WO2004078768A2 - Isocyanate adducts - Google Patents

Isocyanate adducts Download PDF

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Publication number
WO2004078768A2
WO2004078768A2 PCT/GB2004/000916 GB2004000916W WO2004078768A2 WO 2004078768 A2 WO2004078768 A2 WO 2004078768A2 GB 2004000916 W GB2004000916 W GB 2004000916W WO 2004078768 A2 WO2004078768 A2 WO 2004078768A2
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WO
WIPO (PCT)
Prior art keywords
adduct
isocyanate
diisocyanate
carbon atoms
alkyl
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.)
Ceased
Application number
PCT/GB2004/000916
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French (fr)
Other versions
WO2004078768A3 (en
Inventor
Gary Woodward
Ranbir Singh Padda
Gleb Priimov
Kiran Patel
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.)
Albemarle Chemicals UK Ltd
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Albemarle Chemicals UK Ltd
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Publication of WO2004078768A2 publication Critical patent/WO2004078768A2/en
Publication of WO2004078768A3 publication Critical patent/WO2004078768A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds

Definitions

  • This invention relates to alkylene-bridged alkyl phosphonates and in particular to isocyanate adduets thereof, to the use of such adduets as, or in connection with, flame-retardants and to articles made flame-relardanl
  • Flame-relardants are incorporated into many products on the grounds of safely in order to control the spread of fire through the product.
  • Flame- retardants can, for example, act by causing rapid extinguishing of flames, or by making the product difficult to set alight.
  • flame-retardants have conventionally been used to treat fabrics, soft furnishings and the like, and have been incorporated inter alia into foams, paints and resins such as epoxy resins, many other applications are now being actively pursued, especially within the electronics, automotive, aerospace and construction industries .
  • Polyurethane foams are widely used for seating components of all kinds, especially seating components for automobiles. These foams are not inherently flame-retardant (indeed, the products of combustion of many polyurethane foams are very toxic) and therefore some flame-retardant ingredient is required.
  • the said European Patent Application 0 845 474 provided halogen-free oligomeric or polymeric alkylene-bridged alkyl phosphonates having the general formula (I) :
  • n is a whole number from 3 to 20;
  • R 1 and R 5 are each alkyl groups having from 1 to 6 carbon atoms;
  • R 2 and R 4 are each alkyl groups having from 2 to 10 carbon atoms;
  • R is an alkyl group having from 6 to 10 carbon atoms which acts as an "alkylene bridging" group.
  • the present invention provides an adduct of an isocyanate and a halogen-free oligomeric or polymeric phosphonate or organophosphate .
  • the present invention also provides the use of such an adduct as, or in connection with, a flame-retardant.
  • the present invention further provides an article comprising a flame- retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as hereinbefore described.
  • the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate in the presence of a catalyst.
  • organophosphonate is used to form the adduct
  • organophosphate is used, it is suitably of general formula (II) below:
  • R 1 is H or an alkyl group having from 2 to 10 carbon atoms
  • 2 is an alkyl or aryl group having from 2 to 10 carbon atoms
  • R 3 is an alkyl or aryl group having from 2 to 10 carbon atoms
  • R 7 is an alkyl or aryl group having from 2 to 10 carbon atoms
  • R 8 is an alkyl or aryl group having from 2 to 20 carbon atoms
  • n is a whole number from 1 to 20
  • the isocyanate may be selected from the group consisting of tolulene 2,4 isocyanate, tolulene 2,6 diisocyanate, 4,4' methylene diisocyanate, 2,4' methylene diphenyl diisocyantate, polymeric methylene diphenyl diisocyanate, j ⁇ -phenylene diisocyanate, naphthalene-1,5- diisocyanate, 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, « -butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl iso
  • the catalyst may preferably be selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionate, lead octoate, alkali-metal salts, calcium carbonate and ferric acetylacetonate.
  • a 5L glass oil -jacketed reactor was fitted with a reflux condenser, temperature probe, and an overhead mechanical stirrer. Under nitrogen, oligomeric butyl phosphonate (4200g) (as in Example 1 of EP 0 845 474) and slannous octoate (1.26g) were charged into the reactor at room temperature and heated to 100°C. MDI (a mixture of 2,4'- and 4,4'- diphenylmethane diisocyanate, 336g) was added to the reactor via a dropping funnel over 30 minutes. During the addition, the temperature in the reactor rose by 5-10°C. The reaction mixture was then heated to 110°C, and aged for twelve hours. The product obtained was a pale yellow viscous liquid (4488g, 99% yield).
  • Example 1 The product of the Example 1 (above) and the oligomeric butyl phosphonate as in Example 1 of EP 0 845 474, were each used as the flame retardant additive for the production of a high resilience polyurethane foam.
  • the quantities used and the results obtained are shown in Table 1 (below) .
  • Cream Time S 19 Foam Collapse Rise Time S 121 n/a Density Kg/m 3 25.10 n/a

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

An adduct of an isocyanate and a halogen-free oligomeric or polymeric alkyl phosphonate or organophosphate. The adduct may be made by coupling the isocyanate and the phosphonate or phosphate in the presence of a catalyst. Also disclosed is the use of the adduct as, or in connection with, a flame-retardant. The adduct can be used to render foam flame-retardant.

