CN101223220A - Method of preparing polyurethane-moulded articles - Google Patents

Method of preparing polyurethane-moulded articles Download PDF

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Publication number
CN101223220A
CN101223220A CNA2006800262686A CN200680026268A CN101223220A CN 101223220 A CN101223220 A CN 101223220A CN A2006800262686 A CNA2006800262686 A CN A2006800262686A CN 200680026268 A CN200680026268 A CN 200680026268A CN 101223220 A CN101223220 A CN 101223220A
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CN
China
Prior art keywords
composition
hydrogen fluorohydrocarbon
ethylene dichloride
mixture
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.)
Pending
Application number
CNA2006800262686A
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Chinese (zh)
Inventor
文森特·埃诺克斯
克里斯琴·G·M-G·德比恩
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Arkema France SA
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Arkema France SA
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Publication date
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Publication of CN101223220A publication Critical patent/CN101223220A/en
Pending legal-status Critical Current

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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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (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)

Abstract

The invention relates to a method of preparing polyurethane-moulded articles comprising a dense periphery (skin) having a certain hardness and a cellular central part and to foams prepared using same. The invention also relates to a premix comprising an isocyanate-reactive functional composition.

Description

The preparation method of polyurethane-moulded articles
The present invention relates to the method for the moulded parts that a kind of preparation made by urethane and the foams by this method preparation, wherein, this moulded parts has the fine and close outside surface (periphery) (epidermis) and the poriferous circular part (it is called the integral skin foams body) of particular stiffness.
The method of producing urethane foam is usually, in the presence of whipping agent, makes the reaction of organic multiple isocyanate and polyvalent alcohol or polyol blends.Chloro fluorocarbon compound (as trans chlorofluoromethane (CFC-11)) is to use the most frequent whipping agent.Yet these compounds are a kind of threats to ozonosphere.
Proposed to use the less compound of environmental hazard has been replaced Chlorofluorocarbons (CFCs).Thereby, at present, in production of polyurethane foams, having used 1,1-two chloro-1-fluoroethanes (HCFC 141b) are as whipping agent, to obtain to have the foams that thicken epidermis of high surface hardness.Yet HCFC 141 b are considered to environmentally harmful.
Using hydrogen fluorohydrocarbon (particularly 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,2,2-Tetrafluoroethane (HFC-134)) in the polyurethane integral skin foams body is produced is known (US5506275, US6010649) as whipping agent.
In addition, document EP 1345987 has been instructed in the polyurethane-moulded articles with fine and close outside surface and poriferous circular part is produced, and uses 1,1,1,3,3-3-pentafluorobutane (HFC 365mfc) and 1,1,1,2,3,3,3-heptafluoro-propane (HFC 227ea) is as whipping agent.
A theme of the present invention is the method with fine and close outside surface and poriferous circular moulded parts partly that a kind of production is made by urethane, this method comprise make organic multiple isocyanate composition and with the step of the multifunctional composition react of isocyanate reaction, be characterised in that the use anti-form-1, the mixture of 2-Ethylene Dichloride (TDCE) and at least a hydrogen fluorohydrocarbon is as whipping agent.
Preferably, this anti-form-1,2-Ethylene Dichloride are so that anti-form-1, and the weight ratio of 2-Ethylene Dichloride/hydrogen fluorohydrocarbon is that the amount of 4.5-20 is present in the blowing agent blends.
As the hydrogen fluorohydrocarbon, can mention 1,1,1,3 especially, 3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-3-pentafluorobutane (HFC 365mfc), 1,1,1,2,3,3,3-heptafluoro-propane (HFC 227ea) and 1,1,1,3,3,3-HFC-236fa or its mixture.
In the method according to the invention, preferably with respect to the weight of the composition of this and isocyanate reaction, use the anti-form-1 of 2-15wt%, the mixture of 2-Ethylene Dichloride and at least a hydrogen fluorohydrocarbon.Advantageously, with respect to the weight of the composition of this and isocyanate reaction, use the anti-form-1 of 4-15wt%, the mixture of 2-Ethylene Dichloride and at least a hydrogen fluorohydrocarbon.
