Composite compositions

• US 20050070655A1
• Filed: 07/03/2002
• Published: 03/31/2005
• Est. Priority Date: 07/04/2001
• Status: Abandoned Application

• Current Assignee: Surface Specialties SA (Allnex (Luxembourg) & Cy SCA)
• Original Assignee: Surface Specialties SA (Allnex (Luxembourg) & Cy SCA)
• Inventors: Camino, Giovanni, Van Den Bergen, Hugues Bertrand, Wang, Jeffrey
• Application Number:
  US10/482,819
• Publication Number:
  US 20050070655A1
• Time in Patent Office: Days
• US Class Current: 524/445
• CPC Class Codes: C08K 7/00 Use of ingredients characterised by shape
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08K 9/08 Ingredients agglomerated by treatment with a binding agent

Abstract

There is described a composite composition comprising a layered mineral and at least one polymer precursor which is substantially miscible therewith; characterised in that: (i) the composition and/or polymer precursor are polymerisible by radiation to form a polymeric composition; and/or (ii) the polymer precursor comprises a polymer obtained and/or obtainable by polymerisation with radiation. Further described are composite compositions comprising a layered mineral and intercalated therein at least one polymer which is further polymerisable by radiation to form a polymeric network, such as a polymeric coating. Preferred minerals are nanoclays such a montmorillonite in which the counter cation comprises a radiation curable organo functional group covalently bonded thereto (e.g. an acrylate functional onium ion). Processes for making the composites are also described.

Claims

1. A composite composition comprising a layered mineral and at least one polymer precursor which is substantially miscible therewith;

characterised in that;

(i) the polymer precursor is polymerisible by radiation to form a polymeric composition; and

/or

(ii) the polymer precursor comprises a polymer obtained and/or obtainable by polymerisation with radiation.

3. A composition as claimed in claim 1, in which the layered mineral is a natural or synthetic mineral selected from:

kaolins, serpentines, talcs, pyrophyllites, ferropyrophyllites;

smectites montmorillonites;

illites micas glauconites calcdonia;

chlorites vermiculites;

palygorskites;

sepiolites;

mixed layer minerals which may comprise two three or more mineral components in random and/or regular order;

amorphous clays, high alumina clays and/or any suitable mixtures and combinations thereof.

4. A composition as claimed in claim 1, in which the layered mineral selected from:

smectite, montmorillonite, bentonite;

beidellite, nontronite, hectrorite, fluorohectorite, saponite, sauconite;

volkhonskoite, medmontite, pimelite, stevensite, stephanite;

vermiculite, and/or halloysite.

5. A composition as claimed in claim 1, in which the polymer or polymer precursor is formed from oligomers having free radical polymerisable double bonds.

6. A composition as claimed in claim 1, in which the polymer or polymer precursor comprises (meth)acrylated oligomers.

7. A composition as claimed in claim 1, in which the layered mineral comprises nano-layers.

8. A composition as claimed in claim 1, which the layered mineral is exfolliated exfoliated.

9. A composition as claimed in claim 1, in which the layered mineral comprise from about 1% to about 15% by weight of the total composition.

10. A composition as claimed in claim 1, in which the counter cation comprises an activated unsaturated moiety represented by Formula 1′

which may be univalent if a substituent on a cation (such as an onium ion) and/or may bear a positive charge if comprising the whole cation, where Formula 1′

comprises;

11. A composition as claimed in claim 1, in which the counter cation is an optionally substituted onium ion.

12. A composition as claimed in claim 1, in which the counter cation is those represented by the formulae

⁺(MR¹R²R³R⁴);

and/or ⁺(PyR⁴);

where

M is nitrogen or phosphorus;

R¹, R², R³, and R⁴ independently denote hydrogen or an optionally substituted hydrocarbo group, preferably H or hydrocarbyl optionally substituted by one or more hydroxy or carboxy group(s), more preferably H or alkyl, aryl or allyl group, most preferably at least one of which is other than hydrogen and is substituted by a hydroxy or carboxy group; and

Py denotes a pyridinium or an alkyl substituted pyridinium group.

13. A composition as claimed in claim 1, in which the counter cation is represented by one or more of the following formulae

14. A composition as claimed in claim 1, in which the counter cation is selected from the group consisting of:

15. A composition as claimed in claim 1, in which the counter cation comprises at least one moiety, which may comprises an optional substituent on the cation and/or replace any hydroxy and/or carboxy thereon, the moiety selected from group consisting of:

16. A composition as claimed in claim 1, in which the counter cation comprises at least one moiety, which may comprises an optional substituent on the cation and/or replace any hydroxy and/or carboxy thereon, the moiety selected from group consisting of:

17. A composition as claimed in claim 1, in which the counter cation can be further modified to be polymerisable by radiation.

18. A process for preparing a nanoclay as claimed in claim 1 comprising the step of:

(a) replacing cations in a nanoclay with an onium ion functionalised with at least one hydroxy group,

(b) reacting the onium ion with an (optionally substituted) reagent selected from;

(i) maleic or succinic anhydride

 

followed by an (poly)oxirane e.g. glycidyl methacrylate

(ii) (poly)isocyanate (such as those comprising at least one R—

NCO);

optionally in the absence of additional catalyst for urethanisation (e.g. omit dibutyltindilaurate (DBTL));

(iii) methacrylate isocyanate

 

optionally in the absence of additional catalyst for urethanisation (e.g. omit dibutyltindilaurate (DBTL));

(iv) (meth)acrylate

 

where it is preferred that R′

is H or alkyl;

(v) a (poly)oxirane

(vi) a polycarboxylic acid

19. A process for preparing a nanoclay as claimed in claim 18 comprising the step of

(a) replacing cations in a nanoclay with an onium ion functionalised with at least one carboxy group

(b) reacting the onium ion with an optionally substituted cyclo(alkoxy) (meth)acrylate

(c) reacting the onium salt with an (poly)oxirane

(d) reacting the onium salt with a polyol

20. A process as claimed in claim 19 in which the cyclo(alkoxy) (meth)acrylate is of formulae

21. A process as claimed in claim 20 in which the cyclo(alkoxy)(meth) acrylate is an oxirane (alkyl)(meth)acrylate.

22. A process as claimed in claim 21 in which the oxirane (alkyl)(meth)acrylate is an epoxy (meth)acrylate such as either glycidyl methacrylate

23. A process for preparing a nanoclay as claimed in claim 18 comprising the steps of

(a) protonating and/or alkylating an amino functional radiation polymerisable oligomer by radiation to form a cation thereof

(b) ion exchanging the oligomer cation with a cation from a nanoclay to form a clay intercalated with cationic oligomer as counter ion.

24. A process as claimed in claim 23, where the oligomer is an amino (meth)acrylate.

25. A process as claimed in claim 18 which comprises further step of exfoliating the clay.

26. A process as claimed in claim 18 in which the steps are carried out in a single container without intermediate isolation or purification steps.

27. A process as claimed in claim 23 which comprises further step of exfoliating the clay.

28. A nanoclay obtained and/or obtainable by a process as claimed in claim 18 in which the mineral layers are intercalated with polymer.

29. A nanoclay as claimed in claim 28 in which the mineral layers are substantially completely exfoliated.

30. A nanoclay, mineral, coating and/or composition as claimed in claim 28 which is substantially free of tin catalyst.

31. A substrate coated with a film comprising a composition as claimed claim 1.

2. A composite composition comprising a layered mineral such as nanoclay intercalated therein at least one polymer which is further polymerisable by radiation to form a polymeric network, such as a polymeric coating.