Description

ISOCYANATE ADDUCTS
This invention relates to alkylene-bridged alkyl phosphonates and in particular to isocyanate adduets thereof, to the use of such adduets as, or in connection with, flame-retardants and to articles made flame-relardanl
Flame-relardants are incorporated into many products on the grounds of safely in order to control the spread of fire through the product. Flame- retardants can, for example, act by causing rapid extinguishing of flames, or by making the product difficult to set alight. Whilst flame-retardants have conventionally been used to treat fabrics, soft furnishings and the like, and have been incorporated inter alia into foams, paints and resins such as epoxy resins, many other applications are now being actively pursued, especially within the electronics, automotive, aerospace and construction industries .
Polyurethane foams are widely used for seating components of all kinds, especially seating components for automobiles. These foams are not inherently flame-retardant (indeed, the products of combustion of many polyurethane foams are very toxic) and therefore some flame-retardant ingredient is required.
Many of the flame retardants conventionally used in connection with polyurethane foam seating components are found to have a tendency to migrate and/or volatilise from the foams with age. This tendency is particularly disadvantageous in the case of polyurethane foam components of automobile seating, where the migration and/or volatilisation of the flame relardanl leads to "fogging" of glass surfaces, such as windows and instrument panels. Accordingly, in our published European Patent Application 0 845 474, we disclose that certain halogen-free oligomeric or polymeric alkylene-bridged alkyl phosphonates confer acceptable flame-retardant properties on, inter alia, polyurethane foams.
The said European Patent Application 0 845 474 provided halogen-free oligomeric or polymeric alkylene-bridged alkyl phosphonates having the general formula (I) :
Figure imgf000003_0001
where n is a whole number from 3 to 20;
R1 and R5 (which may be the same or different) are each alkyl groups having from 1 to 6 carbon atoms;
R2 and R4 (which may be the same, or different) are each alkyl groups having from 2 to 10 carbon atoms;
and R is an alkyl group having from 6 to 10 carbon atoms which acts as an "alkylene bridging" group.
We have found that the addition to a polyurethane foam-forming reaction mixture of phosphonates according to formula (I) or phosphates according to formula (II) , below, can have a detrimental effect on the mechanical properties of polyurethane foam in some foam formulations (particularly in the case of high resilience foams) , or cause the foam to collapse during manufacturing. We have now found that this detrimental effect can be avoided by forming an isocyanate adduct of a phosphonate according to formula (I) or of a phosphate according to formula (II), below, prior to commencing the foam-forming reaction.
We have also found that it is possible to enhance the low-fogging properties of these alkylene-bridged alkyl phosphonates, when used as flame-retardants for polyurethane foams.
Accordingly, the present invention provides an adduct of an isocyanate and a halogen-free oligomeric or polymeric phosphonate or organophosphate .
The present invention also provides the use of such an adduct as, or in connection with, a flame-retardant.
The present invention further provides an article comprising a flame- retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as hereinbefore described.
Suitably, the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate in the presence of a catalyst.
Where an organophosphonate is used to form the adduct, it is suitably of general formula (I) above. Where an organophosphate is used, it is suitably of general formula (II) below:
Figure imgf000004_0001
wherein R1 is H or an alkyl group having from 2 to 10 carbon atoms;
2 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R3 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R7 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R8 is an alkyl or aryl group having from 2 to 20 carbon atoms;
and n is a whole number from 1 to 20
Suitably, the isocyanate may be selected from the group consisting of tolulene 2,4 isocyanate, tolulene 2,6 diisocyanate, 4,4' methylene diisocyanate, 2,4' methylene diphenyl diisocyantate, polymeric methylene diphenyl diisocyanate, jø-phenylene diisocyanate, naphthalene-1,5- diisocyanate, 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, « -butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, and -toluenesulfonyl isocyanate.
The catalyst may preferably be selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionate, lead octoate, alkali-metal salts, calcium carbonate and ferric acetylacetonate.
The invention will now be illustrated with reference to the following example. Example 1
A 5L glass oil -jacketed reactor was fitted with a reflux condenser, temperature probe, and an overhead mechanical stirrer. Under nitrogen, oligomeric butyl phosphonate (4200g) (as in Example 1 of EP 0 845 474) and slannous octoate (1.26g) were charged into the reactor at room temperature and heated to 100°C. MDI (a mixture of 2,4'- and 4,4'- diphenylmethane diisocyanate, 336g) was added to the reactor via a dropping funnel over 30 minutes. During the addition, the temperature in the reactor rose by 5-10°C. The reaction mixture was then heated to 110°C, and aged for twelve hours. The product obtained was a pale yellow viscous liquid (4488g, 99% yield).
Example 2
The product of the Example 1 (above) and the oligomeric butyl phosphonate as in Example 1 of EP 0 845 474, were each used as the flame retardant additive for the production of a high resilience polyurethane foam. The quantities used and the results obtained are shown in Table 1 (below) .
Table 1
High Resilience Foam Phosphonate of Control Formulations Invention Phosphonate
Standard High Resilience 100.00 100.00 Polymeric Polyol (OH value = 30-34) Water Parts .45 45
(a) Catalyst I Parts .10 10
(b) Catalyst II Parts .06 06 Diethanolamine Parts .10 10
(c) Surfactant Parts .40 0 40 Stannous Octoate Parts .21 0 21 Toluene Di-isocyanate Index 108 108
(d) Phosphonate of Invention Parts ^.00
(e) Control Phosphonate Parts 9.00
Cream Time S 19 Foam Collapse Rise Time S 121 n/a Density Kg/m3 25.10 n/a
Indicative Federal Motor Vehicle Safety Standard 302 Performance
Burn Length Mm n/a
Burn Time n/a
Rating Self -Extinguishing n/a
Notes to Table 1:
(a) An amine catalyst comprising 33% diaza-bicyclo-octane and 67% dipropylene glycol, available as DABCO*33LV
(b) An amine catalyst comprising 70% bis(2-dimethylaminoethyl) ether and 30% dipropylene glycol, available as NIAX*A1
(c) A polyether-modified polysiloxane, available as TEGOSTAB*B8681
(d) The product of Example 1 i.e. oligomeric butyl phosphonate/isocyanate adduct.
(e) the oligomeric butyl phosphonate as in EP 0 845 474, Example 1. *DABCO, NIAX and TEGOSTAB are Registered Trade Marks.

