Compositions containing rosin esters and ethylene polymers
View Patent ↗Disclosed are compositions which include an ethylene polymer derived from at least one polar monomer with one or more ester groups, and a rosin ester. The rosin ester can have a low hydroxyl number (e.g., a hydroxyl number seven or less), a low acid number (e.g., an acid number of ten or less), a relatively low PAN number (e.g., a PAN number less than twenty-five), a relatively high third moment or third power average molecular weight (M z ), (e.g., an M z value in between 2500 and 12000 g/mol), a low sulfur content (e.g., a sulfur content lower than 600 ppm prior to antioxidant addition) or combinations thereof. The compositions can exhibit a high heat stress resistance (e.g., a heat stress pass temperature value higher than 52° C. or in between 48° C. and 60° C.) and/or improved viscosity stability and/or color stability upon thermal aging and/or improved compatibility.
1. A composition comprising,
an ethylene polymer derived from at least one polar monomer with one or more ester groups and ethylene; and
a rosin ester having a hydroxyl number of less than 7, an Mz value between 2500 and 12000, and a sulfur ppm content value of less than 1000 ppm.
2. The composition of claim 1 , wherein the rosin ester has an acid number of 10 or less.
3. The composition of claim 2 , wherein the sum of the hydroxyl number and the acid number is 12 or less.
4. The composition of claim 1 , wherein the rosin ester has a PAN number of 25 or less.
5. The composition of claim 1 , wherein the rosin ester is derived from an alcohol, a rosin, and up to 10 weight %, relative to the total weight of all reactants, of one or more carboxylic acid functional organic compounds;
wherein the one or more carboxylic acid functional organic compounds have an average number of rotatable bonds of 12 or less than 12.
6. The composition of claim 1 , wherein the rosin ester is derived from an alcohol, a rosin and more than zero up to 10 weight %, relative to the total weight of the reactants, of one or more dicarboxylic acid functional organic compounds.
7. The composition of claim 1 , wherein the rosin ester is derived from an alcohol, a rosin and more than zero up to 10 weight %, relative to the total weight of the reactants, of a saturated aliphatic difunctional carboxylic acid selected from the group consisting of succinic acid, glutaric acid, adipic acid, sebacic acid, or 1,4-cyclohexanedicarboxylic acid, and combinations of these acids.
8. The composition of claim 1 , wherein the rosin ester has a Mw value of 1700 to 4000 g/mol, and a Mn value of 1100 to 2000 g/mol.
9. The composition of claim 1 , wherein the rosin ester has a softening point higher than 105.3° C. and lower than 110° C.
10. The composition of claim 1 , wherein the polar monomer comprises a vinyl alkanoate monomer, acrylate ester monomer, methacrylate ester monomer, or mixtures thereof.
11. The composition of claim 1 , wherein the rosin is a tall oil rosin.
12. The composition of claim 1 , wherein the rosin ester, after thermal aging at 177° C. for 10 hours, has a turbidimetric light transmission percentage that exceeds 75% within a temperature range of 80° C. to 180° C.
13. The composition of claim 1 , where the rosin ester is obtained by a process comprising:
contacting a reactant mixture of a rosin and other optional reactants with an alcohol in an esterification reaction, optionally in the presence of an esterification catalyst, and optionally in the presence of 0-0.05% by weight, relative to the total of all reactants, of a disproportionation catalyst;
wherein the optional reactants include at least one carboxylic acid moiety; and
wherein the esterification reaction is at a temperature of at least 170° C.
14. The composition of claim 13 , wherein the esterification reaction is carried out at a maximum temperature of 300° C.
15. The composition of claim 1 , wherein the rosin ester is obtained by a process comprising:
esterifying a reactant mixture comprising:
an unfortified rosin,
one or more dicarboxylic acid functional organic compounds, and
an alcohol;
wherein the reactant mixture has a stoichiometric excess of carboxylic acid functionality over the hydroxyl functionality,
wherein the one or more dicarboxylic acid functional organic compounds are present in an amount of more than 2 weight %, relative to the total weight of the reaction mixture; and have molecular formulas wherein the number of hydrogen atoms is higher than the number of carbon atoms.
16. The composition of claim 15 , wherein the one or more dicarboxylic acid functional organic compounds are present in an amount from 2 to 25 weight %, relative to the total weight of the reactant mixture, and have an average number of rotatable bonds of 12 or less than 12.
17. The composition of claim 16 , wherein the dicarboxylic acid is selected from the group consisting of adipic acid, 3-methyladipic acid, polymerized rosin, rosin dimer, and 1,4-cyclohexanedicarboxylic acid.
18. The composition comprising the rosin ester of claim 14 , wherein the composition is a thermoplastic road marking formulation, a tire formulation or an adhesive formulation.
19. A method of making a rosin ester comprising:
providing a reactant mixture of a rosin, an alcohol, and optional reactants; and
esterifying the reactant mixture to provide the rosin ester, optionally in the presence of an esterification catalyst, and optionally in the presence of 0-0.05% by weight, relative to the total of all reactants, of a disproportionation catalyst;
wherein the optional reactants include at least one carboxylic acid moiety;
wherein the esterification reaction is at a maximum temperature of 300° C.; and
wherein the rosin ester has a hydroxyl number of less than 7, an Mz value between 2500 and 12000, and a sulfur ppm content value of less than 1000 ppm.