WO2010051448A1

WO2010051448A1 - Palm oil-based polyurethane foam products and method of production

Info

Publication number: WO2010051448A1
Application number: PCT/US2009/062767
Authority: WO
Inventors: James T. Mcevoy; Murray D. Metcalfe; William W. Li; Ni Haifeng; Patricia J. Mcclarren
Original assignee: Johnson Controls Technology Co
Current assignee: Johnson Controls Technology Co
Priority date: 2008-10-30
Filing date: 2009-10-30
Publication date: 2010-05-06
Anticipated expiration: 2011-04-30
Also published as: CN102227295A; CN102227295B

Abstract

A foam product, such as for use in a seat such as a seat -cushion, includes an open cell, polyurethane foam material produced from the reaction of an isocyanate material and at least a base polyol including at least a portion of a palm oil-based polyol, a copolymer polyol, water, one or more crosslinkers, a cell opener, catalyst or catalyst package, and a surfactant

Description

PALM OIL-BASED POLYURETHANE FOAM PRODUCTS AND METHOD OF PRODUCTION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional

Patent Application No. 61/109,773, filed October 30, 2008, titled: PALM OIL- BASED POLYURETHANE FOAM PRODUCTS AND METHOD OF PRODUCTION, in the name of McEvoy et al. and to U.S. Provisional Patent Application No. 61/110,258, filed October 31, 2008, titled: PALM OIL-BASED POLYURETHANE FOAM PRODUCTS AND METHOD OF PRODUCTION, in the name of McEvoy et al., which are incorporated by reference herein.

BACKGROUND

[0002] The present disclosure relates generally to open cell, polyurethane foam formulations having non-petroleum based or initiated polyol materials and methods for making foam products including such materials. The present disclosure relates more particularly to open cell, polyurethane foam formulations having a palm oil-based polyol portion and a petrochemical-based polyol portion, and to a method for producing foam products for use in a variety of applications including in particular in a vehicle seat.

[0003] It is generally known to provide a foam cushion for the comfort of an occupant of a seat, whether the seat is a piece of furniture, a piece of equipment, or a vehicle, such as an automobile. It is also generally known to formulate the constituent parts of the foam for such a cushion from petroleum initiated, oil-based polyurethane materials that are reacted with other products to make a foam cushion product. [0004] It is known to derive and utilize materials in the foam formulation process from renewable sources such as soybean, castor, and canola oils. However, despite such knowledge, there remains a lack of commercially viable foam product, including in seating applications, utilizing any meaningful amount of plant oil-based source materials instead of petroleum oil-based materials because it has been unknown how to produce foam products that will meet current petroleum-based performance specifications (including mechanical properties, tensile, tear, elongation, compression set, stress strain [hysteresis loss]) and comfort requirements for such seating applications.

[0005] Accordingly, there is, and there remains, a need to provide a plant oil- based polyurethane foam that can meet the specification requirements for use in various applications, including, without limitation, seating applications in the automotive industry.

SUMMARY

[0006] The specification discloses a non-petroleum-based polyol that is preferably made from natural, more readily renewable resources such as plant oils, and in particular palm oil. In one exemplary embodiment, an open cell, polyurethane foam material is provided from the reaction products of a polyol material including a palm oil-based polyol (with approximately 10% to approximately 90%, and preferably from approximately 22% to approximately 70%, bio-content) present in the polyol in an amount of between 1 and 30 parts per hundred polyol, an isocyanate, a blowing agent, a cell opener, water, and a cross linker(s), to provide a foam material well suited to various applications, including seating applications.

[0007] The exemplary embodiment is capable of producing automotive vehicle seats having at least substantially equivalent performance specifications as compared to known petroleum-based polyurethane foam materials. [0008] Several exemplary embodiments are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary and may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for the claims and/or as a representative basis for teaching one of ordinary skill in the art. Accordingly, except for otherwise expressly stated, all numerical quantities in this description indicating amounts of material are to be understood as modified by the word "substantially" in describing the broadest scope supported herein it being understood that practice within the numerical limit is preferred only.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The foregoing and other features of the exemplary embodiments will become more apparent to one of ordinary skill in the art upon consideration of the following detailed description and the accompanying drawings, in which:

[0010] FIG. 1 is a block diagram of a method to forming a foam material according to an exemplary embodiment.

