WO1999010303A1

WO1999010303A1 - Radiation-curable propenyl compounds, uses thereof, and compositions containing them

Info

Publication number: WO1999010303A1
Application number: PCT/US1998/017110
Authority: WO
Inventors: James Crivello
Original assignee: Research Corporation Technologies, Inc.
Priority date: 1997-08-26
Filing date: 1998-08-19
Publication date: 1999-03-04

Abstract

Disclosed are compounds of formula (1): R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms; R1 is -H or -CH¿3; R?2 is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloloxy, methacryloloxy, or A-(Het)¿0-1?C(O)O- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -O- or -NH-; or R?2¿ is -L-X-(L-R-(OCH=CH-CH¿2R?1)n)1-3 wherein X has any of the structures -Ph0-1-CaH2a-Ph0-1-Ph0-1-(cyclo-C5-20-alkyl)-Ph0-1-, -Ph-Ph-, or -Ph-, wherein Ph is phenylene and a is 1 to 20; -CfH2fC(O)CgH2g -CfH2fOCgH2g, -CfH2fC(O)OCgH2g-, -CfH2fPhCgH2g-, or -CfH2fC(O)NHCgH2g-, wherein f and g are each 1 to 12; and each L is independently a chemical bond or -C(O)O-, -OC(O)O-, -O-, or -NHC(O)O-, provided that each R is bonded to an oxygen atom of L; or X is -C(O)-, each L is a chemical bond, and i is 1. Also disclosed are methods and compositions useful in the radiation-induced polymerization of such compounds.

Description

RADIATION-CURABLE PROPENYL COMPOUNDS, USES THEREOF, AND COMPOSITIONS CONTAINING THEM

The present invention relates to novel radiation- curable propenyl compounds, to radiation - curable compositions containing such compounds, and to processes for forming radiation -cured products from such compounds and compositions.

Radiation curing has become an important and useful technique for applying and curing coatings, inks, and adhesives. As described herein, radiation curing involves presenting a radiation -curable polymer, typically in combination with a photo- initiator, and exposing the composition to radiation in the form of ultraviolet or electron-beam radiation to cause the radiation- curable compound to polymerize.

Radiation curing presents many advantages, such as high rates of throughput, low energy requirements, and low equipment costs. In addition, it is advantageous that users are able to avoid using a solvent when the composition to be radiation -cured is prepared. Solvents typically would lead to environmental and/or safety hazards, and would require additional equipment and handling. steps to remove the solvent .

Propenyl compounds useful in the preparation of polymeric coatings and the like via photopolymerization are disclosed in, for instance, U.S. Patent No. 5,486,545 and U.S. Patent No. 5,567,858. However, there remains a need for radiation- curable compounds, photopolymerizable or otherwise, which provide improved versatility and which can be formulated into a variety of coatings, films and the like readily and rapidly.

The present invention comprises compounds of the formula (1)

wherein n is an integer from 1 to 3;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms; R¹ is -H or -CH₃; R² is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A-CHet)^-

C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -O- or -NH- ; or R² is -L-X- (L-R- (0CH=CH-CH₂R¹)_n)_i wherein X has any of the structures - Ph₀._χ-C_aH_2a- Ph^

-Ph_p^- (cyclo-C₅.₂₀-alkyl) -Ph^- , -Ph-Ph-, or -Ph-, wherein Ph is phenyl ene and a is 1 to 20;

-C_£H_2fC(0)C_gH_2g -C_fH_2£0C_gH_2g, -C_£H_2£C (O) 0C_gH_2g- , -C_fH_2£PhC_gH_2g- , or -C_£H_2£C (0)NHC_gH_2g- , wherein f and g are each 1 to 12; and each L is independently a chemical bond or -C(0)0-, -0C(0)0-, -0-, or -NHC(0)0-, provided that each R is bonded to an oxygen atom of L, and i is an integer from 1 to 3; or X is -C(O)-, each L is a chemical bond, and i is 1.

Furthermore, the compounds in formula (1) , can contain up to (n-1) (OCH₂CH=CHR¹) groups in place of (OCH=CH-CH₂R¹) groups. The present invention is further directed to compositions comprising one or more compounds of said formula (1) , and also comprising one or more photoinitiators in an amount effective to mediate polymerization of said compound when the composition is irradiated with, for instance, ultraviolet radiation or electron beam radiation.

Still further, the present invention is directed to a process of forming a polymeric structure, such as a coating, film, or solid body, comprising' forming the aforementioned composition of one or more compounds of formula (1) and a photoinitiator, and then irradiating the composition with ultraviolet or electron beam radiation effective to polymerize said one or more compounds of formula (1).

Referring to formula (1) , it can be seen that R represents a linear, branched or cyclic alkyl group having at least two substituents and as many as four substituents, one of which is a R² group and up to (n) of which have the formula -0CH=CH-CH₂R^α . As will be described below, up to (n-1) substituents can have the formula -0CH₂CH=CHR¹ instead of -OCH=CHCHR¹. Preferred R groups include the branched structures having the formula CH₃C(CH₂-)₃, or C(CH₂-)₄. Referring again to formula (1) , it can be seen that the R² substituent always contains an oxygen atom which is also bonded to the R group. Thus, R² can be hydroxyl, in which case the resulting compound is referred to herein as "underivatized" . Alternatively, R² can be alkoxy containing 1 to 20 carbon atoms, phenoxy, acryloyloxy, methacryloyloxy, or any of the acyloxy, acyloxycarbonyloxy, or urethane derivatives represented by the formula A-(Het)₀.₁- C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) represents the optional oxygen or NH- atoms . When R² is alkoxy it can optionally be substituted with phenyl, thereby creating for example a benzyloxy substituent. When R² is alkoxy containing two or more carbon atoms, two consecutive carbon atoms thereof can optionally be joined with an oxygen atom to form an epoxy ring. The embodiments wherein R² is other than hydroxyl are at times referred to herein as the derivatized embodiments of the compounds of the present invention. it can also be seen in the definition of formula (1) that R² can be a substituent of the formula -L-X- (L-R- (OCH=CH-CH₂R¹) _n) _i . In these embodiments, a central moiety X is substituted with a total of (i+1) substituents of the formula (-L-R- (0CH=CH-CH₂R¹)_n) . Suitable X groups include, but are not limited to -Ph- groups, wherein -Ph- is phenylene (i.e. 1 , 2 -phenylene, 1 , 3 -phenylene, or 1,4- phenylene) , as well as -Ph-Ph-; -P _o^-C₈H_jg-Ph_o._! groups in which C_aH_2a is an alkylene group containing 1 to 20 carbon atoms; and groups consisting of a C_fH_2£ and a C_gH_2g moiety which are bonded to -C(O)-, -0- , -C{0)0-, -Ph- or -C(0)NH- and f and g are each 1 to 12. The C_aH_2a, C_£H_2£ and C_gH_2g groups can be straight or branched, and they can be attached to adjacent moieties at the same carbon atom (e.g. -CH₂-, CH₃CCH₃) or at different carbon atoms (e.g. -CH₂CH₂ - , -CH₂CH (CH₂CH₃) CH₂CH₂CHCH₂ - ) .

