CA1076748A - Impact energy-absorbing urethane foam - Google Patents

Impact energy-absorbing urethane foam

Info

Publication number
CA1076748A
CA1076748A CA236,925A CA236925A CA1076748A CA 1076748 A CA1076748 A CA 1076748A CA 236925 A CA236925 A CA 236925A CA 1076748 A CA1076748 A CA 1076748A
Authority
CA
Canada
Prior art keywords
range
urethane foam
polyol
molecular weight
prepolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA236,925A
Other languages
French (fr)
Inventor
Kirby E.L. Flanagan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
McCord Corp
Original Assignee
McCord Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by McCord Corp filed Critical McCord Corp
Priority claimed from US05/746,826 external-priority patent/US4116893A/en
Application granted granted Critical
Publication of CA1076748A publication Critical patent/CA1076748A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R19/00—Wheel guards; Radiator guards, e.g. grilles; Obstruction removers; Fittings damping bouncing force in collisions
    • B60R19/02—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects
    • B60R19/18—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects characterised by the cross-section; Means within the bumper to absorb impact
    • B60R19/22—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects characterised by the cross-section; Means within the bumper to absorb impact containing mainly cellular material, e.g. solid foam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

ABSTRACT
An impact energy-absorbing, relatively low density, urethane foam for use in automobile bumpers has a high content of urea linkages and is relatively temperature insensitive i.e.
gives approximately the same physical performance over a wide range of temperature. The foam is water blown in a closed mold from a quasi-prepolymer system. The pack factor is preferably in the range of 1.5 to 8 and the molded density is in the range of 5 to 20 lbs/ft.3.
The foam formulation is based on a prepolymer polyol of a poly (oxypropylene) trio capped with a styrene/acrylonitrile copolymer which is reacted with a 50 to 150 equivalent weight amine or polyol crosslinker of 2 to 6 functionality and with a TDI/glycol or trio quasi-prepolymer, along with a relatively high amount of water.

Description

107~7~8 Urethane foams have been used for some years in automobile trim components, usually contained within a tough vlnyl or ABS skin or shell, for styling purposes and as impact energy-absorbing safety padding. Recent ef-forts have been directed to the manufacture of urethane foam impact energy-absorbing automobile bumpers.
It has been known to water-blow flexible or semi-rigid urethane foams to very low densities, e.g. 3 to 5 lbs./ft.3 and to use such low den-sity urethane foams in automotive applications. However, until now, urethane foams of low densities have not performed well as impact energy-absorbing safety padding because inter alia, they were too soft and, perhaps most important in automotive applications, did not give relatively constant per-formance over the wide range of temperatures encountered in service, i.e.
they were quite temperature sensitive.
According to the present invention, there is provided an impact energy absorbing urethane foam made from the following formulation:
. Parts by weight Polymer polyol 70 - 90 Crosslinker 10 - 30 Water 3 to 5 Diisocyanate prepolymer To yield 90 - 115 Index Catalyst 0 to 2 wherein:
said polymer polyol is a 4000 to 8000 molecular weight polymer of
2 to 6 parts of a poly tC2-C4 oxyalkylene) triol capped with one part of a vinyl aromatic/olefinic C2-C6 nitrile copolymer;
said crosslinker is a polyol haYing a functionality in the range of 2 to 6 and an equivalent weight in the range of 50 to 150; and said diisocyanate prepolymer is a reaction product of an acidified TDI and a polyol selected from the group consisting of a 100 to 1000 mole-cular weight triol and an alkylene glycol selected from diethylene glycol and dipropylene glycol, and has a free isocyanate content in the range of 20 to 35 percent;