[0011] FIG. 2 is a block diagram of a method of molding a component from a foam material including palm oil-based materials according to an exemplary embodiment.

[0012] FIG. 3 is a table setting forth an exemplary composition of standard cushion, back, and bolster formulations including palm oil-based materials.

[0013] FIGS. 4A and 4B are tables showing several physical properties and characteristics of foams formulated with palm oil-based polyol as compared with foams made entirely from petroleum based polyols. DETAILED DESCRIPTION

[0014] Polyurethane-based foam products of both the soft and firm variety can, according to convention, be formed according to a "one shot" process in which, essentially, a first (typically a polyol) stream and a second (typically an isocyanate) stream are mixed and allowed to cure in a mold to form a foam product. The polyurethane-based foam product is typically composed of polyurethane-based base polyol resin, a polyurethane-based copolymer polyol (co-polyol) resin, water, a cross- linker(s), a catalyst (or catalyst package), a surfactant, a cell opener / regulator, and an isocyanate such as, for instance, TDI, MDI or blends thereof (generally, such blends are not less than 5% of either TDI or MDI; e.g., TM20, a blend of 80% TDI and 20% MDI) reacted according to a system 10 as shown in FIG. 1. Various additives can, as known, also be employed to provide different properties.

[0015] Still referring to FIG. 1, the polyurethane foaming system 10 includes the reaction of the base polyol resin blended material 12, a copolymer polyol resin blended material 14, water 16, a cross-linker material(s) 18, a catalyst materia! 20, a surfactant material 22, a cell opener 23 and an isocyanate material 26. The base polyol material 12 may include both petroleum-based base polyol material 11 and a palm oil-based base polyol material 13. The copolymer polyol material 14 may include both petroleum-based copolymer polyol material 15 and palm oil-based copolymer polyol material 17. The base polyol mix 12, the copolymer polyol mix 14, water 16, cross-linker material(s) 18, catalyst 20, surfactant 22 and cell opener 23 are blended to make a poly formulation blend 24. The isocyanate 26 and the polyol formulation blend 24 are mixed to form a foam material 28. The water and catalyst may be used to make a water-blown foam material, thus affecting the desired foam density.

[0016] The polyol material stream is generally composed of polyurethane polymer with, optionally, a propylene oxide "PO" that may be manufactured with potassium hydroxide (KOH) and/or then optionally ethylene oxide ("EO") capped. Another method of manufacturing polyol material includes the use of dimetal catalysts to promote the addition of free radicals. Such dimetal catalysts include, for instance, cobalt /zinc catalyzed or cesium/rubidium catalyzed. The dimetal catalysts can have individual substitution with similar results. For instance, the rubinium catalyst may optionally be substituted for the cobalt catalyst and the cesium catalyst substituted for the zinc catalyst.

[0017] Referring to FIG. 2, the foam reaction is performed in a foaming process 40, which may be a "one shot" process according to an exemplary embodiment or may be any other suitable foaming and molding process. A first step 42 of the foaming process 40 includes mixing the components (as shown in FIG. 1) for making the foam material in a mix head but may alternatively mixed in the mold. In a simultaneous step 44, the foam material is poured into a foam mold tool having a desired shape for producing a foam product such as a seat cushion. In a third step 46, the foam material reacts in the closed mold tool and the foam product is molded in the mold tool. In a fourth step 48, the foam product is allowed to cure or harden. As part of or after the fourth step 48 and while the foam product is still in the mold tool, the foam product may be crushed to provide improved transmissibϋity using a time pressure release ("TPR") process in crushing step 49, as explained further below.

