U.S. patent application number 14/046741 was filed with the patent office on 2014-06-26 for use of low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates as flame retardants in polyurethane or polyisocyanurate foams.
The applicant listed for this patent is Hickory Springs Manufacturing Company. Invention is credited to Jeffrey T. Aplin, Hoover Chew, William J. Layman, JR., Arthurt G. Mack, Techen Tsao.
Application Number | 20140179811 14/046741 |
Document ID | / |
Family ID | 38481934 |
Filed Date | 2014-06-26 |
United States Patent
Application |
20140179811 |
Kind Code |
A1 |
Layman, JR.; William J. ; et
al. |
June 26, 2014 |
USE OF LOW TRIPHENYLPHOSPHATE, HIGH PHOSPHOROUS CONTENT ISOPROPYL
PHENYL PHOSPHATES AS FLAME RETARDANTS IN POLYURETHANE OR
POLYISOCYANURATE FOAMS
Abstract
The present invention relates to the use of low triphenyl
phosphate, high phosphorous content aryl phosphates with high ortho
alkylation as flame retardants in polyurethane or polyisocyanurate
foams or polyurethane or polyisocyanurate foam formulations.
Inventors: |
Layman, JR.; William J.;
(Baton Rouge, LA) ; Mack; Arthurt G.;
(Prairieville, LA) ; Tsao; Techen; (Baton Rouge,
LA) ; Aplin; Jeffrey T.; (Pasadena, TX) ;
Chew; Hoover; (Summerville, SC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hickory Springs Manufacturing Company |
Hickory |
NC |
US |
|
|
Family ID: |
38481934 |
Appl. No.: |
14/046741 |
Filed: |
October 4, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12593379 |
Sep 28, 2009 |
8575225 |
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PCT/US08/57402 |
Mar 19, 2008 |
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14046741 |
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60908287 |
Mar 27, 2007 |
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Current U.S.
Class: |
521/107 |
Current CPC
Class: |
C08K 5/523 20130101;
C08J 9/0038 20130101; C08K 2201/014 20130101; C08G 2101/0025
20130101; C08G 2101/0008 20130101; C08K 5/521 20130101; C08J
2375/04 20130101; C08L 75/00 20130101; C08K 5/523 20130101 |
Class at
Publication: |
521/107 |
International
Class: |
C08K 5/521 20060101
C08K005/521 |
Claims
1. (canceled)
2. (canceled)
3. (canceled)
4. The polyurethane or polyisocyanurate foam formulation according
to claim 21 wherein said polyurethane or polyisocyanurate foam
formulation is a flexible polyurethane foam formulation or a rigid
polyurethane foam formulation.
5. The polyurethane or polyisocyanurate foam formulation according
to claim 21 wherein said polyurethane or polyisocyanurate foam or
polyurethane or polyisocyanurate foam formulation further contains
at least one additional component selected from blowing agents,
surfactants, antioxidants, diluents, and the like.
6. The polyurethane or polyisocyanurate foam formulation according
to claim 5 wherein said alkylated triaryl phosphate ester has an
organic phosphorous content in the range of from about 8 to about
8.4 wt %, based on the total weight of the alkylated triaryl
phosphate ester.
7. The polyurethane or polyisocyanurate foam formulation according
to claim 22 wherein said alkylated triaryl phosphate ester contains
greater than about 90 wt % monalkylphenyl diphenyl phosphates,
based on the total weight of the alkylated triaryl phosphate
ester.
8. The polyurethane or polyisocyanurate foam formulation according
to claim 21 wherein said alkylated triaryl phosphate ester contains
less than about 0.5 wt % TPP based on the total weight of the
alkylated triaryl phosphate ester.
9. The polyurethane or polyisocyanurate foam formulation according
to claim 21 wherein said alkylated triaryl phosphate is made by a
process comprising: a. reacting an alkylated phenol stream
comprising less than about 1 mole % phenol and up to about 25 mole
% dialkyl phenol, both based on the total weight of the alkylated
phenol, with POCl3 in the presence of a first catalyst under first
reaction conditions including temperatures ranging from about
80.degree. C. to about 210.degree. C. thereby producing a first
reaction product comprising greater than about 75 mole %
monoalkylated phenyl-dichloro phosphates, based on the total moles
of the first reaction product; and b. reacting the first reaction
product with an alcohol selected from aryl alcohols, alkyl
alcohols, alkylated aryl alcohols, and mixtures thereof in the
presence of a second catalyst under second reaction conditions
including temperatures ranging from about 90.degree. C. to about
260.degree. C. thereby producing' an alkylated triaryl phosphate
ester; or by a process comprising: a. reacting an alkylated phenol
stream comprising less than about 1 mole % phenol and up to about
25 mole % dialkyl phenol, both based on the total weight of the
alkylated phenol, with POCl3 in the presence of a first catalyst
under first reaction conditions including temperatures ranging from
about 80.degree. C. to about 210.degree. C. thereby producing a
first reaction product comprising greater than about 75 mole %
monoalkylated phenyl-dichloro phosphates, based on the total moles
of the first reaction product; and b. sequentially reacting the
first reaction product with more than one alcohol selected from
aryl alcohols, alkyl alcohols, alkylated aryl alcohols, and
mixtures thereof in the presence of a second catalyst under second
reaction conditions including temperatures ranging from about
70.degree. C. to about 260.degree. C. thereby producing an
alkylated triaryl phosphate ester.
10. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein the alkylated phenol stream comprises
ortho-isopropylphenol (OIP), meta-isopropylphenol (MIP), and
para-isopropylphenol (PIP. constituents.
11. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein the alkylated phenol stream comprises in the
range of from about 64 to about 68 wt. % OIP, in the range of from
about 0.5 to about 2.5 wt. % MIP, and in the range of from about 31
to about 35 wt. % PIP, all based on the total weight of the
alkylated phenol.
12. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein excess POCl3 is stripped from the first reaction
product prior to the first reaction product being reacted with the
alcohol in the presence of the second catalyst.
13. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein said first reaction conditions include the
substantial absence of oxygen.
14. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein a diluent selected from 1,4-dioxane and toluene
is added along with the POCl3, first catalyst, and alkylated
phenol.
15. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein the first reaction product comprises greater
than about 75 mole % monoalkylated phenyl dichloro phosphates,
based on the total moles of the first reaction product excluding
unreacted POCl3, in the range of from about 70 to about 99.9 mole %
monoalkylated phenyl-dichloro phosphates and in the range of from
about 0.1 mole % but less than 30 mole %, bis-(monoalkylated.
phenyl-chloro phosphates, both based on the total moles of the
first reaction product excluding unreacted POCl3.
16. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein the alcohol is selected from decanol, dodecanol,
monoisopropylated phenols, phenol, or mixtures thereof.
17. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein i. the alcohol is added to the first reaction
product to which the second catalyst has already been introduced;
or ii. a mixture of the second catalyst and alcohol are introduced
into the first reaction product.
18. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein said process further comprises: a. adding to the
alkylated aryl phosphate ester an additional amount of alcohol
selected from monoisopropylated phenols, diisopropylated phenols,
phenol, and mixtures thereof, and/or an additional amount of second
catalyst to the alkylated triaryl phosphate ester thus producing an
alcohol-rich alkylated phenyl phosphate product containing excess
alcohol; b. recovering said alcohol-rich alkylated phenyl phosphate
product; and c. removing at least a portion of the excess alcohol
from the alcohol-rich alkylated phenyl phosphate ester product;
wherein the excess alcohol is removed by a method selected from
phase separation stripping, distillation, and mixtures thereof.
19. The polyurethane or polyisocyanurate foam formulation according
to claim 9 wherein said alkylated triaryl phosphate ester is an
isopropylphenyl diphenyl phosphate ester selected from: a.
isopropylphenyl diphenyl phosphate esters comprising in the range
of from about 66 to 100 wt % 2-isopropylphenyl phosphate (2-IPP),
in the range of from about 0.1 to 4 wt % 3-isopropylphenyl
phosphate (3-IPP), and in the range of from about 0.1 to 40 wt %
4-isopropylphenyl phosphate (4-IPP); b. isopropylphenyl diphenyl
phosphate esters comprising in the range of about 63 to about 68
wt. % 2-IPP, in the range of from about 0.5 to about 2.5 wt. %
3-IPP and in the range of from about 30.5 to about 36.5 wt. %
4-IPP; or c. isopropylphenyl diphenyl phosphate esters comprising
about 66 wt. % 2-IPP, about 1 wt. % 3-IPP and about 33 wt. % 4-IPP,
wherein all wt. % are based on the total weight of the
isopropylphenyl diphenyl phosphate ester.
20. (canceled)
21. A polyurethane or polyisocyanurate foam composition comprising
at least one isocyanate, polyol, or combination thereof, and a
flame retarding amount of an alkylated triaryl phosphate ester,
wherein said alkylated triaryl phosphate ester contains at least
one of (a) monoalkylphenyl diphenyl phosphates, (b.
di-(alkylphenyl. phenyl phosphates, (c. dialkylphenyl diphenyl
phosphates; (d. trialkylphenyl phosphates; (e. alkylphenyl
dialkylphenyl pphenyl phosphates, and less than about 1 wt %
triphenyl phosphate ("TPP". and in the range of from about 5 to
about 10 wt % organic phosphoous content, wherein the alkyl
moieties of the alkylated phenyl phosphates and TPP are selected
from methyl, ethyl, n-propopyl, isopropyl, isobutyl,
tertiary-butyl, isoamyl and tertiary-amyl groups, all based on the
total weight of the alkylated triaryl phosphate ester.
22. The polyurethane or polyisocyanurate foam composition according
to claim 21 wherein the alkylated triaryl phosphate ester contains
greater than about 75 wt % monalkylphenyl diphenyl phospates.
23. A molded or extruded article comprising the polyurethane or
polyisocyanurate foam composition of claim 21.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the use of low triphenyl
phosphate, high phosphorous content, aryl phosphates, with high
ortho alkylation as flame retardant compositions in styrenic
polymers.
BACKGROUND OF THE INVENTION
[0002] Polyurethane or polyisocyanurate foams are used in many
applications today. Because of their widespread use, much research
has been done on providing flame retardancy to polyurethane or
polyisocyanurate foams. To this end, halogenated flame retardants
and phosphorus flame retardants have been used to provide these
flame retardant properties. For example, alkylated aryl phosphates
are known in the art to be useful as flame-retardants in such
applications. However, the processes typically used to form
alkylated aryl phosphates produce triphenyl phosphate ("TPP") as a
by-product of the alkylated phenyl phosphate formation reaction and
is unwanted in the final product because of environmental concerns
For example, TPP has been classified as a marine pollutant in some
jurisdictions. Thus, it would be desirable to provide for alkylated
aryl phosphates flame retardants suitable for use in polyurethane
or polyisocyanurate foams having reduced amounts of TPP, when
compared to currently available products, and also flame retarded
polyurethane or polyisocyanurate foams also containing reduced
amounts of TPP.
SUMMARY OF THE INVENTION
[0003] In one embodiment, the present invention relates to the use
of an alkylated triaryl phosphate ester comprising less than about
1 wt % triphenyl phosphate, based on the total weight of the
alkylated triaryl phosphate ester, and an organic phosphorous
content in the range of from about 5 to about 10 wt %, based on the
total weight of the alkylated triaryl phosphate ester, as a flame
retardant in flame retarded polyurethane or polyisocyanurate foams,
flame retarded polyurethane or polyisocyanurate foam formulations,
and processes of making either flame retarded polyurethane or
polyisocyanurate foams or flame retarded polyurethane or
polyisocyanurate foam formulations.
[0004] Thus, in some embodiments, the present invention relates to
a flame retarded polyurethane or polyisocyanurate foam comprising
at least one, in some embodiments only one, alkylated triaryl
phosphate ester, wherein the alkylated triaryl phosphate ester
contains less than about 1 wt % triphenyl phosphate, based on the
total weight of the alkylated triaryl phosphate ester, and in the
range of from about 5 to about 10 wt % organic phosphorous, all
based on the total weight of the alkylated triaryl phosphate
ester.