E~

10'~'~748 said urethane foam being prepared in a closed mold at a pack factor in the range of 1.5 to 8 and having a density in the range of 5 to 20 lbs./
ft.3, a specific energy at 50% C/D greater than 25 in.-lbs./in.3J a tempera- ~ -ture index, -20F/140F of less than 2.5 and at least 90% recovery at 70F
after multiple impact.
The catalyst is conveniently an organo-heavy metal compound or a tertiary amine.
Thus, the invention is concerned with a quite effective impact energy-absorbing urethane foam of relatively low density, less than 20 lbs./
ft.3J that is characterized by its temperature insensitivity and is particular-ly suited for automotive applications.
This foam has a reasonably good specific energy absorptionj at least 25 in.-lbs./in. and an efficiency therefore greater than 50% at any temperature in the range of -20F to 140F. The outstanding property of the foam is its load/temperature index value or its temperature insensitivity.
The 50% compression/deflection (C/D hereafter) value of the foam at -20F, compared to this value at 140FJ differs by a factor of less than 2.5.
The low density foam of this invention is made from an aromatic diisocyanate prepolymer system, water-blown, ~as opposed to hydrofluoro carbon blown) inside of a closed mold. The oam of this invention is not self-skinning. The amount of water used for blowing is relatively large, ~ greater than 1.3 weight percent in all cases, which increases hardness. This ; amount of water produces, of courseJ a large amount of short-chain urea link-ages which probablyJ in part, contribute to the improved performance of the foam. An amine or glycol crosslinker is used to improve moldability and to fbrther increase haTdness.

7`~ 7 -3-,V, - `: .

10'7fà7~

The base polymer polyol used in the foam formulation is specifical-ly a copolymer of 2 to 6 parts by weight of a poly (C2-C4 oxyalkylene) triol and one part by weight of an olefinic C2-C6 nitrile/vinyl aromatic copolymer.
The polymer has a molecular weight in the range of 4000 to 8000. See United States Patent Nos. 3,304,273; 3,383,351 and 3,418,354.
The use of water alone as a crosslinker in the foam formulation may result in a foam that is too "wild" to be formed in a closed mold. In any event, foams have been prepared from the same ingredients e~cept without the use of an organic crosslinker and with a slightly higher water content, 2.0%, and were found to have too low a specific energy to be of interest.
Therefore, a glycol or an~nee crosslinker is used in addition to the water.
The crosslinker has a relatively low molecular weight, a functionality in the range of 2 to 6 and an equivalent weight in the range of 50 to 150.
The foam is prepared by the prepolymer method. The diisocyanate, preferably a TDI, is reacted with a polyol selected from the group consisting ' of 100 to 1000 molecular weight triols and alkylene glycols having 2 to 8 carbon atoms, e.g. diethylene or dipropylene glycol. The prepolymer has a FNCO (free isocyanate) content of 25 to 35% and is used in an amount to give an isocyanate index in therange of 90 to 115%.
A similar foam has been prepared from about the same ingredients by the one-shot method but this foam had physical properties, principally specific energy, lower than that desired.
A conventional catalyst, such as dibutyl tin dilaurate, stannous C octoate or Dabco, is used as required.
Besides the above specific energy absorption and low temperature values of the foam, the fQam has reasonably good elongation, generally great-;~~ er than 50% and reasonably good tensile strength, greater than 75 psi.
~ ~e~r~
' lC~ - 4 -V

