EP0650501A1 - Molded polyurethane foams - Google Patents

Molded polyurethane foams

Info

Publication number
EP0650501A1
EP0650501A1 EP94916718A EP94916718A EP0650501A1 EP 0650501 A1 EP0650501 A1 EP 0650501A1 EP 94916718 A EP94916718 A EP 94916718A EP 94916718 A EP94916718 A EP 94916718A EP 0650501 A1 EP0650501 A1 EP 0650501A1
Authority
EP
European Patent Office
Prior art keywords
polyisocyanate
polyurethane foams
polyol
molded polyurethane
weight
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.)
Withdrawn
Application number
EP94916718A
Other languages
German (de)
English (en)
French (fr)
Inventor
Yoshiaki Miyazaki
Kazuo Mizumura
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.)
Dow Mitsubishi Kasei Ltd
Dow Chemical Co
Original Assignee
Dow Mitsubishi Kasei Ltd
Dow Chemical Co
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
Priority claimed from JP5132352A external-priority patent/JPH06322057A/ja
Priority claimed from JP5132364A external-priority patent/JPH06322058A/ja
Application filed by Dow Mitsubishi Kasei Ltd, Dow Chemical Co filed Critical Dow Mitsubishi Kasei Ltd
Publication of EP0650501A1 publication Critical patent/EP0650501A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G2110/0033—Foam properties having integral skins
    • 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

