BLOWING AGENTS FOR EXTRUDED POLYSTYRENE FOAM AND EXTRUDED POLYSTYRENE FOAM AND METHODS OF FOAMING

FIELD OF THE INVENTION

This invention relates to compositions, methods and systems having utility in connection with extruded thermoplastic foams, including particularly in connection with blowing agents, foamable compositions, foams and articles made with or from polystyrene foams.

BACKGROUND

Certain fluorocarbon fluids have found widespread use as blowing agents. Because of environmental problems, including relatively high ozone depletion potentials, associated with the use of some of the fluorocarbon fluids that have heretofore been used in these applications, it has become increasingly desirable to use fluids having low or even zero ozone depletion potential, such as hydrofluorocarbons (“HFCs”). However, some HFC fluids may have relatively high global warming potentials associated therewith, and it is desirable to use hydrofluorocarbon or other fluorinated fluids having low ozone depletion potential and low global warming potential while maintaining the desired performance properties of the foam.

In terms of performance properties of the foam, it is considered important in many cases that the foam possess excellent thermal insulating properties and other desirable foam characteristics. Another foam characteristic that is important in many applications is the density of the foam. For example, there is a need in many thermal insulating foam applications to have a foam that not only exhibits a low thermal conductivity, but also a relatively low foam density.

A significant challenge has been encountered in efforts to achieve thermoplastic foams that at once have low thermal conductivity (measured after ageing) and low density, and in particular to the achievement of thermoplastic polystyrene foam with a density of less than 32 kg/m³and at the same time an low thermal conductivity. For example, EP 2706086 includes numerous examples of polystyrene foam made using a variety of different blowing agent compositions, including blowing agents comprised of HFO-1234ze and one or more coblowing agents. However, not a single example which used HFO blowing agent was able to achieve a density of less than 34.6 kg/m³, and even the foam made from a blowing agent comprising ethanol and CO2 blowing agent had a density above 32 kg/m³and a relatively high thermal conductivity of 34.7 mW/mK. Similarly, while each of US2019/0211172, US 2018/0327565, WO/2020/041539 and WO/2020/018332 disclose polystyrene foams made from various blowing agent compositions, none of these publications disclose a foam that has a density of less than 32 kg/m3 and at the same time a low thermal conductivity.

Similarly, while JP2021/10388313 indicates that it has as an objection the achievement of foams with good insulating properties using blowing agents comprising HFO-1224yd, there is no disclosure of a specific example that at once achieves a density of less than 32 kg/m³and a low thermal conductivity. In particular, Examples A1 through A15 of JP2021/10388313 suggest that low thermal conductivity foams made from several thermoplastic materials can be formed from blowing agent comprising HFO-1224yd. However, JP2021/10388313 discloses that relatively high (and undesirable) foaming agent loadings are used to produce the foam, and does not disclose that any of the polystyrene foams in these examples was able to achieve a density of less than 32 kg/m³while at the same time achieving a desirably low thermal conductivity.

There has thus been an increasing need for new blowing agent materials that are attractive alternatives to the compositions heretofore used as blowing agents in these and other applications. Applicants have thus recognized a need for new blowing agent compositions that offer effective alternatives to, and are considered environmentally safer substitutes for, previously used blowing agents to make low density, low thermal conductivity thermoplastic foams, and extruded polystyrene foam in particular.

The use of halogenated olefin blowing agents, including hydrofluoroolefins (HFOs) and hydrochlorofluorolefins (HCFOs), is also known, as disclosed for example in US 2009/0305876, which is assigned to the assignee of the present invention and which is incorporated herein by reference.

Notwithstanding the disclosures in each of the '876, applicants have come to appreciate that an unexpected advantage can be achieved in connection with the formation of extruded thermoplastic foams, and in particular extruded polystyrene foams, by using a hydrofluoroolefin, particularly one or more HFOs and/or HFCOs having three or four carbons, such as trans-HCFO-1233zd, cisHFO-1224yd and cis-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)), in combination with at least one carefully selected blowing agent in carefully selected amounts, as explained in detail hereinafter.

SUMMARY

The present invention includes blowing agents for producing thermoplastic foams with excellent thermal insulating properties (including preferably low aged lambda) and low foam density, said blowing agent comprising:

(a) from about 40% by weight to about 70% by weight of one or more HFOs having three or four carbon atoms and/or an HFCOs having three or four carbon atoms being selected from the group consisting of 1224yd(Z), 1233zd(E), 1336mzz(Z) and combinations of these; and

(b) from about 30% to about 60% by weight of isobutane, dimethyl ether, methyl formate, ethanol and combinations of these, provided that the amount of (a) and (b) in the blowing agent is not less than about 90% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1A.

(b) from about 30% to about 60% by weight of isobutane, dimethyl ether methyl formate, ethanol and combinations of these, provided that the amount of (a) and (b) in the blowing agent is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1B.

(b) from about 30% to about 60% by weight of isobutane, dimethyl ether methyl formate, ethanol and combinations of these, provided that that the amount of (a) and (b) in the blowing agent is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1C.

(a) from about 45% by weight to about 60% by weight of one or more HFOs three or four carbon atoms and/or an HFCOs having three or four carbon atoms being selected from the group consisting of 1224yd(Z), 1233zd(E), 1336mzz(Z) and combinations of these; and

(b) from about 40% to about 55% by weight of isobutane, dimethyl ether, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 25% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1D.

(b) from about 30% to about 55% by weight of isobutane, dimethyl ether, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 30% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1E.

(b) from about 40% to about 55% by weight of isobutane, dimethyl ether, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 30% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1F.

(a) from about 25% by weight to about 55% by weight of one or more of 1233zd(E), 1224yd(Z), 1336mzz(Z) and combinations of these; and

(b) from about 25% to about 75% by weight of isobutane, dimethyl ether, methyl formate, ethanol and combinations of these, provided that said methyl formate when present is present in an amount of less than about 15%; and

(c) from about 3% to about 32% by weight of CO₂. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1G.

(a) from about 45% by weight to about 55% by weight of one or more of 1233zd(E), 1224yd(Z), 1336mzz(M) and combinations of these; and

(b) from about 45% to about 55% by weight of isobutane, dimethyl ether, methyl formate and combinations of these, provided that said methyl formate when present is present in an amount of less than about 15%; and

(c) about 3% by weight of CO₂. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1H.

(a) from about 45% by weight to about 55% by weight of a combination of 1233zd(E) and 1336mzz(Z); and

(b) from about 40% to about 50% by weight of isobutane, methyl formate and combinations of these, and optionally CO2, provided that said methyl formate when present is present in an amount of less than about 15%. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 11.

(a) from about 35% by weight to about 45% by weight of 1233zd(E);

(b) from about 10% by weight to about 15% by weight 1336mzz(Z);

(d) optionally methyl formate and optionally CO2, provided that said methyl formate when present is present in an amount of less than about 15%.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1J.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 40% by weight to about 50% by weight of isobutane; and

(d) optionally methyl formate and optionally CO2, provided that said methyl formate when present is present in an amount of not greater than about 10%. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1K1.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 35% by weight to about 50% by weight of isobutane, DME or combinations of these; and

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 35% by weight to about 40% by weight of DME;

(d) about 10% by weight of methyl formate; and

(e) optionally CO2.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1L.

- (a) from about 50% by weight to about 60% by weight of a combination of 1233zd(E) and 1336mzz(Z);
- (b) from about 25% to about 30% by weight of isobutane;
- (c) from about 10% to about 15% by weight of methyl formate; and
- (d) about 3% by weight of CO₂.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1M.

- (a) from about 40% by weight to about 45% by weight of 1233zd(E);
- (b) from about 10% by weight to about 15% by weight of 1336mzz(E);
- (b) from about 25% to about 30% by weight of isobutane;
- (c) from about 10% to about 15% by weight of methyl formate; and
- (d) about 3% by weight of CO2.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1N.

- (a) about 50% by weight of 1224yd(Z);
- (b) about 37% by weight of one or more of isobutane, DME and combinations of these;
- (b) about 9% by weight of methyl formate; and
- (d) about 3% by weight of CO2.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1O.

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent is not less than about 90% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1P.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1Q.

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1R.

(a) from about 40% by weight to about 70% by weight of one or more HFOs three or four carbon atoms and/or an HFCOs having three or four carbon atoms being selected from the group consisting of 1224yd(Z), 1233zd(E), 1336mzz(Z) and combinations of these provided that said 1336mzz(Z) is present in the blowing agent in an amount of from about 8% to about 22% by weight; and

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 15% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1S.

(a) about 43% by weight of 1233zd(E);

(b) about 14% by weight of 1336mmz(Z); and

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1T.

(a) about 37.5 by weight of 1233zd(E);

(b) about 12.5% by weight of 1336mmz(Z);

(d) about 12.5% by weight of methyl formate.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1U1.

