US 8,076,441 B2Granted

Process for bridging organically polymerizable silanes or silane resin systems containing hydroxy- or carboxylic acid groups as well as products obtained with said process

AssigneeFraunhofer-Gesellschaft zur Foerderung der angewandten Forschung e.V.

InventorHerbert Wolter

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Abstract

The present invention relates to a process for cross-linking a silane with the structure (IIa) for the preparation of a product, comprising component (III) twice, in triplicate or in a higher quantity, where the radicals B, R1, Ra, R′, X1 and the indices a and b are defined as above for structure (IIa) and can be identical or different in each case, or for the cross-linking of a condensate, a partial condensate, a polymer or a partial polymer comprising structural units with the structure (IIb) via the bond R1—, characterized in that a silane with the structure (IIa), or an isomer, a re-esterification product or a condensation product of said silane, which condensation product was formed by loss of an alcohol molecule, or a condensate, a partial condensate, a polymer, or a partial polymer comprising structural units of structure (IIb) is reacted with a compound having the structure (IV) Q-R5[-Q′]c, (IV).

Claims22

Dependent claims

A process for reacting a silane with the structure (IIa)

or a re-esterification product, or, in the case X1 is an alkoxy group, a condensation product of said silane formed by the loss of an alcohol molecule,
where the radicals and indices have the following meanings
Ra is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R1 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, substituted with Y, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R′ is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group,
B has the meaning of a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms,
X1 is a group which can enter into a hydrolytic condensation reaction under formation of Si—O—Si bridges,
Y means —OH or —COOH,
a is 1 or 2, and
b is 0 or 1,
via reaction at group Y with a compound having the structure (IV)
Q-R5[-Q′]c, (IV)
where each of Q and each Q′ independently means —NCO, —OH, or —C(O)X′, where —C(O)X′ means a carboxylic acid, an acid anhydride or an activated carbonyl compound in which X′ is a chloride and where each of Q and Q′ independently can be —NCO or —C(O)X′, when the silanes of structure (IIa) as defined above comprise groups Y having the meaning —OH, and
where each Q and Q′ independently can be —NCO or —OH—, when the silanes of structure (IIa) as defined above comprise groups Y having the meaning —COOH,
where R5 means a single bond only when each of Q and Q′ independently are activated carboxylic acid groups and c is equal to 1, otherwise R5 is a radical with c+1 valences, where c is 1 or an integer greater than 1;
wherein said component (III) repeats twice, in triplicate or in a higher quantity, where the radicals B, R1, Ra, R′, X1 and the indices a and b are defined as above for structure (IIa) and can be identical or different for each occurrence of component (III).

13 more elements

A silane of the following structure (V)

where:
B has the meaning of a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms,
R1 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to Z′ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
Ra is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R′ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
X1 is a group which can enter into a hydrolytic condensation reaction under formation of Si—O—Si bridges,
R2 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to Z″ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
Rb is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R″ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
X2 is a group which can enter into a hydrolytic condensation reaction under formation of
Si—O—Si bridges,
B′ has the meaning of a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms,
Z′ and Z″ are independently selected from the group consisting of —NH—C(O)O— bonded to the radical R3 via the NH-group, —NH—C(O)— bonded to the radical R3 via NH-group, or —CO(O)— bonded to the radical R3 via either the C— or O— atom,
R3 means a single bond when c is equal to 1 and Z′ and Z″ are —C(O)O, bonded to the radicals R1 and R2 respectively through an oxygen atom otherwise, R3 is an arbitrarily selected radical which has c+1 valences,
a is 1 or 2,
b is 0 or 1, and
c is 1 or an integer greater than 1.

14 more elements

A condensate or a partial condensate, comprising the following structural unit (VI)

where:
B has the meaning of a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms,
B′ has the meaning of a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms,
R1 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to Z′ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R2 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to B′ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R3 means a single bond when c is equal to 1 and Z′ and Z″ are —C(O)O, bonded to the radicals R1 and R2 respectively through an oxygen atom otherwise, R3 is an arbitrarily selected radical which has c+1 valences,
R4 has the meaning of a bond to another silicon atom, optionally instead of this partially also to another metal atom which can be inserted to silicic acid heteropolycondensates, and in given cases can partly instead be hydrogen,
R4′ has the meaning of a bond to another silicon atom, optionally instead of this partially also to another metal atom which can be inserted to silicic acid heteropolycondensates, and in given cases can partly instead be hydrogen,
Ra is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
Rb is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R′ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
R″ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
X1 is a group which can enter into a hydrolytic condensation reaction under formation of
Si—O—Si bridges,
X2 is a group which can enter into a hydrolytic condensation reaction under formation of
Si—O—Si bridges,
Z′ and Z″ are independently selected from the group consisting of —NH—C(O)O— bonded to the radical R3 via the NH-group, —NH—C(O)— bonded to the radical R3 via NH-group, or —CO(O)— bonded to the radical R3 via either the C— or O— atom,
a is 1 or 2,
b is 0 or 1,
c is 1 or an integer greater than 1, and
d is 1, 2 or 3.