EXAMPLES
The two formulations of Table I illustrate this invention:
TABLE I
Formulation I II
(parts by weight) Polymer polyol (1) 75.0 75.0 Crosslînker:
Pentaerythritol 25.0 Sorbitol polyether (2) ---- 25.0 H20 4.0 4.0 TDI prepolymer ~3) 96.0 82.7 Catalyst-triethylene diamine 0.8 0.8 Properties: (4) Specific Energy (in.-lb./in.3)31.1 27.0 50% C/D-lbs.
@ -20F ---- 18S0 @ 140F 830 960 @ 70F 1325 1160 Temperature Index ---- 1.92 Density, lbs./ft. 5 5 ~ -Notes:
1.) a 6000 molecular weight copolymer of a (a) four parts by weight of a 4500 molecular weight poly (oxypropylene) triol capped with (b) one part by weight of a 50/50 weight ratio acrylonitrile/styrene copolymer, Union Carbide Chemicals Co. Niax* 34-28.
2.) Wyandotte Chemical Cos.' PA14635*sorbitol polyether. It has 6 reactive hydrogens per molecule and an equivalent weight Trademarks P-503 1~7674~
of 115.
3.) a quasi prepolymer of acidified 80/20 TDI and of a polyester triol of 259 molecular weight, Union Carbide B Chemical Co.'s LG-650. The prepolymer has a molecular weight of 190 and a free NCO content of 31. The prepolymer is made by simple mixing of ingredients and allowing the mixture to exotherm.
4.) 4" x 4" x 2" samples were prepared for testing by simple blender mixing of the ingredients in a cup~ pouring the blend in a mold, closing the mold and allowing the foaming reac-tion to go to completion for about six minutes.
As here used "specific energy" i9 a measure of the foam's ability to abæorb energy and is defined as the areà under the load curve of a sample tested in compression as on an Instron Tester. The values are given in inch-pounds/cubic inch at 50%
deflection, in.-lb/in.3 ~50% CD), and are determined as follows:
15 A 4" x 4" x 2" thick block is compressed at 2"/min to 50% CD and the stress/strain plot recorded on graph paper. The area between the loading curve and the horizontal axis is the specific energy.
Ideally, this curve would be square-form. The "efficiency" of the foam is the ratio of the specific energy of the foam over the area of ideal square-form wave.
The temperature index i5 obtained in accordance with ASTM-2406 except that the test is run at the indicated temper-atures, not at 70F as is usual, and the compression/deflection at the lower temperature is divided by that at the higher temper-ature to obtain the actor by which they differ.
The above foams shown in the above of examples havefree blow densities of 2.5 to 3.0 lbs./ft.3 but are blown in closed molds to densities of S to 20 lbs./ft.3. The pack factor i.e. molded density/free blown density is preferably in the range 3~ of 1.5 to 8.

~r~d~

p 503 1076748 THE DRAWING
The drawlng i8 a cro~s-~octlonal vie~ o~ an auto-~obilo bumper incorporatlng tho impact energy ab~orbing roam o~ thls inventlon, ~uch a~ might be used on a 1974 Ford Mustang or a 1974 Pontlac Fir-blrd.
B Rererrlng to the drawing, the bumper con~l~t~ Or a rigid m tal channel 10 mount-d to tho car rra~e (not sho~n) to ~hlch 1~ adh~ ely s-cured a ~olded bun 11 Or the urothane rou~
o~ thls invontlon. A protoctlve-decorative ~loxible skln o~ a 10 densor plastlc 12 overl~y~ the roaa. This can be a ca~t v~nyl V~l C U~
skln or ~e~ ~ormod AES sheet~ but prererably 1~ a molded mlcrocellular selr-skinnlng urethane ~oam 0.150 inches thick.
The urethane ~oam bun i-, o~ cour~e, placed ln a po~ition to receive the impact when the vohicle ¢ontacts other ob~ect~.
15 ~ho urothano roam bun ha~, as a rule, greater than 90f recovery at 70F evon a~ter multiple impacts in the samo area such that the re~idual deror~ation in the bu~per surrace i8 not too unsightly.
.', ` ' :- ~

, .

