of onium salts which may be employed will tnclude diphenyliodonium hexafluoroant~mony or triphenylsulfonium hexafluorophosphate. Other methods which may also be employed to effect the curing of the resins tn order to obtatn the destred glossy tack-free coattng will include an ultraviolet procedure in whtch the restn is subjected to irradiation from an ultraviolet light source which possesses a wave length of from about 1800 to about 3900 Angstroms. Such trradtatton may be obtatned from xenon, mercury-vapor or tungsten lamps or from vartcus types of ultraviolet or visable lasers. The ultravtolet trradtation of the resin may be effected in the presence of an aryl-onium salt, some examples of these salts being dtphenyltodonium hexafluoroantimony or triphenylsulfonium hexafluorophosphate. A third procedure whtch may be employed to effect the curing of the vtnyl ether termtnated urethane resins comprtses a thermal curtng in whtch the restn ts subjected to a temperature ~n the range of from about amb~ent to about 250C tn the presence of an organtc actd or ontum salt, some examples of these actds or salts comprts~ng p-toluene sulfonic acld, methane sulfontc actd, boron trlfluortde, diphenyl~odontum hexafluororantlmony, trlphenylsulfonlum hexafluorophosphate, etc.
The follow~ng examples are g~ven to illustrate the novel vtnyl ether termtnated urethane restn, a method for the synthests of these restns, the cured restns whtch form soltd tack-free coattngs and methods whtch are employed tn this curtng treatment. However, it is to be understood that these examples are given merely for purposes of tllustratton and that the tnvention is not necessartly ltmited thereto.

.;.~

13~3~4 EXAMPLE I:

To form a hydroxy vinyl ether, 250 milliliters of triethylene glycol, along with 7.5 grams of a catalyst comprising ground potassium hydroxide were added to a 500 mL round bottom flask equipped with a mechanical stirrer, reflux condenser and gas inlet tube. The mixture was heated to a temperature of about 190C while purging with nitrogen.
After the temperature was stabilized, a flow of acetylene at a rate of about 1.0 liters/minute was initiated, and the reaction was allowed to continue for a period of 5 hours. The flask was fitted with a distillation head and 125 mL of reaction product was collected which had a boiling range of from 70 to 84C at 0.3 torr. Gas chromatographic analysis disclosed that the product comprised a mixture of 14%
triethylene glycol dlvlnyl ether, 78% triethylene glycol monovinyl ether and 7% unreacted triethylene glycol. Red~stillat~on of the product resulted in the obtent~on of an 85 mL fraction which contained 95g triethylene glycol monovinyl ether.

EXAMPLE II:
To form the desired vinyl ether terminated urethane resin, 3.55 9 (0.014 mole) of diphenylmethane diisocyanate were dissolved in 20 mL
of dry methylene chloride under a nitrogen atmosphere. Following this, 5.0 9 (0.028 mole) of triethylene glycol monovinyl ether were added to the solut~on along with 0.01 9 of dibutylt~n d~laurate. The react~on apparatus became warm after a few m~nutes of stirring the mlxture. At the end of 5 hours the solvent was removed ~n a vacuum and the resulting thick liquid product was recovered.

EXAMPLE III:

In th~s example a 2:1 mole ratio of tr~ethylene glycol monovinyl ether to 2,4-toluene diisocyanate was stirred under an atmosphere of dry nitrogen at room temperature in the presence of 0.1~, dibutyltin dilaurate for a period of 5 hours. At the end of this ' , ~3~;L3~4 period, the solvent was removed in a vacuum and the resulting thick, clear liquid product comprising the vinyl e~her terminated urethane resin was recovered.

EXAMPLE IV:

In this example, one equivalent of triethylene glycol monovinyl ether and 1 equivalent of free isocyanate, which was present in a diphenylmethane diisocyanate e~her prepolymer in a toluene solvent, were stirred at room temperature under dry nitrogen in the presence of a catalyst comprising 0.05Z dibutyltin dilaurate. After a period of 2 hours at room temperature, the solvent was removed under reduced pressure and the thick, clear liquid product was recovered.
EXAMPLE V:

One equivalent of triethylene glycol monovinyl ether and one equivalent of free isocyanate present in a toluene diisocyanate ester prepolymer were reacted to form the desired resin. The reaction was effected by placing the solid prepolymer in a glass vial covered with alum~num foil. The vlal was heated for a period of 20 minutes in an oven at 104C to melt the solid. The equivalent of triethylene glycol monovinyl ether was then stirred into the molten prepolymer along with 0.1~ dibutyltin dilaurate. After an additional period of 1 hour while 2s maintaining the temperature at 104C, the high viscosity, clear liquid resin was recovered.