[0005] The present invention also relates to polyurethane or
polyisocyanurate foam formulations comprising at least one, in some
embodiments only one, alkylated triaryl phosphate ester, wherein
the alkylated triaryl phosphate ester contains less than about 1 wt
% triphenyl phosphate, based on the total weight of the alkylated
triaryl phosphate ester, and in the range of from about 5 to about
10 wt % organic phosphorous, all based on the total weight of the
alkylated triaryl phosphate ester; at least one, in some
embodiments only one, isocyanate, polyol, or combination thereof;
and at least one, in some embodiments only one, blowing agent.
Blowing agents suitable for use in the present invention can be
readily selected by one having ordinary skill in the art, and
typically are selected from water, volatile hydrocarbons,
halocarbons, or halohydrocarbons, or mixtures of two or more such
materials.
[0006] The present invention also relates to a polyurethane or
polyisocyanurate foam formulations derived from at least one, in
some embodiments only one, alkylated triaryl phosphate ester,
wherein the alkylated triaryl phosphate ester contains less than
about 1 wt % triphenyl phosphate, based on the total weight of the
alkylated triaryl phosphate ester, and in the range of from about 5
to about 10 wt % organic phosphorous, all based on the total weight
of the alkylated triaryl phosphate ester; at least one, in some
embodiments only one, isocyanate, polyol, or combination thereof;
and at least one, in some embodiments only one, blowing agent.
[0007] The present invention also relates to a process for forming
a flame retarded polyurethane or polyisocyanurate foam comprising
combining at least one, in some embodiments only one, alkylated
triaryl phosphate ester, wherein the alkylated triaryl phosphate
ester contains less than about 1 wt % triphenyl phosphate, based on
the total weight of the alkylated triaryl phosphate ester, and in
the range of from about 5 to about 10 wt % organic phosphorous, all
based on the total weight of the alkylated triaryl phosphate ester;
at least one, in some embodiments only one, isocyanate, polyol, or
combination thereof; and at least one, in some embodiments only
one, blowing agent in the presence of at least one, in some
embodiments only one, catalyst.
[0008] The alkylated triaryl phosphate esters used as flame
retardants in the present invention can be made by a process
comprising: [0009] a) reacting an alkylated phenol comprising less
than about 1 mole % phenol and up to about 75mole % dialkyl phenol,
both based on the total moles of reactive alkylated phenolics in
the alkylated phenol, with POCl.sub.3 in the presence of a first
catalyst under first reaction conditions including temperatures
ranging from about 80.degree. C. to about 210.degree. C. thereby
producing a first reaction product comprising greater than about 75
mole % monoalkylated phenyl-dichloro phosphates, based on the total
moles of the first reaction product; and [0010] b) reacting the
first reaction product with an alcohol selected from aryl alcohols,
alkyl alcohols, alkylated aryl alcohols, and mixtures thereof in
the presence of a second catalyst under second reaction conditions
including temperatures ranging from about 90.degree. C. to about
260.degree. C. thereby producing an alkylated triaryl phosphate
ester; or [0011] a) reacting an alkylated phenol comprising less
than about 1% phenol and up to about 75 mole % dialkyl phenol, both
based on the total weight of the alkylated phenol, with a molar
excess of POCl.sub.3 in the presence of a first catalyst under
first reaction conditions including temperatures ranging from about
80.degree. C. to about 210.degree. C. thereby producing a first
reaction product comprising greater than about 50 mole %, based on
the total moles of the first reaction product, monoalkylated
phenyl-dichloro phosphates and excess POCl.sub.3; [0012] b)
removing at least a portion of the excess POCl.sub.3 from the first
reaction product to produce an intermediate product, wherein said
intermediate reaction product contains less than 15 mole %
phosphorus, based on the total moles of the intermediate reaction
product, in the form of POCl.sub.3 remains; and [0013] c) reacting
the first reaction product with an alcohol selected from aryl
alcohols, alkyl alcohols, alkylated aryl alcohols, and mixtures
thereof in the presence of a second catalyst under second reaction
conditions including temperatures ranging from about 90.degree. C.
to about 260.degree. C. thereby producing an alkylated triaryl
phosphate ester.
DETAILED DESCRIPTION OF THE INVENTION
[0014] As used herein, "IP's" is meant to refer to
isopropylatedphenols; "OIP" is meant to refer to
ortho-isopropylphenol; "MIP" is meant to refer to
meta-isopropylphenol; "PIP" is meant to refer to
para-isopropylphenol; "TPP" is meant to refer to triphenyl
phosphate; "2,6-DIP" is meant to refer to 2,6-diisopropylphenol;
"2,4-DIP" is meant to refer to 2,4-diisopropylphenol; "2,4,6-TIP"
is meant to refer to 2,4,6-triisoproplylphenol; "2-IPP" is meant to
refer to 2-isopropylphenyl diphenyl phosphate; "3-IPP" is meant to
refer to 3-isopropylphenyl diphenyl phosphate; "4-IPP" is meant to
refer to 4-isopropylphenyl diphenyl phosphate; "2,4-DDP" is meant
to refer to 2,4-diisopropylphenyl diphenyl phosphate; "IPP's" is
meant to refer to isopropylated triphenyl phosphates; "DTPP" is
meant to refer to diisopropylated triphenyl phosphate; and "TTPP"
is meant to refer to triisopropylated triphenyl phosphate.
Alkylated Triaryl Phosphate Esters
[0015] In one embodiment, the present invention relates to
alkylated triaryl phosphate esters. The alkylated triaryl phosphate
esters of the present invention are characterized as containing
less than about 1 wt % TPP, based on the total weight of the
alkylated triaryl phosphate ester, in some embodiments less than
about 0.75 wt % TPP, on the same basis, and in other embodiments,
less than about 0.5 wt % TPP, on the same basis.
[0016] Despite the low concentrations of TPP, the alkylated triaryl
phosphate esters of the present invention still contain a high
amount of phosphorus. Typically the alkylated triaryl phosphate
esters of the present invention contain from about 5 to about 10 wt
% organic phosphorous, based on the total weight of the alkylated
triaryl phosphate ester. Preferably the organic phosphorus content
ranges from about 7 to about 9 wt %, on the same basis, and in more
preferred embodiments the organic phosphorous content ranges from
about 7.5 to about 8.5 wt %, most preferably in the range of from
about 8.0 to about 8.4%, on the same basis.
