GB2392163A

GB2392163A - Soluble phenol-aldehyde condensate

Info

Publication number: GB2392163A
Application number: GB0219380A
Authority: GB
Inventors: Charles Stirling; Nicholas Hendrik Williams
Original assignee: University of Sheffield
Current assignee: University of Sheffield
Priority date: 2002-08-20
Filing date: 2002-08-20
Publication date: 2004-02-25
Also published as: GB0219380D0; WO2004018402A1; AU2003255809A1

Abstract

A soluble oligomer or polymer comprises an open-chain condensate of an aldehyde of formula, R-CHO, wherein R is a substituted or unsubstituted hydrocarbon group, or a precursor or derivative thereof, with a mono- or polyhydric phenol, or a precursor or derivative thereof. R is preferably a fluorinated group. The phenol is preferably resorcianol or pyrogallol. The oligomer or polymer may be chain extended or cross-linked. Also claimed is a method of making the condensate using an acid catalyst. A number of specific condensate structures are also claimed per se.

Description

ALDEHYDE PHENOL CONDENSATES

This invention relates to aldeRyde phenol condensates, and more particularly to certain cve2 ol_gomers and 5 polymers, and mixtures thereof, prepared by the condensation of aldehydes and phenols and precursors or derivatives thereof, and optional introduction of surface

reactive groups.

10 Phenol-aldehyde resins manufactured by polycondensation processes are widely used in industry. An example of such a manufacturing process is described in GB 1089936.

Aldehyde-resorcinol condensations have also been described by Niederl and Vogel, J. Am. Chem. Soc. (1990), 15 62, 2512-14 and Sen and Sinha, J. Am. Chem. Soc. (1923), 45, 2984-96.

AldeLyde phenol cyclic condensates are also known, and, for example, certain cyclic tetrameric structures known 20 variously as calixarenes and cone-type calix [4J resorcinarenes have been described in W097/39077 and EP0671220, together with their use as surface modifying agents. Calixarenes can be prepared, for example, from polyhydrlc phenols and aldebydes by acid-cata]ysed 25 condensation in an organic solvent under reflux or elevated temperature conditions. A detailed review of the different types of calixarenes and their methods of manufacture is given in Bohmer, Angew. Chem. Int. Ed.

Engl.1995, 34, 713-715.

Calixarenes can be difficult to purify, and separation from coloured impurities can also be difficult, which somewhat reduces their useful applications. The development of new aidebyde phenol condensates, which are simpler to manufacture and have improved properties,

À À r Àe À À would therefore be highly desirable.

Certain new open-chain oligomers and polymers, and mixtures of such oligomers and polymers have now been 5 discovered, which are prepared by the acid catalysed condensation of an aldehyde and a mono- or polyhydric phenol, or their precursors or derivatives.

In a first aspect, the invention provides a solvent-

10 soluble oligomer or polymer comprising an open-chain condensate of an aldehyde of formula: R - COO (I)

wherein R is a substituted or unsubst.tuted hydrocarbon group, for example, an alkyl group, or a fluorinated alkyl group, having from 5 to 20 carbon atoms, an alkenyl group, or a fluorinated alkenyl group, having from 5 to 20 20 carbon atoms, an aralkyl group, or a rluorinared aralkyl group, having from 5 to 20 carbon atoms, or a substituted or nonsubstituted aryl or fluorinated aryl group, which alkyl, alkenyl, aralkyl or aryl groups may contain substituent hetero-atoms, or a precursor or 25 derivative thereof, with a mono- or polyhydric phenol, or a precursor or derivative thereof.

In a second aspect, the invention provides a method of manufacturing a solvent-soluble oligomor or polymer 30 comprising an open-chain condensate of an aldehyde of formula (I), or a precursor or derivative thereof, and a mono- or polyhydric phenol, or a precursor or derivative thereof, which comprises condensing the aldebyde and the phenol, or their precursors or derivatives, in the 35 presence of an acid catalyst.

À À 1 C À

À 1 1

À 1 À

Be In a third aspect, the Invention provides a solvent-

soluble open-chain oligomer or polymer, or a mixture of oligomers or polymers, or both, prepared by the acid 5 catalysed condensation of an aldebyde of formula (I), or a precursor or derivative thereof, and a monoor polyLydric phenol, or a precursor or derivative thereof.

In a fourth aspect, the invention provides a method of 10 changing the surface properties of a material, which comprises contacting the materia' with a solution or dispersion of an oligomer or polymer comprising an open-

haln condensate of an aldehyde of formula (I), or a precursor or derivative thereof, and a mono- or l5 polyhydric phenol, or a precursor or derivative thereof, in a liquid medium.

It has been found to be unnecessary to iso].ate or purify individual oligomers and polymers from the condensation 20 reaction mixture, and for many applications it is preferred to use a mixture of oligomers and/or polymers for changing the surface properties of a material in the fourth aspect of the invention.

25 It is frequently found that the reaction products of the method of the second aspect of the invention are colourless mixtures, and for many purposes these are preferred for use in the fourth aspect of the invention.

