Shape memory polymer with polyester and polyacrylate segments and process for its production and programming
The invention relates to a shape memory polymer, to a process for its production and to a process for its programming. The inventive shape memory polymer has at least two switching segments with different transition temperatures (T trans,1 , T trans,2 ) such that the polymer, depending on the temperature, as well as a permanent shape (PF), can also assume at least two temporary shapes (TF 1 , TF 2 ). The first switching segment is based essentially on a polyester of the general formula (I) where n=1 . . . 6 or a copolyester of the general formula (I) with different n or a derivative thereof. The second switching segment is based essentially on a polyacrylate of the general formula (II) in which R is H or CH 3 , and R 1 is a saturated or unsaturated, cyclic or aliphatic, unsubstituted or substituted C1-C10 radical.
1. A shape memory polymer comprising at least two switching segments, in which the shape memory polymer is an AB polymer network in which one of the switching segments is crosslinked by the other switching segment, which is bound terminally at both ends,
and in which a first switching segment is based essentially on a polyester of the general formula I, where n=1, . . . , 6, or a copolyester of general formula I with different values of n, or a derivative of these, and a second switching segment is based essentially on a polyacrylate of general formula II, in which R denotes H or CH 3 and R 1 denotes cyclohexyl C 6 H 11 or in which R denotes CH 3 and R 1 denotes CH 3 or in which R denotes CH 3 and R 1 denotes 2-hydroxyethyl C 2 H 4 OH,
and in which p and q are selected so that the first and second switching segments in the shape memory polymer each form a segregated phase with each phase having at least one transition temperature independently selected from a glass transition temperature and a melt temperature so that the polymer can assume at least two temporary shapes (TF 1 , TF 2 ) in addition to one permanent shape, depending on the temperature:
2. The shape memory polymer according to claim 1 , wherein the first switching segment comprises a poly(ε-caprolactone) segment with n=5 or a derivative thereof, in which the aliphatic carbons, independently of one another, may be substituted with one or two branched or unbranched, saturated or unsaturated C 1 to C 6 radicals.
3. The shape memory polymer according claim 1 , wherein the first switching segment has a number average molecular weight M n in the range of 2000 g/mol to 100,000 g/mol.
4. The shape memory polymer according to claim 1 , wherein an amount by weight of the polyester segment in the shape memory polymer is in the range of 25% to 75%.
5. The shape memory polymer according to claim 1 , wherein the shape memory polymer is an AB polymer network in which polyacrylate segments are crosslinked with polyester chains bound terminally at both ends.
6. A method for producing a shape memory polymer according to claim 1 , wherein a polyester macromonomer of general formula I a, in which n=1, . . . , 6 and Y is a connecting radical, or a copolyester macromonomer of general formula I a, with different values of n or a derivative thereof, wherein R 2 or the second end group R 3 , independently of one another, denotes a polymerizable end group, and an acrylate monomer of general formula II a, in which R is H or CH 3 and R 1 denotes cyclohexyl C 6 H 11 or in which R denotes CH 3 and R 1 denotes CH 3 or in which R denotes CH 3 and R 1 denotes 2-hydroxyethyl C 2 H 4 OH, are copolymerized
7. The method according to claim 6 , wherein R 2 and R 3 each denote a polymerizable end group.
8. The method according to claim 6 , wherein the first end group R 2 and/or the second end group R 3 of the polyester component is/are an acryl radical or a methacryl radical.
9. The shape memory polymer according to claim 3 , wherein the first switching segment has a number average molecular weight M n in the range of 5,000 g/mol to 40,000 g/mol.
10. The shape memory polymer according to claim 3 , wherein the first switching segment has a number average molecular weight M n of 10,000 g/mol.
11. The shape memory polymer according to claim 4 , wherein an amount by weight of the polyester segment in the shape memory polymer is in the range of 30% to 70%.
12. The shape memory polymer according to claim 4 , wherein an amount by weight of the polyester segment in the shape memory polymer is in the range of 50% to 60%.