[0017] The alkylated alkylated triaryl phosphate esters of the
present invention can also be described as containing
monalkylphenyl diphenyl phosphates, di-(alkylphenyl) phenyl
phosphates, dialkylphenyl diphenyl phosphates, dialkylphenyl
diphenyl phosphates, trialkylphenyl phosphates, and mixtures
thereof.
[0018] In some embodiment, the alkylated triaryl phosphate esters
of the present invention are further characterized as containing
greater than about 20 wt % monalkylphenyl diphenyl phosphates,
based on the total weight of the alkylated triaryl phosphate ester.
Preferably, the alkylated triaryl phosphate esters contain greater
than about 75 wt %, on the same basis, monalkylphenyl diphenyl
phosphates, more preferably greater than about 90 wt %, on the same
basis.
[0019] The alkylated triaryl phosphate esters of the present
invention can further be characterized as containing less than
about 80 wt % di-(alkylphenyl) phenyl phosphates, based on the
total weight of the alkylated triaryl phosphate ester. Preferably
the alkylated triaryl phosphate esters of the present invention
contain less than about 25 wt %, more preferably less than about 10
wt %, di-(alkylphenyl) phenyl phosphates, on the same basis.
[0020] The alkylated triaryl phosphate esters of the present
invention can also be further characterized as containing less than
about 50 wt %, based on the total weight of the alkylated triaryl
phosphate ester, dialkylphenyl diphenyl phosphates. However, in
preferred embodiments, the alkylated triaryl phosphate esters of
the present invention contain less than about 25 wt %, more
preferably less than about 10 wt %, dialkylphenyl diphenyl
phosphates, on the same basis. In a most preferred embodiment, the
alkylated triaryl phosphate esters of the present invention contain
less than about 1 wt %, based on the total weight of the alkylated
triaryl phosphate ester, dialkylphenyl diphenyl phosphates. The
inventors hereof have unexpectedly discovered that, in some
embodiments, the removal of unreacted alkylated phenols during the
production of the alkylated triaryl phosphate esters of the present
invention is more efficient for alkylated triaryl phosphate esters
having these concentrations of dialkylphenyl diphenyl
phosphates.
[0021] The amount of trialkylphenyl phosphates present in the
alkylated triaryl phosphate esters of the present invention is
generally less than about 20 wt %, based on the total weight of the
alkylated triaryl phosphate ester. However, in preferred
embodiments, the alkylated phenyl phosphates of the present
invention can contain less than about 2 wt %, on the same basis, of
trialkylphenyl phosphates. In some most preferred embodiments the
level of trialkylphenyl phosphates is less than 0.5 wt %, on the
same basis. The alkylated phenyl phosphates according to the
present invention also comprise less than about 20 wt %, based on
the total weight of the alkylated triaryl phosphate ester,
alkylphenyl dialkylphenyl phenyl phosphates. In most preferred
embodiments the alkylated triaryl phosphate esters of the present
invention contain less than 0.05 wt %, based on the total weight of
the alkylated triaryl phosphate ester, of the alkylphenyl
dialkylphenyl phenyl phosphates.
[0022] Exemplary alkylated triaryl phosphate esters of the present
invention are those a) those that comprise: in the range of from
about 90 to about 92 wt. % IPP, in the range of from about 0.5 to
about 0.75 wt. % TPP, in the range of from about 1 to about 3 wt. %
DTPP, in the range of from about 0.05 to about 0.15 wt. % TTPP, and
in the range of from about 0.5 to about 0.75 wt. % 2,4-DDP; b) in
the range of from about 94 to about 96 wt. % IPP, in the range of
from about 3.5 to about 5.5 wt. % DTPP, and in the range of from
about 0.1 to about 0.3 wt. % TTPP; and c) in the range of from
about 71 to about 73 wt. % IPP, in the range of from about 0.05 to
about 0.15 wt. % TPP, in the range of from about 26 to about 28 wt.
% DTPP, and in the range of from about 0.5 to about 0.7 wt. %
TTPP.
[0023] Monoalkylphenyl diphenyl phosphates, di-(alkylphenyl) phenyl
phosphates, dialkylphenyl diphenyl phosphates, trialkylphenyl
phosphates, and alkylphenyl dialkylphenyl phenyl phosphates,
present in the alkylated triaryl phosphate esters of the present
invention are those wherein the alkyl moieties are selected from
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl,
amyl, isoamyl, tertiary-amyl groups, and cyclohexyl alkyl moieties.
Preferably, the alkyl moieties of at least one of, preferably at
least two of, more preferably all of, the monoalkylphenyl diphenyl
phosphates, di-(alkylphenyl) phenyl phosphates, dialkylphenyl
diphenyl phosphates, trialkyiphenyl phosphates, and alkylphenyl
dialkylphenyl phenyl phosphates, present in the alkylated triaryl
phosphate esters are isopropyl moieties. Thus, for example, in a
most preferred embodiment, the alkylated triaryl phosphate esters
according to the present invention are isopropylphenyl diphenyl
phosphate esters. Of the total isopropylphenyl diphenyl phosphate
esters weight, 0.1 to 99.9 wt % is 2-isopropylphenyl phosphate
(2-IPP), 0.1 to 99.9 wt % is 3-isopropylphenyl phosphate (3-IPP),
0.1 to 99.9 wt % is 4-isopropylphenyl phosphate (4-IPP), all based
on the total weight of the alkylated triaryl phosphate ester. In
the most preferred embodiments 66 to 100 wt % of the
isopropylphenyl phenyl phosphate present in the alkylated triaryl
phosphate esters according to the present invention is
2-isopropylphenyl phosphate (2-IPP), 0.1 to 4 wt % is
3-isopropylphenyl phosphate (3-IPP), 0.1 to 40 wt % is
4-isopropylphenyl phosphate (4-IPP). It should be noted that
although specific ranges of isopropylphenyl phenyl phosphate have
been discussed above, it is within the scope of the present
invention to produce an alkylated triaryl phosphate ester having
any possible relative ratio of 2-IPP, 3-IPP and 4-IPP. However, in
a most preferred embodiment, the alkylated triaryl phosphate esters
according to the present invention are isopropylphenyl diphenyl
phosphate esters wherein in the range of about 63 to about 68 wt. %
of the isopropylphenyl diphenyl phosphate ester is 2-IPP, in the
range of from about 0.5 to about 2.5 wt. % is 3-IPP and in the
range of from about 30.5 to about 36.5 wt. % is 4-IPP, all based on
the total weight of the isopropylphenyl diphenyl phosphate ester.