3() To formula (T) the group R can be a substituted or unsubstiCuted hydrocarbon group, preferably an alkyl group, an alkenyl group, an aralkyl group, or similar, and may contain hetero-atoms, for example, oxygen, nitrogen or sulphur atoms in the alkyl or alkenyl chain, 35 or in substituent side groups of the alkyl, alkenyl or

À.. 1 1 1

À aralkyl groups.

The group R is preferably an alkyl group having from 6 to 18 carbon atoms, more preferably from 7 to 15 carbon 5 atoms, and most preferably from 9 Sac 12 _arbcn atoms. R may be a straight chain or branched chain alkyl group, and may have other substituents having hydrophobic properties, for example, fluorine atoms. Preferably the group R is a perfluoroalkyl group, preferably comprising 1() from 10 to 30 Cluorine atoms, more preferably from 15 to 25 fluorine atoms, or an alkyl chair terminated with a perfluoroalkvl segment having, for example, 6, 8 or 10 carbon atoms.

In other embodiments the group can comprise repeating units such as (-CH2CH?-O-) and/or nitrogen heterocyclic groups, f-cr example, pyridyl nd/or N-aLkyl and S-alkyl groups. The terminal segment can comprise, for example, perfluoralkenyl or hydroxyperfluoroalkyl.

Examples of suitable aldebydes include hexana', octanat, decanal, undec10-al, dodecanal, perFluoro-l---2,2-H-

hexanal, perfluoro-1-H-2,2-H-octanal and perfluoro-1-H-

2,2--decanal. Where R is an alkenyl group (which term in this specification includes both alkene and alkyne groups),

the oligomers and polymers of the invention can be further chain extended or cross-linked, and this is a 30 further aspect of the invention. Chain extension or crosslinking can be accomplished, for example, by the use of ultraviolet light, irradiation, or by other free-

radical initiators. Chain extension or cross-linking may, for example, improve the binding of the aldeLyde 35 phenol condensate to a substrate surface, improve the

À C t e À 1

C À s. strength of any mono- or multllayer film present on the surface, or provide sites for binding other reactive groups. 5 Precursors and derivatives of the aldehyde of formula (I) include the corresponding acetal.s, for example O-1, 3-

dioxanylethyl-O-methyltriethyleneglycol, and the corresponding imines.

10 The mono- or polyLydrc phenol preferably comprises a hydroxylsubstituted benzene ring, for example resorcinol or pyrogallol. Other polyhydric phenols which can be used include, for example, orcinol (5methylbenzene-1,3-

diol), 2- and 5-alkylylresorcinols, and 5 15 methexyresorcinol. Mono- or polyLydric phenols comprising more than one aryl group, or fused aryl groups are, however, not excluded. Examples of such more complex phenols include, for example, diLydroxynaphthaLenes.

Precursors and derivatives of mono- and polyhydri.c phenols that may be used in the invention include, for example, phenyl ethers.

25 In a preferred embodiment of the invention, the oligomer or polymer is an open-chain condensate comprising the unit:

. À À À À À

6.. (OH)p 1 10 '

15 R where n -s an integer greater than or equal to 1, D is 2 or 3, and lR is as previously defined/ the condensate hazings at least one terminal group selected from atoms, alenyl groups, hydroxt,,a.lkyt groups, ii'nydroxys-yl go groups, triLlydroxlary1 groups, perrluoroalkyl groups and perfLoroalkenyl Recoups.

Preferably n is an integer of from 2 to 6.

25 In addition to the terminal groups recited above, the new oligomers and polymers in accordance with the invention can also be terminated by other chain Germinating atoms or croups, as desired.

30 The oligomers and polymers of the present invention preferably have molecule masses of less than around 2500 Dalcons, more preferably less than 2000, most preferably less than 1500 Daltons.

35 Specific examples of oligomers and polymers according to

À t À À I C 1

C C,,,

the invention include: Il'T;: - meow=' =r-$r ca ót2 r,)q CEi Air 57.] Q 10 ''i:';e Li 'l,0ti At C.l.! C2)q tC-F')q Cat C.' 15; Dig,/ -G7-. E!C ^ ori \\,'' -

1 11 ( PA ^ C Li Offs (rF39 v CF; i rat cod CEi CH -id -,/ \=)1 2 CH2 C'47 a, ((l F)q 'CF)i (c'-u CF1 CEDE CF3

Where q is an integer of l rom 6 to 18, 3 0 OH CH OH

HOD,'< yeah 3 cat 35 1 (CHo) r(0H oCH2O) SO 7 ((,H')r(Ch OH 'USA

À À À a.e À C À À

Where r is an Integer off from 1 to 3, s is an integer of from 2 to 4, and R is -Cry, an alkyl qrcup, or a branched perfluoroalkyl group, OH (C2) x(CH2CH2o)yRl (CH2)(CF^r2CH2O)yR and -CAT OH H

He OH (CF9)XR! (CH7)CH=CH2

Where x is an integer of from 6 to 18, preferably 1 to 3, y is an integer of from 4 to 16, preferably 2 to 4, and R: is as before.

