Biodegradable polymers, the preparation thereof, and the use thereof for producing biodegradable moldings
First Claim
1. A biodegradable polyether ester Q2 havinga molecular weight (Mn) of from 6000 to 80,000 g/mol,a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester Q2 at 25°
- C.), anda melting point of from 50 to 200°
C.,which is obtained by reacting a mixture essentially comprising(d1) from 95 to 99.9% by weight of a polyether ester P1 which hasa molecular weight (Mn) of from 5000 to 80,000 g/mol,a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising(a1) a mixture essentially comprising2- 95mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof,5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and0-5 mol% of a compound containing sulfonate groups,where the total of the individual mole percentages is 100 mol%, and(a2) a mixture of dihydroxy compounds essentially comprising(a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols,(a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --H where n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof,where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1, and(a3) from 0 to 5 mol%, based on (a1), of a compound D having at least three groups capable of ester formation,(d2)from 0.1 to 5% by weight of a bisoxazoline C1, where the total of the individual mole percentages is 100 mol%, and(d3) from 0 to 5 mol%, based on component (a1) employed in the preparation of P1, of compound D.
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Accused Products
Abstract
Biodegradable polymers comprising a polyether ester P1 obtained by reacting
a first mixture of
20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof,
5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and
0-5 mol% of a compound containing sulfonate groups,
and a second mixture of
15-99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols,
85-0.2 mol% of a dihydroxy compound I
HO-- (CH.sub.2).sub.n --O!.sub.m --H
(n=2, 3 or 4, m=2-250)
with
0-5 mol%, based on the first mixture, of a compound D having at least three groups capable of ester formation,
and a bisoxazoline C1, their preparation and their use in the manufacture of biodegradable molding materials.
51 Citations
19 Claims
-
1. A biodegradable polyether ester Q2 having
a molecular weight (Mn) of from 6000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester Q2 at 25° - C.), and
a melting point of from 50 to 200°
C.,which is obtained by reacting a mixture essentially comprising (d1) from 95 to 99.9% by weight of a polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1) a mixture essentially comprising 2- 95mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, and (a2) a mixture of dihydroxy compounds essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, (a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1, and(a3) from 0 to 5 mol%, based on (a1), of a compound D having at least three groups capable of ester formation, (d2)from 0.1 to 5% by weight of a bisoxazoline C1, where the total of the individual mole percentages is 100 mol%, and (d3) from 0 to 5 mol%, based on component (a1) employed in the preparation of P1, of compound D. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14)
- C.), and
-
15. A biodegradable polymer T1 having
a molecular weight (Mn) of from 10,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polymer T2 at 25° - C.), and
a melting point of from 50 to 235°
C.,which is obtained by reacting a polyether ester Q1 which has a molecular weight (Mn) of from 5,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester Q1 at 250C.), and a melting point of from 50 to 235°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, where Q1 is obtained by reacting a mixture essentially comprising (c1) a polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80.000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1) a mixture essentially comprising 20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, and (a2) a mixture of dihydroxy compounds essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, (a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1, and(a3) from 0 to 5 mol%. based on (a1), of a compound D having at least three groups capable of ester formation, (c2) 0.01 to 50% by weight, based on (c1), of a hydroxy carboxylic acid B1 of the formula IIa or IIb ##STR8## where p is an integer from 1 to 1500, r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, --(CH2)k --, where k is an integer from 1 to 5, --C(R)H-- and --C(R)HCH2 --, where R is methyl or ethyl, and (C3) 0 to 5 mol%, based on component (a1), employed in the preparation of P1, of compound D, with (e1) 0.1 to 5% by weight, based on the polyether ester Q1 , of a bisoxazoline C1, and (e2) 0 to 5 mol%, based on component (a1) employed in the preparation of the polyether ester Q1 , of compound D.
- C.), and
-
16. A biodegradable polymer T3 having
a molecular weight (Mn) of from 10,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polymer T3 at 25° - C.), and
a melting point of from 50 to 235°
C.,which is obtained by reacting (g1) a polyether ester P2 which has a molecular weight (Mn) of from 5000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P2 at 25°
C.), andmelting point of from 50 to 235°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P2 is obtained by reacting a mixture essentially comprising (b1) a mixture essentially comprising 20 to 95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5 to 80 mol% of terephthalic acid or ester forming derivatives thereof or mixtures thereof, and 0 to 5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, (b2) a mixture of dihydroxy compounds, essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, and (a22) from 85 to 0.2 mol% of a dihydroxy compound containing ether functionalities of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (b1) to (b2) is of from 0.4;
1 to 1.25;
1,(b3)from 0.01 to 100% by weight, based on component (b1), of a hydroxy carboxylic acid B1 of the formula IIa or IIb ##STR9## where p is an integer from 1 to 1500, r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, --(CH2)k --, where k is an integer from 1 to 5, --C(R)H-- and --C(R)HCH2 --, where R is methyl or ethyl, and (b4) from 0 to 5 mol%, based on component (b1), of a compound D having at least three groups capable of ester formation, or (g2) a mixture essentially comprising the polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80.000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1) a mixture essentially comprising 20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, and (a2) a mixture of dihydroxy compounds essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, (a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2. 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1. and(a3) from 0 to 5 mol%. based on (a1), of a compound D having at least three groups capable of ester formation, and 0.01 to 50% by weight, based on P1, of the hydroxy carboxylic acid B1, or (g3) a mixture essentially comprising polyether esters P1 which differ from one another in composition, with 0.1 to 5% by weight, based on the polyether ester (g1), (g2) or (g3), of a bisoxazoline C1, and 0 to 5 mol%, based on component (a1) or (b1) employed in the preparation of the polyether ester (g1), (g2) or (g3), of compound D.