In an exemplary embodiment of the present invention, the alkylated
triaryl phosphate esters according to the present invention are
isopropylphenyl diphenyl phosphate esters wherein about 66 wt. % of
the isopropylphenyl diphenyl phosphate ester is 2-IPP, about 1 wt.
% is 3-IPP and about 33 wt. % is 4-IPP, on the same basis. The
alkylated triaryl phosphate esters of the present invention can
suitably be formed by a process comprising reacting an alkylated
phenol with POCl.sub.3 in the presence of a first catalyst, thus
forming a first reaction product. The first reaction product is
then reacted with an alcohol selected from aryl alcohols, alkyl
alcohols, alkylated aryl alcohols, and mixtures thereof in the
presence of a second catalyst under second reaction conditions
including temperatures ranging from about 90.degree. C. to about
260.degree. C. thereby producing an alkylated triaryl phosphate
ester according to the present invention. It should be noted that
the reaction that produces the first reaction product is sometimes
referred to as the first reaction herein, and the reaction of the
first reaction product with the alcohol is sometimes referred to
herein as the second reaction.
First Reaction--Alkylated Phenol
[0024] Alkylated phenols suitable for use in the first reaction
include those wherein the alkyl group is selected from methyl,
ethyl, n-propyl, isopropyl, isobutyl, tertiary-butyl, amyl,
isoamyl, tertiary-amyl alkyl moieties, and cyclohexyl, preferably
isopropyl moieties.
[0025] Preferably, the alkylated phenol that is reacted with the
POCl.sub.3 in the presence of the first catalyst contains less than
1 mole % phenol and less than 25 mole % dialkyl phenol, both based
on the total moles of reactive alkylated phenols (as described
below) in the alkylated phenol. In a more preferred embodiment, the
alkylated phenol contains less than 0.5 mole % phenol and less than
15 mole % dialkyl phenol, both based on the total moles of reactive
alkylated phenols in the alkylated phenol. In a most preferred
embodiment, the alkylated phenol contains less than 0.5 mole %
phenol and less than 5 mole % 2,4-diisopropylphenol, both based on
the total moles of reactive alkylated phenolics in the alkylated
phenol. In preferred embodiments, the dialkyl phenol of the
alkylated phenol is 2,4-disiopropylphenol.
[0026] In an even more preferred embodiment, the alkylated phenol
stream comprises essentially OIP, MIP, and PIP constituents. In
this embodiment, it is preferred that the alkylated phenol stream
comprise in the range of from about 64 to about 68 wt. % OIP, in
the range of from about 0.5 to about 2.5 wt. % MIP, and in the
range of from about 31 to about 35 wt. % PIP, all based on the
total weight of the alkylated phenol.
[0027] "Total moles of reactive alkylated phenols" and "Reactive
alkylated phenol" as used herein is meant to refer to the total
moles of alkylated phenols that are part of the reaction between
the alkylated phenol and the POCl.sub.3. This unit of measure is
used herein because unreactive alkylated phenols are also present
in the alkylated phenol. For example, 2,6-DIP and 2,4,6-TIP are
common impurities in an IP's stream but are for all intents and
purposes unreactive. For example, see Table 1 below, which
describes one example of an alkylated phenol suitable for use
herein:
TABLE-US-00001 TABLE 1 Isopropylated Phenol Stream GC Reactive
Component FW wt % Mole/100 g moles/100 g Phenol 94.11 0.35 0.0037
0.0037 OIP 136.19 59.48 0.4367 0.4367 PIP 136.19 29.76 0.2185
0.2185 2,6-DIP 178.27 4.25 0.0238 Inert 2,4-DIP 178.27 5.83 0.0327
0.0327 2,4,6-TIP 220.35 0.32 0.0015 Inert Average FW 139.76
*134.83
[0028] In Table 1, the amounts described herein as based on the
total moles of reactive alkylated phenols would thus be based on
134.83 moles.
First Reaction--POCl.sub.3
[0029] The amount of POCl.sub.3 used herein can be a molar
equivalency, in some embodiments a molar excess, and in other
embodiments, less than a molar equivalency. By a molar equivalency
of POCl.sub.3, it is meant that a molar ratio of about 1 moles of
POCl.sub.3 to about 1 mole of reactive alkylated phenol. By a molar
excess of POCl.sub.3, it is meant that a molar ratio of greater
than 1 moles of POCl.sub.3 to 1 mole of reactive alkylated phenol.
Preferably a molar excess is in the range of from about 1.0 to
about 5.0 moles of POCl.sub.3 to about 1 mole of reactive alkylated
phenol, and more preferably in the range of from about 1.15 to
about 2.5 moles of POCl.sub.3 to about 1 mole of reactive alkylated
phenol are used in the practice of this embodiment of the present
invention.
[0030] By less than a molar equivalency of POCl.sub.3, it is meant
a molar ratio of less than 1 mole of POCl.sub.3 to 1 mole of
reactive alkylated phenol. For example, in one embodiment, which
would produce a first reaction product having significantly higher
DTTP and TTPP, a molar excess of alkylated phenol can be used, i.e.
less than a molar equivalency of POCl.sub.3. In this embodiment, it
is preferred to use greater than in the range of from about 1 to
about 2, preferably in the range of from 1.1 to about 1.2, moles of
reactive alkylated phenol per mole of POCl.sub.3.
[0031] Reactive alkylated phenol is defined above.