The organic multiple isocyanate that is applicable to the inventive method comprises all those organic multiple isocyanates that are used to prepare the polyurethane integral skin foams body commonly known in the art, particularly aromatic polyisocyanate as with its 2,4 ', 2,2 ' and 4, '-diphenylmethane diisocyanate of 4 ' isomeric forms and composition thereof, '-diphenylmethane diisocyanate (MDI) has the mixture that is called " slightly " MDI or polymeric MDI (polymethylene polyphenylene polyisocyanates) oligopolymer greater than 2 isocyanate functionality with these, with its 2,4 and 2, tolylene diisocyanate of 6 isomeric forms and composition thereof, 1,5-naphthalene diisocyanate and 1, the diisocyanate based benzene of 4-(diisocyanatobenzene).Can mention other organic multiple isocyanate, particularly aliphatic diisocyanate such as isophorone diisocyanate, 1, the diisocyanate based hexane of 6-and 4,4 '-diisocyanate based dicyclohexyl methyl hydride.Also can use modified polyisocyanate, the prepolymer that for example contains urethane, urea, biuret, allophanate (allophonate), carbodiimide or uretdione (uretdione) group or have isocyanate end.
Be applicable to that the inventive method and multifunctional composition isocyanate reaction comprise that all commonly known in the artly are used to prepare those of polyurethane integral skin foams body.Being used to of particularly important prepares the polyvalent alcohol and the polyol blends for the hydroxy functionality of average hydroxyl exponential sum 2-3 with 20-200, particularly 20-50mg KOH/g of semirigid polyurethane integral skin foams body.For polyether glycol, molecular weight is preferably 2000-8000; For polyester polyol, it is preferably 2000-4000.The polyvalent alcohol that is particularly preferred for preparing rigid olyurethane integral skin foams body is the polyether glycol of the hydroxy functionality of the average hydroxyl exponential sum 2-6 with 300-1850, preferred 350-650mg KOH/g, preferred 3-4.Also can use the mixture of different polyvalent alcohols; The ratio of this mixture depends on the purposes of this integral skin foams body and the epidermal surface hardness of expectation.
Specifically, the polyether glycol that is applicable to the inventive method is the reaction product that alkylene oxides such as oxyethane and/or alkylene oxide (as oxyethane and/or propylene oxide) and per molecule contain the initiator of 2-8 reactive hydrogen atom.As initiator, can mention polyvalent alcohol especially, as ethylene glycol, propylene glycol, glycerol, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, sorbyl alcohol and sucrose; Polyamines is as quadrol, tolylene diamine (TDA), diaminodiphenyl-methane (DADPM) and polymethylene polyphenylene polyamines; And amino alcohol, as thanomin and diethanolamine and composition thereof.Those that suitable polyester polyol obtains for two pure and mild polyvalent alcohols with high functionality more by sufficient quantity and dicarboxylic acid or poly carboxylic acid (as hexanodioic acid, pentanedioic acid and phthalic acid) condensation.As the polyvalent alcohol of other type, can mention polythioether, polymeric amide, polyesteramide, polycarbonate, polyacetal, polyolefine and polysiloxane especially with terminal hydroxy group.
The amount of the polyisocyanate compound that is used to react and depend on the character of the polyurethane integral skin foams body that will prepare with the polyfunctional compound's of isocyanate reaction amount, and can easily determine by those skilled in the art.
Usually, the compound of water or other release of carbon dioxide and blowing agent blends of the present invention use jointly.When water exists as co-foaming agent, based on the weight of the compound of isocyanate reaction, the amount of used water is usually less than 1 weight %, preferably is lower than 0.5 weight %.
Except that polyisocyantates composition and with the multifunctional composition and whipping agent of isocyanate reaction, this reaction mixture can comprise the conventional additives that is incorporated in the polyurethane integral skin foams body production formula.Should comprise linking agent for example low molecular weight polyols such as ethylene glycol, 1 by optional additive, 4-butyleneglycol, glycerol, TriMethylolPropane(TMP) and trolamine, urethane catalyst is tin compound such as stannous octoate or dibutyl tin dilaurate for example, or tertiary amine is as 1,4-diaza-(2,2,2)-bicyclooctane, two (2-dimethylaminoethyl) ether, dimethylcyclohexylamine or triethylenediamine, tensio-active agent, fire retardant such as halogenated alkyl phosphate ester such as trichlorine propyl phosphate and filler such as carbon black.