Definitions

  • the present invention relates to molded polyurethane foams having excellent abrasion resistance useful for automotive material for steering wheels, headrests and armrests, material for furniture and the like.
  • Integral skin polyurethane foams having fine skin are well-known to the public and are widely utilized as automotive material for steering wheels, headrests and armrests, and material for furniture and the like in various fields.
  • the formation of the skin layer in the integral skin foams is based on the function of a blowing agent such as chlorofluorocarbon ("CFC") in the exothermic reaction of a polyisocyanate with a polyol.
  • CFC chlorofluorocarbon
  • the use of a physical blowing agent such as CFC provides to the foams excellent skin properties which are required to the stated products.
  • a chemical blowing agent such as water does not usually provide any excellent skin properties to the foams.
  • Some approaches to provide excellent skin properties to molded polyurethane foams have included, for example, those described in Japanese Kokai Patent No. H03-24108, in which a specific catalyst mixture comprising a urethane catalyst and a carbodiimide catalyst is employed to provide low core density in the presence of a non-reactive physical blowing agent, and Japanese Kokai Patent No. H03-33120, in which a specific catalyst mixture is employed in the presence of water as the primary blowing agent.
  • the technology disclosed in the latter patent may be useful as an alternative technology of a CFC based blowing agent under the Freon Regulation.
  • the purpose of the present invention is to provide molded polyurethane foams having excellent abrasion resistance under shorter demolding time.
  • the present invention provides molded polyurethane foams prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst wherein (a) the polyisocyanate comprises a mixture of (i) from 2 to 30 weight percent polymethylene polyphenyl polyisocyanate ("Polymeric MDI") and (ii) a NCO-terminated prepolymer prepared from the reaction of an organic polyisocyanate with 20 to 45 weight percent poly(oxytetramethylene)glycol (“PTMG”), said weight percents being based on the total weight of organic polyisocyanate, poly(oxytetramethylene)glycol and polymethylene polyphenyl polyisocyanate, and (b) the polyol contains at least 30 weight percent polymer polyol prepared from the reaction of
  • the present invention also provides molded polyurethane foams prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst wherein (a) the polyisocyanate comprises a NCO-terminated prepolymer prepared from the reaction of (i) an organic polyisocyanate, (ii) from 2 to 30 weight percent polymethylene polyphenyl polyisocyanate and (iii) from 20 to 45 weight percent poly(oxytetr__methylene)glycol, said weight percents based on the total weight of the polyisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol, and (b) the polyol contains at least 30 weight percent polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenic unsaturated monomer, and the catalyst contains an organotin compound.
  • the polyisocyanate comprises a NCO-terminated prepoly
  • Suitable polyisocyanates useful in the present invention include, for example, a mixture of a polymeric MDI and a NCO-terminated prepolymer prepared from the reaction of an organic polyisocyanate with PTMG, or a NCO-terminated prepolymer prepared from the reaction of an organic polyisocyanate containing a polymeric MDI with PTMG.
  • Suitable organic polyisocyanates useful in the present invention include, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates or hetrocyclic polyisocyanates which are well-known to the public in polyurethane or polyurea industrial field. More specifically, suitable organic polyisocyanates include, for example, 1,6-hexamethylene diisocyanate, cyclohexane-1,4 diisocyanate, 1,4-xylilene diisocyanate. 2,4-toluene diisocyanate.
  • MDI 4,4' ⁇ diphenylmethane diisocyanate
  • preferable polyisocyanates are aromatic polyisocyanates such as MDI, a polymeric MDI, modified polyisocyanates thereof and the mixture thereof.
  • Suitable poly(oxytetramethylene)glycol is a linear polyetherpolyol having a primary hydroxy group in its both terminals and has an weight average molecular weight of about 300 to about 3,000.
  • the preferable molecular weight of PTMG to be employed in the preparation of the NCO-terminated prepolymer of the present invention is from about 500 to about 2.400.
  • the NCO-terminated prepolymer is prepared by reacting PTMG with an excess amount of an organic polyisocyanate in the range of temperature of about 40 to about 100°C.
  • the NCO content of the prepolymer is from about 14 to about 28 weight percent ("wt%") and the PTMG content of the prepolymer is from about 10 to about 50 wt%, preferably, about 20 to about 45 wt%.
  • One of the polyisocyanates useful in the present invention is a mixture of a polymeric MDI and the stated PTMG-based prepolymer.
  • the polymeric MDI content of the poly- isocyanate mixture is from about 1 to about 40 wt%, preferably, about 2 to about 30 wt%, more preferably, about 5 to about 20 wt%.
  • the another polyisocyanate useful in the present invention is a prepolymer prepared from the reaction of an organic polyisocyanate containing a polymeric MDI with PTMG.
  • the NCO content of the prepolymer is from about 14 to about 28 wt% and the PTMG content of the prepolymer is from about 10 to about 50 wt%, preferably, about 20 to about 45 wt%.
  • the polymeric MDI content in the prepolymer is from about 1 to about 40 wt%, preferably, about 2 to about 30 wt%, more preferably, about 5 to about 20 wt%.
  • Suitable polyols useful in the present invention include, for example, polyetherpolyols prepared from the reaction of alkyleneoxides such as ethyleneoxide, propyleneoxide and butyleneoxide with low molecular weight polyols such as ethyleneglycol, propyleneglycol, glycerol, trimethyrolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose, or polyamines such as ethylenediamine, xylilenediamine, piperazine and N-N-dimethylamino alkylamine, polymer polyols prepared from the reaction of the stated polyetherpolyols with ethylenic unsaturated monomers such as acrylonitrile, styrene, butadiene, methyl methacrylate, acrylic amide and vinyl acetate, or polyesthers prepared from the reaction of the stated low molecular weight polyols with polycarboxylic acids such as succ
  • a polymer polyol is recommended to use as a polyol in order to improve abrasion resistance of molded polyurethane foams of the present invention.
