AU628479B2 - Vinyloxy hydroxyalkylcycloalkane and preparation therefor - Google Patents

Description

OPI DATE 05/09/90 PCi' A0JP DATE 11/10/3O APPLN. I D 4j9557 PCT NUMBER PCT/US90/0OO34 INTERNATIONAL APPLICATION PUBLISHED UNDER THE Y)ATENT COOPERATION TREATY (PCT) (511 Interna~tioInal P,,tent'Classificatn 5 I i1iInterna~tinal Pubica2tion Nuimber: WO 90/09364 C07C 41/08, 43/178 Al (43) International Publication Date: 23 August 1990 (23.08.90) (21) International Application Number: (22) International Filing Date: Priority data: 307,457 8 Februa 371,168 26 June 1 PCT/US9O/00034 4 January 1990 (04.01.90) (81) Designated States: AT (European patent), AU, BE (European patent), CA, CR (European patent), DE (European patent), DK (European patent), ES (European patent), FR (European patent), GB (European patent), IT (European patent). JP, LU (European patent), NI. (European patent), SE (European patent).

ry 1989 (08.02.89) 989 (26.06.89) Pnmhisha SECTION I DIRECTION SEE FOLIO q NAME DIRECTED TES? 1 V J i n- n S >C.

g Ig W uck,-\ iC3 C\ 9f4-QQ.+ 1 UJI m\4 F-C) I) ,j Li C s.R Qr a t 07470 (US) 6 (54)Title: VINYLOXY HYDROXYALKYLCYCLOALKANE AND P .EPARATION THEREFOR (57) Abstract The invwntion relates to a vinyloxy hydroxtyalkyl cycloalkylene having the formula HO(CH 2

CH,,

wherein x has a value of from I to 10; x' has a value of from 0 t, 10 and A is a cycloalkylene gro-up having from 3 to 8 carbon atoms in the ring and is optionally substituted with lower alkyl. The invention also relates to the method for synthesizing the above compounds.

WO 90/09364 PCT/US90/0003 4 VINYLOXY HYDROXYALKYLCYCLOALKANE AND PREPARATION THEREFOR BACKGROUND OF THE INVENTION This invention relates to compounds having a vinyl group and a hydroxyl group as terminal groups of the compound. More particularly, this invention relates to monomers which possess a vinyl ether substituent and a hydroxyl substituent.

Urethane polymers have had great commercial success when used as protective coatings, films and adhesives. The genesis for these polymers is usually a monomer having both an acrylic functional group and a hydroxyl functional group. In the process for making a protective coating or film the hydroxyl group is converted to a urethane group by reaction with an isocyanate. The resulting acrylic urethane monomer is then applied to a surface and cured thereon by radiation. However, this process for producing urethane coatings and films has many shortcomings.

Since the polymerization and curing of acrylic functional groups proceeds by a free radical mechanism, polymerization and curing must be carried out in the absence of air, a known free radical inhibitor. Tl.e oxygen free atmosphere can be achieved by effecting the polymerization under a blanket of nitrogen; however this requirement greatly increases the cost of the process.

Another disadvantage in the preparation of acrylic urethane coatings is that a curing rate sufficiently high to meet certain requirements such as coatings for automotive fascia, etc., are not achievable by radiation exposure. Finally, it is found that urethane coatings made from acrylic urethane monomers have poor adhesion to hard, smooth surfaces such as metal or glass.

I i i_:L WO 90/09364 PCT/US90/000 34 2- It is therefore an object of this invention to provide a compound which can be converted to a urethane monomer having a high radiation cure rate in the absence or presence of air to produce a coating of excellent adherence to hard surfaces such as glass or metal.

Another object is to provide an economical and commercially feasible process for the manufacture of the present cotmpounds.

Still another object is to provide a substrate coated with the present compound which possesses superior stability.

These and other objects of the invention will become apparent from the following description and disclosure.

THE INVENTION In accordance with this invention, there is provided a vinyloxy hydroxyalkyl cycloalkane compound having the structure

HO(CH

2 )x-A-(CH 2 )x,OCH=CH2 wherein x has a value of from 1 to 10; x' has a value of from 0 to 10 and A is a cycloalkylene group having from 3 to 8 carbon atoms in the ring and is optionally substituted with lower alkyl. Preferred of this group are those compounds wherein x and x' each have a value of from 1 to 4 and, most preferably, where A is cyclohexylene.