The condensation reaction can be performed at ambient temperatures, although the use of elevated temperatures is not excluded, provided that the principal products of the reaction are openchain condensates. Preferably the 20 condensation reaction 1S carried out at a temperature of from 15 to 30 C.

It has been Sound chat the products of the condensation

<, À 1 8

1 1 1 #,

I I À t À 1

reaction also depend upon the reaction time A reaction time of from 1 to 48 hours, preferably from 10 to 20 hours, for example, about 16 hours, is usually appropriate, but shorter or longer times can be used to 5 produce different product mixtures as desired.

The condensation reaction is preferably carried out without the presence of a solvent, and for example, the reactants, together with the acid catalyst, can be ground 10 together in a suitable vessel. It has been found that such solventiess procedures usually give rise to colourless products, usually in a period of minutes.

Where a solvent is present, it has been found that the nature of the organic solvent influences the chain length 15 of the oligomers and polymers. Sultable solvents that may be used are aprotic organic solvents such as, for example, tetrahydrofuran (THE), ethyl acetate, and ether.

The nature of the catalyst influences the reaction yield, 20 and strong acids such as hydrochloric acid, trifluoroacetic acid and sulphuric acid are preferred.

Other acids that can be used include toluene-p-sulfonic acid and oxalic acid.

25 The ratio of the reactants influences the complexity of the product mixture obtained, and preferred equivalent ratios include, for example, 1:1, 1:1.5, and 2:1 phenol: aldehyde.

30 The method of the fourth aspect of the invention can be used to change the surface properties of a wide range of materials. In many instances, the method can be used to change the contact angle of a surface to water or oil droplets, or to render a surface hydrophobic or water 35 repellent and/or oleophobic or oil repellent. In this

r I; 1 1 À 1. I Ir aspect, the method can be applied to a wide range of substrates, and especially hydrophilic substrates including, for example, paper, cotton, wood, leather, hair, teeth; metals, for example, steel, zinc, copper, 5 nickel, and aluminium; stone, glass; fabrics (especially hydrophilic synthetic fabrics), and hydrophilic polymeric materials. Other substrates, such as plastics materials and metals can be rendered oleophobic by the method of the invention. Oleophobic properties are particularly 10 improved by the use of fluoro-substltuted aldebyde phenol condensates according to the invention. For example, application of the fluoro-substituted condensates in aqueous emulsions, after drying, can render surfaces painted with emulsion paint both hydrophobic and 15 oleophobic. Other surface properties, for example, conductivity, may also be changed by the method of the invention. In the method of the fourth aspect of the invention, the 20 aldebyde phenol condensate solution or dispersion can simply be sprayed on to the substrate, or the substrate can be dipped into the solution or dispersion as appropriate. The aldebyde phenol condensate can be applied dissolved or dispersed in an organic solvent, 25 such as, for example, tetrahydrofuran or acetone.

Alternatively, the aldehyde phenol condensate can be applied as a dilute aqueous emulsion, comprising a small quantity of a volatile organic solvent. 'I'he concentration of the aldehyde phenol condensate in the solvent or 30 emulsion is preferably from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, most preferably from 0.05 to 1.5% by weight. The method is preferably carried out at ambient temperatures up to about 30 C.

35 In another important fifth aspect of the invention, the

t I I I If I t I t I I I Iret r I I I I

1 tar 1 1 1 À 8 phenol aldehyde condensates of the first aspect or the nventicn can be further reacted to introduce surface reactive groups into the oLigomer or polymer chain. By "surface reactive groups" in this specification is meant

5 groups which are capable of reacting with surfaces in order to bind the oligomer or polymer thereto. Such groups include, for example, aromatic ring substituents such as amino groups, especially when flanked by hyriroxyl groups, and unsaturated ether groups.

In the method cf the ri'th aspect c- the invention, the aldehyde thence condensates or che first aspect of We invention can, 'or example, be reacted with primary or secondary atones together with formalde.vde to give 15 Mann ch Products -A which a hydrogen atom ';lcnkec ball ydrox;, l:grcups On a arcatc ring is repicced by -.

monoalk;.,laminomethyi or dial<:ylaminomethyl group. Such new cl Comers and ovmers con give improved' binding Lo metals and are also included in the invencicn. Suen 0 compounds can, for exampl_, 'rave the formula: 25 The oH I 35 n x

À #. À eee À.. eas Where X is -CH'NR2 or -ORE, R2 is a substituted or un-

substituted alkyl or alkenyl group, preferably having from 1 to 6 carbon atoms, and R and n are as previously 5 defined.

In another example of the method of the fifth aspect of the invention, the aldeLyde phenol condensates of the first aspect of the invention can be partially or 10 completely etherified by treatment with a base and an appropriate alkenyl halide, for example, an allyl or propargyl halide, to insert one or more polymerisable groupings into the aromatic ring which are important for film durability in certain applications of the method of 15 the fourth aspect of the invention. Such new oligomers and polymers are also included in the invention and can, for example, have the formula: , l R -: I i, O H j p I 11 J '

I, 20! R 1 n

À: cle.:.:: c: À 1

* Where R3 is a polymerisable group, for example, an alkenyl, alkynyl, or alkoxycarbony groom, p is 2 or 3, is l or 2, and n is as previously defined.