EXAMPLE VI:
The vinyl ether terminated urethane resins which were prepared in Examples III, IV and V above were treated with a catalyst comprising 1% di-t-butylphenyliodonium hexafluoroantimony. The resins were then coated on a polyethylene-covered substrate and each sample was ~rrad~ated at 2.0 Mrads with a 160 KeV electron beam. Each of the samples cured to give tack-free flexible coatings.

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EXAMPLE VII:

In this example, the vinyl ether terminated urethane resin which was prepared according to Example II above was combined with 4% of a triarylsulfonium salt catalyst and coated in a thin layer on a polyethylene sheet. The sheet was suspended in a Rayonett Photochemical Reactor equipped with 350 nm lamps. After a 15 second exposure to the ultraviolet light in a nitrogen atmosphere, a tack free glossy coating was obtained.
EXAMPLE VIII:

A series of vinyl ether terminated urethane resins were prepared by reacting different stoichiometric ratios of triethylene glycol monovinyl ether (TEGMYE), diphenylmethane diisocyanate (MDI), and trimethylol propane (TMP). In all cases a 1:1 ratio of hydroxy groups to isocyanate groups was maintained. The mixtures were stirred at room temperature in a solution of triethylene glycol divinyl ether (TEGDVE) under nitrogen in the presence of dibutyltin dilaurate. The viscosity 20 of the resins and the molecular weight were determined. These results are set forth in Table I below:

Mole Ratio Restn ViscosityMolecular Weight TEGMVE : MDI: TMP (cps) No. Avg. Wt. Avg.
3 3 1 1,130 1,273 3,~88 7 8 3 3,140 1,372 4,861 30 4 5 2 8,380 1,577 8,160 A catalyst comprising 3% of a triarylsulfonium salt was added to each of the three resins which were obtained according to the above paragraph. The mixtures were then each coated onto separate 13~4;3~4 polyethylene sheets and irradiated with a 160 KeV electron beam. The coatings were all tack-free after a dose of 3.0 Mrad. When a catalyst comprising lX of a diaryliodonium salt was used in place of the sulfonium salt, catalyst curing was obtained utilizing only a dose of 5 0.5 Mrad.

EXAMPLE IX:

In this example, a vinyl ether terminated urethane resin was lO obtained by stirring a 2:1 mole ratio mixture of triethylene glycol monov~nyl ether and d~cyclohexylmethane 4,4'-diisocyanate under a dry - nitrogen atmosphere in the presence of O.OSX dibutyltin dilaurate. At the end of S hours, the resulting product comprised a white, soft waxy sol~d wh~ch melted at about 40C to g~ve a clear thick l~quid. Gel 15 permeat~on chromatography showed that the product cons~sted mostly of a s~mple 2:1 adduct.
A higher molecular weight resin was obtained by includ~ng triethylene glycol ln the reaction mixture as a cha~n extender. The reaction was effected by treating a m~xture of tr~ethylene glycol, 20 TEGMYE and the di~socyanate ~n a mole rat~o of 2:2:1 v~nyl ether to isocyanate to glycol. The resulting res~n had an average molecular weight of 1,575 and was in the form of a low melting waxy sol~d.
The two res~ns wh1ch were prepared according to the above paragraphs were comb~ned w~th a triarylsulfon~um salt catalyst, coated 25 onto polyethylene sheets and suspended ln a Rayonett Photochemlcal Reactor equlpped w~th 350 nm lamps. After a 30 second exposure to the ultrav~olet l~ght, tack-free clear glossy coat~ngs were obta~ned.
To ~llustrate another method of cur~ng, the res~ns were also combined w~th an iodon~um salt catalyst and irrad~ated w~th 160 KeV
30 electron beam. After a dose of 1.0 Mrad energy, aga~n tack-free clear glossy coat~ngs were obta~ned.

Claims (32)

1. A process for the preparation of a vinyl ether terminated urethane resin which comprises reacting the mixture resulting from the addition of acetylene to an organic polyol with an isocyanate-containing compound at reaction conditions, and recovering the resultant vinyl ether terminated urethane resin.

2. The process as set forth in Claim 1 in which said reaction conditions include a temperature in the range of from about ambient to about 125°C and about atmospheric pressure.

3. The process as set forth in Claim 1 in which said reaction is effected in the presence of a tin-containing catalyst.

4. The process as set forth in Claim 1 in which said tin-containing catalyst is dibutyltin dilaurate.

5. The process as set forth in Claim 1 in which said organic polyol comprises triethylene glycol and said isocyanate containing compound comprises 2,4-toluene diisocyanate or a mixture of 2,4- and 2,6-toluene diisocyanate.