WO 90/09364 pCT/US90/0003 4 -3- The compounds of this invention are useful chemical intermediates. For example, these products can be polymerized to branched structures having repeating units of -(H-CH2) n

O

(CH

2 )x,-A-(CH2)xOH The polymer chains, in turn, can be cross-linked at the terminal hydroxy group by condensation, by dehydration or by reaction with polyols, such as diols, to form the corresponding ethers. Additionally, they can be reacted with diacids, both aliphatic and aromatic dicarboxylic acids, to form the corresponding esters. These polymers, because of branching and/or cross-linking provide coatings which are more resistant to chemical attack and abrasion than linear types and are adapted to curing by irradiation at a reasonably high rate. Also, the polymers provide a harder more durable surface on the substrate after curing than the linear polymerized products. A major advantage of the present products is their ability to be converted to vinyl ether urethanes by reaction with an isocyanate, e.g. according to the equation: 2HO(CH 2 )x-A-(CH 2 )xOCH=CH 2

C

6

H

4

(NCO)

2 0 0 CH2=CHO ((CH),-A-CH 2 x -HN NH- C O

(CH

2 x A- (CH 2 OCH=CH2

J-

WO 90/09364 PCT/US90/00034 4 These urethanes polymerize and are rapidly cured by a zationic mechanism activated by radiation, e.g. from UV light or an electron beam source, to form hard, durable coatings; thus eliminating the need for formation under a blanket of nitrogen which is required by free radical polymerization and curing.

It is readily apparent that the present compounds can also be employed as monomers in copolymerizations with other monomers selected from the groups consisting of olefinic compounds, maleic anhydride, vinyl pyrrolidone, acrylics, methacrylics, etc. The products in their non-polymerized state are also useful in the formation of many non-polymeric compounds through condensation, dehydration, esterification, substitution at the hydroxy site or addition to the terminal vinyl group; thus providing useful' multifunctional reaction intermediates.

The present products are readily synthesized by reacting a diol corresponding to the formula

HO(CH

2 )x-A-(CH 2 )xOH with acetylene. Examples of suitable diols include 1,4-di(hydroxymethyl) cyclohexane; cyclooctane; 1,3-di(hydroxyethyl) ethylcyclopentane; 4(4-hydroxycyclohexyl) butanol; (3-hydroxy)-2,5-dimethyl-cyclooctyl decanol; etc. In this reaction the mole ratio of diol to acetylene can vary between about 1:1 and about 1:1.5. At low reaction pressure, the acetylene can be introduced into the reaction zone without dilution; however, at elevated pressures, it is recommended that an inert non-oxygen contaning gaseous diluent such as nitrogen, a C1-C 3 WVO 90/09364 pCrIUS90/00034 alkane or helium be used to dilute the acetylene reactant. When the diluet is employed, acetylene concentration as low asAlO% can be used although between about 40 and about 60 wt. acetylene in diluent is most preferred.

The above reaction is carried out in an oxygen free atmosphere which is generally achieved by purging with nitrogen and is effected in the presence of a basic catalyst such as an alkali metal hydroxide, e.g. potassium hydroxide, or sodium hydroxide as potassium alkoxide or an amine. The concentration of catalyst employed can range from about 0.1% to about 5% by weight.

The process is effected at a temperature of between about 1200C. and about 200 0 C. under from about to about 200 psig. in a period of from about 2 to about hours reaction time. Preferred conditions include a temperature of between about 140 0 C. and about 170 0

C.,

under between about 50 and about 100 psig. for a period of from about 4 to about 8 hours.

Having thus generally described the invention, reference is now had to the following examples wh.ich illustrate preferred embodiments but which are not to be construed as limiting to the scope of the invention as more broadly set forth above and in the appended claims.

Molten l,4-bis-(hydroxymethyl) cyclohexane (1802.6 grams) and 36 grams of potassium hydroxide pellets were charged with a one gallon autoclave. The autcicave was purged three times with nitrogen, then evacuated to 10 mm of mercury pressure and heated at 900C.

for 30 minutes to remove water of reaction.

WO 90/09364 PCT/US90/00034 6 Propane gas was introduced into the autoclave to psi and the autoclave heated to 160 0 C. Additional propane gas was added at 160°C. until the pressure reached 100 psi. Acetylene was then introduced until a total pressure of 200 psi was achieved. After 6.5 hours at 200 psi and 160 0 C. the autoclave was cooled to room temperature, purged 3 times with nitrogen, and its contents discharged.

The crude product (1,816 was distilled under vacuum (1 mm Hg) using a 15 plate Oldershaw column, and a clear water white fraction boiling between 95 0 C. and 110 0 C. was collected. The fraction boiling at 102 0

C.

weighed 263 grams and was identified as 99.3% pure monovinyl ether of 1,4-bis-hydroxymethyl cyclohexane by nmr, using CD C13 solvent.