5 Various embodiments of oligomers and polymers and methods of manufacturing and using them in accordance with the invention are illustrated by the fol ow ng Examples.

Evaluation of the surface modifications obtained is by lo dip and dry treatment of standard k tchen paper with known concentrations of oligomers and polymers followed by drying under standard conditions in air either at ambient temperature or at 140C. Oil refers to standard reagent grade liquid paraffin. NMR refers to proton NMR 15 in acetone. MAI.DI refers to matrix assisted desorpticn ionisation spectrometry which is a non-fragmenting method for obtaining molecular masses in the region 500 to 25,000 daltons. THE refers to tetrabydrofuran and TEA refers to trifluoroacetic acid.

Example l

Perfluoro-l-H-2,2-H-decanal (0.57 g) (derived from perfluoroocLyl iodide and ethyl vinyl ether) together 25 with resorcinol (136 mg, l equiv.) in tetrahydrofuran (TIlF) (.5 ml.) were treated with cone. hydrochloric acid (lml.). The mixture was stirred at 20 C for 24h. The slightly turbid mixture was evaporated in vacuo at 25mm and 50 C to give a residue (660 mg.) MALDI (Figure 1) 30 spectrometry showed molecular weight (663) consistent with a 2:l phenol: aldehyde condensate as the main product. NMR was consistent with this structure. This material gave high and persistent contact angles with water and with oil on kitchen paper treated by dipping in 35 a 0.2% solution of the material in THE at ambient

. À: À À À.: : À:..DTD: À À À, ., a À.e À À À temperature and drying at 140 . These effects persisted for at least 5 days. When the kitchen paper was treated with a 0.1% solution of the material in THF, water beads disappeared after 5 min. but oil beads persisted for at 5 least 24h.

Example 2

Perfluoro-1-H-2,2-H-decanal (513 mg.) and resorcinol (122 10 mg, 1 equiv.) in ether (5 ml.) were treated with trifluoroacetic acid (lml.) and the mixture was stirred at 20 C for l9h. Evaporation as above gave a residue (513 mg), (MALDI Figure 2). Kitchen paper, treated with this material as a 0.2% solution in THF at ambient 15 temperature, floated on water for at least 17 h and oil drops gave high contact angles. Water drops had lower contact angles than for the pyrogallol derived material of Example 3 below.

20 When ethyl acetate was used as the reaction solvent, MALDI spectrometry showed the main product to be the 2:3 phenol: aldehyde condensate.

When cone. HCl (lml.) was used in place of 25 trifluoroacetic acid and with a reaction time of 24 h, the slightly turbid reaction mixture was evaporated to give a product (660 mg) whose MALDI spectrum showed 2:T phenol condensate as well as other products with slightly larger molecular weights. At 0.2% in THF, this material 30 gave oil and water protection over 4 days to kitchen paper floating on the surface of water.

Example 3

35 Perfluoro-1-H-2,2-H-decanal (621 mg) and pyrogallol

q À À À c e I (169mg, 1 equiv.) in ether (5 ml.) were treated with trifluoroacetlc acid (lml.) and the mixture was stirred at 20 C for 60 h. The mixture was evaporated in vacua at 50 to give a residue (657mg.). This material gave high 5 and persistent contact angles with oil on kitchen paper treated by dipping in a 0. 290 THF solution of the material at ambient temperature, and drying at 140 . Paper floated for 5 days and there was no oil soak in. The same results were obtained with tetrahydrofuran (TIFF) as 10 reaction solvent.

When cone. HCI (lml.) was used in place of trifluoroacetic acid and with a reaction time of 24 h, the slightly turbid reaction mixture was evaporated to 15 give a product (660 mg) whose MALDI (Figure 3) spectrum showed 2:1 phenol condensate as well as other products with slightly larger molecular weights.

At 0.2% in THF, this material gave oil and water protection over 4 days to kitchen paper floating on the 20 surface of water.

Example 4

Perfluoro-1-H-2,2-H-decanal (570 mq) and pyrogallol 25 (233mg, 1.5 equiv.) in THF (5.5 ml.) were treated with cone. hydrochloric (lml.) and the mixture was stirred at 20 C for 24 A. The mixture was evaporated in vacuo at 50 to give a residue (710 mg.) MALDI (Figure 4) spectrometry showed a complex mixture of materials in the molecular 30 weight range 565 to 887.

This material gave high and persistent contact angles with oil on kitchen paper treated with a 0.2% solution in THF, dipped at ambient temperature and dried at 140 .

Contact angles with water were low but paper floated on 35 water 5 days and there was no oil soak in.

1 # À a When, in the method of Example 4, Ally was replaced by ethyl acetate as solvent and the react on. was carried out at 20 C for 60 hours, the product was shown by MAL,DI 5 (Figure 5) spectrometry to contain two se s of ollgomers with molecular weights centred a- 663 and 1303 respectively. The surface effects were similar to those of Example 4.