6. The process as set forth in Claim 1 in which said organic polyol comprises triethylene glycol and said isocyanate compound is diphenylmethane diisocyanate.

7. The process as set forth in Claim 1 in which said organic polyol comprises triethylene glycol and said isocyanate compound is dicyclohexylmethane diisocyanate.

8. The process as set forth in Claim 1 in which said organic polyol comprises diethylene glycol and said isocyanate compound is 2,4-toluene diisocyanate or a mixture of 2,4- and 2,6-toluene diisocyanate.

9. The process as set forth in Claim 1 in which said organic polyol comprises 1,6-hexanediol and said isocyanate compound is dicyclohexylmethane diisocyanate.

10. A polymer resulting from the reaction of (a) a hydroxy mono vinyl ether;
(b) a diisocyanate;
(c) an organic polyol in the presence of a solvent under suitable reaction conditions.

11. The polymer of Claim 10 where the solvent is a divinyl ether.

12. The polymer of Claim 10 wherein said hydroxy mono vinyl ether of (a) is the product of the reaction of acetylene with at least one polyol selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, pentaerythritol, 1,4-cyclohexane dimethanol, tris(2-hydroxyethyl) trimethylol propane, 1,4-bis(2-hydroxyethyl) phenylether, 1,2-bis(2-hydroxyethyl) phenyl ether, 1,3-bis(2-hydroxyethyl) phenylether, and bis(2-hydroxyethyl) bisphenol-A.

13. The polymer of Claim 10 wherein said diisocyanate of (b) is at least one member of the group consisting of 2,4-toluene diisocyanate, mixtures of 2,4 and 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenyl propane diisocyanate, and dicyclohexylmethane diisocyanate.

14. The polymer of Claim 10 wherein the polyol of (c) is the same as the polyol reacted with acetylene to prepare the hydroxy mono vinyl ether of (a).

15. The polymer of Claim 10 wherein said polyol of (c) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-

16 pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, pentaerythritol, 1,4-cyclohexane dimethanol tris(2-hydroxyethyl) trimethylol propane, 1,4-bis(2-hydroxyethyl) phenylether, 1,2-bis(2-hydroxyethyl) phenyl ether, 1,3-bis(2-hydroxyethyl) phenylether, and bis(2-hydroxyethyl) bisphenol-A.
16. The polymer of Claim 11 wherein the hydroxy monovinyl ether, polyol, and divinyl ether are the products of the reaction of acetylene with an excess of said polyol.

17. The polymeric material that results from curing the polymer of Claim 10.

18. The polymeric material of Claim 17 cured by irradiation with an electron beam.

19. The polymeric material of Claim 18 wherein the energy dosage of said electron beam is in the range of from about 0.1 to about 10.0M rads.

20. The polymeric material of Claim 18 cured in the presence of an effective onium salt.

21. The polymeric material of Claim 17 cured by exposure to an ultraviolet light source.

22. The polymeric material Claim 21 cured in the presence of an effective aryl-onium salt.

23. The polymeric material of Claim 17 cured by thermal treatment at an elevated temperature in the presence of an effective organic acid or an onium salt.

24. The polymeric material of Claim 10 where said polyol is triethylene glycol and said diisocyanate is 2,4 toluene diisocyanate.

25. The polymeric material of Claim 10 where said polyol is triethylene glycol and diisocyanate is a 2,4 toluene diisocyanate ester prepolymer.

26. The polymeric material of Claim 10 where said polyol is triethylene glycol and said diisocyanate is diphenylmethyl diisocyanate.

27. A method of obtaining tack-free coating which comprises subjecting the polymer of Claim 10 to curing conditions and recovering the resultant tack-free coating.

28. The method of Claim 27 wherein said curing conditions comprises irradiation of said polymer with an electron beam in which the energy dosage is in the range of from about 0.1 to about 10M rads in the presence of an effective onium salt.

29. The method of Claim 27 wherein said curing conditions comprise exposure to an ultraviolet light source in the presence of an effective aryl-onium salt.

30. The method of Claim 27 wherein said curing conditions comprise thermal treatment at an elevated temperature in the presence of an effective organic acid or an onium salt.

31. The polymer of Claim 10 wherein the mol ratio of hydroxy and isocyanate moieties is within the range of about 0.8:1 to about 1.2:1.

32. The polymer of Claim 10 wherein the mol ratio of hydroxy moieties from the hydroxy mono vinyl ether of (a) to the hydroxy moieties from the polyol of (c) is within the range of about 2.3 to about 1:1.