WO2014165426A1 - Systèmes ignifuges - Google Patents

Systèmes ignifuges Download PDF

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Publication number
WO2014165426A1
WO2014165426A1 PCT/US2014/032317 US2014032317W WO2014165426A1 WO 2014165426 A1 WO2014165426 A1 WO 2014165426A1 US 2014032317 W US2014032317 W US 2014032317W WO 2014165426 A1 WO2014165426 A1 WO 2014165426A1
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WO
WIPO (PCT)
Prior art keywords
flame retardant
amine
target material
adduct
retardant system
Prior art date
Application number
PCT/US2014/032317
Other languages
English (en)
Inventor
Nikolas Kaprinidis
Rajendra SUNDAR
Guillermo MARQUEZ
Klaus Breuer
Michael Siemer
Juergen Frank
Heinz Herbst
Original Assignee
Basf Corporation
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 Basf Corporation filed Critical Basf Corporation
Publication of WO2014165426A1 publication Critical patent/WO2014165426A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present disclosure relates to non-halogenated reactive flame retardant systems, specifically systems which incorporate vinyl phosphonic acid (VPA) or vinyl phosphonic acid dimethyl ester (VPSDME) or derivatives thereof and amine adducts, into, e.g., epoxy resins, polyurethanes, unsaturated polyesters, polyamides, polycarboxylates, polyurea systems and polyurea/polyurethane hybrid systems, etc. These systems exhibit flame retardant efficiency and quality under specific flame retardant protocols.
  • VPA vinyl phosphonic acid
  • VPSDME vinyl phosphonic acid dimethyl ester
  • the flame retardant adduct includes vinyl phosphonic acid (VPA), vinyl phosphonic acid dimethyl ester (VPSDME), or a derivative thereof, and an amine.
  • the flame retardant adduct is crosslinked with the target material to form the flame retardant system.
  • the flame retardant system disclosed herein is a non-halogenated reactive system.
  • the flame retardant component used in the system described herein i.e., vinyl phosphonic acid (VPA), vinyl phosphonic acid dimethyl ester (VPSDME), and/or derivatives thereof (e.g., dialkyl or diarylesters), contain phosphor.
  • Phosphor containing materials are known to have fire retardant properties.
  • the use of phosphor in additives has been limited, as phosphorous-containing additives tend to have poor stability and a reduced tendency for polymerization.
  • amines e.g., diamines, alkanolamines
  • the amine groups of the adduct are capable of crosslinking with a target material.
  • suitable target materials include, e.g., epoxies, polyesters, polyurethanes, polyamides, polycarboxylates, polyurea systems, and polyurea/polyurethane hybrid systems, etc., or cellulosic materials.
  • the crosslinking between the amine groups and the target material permanently, and thus reactively, incorporates the VPA, or the VPSDME, or the derivative thereof, into the material, making the entire system flame retardant due to the phosphor containing portion of the adduct incorporated therein.
  • VPA-amine, or VPSDME-amine, or derivative-amine adducts disclosed herein have numerous benefits over brominated flame retardants, as well as conventional phosphor-containing additives.
  • the VPA- amine, or VPSDME-amine, or derivative-amine adducts used in the present disclosure i) are non-halogenated, ii) have an effective fire retardant mechanism due to their high phosphorous content, iii) exhibit low toxicity, iv) are easy to handle as a liquid form, v) do not migrate or vaporize, and vi) have low volatility.
  • VPA or VPSDME, or a derivative thereof (e.g., dialkyls or diarylesters), is reacted with an amine through nucleophilic addition (i.e., Michael Addition).
  • nucleophilic addition i.e., Michael Addition
  • This example of the adduct may be formed by the nucleophilic reaction of
  • VPSDME with an alkanolamine, namely diethanolamine.
  • the amine is a secondary amine or a primary amine.
  • the amine may be a mono- or poly-functional primary amine.
  • the amine is a diamine (e.g., a primary diamine).
  • Diamines which may be used in the examples disclosed herein include, e.g., those of the formula: where R is Ci -C2o- Some specific examples of suitable diamines include
  • the R is C 6 -C 2 o and the diamine is an aromatic diamine, such as m- or p-phenylenediamine.
  • the R is C7-C20 and the diamine is an arylaliphatic diamine, such as m- or p-xylylenediamine.
  • Examples of the amine disclosed herein, including any of the secondary or primary diamines, has a weight average molecular weight of less than about 100, less than about 90, less than about 80, less than about 70, less than about 60, less than about 50, less than about 40, less than about 30, less than about 20, or less than about 10.
