High impact polystyrene having high modulus and resistance to environmental stress cracking
High impact polystyrenes and related monovinyl aromatic polymers generally have either a high modulus or good resistance to environmental stress cracking. The present invention is directed at polymeric materials having both a high modulus and good resistance to environmental stress cracking thus enabling the down gauging of parts, and or the use of the materials in new applications. The invention is predicated on the use of one or more, or even all of the following features: a high molecular weight matrix polymer, reduced concentration of elastomeric polymer, or methods that result in large rubber particle size.
1. A composition comprising:
a rubber-modified monovinyl aromatic polymer
i) including about 90 weight percent or more of a monovinyl aromatic polymer matrix, based on the total weight of the rubber-modified monovinyl aromatic polymer; and
ii) from about 2 to about 7.5 weight percent of one or more elastomeric polymers, based on the total weight of the composition; wherein the one or more elastomeric polymers are cross-linked and have a volume average diameter of 5 μm to 30 μm; and
greater than 2 weight percent to 7 weight percent mineral oil, based on the total weight of the composition;
wherein the monovinyl aromatic polymer matrix is derived from one or more monovinyl aromatic monomers, and the monovinyl aromatic polymer matrix has a sufficiently high molecular weight so that the retention in the elongation at break after 10 days in corn oil at 1% strain is about 15% or more;
the monovinyl aromatic polymer matrix is sufficiently rigid so that the composition has a tensile modulus of about 1500 MPa or more as measured according to ISO 527-2; and
the monovinyl aromatic polymer matrix includes a soluble portion that is soluble in tetrahydrofuran at 25° C. and an insoluble portion that is insoluble in tetrahydrofuran at 25° C., wherein the molecular weight of the soluble portion of the monovinyl aromatic polymer matrix is characterized by a weight average molecular weight of 200,000 to about 280,000 g/mol and a polydispersity index of 3.0 or more; and
the composition has a gel content in 25° C. toluene of about 27.8 weight percent to about 31.1 weight percent, after heating to 280° C. for 2 hours under nitrogen.
2. The composition of claim 1 , wherein the elastomeric polymer has an average diameter from 6 μm to 15 μm, and the elastomeric polymer includes at least 75 weight percent butadiene monomer based on the total weight of the elastomeric polymer.
3. The composition of claim 1 , wherein the soluble portion of the monovinyl aromatic polymer matrix has a weight average molecular weight of 205,000 g/mol or more, and includes about 95 weight percent to about 100 weight percent styrene, based on the total weight of the monvinyl aromatic polymer matrix.
4. The composition of claim 3 , wherein the elastomeric polymer is present as grafted and cross-linked rubber particles dispersed within the monovinyl aromatic polymer matrix.
5. The composition of claim 4 , wherein the monovinyl aromatic polymer matrix consists essential of styrene, and is sufficiently rigid and the concentration of the elastomeric polymer is sufficiently low so that the tensile modulus of the composition is about 1600 MPa or more.
6. The composition of claim 5 , wherein the one or more elastomeric polymers are present in an amount from about 3 to about 7.1 weight percent, based on the total weight of the composition.
7. The composition of claim 6 , wherein the rubber-modified monovinyl aromatic polymer is a reactor blend having the one or more monovinyl aromatic monomers polymerized in the presence of the one or more elastomeric polymers.
8. The composition of claim 7 , wherein the molecular weight distribution of the soluble portion of the monovinyl aromatic polymer is characterized by a polydispersity index of 3.0 to 8.
9. The composition of claim 8 , wherein the soluble portion of the monovinyl aromatic polymer is characterized by a z-average molecular weight of about 360,000 g/mol or more.
10. The composition of claim 9 , wherein the concentration of the elastomeric polymer is about 4 weight percent or more based on the total weight of the composition, and wherein, and the elastomeric polymer has an average diameter from 6 μm to 15 μm.
11. The composition of claim 10 , wherein the composition consists of the monovinyl aromatic polymer, the elastomeric polymer and the mineral oil.