18 more elements

A polymerisate or a partial polymerisate, comprising the following structural unit (VII)

where:
B* is a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms, or such a straight-chain or branched organically polymerizable group, the double bond of which has already reacted,
B*′ is a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms, or is such a straight-chain or branched organically polymerizable group, the double bond of which has already reacted,
R1 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to Z′ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R2 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, that is bound to B*′ and that can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R3 means a single bond when c is equal to 1 and Z′ and Z″ are —C(O)O bonded to the radicals R1 and R2 respectively through an oxygen atom, otherwise, R3 is an arbitrarily selected radical which has c+1 valences,
R4 has the meaning of a bond to another silicon atom, optionally instead of this partially also to another metal atom which can be inserted to silicic acid heteropolycondensates, and in given cases can partly instead be hydrogen,
R4′ has the meaning of a bond to another silicon atom, optionally instead of this partially also to another metal atom which can be inserted to silicic acid heteropolycondensates, and in given cases can partly instead be hydrogen,
Ra is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
Rb is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R′ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
R″ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
X1 is a group which can enter into a hydrolytic condensation reaction under formation of Si—O—Si bridges,
X2 is a group which can enter into a hydrolytic condensation reaction under formation of Si—O—Si bridges,
Z′ and Z″ are independently selected from the group consisting of —NH—C(O)O— bonded to the radical R3 via the NH-group, —NH—C(O)— bonded to the radical R3 via NH-group, or —CO(O)— bonded to the radical R3 via either C— or O—,
a is 1 or 2,
b is 0 or 1,
c is 1 or an integer greater than 1, and
d is 1, 2 or 3.

16 more elements

A process for reacting a condensate, a partial condensate, a polymer or a partial polymer comprising structural units having structure (IIb)

wherein R1, Ra, R′, X1, and Y can be identical or different and have following meaning:
Ra is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at its end opposite the silicon atom,
R1 is an open-chain and/or cyclic alkylene, arylene, or alkylene-arylene group having 1 to 10 carbon atoms in each case, substituted with Y, which can be interrupted by one or more oxygen or sulfur atoms or carboxyl or amino groups or can carry such atoms/groups at one of its ends,
R′ is an open-chain and/or cyclic alkyl, alkenyl, aryl, or alkylaryl, or arylalkyl group,
B* is a straight-chain or branched organically polymerizable group with at least one C═C double bond and at least 2 carbon atoms, or is such a straight-chain or branched organically polymerizable group, the double bond of which has already reacted,
X1 is a group which can enter into a hydrolytic condensation reaction under formation of Si—O—Si bridges,
Y means —OH or —COOH,
and R4 has the meaning of a bond to another silicon atom, optionally instead of this partially also to another metal atom which can be inserted to silicic acid heteropolycondensates, and in given cases can partly instead be hydrogen,
a is 1 or 2,
b is 0 or 1, and
d is 1, 2 or 3,
wherein said condensate, a partial condensate, a polymer, or a partial polymer comprising structural units of structure (IIb), is reacted via reaction at group Y with a compound having the structure (IV)
Q-R5[-Q′]c, (IV)
where each of Q and Q′ independently means —NCO, —OH, or —C(O)X′, where —C(O)X′ means a carboxylic acid, an acid anhydride or an activated carbonyl compound in which X′ is a chloride and
where each of Q and Q′ can be —NCO or —C(O)X′, when the condensates or a polymerisate of structure (IIb) as defined above comprises groups Y having the meaning
—OH, and
where each of Q and Q′ independently can be —NCO or —OH—, when the condensates/polymerisates of structure (IIb) as defined above comprise groups Y having the meaning —COOH,
where R5 means a single bond only when each of Q and Q′ independently are activated carboxylic acid groups and c is equal to 1, otherwise R5 is a radical with c+1 valences wherein c is 1 or an integer greater than 1.

15 more elements

Dependencies are inferred from the claim text.

Facts

Application: 11/910,862Filed 18 Apr 2006
Priority: DE 10 2005 018 05919 Apr 2005
Published: US 2008/0319127 A125 Dec 2008
Granted: 13 Dec 2011
Term ends: Not estimatedThe source records don’t support an estimate.

Classification9 codes

C08G 77/22
Polysiloxanes: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
C07F 7/1804
Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages: compounds having Si-O-C linkages
C08G 77/20
Polysiloxanes: containing silicon bound to unsaturated aliphatic groups
C08G 77/388
Containing atoms other than carbon, hydrogen, oxygen or silicon: containing nitrogen