(a) about 40% by weight of 1233zd(E);

(b) about 13% by weight of 1336mmz(Z);

(d) about 13% by weight of methyl formate.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1U2.

(a) about 41% by weight of 1233zd(E);

(b) about 14% by weight of 1336mmz(Z);

(d) about 14% by weight of methyl formate; and

(e) about 3% by weight of CO₂.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1U3.

(a) about 28% by weight of 1336mmz(Z);

(b) about 39.5% by weight of ethanol;

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1V.

(a) about 53% by weight of 1224yd(Z); and

(b) about 47% by weight of isobutane.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1W1.

(a) about 48% by weight of 1224yd(Z);

(b) about 42% by weight of isobutane; and

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1W2.

(a) about 50% by weight of 1224yd(Z);

(b) about 37.5% by weight of isobutane;

(d) about 3% by weight of CO₂.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1W3.

(d) about 51.6% by weight of 1224yd(Z);

(e) about 38.7% by weight of DME; and

(f) about 9% by weight of methyl formate.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1X1.

(a) about 50% by weight of 1224yd(Z);

(b) about 37.5% by weight of DME;

(d) about 3% by weight of CO₂.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 1X2.

(a) from about 45% by weight to about 70% by weight of a combination of 1233zd(E) and 1336mzz(Z), provided that said 1336mzz(Z) is present in the blowing agent composition in an amount of from about 8% to about 22% by weight; and

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent composition in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent composition is not less than about 90% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2A.

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent composition in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2B.

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent composition in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent composition is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2C.

(b) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent composition in an amount of at least about 15% by weight, and further provided that the amount of (a) and (b) in the blowing agent composition is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2D.

(a) from about 10% by weight to about 20% by weight of 1336mzz(Z);

(b) from about 35% by weight to about 55% by weight of 1233zd(E); and

(c) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 15% by weight, and further provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2E.

(a) from about 10% by weight to about 20% by weight of 1336mzz(Z);

(b) from about 35% by weight to about 55% by weight of 1233zd(E); and

(a) from about 10% by weight to about 20% by weight of 1336mzz(Z);

(b) from about 35% by weight to about 55% by weight of 1233zd(E); and

(c) from about 30% to about 60% by weight of isobutane, methyl formate and combinations of these, provided that said isobutane is present in the blowing agent in an amount of at least about 15% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2G.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E); and

(c) from about 15% to about 45% by weight of isobutane, provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 80% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2H.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E); and

(c) from about 40% to about 45% by weight of isobutane, provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 21.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E); and

(c) from about 40% to about 45% by weight of isobutane, provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2J.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E); and

(c) from about 40% to about 45% by weight of isobutane. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2K.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E);

(d) from about 10% to about 20% by weight to about of methyl formate, provided that the amount of (a), (b), (c) and (d) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2L.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E);

(d) from about 10% to about 20% by weight to about of methyl formate, provided that the amount of (a), (b), (c) and (d) in the blowing agent composition is not less than about 97% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2M.

(a) from about 10% to about 20% by weight of 1336mzz(Z);

(b) from about 35% to about 50% by weight of 1233zd(E);

(d) from about 10% to about 20% by weight to about of methyl formate.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 2N.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z); and

(b) from about 40% by weight to about 50% by weight of isobutane. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 3A.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 40% by weight to about 50% by weight of isobutane, provided that the amount of (a) and (b) in the blowing agent composition is not less than about 90% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 3B.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 40% by weight to about 50% by weight of isobutane; and

(c) methyl formate, provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 3C.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 40% by weight to about 50% by weight of isobutane; and

(c) at least about 5% by weight of methyl formate, provided that the amount of (a), (b) and (c) in the blowing agent composition is not less than about 95% by weight. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 3D.

(a) from about 45% by weight to about 55% by weight of 1224yd(Z);

(b) from about 40% by weight to about 50% by weight of isobutane; and

(c) at least about 5% by weight of methyl formate. For the purposes of convenience, blowing agent in accordance with this paragraph are referred to herein as Blowing Agent 3E.

(a) about 53% by weight of 1224yd(Z); and

(b) about 47% by weight of isobutane.

For the purposes of convenience, blowing agent in accordance with this paragraph are referred to herein as Blowing Agent 3F.

(a) about 49% by weight of 1224yd(Z);

(b) about 42% by weight of isobutane; and

(c) about 9% by weight of methyl formate. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 3G.

(a) about 12.5% by weight of 1336mzz(Z);

(b) about 37.5% by weight of 1233zd(E);

(b) about 37.5% by weight of isobutane; and

(c) about 12.5% by weight of methyl formate. For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 4A.

(a) about 13% by weight of 1336mzz(Z);

(b) about 40% by weight of 1233zd(E);

(d) about 13% by weight of methyl formate.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 4B.

(a) about 14% by weight of 1336mzz(Z);

(b) about 43% by weight of 1233zd(E); and

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 4C.

(a) about 16% by weight of 1336mzz(Z);

(b) about 48% by weight of 1233zd(E);

(d) about 16% by weight of methyl formate; and

(e) about 4% by weight of carbon dioxide.

For the purposes of convenience, blowing agents in accordance with this paragraph are referred to herein as Blowing Agent 4D.

The present invention also includes methods of forming foam that use the blowing agents of the present invention, including Blowing Agents 1-4, and the present invention also includes foams that contain and/or are made by methods that use the blowing agents of the present invention, including Blowing Agents 1-4, as explained in detail herein. As used herein, reference to a defined blowing agent or a range of defined blowing agents, such as Blowing Agents 1-4, includes all blowing agents so defined, including any numbered blowing agent that includes a suffix, such as Blowing Agent 4 meanings that each of Blowing Agent $A, Blowing Agents 4B, Blowing Agent 4C and Blowing Agent 4D are specifically included.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic representation of an extrusion system and process according to one embodiment of the invention and according to the examples herein.

FIG. 2 is a chart showing test results from Comparative Examples C1 and C22.

FIG. 3 is a chart showing test results from Comparative Examples C24 and C42.

DEFINITIONS

1234ze means 1,1,1,3-tetrafluoropropene, without limitation as to isomeric form.

Trans1234ze and 1234ze(E) each mean trans1,3,3,3-tetrafluoropropene. 1233zd means 1-chloro-3,3,3-trifluoropropene, without limitation as to isomeric form.

trans1233zd and 1233zd(E) each means trans1-chloro-3,3,3-trifluoropropene.

cis1224yd means cis1-chloro-2,3,3,3-tetrafluoropropane.

Cis1336mzz and 1336mzz(Z) each mean cis-1,1,1,4,4,4-hexafluorobutene.

Trans1336mzz and 1336mzz(E) each mean trans1,1,1,4,4,4-hexafluorobutene.

Methyl formate means the following compou text missing or illegible when filed

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Methylal means dimethoxymethane ((CH3O)2CH2).

Dimethyl ether and DME each means the following comp text missing or illegible when filed

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Isobutane and iC4 and isoC4 each mean 2-methyl propane.

Ethanol and EtOH each mean CH₃CH₂OH.

Closed cell foam means that a substantial volume percentage of the cells in the foam are closed, for example, about 20% by volume or more.

Styrene moiety means the compounds having the structure text missing or illegible when filed

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and all compounds in which one or more of the hydrogens are substituted. text missing or illegible when filed

Polystyrene, polystyrene resin, and PS each mean a polymer that is made from monomers that includes the styrene moiety, including homopolymers thereof, copolymers, and blends of polymers that include such homopolymers and/or copolymers.

XPS foam means polystyrene that has been formed into a foam in an extrusion process.

Aged thermal conductivity and aged lambda each means thermal conductivity measured as described in the examples.

Density means foam density as measured in the examples.

DETAILED DESCRIPTION

Blowing Agent

The blowing agent of the present invention, including each of Blowing Agents 1-4, may include one or more co-blowing agents other than those specified, provided they are of a type and amount that does not impair the ability of the blowing agent to be used to form polystyrene foam, and in particular XPS foam, having one or more of the density and thermal conductivity properties described herein as aspects of the invention. Within this parameter, and by way of example only, the blowing agents of present blowing agent of the present invention, including each of Blowing Agents 1-4, may further include, in certain applications and in appropriate amounts, one or more of the following: saturated hydrocarbons having 3 to 5 carbon atoms such as propane, normal butane, and cyclopentane, ethers such as ethyl ether, diethylether, and methyl ethyl ether, alkyl chlorides such as methyl chloride and ethyl chloride, alcohols such as methanol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, aryl alcohol, crotyl alcohol, and propargyl alcohol, ketones and esters.