[0018] In a fifth step 50, after the foam product is sufficiently cured, the foam product is de-molded from the mold tool. In a sixth step 52, the de-molded, foamed product is alternatively, but preferably, crushed a pre-selected amount (% of foam thickness) for a given number of times at a pre-selected time period after de-mold. Alternatively, as described above, the product may be crushed while still in the mold. The resulting foam product may be in the shape of a block having particular dimensions or may have a particular contoured shape usable for a particular application, such as a seat base cushion, seat back cushion, armrest for cushions, or head restraint cushion, according to alternative embodiments.

[0019] According to an exemplary embodiment, at least a portion of the components for the foam making process are, as already noted, derived from more readily renewable (e.g., "green"), natural source, and more particularly from palm oil or palm kernel oil. In the exemplary embodiment, the palm oil-based polyol is derived from palm kernels. Herein, palm oil derived from either source is referred to generically as "palm oil," and the palm-derived material is generically referred to as a "palm oil-based" material.

[0020] The palm oil-based polymer material may be processed by adding a

PO to the base material. More specifically, the base polyol is constructed by the addition of PO to increase the base polyol molecular weight. This is followed by the addition of EO, with the result that the natural product content is decreased and the molecular weight is increased. The net bio-content can be anywhere from approximately 10% to approximately 90%, and preferably from approximately 22% to approximately 70%, depending on the natural oil and final composition, as well as the target molecular weight (in the illustrated embodiment, approximately 4,600).

[0021] To the extent the palm oil material is characterized by less than the conventionally preferred functionality of 3, sugar material such as sucrose or sorbitol can be added to raise the overall functionality.

[0022] In the illustrated embodiment, the palm oil-based polymer material has hydroxyl numbers preferably of from approximately 30 to 40 to provide a foam product for use in a seat cushion, an armrest cushion, a headrest, seat cover, etc.

[0023] Referring to FIG. 2, it is generally understood to mix the above- specified components by pouring two streams of the materials into a mold, closing the mold, and allowing the components to react, all as noted above. This reaction is exothermic, although auxiliary heat (approximately 150°- 170⁰F) is typically applied to the mold to help reduce the amount of time to cure the foam and thereby more quickly produce the foam product. After the foam is cured for a period of time (typically from 2 to 10 minutes, depending upon processing limitations or other manufacturing considerations), the foam product is optionally crushed in the mold using a TPR process. TPR includes reducing the sealing pressure of the mold to allow gas to escape the foam and mold during cure and/or prior being removed from the mold (i.e. "de-mold") and/or is then optionally, mechanically crushed (and may be repeatedly crushed) using a crushing apparatus such as a vacuum, a hard roller, or a brush crusher. The mechanical crushing apparatus applies a predetermined force to obtain a predetermined amount of reduction in thickness at a particular time (e.g. from 15 seconds to 60 minutes, and more preferably from 90 seconds to 2 minutes) after de-mold and for a given period of crush time.

[0024] Referring next to Table 1, an exemplary polyurethane foam formulation providing exemplary ranges of the amount of constituents of the foam process (as shown in FIG. 1) is shown. As evidenced in Table 1, the base polyol and the copolymer polyol comprise the majority of the foam. Accordingly, an appreciable increase in foam material from natural renewable sources may be made by using polyols derived from a renewable source, such as palm oil.

TABLE 1: EXEMPLARY FOAM COMPOSITION Component Amount (parts per hundred)