  • the amine is an alkanolamine (e.g., a primary alkanolamine).
  • alkanolamines that may be used in the examples disclosed herein include, e.g., those of the formula: R a R where R a , R b and R c are independently selected from H, Ci-alkyl through C 5 -alkyl, and Ci-hydroxyalkyl through Cio-hydroxyalkyl, as long as any one (or more) of R a , R b or R c is a hydroxyalkyl.
  • suitable alkanolamines include
  • diethanolamine diisopropanolamine
  • methyldiethanolamine methyldiethanolamine
  • butyldiethanolamine methyldiisopropanolamine
  • the alkanolamine is selected from water-soluble, linear or branched aliphatic compounds which include, per molecule, at least two functional amino groups, e.g.,
  • R 2 R wherein A is any C2-C18 -alkylene, which may be unsubstituted or substituted by one or more groups selected independently from alkyls, hydroxyalkyls, cycloalkyls, and OH, and wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, hydroxyalkyls, alkyls, and cycloalkyls, as long as any one (or more) of R 1 , R 2 , R 3 or R 4 is the hydroxyalkyl.
  • alkanolamines have a weight average molecular weight of less than about 100, less than about 90, less than about 80, less than about 70, less than about 60, less than about 50, less than about 40, less than about 30, less than about 20, or less than about 10.
  • melamine may be used as the amine-containing compound in the adduct.
  • the amine may have a weight average molecular weight ranging from 100 to 150.
  • the molar ratio of the VPA or the VPSDME or the derivative thereof to any examples of the amine disclosed herein (e.g., primary, secondary, diamine, and/or alkanolamine, etc.) in the adduct is from about 1 : 10 to about 10:1 ; from about 1 :9 to about 9:1 ; from about 1 :8 to about 8:1 ; from about 1 :7 to about 7:1 ; from about 1 :6 to about 6:1 ; from about 1 :5 to about 5:1 ; from about 1 :4 to about 4:1 ; from about 1 :3 to about 3:1 ; from about 1 :
  • the ratio of VPSDME or the derivative thereof to any example of the diamine may range from about 1 : 10 to about 10:1 or from about 1 :2 to about 2:1 .
  • the ratio of VPSDME or the derivative thereof to any example of the alkanolamine may range from about 1 : 10 to about 10:1 or from about 1 :2 to about 2:1 .
  • any examples of the resulting VPA- amine, or VSPDME-amine, or derivative-amine adduct may then be incorporated into the target material to form the flame retardant system.
  • the target material may be selected from epoxy resins, polyurethanes, unsaturated polyesters, polyamides, polycarboxylates, polyurea systems, and polyurea/polyurethane hybrid systems, etc. or cellulosic materials.
  • the adduct As a result of the incorporation of the adduct into the target material, the material itself exhibits flame retardant properties.
  • the desired target material is dissolved in a solvent to form a target solution.
  • the desired epoxy may be mixed with methoxypropanol or some other suitable solvent.
  • the target solution may be prepared at any suitable temperature, which depends, at least in part, on the target material used. In an example utilizing an epoxy resin, the dissolution temperature may be about 80°C. Dissolution may be allowed to occur until a homogeneous solution is obtained (e.g., as observed by the human eye).
  • multiple target solutions of different target materials may be made and then combined together.
  • two epoxy solutions may be prepared and combined. For example, a first solution of a cresol novolac resin (an epoxy) may be prepared in methoxypropanol, and a second solution of a phenol-formaldehyde novolac resin (another epoxy) may be prepared in
  • methoxypropanol may then be combined together and homogenized. Homogenization may take place for any suitable time and at any suitable temperature. In the previous example involving the two epoxy solutions, homogenization may occur for about 30 minutes at about 60°C.
  • VSPDME-amine, or derivative-amine adduct may be added to the target solution, or the target solution may be added to the VPA- amine, or VSPDME-amine, or derivative-amine adduct.
  • the amount of the VPA- amine, or VSPDME-amine, or derivative-amine adduct added may range anywhere from about 5% to about 20% based upon the total weight of the target material solution. In an example, the amount of the VPA- amine, or VSPDME-amine, or derivative-amine adduct is about 16% of the target material solution. In some of the examples disclosed herein, it may be desirable to use the VPA- amine, or VSPDME-amine, or derivative-amine adduct without any other flame retardant additives.
  • Homogenization may then be performed for at least 15 minutes, or until the adduct is dissolved.
  • a catalyst may also be mixed in.
  • VPA-amine or VSPDME-amine, or derivative- amine adduct crosslinks with the target material to form the flame retardant system. Examples of the flame retardant system will now be described.