Other additives may also be included, again to the extent that the type and amount does not impair the ability of the blowing agent to be used to form polystyrene foam, and in particular XPS foam, having the density and thermal conductivity properties described herein as aspects of the invention. Within this parameter, and by way of example only, the blowing agents of present blowing agent of the present invention, including each of Blowing Agents 1-4, may include one or more of the following: processing aids, flame retardants, coloring agents, stabilizers, surfactants, polymer modifiers, toughening agents, colorants, dyes, solubility enhancers, rheology modifiers, plasticizing agents, flammability suppressants, antimicrobial agents, viscosity reduction modifiers, fillers, vapor pressure modifiers, nucleating agents, catalysts and the like.

Foams

The present invention includes also thermoplastic foam, including and preferably PS foam and even more preferably XPS foam, comprising PS resin and a blowing agent of the present invention, including each of Blowing Agents 1-4.

The present invention includes XPS foam comprising:

(a) thermoplastic polymer cells comprising PS cell walls forming closed cells; and

(b) Blowing Agent 1 contained in the closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1.

The present invention includes XPS foam comprising:

(a) thermoplastic polymer cells comprising PS cell walls forming closed cells; and

(b) Blowing Agent 2 contained in the closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 2.

The present invention includes XPS foam comprising:

(a) thermoplastic polymer cells comprising PS cell walls forming closed cells; and

(b) Blowing Agent 3 contained in the closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 3.

The present invention includes XPS foam comprising:

(a) thermoplastic polymer cells comprising PS cell walls forming closed cells; and

(b) Blowing Agent 4 contained in the closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 4.

The present invention includes XPS foam made with Blowing Agent (using the Blowing Agent numbers as defined above) as identified in the following XPS Foam Table and having the foam properties as defined in the XPS Foam Table:

XPS Foam Table

Foam Density,
Aged Thermal

Foam No.
Blowing Agent
kg/m³
Conductivity, mW/Mk

XPSF1A1
1A
=<34
=<34

XPSF1B1
1A
=<34
=<33

XPSF1C1
1A
=<34
=<32

XPSF1D1
1A
=<34
=<31

XPSF1E1
1A
=<34
=<30

XPSF1F1
1A
=<34
=<29

XPSF1A2
1A
=<33
=<34

XPSF1B2
1A
=<33
=<33

XPSF1C2
1A
=<33
=<32

XPSF1D2
1A
=<33
=<31

XPSF1E2
1A
=<33
=<30

XPSF1F2
1A
=<33
=<29

XPSF1A3
1A
=<32
=<34

XPSF1B3
1A
=<32
=<33

XPSF1C3
1A
=<32
=<32

XPSF1D3
1A
=<32
=<31

XPSF1E3
1A
=<32
=<30

XPSF1F3
1A
=<32
=<29

XPSF1A4
1A
=<31
=<34

XPSF1B4
1A
=<31
=<33

XPSF1C4
1A
=<31
=<32

XPSF1D4
1A
=<31
=<31

XPSF1E4
1A
=<31
=<30

XPSF1F4
1A
=<30
=<29

XPSF1A5
1A
=<30
=<34

XPSF1B5
1A
=<30
=<33

XPSF1C5
1A
=<30
=<32

XPSF1D5
1A
=<30
=<31

XPSF1E5
1A
=<30
=<30

XPSF1F5
1A
=<30
=<29

XPSF2A1
1D
=<34
=<34

XPSF2B1
1D
=<34
=<33

XPSF2C1
1D
=<34
=<32

XPSF2D1
1D
=<34
=<31

XPSF2E1
1D
=<34
=<30

XPSF2F1
1D
=<34
=<29

XPSF2A2
1D
=<33
=<34

XPSF2B2
1D
=<33
=<33

XPSF2C2
1D
=<33
=<32

XPSF2D2
1D
=<33
=<31

XPSF2E2
1D
=<33
=<30

XPSF2F2
1D
=<33
=<29

XPSF2A3
1D
=<32
=<34

XPSF2B3
1D
=<32
=<33

XPSF2C3
1D
=<32
=<32

XPSF2D3
1D
=<32
=<31

XPSF2E3
1D
=<32
=<30

XPSF2F3
1D
=<32
=<29

XPSF2A4
1D
=<31
=<34

XPSF2B4
1D
=<31
=<33

XPSF2C4
1D
=<31
=<32

XPSF2D4
1D
=<31
=<31

XPSF2E4
1D
=<31
=<30

XPSF2F4
1D
=<30
=<29

XPSF2A5
1D
=<30
=<34

XPSF2B5
1D
=<30
=<33

XPSF2C5
1D
=<30
=<32

XPSF2D5
1D
=<30
=<31

XPSF2E5
1D
=<30
=<30

XPSF2F5
1D
=<30
=<29

XPSF3A1
1F
=<34
=<34

XPSF3B1
1F
=<34
=<33

XPSF3C1
1F
=<34
=<32

XPSF3D1
1F
=<34
=<31

XPSF3E1
1F
=<34
=<30

XPSF3F1
1F
=<34
=<29

XPSF3A2
1F
=<33
=<34

XPSF3B2
1F
=<33
=<33

XPSF3C2
1F
=<33
=<32

XPSF3D2
1F
=<33
=<31

XPSF3E2
1F
=<33
=<30

XPSF3F2
1F
=<33
=<29

XPSF3A3
1F
=<32
=<34

XPSF3B3
1F
=<32
=<33

XPSF3C3
1F
=<32
=<32

XPSF3D3
1F
=<32
=<31

XPSF3E3
1F
=<32
=<30

XPSF3F3
1F
=<32
=<29

XPSF3A4
1F
=<31
=<34

XPSF3B4
1F
=<31
=<33

XPSF3C4
1F
=<31
=<32

XPSF3D4
1F
=<31
=<31

XPSF3E4
1F
=<31
=<30

XPSF3F4
1F
=<30
=<29

XPSF3A5
1F
=<30
=<34

XPSF3B5
1F
=<30
=<33

XPSF3C5
1F
=<30
=<32

XPSF3D5
1F
=<30
=<31

XPSF3E5
1F
=<30
=<30

XPSF3F5
1F
=<30
=<29

XPSF4A1
1G
=<34
=<34

XPSF4B1
1G
=<34
=<33

XPSF4C1
1G
=<34
=<32

XPSF4D1
1G
=<34
=<31

XPSF4E1
1G
=<34
=<30

XPSF4F1
1G
=<34
=<29

XPSF4A2
1G
=<33
=<34

XPSF4B2
1G
=<33
=<33

XPSF4C2
1G
=<33
=<32

XPSF4D2
1G
=<33
=<31

XPSF4E2
1G
=<33
=<30

XPSF4F2
1G
=<33
=<29

XPSF4A3
1G
=<32
=<34

XPSF4B3
1G
=<32
=<33

XPSF4C3
1G
=<32
=<32

XPSF4D3
1G
=<32
=<31

XPSF4E3
1G
=<32
=<30

XPSF4F3
1G
=<32
=<29

XPSF4A4
1G
=<31
=<34

XPSF4B4
1G
=<31
=<33

XPSF4C4
1G
=<31
=<32

XPSF4D4
1G
=<31
=<31

XPSF4E4
1G
=<31
=<30

XPSF4F4
1G
=<30
=<29

XPSF4A5
1G
=<30
=<34

XPSF4B5
1G
=<30
=<33

XPSF4C5
1G
=<30
=<32

XPSF4D5
1G
=<30
=<31

XPSF4E5
1G
=<30
=<30

XPSF4F5
1G
=<30
=<29

XPSF5A1
1J
=<34
=<34

XPSF5B1
1J
=<34
=<33

XPSF5C1
1J
=<34
=<32

XPSF5D1
1J
=<34
=<31

XPSF5E1
1J
=<34
=<30

XPSF5F1
1J
=<34
=<29

XPSF5A2
1J
=<33
=<34

XPSF5B2
1J
=<33
=<33

XPSF5C2
1J
=<33
=<32

XPSF5D2
1J
=<33
=<31

XPSF5E2
1J
=<33
=<30

XPSF5F2
1J
=<33
=<29

XPSF5A3
1J
=<32
=<34

XPSF5B3
1J
=<32
=<33

XPSF5C3
1J
=<32
=<32

XPSF5D3
1J
=<32
=<31

XPSF5E3
1J
=<32
=<30

XPSF5F3
1J
=<32
=<29

XPSF5A4
1J
=<31
=<34

XPSF5B4
1J
=<31
=<33

XPSF5C4
1J
=<31
=<32

XPSF5D4
1J
=<31
=<31

XPSF5E4
1J
=<31
=<30

XPSF5F4
1J
=<30
=<29

XPSF5A5
1J
=<30
=<34

XPSF5B5
1J
=<30
=<33

XPSF5C5
1J
=<30
=<32

XPSF5D5
1J
=<30
=<31

XPSF5E5
1J
=<30
=<30

XPSF5F5
1J
=<30
=<29

XPSF6A1
1K
=<34
=<34

XPSF6B1
1K
=<34
=<33

XPSF6C1
1K
=<34
=<32

XPSF6D1
1K
=<34
=<31

XPSF6E1
1K
=<34
=<30

XPSF6F1
1K
=<34
=<29

XPSF6A2
1K
=<33
=<34

XPSF6B2
1K
=<33
=<33

XPSF6C2
1K
=<33
=<32

XPSF6D2
1K
=<33
=<31

XPSF6E2
1K
=<33
=<30

XPSF6F2
1K
=<33
=<29

XPSF6A3
1K
=<32
=<34

XPSF6B3
1K
=<32
=<33

XPSF6C3
1K
=<32
=<32

XPSF6D3
1K
=<32
=<31

XPSF6E3
1K
=<32
=<30

XPSF6F3
1K
=<32
=<29

XPSF6A4
1K
=<31
=<34

XPSF6B4
1K
=<31
=<33

XPSF6C4
1K
=<31
=<32

XPSF6D4
1K
=<31
=<31

XPSF6E4
1K
=<31
=<30

XPSF6F4
1K
=<30
=<29

XPSF6A5
1K
=<30
=<34

XPSF6B5
1K
=<30
=<33

XPSF6C5
1K
=<30
=<32

XPSF6D5
1K
=<30
=<31

XPSF6E5
1K
=<30
=<30

XPSF6F5
1K
=<30
=<29

XPSF7A1
1L
=<34
=<34

XPSF7B1
1L
=<34
=<33

XPSF7C1
1L
=<34
=<32

XPSF7D1
1L
=<34
=<31

XPSF7E1
1L
=<34
=<30

XPSF7F1
1L
=<34
=<29

XPSF7A2
1L
=<33
=<34

XPSF7B2
1L
=<33
=<33

XPSF7C2
1L
=<33
=<32

XPSF7D2
1L
=<33
=<31

XPSF7E2
1L
=<33
=<30

XPSF7F2
1L
=<33
=<29

XPSF7A3
1L
=<32
=<34

XPSF7B3
1L
=<32
=<33

XPSF7C3
1L
=<32
=<32

XPSF7D3
1L
=<32
=<31

XPSF7E3
1L
=<32
=<30

XPSF7F3
1L
=<32
=<29

XPSF7A4
1L
=<31
=<34

XPSF7B4
1L
=<31
=<33

XPSF7C4
1L
=<31
=<32

XPSF7D4
1L
=<31
=<31

XPSF7E4
1L
=<31
=<30

XPSF7F4
1L
=<30
=<29

XPSF7A5
1L
=<30
=<34

XPSF7B5
1L
=<30
=<33

XPSF7C5
1L
=<30
=<32

XPSF7D5
1L
=<30
=<31

XPSF7E5
1L
=<30
=<30

XPSF7F5
1L
=<30
=<29

XPSF8A1
1N
=<34
=<34

XPSF8B1
1N
=<34
=<33

XPSF8C1
1N
=<34
=<32

XPSF8D1
1N
=<34
=<31

XPSF8E1
1N
=<34
=<30

XPSF8F1
1N
=<34
=<29

XPSF8A2
1N
=<33
=<34

XPSF8B2
1N
=<33
=<33

XPSF8C2
1N
=<33
=<32

XPSF8D2
1N
=<33
=<31

XPSF8E2
1N
=<33
=<30

XPSF8F2
1N
=<33
=<29

XPSF8A3
1N
=<32
=<34

XPSF8B3
1N
=<32
=<33

XPSF8C3
1N
=<32
=<32

XPSF8D3
1N
=<32
=<31

XPSF8E3
1N
=<32
=<30

XPSF8F3
1N
=<32
=<29

XPSF8A4
1N
=<31
=<34

XPSF8B4
1N
=<31
=<33

XPSF8C4
1N
=<31
=<32

XPSF8D4
1N
=<31
=<31

XPSF8E4
1N
=<31
=<30

XPSF8F4
1N
=<30
=<29

XPSF8A5
1N
=<30
=<34

XPSF8B5
1N
=<30
=<33

XPSF8C5
1N
=<30
=<32

XPSF8D5
1N
=<30
=<31

XPSF8E5
1N
=<30
=<30

XPSF8F5
1N
=<30
=<29

XPSF9A1
1O
=<34
=<34

XPSF9B1
1O
=<34
=<33

XPSF9C1
1O
=<34
=<32

XPSF9D1
1O
=<34
=<31

XPSF9E1
1O
=<34
=<30

XPSF9F1
1O
=<34
=<29

XPSF9A2
1O
=<33
=<34

XPSF9B2
1O
=<33
=<33

XPSF9C2
1O
=<33
=<32

XPSF9D2
1O
=<33
=<31

XPSF9E2
1O
=<33
=<30

XPSF9F2
1O
=<33
=<29

XPSF9A3
1O
=<32
=<34

XPSF9B3
1O
=<32
=<33

XPSF9C3
1O
=<32
=<32

XPSF9D3
1O
=<32
=<31

XPSF9E3
1O
=<32
=<30

XPSF9F3
1O
=<32
=<29

XPSF9A4
1O
=<31
=<34

XPSF9B4
1O
=<31
=<33

XPSF9C4
1O
=<31
=<32

XPSF9D4
1O
=<31
=<31

XPSF9E4
1O
=<31
=<30

XPSF9F4
1O
=<30
=<29

XPSF9A5
1O
=<30
=<34

XPSF9B5
1O
=<30
=<33

XPSF9C5
1O
=<30
=<32

XPSF9D5
1O
=<30
=<31

XPSF9E5
1O
=<30
=<30

XPSF9F5
1O
=<30
=<29

XPSF10A1
1T
=<33
=<34

XPSF10B1
1T
=<33
=<33

XPSF10C1
1T
=<33
=<32

XPSF10D1
1T
=<33
=<31

XPSF10E1
1T
=<33
=<30

XPSF10F1
1T
=<33
=<29

XPSF10A2
1T
=<32
=<34

XPSF10B2
1T
=<32
=<33

XPSF10C2
1T
=<32
=<32

XPSF10D2
1T
=<32
=<31

XPSF10E2
1T
=<32
=<30

XPSF10F2
1T
=<32
=<29

XPSF10A3
1T
=<31
=<34

XPSF10B3
1T
=<31
=<33

XPSF10C3
1T
=<31
=<32

XPSF10D3
1T
=<31
=<31

XPSF10E3
1T
=<31
=<30

XPSF10F3
1T
=<30
=<29

XPSF10A4
1T
=<30
=<34

XPSF10B4
1T
=<30
=<33

XPSF10C4
1T
=<30
=<32

XPSF10D4
1T
=<30
=<31

XPSF10E4
1T
=<30
=<30

XPSF10F4
1T
=<30
=<29

XPSF11A1
1U1
=<32
=<34

XPSF11B1
1U1
=<32
=<33

XPSF11C1
1U1
=<32
=<32