In formula (1) , L represents a linking group between the X moiety in each of the substituted R groups. Suitable linking groups L include a single chemical bond, -C(0)0-, -OC(0)0-, -O- , and -NHC(0)0- bearing in mind that in any case each R group is bonded to an oxygen atom of the linking group L. Also, when'L is a chemical bond, X can be -C(0)-.

Specific preferred examples of compounds in accordance with this description are provided hereinbelow.

The choice of routes for synthesizing the compounds of the present invention is dictated principally by the particular target compound desired. As will be seen below, in many cases there are several different routes available to synthesize a particular compound . To synthesize those embodiments of the present invention wherein R² is -OH, the preferred route is isomerization of the allyl ether analog of the desired propenyl compound. Those allyl ether analogs thus have the formula (1-A)

wherein R, R₁ and n are as defined herein. This allyl precursor, if not available commercially, can be prepared by reacting a precursor of formula R(OH)_n+1 with an appropriate number of moles of an allyl chloride of the formula Cl -CH_j-CH^CHR¹ (or the corresponding bromide) calculated to provide the desired hydroxyl substituted compound of formula (1- A) .

The allyl ether precursor of formula (1-A) is converted to the desired propenyl product by isomerization of the allyl compound. This isomerization is carried out in the presence of a small but effective amount of a catalyst for the isomerization, in the presence or absence of a solvent which is inert to the reactant, product and catalyst. Catalysts for the isomerization include strong bases, such as potassium t-butoxide-DMSO, and sodium amide. Other suitable catalysts for this isomerization include transition metal -containing catalysts, such as tris (triphenylphosphine) ruthenium (II) dichloride, tris (triphenylphosphine) rhodium (I) chloride, ruthenium on alumina, and iron pentacarbonyl .

While complete isomerization of all allyl groups present to propenyl is preferred, it is also contemplated that some but not all allyl groups isomerize to propenyl.

Compounds of formula (I) wherein R² is alkoxy, phenoxy, acryloyloxy, methacryloyloxy, or A- (Het) _Q.AC (O) O- can be synthesized in either of two ways. One way involves the formation of the propenyl - substituted compound as described above wherein R² is hydroxyl, followed by derivatization of the hydroxyl - substituent by reaction thereof with a suitable reagent by which the desired R² group replaces the hydroxyl group. For instance, when the desired R² group is alkoxy, the corresponding hydroxyl - substituted compound can be reacted with the corresponding alkyl halide, such as alkyl bromide, under alkaline conditions. When the desired R² group is phenoxy; the hydroxyl -substituted compound of formula (1) can be reacted with p- toluene sulfonyl chloride to form an intermediate tosylate ester, which is then reacted with phenol to form the desired phenoxy compound. Acyloxy derivatives such as acryloyloxy, methacryloyloxy, A-0-C(0)0- and A-C(0)0- derivatives can be formed by reacting the corresponding acyl chloride or anhydride with the compound of formula (1) wherein R² is -OH. The urethane derivatives, of the formula A-NH-C (0)0- can be formed by reacting the corresponding isocyanate with a compound of formula wherein R² is -OH.

Another route for synthesizing compounds of formula (1) involves first reacting the allyl ether precursor having formula (1-A) to derivatize the hydroxyl group by employing any of the procedures available for derivatizing the hydroxyl -substituted propenyl compound, so as to form a suitably derivatized allyl compound, and then isomerizing the derivatized allyl compound to the desired propenyl product. The isomerization conditions and catalysts suitable for the isomerization are the same as described hereinabove with respect to isomerization of compounds of formula (1-A).

To produce compounds of the formula (1) wherein the R² substituent contains a linking group as defined hereinabove, it is preferred first to react the allyl analog wherein R² is hydroxyl, with a compound corresponding to the formula X-( -Z)_i+1. For this reactant, X is as defined above and the linking groups L are as defined hereinabove. The terminal group Z is any capping group which will leave the L group (or, when L is a chemical bond, leave the X group) upon reaction with the hydroxyl - substituted allyl reactant so as to permit formation of the desired linkage between the L groups and R groups. For instance, when the L groups are to be ester linkages between the X group and the respective R moieties, the group Z can be hydrogen or lower alkyl such that the reaction between the precursor X(-L-Z)_i+1 is a matter of esterification or transesterification. Other routes and suitable reactants permitting the incorporation of other L linking groups disclosed herein will be apparent to those of ordinary skill in this art. Following formation of the intermediate allyl analog in this manner, the intermediate is isomerized in the presence of any of the isomerization catalysts described hereinabove to form the product propenyl derivative having a plurality of propenyloxy groups attached to the X moiety through the R moiety and the L linking groups.

One example of the synthesis of such a multifunctional compound is the following: (termed herein Scheme A) :

TIPO

catalyst

Analogous compound where the 1 , 4 -phenylene is replaced by linear, branched or cyclic alkylene, or by other position isomers of phenylene, can be made by the same procedure from the appropriate diester.

Compounds containing -C(O)- in place of the - (0)CC₆H₄C(0) - moiety in Scheme A can be prepared by an analogous procedure from the diallyl precursor and diethyl carbonate in the presence of TIPO, (titanium tetra- isopropoxide) to form the allyl analog of the desired final product, followed by catalytic isomerization of the allyl groups to propenyl.

Compounds containing phenylene or straight, branched or cyclic alkylene in place of the - (0) CC₆H₄C (O) - moiety on Scheme A can be prepared by reacting the diallyl precursor and X-(hal)₂, wherein hal is chlorine, bromine or iodine, in the presence of e.g. NaOH or KOH, to form the allyl analog of the desired final product, followed by catalytic isomerization of the allyl groups to propenyl.

