Functionalized and polymerizable polymer

Details Functionalized and polymerizable polymer Functionalized and polymerizable polymer

1999-08-20

2002-11-12

Mullis, Jeffrey (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S207000, C525S210000, C525S211000, C525S227000, C526S258000, C526S281000, C526S282000, C526S283000, C526S284000

Reexamination Certificate

active

06479592

ABSTRACT:

The invention relates to a functionalized and polymerizable polymer, a process for the preparation thereof, the use thereof and compositions containing the polymer.
Polymers functionalized by carboxyl groups, such as poly(acrylic acid) and poly(methacrylic acid) as well as homo- and copolymers based on maleic acid or fumaric acid, are widely used in technology. They are used, inter alia, as flocculating agents or thickeners, as a component of coatings or adhesives and as a leather or textile auxiliary (cf Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A21, VCH Publisher, Weinheim 1992, page 143 et seq. and Encyclopedia of Polymer Science and Engineering, Vol. 9, Wiley & Sons, New York 1987, page 225 et seq.). Polyacrylic acid is also used in the dental field as a constituent of so-called carboxylate cements or of aluminosilicate-polyacrylic acid cements (cf K. Körber, K. Ludwig, Zahnärztliche Werkstoffkunde und Technologie, Thieme-Verlag, Stuttgart-New York 1982, page 57 et seq.).
Furthermore, in recent years, so-called glass ionomer cements have gained great practical interest. These are cements which are prepared from mixtures of a Ca—Al—F silicate glass powder with an aqueous solution, e.g. of an acrylic acid-maleic acid copolymer. They are used in the dental field as fixing cements, filling materials, base materials, adhesives or fissure sealants (cf A. D. Wilson, J. D. McLean, Glasionomerzement, Quintessens-Verlag, Berlin 1988, page 21 et seq.). In the case of so-called light-curing glass ionomer cements, polymerizable cross-linking monomers and initiators are also added to customary glass ionomer cements, which results in an acceleration of material curing and improvement of the mechanical properties. A further improvement in material properties can be achieved by the use of polycarboxylic acids which bear lateral groups capable of polymerization. Such polycarboxylic acids can be prepared e.g. by polymer-analogous reaction of polyacrylic acid with allyl isocyanate oder 2-isocyanatoethyl methacrylate (cf EP-B-323 120 and S. B. Mitra, Amer. Chem. Soc., Polym. Div., Polym. Prep. 32, (1991) page 517) or e.g. by reaction of oligomaleic acid anhydride with 2-hydroxyethyl methacrylate (cf EP-B-219 058). Corresponding polymers can also be obtained by polymer-analogous reaction of polyacrylic acid with glycidyl methacrylate (cf U.S. Pat. No. 3,872,047). With all these reactions, however, the known disadvantages of polymer-analogous reactions, such as impeded accessibility of the functional groups, non-separability of by-products or the occurrence of ring-closure reactions or crosslinking reactions, have to be accepted (cf M. Fedtke, Reaktionen an Polymeren, Verlag für Grundstoffindustrie, Leipzig 1985, page 17 et seq.).
Furthermore, it is known that mono- or bicyclic alkenes, such as e.g. cyclopentene or norbornene, can be subjected to a ring-opening polymerization with catalysts of olef in metathesis, e.g. MoO
3
/Al
2
O
3
or WCl
6
/(C
2
H
5
)
3
Al. This type of reaction is also called metathesis polymerization (cf Encyclopedia of Polymer Science and Engineering, Vol. 9, J. Wiley & Sons, New York, 1987, page 634 et seq. and K. J. Ivin, Olef in Metathesis, Academic Press, London 1983). A ring-opening metathesis polymerization (ROMP) is also possible in the case of polar compounds, such as 7-oxa-bicyclo[2.2.1]hept-5-ene derivatives which have polar substituents in the 2- or 3-position, such as alkoxy, hydroxyalkyl, alkoxycarbonyl, carboxyl or carboxylic acid anhydride, in aqueous-alcoholic reaction medium with ruthenium(III) chloride as catalyst (cf B. M. Novak, R. H. Grubbs, J. Amer. Chem. Soc. 110, (1988) page 960, 7542, W. J. Feast, D. B. Mallison, Polymer 32 (1991) page 558 and A. Y. Lu et al. Makromol. Chem. Phys. 195 (1994) page 1273). Furthermore, the ROMP of cyclooct-5-enyl methacrylate is also known which results in radically crosslinkable polymers (cf B. R. Maughon, R. H. Grubbs, Amer. Chem. Soc., Polym. Div., Polym. Prep. 36, (1995) page 471).