XPSF11D1
1U1
=<32
=<31

XPSF11E1
1U1
=<32
=<30

XPSF11F1
1U1
=<32
=<29

XPSF11A2
1U1
=<31
=<34

XPSF11B2
1U1
=<31
=<33

XPSF11C2
1U1
=<31
=<32

XPSF11D2
1U1
=<31
=<31

XPSF11E2
1U1
=<31
=<30

XPSF11F2
1U1
=<31
=<29

XPSF11A3
1U1
=<30
=<34

XPSF11B3
1U1
=<30
=<33

XPSF11C3
1U1
=<30
=<32

XPSF11D3
1U1
=<30
=<31

XPSF11E3
1U1
=<30
=<30

XPSF11F3
1U1
=<29
=<29

XPSF11A4
1U1
=<29
=<34

XPSF11B4
1U1
=<29
=<33

XPSF11C4
1U1
=<29
=<32

XPSF11D4
1U1
=<29
=<31

XPSF11E4
1U1
=<29
=<30

XPSF11F4
1U1
=<29
=<29

XPSF12A1
1U2
=<32
=<34

XPSF12B1
1U2
=<32
=<33

XPSF12C1
1U2
=<32
=<32

XPSF12D1
1U2
=<32
=<31

XPSF12E1
1U2
=<32
=<30

XPSF12F1
1U2
=<32
=<29

XPSF12A2
1U2
=<31
=<34

XPSF12B2
1U2
=<31
=<33

XPSF12C2
1U2
=<31
=<32

XPSF12D2
1U2
=<31
=<31

XPSF12E2
1U2
=<31
=<30

XPSF12F2
1U2
=<31
=<29

XPSF12A3
1U2
=<30
=<34

XPSF12B3
1U2
=<30
=<33

XPSF12C3
1U2
=<30
=<32

XPSF12D3
1U2
=<30
=<31

XPSF12E3
1U2
=<30
=<30

XPSF13A1
1U3
=<32
=<34

XPSF13B1
1U3
=<32
=<33

XPSF13C1
1U3
=<32
=<32

XPSF13D1
1U3
=<32
=<31

XPSF13E1
1U3
=<32
=<30

XPSF13F1
1U3
=<32
=<29

XPSF13A2
1U3
=<31
=<34

XPSF13B2
1U3
=<31
=<33

XPSF13C2
1U3
=<31
=<32

XPSF13D2
1U3
=<31
=<31

XPSF13E2
1U3
=<31
=<30

XPSF13F2
1U3
=<31
=<29

XPSF13A3
1U3
=<30
=<34

XPSF13B3
1U3
=<30
=<33

XPSF13C3
1U3
=<30
=<32

XPSF13D3
1U3
=<30
=<31

XPSF13E3
1U3
=<30
=<30

XPSF14A1
1V
=<34
=<34

XPSF14B1
1V
=<34
=<33

XPSF14C1
1V
=<34
=<32

XPSF14D1
1V
=<34
=<31

XPSF14E1
1V
=<34
=<30

XPSF14F1
1V
=<34
=<29

XPSF14A2
1V
=<33
=<34

XPSF14B2
1V
=<33
=<33

XPSF14C2
1V
=<33
=<32

XPSF14D2
1V
=<33
=<31

XPSF14E2
1V
=<33
=<30

XPSF14F2
1V
=<33
=<29

XPSF14A3
1V
=<32
=<34

XPSF14B3
1V
=<32
=<33

XPSF14C3
1V
=<32
=<32

XPSF14D3
1V
=<32
=<31

XPSF14E3
1V
=<32
=<30

XPSF14F3
1V
=<32
=<29

XPSF14A4
1V
=<31
=<34

XPSF14B4
1V
=<31
=<33

XPSF14C4
1V
=<31
=<32

XPSF14D4
1V
=<31
=<31

XPSF14E4
1V
=<31
=<30

XPSF14F4
1V
=<30
=<29

XPSF14A5
1V
=<30
=<34

XPSF14B5
1V
=<30
=<33

XPSF14C5
1V
=<30
=<32

XPSF14D5
1V
=<30
=<31

XPSF14E5
1V
=<30
=<30

XPSF14F5
1V
=<30
=<29

XPSF15A1
1W1
=<32
=<34

XPSF15B1
1W1
=<32
=<33

XPSF15C1
1W1
=<32
=<32

XPSF15D1
1W1
=<32
=<31

XPSF15E1
1W1
=<32
=<30

XPSF15F1
1W1
=<32
=<29

XPSF15A2
1W1
=<31
=<34

XPSF15B2
1W1
=<31
=<33

XPSF15C2
1W1
=<31
=<32

XPSF15D2
1W1
=<31
=<31

XPSF15E2
1W1
=<31
=<30

XPSF15F2
1W1
=<31
=<29

XPSF15A3
1W1
=<30
=<34

XPSF15B3
1W1
=<30
=<33

XPSF15C3
1W1
=<30
=<32

XPSF15D3
1W1
=<30
=<31

XPSF15E3
1W1
=<30
=<30

XPSF16A2
1W2
=<33
=<34

XPSF16B2
1W2
=<33
=<33

XPSF16C2
1W2
=<33
=<32

XPSF16D2
1W2
=<33
=<31

XPSF16E2
1W2
=<33
=<30

XPSF16F2
1W2
=<33
=<29

XPSF16A3
1W2
=<32
=<34

XPSF16B3
1W2
=<32
=<33

XPSF16C3
1W2
=<32
=<32

XPSF16D3
1W2
=<32
=<31

XPSF16E3
1W2
=<32
=<30

XPSF16F3
1W2
=<32
=<29

XPSF16A4
1W2
=<31
=<34

XPSF16B4
1W2
=<31
=<33

XPSF16C4
1W2
=<31
=<32

XPSF16D4
1W2
=<31
=<31

XPSF16E4
1W2
=<31
=<30

XPSF16F4
1W2
=<30
=<29

XPSF16A5
1W2
=<30
=<34

XPSF16B5
1W2
=<30
=<33

XPSF16C5
1W2
=<30
=<32

XPSF16D5
1W2
=<30
=<31

XPSF16E5
1W2
=<30
=<30

XPSF16F5
1W2
=<30
=<29

XPSF17A1
1W3
=<32
=<34

XPSF17B1
1W3
=<32
=<33

XPSF17C1
1W3
=<32
=<32

XPSF17D1
1W3
=<32
=<31

XPSF17E1
1W3
=<32
=<30

XPSF17F1
1W3
=<32
=<29

XPSF17A2
1W3
=<31
=<34

XPSF17B2
1W3
=<31
=<33

XPSF17C2
1W3
=<31
=<32

XPSF17D2
1W3
=<31
=<31

XPSF17E2
1W3
=<31
=<30

XPSF17F2
1W3
=<31
=<29

XPSF17A3
1W3
=<30
=<34

XPSF17B3
1W3
=<30
=<33

XPSF17C3
1W3
=<30
=<32

XPSF17D3
1W3
=<30
=<31

XPSF17E3
1W3
=<30
=<30

XPSF18A1
1X1
=<32
=<34

XPSF18B1
1X1
=<32
=<33

XPSF18C1
1X1
=<32
=<32

XPSF18D1
1X1
=<32
=<31

XPSF18E1
1X1
=<32
=<30

XPSF18F1
1X1
=<32
=<29

XPSF18A2
1X1
=<31
=<34

XPSF18B2
1X1
=<31
=<33

XPSF18C2
1X1
=<31
=<32

XPSF18D2
1X1
=<31
=<31

XPSF18E2
1X1
=<31
=<30

XPSF18F2
1X1
=<31
=<29

XPSF18A3
1X1
=<30
=<34

XPSF18B3
1X1
=<30
=<33

XPSF18C3
1X1
=<30
=<32

XPSF18D3
1X1
=<30
=<31

XPSF18E3
1X1
=<30
=<30

XPSF19A1
1X2
=<32
=<34

XPSF19B1
1X2
=<32
=<33

XPSF19C1
1X2
=<32
=<32

XPSF19D1
1X2
=<32
=<31

XPSF19E1
1X2
=<32
=<30

XPSF19F1
1X2
=<32
=<29

XPSF19A2
1X2
=<31
=<34

XPSF19B2
1X2
=<31
=<33

XPSF19C2
1X2
=<31
=<32

XPSF19D2
1X2
=<31
=<31

XPSF19E2
1X2
=<31
=<30

XPSF19F2
1X2
=<31
=<29

XPSF19A3
1X2
=<30
=<34

XPSF19B3
1X2
=<30
=<33

XPSF19C3
1X2
=<30
=<32

XPSF19D3
1X2
=<30
=<31

XPSF19E3
1X2
=<30
=<30

In preferred embodiments, for each of the foams in the Foam XPS Table above having a density value indicated as being equal to or below an indicated density, the foam has a density of greater than 25 kg/m³, or of greater than 26 kg/m³, or of greater than 27 kg/m³, or of greater than 28 kg/m³.

In preferred embodiments, for each of the foams in the Foam XPS Table above having an aged lambda value indicated as being equal to or below an indicated aged lambda, the foam has an aged lambda of greater than 25 mW/mK, or of greater than 26 mW/mK, or of greater than 27 mW/mK, or of greater than 28 mW/mK.

The present invention includes XPS foam including each of Foams 1-4, wherein the foam has a density of 34 kg/m³or less and aged thermal conductivity of 32 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5A.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 33 kg/m³or less and aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5B.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 32 kg/m³or less and aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5C.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 31 kg/m³or less and aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5D.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 31 kg/m³or less and aged thermal conductivity of 30 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5E.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 31 kg/m³or less and aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5F.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 30 kg/m³or less and aged thermal conductivity of 30 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5G.

The present invention includes XPS foam, including each of Foams 1-4, wherein the foam has a density of 30 kg/m³or less and aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5H.

The present invention includes XPS foam, including each of Foams 1-10, wherein the foam is a closed cell foam. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5I.

The present invention includes XPS foam, including each of Foams 1-10, wherein the foam is a closed cell foam having at least 50% by volume of closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5J.

The present invention includes XPS foam, including each of Foams 1-10, wherein the foam is a closed cell foam having at least 90% by volume of closed cells. For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 5K.