  • Suitable polymer polyols include, for example, polymer polyols prepared from the reaction of a polyetherpolyol with acrylonitrile only or a mixture of acrylonitrile and other ethylenic unsaturated monomer such as styrene.
  • the amount employed of the polymer polyol should be determined under consideration of other properties such as processability since the polymer polyols have generally high viscosity.
  • the amoimt employed of the polymer polyol in the total polyol is at least 30 wt%, preferably, about 30 to about 70 wt%, more preferably, about 35 to about 60 wt%.
  • Suitable blowing agents useful in the present invention include, for example, water, chlorofluorocarbon ("CFC") or a mixture thereof.
  • the suitable blowing agent is water only or a blowing agent containing water as primary component.
  • the amount employed of water is from about 0.05 to about 5 parts by weight (“pbw”) based on the total polyol, preferably, about 0.1 to about 3 pbw, more preferably, about 0.3 to about 2 pbw.
  • Solvents, having low boiling point such as pentane, methyienechloride, dichloromethane and 4,4'-diaminodiphenylmethane, can optionally be employed as a blowing agent together with water.
  • organotin catalysts include, for example, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dihexyltin diacetate, dimethyltin dimercaptide, dibuthyltin dimercaptide, diocthyltin dimercaptide, di-2-ethylhexyltin oxide, stannous octoate and stannous oleate.
  • organotin compounds more preferable compound is a mercaptide type organotin compound such as dibutyltin dimercaptide, having good hydrolysis resistance.
  • the amount employed of the organotin catalyst is less than 0.5 pbw, preferably about 0.01 to about 0.5 pbw, more preferably about 0.03 to about 0.1 pbw, based on the total polyol of 100 pbw.
  • Suitable other catalysts to be optionally employed in the present invention include, for example, tertiary amine compounds such as trialkylamines like trimethylamine and triethylamine, heterocyclic amines like N-alkylmorpholine. ethers like 2,2'-bis -(dimethylamino)diethylether, aliphatic polyamines like 1 ,4-dimethylpiperazine, triethylenediamine, N,N,N',N'- tetramethyl-l,3-butanedi__mine and N-methyldiethanolEimine, or a mixture thereof.
  • the amount employed of the amine type catalyst is usually within the range well-known to the public in the polyurethane chemistry.
  • Suitable cross-linking agents to be optionally employed in the present invention include, for example, amine-based low molecular weight polyols such as triethanolamine and diethanolamine, and low molecular weight polyols such as ethyleneglycol, diethyleneglycol, butanediol, trimethyrolpropane and glycerol, or a mixture thereof.
  • the amoimt employed of the cross-linking agent is usually from about 2 to about 20 pbw based on the total polyol, preferably, about 3 to about 10 pbw.
  • molded polyurethane foams of the present invention can be manufactured in accordance with prior making methods such as open-mold process or closed-mold process.
  • MDI diphenylmethane diisocyanate
  • PAPI-135 Polymeric MDI
  • polyetherpolyol having an average equivalent weight of 1,600 and capped ethyleneoxide (EO) content of 14 wt% (“Polyol PI"), prepared from the reaction of glycerol as an initiator with propyleneoxide (PO), was selected as another polyol component.
  • EO ethyleneoxide
  • Polyol PI capped ethyleneoxide
  • Various NCO-terminated prepolymers were prepared employing the stated polyisocyanate components and polyols components. The composition of each prepolymer and polyisocyanate mixture is shown in Table 1, Table 2 and Table3.
  • Polyol P2 A propyleneoxide (“PO")-added polyetherpolyol initiated with glycerol (Functionality ⁇ , Average equivalent weight (“EW”): 1,600, PO content:83 wt%, Capped EO content: 17 wt%) This polyetherpolyol was prepared capping EO after the reaction of glycerol as an initiator with PO in the presence of potassium hydroxide as a catalyst.
  • PO propyleneoxide
  • EW Average equivalent weight
  • Polyol CPP1 A polymer polyol (Functionality ⁇ , OH value:28. solid content:20 wt%) This polymer polyol was prepared polymerising the stated Polyol P2 with acrylonitrile.
  • Polyol CPP2 A polymer polyol (Functionality ⁇ , OH value:28. solid content:20 wt%) This polymer polyol was prepared polymerising the stated Polyol P2 with a monomer mixture of acrylonitrile styrene (70/30 weight ratio).
  • Organotin type catalyst Dibutyltin dimercaptide (FOMREZ UL-l:Witco)
  • Amine type catalyst 1 Triethylenediamine (dipropyleneglycol 33 % solution)
  • Amine type catalyst 2 Bis(dime_hylaminoethyl)ether
  • Cross-linking agent monoethyleneglycol (MEG) Blowing agent: Water; Trichlorofluoromethane (CFC-11)
  • a polyol and other additives except a polyisocyanate were mixed for 10 seconds at 3,000 r.p.m.
  • the polyisocyanate measured was mixed with the polyol mixture for 3 seconds at 3,000 r.p.m. and continually the mixture was injected into an iron-made mold being maintained under 50 °C.
  • a polyurethane foam was demolded from the mold.
  • the surface properties such as blistering and skin delamination of the foam obtained were immediately observed as an evaluation of demoldability.
  • the results are shown in each Table. The meaning of each mark is as follows. "A” means "good", “B” means “almost good” and "C” means "not good”.
  • testing samples having outer peripheral length of about 80 mm were cut and prepared from a foam moldings (steering wheel) obtained as stated above.
  • the foam moldings was prepared covering an iron-made pipe (outside diameter: 14 mm) with polyurethane foam (shape of a cross section to the diameter-direction: ellipse having a 28 mm long diameter and a 23 mm short diameter).
  • the abrasion resistance of the testing sample was evaluated using a testing machine for abrasion resistance, "SUGA FR-2-S Type" (produced by Suga Test Instruments in Japan).
  • the testing sample was set in the machine as the outer surface of the sample contacted a white cloth
  • the molded polyurethane foams of the present invention can be produced under very cycle times and can be useful for automotive material such as steering wheels, headrests and armrests, material for furniture and the like, in which abrasion resistance is required.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
EP94916718A 1993-05-12 1994-05-10 Molded polyurethane foams Withdrawn EP0650501A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP132364/93 1993-05-12
JP5132352A JPH06322057A (ja) 1993-05-12 1993-05-12 ポリウレタンフォーム成形品
JP132352/93 1993-05-12
JP5132364A JPH06322058A (ja) 1993-05-12 1993-05-12 ポリウレタンフォーム成形品
PCT/US1994/005173 WO1994026800A1 (en) 1993-05-12 1994-05-10 Molded polyurethane foams