Base polyol 1-99

Palm polyol 1-30

Copolymer polyol 0-98

Water 1.5-6.0

Crosslinkers 0.5-3.5

Catalyst 0.01-1.5

Surfactant 0.1-2.5

Cell opener 0-5

[0025] Exemplary components include, for the base polyol, the commercially available XSS630 (from The Dow Chemical Company, Midland, Michigan), for the palm oil-based base polyol, the commercially available 1800/6 (a 70% bio-content palm oil polyol from Maskimi Polyol Sdn. Berhad, Sekangor Darul Ehsan, Malaysia (www,maskimi.com.my)); for the copolymer polyol, the commercially available SPECFLEX NC700 (from The Dow Chemical Company, Midland, Michigan); for the cell opener, the commercially available 4053 Voranol Polyether Polyol cell opener (from The Dow Chemical Company, Midland, Michigan); catalysts include a gellation catalyst (the commercially available diazobicydo[2.2.2]octane ("DABCO") amine catalyst TEDA 33LV (from Air Products and Chemicals, Inc., Allentown, Pennsylvania)), a balanced delayed action catalyst (the commercially available Capa 225 (C225) poly-caprolactone (from Momentive Performance Materials, Inc., Albany, New York)), a blowing catalyst (the commercially available A337 (from Momentive Performance Materials, Inc.)); for the cross-linkers, a diethanolamine ("DEOA") cross-linker and glycerin (both commercially available from Global Commodity); and for the surfactant, the commercially available L3150 (from Evonik Industries, AG, Essen, Germany) and B8715 (from Momentive Performance Materials, Inc.).

[0026] In one exemplary formulation, shown in Table 2, below, the components (such as those exemplified above), are provided in the following exemplary ranges. In respect of the crossl inkers of Table 2, exemplary ranges of each individual crosslinker (DEOA and glycerine) are, more particularly, preferably in the range of 0.5-1.5 parts per hundred DEOA and 0.3-1.2 parts per hundred for glycerine.

TABLE 2: IMPROVED EXEMPLARY FOAM COMPOSITION

Component Amount (parts per hundred)

Base polyol 19-99

Palm polyol 1-30

Copolymer polyol 0-80

Water 2.2-4.2

Crosslinkers 0.8-2.7

Catalyst 0.2-0.6

Surfactant 0.5-1.2

Cell opener 0-2

[0027] A cell opener is most often employed when a foam is formulated for rapid cure, as this creates a high exothermic reaction resulting in foam shrinkage. A cell opener may also be used when the foam product is not able to be crushed for cost reasons, because the foam material is poured or injected behind or inside a rigid frame, because crushing the foam product would cause appearance issues, such as with foam poured or injected behind a flexible cover stock, etc.

[0028] According to the exemplary embodiment, the foam formulation includes a high-acid polyester polyol material (polyester polyol having trace acids between 0.5% and 8.5% of the polyol) as a cell-opener. An alternative cell opener is made from high EO content polyether polyol such as Dow 4053, Bayer 9199, or Dow 1421. The cell opener is configured to open the cells of the foam by holding the water (by hydrogen bonding) / catalyst (the acid forms a salt) until an elevated temperature is reached. Because the catalyst/water is held and the reaction is delayed, soft segments (urethane) form first during the curing of the foam. When the elevated temperature is reached (e.g., as the heat of reaction increases), the blowing catalyst salt is broken to acid and catalyst and the foam cells are opened and the foam forms urea or hard segments in a more evenly distributed manner. This allows for better durability, wet set properties, and dynamic ride properties. According to current methods, extra density is often added to meet wet sets. A chemical additive may be used to reduce wet set and reduce the weight of the foam. The acid content of the palm oil acts as a cell-opener determinative of the size of the cells in the finished foam product.

[0029] It should be understood that any process disclosed in this application for the production of a natural oil-based base polyol may also be used to create a copolymer polyol as described above or with another process known in the art. The copolymer polyol material can be created with the palm oil-based polyol by the addition of stryene acrylonitrile ("SAN"), corn starch, or urea to create additional hardness in the foam system.

[0030] Referring next to FIG. 3, there are shown preferred foam compositions for the creation of foam products to perform to cushion, back, and bolster foam specifications. These foams are produced in a "one-shot" process as generally described above in the present disclosure. [0031] Referring in particular now to FIGS. 4A and 4B, there is shown comparison data for the properties of foam products (more specifically, foam automobile seat cushions and seat backs) made according to a control sample (designated "KPC Polyol" and having 100 parts per hundred petroleum-based polyol) and a plant oil-based foam blend material (designated "KPC/NOP Polyol") having 93 parts per hundred polyol of a petroleum-based poiyol and 7 parts per hundred of palm oil-based polyol. As shown, in almost all cases equivalent or improved performance for a variety of standardized tests (including, apparent density, tensile strength, elongation, tear strength, compression set, impact resilience and flammability) identified in Table 3, below, was exhibited by the foam products formulated with palm oil-based polyol.