First Catalyst
[0032] Catalysts suitable for use as the first catalyst herein can
be selected from tertiary amines such as trialkyl amines,
dialkylaryl amines, and heterocyclic tertiary amines such as 1,4
Diazabicyclo[2,2,2]octane (DABCO); aromatic amines such as pyridine
and substituted pyridines with N,N-dimethylaminopyridine being
preferred from this group; pyrimidines and its derivatives;
pyrazine and its derivatives; pyroles and its derivatives;
imidizoles, its derivatives and their corresponding mineral and
organic acid salts with N-methylimidazole, imidiazole and its
derivatives being preferred from this group; quaternary ammonium
salts; quaternary phosphonium salts; tetrakis dialkylamino
phosphonium salts having the general formula
P(NRR').sub.4.sup.+X.sup.- especially tetrakis diethylamino
phosphonium Bromide having the formula
P(NEt.sub.2).sub.4.sup.+Br.sup.-; alkali metal halide catalysts;
and alkali earth metal halides, oxides, sulfates, sulfonates,
hydroxides, and phosphates. It should be noted that any alkali
metal halide and salts, e.g. ammonium, phosphonium, etc., as
described above, can be used as long as the salt/halide has
appreciable solubility to initiate the reaction with POCl.sub.3
such that co-produced hydrogen chloride ultimately converts the
metal catalyst salt to the metal chloride salt. Non-limiting
examples of alkali metal and alkali earth metal catalysts include
AlCl.sub.3, MgCl.sub.2, CaCl.sub.2, NaCl, KCl, FeCl.sub.3, LiCl,
TiCl.sub.4, SbCl.sub.4, AgCl and BaCl.sub.2. Non-limiting examples
of suitable quaternary ammonium salts include tetrabutylammonium
halide, tetra alkyl or mixed alkyl ammonium mineral or organic acid
salt. Non-limiting examples of suitable quaternary phosphonium
salts include any tetra-alkyl or tetra-aryl phosphonium salt.
Preferably the first catalyst is selected from quaternary ammonium
salts, quaternary phosphonium salts, tetrabutylammonium chloride,
MgCl.sub.2, and pyridine. In one preferred embodiment the first
catalyst is tetrabutylammonium chloride. In yet another preferred
embodiment the first catalyst is MgCl.sub.2. In a particularly
preferred embodiment, the first catalyst is pyridine.
First Reaction Conditions
[0033] The POCl.sub.3 and alkylated phenol are reacted under first
reaction conditions that include temperatures ranging from about
75.degree. C. to about 210.degree. C. Preferably, first reaction
conditions include temperatures ranging from about 80.degree. C. to
about 150.degree. C., more preferably temperatures ranging from
about 90.degree. C. to about 140.degree. C. The reactants and first
catalyst can be combined, contacted, etc. in any order. However, it
is preferred that the alkylated phenol reactant be added to the
POCl.sub.3 reactant. It has been found that an alkylated phenol
phosphate with superior viscosity, i.e. less viscous, can be
produced by combining the reactants and catalyst in this order. In
a more preferred embodiment, the alkylated phenol is added to a
reaction vessel containing both the POCl.sub.3 reactant and first
catalyst.
[0034] It should be noted that the reaction between the alkylated
phenol and POCl.sub.3 produces HCl gas, which can cause undesirable
cleavage and/or transesterification reactions. Thus, in preferred
embodiments, first reaction conditions also include venting of HCl
gas. This venting can be conducted by any means known to be
effective at venting HCl gas from a reaction vessel. However, in
preferred embodiments, the venting is accomplished by conducting
the reaction under first reaction conditions that include
sub-atmospheric pressures, i.e. under a vacuum. The amount of
vacuum used is readily selected by one having ordinary skill in the
art taking into consideration that too much vacuum would cause the
reaction temperature to fall outside of the ranges described above,
thus slowing the reaction rate. Further, while vacuum pressures are
preferred, the reaction can be conducted at atmospheric pressures
up to about 5 psig and still produce a desirable product, albeit at
a reduced rate. A pressure significantly above 5 psig would slow
the reaction rate somewhat more and potentially lead to the
undesirable cleavage and/or transesterification reactions.
[0035] In preferred embodiments, first reaction conditions further
include the substantial absence of oxygen.
First Reaction--Optional Diluent
[0036] In some embodiments, a diluent can be added along with the
POCl.sub.3, first catalyst, and alkylated phenol. Diluents suitable
for use herein are those that i) do not react substantially with
the reagents, products and co-products, including HCl, utilized or
generated during the first and/or second reactions; and ii) do not
substantially reduce the catalytic activity of the first and/or
second catalyst. In preferred embodiments, diluents suitable for
use herein can be further characterized as those that iii) do not
lower the reaction temperature such that the reaction rate slows
significantly to the point of not being commercially feasible, i.e.
below the ranges disclosed herein. It should be noted that the
diluent can be added as a complex with the first catalyst.
Non-limiting examples of suitable diluents include a) hydrocarbon
solvents, such as heptane, petroleum ethers, methylcyclohexane and
boiling point heptane; b) aromatic hydrocarbons such as toluene,
xylene(s) and ethyl benzene; c) halo hydrocarbons and halo aromatic
hydrocarbons such as chlorobenzene, dibromomethane, dibromoethane,
and all isomers of trichloroethylene; d) ether solvents such as,
tetrahydrofuran or 1,4-dioxane. Preferably, if an ether diluent is
used, the diluent is 1,4-dioxane. In a most preferred embodiment,
the diluent is toluene.
First Reaction Product
[0037] The reaction of the POCl.sub.3 and alkylated phenol produces
a first reaction product comprising greater than about 50 mole %
monoalkylatedphenyl dichloro phosphates, based on the total moles
of the first reaction product excluding unreacted POCl.sub.3 and
any added diluent.
[0038] In some embodiments, the first reaction product can comprise
in the range of from about 70 to about 99.9 mole %
monoalkylatedphenyl dichloro phosphates, on the same basis, and in
the range of from about 0.1 mole % to about 30 mole %
bis-(monoalkylated)phenyl-chloro phosphates, on the same basis.
[0039] By excess POCl.sub.3 it is meant any POCl.sub.3 that did not
react with the alkylated phenol, i.e. unreacted POCl.sub.3.
Typically, the first reaction product comprises in the range of
from about 5 to about 80 mole % unreacted POCl.sub.3, based on the
total phosphorus in the first reaction product, as determined by
some suitable method, preferably quantitative P-31 NMR. The amount
of unreacted POCl.sub.3 in the first reaction product is obviously
dependent on the amount of POCl.sub.3 used in the first reaction
stage. For example, if less than a molar equivalency of POCl.sub.3
is used, then the first reaction product can contain substantially
no excess POCl.sub.3, depending on the efficiency of the reaction
between the alkylated phenol and POCl.sub.3; however, if a molar
excess of POCl.sub.3 is used, then the amount of excess POCl.sub.3
will depend on the efficiency of the reaction and on the amount of
POCl.sub.3 used. In the practice of the present invention, if less
than a molar equivalency, or up to about a 15% molar excess of
POCl.sub.3, is used to produce the first reaction product, then the
first reaction product can be, and in some embodiments is, directly
reacted with an alcohol without removal of unreacted
POCl.sub.3.