The styrene resin for use in the present invention, including each of the foams identified in the XPS FOAM TABLE above, in each of Foams 1-5 and each of Methods 1-10, is not particularly limited and examples of the styrene resin include homopolymers of styrene monomers such as styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, bromostyrene, chlorostyrene, vinyltoluene, and vinylxylene, or copolymers of two or more of the monomers, copolymers obtained by copolymerization of the styrene monomer with at least one or two or more of monomers such as divinylbenzene, butadiene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, maleic anhydride, and itaconic anhydride, and the like. The monomers to be copolymerized with the styrene monomer, such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, maleic anhydride, and itaconic anhydride, can be used with such an amount that the physical properties, such as compressive strength, of the extruded polystyrene foam to be produced are not impaired. The styrene resin for use in the present invention is not limited to the homopolymers or the copolymers of the styrene monomers and may be a blend of the homopolymers or the copolymers of the styrene monomers and the homopolymers or the copolymers of the other monomers, and a diene rubber reinforced polystyrene or an acrylic rubber reinforced polystyrene can be blended. The styrene resin for use in the present invention may be a styrene resin having a branched structure for the purpose of adjusting the melt volume rate (hereinafter also referred to as MVR), a melt viscosity and a melt tension in molding, and the like.

According to preferred embodiments, the foams of the present invention, including each of the foams identified in the XPS FOAM TABLE above and in each of Foams 1-5, are formed from a general purpose styrene resin, preferably having an MVR of 0.1 to 50 g/10 minutes. Such resins are preferably used in the respect that a thermoplastic resin foam in which the moldability in extrusion foam molding is excellent, the discharge amount in molding, the thickness and the width and the apparent density or the closed cell ratio of the obtained extruded polystyrene foam can be adjusted to desired values. The MVR of the styrene resin can include from 0.3 to 30 g/10 minutes, or 0.5 to 25 g/10. In the present invention, the MVR is measured by ISO 1133.

In the present invention, among the styrene resin mentioned above, polystyrene resin is suitable in the respect of economical efficiency and processability. When higher heat resistance is required in an extruded foam, it is preferable to use a styrene-acrylonitrile copolymer, (meth)acrylic acid-copolymerized polystyrene, maleic anhydride-modified polystyrene. When a higher impact resistance is demanded in an extruded foam, it is preferable to use rubber-reinforced polystyrene. The styrene resin may be used alone or two or more kinds of styrene resin different in a copolymerization component, a molecular weight and a molecular weight distribution, a branched structure, an MVR, and the like may be used as a mixture.

The PS used to form the present foams, including the foams identified in the XPS FOAM TABLE above and in each of each of Foams 1-5, and which is used in accordance with the present methods, including each of Methods 1-10, can have properties within each of the broad, intermediate and narrow ranges identified in the following table:

Broad
Intermediate
Narrow

Range
Range
Range

Polymer

property,

Melt Volume
0.1-50
10-40
15-30

Rate, ISO 1133

(cm3/10 min.)

Vicat Softening
90-115
95-110
95-105

Temperature

VST/B/50 (50N,

50° C./h)

Melting
100-350
150-300
180-280

Temperature,

Tm, ° C.

Methods

Applicants have found that unexpected advantages can be achieved with respect to the preparation of thermoplastic foams, including the foams identified in the XPS FOAM TABLE above and in each of each of Foam 1-Foam 5, by using a blowing agent of the present invention in the foam forming process.

In particular aspects, the present invention includes method for making thermoplastic XPS foam comprising:

(i) providing PS; and

(ii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 1.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing a thermoplastic material;

(ii) extruding the thermoplastic material; and

(iii) foaming the thermoplastic material using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 2.

The present invention also provides methods for forming XPS comprising:

(i) providing a thermoplastic polystyrene;

(ii) extruding the thermoplastic polystyrene; and

(iii) foaming a polystyrene foam using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 3.

The present invention also provides methods for making XPS foams comprising:

(i) providing PS; and

(ii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 33 kg/m3 or less and an aged thermal conductivity of 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4A.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of of about 33 kg/m3 or less and an aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4B.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 33 kg/m3 or less and an aged thermal conductivity of 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4C.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 33 kg/m3 or less and an aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4D.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 33 kg/m3 or less and an aged thermal conductivity of 28 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4E.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 32 kg/m3 or less and an aged thermal conductivity of 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4F.

The present invention also provides methods for making XPS foams comprising:

(i) providing PS; and

(ii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of of about 32 kg/m3 or less and an aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4G.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 32 kg/m3 or less and an aged thermal conductivity of 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4H.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 32 kg/m3 or less and an aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 41.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of less about 32 kg/m3 and an aged thermal conductivity of 28 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4J.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 31 kg/m3 or less and an aged thermal conductivity of 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4K.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 31 kg/m3 or less and an aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4L.

The present invention also provides methods for making XPS foams comprising:

(i) providing PS; and

(ii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 31 kg/m3 or less and an aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4M.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 31 kg/m3 or less and an aged thermal conductivity of 28 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4N.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 30 kg/m3 or less and an aged thermal conductivity of 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 40.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of less about 30 kg/m3 and an aged thermal conductivity of 31 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4P.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 30 kg/m3 or less and an aged thermal conductivity of 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 40.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing PS;

(ii) extruding PS; and

(iii) foaming the PS using any one of the blowing agents of the present invention, including each of Blowing Agent 1 through Blowing Agent 4, wherein the foam has a density of about 30 kg/m3 or less and an aged thermal conductivity of 29 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 4R.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 6 wherein said blowing agent is used in an amount of from about 4 parts per hundred of thermoplastic resin material (hereinafter “pph” or “pphr”) to about 10 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 5.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of from about 5 pphr to about 9 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 6A.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of from about 5 pphr to about 8 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 6B.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of from about 5 pphr to less than about 8 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 6C.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of from 6 pphr to 10 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 7.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of from about 6 pphr to about 9 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 8.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 4, wherein said blowing agent is used in an amount of about 7 pphr. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 9.

The present invention also provides methods for making thermoplastic foams, including each of Method 1 through Method 9, wherein said step of providing said thermoplastic material or PS comprises including in said thermoplastic material one or more optional components selected from surfactants, polymer modifiers, toughening agents, colorants, dyes, solubility enhancers, rheology modifiers, plasticizing agents, flammability suppressants, antimicrobial agents, viscosity reduction modifiers, fillers, vapor pressure modifiers, nucleating agents, catalysts and the like. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 10.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing a melt comprising, or consisting essentially of, polystyrene and a blowing agent, including each of Blowing Agents 1-5, wherein the amount of said blowing agent is present in the melt in an amount of from about 5 pph to less than 10 pph;

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 34 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 34 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11A.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 33 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 33 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11B.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 32 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11C.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 31 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11 D.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 30 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 32 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11E.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 30 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 31 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11F.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 30 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11G.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing a melt comprising, or consisting essentially of, polystyrene and Blowing Agent 1K1, wherein the amount of said blowing agent is present in the melt in an amount of from about 5 pph to less than 9 pph;

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 32 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 33 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11H.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than 32 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11I.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to not greater than 31.5 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than 30 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11J.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to not greater than 30 kg/m³and an aged thermal conductivity of from about 25 mW/mk to not greater than 30 mW/mk. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11K.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing a melt comprising, or consisting essentially of, polystyrene and Blowing Agent 1K2, wherein the amount of said blowing agent is present in the melt in an amount of from about 5 pph to less than 9 pph;

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 32 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 33 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11L.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(i) providing a melt comprising, or consisting essentially of, polystyrene and Blowing Agent 1L, wherein the amount of said blowing agent is present in the melt in an amount of from about 5 pph to less than 9 pph;

(ii) extruding the melt; and

(iii) foaming the melt to form an extruded polystyrene foam having a density of from about 25 kg/m³to less than about 32 kg/m³and an aged thermal conductivity of from about 25 mW/mk to less than about 33 mW/mk or less. For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Method 11P.

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The present invention also provides methods for forming extruded thermoplastic foam comprising:

(ii) extruding the melt; and

The methods of the present invention, including each of Methods 1-10, can be formed from any PS resin, including general purpose styrene resin, preferably having an MVR of 0.1 to 50 g/10 minutes, more preferably of from 10 to 40 g/10 minutes, more preferably from 10 to 30 g/10 minutes.

The methods can be carried out, by way of example, using extrusion equipment of the general type disclosed in FIG. 1, which is described below in more detail below in connection with the examples. It will be appreciated that while FIG. 1 shows only a single feed point for introducing blowing agent into the extrusion process, the use of multiple feed points to introduce the blowing agent may be used. Furthermore, it will be appreciated that the term “blowing agent” as used herein, including each of Blowing Agents 1-4, includes not only the defined set of components introduced into the extruder when there is a single introduction point, but also the aggregate combination of components that may be introduced at plural points into the extrusion or other foaming equipment.

EXAMPLES

The following examples are provided for the purpose of illustrating the present invention but without limiting the scope thereof.