  • the VPA-amine, or VSPDME-amine, or derivative-amine adduct may be added to, e.g., epoxy to create a flame/fire retardant epoxy system.
  • suitable epoxies include an epoxy cresol novolac resin (e.g., ARALDITE® ECN 1280 from Huntsman) and/or a phenol- formaldehyde resin (e.g., DURITE® SD-1702 from Momentive Specialty
  • the VPA-amine, or VSPDME-amine, or derivative- amine adduct may be added to, e.g., an isocyanate to create a flame/fire retardant polyurethane system.
  • suitable isocyanates include 2,4-Toluene diisocyanate (TDI); 2,6-Toluene diisocyanate (TDI); mixtures of 2,4- and 2,6- Toluene diisocyanate; 2,2-Diphenylmethane diisocyanate; 2,4-Diphenylmethane diisocyanate; 4,4-Diphenylmethane diisocyanate (MDI, i.e., methylene-4,4'- diphenyl diisocyanate); mixtures of 2,2-, 2,4-, and 4,4- Diphenylmethane
  • TDI 2,4-Toluene diisocyanate
  • TDI 2,6-Toluene diisocyanate
  • diisocyanate polymeric forms of 2,2-, 2,4-, or 4,4- Diphenylmethane diisocyanate (PMDI) and mixtures thereof; 1 ,6-Hexane diisocyanate (HDI, i.e., hexamethylene diisocyanate); 1 -lsocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI, i.e., isophorone diisocyanate); 1 ,5-Naphthalene diisocyanate (NDI); 1 ,4-Phenylene diisocyanate (PDI); and 4,4,4-Triphenylenemethane tri isocyanate.
  • HDI i.e., hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • NDI naphthalene diisocyanate
  • PDI ,4-Phenylene diisocyanate
  • the VPA-amine, or VSPDME-amine, or derivative-amine adduct may be reacted with the isocyanate to form a prepolymer.
  • One example of the prepolymer is formed from the reaction of MDI with a VSPDME-amine adduct.
  • the VSPDME-amine adduct may be formed using VSPDME and 1 ,3- diaminopropane, and then the VSPDME-amine adduct may be reacted with MDI to form the following prepolymer:
  • n ranges from 2 to 500.
  • Another example of the prepolymer is formed from the reaction of PMDI with a VSPDME-amine adduct.
  • the prepolymer is formed from the reaction of PMDI with a VSPDME-amine adduct.
  • VSPDME-amine adduct may be formed using VSPDME and 1 ,3-diaminopropane, and then the VSPDME-amine adduct may be reacted with PMDI to form the followin prepolymer:
  • n and n' each range from 2 to 500.
  • any of the adducts disclosed herein and any of the isocyanates disclosed herein may be used to form the prepolymer.
  • the prepolymer may then be reacted with a polyol blend to form a flame/fire retardant polyurethane molecule.
  • the polyol blend may include polyetherols with 1 to 4 reactive hydroxyl groups and a weight average molecular weight ranging from about 50 to about 3000, alone or in combination with any of chain extenders, cross linkers, blowing agents, amine catalysts, organometallic catalysts containing metal(s) from groups 1 1 , 12, 14, and/or 15 of the periodic table, antioxidants, UV stabilizers, organic pigments and/or dyes, inorganic pigments, dispersing agents, surfactants, water scavengers, heat stabilizers, or combinations thereof.
  • the polyol blend may include polyesterols with 1 to 4 reactive hydroxyl groups and a weight average molecular weight ranging from 50 and 3000, alone or in combination with any of chain extenders, cross linkers, blowing agents, amine catalysts, organometallic catalysts containing metal(s) from groups 1 1 , 12, 14, and/or 15 of the periodic table, antioxidants, UV stabilizers, organic pigments and/or dyes, inorganic pigments, dispersing agents, surfactants, water scavengers, heat stabilizers, or combinations thereof.
  • the polyol blend may include mixtures of the above listed components (e.g., a combination of the polyetherol(s) and polyesterol(s), with or without any combination of the other components).
  • reaction of the prepolymer and the polyol blend will form a fire/flame retardant polyurethane having the VPA- amine, or VSPDME- amine, or derivative-amine adduct incorporated therein.
  • the VPA- amine, or VSPDME-amine, or derivative-amine adduct may be added to, e.g., unsaturated acids or cellulosic fibers to create a flame/fire retardant polyester system or a flame/fire retardant cellulosic system, respectively.
  • the amine used in the adduct is any example of the alkanolamine.