TABLE 3

TEST DESCRIPTION/STANDARD ACCEPTANCE CRITERIA APPARENT DENSITY / ES-X62102/ES-X832184.1

Seat Cushion 0.045 +/- 0.0075 g/cm3 Seat Back 0.035 +/- 0.0035 g/cm3

TENSILE STRENGTH TEST (Test speed: 200 mm/min) / ES-X62102/ES-X83218 4.2

Seat Cushion (0.045 +/- 0.0045 g/cm3) 1 kgf/cm MIN Seat Back (0.035 +/- 0.0035 g/cm3) 1 kgf/cm MIN

ELONGATION (%)

Seat Cushion (0.045 +/- 0.0045 g/cm3) 120% Min Seat Back (0.035 +/- 0.0035 g/cm3) 120% Min

TEAR STRENGTH TEST / ES-X62102/ES-X83218 4.3

Seat Cushion (0.045 +/- 0.0045 g/cm3) 0.5 kgf/cm MIN Seat Back (0.035 +/- 0.0035 g/cm3) O.S kgtfcm MIN

COMPRESSION SET: Seat cushion (0.045 +/- 0.0045 g/cm3) / ES-X62102/ES-X832184.7

70c x 22 hours (50%) 7% Max 80c x 22 hours (75%) 25% Max 50c, 95% RH x 22 hours (50%) 35% Max COMPRESSION SET: Seat back (0.035 +/- 0.035 g/cm3) / ES-X62102/ES-X832184.7

70c x 22 hours (50%) 7% Max 80c x 22 hours (75%) 25% Max 50c, 95% RH x 22 hours (50%) 35% Max

IMPACT RESILIENCE TEST / ES-X62102/ES-X832184.15

Seat Cushion (0.045 +/- 0.0045 g/cm3) 60% MIN Seat Back (0.035 +/- 0.0035 g/cm3) 60% MIN

FLAMMABILITY TEST / ES-X60410

Normal State

Seat Cushion (0.045 +/- 0.0045 g/cm3) 80 mm/min MAX Seat Back (0.035 +/- 0.0035 g/cm3) 80 mm/min MAX

[0032] Foam with increased palm oil-based polyol content as described in this disclosure may be used for many automotive applications including molded foams for seating. Seating formed from the foam described above may be used for a variety of vehicles, including but not limited to passenger vehicles (e.g., cars or automobiles, vans, sport or cross-over utility vehicles), light trucks, busses, medium trucks such as box trucks, heavy trucks, fire engines, dump trucks, landscaping vehicles, excavators, industrial vehicles, mobile cranes, armored vehicles, aircraft, and any and all other seating applications.

[0033] The palm oil-based polyol foam formulations may be used in a numerous components of the vehicle seat including the seat bolster cushion, the seat cover, the head restraint, the seat back cushion, and the seat base cushion. Further, the palm oil-based polyol foam formulations may also be used in pour-in-place manufactured components. The palm oil-based polyol foam formulations may also be used in elastomers, and items such as shoe soles and plastic replacements. And the palm oil-based polyol foam formulations may further be used in any and all other products that can be made from such material.

[0034] According to other various exemplary embodiments, the palm oil- based polyol foam formulations disclosed herein may be used for other automotive interior components, including a headliner, a door panel, an instrument panel, a steering wheel, and carpeting.

[0035] The construction and arrangement of the elements of the processes for forming polyurethane foam shown in the various exemplary embodiments disclosed, including the best embodiment, are illustrative only. Only a few embodiments of the present disclosure are described in detail herein. Those of ordinary skill in the art who review this disclosure will readily appreciate that modifications are possible without departing from the novel teachings and advantages of the disclosure as limited only by the following claims.