Optional POCl.sub.3
[0040] If excess POCl.sub.3 is used in producing the first reaction
product, then it is preferred that at least a portion of the excess
POCl.sub.3 be removed from the first reaction product, thereby
producing an intermediate reaction product. In preferred
embodiments, the amount of excess POCl.sub.3 removed from the first
reaction product is that amount necessary to produce an
intermediate product containing less than about 15 mole %,
preferably less than about 10 mole %, more preferably less than
about 5 mole %, most preferably less than about 1 mole %,
POCl.sub.3, all based on the total phosphorus in the first reaction
product. In a particularly preferred embodiment, substantially all
unreacted POCl.sub.3 is removed from the first reaction product,
which in some embodiments can produce an intermediate reaction
product that contains substantially no unreacted alkylated phenol.
However, it should be noted that if the intermediate reaction
product is reacted with phenol, the amount of unreacted POCl.sub.3
removed from the first reaction product must be that amount
necessary to produce an intermediate product containing less than
about 1.2 mole %, preferably less than about 1 mole % of total
organic phosphorus.
[0041] The method by which the POCl.sub.3 is removed from the first
reaction product to produce the intermediate product is not
critical to the present invention, and non-limiting examples of
suitable removal techniques include vacuum distillation, flashing,
stripping, vacuum stripping, and the like. In preferred
embodiments, POCl.sub.3 is removed by vacuum stripping. Vacuum
stripping can suitably be carried out by heating the first reaction
product to within the range of about 115.degree. C. to about
170.degree. C., under constant agitation and vacuum in the range of
from about 700 mmHg to about 0.001 mmHg. It is within the scope of
the present invention that a nitrogen purge accompany the vacuum
stripping. It is also within the scope of the present invention to
add an inert "chaser" solvent at the end of the vacuum stripping to
reduce the POCl.sub.3 in the intermediate reaction product to less
than 1 mole %, based on the intermediate reaction product. If a
chaser solvent is used, it is preferred to use toluene,
methylcyclohexane, boiling-point heptanes or n-heptane.
[0042] It should be noted that, while not necessary, in some
embodiments, the optional POCl.sub.3 removal is accompanied by the
removal of a portion of any diluent added during the first
reaction. In this embodiment, conditions can be adjusted to within
the above ranges and means selected from those described above to
provide for more efficient removal of both the POCl.sub.3 and
diluent.
Second Reaction
[0043] In the practice of the present invention, the first reaction
product or intermediate reaction product is reacted with an alcohol
selected from aryl alcohols including phenol, alkyl alcohols,
alkylated aryl alcohols, and mixtures thereof in the presence of a
second catalyst or processed to remove at least a portion of excess
POCl.sub.3.
[0044] In an alternative embodiment, the first reaction product or
intermediate product can be reacted sequentially with more than one
alcohol selected from aryl alcohols including phenol, alkyl
alcohols, alkylated aryl alcohols, and mixtures thereof. In this
embodiment, it is preferred that the first reaction product or
intermediate product be reacted with a first alcohol, and when the
first alcohol has been consumed, as determined by a suitable method
such as P.sup.31 NMR, a second alcohol, preferably different from
the first alcohol, be added.
[0045] More preferably, in this embodiment, the first alcohol is
divided into a first and second portion. The first reaction product
or intermediate reaction product is reacted with the first portion
of the first alcohol until substantially all of the first portion
of the first alcohol is consumed, as determined by a suitable
method such as P.sup.31 NMR. After substantially all of the first
portion of the first alcohol has been consumed, the second portion
of the first alcohol is added, and the reaction allowed to continue
until substantially all of the second portion of the first alcohol
has been consumed, as determined by a suitable method such as
P.sup.31 NMR, thus producing a first intermediate reaction product
comprising at least aryl dichlorophosphate and chloro
diarylphosphate.
[0046] The first intermediate reaction product, which is richer, in
chloro diarylphosphates then the first reaction product, is then
reacted with an effective amount of the second alcohol. By an
effective amount of the second alcohol, it is meant that amount of
the second alcohol that is effective at converting substantially
all of the aryl dichlorophosphate and chloro diarylphosphate to
alkylated triaryl phosphate esters according to the present
invention.
[0047] In this embodiment, the first and second alcohol can be
independently selected from aryl alcohols including phenol, alkyl
alcohols, alkylated aryl alcohols, and mixtures thereof.
[0048] Non-limiting examples of suitable alkylated aryl alcohols
are those wherein the alkyl group contains from about 1 to about 5
carbon atoms such as methyl. Non-limiting examples of suitable
alkyl alcohols are those wherein the alkyl group contains from
about 1 to about 20 carbon atoms such as n-decanol. Preferably the
alcohol is selected from phenol, decanol, dodecanol or mixtures
thereof and in a most preferred embodiment, the alcohol is
phenol.
Second Catalyst
[0049] Catalysts suitable for use as the second catalyst herein can
be selected from quaternary ammonium salts, quaternary phosphonium
salts, MgCl.sub.2, CaCl.sub.2, AlCl.sub.3, KCl, FeCl.sub.3, LiCl,
and BaCl.sub.2. Non-limiting examples of suitable quaternary
ammonium salts and quaternary phosphonium salts include are those
listed above in relation to the first catalyst. Preferably the
second catalyst is selected from MgCl.sub.2, CaCl.sub.2,
AlCl.sub.3, KCl, FeCl.sub.3, LiCl, and BaCl.sub.2. More preferably
the second catalyst is MgCl.sub.2.
Second Reaction Conditions
[0050] The first reaction product or intermediate reaction product
and alcohol are reacted in the presence of the second catalyst
under second reaction conditions including temperatures ranging
from about 75.degree. C. to about 260.degree. C. Preferably, second
reaction conditions include temperatures ranging from about
100.degree. C. to about 180.degree. C., most preferred from about
140.degree. C. to about 150.degree. C. The first reaction product
or intermediate reaction product, alcohol, and second catalyst can
be combined, contacted, etc., in any order. For example, the first
reaction product or intermediate reaction product, alcohol, and
second catalyst can be co-fed to a reaction vessel, the first
reaction product or intermediate reaction product can be added to a
reaction vessel containing the alcohol and second catalyst, etc.