Compounds containing a - (O) CNH-X-NHC (0) linkage in place of the - (0) CC₆H₄C (0) - moiety in Scheme A can be prepared by reacting the diallyl precursor with the polyisocyanate X(NC0)_i in the presence of e.g. stannous octoate to form the analog of the desired final product, followed by catalytic isomerization of the allyl groups to propenyl.

Compounds containing a - (0) CO-X-OC (0) - linkage in place of the - (0) CC₆H₄C (0) -moiety in Scheme A can be prepared by reacting the diallyl precursor with X(0C(0)Cl)_i in the presence of e.g. tributylamine to form the allyl analog of the desired final product, followed by catalytic isomerization of the allyl groups to propenyl .

The propenyl compounds of formula (1) are readily polymerized by exposure to ultraviolet or electron beam radiation in the presence of a cationic photoinitiator . Among those photoinitiators which may be used to achieve polymerization are diazonium salts, diaryliodonium salts, triarylsulfonium salts, diaryliodosonium salts, triarylsulfoxonium salts, dialkylphenacylsulfonium salts, and dialkyl-4- hydroxyphenylsulfonium salts. Typically, these salts contain complex metal halide or other non-nucleophilic ions such as BF₄ ^", PF₆ ^" , SbF₆ ^", AsF₆ ^", C10₄ ^", CF₃S0₃\ (C₆F₆)₄B^" and the like. Examples of suitable photoinitiator salts are described hereinbelow and include those described in Crivello and Dietliker, in Chemistry & Technology of UV & EB Formulation For Coatings, Inks & Paints, Vol. 3, 1991, page 329, the disclosure of which is hereby incorporated herein by reference.

The amount of photoinitiator should be in the range of about 0.1 to 10% by weight based on the weight of the compound or compounds of formula (1) . As noted herein, the compositions containing compounds of formula (1) and one or more photoinitiators for polymerization of such compounds comprises one aspect of the present invention.

Rapid and complete polymerization of the compounds of formula (1) can be achieved by irradiating the composition with an electron beam dose on the order of 0.1 to 10 Mrad or ultraviolet radiation flux on the order of 10-30 mW/cm². Higher energy levels are also useful, especially when higher throughput speeds are desired or thicker masses of polymer are presented.

Photopolymerizable compositions containing the compounds for formula (I) can also contain any of the other additives customary for such uses, in the amounts thereof adequate to enable the additive to perform its desired function. Such additives include photosensitizers, fillers, flow control agents and the like. Examples of suitable materials for providing these functions abound in this field and are well known to those experienced in this field, and include the materials which are employed for those functions with other radiation- curable monomers such as acrylates and vinyl ethers. In addition, other comonomers may be present such as epoxies, vinyl ethers and 1-butenyl ethers. Films and coatings formed by irradiation of compositions containing any of the compounds of formula (I) exhibit satisfactory and even superior mechanical strength, adhesion to substrate, high temperature stability, and high reactivity. It is not necessary to formulate the photo-polymerizable or electron beam-polymerizable composition in a solvent, thus permitting the operator to avoid the hazards and inconvenience of using solvents. The following Table 1 identifies particular R² substituents which are referred to in the following examples and discussion:

Table 1

In the following Examples, derivatives of trimethylolpropane diallyl ether and of trimethylolpropane dipropenyl ether were prepared. The diallyl ether derivatives are identified with the number of the substituents in the R² position followed by the letter A, and dipropenyl ether derivatives are identified with the number of the substituent in the R² position followed by the letter P.

Examples

*H-NMR spectra were recorded either on a

Varian XL- 200 MHZ or Unity 500 MHZ spectrometer at room temperature in CDC1₃. Elemental analyses were performed by Atlantic Microlabs Inc, Norcross, GA.

Routine infrared spectra were obtained on a Midac FT- IR. Real-time IR were recorded on a Midac FT-IR (Midac Corp., Irvine, CA) equipped with a liquid nitrogen cooled MCT-detector at a scan rate of 270 scans per minute and a resolution of 4 cm^"1. The data was recorded using the software program LabCalc (Galactic Software, Salem CT) and processed with Grams/386 (Galactic Software, Salem CT) . The FT-IR was equipped with a UVEXS Co. Model SCU 110 UV lamp fitted with a fiber optical cable. The UV radiation flux on the sample was 17-18 mW/cm² .

Trimethylolpropane Di (1 -propenyl) methyl ether (IP)

Trimethylolpropane diallyl ether (20 g, 93 mmol), 14.1 g (112 mmol) of dimethyl sulfate, 4.48 g (112 mmol) of powdered sodium hydroxide and 50 mL of toluene were combined in a three neck round bottom flask equipped with a thermometer, overhead stirrer and a reflux condenser. The suspension was stirred for 10 minutes at 40°C. Tetra-n-butylammonium bromide (0.2 g) were added and the suspension was heated to 110°C for 6 hours. The solution was cooled to room temperature, extracted with a 1 M sodium hydroxide solution, washed three times with water and the solvent was evaporated. The residue was subjected to fractional distillation under reduced pressure (b.p. 55°C/0.3 mm, Yield: 19.4 g; 91%).

^JH-NMR (CDC1₃) :δ(ppm) 0.84 (t,3H), 1.42 (quart., 2H), 3.28 (s,2H), 3.34 (s,7H), 3.96 (d,4H), 5.16 (d,2H), 5.25 (d,2H), 5.89 (m,2H)

Allyl ether 1A (17 g,74 mmol) and 0.02 g (22 μmol) of tris (triphenylphosphine) ruthenium (II) dichloride were heated under nitrogen for 1 hour to 160°C. The propenyl ether IP was distilled under reduced pressure (b.p. 48°C/0.25mm; Yield:16.7 g, 98%) .

*H-NMR (CDC1₃) :δ=0.84 (m,3H), 1.42 (m,2H), 1.56 (d, 3H,CH₃ trans -propenyl ether), 1.59 (d,3H,CH₃ cis- propenyl ether), 3.28 (s,2H), 3.35 (s,3H), 3.52 (s,2H, trans -propenyl ether), 3.62 (s , 2H, cis -propenyl ether), 4.33 (m, IH, cis -propenyl ether), 4.78 (m,lH, cis- propenyl ether), 5.95 (m, IH, cis-propenyl ether), 6.21 (d, IH, trans -propenyl ether)

Elemental Analysis : Calculated for C₁₃H₂₄0₃, C, 68.38 %, H, 10.59%.