About the enforcement of preparation integral skin foams body method of the present invention, can adopt known technology and conventional blending means.
Method of the present invention has Global warming influence still less, and it is favourable with respect to European F-gas (F-gas) bill in application that relates to discharging such as flexible foam.This enforcement also promotes because of better the flowing that viscosity degradation causes by the mixture that comprises two kinds of reactive component.
Of the present invention another themes as multifunctional composition, the anti-form-1 that comprises with isocyanate reaction, the pre-composition of 2-Ethylene Dichloride and at least a hydrogen fluorohydrocarbon.
In this pre-composition, anti-form-1, the weight ratio of 2-Ethylene Dichloride and hydrogen fluorohydrocarbon advantageously is 4.5-20/1.
With respect to 100 weight parts and multifunctional composition isocyanate reaction, anti-form-1 in this pre-composition, the amount of 2-Ethylene Dichloride and hydrogen fluorohydrocarbon or hydrogen fluorohydrocarbon class is expressed as the 0.1-15 weight part, preferred 0.3-12 weight part.
On the one hand, with respect to the pre-composition that only comprises as the hydrocarbon of whipping agent, pre-composition according to the present invention provides the advantage with much higher flash-point; On the other hand, with respect to the pre-composition that only comprises the hydrogen fluorohydrocarbon, the total cost of pre-composition of the present invention is lower.
In addition, this pre-composition has almost nil ozone depletion potential (ODP).
Of the present invention another themes as a kind of integral skin foams body that can obtain according to aforesaid method.
Experimental section
Described test is used based on the composition (I) of polyvalent alcohol and is implemented, and said composition comprises:
Bayfit  PU 10WF15 (polyvalent alcohol that Bayer sells) 55.7 weight parts
Daltocel  XF417 (polyvalent alcohol that Huntsman sells) 34.35 weight parts
Ethylene glycol 8.5 weight parts
Jeffcat  ZR 40 (catalyzer that Huntsman sells) 0.85 weight part
Jeffcat  ZR 22 (catalyzer that Huntsman sells) 0.2 weight part
Tegostab  B8715LF (tensio-active agent that Goldschmidt sells) 0.2 weight part
Dabco EG (catalyzer that Air Products sells) 0.1 weight part
Water 0.1 weight part
Embodiment 1
At room temperature in the described composition of 100 weight parts (I), add premixed 6 weight part anti-form-1s, hydrogen fluorohydrocarbon 245 fa of 2-Ethylene Dichloride and 1 weight part.
Acutely mix these components then to obtain composition (II).
Next, at room temperature the composition (II) of 100 weight parts is mixed with the Suprasec  2030 of 50 weight parts (polyisocyanates that Huntsman sells), then at room temperature, this mixture that obtains of part is reacted in container.According to ISO 845 standards, the foams that obtain have 190kg/m 3Density.
This mixture that obtains is poured in the aluminum die with another part, remains on then under the 40-45 ℃ of temperature.Seal this mould subsequently, and after reaction, obtain having 350kg/m according to ISO 845 standards 3The foams of total body density.In addition, this integral skin foams body has good quality.
Daltocel, Jeffcat and Suprasec are the trade mark of Huntsman.
Embodiment 2-7
In the composition (I) of 100 weight parts, add a large amount of whipping agents (embodiment 2-4,7) or have anti-form-1, the blowing agent blends of 2-Ethylene Dichloride (TDCE) makes the Suprasec  2030 of this mixture that obtains of 100 weight parts and 50 weight parts react under 40-45 ℃ of temperature in aluminum die then.
This simple list has been summed up the character of these foams that obtain.In addition, give independent every kind of whipping agent flash-point or as with the flash-point of TDCE mixture.
Embodiment 2 3 4 5 6 7
Whipping agent Skellysolve A HFC 245 fa Solkane 3,65/,227 87/13 weight ratios TDCE+ Solkane 365/227 TDCE/Solkane 85/15 weight ratio of embodiment 4 TDCE+HFC 245 fa 85/15 weight ratio Pentamethylene
Based on 100 weight part compositions (I), the amount of whipping agent (weight part) 4.5 5.5 9.5 12 12 8
ISO 845 density kg/m 3 383 364 368 392 388 390
DIN 53505 Shore A hardness 59 62 59 61 58 63
ISO 2439 penetration hardnesses, kg 20 20 19 17 22 20
ISO 1798 tensile strength, kPa 1251 1314 1223 1215 1402 1419
ISO 1798 elongations, % 49 54 49 46 63 55
DIN 53515 tear strengths, N/m 5909 5716 5359 5960 5516 5906
ISO1856 compression set under 70 ℃/50% deflection 10 13 12 12 10 9
DIN 53516 wearing and tearing, mg 440 487 521 406 529 356
The vision quality of epidermis Fabulous Good Good Good Good Fabulous
The flash-point of composition (II) -28 No flash-point No flash-point 30 50 ＜0