Claims

1. An adduct of an isocyanate and ; a halogen-free oligomeric or polymeric alkyl phosphonate or organophos'
2. An adduct as claimed in claim 1 in which the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate or phosphate in the presence of a catalyst.
3. An adduct as claimed in any one of the preceding claims in which an organophosphonate is used to form the adduct and is of the general formula (I):
Figure imgf000008_0001
where n is a whole number from 3 to 20;
R1 and R5 (which may be the same, or different) are each alkyl groups having form 1 to 6 carbon atoms;
R2 and R4 (which may be the same or different) are each alkyl groups having from 2 to 10 carbon atoms; and
R3 is an alkyl group having from 6 to 10 carbon atoms, which acts as an "alkylene bridging" group.
4. An adduct as claimed in either of claims 1 or 2, in which an organophosphate is used to form the adduct and is of the general formula (II):
Figure imgf000009_0001
wherein n is a whole number from 1 to 20;
R1 is H or an alkyl or aryl group having from 2 to 10 carbon atoms;
R2 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R3 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R7 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R8 is an alkyl or aryl group having from 2 to 20 carbon atoms.
5. An adduct as claimed in any one of the preceding claims in which the isocyanate is selected from the group consisting of; tolulene 2,4-diisocyanate, tolulene 2,6-diisocyanate, 4,4' -methylene diisocyanate, 2, 4 '-methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, ?-phenylene diisocyanate, naphthalene- 1,5 -diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, ra-butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, and j9-toluenesulfonyl isocyanate.
6. An adduct as claimed in any one of the preceding claims in which the catalyst is selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionale, lead octoate, alkali-metal salts, calcium carbonate and ferric acelylacelonate.
7. The use of an adduct as claimed in any one of claims 1 to 6 as, or in connection with, a flame-retardant.
8. An article comprising a flame-retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as claimed in any one of claims 1 to 6.
9. An adduct substantially as described herein with reference to the examples.
PCT/GB2004/000916 2003-03-04 2004-03-04 Isocyanate adducts Ceased WO2004078768A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0304831A GB0304831D0 (en) 2003-03-04 2003-03-04 Isocyanate adducts
GB0304831.1 2003-03-04

Publications (2)

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WO2004078768A2 true WO2004078768A2 (en) 2004-09-16
WO2004078768A3 WO2004078768A3 (en) 2004-12-02

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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0762225A (en) * 1993-08-25 1995-03-07 Akzo Kashima Ltd Flame retardant composition for flexible polyurethane foam
GB9623584D0 (en) * 1996-11-13 1997-01-08 Albright & Wilson Uk Ltd Alkylene-bridged alkyl phosphonates
US5880243A (en) * 1997-04-23 1999-03-09 Weyerhaeuser Company Fire retardant composite products of cellulose impregnated with isocyanate compositions

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WO2004078768A3 (en) 2004-12-02

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