Found C:, 68.36%; H,10.55%

Synthesis of Trimethylolpropane Di (1 -propenyl) Butyl (2A) and Octyl (3A) Ethers Trimethylolpropane diallyl ether (10 g, 46.7 mmol), 93.3 mmol of n-butyl or n-octyl bromide, 15.7g of potassium hydroxide and 90 mL of DMSO were stirred for two hours at room temperature. The solution was diluted with 200 mL of water and extracted twice with 50 mL of ethyl acetate. The combined organic phases were washed with water and then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue was distilled under reduced pressure yielding 67% 2A (b.p. 110°C/0.1mm) .

²H-NMR (CDCl_j) : δ(ppm)=0.84 (m,6H), 1.35 (quint., 2H), 1.42 (quart. ,2H), 1.57 (quint. ,2H), 3.28 (s,2H), 3.34 (s,4H), 3.40 (t,2H), 3.96 (d,4H), 5.16 (d,2H), 5.25 (d,2H) , 5.89 (m,2H)

In a similar fashion, 3A (b .p.145°C/0.05 mm) was prepared in 56% yield.

*H-NMR (CDCI₃) : δ(ppm)=0.84 (m,6H), 1.25-1.36 (m,8H), 1.42 (quart., 2H) , 1.53 (quint. ,2H), 3.28 (s,2H), 3.32 (s,4H), 3.39 (t,2H), 3.96 (d,4H), 5.16 (d,2H), 5.25 (d,2H) , 5.89 (m,2H)

Both of the allyl ethers 2A and 3A were isomerized completely by heating at 170°C for 1 hour with 0.02 g (22 μmol) of tris (triphenylphosphine) ruthenium (II) dichloride as the catalyst . Trimethylolpropane di (1 -propenyl ) n-butyl ether 2P (b.p. 113°C/0.2mm) was obtained in a 95% yield.

^:H-NMR (CDC1₃) : δ(ppm)=0.82-0.90 (m,6H), 1.38 (m,2H) 1.38-1.59 (m,12H), 3.28 (s,2H), 3.39 (t,2H), 3.55 (s , 2H, trans -propenyl ether), 3.64 (s , 2H, cis-propenyl ether), 4.33 (m, IH, cis -propenyl ether), 4.78 (m, IH trans -propenyl ether), 5.95 (m, IH, cis -propenyl ether), 6.12 (d, IH, trans -propenyl ether)

Elemental Analysis: Calculated for C₁₆H₃₀O₃ :C, 73.57%;

H:11.73%.

Found: C, 73.63%; H, 11.70%.

Trimethylolpropane di (1 -propenyl) n-octyl¹ ether 3P was obtained in 98% yield (b.p. 155°C/0.1 mm) .

^:H-NMR (CDCI₃) : δ(ppm)=0.80-0.91 (m,6H), 1.22-1.61 (m,22H) 3.30 (s,2H), 3.39 (m,2H), 3.55 (s, 2H, trans- propenyl ether), 3.64 (s,2H, cis-propenyl ether), 4.33 (m,lH, cis-propenyl ether), 4.78 (m,lH, trans -propenyl ether), 5.95 (m,lH, cis-propenyl ether), 6.12 (d,lH, trans -propenyl ether)

El emental Analysis : Calculated for C₂₀H₃₈O₃ : C , 73 . 57% ;

H , 11 . 73%

Found : C , 73 . 63% ; H , 11 . 70% . Synthesis of Trimethylolpropane Di (1 -propenyl) phenyl Ether (4A)

Trimethylolpropane diallyl ether (30 g, 140 mmol) , 50 mL of pyridine and 50 mL of toluene were combined in a two neck flask. The solution was heated to 60°C and 38.13 g (200 mmol) p- toluenesulfonyl chloride dissolved in 100 mL of chloroform were added dropwise over a period of 1 hour. The solution was stirred at 60°C for an additional three hours. After cooling to room temperature, the solution was extracted with saturated sodium bicarbonate solution until no more carbon dioxide was evolved. After washing three times with water, the solvent was evaporated and the crude product used for further reactions. The yield of trimethylolpropane diallyl ether tosylate ester was 46.1 g (89%) .

*H-NMR (CDC1₃) :δ(ppm) 0.79 ppm (t,3H), 1.3 (quart ., 2H)

2.42 (s,3H), 3.22 (s,4H), 3.83 (d,4H), 3.96 (s,2H),

5.14 (d,2H), 5.19 (d,2H), 5.89 (m,2H), 7.32 (d,2H), 7.78 (d,2H)

El emental Analysis : Calculated f or C₁₉H₂₈0₅ : C , 61 . 93% ; H ,

7 . 66% .

Found : C , 61 . 77% ; H , 7 . 61%

Potassium tert-butoxide (3.04 g, 27.1 mmol) were dissolved in 30 mL of DMSO. Phenol (2.55 g, 27.1 mmol) was added and the solution heated under nitrogen to 70°C. There were added 5 g (13.57 mmol) of trimethylolpropane diallyl ether tosylate and the dark solution was stirred at 70°C for 6 hours. After cooling, the solution was diluted with 70 mL water and then extracted twice with 60 mL ethyl acetate. The combined organic extracts were washed three times with

- 5* 50 mL portions of water, dried over Na₂S0₄ and the solvent removed by evaporation. The residue was distilled under reduced pressure (0.1 mm) at 150°C to give 2.01 g (51%) of colorless liquid 4A.

¹⁰ 'H-NMR (CDCl₃):δ= 0.90 ppm (t,3H), 1.57 (quart ., 2H) 3.42 (s,4H), 3.88 (s,2H), 3.96 (d,4H), 5.16 (d,2H), 5.25 (d,2H), 5.89 (m,2H), 6.91 (m, 3H) , 7.24 (m,2H)

The allyl ether was quantitatively !5 isomerized 'at 175°C for 1 hour with 0.02 g (22 μmόl) of tris (triphenylphosphine) ruthenium (II) dichloride as the catalyst. The yield of 4P (b.p. 155°C/0.2 mm) was 97%.

