Alkoxysilyl-containing adhesive sealants having improved tear propagation resistance

Patent metadata

Field	Value
Publication number	US-10087278-B2
Application number	US-201615395449-A
Country	US
Kind code	B2
Filing date	Dec 30, 2016
Priority date	Feb 4, 2016
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

Specific alkoxysily-modified polymers bearing alkoxysilyl groups distributed randomly or in block fashion along the polyether chain, and not just located at the chain termini, a process for preparing these alkoxysilyl-modified polymers, and compositions comprising these alkoxysilyl-modified polymers are provided.

First claim

The invention claimed is:

1. An alkoxysilyl-modified polymer of formula (I)
M i D j UR u AP v   Formula (I)

wherein the M and D fragments are not linked directly to one another but are linked with one another via the UR groups, the AP groups, or both, and the UR and AP groups are not linked directly to one another but are linked with one another via the M fragments, the D fragments, or both
wherein
i=1 to 2,
j=1 to 10,
u=0 to 11
V=0 to 6,
with the proviso that u+v≥1,
wherein each M is independently an alkoxysilyl-modified polyether radical of formula (Ia)

wherein
a=0.1 to 100,
b=2 to 1000,
c=0 to 200,
d=0 to 200,
w=0 to 200,
y=0 to 500,
e=1 to 10,
f=0 to 2
g=1 to 3,
with the proviso that g+f=3,
h=0 to 10,
wherein the groups with the indices a, b, c, d, w and y are freely permutable over a molecule chain, and each of the groups with the indices w and y do not follow itself or the other respective group, and with the proviso that the monomer units of the fragments having the indices a, b, c, d, w and y, and wherein each R 1 is independently a saturated or unsaturated, linear or branched organic hydrocarbyl radical optionally substituted by at least one heteroatom selected from the group consisting of O, S, and N, each R 2 is independently an alkyl group comprising 1 to 8 carbon atoms, each R 3 is independently an alkyl group comprising 1 to 8 carbon atoms, each R 4 is independently a hydrogen radical, an alkyl group comprising 1 to 20 carbon atoms, an aryl group, or an alkaryl group, each R 5 is independently a hydrogen radical or an alkyl group comprising 1 to 8 carbon atoms, or R 4 and one of the R 5 radicals may together forma ring including the atoms to which R 4 and R 5 are bonded, each R 6 and R 7 are independently a hydrogen radical, an alkyl group comprising 1 to 20 carbon atoms, an aryl group, an alkaryl group, or an alkoxy group, each R 11 is independently an optionally substituted saturated or unsaturated, aliphatic or aromatic hydrocarbyl radical comprising 2 to 30 carbon atoms, each R 13 and R 14 are independently hydrogen or an organic radical, or R 13 , R 14 , or both may be absent and wherein R 13 and R 14 are absent, a C═C double bond is in place of the R 13 and R 14 radicals, the bridging Z fragment may be present or absent, wherein, in the absence of the bridging Z fragment, R 15 and R 16 are each independently hydrogen or an organic radical, and, wherein one of the radicals R 13 or R 14 is absent, the respective geminal radical is an alkylidene radical, wherein, in the presence of the bridging Z fragment, R 15 and R 16 are hydrocarbyl radicals bridged cycloaliphatically or aromatically via the Z fragment, wherein Z is an optionally substituted divalent alkylene or alkenylene radical, with the proviso that the sum total of all indices b in formula (Ia) and formula (II) is at least 5 and the sum total of all indices a in formula (Ia) and formula (II) is greater than 2,
and wherein
D is a polyether radical -(D A ) t D x wherein t is 2,
wherein
D x is a t-valent functional, saturated or unsaturated, linear or branched organic hydrocarbyl radical optionally substituted with at least one heteroatom selected from the group consisting of O, S, Si and N, wherein each D A radical is covalently bonded to the D X radical,
or D x is a multiply fused phenolic group, and wherein D A is a fragment of formula (II)