10 Example 4a

E'erfluoro-1-H-2,2-H--octanal (3.4 g.), pyrogallol (1.18 g. 1 equivalent) and toluene-p-sulfonic acid (5 mg.) were ground together for lO minutes and then set aside at 20 . After 18 h. the mixture was a viscous gum and 15 after 42 h was an amorphous solid. The product at 0. 2 5 in THE gave excellent long term (<1 week) water and oil resistance to kitchen paper. MALDI showed mass peaks at 1016 and 1032 consistent with a 2:1 aldebyde pyrogallol condensate (Figure 6).

Example 4b

Perfluoro-1-H-2, 2--octanal (1.0 g.2.76 meal), undec-

10-enal (232 mg. 1.38 moot.) pyrogallol (0.52 g. 4.14 mMol) and toluene-p- sulfonic acid (2.6 mg.) were 25 ground together for 15 minutes and then set aside at 20 . After 60 h., the mixture was ground with light petroleum bp 40-60 to remove any unreacted undecenal and the mixture was filtered to give the product (836 mg). NMR showed incorporation of both aldehydes 30 (terminal vinyl group and perfluoroalkyl chains) in this product and MAL3I showed a mixture of many components (Figure 7). A strong peak at 978 was consistent with combination of two pyrogallol residues

À. À... :: '. with one each of the aldehydes. Kitchen paper test at 0.2 % in THE showed 5 minute resistance to oil and water drops.

Example 5

(i) Decanal (1.1 g,) and pyrogallol (883 mg., 1 equiv.) in tetrahydrofuran (5 ml.) were treated with cone. sulfuric acid (1 drop, 33 mg.) and the mixture was stirred for 65 he at 20 C. Sodium 10 bicarbonate (60 mg.) was added and after being thoroughly stirred the mixture was poured into ice-water (200 ml.). The gummy insoluble product was removed and dissolved in methanol.

Evaporation gave the product (1.45 g.). NOR was 15 consistent with aldeLyde-phenol oligomers. Tests of kitchen paper dipped at ambient temperature in a 0.5% tetrahydroturan solution of the product showed that it conferred the ability to float on water. 20 (ii) Decanal (l.2g.) and pyrogallol (969 mg., 1 equiv.) in tetrahydrofuran (5 ml.) were treated with trifluoroacetic acid (2ml.) and the mixture was stirred for 19 hr at 20 C. A portion (2.5 ml.) of the solution was removed and evaporated to give 25 the product (740 mg.) The NMR showed an aldehyde phenol condensate and MALDI (Figure 8) was consistent with a 4:4 non cyclic oligomer.

In the kitchen paper drip and dry test using a 0.5% solution in acetone the paper floated for 12h. and gave 30 high contact angles with water. At 0.25%, paper gives a high (ca. 80 ) water contact angle but water drops soaked in after 2 min. After 5 days, the remainder of the solution was 35 evaporated to give a residue (1.29 A.), which was much

À À . À 1

À. À..

less soluble in chloroform than the shorter term material. NMR was closely similar to the previous (short reaction time material). MALDI (Figure 9) showed a main product with a slightly higher (10-/7) molecular weight.

The kitchen paper dip and dry test with a 0.5% solution in acetone showed improved water resistance but lower than in the preceding Examples.

10 Formation of the aldebyde phenol condensates can also be achieved by grinding the reagents together in the absence of a solvent. Typically, pyrogallol (0.9 g.) and decanal (1.1 g., 1 equiv.) were ground in a pestle and mortar for 15 minutes with toluene-p-sulfonic acid hydrate (15 mg.).

15 The mixture gradually became more and more viscous and at the end of the grinding period gave a free flowing solid.

The same results were achieved with the use of 1.2 mg. of toluene-psulfonic acid but with a reaction time of 60 hours. The NMR spectrum of the product obtained was 20 essentially identical with that obtained as above. The paper test gave very high contact angles and excellent persistence using 1% by weight solutions of the product in THE. The product has an advantage over the solution-

based procedure of giving essentially colourless test 25 solutions and samples.

Example 6

Decanal (1.418g.) and resorcinol (lg.) in tetrahydrofuran 30 (5 ml.) were treated with trifluoroacetic acid (1 ml.) and the mixture was stirred for 28 hr. Evaporation gave a residue(2.3g.) whose NMR showed phenol-aldehyde condensate. At 0.5% at 20 C in acetone the kitchen paper dip and dry test showed water beading but 2 min soak-in 35 time. At 1% in THE kitchen paper floated on water for

be:.:: l:: c' many hours and water drops persisted for many hours also.

When the acid catalyst was cone. HCl (lml.) and THF (7 ml.) was the solvent, NMR again showed the product to be 5 aldeLyde-phenol condensate and in the kitchen paper dip and dry test at 0.5% in THF the water soakin time was again ca 2 min. At 1% in THF there was good persistence of floating and drops but somewhat less well than with 1' FA catalysis.