20 ^-NMR (CDC1₃) :δ(ppm) 0.90 (m,3H), 1.50-1.64 (m, 8H) , 3.65 (d,2H, trans -propenyl ether), 3.78 (d,2H, cis- propenyl ether), 3.88 (t,2H), 4.37 (m, IH, cis -propenyl ether), 4.78 (m, IH, trans -propenyl ether), 5.95 (m,lH, cis-propenyl ether), 6.22 (d, IH, trans -propenyl ether),

25 6.91 (m,3H) , 7.24 (m,2H)

Elemental Analysis: Calculated for C₁₈H₂₆0₃ : C, 74.45%; H, 9.02 %. Found: C, 74.55%; H, 9.02%

30

35 Synthesis of Trimethylolpropane Di (1 -propenyl) ether Acetate (5P)

Trimethylolpropane diallyl ether (20 g, 93.3 mmol) and 12.4 mL (121 mmol) of acetic anhydride were dissolved in 40 mL of toluene. One drop of pyridine was added and the solution heated to reflux for 16 h. After cooling, the solution was extracted with saturated sodium bicarbonate solution until no more gas was evolved. The solution was washed with water, and the organic layer separated and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator and the residue distilled under reduced pressure. The fraction boiling at 76°C/0.025 mm was collected. The yield of 5A was 22.7 g (95%) .

^:H-NMR (CDCl_j) :δ(ppm) 0.83 (t,3H), 1.43 (quart., 2H), 2.05 (s,3H), 3.33 (s,4H,), 3.93 (d,4H), 4.03 (s,2H), 5.15 (d,2H), 5.24 (d,2H), 5.87 (m,2H)

The isomerization of 5A to 5P was conducted with tris (triphenylphosphine) ruthenium (II) dichloride as the catalyst at 190°C under N₂. After 20 minutes the conversion to the propenyl ether 5P was complete as determined by ^-NMR. The product was purified by fractional vacuum distillation to yield compound 5P in 97% overall yield (b.p. 82°C/0.05 mm).

^XH-NMR (CDC1₃) :δ(ppm) 0.87 (m,3H), 1.46 (m,2H), 1.53- 1.59 (m,6H), 2.06 (s,3H), 3.57 (d, 2H, trans -propenyl ether) , 3.63 (d, 2H, cis-propenyl ether), 4.02 (t,2H), 4.37 (m, IH, cis -propenyl ether), 4.77 (m,lH,trans- propenyl ether), 5.91 (m, IH, cis -propenyl ether), 6.21 (d, IH, trans -propenyl ether)

Elemental Analysis: Calculated for C₁₄H₂₄0₄ :C , 65.60%; H,9.44% Found: C, 65.49%; H,9.48%

Preparation of Trimethylolpropane Di (1 -propenyl) Ether Acrylate (6P)

There were combined 10 g (47 mmol) of trimethylolpropane diallyl ether, 30 g (0.234 mol) of n-butyl acrylate and 0.5 g of titanium (IV) tetra isopropoxide (TIPO) was added. The solution was stirred under nitrogen at 150°C for 10 hours. After this time, the solvent and the excess n-butyl acrylate were removed by distillation under reduced pressure. The fraction boiling at 112°C/0.05 mm was collected. The yield of 6A was 7.06 g (56%) .

*H-NMR (CDC1₃) :δ(ppm) 0.87 (t,3H) , 1.43 (quart., 2H) , 3.36 (s,4H) , 3.92 (d,4H) , 4.12 (s,2H) , 5.15 (d,2H) , 5.22 (d,2H) , 5.79-5.89 (m, 3H) , 6.12 (m,lH) , 6.39 (d,lH)

Elemental Analysis: Calculated for C₁₅H₂₄0₄:C, 67.14%;

H, 9.01%.

Found: C, 67.21%; H, 9.12%. Allyl ether 6A was quantatively isomerized 1 as described in the previous examples by heating for 20 minutes at 190°C under nitrogen. The conversion was complete after 25 minutes. The distilled product was extremely sensitive to air and polymerization took 5 place upon exposure to air. Attempts to stabilize the compound by adding such free radical inhibitors as hydroquinone and tert. -butyl catechol also resulted in polymerization during the isomerization reaction.

0 ³H-NMR (CDC1₃) :δ(ppm) 0.87 (m,3H), 1.50 (m, 8H) , 3.58 (d,2H), 3.65 (d,2H), 4.15 (t,2H), 4.38 (m,lH, cis- propenyl ether), 4.77 (m, IH, trans -propenyl ether), 5.80-6.41 (m,5H)

5 Preparation of 1- Propenyl Ether Substituted Uretha,nes 8P and 9P

Combined in a 100 mL round bottom flask equipped with a magnetic stirrer, reflux condenser and nitrogen inlet were 10 g (46.7 mmol) of 0 trimethylolpropane diallyl ether and 61 mmol of either phenyl isocyanate or n-butyl isocyanate, then 0.01 g

(0.15 mmol) of di -n-butyltin dilaurate were added.

The solutions were stirred at room temperature for 30 minutes and then heated to 60°C and stirred for an

^ additional 30 minutes. After cooling, the products were purified by distillation in a Bϋchi microdistillation apparatus.

0

5 8A was obtained in 97% yield with a b.p. of 180°C/0.1 mm.

^-NMR (CDCl_j) :δ(ppm) 0.85 (t,3H), 0.92 (t,3H), 1.32- 1.50 (m,6H), 3.17 (m,2H), 3.30 (s,4H), 3.91 (d,4H), 4.02 (s,2H), 5.13 (d,2H), 4.61 (s,lH, NH) , 5.24 (d,2H) , 5.86 (m,2H) .

9A was not distillable, and was purified by removing the starting isocyanate by heating in the microdistillation apparatus to 180°C for 1 h under high vacuum (0.05 mm) . The yield was 94%.

*H-NMR (CDCI₃) :δ(ppm) 0.87 (t,3H), 1.46 (quart., 2H),

3.37 (s,4H), 3.96 (d,4H), 4.18 (s,2H), 5.16 (d,2H), 5.25 (d,2H),, 5.88 (m,2H), 6.60 (s,lH,NH), 7.05 (t,v

IH) , 7.30-7.41 (m,4H) .

Isomerizations of 8A and 9A were conducted with the ruthenium catalyst under nitrogen.

8A was isomerized to 8P in 8% yield after 2h at 180°C and purified by vacuum microdistillation (b.p. 182°C/0.1 mm) .