The examples utilized an extrusion apparatus substantially as illustrated in FIG. 1. In particular, the apparatus included a raw material feed hopper 10 for holding polystyrene feed material 15, together with any optional components (which may be added with the polystyrene or optionally elsewhere in the process depending on the particular needs of the user). In the case of the examples hereof, the polystyrene feed is in the form of general purpose polystyrene pellets sold by Ineos under the trade designation Styrolution 156F and having the following properties:

Property,

Test

Condition
Standard
Unit
Values

Melt Volume Rate,
ISO 1133
cm³/10 min
28

200° C./5 kg

Vicat Softening
ISO 306
° C.
101

Temperature

VST/B/50 (50N,

50° C./h)

Melt Temperature
ISO 294
° C.
180-280

Range

The feed material also included the flame retardant sold under the trade designation Apryos 5PB12HT, the nucleating agent (GRANIC 2281) and processing aid (Zinc Stearate). The total of the raw material feed stream 15 used to form the foam and introduced into the single screw extruder 20 are based on the following concentrations of components:

Component
pph

polystyrene (Styrolution 156F)
100

Copolymer (Low density
0.3

polyethylene - PE 003 from

Repsol)

flame retardants (Apyros
2

5PB12HT)

nucleating agent (GRANIC 2281 -
0.8

talc)

processing aid (Zinc Stearate)
0.8

Blowing agent (total of all co-
5.2-9

blowing agents)

The feed materials 15, excluding the blowing agent, were charged to the hopper and delivered to the screw extruder 10 at a nominal rate of about 3.3 kilograms per hour and the screw operated with at a nominal 85 rpm. The extruder 20 had thermocouples (not shown) located at three points along the length thereof and a pressure sensor (not shown) at the discharge end 20A of the extruder. A mixer section 30 was located at the discharge end 20A of the extruder for receiving blowing agent components via one or more metering pumps 40A and 40B and mixing those blowing agents into the polystyrene melt in the mixer section. Sensors (not shown) were included for monitoring the temperature and pressure of the mixer section 30. The mixer section 30 discharged the melt with the blowing agent into a pair of melt coolers 50 oriented in series, with temperature sensors (not shown) located in each cooler to monitor the melt temperature. The melt was then extruded through a die 60 which also had temperature and pressure sensors (not shown) for monitoring the pressure and temperature at the die. The die pressure was varied from 70 to 100 bars to minimize the density for each blowing agent tested and the die temperature was kept at 128° C. Exiting the die was a foamed sheet of polystyrene 70 which is carried away from the extrusion equipment by a conveyor belt 80.

The equipment illustrated in FIG. 1 and described above was used for each of the experimental tests described in the examples below to form a foam. After the foam is formed, the density and aged thermal conductivity (also referred to as “aged lambda”) were measured. The aged lambda values were measured according to ISO 11561:199 (providing similar results as European Standard BS EN 13164:2012+A1:2015), modified in accordance with the description proved below:

Day 0—the foam is extruded

Day 1—initial thermal conductivity of the block (skins, 120×120 mm, thickness of 15-20 mm) is determined at 10° C.+/−2° C.

Day 4—slicing of the block into 6 mm thick slices is performed (with skins removed) to obtain one slice per extruded sample that is 23 mm wide and 120 mm long and then at least 4 slices are stacked; thermal conductivity of the stack is measured at 10° C.+/−2° C. and then the slices are separated and kept at about 23° C. and 50% relative humidity.

Days 6-36—the procedure of Day 4 is repeated every two or three days until about 28 days is reached to obtain aged thermal conductivity by Method A, which comprises plotting the lambda values against time and then calculating aged thermal conductivity (λaged).

Comparative Examples C1-C23—XPS Foam

Twenty three (23) extruded polystyrene foams were produced using the equipment and materials described above and illustrated in FIG. 1. All of the foams were prepared using the same raw materials except a different blowing agent was used in each case, as indicated in Table C1-C23 below. In each case, the die pressure which minimized the foam density was determined and used to produce the foam.

After the foam was formed, the density and aged thermal conductivity (also referred to as “aged lambda”) were measured in accordance with the descriptions above. The results are reported in Table C1-C23 below.

TABLE C1-C23

Blowing Agent

Aged

Blowing Agent
Components, wt % in
Density ·
Lambda,

Ex
Components, wt % in melt
Blowing Agent
kg/m³
mW/mK

C1
3.2%
2.8%

53.3%
46.7%

31-33
34

CO2
EtOH

CO2
EtOH

C2
3%
2.2%

57.7%
42.3%

35-37
34.5

CO2
EtOH

CO2
EtOH

C3
4%
3.4%

54%
46%

40.5
31.5

1234ze(E)
EtOH

1234ze(E)
EtOH

C4
3.5%
3.5%

50%
50%

43
33

1234ze(E)
EtOH

1234ze(E)
EtOH

C5
3%
3.5%

46.2%
53.8%

42.5
33

1234ze(E)
EtOH

1234ze(E)
EtOH

C6
3%
3.5%
1%
40%
46.7%
13.3%
38
33.5

1234ze(E)
EtOH
CO2
1234ze(E)
EtOH
CO2

C7
3.5%
3%
1%
46.7%
40%
13.3%
38.5
33.5

1234ze(E)
EtOH
CO2
1234ze(E)
EtOH
CO2

C8
7%
2%

77.8%
22.2%

47
32

1234ze(E)
EtOH

1234ze(E)
EtOH

C9
4%
3.5%

53.3%
46.7%

47.6
36

1234ze(E)
EtOH

1234ze(E)
EtOH

C10
4%
3.5%
1%
47%
41%
12%
38
31

1234ze(E)
Acetone
CO2
1234ze(E)
Acetone
CO2

C11
4%
3.5%
1%
47%
41%
12%
42.5
31

1234ze(E)
CycloC6
CO2
1234ze(E)
Acetone
CO2

C12
4%

2%
66.7%

66.7%
47.5
32.5

1233zd(E)

CO2
1233zd(E)

CO2

C13
1%
3%
2%
16.7%
50%
33.3%
45.5
31

1234ze(E)
1233zd(E)
CO2
1234ze(E)
1233zd(E)
CO2

C14
2%
2%
1.5%
36.4%
36.4%
27.3%
49.5
30

1234ze(E)
1233zd(E)
CO2
1234ze(E)
1233zd(E)
CO2

C15
4%
3.5%
1%
47%
41%
12%
38
32

1234ze(E)
CycloC5
CO2
1234ze(E)
CycloC5
CO2

C16
4%
4%
1%
44%
44%
11%
36.5
31.5

1234ze(E)
CycloC5
CO2
1234ze(E)
CycloC5
CO2

C17
4%
1.5%

73%
27%

42.6
28.6

1234ze(E)
IsoC4

1234ze(E)
IsoC4

C18
4%
4%

50%
50%

35
31

1234ze(E)
methyl

1234ze(E)
methyl

formate

formate

C19
4%
3.5%

53%
47%

37.5
31.5

1234ze(E)
methyl

1234ze(E)
methyl

formate

formate

C20
4%
2.5%

62%
38%

43.5
29.5

1234ze(E)
methyl

1234ze(E)
methyl

formate

formate

C21
4%
2.5%
0.75%
55%
35%
10%
41
30.5

1234ze(E)
methyl
CO2
1234ze(E)
methyl
CO2

formate

formate

C22
4%
2.5%

73%
27%

44.5
29

1234ze(E)
methyl

1234ze(E)
DME

formate

C23
4%
2.5%
0.75%
55%
35%
10%
39.5
29

1234ze(E)
methyl
CO2
1234ze(E)
DME
CO2

formate

As can be seen from Table C1-C23 above, the tests used 23 different combinations of co-blowing agents, with the combinations being based on two or more of the following:

- Carbon Dioxide (CO2)
- Ethanol (EtOH)
- 1234ze(E)
- 1233zd(E)
- Ethanol (EtOH)
- Acetone
- Cyclohexane (CycloC6)
- Cyclopentane (CycloC5)
- Isobutane (IsoC6)
- methylformate
- dimethylether (DME)

The results of this experimental work show, in general, that it was not possible to achieve a polystyrene foam that had a density less than about 34 kg/m3 and at the same time having an aged thermal conductivity below about 33.5 mW/mk, which is a preferred combination of density and thermal conductivity properties that is considered in desirable. The data from these 23 runs is illustrated in FIG. 2, which also illustrates that none of the produced foams was able to achieve this combination of properties (represented by the region bounded by the small-dash custom-character arrows. More preferably in many applications, it is desirable to provide a polystyrene foam that has a density that is about 33 kg/m3 or less and at the same time an aged thermal conductivity below about 32.5 mW/mk (represented by the region bounded by the medium-dash arrows), and all of the data above is even further from achieving this desired combination of properties. Finally, none of these foams had a density that is about 32 kg/m3 or less and at the same time an aged thermal conductivity below about 32.5 mW/mk (represented by the region bounded by the large-dash custom-character arrows), which the most preferred set of these properties for XPS foam according to the present application.

