IP Library › Granted Patent US 9,234,098
Granted Patent B2
US 9,234,098 · App. 13/262,755 · Granted Jan 12, 2016

Method for the production of composite materials

Inventors: Hannah Maria König (Mannheim, DE); Hans-Joachim Hähnle (Neustadt, DE); Arno Lange (Bad Dürkheim, DE); Samira Nozari (Mannheim, DE); Gerhard Cox (Bad Dürkheim, DE); Rainer Dyllick-Brenzinger (Neustadt, DE); Stefan Spange (Orlamünde, DE); Tina Löschner (Augustusburg, DE)
Assignee: BASF SE
C08L83/02B82Y30/00C08J5/005C08K3/36
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Quick Facts
Patent No.
US 9,234,098
App. No.
13/262,755
Granted
Jan 12, 2016
Kind
B2
Abstract

The present invention relates to a process for producing a nanocomposite material from a) at least one inorganic or organometallic metal phase; and b) an organic polymer phase; comprising the polymerization of at least one monomer M which have at least one first polymerizable monomer unit A which has a metal or semimetal M, and at least one second polymerizable organic monomer unit B which is joined to the polymerizable unit A via a covalent chemical bond, under polymerization conditions under which both the polymerizable monomer unit A and the polymerizable unit B polymerize with breakage of the bond between A and B, the monomers M to be polymerized comprising a first monomer M1 and at least one second monomer M2 which differs at least in one of the monomer units A and B from the monomer M1 (embodiment 1), or the monomers to be polymerized comprising, as well as the at least one monomer M, at least one further monomer other than the monomers M, i.e. a conventional monomer which does not have a monomer unit A and is copolymerizable with the monomer unit B (embodiment 2).

Claims (73)

1. A process for producing a nanocomposite material comprising

a) at least one inorganic or organometallic metal phase; and

b) an organic polymer phase;

the process comprising polymerizing at least one monomer which comprises

at least one first polymerizable monomer unit A which has a metal or semimetal M, and

at least one second polymerizable organic monomer unit B which is joined to the polymerizable unit A via a covalent chemical bond,

under polymerization conditions under which both the polymerizable monomer unit A and the polymerizable unit B polymerize with breakage of the bond between A and B;

the monomers to be polymerized comprising:

a first monomer M1 and at least one second monomer M2 which each comprise at least one first polymerizable monomer unit A and at least one second polymerizable organic monomer unit B, which differ at least in one of the monomer units A and B, or

the monomers to be polymerized comprising, as well as the at least one monomer to be polymerized comprising at least one first polymerizable monomer unit A and at least one second polymerizable organic monomer unit B, at least one further, different monomer which does not have a monomer unit A and is copolymerizable with the monomer unit B.

2. The process according to claim 1 , wherein the metal or semimetal is selected from the group consisting of B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi, and mixtures thereof.

3. The process according to claim 1 , wherein the metal or semimetal M comprises silicon to an extent of at least 90 mol %, based on the total amount of M.

4. The process according to claim 1 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs from the monomer M1 at least in one of the monomer units A and B, and the molar ratio of the monomers M1 and M2 relative to one another is in the range from 5:95 to 95:5.

5. The process according to claim 1 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs from the monomer M1 at least in the monomer unit A.

6. The process according to claim 1 , wherein the monomers which have at least one monomer unit A and at least one monomer unit B are described by the general formula I:

in which

M is a metal or semimetal;

R 1 , R 2 may be the same or different and are each an Ar—C(R a ,R b )—radical in which Ar is an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl, and R a , R b are each independently hydrogen or methyl or together are an oxygen atom or a methylidene group (═CH 2 ),

or the R 1 Q and R 2 G radicals together are a radical of the formula A

 in which A is an aromatic or heteroaromatic ring fused to the double bond, m is 0, 1 or 2, the R radicals may be the same or different and are selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl, and R a , R b are each as defined above;

G is O, S or NH;

Q is O, S or NH;

q according to the valency and charge of M is 0, 1 or 2;

X, Y may be the same or different and are each O, S, NH or a chemical bond;

R 1′ , R 2′ may be the same or different and are each C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, aryl or an Ar′—C(R a′ ,R b′ )— radical in which Ar′ is as defined for Ar and R a′ , R b′ are each as defined for R a , R b , or R 1′ , R 2′ together with X and Y are a radical of the formula A, as defined above,

or, when X is oxygen, the R 1′ radical may be a radical of the formula:

in which q, R 1 , R 2 , R 2′ , Y, Q and G are each as defined above and # means the bond to X.

7. The process according to claim 5 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise at least one monomer of the general formula II:

in which

M is a metal or semimetal;

A and A′ are each an aromatic or heteroaromatic ring fused to the double bond;

m and n are each independently 0, 1 or 2;

G and G′ are the same or different and are each independently O, S or NH;

Q and Q′ are the same or different and are each independently O, S or NH;

R and R′ are the same or different and are each independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl; and

R a , R b , R a′ and R b′ , are each independently selected from hydrogen and methyl, or R a and R b and/or R a′ and R b′ in each case together are an oxygen atom.