^- MR (CDC1₃) :δ=0.80 - 0.95 ppm (m,6H), 1.30-1.60 (m,12H), 3.18 (m,2H), 3.47 (d,2H, trans -propenyl ether), 3.62 (d, 2H, cis -propenyl ether), 4.04 (d,2H),

4.38 (m, IH, cis -propenyl ether), 4.62 (s,lH, NH) , 4.78 (m, IH, trans -propenyl ether), 5.93 (m, IH, cis -propenyl ether), 6.21 (d,lH, trans -propenyl ether)

Elemental Analysis: Calculated for C₁₇H₃₁N0₄ : C, 65.14%; H,9.97%; N,4.47%. Found: C, 65.89%; H, 10.18%; N,4.05%.

9A was isomerized to 9P in 89% yield after 2h at 180°C. Purification was accomplished by vacuum microdistillation (b.p. 190°C/0.025 mm).

^-NMR (CDC1₃) :δ=0.80 - 1 ppm (m,6H), 1.45-1.70 (m, 8H) , 3.69-3.80 (m,4H), 4.20 (d,2H), 4.39 (m,lH, cis- propenyl ether), 4.79 (m, IH, trans -propenyl ether), 5.92 (m, IH, cis -propenyl ether), 6.22 (d,lH,trans- propenyl ether), 6.81 (s,lH,NH), 7.05 (t,lH), 7.29>- 7.40 (m,4H)

Elemental Analysis: Calculated for C₁₉H₂₇N0₄ : C, 68.44%; H, 8.16%; N, 4.20%. Found: C, 68.38%; H, 8.13%; N, 4.08%

UV Cure of Novel Monomers

Thin films (-25 μm) of the liquid monomers containing 0.5 mol% of I0C10 ( (4 -n-decyloxyphenyl) phenyliodonium hexafluoroantimonate) photoinitiator were drawn onto glass or steel panels and irradiated using a GE H3T-7 200 W medium pressure mercury arc lamp mounted at a distance of 12 cm from the sample. This apparatus was equipped with a mechanical shutter which could be opened to expose the samples to UV irradiation. With monomers 1P-7P, polymerization of the monomers took place within 0.5-1 second to give crosslinked solid films of the polymer. Monomer 8P did not polymerize under these conditions while longer irradiation times (1-2 minutes) were required to polymerize monomer 9P.

The polymerizations were also followed in detail by real-time infrared spectroscopy (RTIR) , a method described by Decker and Moussa in J. Polym. Sci. Part a: Polym. chem. , 28, 4329 (1990). For this solutions of the photoinitiator (IOClO) in a concentration of 0.5 mol% in the monomers were prepared. The solution was coated on a commercially available Saran® film (polyvinylidene chloride) . ^'•'The films were then covered by a second Saran film and this assembly mounted in conventional 5 x 5 cm slide frames. This sandwich was placed in a horizontally mounted Midac Corp. FT-IR spectrometer. The instrument was equipped with a UVEXS Co. Model SCU 110

UV lamp fitted with a fiber optic cable and the probe of the fiber optic cable positioned so as to direct UV irradiation onto the sample window of the spectrometer. UV intensity was measured with the aid of a Control Cure Radiometer and found to be 18-19 mW/cm². To determine the rate of polymerization the

IR band at 1660 to 1670 cm^"1 was followed. The conversion was calculated by integrating the areas of the peak at t₀ and t_end. The initial slopes of the curves (R_p[M]₀) were determined and are considered to be a measure of the reactivity of the monomers. In these studies, the acrylate substituted monomer 6P was not included since it is too unstable to be measured under air without polymerizing by oxygen induction. The results of the measurements are displayed and summarized in Table 2.

The results show that the methyl ether substituted monomer IP has the highest rate of polymerization. This is expected since it this monomer does not contain polar groups which could interfere with the propagating carbenium ions. In addition, the methyl ether group is relatively small, so that steric factors are also small. The n-butyl and n-octyl ethers (2P and 3P) undergo rather sluggish photopolymerizations with IOC10. The reason for the surprisingly low rates of polymerization is the limited solubility of the photoinitiator (IOC10) in these monomers. In contrast, when the polymerization is carried out using the much more soluble commercially available di (docecylphenyl) iodonium hexafluoroantimonate (UV 9380C) , both monomers polymerize very rapidly and to high conversions. The n-octyl ether, 3P, polymerizes with a higher conversion of the propenyl ether groups than the n- butyl ether 2P. One reason may be when the former monomer is polymerized a polymer which possesses a lower glass transition temperature is produced. -21

Table 2

Study of the UV Induced Polymerization of 1- Propenyl

Ether Monomer Compositions

* -IOC10 is (4 -n-decyloxyphenyl) iodonium hexafluoroantimonate and UV 9380C is di (dodecylphenyl) phenyliodonium hexafluoroantimonate

Claims

What Is Claimed Is:

1. A compound of the formula (1)

(0CH=CH-CH₂R¹)_n (1)

wherein n is an integer from 1 to 3;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms;

R¹ is -H or -CH₃;

R² is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A-(Het)₀.₁- C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -0- or -NH-; or R² is -L-X- (L-R- (0CH=CH-CH₂R¹)_n) i wherein up to (n- 1) -0CH=CH-CH₂R₁ groups can instead be -0CH₂CH=CHR¹; wherein X has any of the structures - Ph₀.₁-C_aH_2a- Ph^ -Pl _j- (cyclo-C₅.₂₀- alkyl) -Ph_g^- , -Ph-Ph-, or -Ph-, wherein Ph is phenylene and a is 1 to 20; -C_£H_2£C(0)C_gH_2g -C_£H_2£0C_gH_2g, -C_£H_2fC (O) 0C_gH_2g- , -C_£H_2£PhC_gH_2g- , or -C_£H_2£C (0) NHC_gH_2g- , wherein f and g are each 1 to 12; and each L is independently a chemical bond or -C(0)0-, -0C(0)0-, -0-, or -NHC(0)0-, provided that each R is bonded to an oxygen atom of L, and i is an integer from 1 to 3; or X is -C(O)-, each L is a chemical bond, and i is 1.

A compound according to claim 1 wherein

R¹ is -H.

3. A compound according to claim 1 of the formula

4 . A compound according to claim 1 of the formula R² - CH X₂₂C—

C4-4H1-J"R¹ )' 3

5. A compound according to claim 1 wherein R² is -OCH₃, -OC₄H₉, -OC₈H₁₇, -OC₆H₅, -0C(0)CH₃, -0C(0)CH=CH₂, -OC(0)OC₄H₉, -OC(0)NHC₄H₉ or -OC (0) NH-C₆H₅

6. A compound according to claim 1 wherein R¹ is -H and R² is -OC (0) -C₆H₄ -C (0) 0-R- (0CH=CHCH₃) ₂.

7. A composition comprising a compound according to claim 1 and an effective amount of a photoinitiator for radiation- induced polymerization thereof .