10 - Example 6a

Pyrogallol (1 g.), decanal (1.24 g. l equivalent) and toluene-p-sulfonic acid (1.2 mg.)were ground together with a pestle and mortar. After 5 min. there was 15 thickening of the mixture and after 2 days it had set to a hard white solid. MALDI showed the main component to be a tetrameric phenol-aldeLyde condensate (Eigure 10). Example 6b

20 Decanal (2.83g.) resorcinol (2g. 1 equivalent) and toluene-p-sulfonic acid (6 mg) were ground together for 10 minutes and then set aside at 20 for 15 h. The hard solid which resulted (was dissolved in acetone (60 ml.) and anhydrous potassium carbonate (15 g.) was 25 added. The mixture was stirred under reflux for 15 minutes and then a solution of propargyl bromide (80 w/w in toluene, 1.2 g. 50% hydroxyl equivalent) in acetone (5 ml.) was added to the reflowing solution in three equal portions at 20 minute intervals. The 30 mixture was then boiled under reflex for 2 days and poured into water (150 ml.). The mixture was extracted with ether (3 x 60 ml.) and the extracts were washed successively with 1M HCL and water. The extracts were

. a.:.::::: ee dried (and evaporated to give the product (4.5 g.). The IR spectrum (Figure lla) showed bands at 3312 cm-l (triple bond C-H) and at 2123 cml (C-C triple bond).

MALDI showed a mixture of compounds (figure 11).

5 Kitchen paper test for water at 1% in THE showed excellent water resistance Example 6c

Decanal (7.09 g.) resorcinol (5 g. l equivalent) and 10 toluene-psulfonic acid (Smg) were ground together for 10 minutes and then set aside at 20 for 15 h. A -

portion (l g.) of the hard solid which resulted after 60h. was further ground with dibutylamlne (484 mg. 1 equivalent for a Mannich reaction), paraformaldehyde 15 (350 mg., 3 moles excess) and toluene-p-sulfonic acid (5 my.). After 16 h., the mixture was taken up in acetone (50 ml.) and filLcred to remove excess of paraformaLdebyde. The filtrates were evaporated in vacua to constant weight to remove any abreacted 20 dibutylamine, giving the product whose NMR showed a peak for methylene groups adjacent to nitrogen absent from the starting material and an intensified terminal methyl group signal. MALDI showed a mixture of compounds (Figure 12). Reaction schemes for Examples 25 6b and 6c are illustrated in Figure 14.

Example 7

0-1,3 -Dioxanylethyl -O-methyltriethyleneglycol Triethyleneglycol monomethyl ether (2.29 g) and 1,3- -

30 dioxanylethyl bromide (4g.) (50% excess) were dissolved

.' ce.:: ': . in 60-80 petrol (20ml). Tetrabutylammonium bromide (0.324g) was added together with sodium hydroxide (14 g.) in water (14 ml.). The mixture was stirred vigorously under reflex for 21 h cooled, and brought 5 close to neutrality by dropwise addition of cone. HCL.

After complete neutralization with acetic acid, the top layer (petrol) was removed and evaporated to give a residue (2.02g) which was kugelled. Er. 1 bath 125 /25 mm (0.20 g.) Fr bath 240 /9mm (1.15 g) NMR 10 consistent with the coupled structure. -

Aldehyde-pyrogallol Condensate I2he above dioxanyl PEG ether (910 mg) and pyrogallol (413 mg., 1 mole) were dissolved in ethanol under argon and cone. hydrochloric acid (0.6 ml) was added. The 15 mixture was allowed to stand at 20 for 18h. Water (4O ml) was added, the mixture was warmed and decanted. ''I' he decantate was evaporated (l.3g) (no IR carbonyl group)and was extracted with cold acetone leaving a dark residue A. Evaporation of the acetone solution gave a 20 residue (709 mg) whose NMR spectrum was consistent with an aldehyde phenol condensate. The reaction scheme is illustrated in Figure 15.

The insoluble material A was extracted with boiling THE. Evaporation of the THE solution gave a dark 25 residue which was extracted with cold acetone (15ml) to give a clear extract giving, on evaporation, a residue

., r e À, # À À À a (190 mg) as a dark powder softening at 97-100 and melting at 157-9 À MALDI was consistent with that of the PEG pyrogallol tetramer together with some lower; molecular weight condensates (Figure 13). This 5 material applied on a dip and dry basis at 0.6% in methanol to steel gives a change in contact angle from 70 to 10 .

The reader's attention is directed to all papers and 10 documents which are filed concurrently with or previous to this specification in connection with this application

and which are open to public inspection with this specification, and the contents of all such papers and

documents are incorporated Herein by reference.

All of the features disclosed in this specification

(including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, 20 except combinations where at least some of such features and/or steps are mutually exclusive.

Each feature disclosed in this specification (including

any accompanying claims, abstract and drawings), may be 25 replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series

_ t ,,, 1 1 À À À À À

of equivalent or similar features.