Claims (6)

1. the method for the moulded parts made by urethane of a production with fine and close outside surface and poriferous circular part, this method comprise make organic multiple isocyanate composition and with the step of the multifunctional composition react of isocyanate reaction, be characterised in that with anti-form-1 the mixture of 2-Ethylene Dichloride and at least a hydrogen fluorohydrocarbon is as friendly infusion.
2. the method for claim 1 is characterised in that described anti-form-1, and the weight ratio of 2-Ethylene Dichloride/hydrogen fluorohydrocarbon is 4.5-20.
3. claim 1 or 2 method are characterised in that described hydrogen fluorohydrocarbon is selected from 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-3-pentafluorobutane and 1,1,1,2,3,3,3-heptafluoro-propane or its mixture.
4. each method among the claim 1-3 is characterised in that also to make water as whipping agent.
5. comprise the multifunctional composition, the anti-form-1 that react with polyisocyanates, the pre-composition of 2-Ethylene Dichloride and at least a hydrogen fluorohydrocarbon is characterised in that described anti-form-1, and the weight ratio of 2-Ethylene Dichloride/hydrogen fluorohydrocarbon is 4.5-20.
6. foams that obtain according to each method among the claim 1-4.
CNA2006800262686A 2005-06-29 2006-05-18 Method of preparing polyurethane-moulded articles Pending CN101223220A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0506626A FR2887889B1 (en) 2005-06-29 2005-06-29 PROCESS FOR PREPARING MOLDED POLYURETHANE ARTICLES
FR0506626 2005-06-29

Publications (1)

Publication Number Publication Date
CN101223220A true CN101223220A (en) 2008-07-16

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CNA2006800262686A Pending CN101223220A (en) 2005-06-29 2006-05-18 Method of preparing polyurethane-moulded articles

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EP (1) EP1904562A1 (en)
JP (1) JP2008545036A (en)
CN (1) CN101223220A (en)
FR (1) FR2887889B1 (en)
WO (1) WO2007003726A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102421832A (en) * 2009-05-01 2012-04-18 阿科玛股份有限公司 Foamed polyvinylidene fluoride structure

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2899234B1 (en) * 2006-03-31 2017-02-17 Arkema EXPANSION AGENT COMPOSITION

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1425363A4 (en) * 2001-06-01 2004-10-20 Honeywell Int Inc Compositions of hydrofluorocarbons and trans-1,2-dichloroethylene
AU2003220343A1 (en) * 2002-03-14 2003-09-29 Honeywell International Inc. Compositions of pentafluoropropane
US7144926B2 (en) * 2003-01-02 2006-12-05 Arkema Inc. Blowing agent blends
US6793845B1 (en) * 2003-04-22 2004-09-21 Atofina Chemicals, Inc. Foam premixes having improved processability
US6764990B1 (en) * 2003-06-04 2004-07-20 Honeywell International Inc. Azeotrope-like compositions of pentafluoropropane, chloropropane and dichloroethylene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102421832A (en) * 2009-05-01 2012-04-18 阿科玛股份有限公司 Foamed polyvinylidene fluoride structure
CN102421832B (en) * 2009-05-01 2015-04-22 阿科玛股份有限公司 Foamed polyvinylidene fluoride structure

Also Published As

Publication number Publication date
EP1904562A1 (en) 2008-04-02
FR2887889B1 (en) 2007-08-31
JP2008545036A (en) 2008-12-11
WO2007003726A1 (en) 2007-01-11
FR2887889A1 (en) 2007-01-05

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Open date: 20080716