Moreover, bicyclic methacrylates are also known. Thus, U.S. Pat. No. 4,054,233 discloses the synthesis and polymerization of bicyclo[2.2.1]hept-5-en-2-ylmethyl methacrylate in conjunction with peroxidically crosslinkable layers. According to SU-A-1 776 673 and Chem. Abst. 199, 272563, bicyclo[2.2.1]hept-5-en-2-ylmethyl methacrylate or borneol methacrylate is used in the preparation of PVC having improved heat stability. CA-A-1 013 095 discloses adhesive polymers based on reaction products of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride with hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl methacrylate. Radically crosslinkable polyimides which are accessible via 7-oxa-5,6-dicarboxyimid-N-yl-bicyclo[2.2.1]hept-2-ene acrylate are known from T. M. Pyriadi, I. U. Altmamimi, Macromol. Rep. A31, (1994) page 191. Finally, products of the reaction of dicyclopentadiene with (meth)acrylic acid are also known (cf S. Teshigahara, Y. Kano, Toso Kenkyu Hokoko, 35 (1991) page 47 and Chem. Abstr. 116, 84740).
The object of the invention is to make available a functionalized and polymerizable polymer which can be prepared in a simple manner and radically polymerized at room temperature, exhibits good adhesion to various substrates, forms cements with reactive fillers and therefore can be used in particular as a component of cements, coating materials, adhesives or composites and preferably of dental materials. This object is achieved by the functionalized and polymerizable polymer according to Claims
1
and
2
.
The subject matter of the present invention is also a process for the preparation of the polymer according to Claim
3
, the use thereof according to Claims
4
and
5
, and compositions containing the polymer according to Claims
6
to
9
.
The functionalized and polymerizable polymer according to the invention is characterized by the fact that it has the following repeat units (IA), (IB) and (IC):
where X, A—B, Y, P, Z, U, V, T, R
1
, R
2
, R
3
, R
4
and R
5
independently of one another have the following meanings:
X=CH
2
or O;
A—B=C—C or C═C;
Y=CH
2
O, CO—O or COO−R
1
—O, where R
1
=substituted or unsubstituted C
1
to C
5
alkylene or oxyalkylene;
P=a polymerizable group, namely CH
2
═CH—CO—, CH
2
═C(CH
3
)—CO—, CH
2
═CH—CH
2
— or CH
2
═CH—C
6
H
5
—CH
2
—;
Z=H, COOH, substituted or unsubstituted C
1
to C
12
alkyl or COOR
4
, where R
4
=substituted or unsubstituted C
1
to C
12
alkyl or C
6
to C
14
aryl,
U=COOH or COOR
5
, where R
5
=substituted or unsubstituted C
1
to C
12
alkyl or C
6
to C
14
aryl;
V=H, COOH, CH
2
—OH, OR
2
or CO—OR
2
, where R=substituted or unsubstituted C
1
to C
12
alkyl or C
6
to C
14
aryl; and
T=O, NH or NHR
3
, where R
3
=substituted or unsubstituted C
1
to C
12
alkyl or C
6
to C
14
aryl; and
where the mole fraction a of the unit (IA), the mole fraction b of the unit (IB) and the mole fraction c of the unit (IC) are as follows:
a=0.05 to 1.0;
b=0 to 0.95; and
c=0 to 0.90.
The polymer is preferably built up from the units (IA) and optionally (ID) and optionally (IC).
Furthermore, A—B and X are also chosen independently of one another in the individual five-membered rings.
The alkyl and aryl groups of Z, R
1
, R
2
, R
3
, R
4
and R
5
can optionally be substituted by one or more simple functional groups, in particular COOH, OH, C
1
to C
6
alkoxy or halogen.
For simplication, the polymer according to the invention is in the following represented by the general formula (I):
The type of simplifying representation chosen in formula (I) is also used analogously for other compounds in the description and in the claims.
Preferred definitions which can be chosen independently of one another exist for the above-mentioned variables of the polymer according to the invention, these definitions being as follows:
X=CH
2
or O;
A—B=C—C;
Y=CH
2
O or CO—O—R
1

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