12. A composition consisting of:
a rubber-modified monovinyl aromatic polymer consisting of
i) about 90 weight percent or more of a monovinyl aromatic polymer matrix, based on the total weight of the rubber-modified monovinyl aromatic polymer; and
ii) from about 2 to about 7.5 weight percent of one or more elastomeric polymers, based on the total weight of the composition; wherein the one or more elastomeric polymers is cross-linked and have a volume average diameter of 5 μm to 30 μm; and
greater than 2 weight percent to 7 weight percent mineral oil, based on the total weight of the composition;
wherein the monovinyl aromatic polymer matrix is derived from one or more monovinyl aromatic monomers, and the monovinyl aromatic polymer matrix has a sufficiently high molecular weight so that the retention in the elongation at break after 10 days in corn oil at 1% strain is about 15% or more;
the monovinyl aromatic polymer matrix is sufficiently rigid so that the composition has a flexural modulus of about 1500 MPa or more as measured according to ISO 178; and
the monovinyl aromatic polymer matrix includes a soluble portion that is soluble in tetrahydrofuran at 25° C. and an insoluble portion that is insoluble in tetrahydrofuran at 25° C., wherein the molecular weight of the soluble portion of the monovinyl aromatic polymer matrix is characterized by a weight average molecular weight of 200,000 to about 280,000 g/mol and a polydispersity index of 2.7 or more; and
the composition has a gel content in 25° C. toluene of about 27.8 weight percent to about 31.1 weight percent, after heating to 280° C. for 2 hours under nitrogen.
13. The composition of claim 1 , wherein
the soluble portion of the monovinyl aromatic polymer is characterized by a weight average molecular weight of 205,000 g/mol or more;
the molecular weight distribution of the soluble portion of the monovinyl aromatic polymer is characterized by a polydispersity index of 3.0 or more;
the monovinyl aromatic polymer includes about 95 weight percent or more styrene, based on the total weight of the monovinyl aromatic polymer;
the concentration of the elastomeric polymer is sufficiently low so that the tensile modulus of the composition is about 1700 MPa or more;
the monovinyl aromatic polymer is characterized by a z-average molecular weight of about 360,000 g/mol or more;
the concentration of the elastomeric polymer is 7.1 weight percent or less, based on the total weight of the composition;
the concentration of the elastomeric polymer is about 4 weight percent or more based on the total weight of the composition; and
the elastomeric polymer includes at least 75 weight percent butadiene monomer based on the total weight of the elastomeric polymer.
14. The composition of claim 13 , wherein the elastomeric polymer has an average diameter from 6 μm to 15 μm.
15. A refrigerator liner including a composition of claim 13 .
16. The refrigerator liner of claim 15 , wherein the refrigerator liner is characterized by ESCR performance determined by retention in elongation at break after 10 days in corn oil at 1% strain of about 15% or more.
17. A process including a step of extruding and/or thermoforming the composition of claim 13 to form a refrigerator liner.
18. A method of forming a composition comprising the steps of:
i) polymerizing one or more monovinyl aromatic monomers in the presence of one or more elastomeric polymers and cross-linking the one or more elastomeric polymers in a devolatilization step to form a rubber-modified monovinyl aromatic polymer; including a soluble portion that is soluble in tetrahydrofuran at 25° C. and an insoluble portion that is insoluble in tetrahydrofuran at 25° C., wherein the molecular weight of the soluble portion of the a monovinyl aromatic polymer matrix is characterized by a weight average molecular weight of 200,000 to about 280,000 g/mol and a polydispersity index of 3.0 or more; and
ii) preparing a polymeric composition by blending at least the rubber-modified monovinyl aromatic polymers and 2 weight percent to 7 weight percent of mineral oil;
wherein the rubber-modified monovinyl aromatic polymer includes:
i) about 90 weight percent or more of the monovinyl aromatic polymer matrix, based on the total weight of the polymeric composition; and
ii) from about 2 to about 7.5 weight percent of the one or more elastomeric polymers, based on the total weight of the rubber-modified monovinyl aromatic polymer;
wherein the one or more elastomeric polymers is cross-linked and has a volume average diameter of 5 μm to 30 μm;
the monovinyl aromatic polymer matrix has a sufficiently high molecular weight so that the retention in the elongation at break after 10 days in corn oil at 1% strain is about 15% or more;
the monovinyl aromatic polymer matrix is sufficiently rigid so that the composition has a tensile modulus of about 1500 MPa or more as measured according to 527-2; and
the composition has a gel content in 25° C. toluene of about 27.8 weight percent to about 31.1 weight percent, after heating to 280° C. for 2 hours under nitrogen.
19. The process of claim 18 , wherein the elastomeric polymer has an average diameter from 6 μm to 15 μm.
20. The method of claim 19 , wherein the monovinyl aromatic polymer matrix includes 95 weight percent or more styrene, based on the total weight of the monovinyl aromatic polymer matrix.