Comparative Examples C24-C42—XPS Foam

Additional testing was conducted in a continuing effort to determine whether any blowing agent blends existed that could produce a foam in one or more of the lower quadrants in FIG. 2. Of the additional testing performed nineteen additional blowing agents blends were not able to produce such a desired foam. The same procedure was used as describe in Comparative Examples 1-23 to produce the results reported in Table C24-C42 below.

TABLE C24-C42

Blowing Agent Components, pphr
Blowing Agent Components, wt % of BA

Ex
ze
zd
mmz
yd
isoC4
MF
DME
CO2
ze
Zd
mmz
yd
IsoC4
MF
CO2
Den
λ_A

C24
4

1.5

72.7
0
0.0
0.0
27.3
0.0
0.0
42.6
28.6

C25
3
1

2.5

46.2
15.4
0.0
0.0
38.5
0.0
0.0
40.3
27.3

C26
2

2

3
0.75

0.25
25.0
0.0
25.
0.0
37.5
9.4
3.1
38.5
28.6

C27
2

2

3

28.6
0.0
28.6
0.0
42.9
0.0
0.0
37.6
27.8

C28
1.5

2.5

3
0.75

0.25
18.8
0.0
31.3
0.0
37.5
9.4
3.1
37.5
27.7

C29
1.5

2.5

2
1

0.25
20.7
0.0
34.5
0.0
27.6
13.8
3.5
37.5
28.1

C30
2

2

2.5

30.8
0.0
30.8
0.0
38.5
0.0
0.0
38.2
27.4

C31
4

1.5
1

0.25
61.6
0.0
0.0
0.0
23.1
15.4
0.0
36.4
29.2

C32
4

0.75
1.5
0.25
61.5
0.0
0.0
0.0
0.0
11.5
3.9
34.8
30.2

C33
3
1

2.5
0.75

0.25
40.0
13.3
0.0
0.0
33.3
10.0
3.3
34
27.9

C34
1
3

2.5

15.4
46.2
0.0
0.0
38.5
0.0
0.0
34
28.9

C35
2

1
2.5
1

0.25
30.8
0.0
0.0
15.4
38.5
15.4
0.0
36.9
29.94

C36

1
3

2.5
1

0.25
0.0
12.9
38.7
0.0
32.3
12.9
3.2
35.5
28.5

C37

2
2

3

0.0
28.6
28.6
0.0
42.9
0.0
0.0
34.8
28.6

C38

4

3.5
0

0.0
0.0
53.3
0.0
46.7
0.0
0.0
38.3
28.1

C39

1
3
3

0
0.0
14.3
42.9
42.9
0.0
0.0
37.2
28.8

C40

4

3.5
0.75

0.25
0.0
0.0
47.1
0.0
41.2
8.8
2.9
35.8
27.9

C41

1
3
3
1

0.25
0
0
12.1
36.4
36.4
12.1
3.3
34.7
29.1

C42

4

3.5
0.75

0.0
0.0
48.5
0.0
42.4
9.9
0.0
33.8
28.1

As can be seen from Table C24-C42 above, the tests used 19 different combinations of co-blowing agents, with the combinations being based on two or more of the following:

- Carbon Dioxide (CO2)
- 1234ze(E) (referred to as “ze” in example tables)
- 1233zd(E) (referred to as “ze” in example tables)
- Cis1336mzz (referred to as “mzz” in the example tables)
- Cis1224yd (referred to as “yd” in the example tables)
- Isobutane (referred to as “IsoC4” in the example tables)
- methylformate (referred to as “MF” in the example tables)
- dimethylether referred to as “DME” in the example tables)

The results of this experimental work were also not able to achieve a polystyrene foam that had a density less than about 34 kg/m3 and at the same time having an aged thermal conductivity below about 33.5 mW/mk, or any other of the preferred combinations of density and thermal conductivity properties that are described herein. The data from these 19 runs is illustrated in FIG. 3.

Examples 1—XPS Foam from Blowing Agent Consisting of 1233zd(E), 1234Ze(E), and One or More of Isobutane, Methyl Formate and CO2

A series of foam extrusion runs were conducted using the same equipment, the same operating criteria, and the same raw materials as described above in connection with the Comparative Examples, except that the blowing agents as identified in Table E1-E4 below were used and produced a foam having the properties as reported in Table E1-E4 below:

TABLE E1-E4

Aged

PPHR,

Density
Lambda

Ex.
BA in
Wt % in Blowing Agent
(kg/
(mW/

No.
melt
mzz
zd
iC4
MF
CO2
m3)
mk)

E1
8
12.5
37.5
37.5
12.5
0
29.6
30.6

E2
7.5
13.3
40
33.3
13.3
0
31.1
29.9

E3
7
14.3
42.9
42.9
0
0
31.3
29.3

E4A
7
16.0
48
16
16
4
30.1
30.3

E4B
7.25
13.8
41.4
27.6
13.8
3.45
30.1
29.9

As can be seen from Table E1-E4, applicants have unexpectedly found that certain blowing agents can be formulated based on a combination of 1336mzz(Z), 1233zd(E) and isobutane, both without and with one or more of methyl formate and/or CO₂, which are able to achieve thermoplastic foams having density and aged lambda values within all three of the quadrant definitions shown in FIG. 2 and described in Comparative Example C1-C23.

Examples 5-8—XPS Foam from Blowing Agent Consisting of 1224yd(Z) and One or More of Isobutane, Dimethyl Ether (DME), Methyl Formate (MF) and CO2

A series of foam extrusion runs were conducted using the same equipment, the same operating criteria, and the same raw materials as described above in connection with the Comparative Examples, except that the blowing agents as identified in Table E5-E8 below were used and produced a foam having the properties as reported in Table E5-E8 below:

TABLE E5-E8

Aged

PPHR,

Density
Lambda

Ex.
BA in
Wt % in Blowing Agent
(kg/
(mW/

No.
melt
1224yd
iC4
MF
DME
CO₂
m3)
mk)

E5
7.5
53.3
46.7
0
0
0
30.8
29.3

E6
8.25
48.5
42.4
9.1
0
0
29.4
29.7

E7
7.75
51.6
0
9.7
38.7
0
31.4
33.0

E8
8
50
0
37.5
9.4
3.1
30.8
33.2

As can be seen from Table E5-E8, applicants have unexpectedly found that certain blowing agents based on a combination of 1224yd, isobutane and/or methyl formate, and optionally but preferably methyl formate and/or CO₂are able to achieve thermoplastic foams having density and aged lambda values within the largest quadrant of FIG. 2, and more surprisingly Examples E5 and E6 are within even the narrowest quadrant definition shown in FIG. 2 and described in Comparative Example C1-C23.

Examples 9-10—XPS Foam from Blowing Agent Consisting of 1224yd(Z), Isobutante (iC4), and One or More of Methyl Formate (MF) and CO₂

A series of foam extrusion runs were conducted using the same equipment, the same operating criteria, and the same raw materials as described above in connection with the Comparative Examples, except that the blowing agents as identified in Table E9-E10 below were used and except that twice the weight of talc was used. Foams having the properties as reported in Table E9-E10 below were produced:

TABLE E9-E10

Aged

PPHR,

Density
Lambda

Ex.
BA in
Wt % in Blowing Agent
(kg/
(mW/

No.
melt
1224yd
iC4
MF
CO₂
m3)
mk)

E9
8.25
51.6
38.7
9.7
0
32.1
29.8

E10
8
50
37.5
9.4
3.1
31
29.5

As can be seen from Table E9-E10, applicants have unexpectedly found that certain blowing agents based on a combination of 1224yd, isobutane and one or more of methyl formate and CO₂, are able to achieve thermoplastic foams having density and aged lambda values within about the narrowest quadrant of FIG. 2.

Example 11—XPS Foam from Blowing Agent Consisting of 1336mzz(Z), Ethanol, and CO₂

A series of foam extrusion runs were conducted using the same equipment, the same operating criteria, and the same raw materials as described above in connection with the Comparative Examples, except that the blowing agent as identified in Table E11 below was used. Foam having the properties as reported in Table E11 below was produced:

TABLE E11

Aged

PPHR,

Density
Lambda

Ex.
BA in
Wt % in Blowing Agent
(kg/
(mW/

No.
melt
1336mzz(Z)
EtOH
CO₂
m3)
mk)

E11
8.85
28.3
39.6
32.2
31.8
32.3

As can be seen from Table E11, applicants have unexpectedly found that certain blowing agents based on a combination of 1336mzz(Z), ethanol and CO₂, are able to achieve thermoplastic foams having density and aged lambda values within the narrowest quadrant of FIG. 2.

BLOWING AGENTS FOR EXTRUDED POLYSTYRENE FOAM AND EXTRUDED POLYSTYRENE FOAM AND METHODS OF FOAMING

Information

Publication Number

Date Filed

Date Published

Inventors

Original Assignees

CPC

International Classifications

Abstract

Description

Claims

CROSS REFERENCE TO RELATED APPLICATIONS

Provisional Applications (1)