8. The process according to claim 7 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs at least in the monomer unit A from the monomer M1, the monomer M1 being selected from the monomers of the formula II.

9. The process according to claim 7 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs in at least one of the monomer units A from the monomer M1, the monomer M1 being selected from the monomers of the formula II and the at least one further monomer M2 being selected from the monomers of the formula III:

in which

M is a metal or semimetal;

A is an aromatic or heteroaromatic ring fused to the double bond;

m is 0, 1 or 2;

q according to the valency and charge of M is 0, 1 or 2;

G is O, S or NH;

Q is O, S or NH;

R are selected independently from halogen, CN, C 1 -C 6 -alkoxy, C 1 -C 6 alkoxy and phenyl;

R a , R b are each independently selected from hydrogen and methyl, or R a and R b together are an oxygen atom or a methylidene group, and

R c , R d are the same or different and are each selected from C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl and aryl.

10. The process according to claim 7 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs from the monomer M1 at least in one of the monomer units A, the monomer M1 being selected from the monomers of the foimula II, and the at least one further monomer M2 being selected from aromatic compounds which have at least two trialkylsilyloxymethyl groups and/or aryldialkylsilyloxymethyl groups bonded to the same or different phenyl rings.

11. The process according to claim 7 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs in the monomer units B and optionally A from the monomer M1, the monomer M1 being selected from the monomers of the formula II and the at least one further monomer M2 being selected from the monomers of the formula IV:

in which:

M is a metal or semimetal;

Ar, Ar′ are the same or different and are each an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents selected from halogen, CN, C 1 -C 6 -alkyl, C 1 C 6 -alkoxy and phenyl;

R a , R b , R a′ , R b′ are each independently selected from hydrogen and methyl, R a , or R b and/or R a′ and R b′ in each case together are an oxygen atom;

q according to the valency of M is 0, 1 or 2;

X, Y may be the same or different and are each O, S, NH or a chemical bond; and

R 1′ , R 2′ may be the same or different and are each C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, aryl or an Ar″—C(R a″ ,R b″ )— radical in which Ar′ is as defined for Ar and R a″ , R b″ are each as defined for R a , R b , or R 1′ , R 2′ together with X and Y are a radical of the formula A as defined above.

12. The process according to claim 6 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise at least one monomer of the general formula IV as defined in claim 11 .

13. The process according to claim 11 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise at least one monomer of the general formula V:

in which

M is a metal or semimetal;

Ar, Ar′ are the same or different and are each an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl;

R a , R b , R a′ , R b′ are each independently selected from hydrogen and methyl, or R a and R b and/or R a′ and R b′ in each case together are an oxygen atom; and

q according to the valency of M is 0, 1 or 2.

14. The process according to claim 13 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs at least in the monomer unit A from the monomer M1, the monomer M1 being selected from the monomers of the formula V and the at least one further monomer M2 being selected from the monomers of the formula V which differ in the (semi)metal M from the monomer M1.

15. The process according to claim 13 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs in the monomer units A and B from the monomer M1, the monomer M1 being selected from the monomers of the formula V and the at least one further monomer M2 being selected from the monomers of the formula III as defined in claim 9 .

16. The process according to claim 13 , wherein the monomers to be polymerized, which have at least one monomer unit A and at least one monomer unit B, comprise a first monomer M1 and at least one second monomer M2 which differs at least in the monomer unit A from the monomer M1, the monomer M1 being selected from the monomers of the formula V and the at least one further monomer M2 being selected from the monomers of the formula VI:

in which

M is a metal or semimetal;

Ar, Ar′ are the same or different and are each an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents selected from halogen, CN, C 1 -C 6 -alkyl, C 1 C 6 -alkoxy and phenyl;

R a , R b , R a′ , R b′ are each independently selected from hydrogen and methyl, or R a and R b and/or R a′ and R b′ in each case together are an oxygen atom; and

q according to the valency of M is 0, 1 or 2; and

R c , R d are the same or different and are each selected from C 1 -C 6 - alkyl, C 3 -C 6 -cycloalkyl and aryl.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 24, 2011
From: KOENIG, HANNAH MARIA; HAEHNLE, HANS-JOACHIM; LANGE, ARNO; NOZARI, SAMIRA; COX, GERHARD; DYLLICK-BRENZINGER, RAINER; SPANGE, STEFAN; LOESCHNER, TINA
To: BASF SE
Reel/Frame 027108/0232 →
Priority Claims (1)
EP 09157335 · Apr 3, 2009 · regional
Continuity (1)
Related Publication 20120091400A1 · Apr 19, 2012