Claims

WHAT IS CLAIMED IS:

1. An open cell, foam product for use in a seat application, wherein the open cell foam product is produced from the reaction product of a polyol formulation blend (24) and an isocyanate (26), wherein the polyol formulation blend (24) comprises:

a base polyol (12) including between 1 and 15 parts per hundred of a palm oil-based polyol material and a petroleum-based polyol material wherein a propylene oxide is added to the base polyol to increase its molecular weight;

a copolymer polyol (14) including between 1 and 15 parts per hundred of a palm oil-based polyol material and a petroleum-based polyol material wherein sorbitol, blended with glycerin, is added to produce a copolymer polyol;

water (16);

a crosslinker (18);

a cell opener (23);

a catalyst (20); and

a surfactant (22).

2. The foam product of Claim 1, wherein the palm oil-based polyol material includes a net bio-content of between approximately 10% and 90%.

3. The foam product of Claim 2, wherein the palm oil-based polyol material includes a net bio-content of between approximately 22% and 70%.

4. The foam product of Claim I₅ wherein the palm oil-based polyol material is blended with a sugar material to raise the overall functionality of the palm oil-based polyol material.

5. The foam product of Claim 4, wherein the sugar material is one of sucrose and sorbitol.

6. The foam product of Claim 1 , wherein the palm oil-based polyol material has a hydroxyl number of between approximately 25 and 60.

7. The foam product of Claim 6, wherein the palm oil-based polyol material has a hydroxyl number of between approximately 30 and 40.

8. The foam product of Claim 1, wherein the cell opener is a high-acid polyester polyol material having trace acids of between approximately 0.5% and 9.5% of the polyol material.

9. The foam product of Claim 8, wherein the cell opener is a high-acid polyester pofyol material having trace acids of between approximately 3.5% and 8.5% of the polyol material.

10. The foam product of Claim 1, wherein the palm oil-based polyol material has a functionality of between approximately 2.5 and 3.5.

11. The foam product of Claim 1, wherein the copolymer polyol material is a blend of between 1 and 100 parts per hundred of palm oil-based copolymer polyol and between 0 and 99 parts of petroleum oil-based copolymer polyol reacted with at least one of a styrene-acrylonitrile, corn starch, and urea to increase the hardness of the foam product.

12. A method of producing an open cell foam product, for use in a seat application, wherein the open cell foam product is produced from the reaction product of a polyol formulation blend (24) and an isocyanate (26), the method comprising the steps of:

formulating a base polyol (12) including between 5 and 15 parts per hundred of a palm oil-based polyol material (13) and a petroleum-based polyol material (11) wherein a propylene oxide is added to the base polyol (12) to increase its molecular weight; a copolymer polyol (14) including between 5 and 15 parts per hundred of a palm oil-based polyol material (13) and a petroleum-based polyol material (11) wherein sorbitol, blended with glycerin, is added to produce a copolymer polyol (14); water (16); a crosslinker (18); a cell opener (23); a catalyst (20); and a surfactant (22);

mixing the polyol blend materia! (24) with a isocyanate material (26) in a mix head to create a foam material;

pouring the foam material into a foam mold tool to form a foam product;

curing the foam product so that the foam product retains its shape; and

demolding the foam product from the mold tool.

13. The method of producing a foam product of Claim 12, the method further comprising the step of crushing the foam product, after the foam material is poured into the mold tool, to provide improved transmissibility using a time-pressure release process.

14. The method of producing a foam product of Claim 13, wherein the time- pressure release process comprises reducing the sealing pressure of the mold to enable gas to escape the foam and mold during curing and prior to de-molding.

15. The method of producing a foam product of Claim 14, wherein the time- pressure release process further comprises crushing the foam product using a crushing apparatus which applies a predetermined force to obtain a predetermined amount of reduction in thickness at a predetermined timed after de-molding and for a predetermined period of crush time.