For example, Example 1 was repeated except that cyclooctane is substituted for 1,4-bis-(hydroxymethyl) cyclohexane. The divinyl ether product is recovered in greater than 90% yield.

Claims (12)

1. A method of synthesizing the compound having the structural formula HO (CH 2 x-A- (CH 2 x OCH=CH2 wherein x has a value of from 1 to 10; x' has a value of from 0 to 10 and A is a cycloalkylene group having from 3 to 8 carbon atoms in the ring and is optionally substituted with lower alkyl which comprises reacting a diol having the structure HO(CH 2 )x-A-(CH 2 )xOH wherein x, x' and A are as defined with acetylene in an inert diluent in an oxygen free atmosphere at a temperature of from about 120 0 C. and .abet 200 0 C. under a pressure of from about 10 psig. to aboct 200 psig. and recovering the product of the process.

2. The method of Claim 1 wherein the reaction is effected under a pressure of from about 20 psig. to about 100 psig. and the acetylene is diluted with an inert gas.

3. The method of Claim 2 wherein the concentration of acetylene in said gas is between about and about 60% by weight. 8

4. The method of Claim 2 wherein said gas is selected from the group of nitrogen, a C 1 to C 3 alkane and helium.

The method of Claim 4 wherein said gas is propane.

6. The method of Claim 2 wherein acetylene is diluted to a concentration of between about 40% and about 60% by weight.

7. The method of Claim 1 wherein said reaction is effected at a temperature of between about 140 0 C. and about 170 0 C. under from about pqig. to about 100 psig. in the presence of a basic catalyst.

8. The method of Claim 7 wherein said catalyst is an alkali metal hydroxide.

9. The method of Claim 2 wherein said diol is bis(hydroxymethyl) cyclohexane.

The product of the method of Claim 1 in at least 90% purity.

11. A method of synthesizing a vinyloxy hydroxyalkylcycloalkane of the formula as set out in claim 1 substantially as hereinbefore described with reference to Example 1. S* DATED this TWENTY-FIRST day of MAY 1992 ISP Investments Inc. Patent Attorneys for the Applicant SPRUSON FERGUSON i /1546u INTERNATIONAL SEARCH REPORT International Application No, PCT/US9O/00034 1. CLASSIFICATION OF SUBJECT MATTER (it severvl -ciassifc~lion hSYmcols aboly. irccate all) According to International Patent Classification (IPC) or jo coin National Classrtlcailon and IPC C07C 41/08, 43/178 U.S. Cl: 568/670 11 FIELDS SEARCHED Minimum Documentation Searched Classillcation System Classiication Symbols U.S. 568/670 Documentation Searched other than Minimun Documnentation to the Extent that, such Documents are Included m the Fields Searched I IIl DOCU MENTS CONSIDERED TO GE RELEVANT'I Category l iaton of Document, 11with indication, where aooroorilte, Of the relevaint passages

12 X JP, A, 62-288666, 15 December 1987, See entire document I Relevant to Cla"' No I2 1-9 US, A, 4,775,732 (LAPIN) See entire document 04 October 1988 *Special catlgoe of Cited documents! 10 'IT" later document published after the intertnational rii'q :W1e document! defining the Ieea slate of the art ahich isno or priority dtt and not in conflict with the 31ao o C-1 coadee a eo prtulerleac cited to understand the principle or theory Uncterli,q *-e consdere to e ofpa= elevnceinve'ntion 1" earlier document but pubolsed an or after the international I*X doun of perticular relevance: the claimed m~e&, filing date cannot beit considered novel or cannot be consope. '0 document which may throw double on priority claimls) or involve an Inventive atop which as Cited to establish thoi publication date ot another "Y document of particular relevance: the claimed citation or other Special reason (ase ,pecified) cefina ie considered to involve an inventive sivo I.e "0D" document referring to an oral disclosure, use, exhibition or document is combined with one or mors Other S..c other means Ments, sach combination being obvious to a person e3 'IF" document publiahed prior to the international rlting date but in the art, later than the priority date Claimed 114" document member of the aome oatant family IV. CINTIPICATIOM Date ot the Actual Completion of the International Search Date of Mailing ot thia Internivionat Search Report 02 April 1990 2 7APR 191111 Into.1atlflal Searching Authority Signature of Authorized Officer i ISA/US Bruce D. Gray 6A(T~ Fuvit~~~~A 41C YI:tO1 we t