8. A composition according to claim 7 wherein R¹ is -H.

9. A composition according to claim 7 wherein said compound has the formula

10. A composition according to claim 7 wherein said compound has the formula

R² - CH₂C ( CH₂0CH=CH - CH_jR¹ ) ₃

11. A composition according to claim 7 wherein R² is -OCH₃, -OC₄H₉, -OC₈H₁₇, -OC₆H₅, -0C(0)CH₃,

-0C(0)CH=CH₂, -OC(0)OC₄H₉, -OC(0)NHC₄H₉ or -OC (0) NH-C₆H₅

12. A composition according to claim 7 wherein R¹ is -H and R² is -OC (O) -C₆H„ -C (0) 0-R- (0CH=CHCH₃)₂.

13. A process for forming a polymer comprising (a) forming a mixture comprising one or more compounds according to claim 1 and at least one cationic photoinitiator for polymerization of said compound, and

(b) irradiating said mixture with ultraviolet light or electron beam radiation of an energy level, and for a time, sufficient to polymerize said one or more compounds.

14. A process according to claim 13 wherein R¹ is -H.

15. A process according to claim 13 wherein said compound has the formula

16. A process according to claim 13 wherein said compound has the formula

R² - CH₂C ( CH₂0CH=CH - CH,!*¹ ) ,

17. A process according to claim 13 wherein R² is -0CH₃, -OC₄H₉, -OC₈H₁₇, -OC₆H₅, -0C(0)CH₃, -0C(0)CH=CH₂, -OC(0)OC₄H₉, -OC(0)NHC₄H₉ or -OC (0) NH-C₆H₅

18. A process according to claim 13 wherein

R¹ is -H and R² is -OC (0) -C _6fiHH₄,--CC((0O))00--RR-- ((OOCCHH==CCHHCCHH₃,))₂.

19. A product produced by the process of any one of claims 13 to 18.

20. A process of making a compound of the formula (1)

wherein n is an integer from 1 to 3;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms;

R¹ is -H or -CH₃;

R² is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A-(Het)₀.₁- C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -0- or -NH- ; comprising isomerizing a compound of the formula (2)

to said compound of the formula (1) in the presence of an effective amount of a catalyst for said isomerization .

21. A process according to claim 20 wherein R¹ is -H.

22. A process according to claim 20 wherein said compound has the formula

23. A process according to claim 20 wherein said compound has the formula

R² - CH₂C ( CH₂0CH=CH - CH-_jR¹ ) ₃

24. A process according to claim 20 wherein R² is -OCH₃, -OC₄H₉, -OC₈H₁₇, -OC₆H₅, -OC(0)CH₃, -OC(0)CH=CH₂, -OC(0)OC₄H₉, -OC(0)NHC₄H₉ or -OC (O) NH-C₆H₅

25. A process of making a compound of the formula (1)

wherein n is an integer from 1 to 3 ;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms; R¹ is -H or -CH₃;

1 R² is alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring,

5 phenoxy, acryloyloxy, methacryloyloxy, or A-(Het)₀.₁- C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -0- or -NH-; comprising isomerizing an allyl compound of the formula HO-R- (OCH₂CH=CHR¹) _n to a propenyl compound of

10 the formula HO-R- (OCH=CHCH₂R¹) in the presence of an effective amount of a catalyst for said isomerization, and then replacing the -OH group on said propenyl compound with R².

--5 26. A process according to claim 25 wherein

R¹ is -H.

27. A process according to claim 25 wherein said compound has the formula

20

25

28 . A process according to claim 25 wherein said compound has the formula

R² - CH,C (CH₂OCH=CH - CH-R¹ ) ,

30

35

29. A process according to claim 25 wherein R² is -OCH₃, -OC₄H₉, -OC₈H₁₇, -OC₆H₅, -OC(0)CH₃,

-OC(0)CH=CH₂, -OC(0)OC₄H₉, -OC(0)NHC₄H₉ or -OC (O) NH-C₆H₅

30. A process of making a compound of the formula

X- (L-R- (OCH=CHCH₂R¹)_n)_i

wherein n is an integer from 1 to 3; R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms;

R¹ is -H or -CH₃; wherein X has any of the structures -Ph₀.₁-C_aH_2a-Ph₀.₁ -Ph_p^- (cyclo-C₅.₂₀-alkyl) -Ph_g^- , -Ph-Ph-, or -Ph-, wherein Ph' is phenylene and a is 1 to 20;

-C_fH_2£C(0)C_gH_2g -C_fH_2£OC_gH_2g, -C_£H_2£C (0) OC_gH_2g- , -C_£H_2£PhC_gH_2q- , or -C_£H_2£C (0) NHC_gH_2g- , wherein f and g are each 1 to 12; and each L is independently a chemical bond or -C(0)0-, -0C(0)0-, -0-, or -NHC(0)0-, provided that each R is bonded to an oxygen atom of L, and i is an integer from 1 to 3; or X is -C(0) -, each L is a chemical bond, and i is 1. comprising reacting an allyl compound of the formula HO-R- (0CH₂CH=CHR¹) _n with a compound containing a moiety of the formula X- (L-)_i+1) to form an intermediate of the formula X- (L-R- (OCH-_jCH^CHR¹) _n) _i+1) and then isomerizing said intermediate to said compound of formula (1) in the presence of an effective amount of a catalyst for said isomerization.