Publications (1)

Publication Number Publication Date
EP0650501A1 true EP0650501A1 (en) 1995-05-03

Family

ID=26466945

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94916718A Withdrawn EP0650501A1 (en) 1993-05-12 1994-05-10 Molded polyurethane foams

Country Status (6)

Country Link
EP (1) EP0650501A1 (pt)
CN (1) CN1110877A (pt)
AU (1) AU679997B2 (pt)
BR (1) BR9405366A (pt)
CA (1) CA2139654A1 (pt)
WO (1) WO1994026800A1 (pt)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100489003C (zh) * 2003-12-24 2009-05-20 日本聚氨酯工业株式会社 软质聚氨酯泡沫体的制造方法、导电性软质聚氨酯泡沫体的制造方法、导电辊及其制造方法
ES2655387T3 (es) 2008-07-18 2018-02-19 Dow Global Technologies Llc Estructuras celulares y espumas de poliuretano viscoelásticas
CN103788337B (zh) * 2014-01-14 2015-12-02 北京理工大学 一种用于外墙外保温的阻燃聚氨酯硬质泡沫塑料及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1204100A (en) * 1968-05-15 1970-09-03 Bayer Ag Process for the production of foam plastics which contain urethane groups
DE3113690A1 (de) * 1981-04-04 1982-10-28 Elastogran GmbH, 2844 Lemförde "verfahren zur herstellung von geschlossenzelligen polyurethan-formteilen mit einer verdichteten randzone"
GB8911853D0 (en) * 1989-05-23 1989-07-12 Ici Plc Co2 blown integral skin foams
EP0451559A3 (en) * 1990-04-05 1992-11-25 Basf Corporation (A Delaware Corp.) Integral skin polyurethane foam
IT1240635B (it) * 1990-05-04 1993-12-17 Dow Italia Polimeri poliuretanici microcellulari preparati da tre polimeri di poli (tetrametilen) glicoli con gruppi isocianato terminali
US5491175A (en) * 1992-04-10 1996-02-13 The Dow Chemical Company Polyurethane foam molding
US5234961A (en) * 1992-12-07 1993-08-10 Basf Corporation Polyurethane water-blown integral skin system produced with a polyterahydrofuran prepolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9426800A1 *

Also Published As

Publication number Publication date
BR9405366A (pt) 1999-09-08
CN1110877A (zh) 1995-10-25
AU679997B2 (en) 1997-07-17
WO1994026800A1 (en) 1994-11-24
AU6829794A (en) 1994-12-12
CA2139654A1 (en) 1994-11-24

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