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Supplementary Disclosure Additional aromatic diisocyanates which may be used in the prepoly-mers of the foam formulations of the invention are methylene bis(4-phenyl iso-cyanates) (referred to as MDI's). Thus, overall the invention affords an im-pact energy-absorbing urethane foam made from the following formulation:
Parts by weight Polyol 70 to 90 Crosslinker 10 to 30 ; Water 1 to 5 Prepolymer To yield 90-115~ Index Catalyst 0 to 2 Wherein: ' said polymer polyol has a molecular weight in the range of 4000 to 8000 and comprises in the range of 2 to 6 parts of a poly (C2-C4 oxyalkylene) triol reacted with one part of a vinyl aromatic/olefinic C2-C6 nitrile monomer mixture;
said crosslinker is a polyol having a functionality in the range of 2 to 6 and an equivalent weight in the range of 50 to 150;
said prepolymer is a reaction product of (a) an aromatic diisocyanate selected from the group consisting of MDI and TDI and (b) a polyol selected from the group consisting of a 100 to 1000 molecular weight triol and a 100 to 200 molecular weight ether glycol and has a free isocyanate content in the range of 20 to 35 percent; and said urethane foam being prepared in a closed mold at a pack factor in the range of 1.5 to 8 and having a density in the range of 5 to 20 lbs./ft. , a specific energy at 50% C/D greater than 25 in.-lbs./in.3, a temperature in-dex -20F/140F of less than 2.5 and at 10ast 90% recovery at 70F after multi-ple impact.
When using MDI, the amount of water used for blowing can be less and should be greater than 1% by weight.
~ The prepolymer generally has a FNC0 (free isocyanate) content of 20 :

~ 8-to 35% and is used in an amount to give an isocyanate index in the ran~e of 90 to 115%.
The followlng is the preferred ranges of the ingredients:
Parts by Weight Polyol 70 to 90 Crosslinker 10 to 30 ; Water 1 to 5 Prepolymer To yield 90-115% Index Catalyst 0 to 2 lp C The following Example illustrates this aspect of the invention.
Example ~$
A foam formulation was prepared with the following composition.
Parts by Weight Polyol 5 0 (1) Crosslinker 25.0 (2) Water 1.5 Triethylene diamine 0.8 MDI Prepolymer 70.2(3) Blowing Agent 0 (1) ~IAX 31-28 (Union Carbide).
(2) Sorbitol Polyether (Wyandotte).
(3) E-451 (Mobay Chemical Company, Division of Baychem Corp., ; Pittsburgh, Pennsylvania 15205). This is a 50/50 blend of Mobay~s Mondur PF
and Mondur CD. It has a FNC0 of about 27-28 and is a linear polymer with a ;~ high degree of aromaticity. Mondur PF is a tripropylene glycol adduct of MDI.
Mondur CD is a "liquid" or modified MDI that contains a small amount of some trimers and carbodiimides which d1srupt the symmetry and inhibit the crystal--. lization of the final prepolymer molecule and help keep the mixture liquid, which is a convenience. Isonate*143L (Up~ohn Company, Industrial Chemicals Division, North Haven, Connecticut 06473) is the rough equivalent of Mondur CD.
The foam is made by simply blending the ingredients as in a mixing head at room temperature. The foam has a cream time of 24 seconds, a rise ~ t~ks ~? _g_ ~ ~ .

~076748 time of 76 seconds, and ls tack free in 145 seconds. Its free blown density is 4.55 lbs./ft.3 A fluorohydrocarbon blowing agent can be used to reduce and control the molded density.

, , . ,

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An impact energy absorbing urethane foam made from the following formulation:

wherein:
said polymer polyol is a 4000 to 8000 molecular weight polymer of 2 to 6 parts of a poly (C2-C4 oxyalkylene) triol capped with one part of a vinyl aromatic/olefinic C2-C6 nitrile copolymer;
said crosslinker is a polyol having a functionality in the range of 2 to 6 and an equivalent weight in the range of 50 to 150; and said diisocyanate prepolymer is a reaction product of an acidified TDI and a polyol selected from the group consisting of a 100 to 1000 mole-cular weight triol and an alkylene glycol selected from diethylene glycol and dipropylene glycol, and has a free isocyanate content in the range of 20 to 35 percent;
said urethane foam being prepared in a closed mold at a pack factor in the range of 1.5 to 8 and having a density in the range of 5 to 20 lbs./ft.3, a specific energy at 50% C/D greater than 25 in.-lbs./in.3, a temperature index, -20°F/140°F of less than 2.5 and at least 90% recovery at 70°F after multiple impact.
2. The urethane foam of claim 1 wherein:

said polymer polyol is a 6000 molecular weight copolymer of a 4500 molecular weight poly (oxypropylene) triol capped with a 50/50 styrene/
acylonitrile copolymer;
said crosslinker is selected from the group consisting of a pentaerythritol, triethonolamine and a sorbitol polyether having 6 reactive hydrogens and an equivalent weight of 115;
said diisocyanate prepolymer is the reaction product of acidified TDI and a polyether triol of about 259 molecular weight, and has a free isocyanate content of about 31; and said catalyst is triethylene diamine.
3. A bumper assembly comprising a backing member adapted to be mounted to a motor vehicle and faced with, in an impact receiving position, the urethane foam of claim 1.
4. The bumper assembly of claim 3 wherein said urethane foam is over-layed with a conforming protective, decorative and flexible skin of a denser plastic.

Claims Supported by the Supplementary Disclosure
5. An impact energy-absorbing urethane foam made from the following formulation:

Wherein:
said polymer polyol has a molecular weight in the range of 4000 to 8000 and comprises in the range of 2 to 6 parts of a poly (C2-C4 oxyalkylene) triol reacted with one part of a vinyl aromatic/olefinic C2-C6 nitrile mono-mer mixture;
said crosslinker is a polyol having a functionality in the range of 2 to 6 and an equivalent weight in the range of 50 to 150;
said prepolymer is a reaction product of (a) an aromatic diisocyan-ate selected from the group consisting of MDI and TDI and (b) a polyol select-ed from the group consisting of a 100 to 1000 molecular weight triol and a 100 to 200 molecular weight ether glycol and has a free isocyanate content in the range of 20 to 35 percent; and said urethane foam being prepared in a closed mold at a pack factor in the range of 1.5 to 8 and having a density in the range of 5 to 20 lbs./ft.3, a specific energy at 50% C/D greater than 25 in.-lbs./in.3, a tem-perature index -20°F/140°F of less than 2.5 and at least 90% recovery at 70°F
after multiple impact.
6. The urethane foam of claim 5 wherein said prepolymer is the reaction product of MDI and a polyether triol.
7. A bumper assembly comprising a backing member adapted to be mounted to a motor vehicle and faced with, in an ampact receiving position, the ure-thane foam of claim 5.
8. The bumper assembly of claim 7 wherein said urethane foam is overlaid with a conforming protective, decorative and flexible skin of a denser plastic.
CA236,925A 1976-12-02 1975-10-02 Impact energy-absorbing urethane foam Expired CA1076748A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/746,826 US4116893A (en) 1974-06-21 1976-12-02 Impact energy-absorbing urethane foam

Publications (1)

Publication Number Publication Date
CA1076748A true CA1076748A (en) 1980-04-29

Family

ID=25002506

Family Applications (1)

Application Number Title Priority Date Filing Date
CA236,925A Expired CA1076748A (en) 1976-12-02 1975-10-02 Impact energy-absorbing urethane foam

Country Status (3)

Country Link
AU (1) AU511812B2 (en)
CA (1) CA1076748A (en)
DE (1) DE2750069A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2436154A2 (en) * 1978-09-15 1980-04-11 Mccord Corp Impact-resistant polyurethane foam for bumpers - prepd. from polymer-poly:ol, crosslinking agent, water and prepolymer derived from aromatic di:isocyanate
US4616866A (en) * 1983-12-30 1986-10-14 Michael Ladney, Jr. Vehicle bumper
JPS6146744A (en) * 1984-08-14 1986-03-07 Kanegafuchi Chem Ind Co Ltd Car bumper core member
US4994502A (en) * 1987-07-01 1991-02-19 Basf Corporation Process for the preparation of integral skin polyurethane steering wheels
GB9101862D0 (en) * 1991-01-29 1991-03-13 Ici Plc Microcellular polyurethane elastomers
US5232957A (en) * 1992-09-11 1993-08-03 Davidson Textron Inc. RIM molded energy absorbing polyurethane foam

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Publication number Publication date
AU3110477A (en) 1979-06-07
DE2750069A1 (en) 1978-06-08
AU511812B2 (en) 1980-09-04

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