31. A process according to claim 30 wherein R¹ is -H.

32. A process according to claim 30 wherein said compound has the formula

33. A process according to claim 30 of the formula

X- (L -CH_?C (CH₂0CH=CH -CH-^R¹) ₃) _i+1

34. A process according to claim 30 wherein said compound has the formula (CH₃CH=CHO)₂-R-OC(0) -C₆H₄ -C (0) 0-R- (0CH=CHCH₃) ₂1

AMENDED CLAIMS

[received by the International Bureau on 21 January 1999 (21.01.99); original claims 1-34 replaced by new claims 1-21 (7 pages)]

1. A compound of the formula (1)

(OCH^H-CH-R¹)-, sr (l)

wherein n is an integer from 1 to 3;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms ; R¹ is -H or -CH₃; R² is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A-(Het)₀.₁- C(0)0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -0- or -NH-; or R² is -L-X- (L-R- (OCH=CH-CH₂R¹)_n)₁ wherein up to (n-1) -OCH=CH-CH₂R₁ groups can instead be -OCH₂CH=CHR¹; wherein X has any of the structures ■ Ph₀.₁- C_AE_2a- 'Ph_t>._l -Ph₀..- (cyclo-C₃.₂₀- alkyl) -Ph₀.,- , -Ph-Ph-, or -Ph-, wherein Ph is phenylene and a is 1 to 20; -C_£H_2ΣC(0)C_ςH_2β -C_£H,_sOC_βH_3g, -C_tH„C (O) 0C_gH_2(-- , -C_fH_2£PhC_σH_2α- , or "'C_CH₂₍C (0)NHC,-K_Zg- , wherein f and g are each 1 to 12; and each L is independently a chemical bond or -C(0)0-, -0C(0)0-, -0-, or -NHC(0)0-, provided that each R is bonded to an oxygen atom of L, and i is an integer from 1 to 3 ; or X is -C(O) -, each L is a chemical bond, and i is 1. . A compound according to claim 1 wherein R¹ is -H.

3. A compound according to claim 1 of the formula

4 . A compound according to claim 1 of the f orm l

R² - CH-C ( CH₂0CH=CH - CH^¹ ) ,

5. A compound according to claim 1 wherein R² is -OCH₃, -OC_aH₉. -OC₈H₁₇, -0C₆H_s, -OC(0)CH₃.

-OC(0)CH=CH,, -OC(0)OC,H₉, -0C(0)NHC_cH₉ or -OC (0)NH-C₆H_5,

6. A compound according to claim 1 wherein R' is -H and R² is -OC (0) -C_SH,-C (0) 0-R- (0CH=CHCH₃) ₂.

7. A composition comprising a compound according to any one of claims 1-6 and an effective amount of a photoinitiator for radiation- induced polymerization thereof .

8. A process for forming a polymer comprising (a) forming a mixture comprising one or more compounds according to claim 1 and at least one cationic photoinitiator for polymerization of said compound, and (b) irradiating said mixture with ultraviolet light or electron beam radiation of an energy level, and for a time, sufficient to polymerize said one or more compounds .

3 . A process of making a compound of the formula (1)

wherein n is an integer from 1 to 3; R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms ; R¹ is -H or -CH₃; R² is -OH, alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A- (Het) ,^-C (0) O- wherein

A is alkyl containing I to 20 carbon atoms, and (Het) is

-O- or -NH- ; comprising isomerizing a compound of the formula (2)

^ ² to said compound of the formula (1) in the presence of an effective amount of a catalyst for said isomerization.

10. A process of making a compound of the formula (1)

wherein n is an integer from 1 to 3 ;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms;

R² is alkoxy containing 1 to 20 carbon atoms which is optionally substituted with phenyl and two consecutive carbon atoms of which are optionally bonded to an oxygen atom to form an epoxy ring, phenoxy, acryloyloxy, methacryloyloxy, or A- (Het) _0-1-C (O) 0- wherein A is alkyl containing 1 to 20 carbon atoms, and (Het) is -0- or -NH-; comprising iεo erizing an allyl compound of the formula HO-R- (OCHjCHsCHR¹)., to a propenyl compound of the formula HO-R- (OO^CHCH-R¹) in the presence of an effective amount of a catalyst for said isomerization, and then replacing the -OH group on said propenyl compound with R².

11. A process according to any one of claims 8-10 wherein R¹ is -H.

12. A process according to any one of claims 8-10 wherein said compound has the formula

13. A process according to any one of claims 8-10 wherein said compound has the formula

R^z-CH₂C (CH₂OCH=CH-CH_jR¹) ₃

14. A process according to any one of claims 8 to 10 wherein R² is -OCH₃, -OC₄H-, -OC₈H_17/ -OC₆H₅, -

OC(0)CH,, -OC(0)CH=CH₂, -OC(0)OC₄H₉, -OC (0) NHC„H₉ or - OC(0)NH-C₆H₅

15. A process according to any one of claims 8-10 wherein R¹ is -H and R² is -OC (O) -C₆H₄ -C (0) O-R-

(OCH=CHCH₃)₂.

16. A product produced by the process of any one of claims S to 15.

17. A process of making a compound of the formula

wherein n is an integer from 1 to 3;

R is linear, branched or cyclic alkyl containing 1 to 6 carbon atoms ; R^λ is -H or -CH-; ' wherein X has any of the structures -Ph₀.₁-C_aH_2a-Ph₀.₁

-Ph₀.._- (cyclo-C₃._S0-alkyl) -Ph,,._!- , -Ph-Ph-, or -Ph-, wherein Ph is phenylene and a is 1 to 20;

-CH_2fC(0)C,H_2a -C_fH_2f0C,H_-ff. -C_fH„C (0) 0C_gH_2g- , -C_fH„PhC,H_2g- , or -C_fH_2fC(0)NHC,H_2g- , wherein f and g are each 1 to 12; and each L is independently a chemical bond or

-C(0)0-, -0C(0)0-, -0-, or -NHC(0)0-, provided that each R is bonded to an oxygen atom of L, and i is an integer from 1 to 3; or X is -C(0)-, each L is a chemical bond, and i is 1. comprising reacting an allyl compound of the formula HO-R- (0CH₂CH=CHR¹)_n with a compound containing a moiety of the formula X-(L-)_{i l)} to form an intermediate of the formula X- (L-R- (0CH₂CH=CHR¹) _a) _i ) and then isomerizing said intermediate to said compound of formula (1) -in the presence of an effective amount of a catalyst for said isomerization.

18. A process according to claim 17 wherein R^* is -H.

19. A process according to claim 17 wherein said compound has the formula

CH,OCH=CH-CH,R¹ I X- (L-CH₂C-CH₂CH₃)_i+1

CH₂OCH=CH-CH,R¹

20. A process according to claim 17 of the formula X - ( L - CH₂C ( CH₂OCH=CH - CH^¹ ) ₃ ) _l+1

21. A process according to claim 17 wherein said compound has the formula (CH₃CH=CHO)₂-R-OC(0) -C₃H_t-C (0) 0-R- ( OCH=CHCH₃ ) ₂.