  • Respective stock solutions of ARALDITE® ECN 1280 (85 % w/w, Sol. 1 ) and Bakelite PF 0790 (50 % w/w, Sol. 2) were prepared in methoxypropanol (MP). Each of the stock solutions was dissolved at 80°C until homogeneous solutions were obtained.
  • the comparative sample flame retardant additives were 9,10-dihydro-9- oxa-10-phosphaphenanthrene-10-oxide (DOPO), or a combination of DOPO and MARTINAL® OL-104 WE (aluminum hydroxide, Albemarle Corp.).
  • DOPO 9,10-dihydro-9- oxa-10-phosphaphenanthrene-10-oxide
  • MARTINAL® OL-104 WE aluminum hydroxide, Albemarle Corp.
  • the comparative flame retardant target solutions and the sample flame retardant target solution compositions are shown in Table 1 .
  • a brush was used to impregnate glass fiber wovens (type 7626) with the comparative flame retardant target solutions (Comp. 1 and Comp. 2) and with the sample flame retardant target solution (Sample).
  • the respective impregnated wovens were pre-cured in an explosion-proof oven at about 170°C for about 120 seconds.
  • the resulting prepregs were into pieces 15.5 cm x 12 cm, lengthwise and crosswise. Five prepreg layers of each type were respectively pressed into a mold, alternately lengthwise and crosswise, and were pressed using 2
  • PTFE polytetrafluoroethylene
  • prepreg comparative samples Comp. 1 and Comp. 2 prepregs
  • prepreg samples Sample prepregs
  • the prepreg comparative samples and prepreg samples were exposed to flame retardant testing, using UL 94 (a plastics flammability standard released by Underwriters Laboratories of the USA).
  • UL 94 a plastics flammability standard released by Underwriters Laboratories of the USA.
  • ranges provided herein include the stated range and any value or sub-range within the stated range.
  • a range from about 5% to about 20% should be interpreted to include not only the explicitly recited limits of about 5% to about 20%, but also to include individual values, such as 6%, 7.5%, 16%, etc., and sub-ranges, such as from about 10% to about 18%, from about 8% to about 15%, etc.
  • sub-ranges such as from about 10% to about 18%, from about 8% to about 15%, etc.
  • “about” is utilized to describe a value, this is meant to encompass minor variations (up to +/- 10%) from the stated value.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

La présente invention porte sur des systèmes ignifuges qui comprennent un produit d'addition ignifugeant et un matériau cible. Le produit d'addition ignifugeant comprend de l'acide vinylphosphonique (VPA), de l'ester diméthylique de l'acide vinylphosphonique (VPSDME) ou un dérivé de ceux-ci et une amine. Le produit d'addition ignifugeant est réticulé avec le matériau cible pour former le système ignifuge.
PCT/US2014/032317 2013-04-01 2014-03-31 Systèmes ignifuges WO2014165426A1 (fr)

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US201361806973P 2013-04-01 2013-04-01
US61/806,973 2013-04-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10988844B2 (en) 2015-01-20 2021-04-27 Basf Coatings Gmbh Process for producing flexible organic-inorganic laminates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020119317A1 (en) * 1999-12-13 2002-08-29 Jospeh Gan Flame retardant phosphorus element-containing epoxy resin compositions
US20130059952A1 (en) * 2010-01-15 2013-03-07 Basf Se Phospho-substituted alkoxyamine compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020119317A1 (en) * 1999-12-13 2002-08-29 Jospeh Gan Flame retardant phosphorus element-containing epoxy resin compositions
US20130059952A1 (en) * 2010-01-15 2013-03-07 Basf Se Phospho-substituted alkoxyamine compounds

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LAOUTID, FOUAD ET AL.: "New prospects in flame retardant polymer materials: from fundamentals to nanocomposites.", MATERIALS SCIENCE AND ENGINEERING: R: REPORTS., vol. 63, no. 3, 2009, pages 100 - 125 *
LU , SHUI- YU ET AL.: "Recent developments in the chemistry of halogen-free flame retardant polymers.", PROGRESS IN POLYMER SCIENCE ., vol. 27, no. 8, 2002, pages 1661 - 1712 *
NGUYEN, CONGTRANH ET AL.: "Thermal stabilities and flame retardancies of nitrogen-phosphorus flame retardants based on bisphosphoramidates.", POLYMER DEGRADATION AND STABILITY., vol. 93, no. 6, 2008, pages 1037 - 1043 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10988844B2 (en) 2015-01-20 2021-04-27 Basf Coatings Gmbh Process for producing flexible organic-inorganic laminates

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