The invention is not restricted to the details of any foregoing embodiments. The invention extends to any 5 novel one, or any novel combination, of the features disclosed in this specification (including any

accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

1 1 À À

À 1

# CLAIMS

1. A solvent-soluble oligomer or polymer comprising an 5 open-chain condensate of an aldebyde of formula: R - CHO (I)

wherein R is a substituted or unsubstituted hydrocarbon group, or a precursor or derivative thereof, with a mono or polyhydric phenol, or a precursor or derivative lO thereof.

2. An oligomer or polymer according to claim 1, wherein R is an alkyl group, or a fluorinated al.kyl group, having from 5 to 20 carbon atoms, an alkenyl group, l5 or a fluorinated alkenyl group, having from h to.0 carbon atoms, an aralkyl group, or a fluorinated aralkyl group, having from 5 Lo 20 carbon atoms, or a substituted or non-substituted aryl or fluorinated aryl group, which alkyl, alkenyl., aralkyl or aryl 20 groups may contain substituent hetero-atoms.

3. An oligomer or polymer according to claim 2, in which R IS an alkyl group, an alkenyl group, a hydroxyalkyl group or a perfluoroalkyl. group.

2S 4. An oligomer or polymer according to any one of claims 1 to 3, that is present in a mixture of such oligomers or polymers.

30 5. An oligomer or polymer according to any one of the preceding claims, that IS colourless.

6. An oligomer or polymer according to any one of the preceding claims, in which the group R is an alkyl 35 group having from 7 to 15 carbon atoms.

c - 7. An oligomer or polymer accor-,i.g to claim 6, in wh On the group R is a fluorinated alkyl group.

5 8. An oligomer or polymer according to any one of claims 1 to 5, in which the group R is an alkenyl group having from 7 to 15 carbon acoms.

9. An oligomer or polymer according to claim 8, Shot is 10 capabl_ of chan exrers-o. or cross-link-ny in the presence of a free-radical initiator.

1C. An c lgomer on polymer according to my one of the preceding claims, whe-r_in the:acno- or polyLvdrc o phenol comprises a h.oxyl-subs.iuted benzene ring. 1. An oigomer Or polymer accordance to any one or- che preceedi.n<., C aids, which is a. oen-chain condensate 0 ccTpr sing the units: r _ n 35 R '3

t I 8 r r À À À 1 1

r 1 À À

where n is an integer greater than or equal to 1, p is 2 or 3, and R is as previously defined, the condensate having at least one terminal group selected from H atoms, 5 al.kenyl groups, hydroxyalkyl groups, dThydroxyaryl groups and trihydroxyaryl groups.

12. An oligomer or polymer according to claim 11, wherein n is an integer of from 2 to 4.

13. An oligomer or polymer according to any one of the preceding claims, having a molecular mass of less than 2000 Daltons.

15 14. An oligmer or polymer according to one of the following formulae:

l Ir I: À À À À 1 ' 1

:':. _, OH QH

-0,, He,_ OH 5 1 f q c=7 (3f] 1911 OH tIc-f('ll 110 oF;}10.H 1 0 \\ '':1_ j 1 1 C! id,,, all (CF^,4 vCF2) 7 OF; (ACE

G'H OH

A,;,,, OH.L; ma,' OEl 1t 11 1,1 1 ;,,',:

i 11 C'1- CH

fCF q jFJq C'3 CF7

G \f.; H Ofl li tH CHm 'I 2 - t; 5. I f'2)q f fFjq (ll F)q CF3 C F7

Where q '. an i.nteger or from 6 to 18.

30 15. An oligomer or polymer according to the fcrmula: OH H -

C,,.J<.,,,,.H J. 'C - \ '^H

(;' 2),nCH2CH2C)si=l (CH,',.-C- Ci--.!SFi

: I r À À À

where r is an integer of from 1 to 3, s is an integer of from 2 to and Ris Cp3 or a branched perfluoroalkyl 5 group.

16. An oligomer or polymer according co the formula: Hc<,,,4 OH HO, f 0H H5:rJ_-G' (CH2)(CH2CH2O)yRI (CH2)x(C2CH20)yR 0 r OF AH l pH ITOH HOW OH HOVH

(CFo)XR1 (CH2)yCH=cH2 Where x is an Lnteqer of from 6 to 18, y is an integer of from 4 to 16 and R: is -CF3, an alkyl group, or a branched perfluoralkyl group.

17. An ol.igomer or polymer substantially as hereinbefore described.

. T À À 1 :' I' lll.':' 18. A method of manufacturing a solvent-soluble oligomer or polymer comprising an open-chain condensate of an aldehyde of formula (I), or a precursor or derivative thereof, and a mono- or polyhydric 5 phenol, or a precursor or derivative thereof, which comprises condensing the aldehyde and the phenol, or their precursors or derivatives, in the presence of an acid catalyst.

10 19. A method according to claim 18, wherein the group R in formula (I) is an alkyl group having from 7 to 15 carbon atoms.

20. A method according to claim 18 or 19, wherein the 15 group R is a fluorinated alkyl group.

21. A method according to any one of claims 18 to 20, wherein the group R is a perfluorinated alkyl group comprising from 15 to 25 fluorine atoms.