wherein
a=0.1 to 100,
b=2 to 1000,
c=0 to 200,
d=0 to 200,
w=0 to 200,
y=0 to 500,
e=1 to 10,
f=0 to 2
g=1 to 3,
with the proviso that g+f=3,
h=0 to 10,
wherein the groups with the indices a, b, c, d, w and y are freely permutable over a molecule chain, and each of the groups with the indices w and y do not follow itself or the other respective group,
wherein the indice a in the fragment M is greater than two times the indice a in the fragment D in the formula (I), and wherein
each R 2 is independently an alkyl group comprising 1 to 8 carbon atoms,
each R 3 is independently an alkyl group comprising 1 to 8 carbon atoms,
each R 4 is independently a hydrogen radical, an alkyl group comprising 1 to 20 carbon atoms, an aryl group, or an alkaryl group,
each R 5 is independently a hydrogen radical or an alkyl group comprising 1 to 8 carbon atoms,
or R 4 and one of the R 5 radicals may together form a ring including the atoms to which R 4 and R 5 are bonded,
each R 6 and R 7 are independently a hydrogen radical, an alkyl group comprising 1 to 20 carbon atoms, an aryl group, an alkaryl group, or an alkoxy group,
each R 11 is independently an optionally substituted saturated or unsaturated, aliphatic or aromatic hydrocarbyl radical comprising 2 to 30 carbon atoms,
each R 13 and R 14 are independently hydrogen or an organic radical,
or R 13 , R 14 , or both may be absent, and wherein R13 and R14 are absent a C═C double bond is in place of the R 13 and R 14 radicals,
the bridging Z fragment may be present or absent,
wherein, in the absence of the bridging Z fragment,
R 15 and R 16 are each independently hydrogen or an organic radical, and,
wherein one of the radicals R 13 or R 14 is absent, the respective geminal radical is an alkylidene radical,
wherein, in the presence of the bridging Z fragment,
R 15 and R 16 are hydrocarbyl radicals bridged cycloaliphatically or aromatically via the Z fragment,
wherein Z is an optionally substituted divalent alkylene or alkenylene radical,
each UR is independently a divalent radical of form —U-D C -U—, wherein U is a —C(O)NH— group bonded via the nitrogen to D C ,
each D C is independently a divalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbyl radical comprising 1 to 30 carbon atoms, selected from alkyl, alkenyl, aryl or alkaryl radicals, and optionally substituted
by at least one heteroatom selected from the group consisting of O, N and S, each AP is independently a radical of general formula (IIIa) or (IIIb)

2. The alkoxysilyl-modified polymer according to claim 1 , wherein in formula (I),
i=1 to 2,
j=1 to 6,
u=j+1
v=0,
wherein the fragment M corresponds to formula (Ia) wherein
a=0.1 to 50,
b=10 to 500,
c=0 to 20,
d=0 to 20,
w=0 to 20,
y=0 to 20,
e=1 to 10,
f=0 to 2,
g=1 to 3,
with the proviso that g+f=3,
and h=1, 2 or 3, and
wherein the fragment D corresponds to formula (II) wherein
a=0 to 10,
b=10 to 700,
c=0 to 20,
d=0 to 20,
w=0 to 20,
y=0 to 20,
e=1 to 10,
f=0 to 2,
g=1 to 3,
with the proviso that g+f=3,
and h=1, 2 or 3
and wherein
each UR is independently a divalent radical of the form
—U-D C -U—, wherein each D C is independently a divalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbyl radical comprising 1 to 30 carbon atoms.

3. A method of making the alkoxysilyl-modified polymer according to claim 1 , the method comprising the steps of:
(1) reacting at least one dihydroxy-functional starter (A) selected from the group consisting of alcohols with at least one alkylene oxide and polyetherols, with an alkylene oxide and an e

Assignees

• Evonik Degussa Gmbh

Inventors

• Lobert Matthias
• Lewin Anke
• Knott Wilfried
• Schubert Frank
• Ferenz Michael

Classifications

• C08G18/4804

  Two or more polyethers of different physical or chemical nature · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/10

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G18/289

  containing silicon · CPC title

• C09J175/08

  from polyethers · CPC title