- C.), and
-
17. A process for preparing a biodegradable polyether ester Q2 having
a molecular weight (Mn) of from 6000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester Q2 at 25° - C.), and
a melting point of from 50 to 200°
C.,which comprises in a first step preparing (d1) a polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which had both hydroxyl and carboxy end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1) a mixture essentially comprising 20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, and (a2) a mixture of dihydroxy compounds essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, (a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2. 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1. and(a3) from 0 to 5 mol%. based on (a1), of a compound D having at least three groups capable of ester formation, and in a second step reacting a mixture essentially comprising (d1) with (d2)from 0.1 to 5% by weight of a bisoxazoline C1, and (d3) from 0 to 5 mol%, based on component (a1) employed in the preparation of P1, of compound D.
- C.), and
-
18. A process for preparing a biodegradable polymer T1 having
a molecular weight (Mn) of from 10,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polymer Ti at 25° - C.), and
a melting point of from 50 to 235°
C.,which comprises in a first step preparing a polyether ester Q1 which has a molecular weight (Mn) of from 5,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester Q1 at 25°
C.), anda melting point of from 50 to 235°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, where Q1 is obtained by reacting a mixture essentially comprising (c1) a polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80.000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1) a mixture essentially comprising 20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol% and (a2) a mixture of dihydroxy compounds essentially comprising (a22) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, (a22) from 85 to 0.2 mol% of a dihydroxy compound of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1, and(a3) from 0 to 5 mol%. based on (a1), of a compound D having at least three groups capable of ester formation, (c2) 0.01 to 50% by weight, based on (c1), of a hydroxy carboxylic acid B1 of the formula IIa or IIb ##STR10## where p is an integer from 1 to 1500, r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, --(CH2)k --, where k is an integer from 1 to 5, --C(R)H-- and --C(R)HCH)--, where R is methyl or ethyl, and (c3) 0 to 5 mol%, based on component (a1), employed in the preparation of P1, of compound D, and in a second step reacting Q1 with (e1)from 0.1 to 5% by weight, based on the polyether ester Q1 , of a bisoxazoline C1, and (e2)from 0 to 5 mol%, based on component (a1) employed in the preparation of the polyether ester Q1, of compound D.
- C.), and
-
19. A process for preparing a biodegradable polymer T3 having
a molecular weight (Mn) of from 10,000 to 100,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polymer T3 at 25° - C.), and
a melting point of from 50 to 235°
C.,which comprises in a first step preparing (g1) a polyether ester P2 which has a molecular weight (Mn) of from 5000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P2 at 25°
C.), anda melting point of from 50 to 235°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P2 is obtained by reacting a mixture essentially comprising (b1) a mixture essentially comprising 20 to 95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5 to 80 mol% of terephthalic acid or ester forming derivatives thereof or mixtures thereof, and 0 to 5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, (b2) a mixture of dihydroxy compounds essentially comprising (a2 l) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10- -cycloalkanediols, and (a22) from 85 to 0.2 mol% of a dihydroxy compound containing ether functionalities of the formula I
space="preserve" listing-type="equation">HO-- (CH.sub.2).sub.n --O!.sub.m --Hwhere n is 2, 3 or 4 and m is an integer from 2 to 250, or mixtures thereof, where the molar ratio of (b1) to (b2) is of from 0.4;
1 to 1.25;
1,(b3)from 0.01 to 100% by weight, based on component (b1), of a hydroxy carboxylic acid B1 of the formula IIa or IIb ##STR11## where p is an integer from 1 to 1500, r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, --(CH2)k --, where k is an integer from 1 to 5, --C(R)H-- and --C(R)HCH2 --, where R is methyl or ethyl, and (b4) from 0 to 5 mol%, based on component (b1), of a compound D having at least, three groups capable of ester formation, or (g2) a mixture essentially comprising the polyether ester P1 which has a molecular weight (Mn) of from 5000 to 80,000 g/mol, a viscosity number of from 30 to 450 g/ml (measured in o-dichlorobenzene/phenol (50/50 ratio by weight) at a concentration of 0.5% by weight of polyether ester P1 at 25°
C.), anda melting point of from 50 to 200°
C.,and which has both hydroxyl and carboxyl end groups, where the molar ratio of carboxyl end groups to hydroxyl end groups is greater than one, and where P1 is obtained by reacting a mixture essentially comprising (a1l) a mixture essentially comprising 20-95 mol% of adipic acid or ester-forming derivatives thereof or mixtures thereof, 5-80 mol% of terephthalic acid or ester-forming derivatives thereof or mixtures thereof, and 0-5 mol% of a compound containing sulfonate groups, where the total of the individual mole percentages is 100 mol%, and (a2) a mixture of dihydroxy compounds essentially comprising (a21) from 15 to 99.8 mol% of a dihydroxy compound selected from the group consisting of C2 -C6 -alkanediols and C5 -C10 -cycloalkanediols, and (a22) from 85 to 0.2 mol% of a dihydroxy compound containing ether functionalities of the formula I, where the molar ratio of (a1) to (a2) is from 0.4;
1 to 1.5;
1, and(a3) from 0 to 5 mol%, based on component (a1), of a compound D having at least three groups capable of ester formation, and from 0.01 to 50% by weight, based on polyether ester P1, of the hydroxy carboxylic acid B1, or (g3) a mixture essentially comprising polyether esters P1 which differ from one another in composition, and in a second step reacting (g1) or (g2) or (g3) with 0.1 to 5% by weight, based on the polyether ester (g1), (g2) or (g3), of a bisoxazoline C1, and 0 to 5 mol%, based on (a1) or (b1) employed in the preparation of the polyether ester (g1), (g2) or (g3), of compound D.
- C.), and
Specification