22. A method according to any one of claims 18 to 21, wherein the aldeLyde is hexanal, octanal, decanal, undec-10-al, dodecanal, pefluoro-1H-2,2-H-hexanal, perfluoro-1--2,2-H-octanal and perfluoro-1-H-2,2-H 25 decanaL. 23. A method according to any one of claims 18 to 22, wherein the group R is an alkenyl group.

30 24. A method according to claim 23, which further comprises polymerizing the condensate in the presence of a free-radical initiator.

25. A method according to any one of claims 18 to 24, in 35 which the mono- or polyhydric phenol comprises a

T l r À l À l 1 1 i À I 1 À 1 1 1 1

hydroxyl-substituted benzene ring.

26. A method according to any one of claims 18 to 25, in which the monoor polyLydric phenol is resorcinol 5 or pyrogallol.

27. A method according to any one of claims 18 to 26, in which the precursor or derivative of the aldehyde of formula (l:) is an acetal or an imine.

28. A method according to any one of claims 18 to 21, in which the precursor or derivative of the mono- or polyLydric phenol is a phenyl ether.

15 29. A method according Lo any one of claims l8 to 28, that is carried out at a temperature of from 15 to 30 C.

30. A method according to any one of claims 18 to 29, 20 that is carried out in the presence of an aproLic organic solvent.

31. A method according to any one of claims 18 to 30, that is carried out in the presence of a strong acid 25 catalyst. 32. A method according to any one of claims 18 to 31, I wherein the phenol to aldehyde equivalent ratio is from 1:1 to 2:1.

33. A method according to any one of claims 18 to 32, which further comprises reacting the phenol aldehyde condensate to introduce surface reactive groups into the oligomer or polymer chain.

l 1 1 1 1 1 1..CLME: 34. A method according to claim 33, which comprises the step of reacting the aldehyde phenol condensate with a primary or secondary amine together with 5 formaldehyde to give a Mannich product in which a hydrogen atom flanked by hydroxyl groups on an aromatic ring is replaced by a monoalkylaminomethyl or dialkylaminomethyl group.

10 35. A method according to claim 34, in which the amine is dibutylamine.

36. A method according to claim 33, which comprises the step of partially or completely etherifying the 15 aldebyde phenol condensate with a base and an alkenyl halide to insert polymerisable groups therein. 37. A method according to claim 36, in which the alkenyl 20 halide is an allyl or propargyl halide.

38. A method for the manufacture of an oligomer or polymer substantially as described in the Examples.

25 39. A method for the manufacture of an oligomer or polymer substantially as hereinbefore described.

40. A solvent-soluble open-chain oligomer or polymer, or a mixture of oligomers or polymers, or both, 30 prepared by the acid catalysed condensation of an aldehyde of formula (I), or a precursor or derivative thereof, and a mono- or polyhydric phenol, or a precursor or derivative thereof.

35 41. An oligomer or polymer prepared by a method

Be::e À:e::: À ace:::: t.

:. ece according to any one of claims 18 to 39.

42. An oligomer or polymer, or mixture of oligomers or polymers, or both, according to any one of claims 1 5 to 17 when prepared by a method according to any one of claims 18 to 39.

43. A method of changing the surface properties of a material, which comprises contacting the material 10 with a solution or dispersion of an oli.gomer or polymer comprising an open-chain condensate of an aldehyde of formula (I), or a precursor or derivative thereof, and a mono- or polyLydric phenol, or a precursor or derivative thereof, in a 15 liquid medium.

44. method according to claim 43, wherein there is used a mixture of oLigomers and/or polymers.

20 45. A method according to claim 44 or 45, wherein there is used an oligomer or polymer according to any one of claims 1 to 17.

46. A method according to any one of claims 43 to 45 25 wherein there is used an oligomer or polymer prepared by a method according to any one of claims 18 to 39.

47. A method according to any one of claims 43 to 46, in which the aldehyde phenol condensate is applied dissolved or dispersed in an organic solvent.

48. A method according to claim 47, wherein the concentration of the aldebyde phenol condensate in 35 the solvent is from 0.01 to 5% by weight.

et::. À À:*::: ::':e:::::::e 9. A. method cr chancing the surface prcoer ies Cal a substrate substantially as described _n the Examples.

50. a method of changing i.he surface prapert es Q_ a substrate substantially as heeinbe ore described.

51. An cl gc.er O.'- polymer hav.rg the formula: 1 '. H \,- OH

'. L Al n 26 Where X is -CH NR2. On -ORE, Rut is a substituted or un substitutec. alky' or c2keryl group, creerabl having from 1 to carbon atoms, R s a subsitutecl Or ursubstituted hydrocarbon group and n is an integer greater than or equal to 1.

-!) -. _ it,

c * c c seer À... 52. An olisomer or polymer having the formula: l 5 1, _ 1

(R-G, OH) P-d i'- i A r I 1 1

! n Where 3 is a polymeric sable group, for example, an z:0 alkenvl, aLkyny2, or lko:<ycarbonyl group, p is 2 or 3, d i s 1 or 2, and n s an integer greater than or equal to 1.