However, it is preferred that the alcohol, preferably in the molten
or liquid state, be added to the first reaction product reactant or
intermediate reaction product to which the second catalyst has
already been introduced. The inventors have unexpectedly discovered
that combining, contacting, etc. the first reaction product or
intermediate reaction product, second catalyst and alcohol in this
manner provides for an alkylated phenol phosphate having TPP
concentrations lower than those formed when the reactants are not
added in this manner. In this embodiment, the catalyst is
preferably present with the alcohol, but it can be co-fed or fed
after the intermediate product.
[0051] In preferred embodiments, second reaction conditions further
include the substantial absence of oxygen.
[0052] The reaction of the first reaction product or intermediate
reaction product and alcohol produces an alkylated triaryl
phosphate ester according to the present invention, as described
above.
Optional Processing of Alkylated Triaryl Phosphate Ester
[0053] In some embodiments, it may be desirable to further refine
the alkylated triaryl phosphate ester produced from the present
process, for example to remove any excess alcohol that may be
present in the alkylated triaryl phosphate ester. Further
processing can also include adding an additional amount of alcohol
such as monoisopropylated phenols, diisopropylated phenols, phenol,
and mixtures thereof and/or second catalyst to the alkylated
triaryl phosphate ester. The alcohol-rich alkylated triaryl
phosphate ester product comprising excess alcohol can then be
recovered, and at least a portion, preferably substantially all, of
the excess alcohol removed by, for example, phase separation and/or
stripping and/or distillation. In preferred embodiments, steam
stripping is used.
[0054] The alkylated triaryl phosphate ester may also be washed one
or more times with an acid, a base, or water. In this embodiment,
the alkylated triaryl phosphate ester can first be washed with an
acid and/or base, preferably a base, and then washed with water. In
this embodiment, it is preferred to wash the alkylated triaryl
phosphate ester with a base such as NaOH, preferably a diluted base
comprising in the range of about 1 to about 5 wt. %, based on the
diluted base, NaOH, in the range of about 1 to about 4 times,
followed by washing with water until the pH of the water recovered
from the washing is in the range of from about 7 to about 9.
[0055] In another embodiment, the alkylated triaryl phosphate ester
can also be processed in a wipe film evaporator, a distillation
column, or other similar separation device, in conjunction with the
above further refinement processes or as a stand-alone
refinement.
Use of Alkylated Triaryl Phosphate Esters as Flame Retardant
[0056] The alkylated triaryl phosphate esters of the present
invention are suitable for use as a flame retardant in polyurethane
or polyisocyanurate foams and polyurethane or polyisocyanurate foam
formulations. Thus, in some embodiments, the present invention
relates to polyurethane or polyisocyanurate foams, polyurethane or
polyisocyanurate foam formulations, and processes for forming flame
retarded polyurethane or polyisocyanurate foam formulations, both
rigid and flexible, all containing a flame retarding amount of at
least one, in some embodiments only one, alkylated triaryl
phosphate ester, as described herein. In some embodiments, the
present invention relates to polyurethane foams, polyurethane foam
formulations, and processes for forming flame retarded polyurethane
foam formulations, both rigid and flexible, in some embodiments
flexible all containing a flame retarding amount of at least one,
in some embodiments only one, alkylated triaryl phosphate ester, as
described herein. By a flame retarding amount of alkylated triaryl
phosphate ester, it is meant in the range of from about 5 to about
75 wt. % of the at least one alkylated triaryl phosphate ester,
based on the total weight of the polyurethane or polyisocyanurate
foams or polyurethane or polyisocyanurate foam formulations. In
preferred embodiments, a flame retarding amount of alkylated
triaryl phosphate ester is to be considered in the range of from
about 5 to about 70 wt. %.
[0057] The polyurethanes and polyisocyanurates, the foams thereof,
and methods of preparing such polymers are very well known in the
art and are reported in the literature. See, for example,
Encyclopedia of Polymer Science and Technology, vol. 11, pgs. 506
563 (1969 Wiley & Sons) and vol. 15, pp. 445 479 (1971 Wiley
& Sons), U.S. Pat. Nos. 3,974,109; 4,209,609; 4,405,725;
4,468,481; 4,468,482; 5,102,923; 5,164,417; 7,045,564; and
7,153,901; and U.S. patent application Ser. No. 11/569,210, which
are all incorporated herein by reference in their entirety. For
example, flexible polyurethane foams are typically prepared by
chemical reaction between two liquids, isocyanates and polyols. The
polyols are polyether or polyester polyols. The reaction readily
occurs at room temperature in the presence of a blowing agent such
as water, a volatile hydrocarbon, halocarbon, or halohydrocarbon,
or mixtures of two or more such materials. Catalysts used in
effecting the reaction include amine catalysts, tin-based
catalysts, bismuth-based catalysts or other organometallic
catalysts, and the like. Surfactants such as substituted silicone
compounds are often used in order to maintain homogeneity of the
cells in the polymerization system. Hindered phenolic antioxidants,
e.g., 2,6-di-tert-butyl-para-cresol and
methylenebis(2,6-di-tert-butylphenol), can be used to further
assist in stabilization against oxidative degradation.
[0058] As noted above, in some embodiments, the present invention
also relates to a polyurethane or polyisocyanurate foam formulation
comprising a flame retarding amount of at least one, in some
embodiments only one, alkylated triaryl phosphate ester, as
described herein; at least one, in some embodiments only one,
isocyanate or polyol; and at least one, in some embodiments only
one, blowing agent, and polyurethane or polyisocyanurate foams,
both rigid and flexible, formed therefrom. Blowing agents suitable
for use herein include water, a volatile hydrocarbon, halocarbon,
or halohydrocarbon, or mixtures of two or more such materials.
[0059] In addition to these components the polyurethane or
polyisocyanurate foams and foam formulations can contain any other
component known in the art and used in the formation for flexible
and rigid polyurethane or polyisocyanurate foams, and these other
components used in forming polyurethane polymerization formulations
or recipes are well known to those of ordinary skill in the art.
For example, the polyurethane or polyisocyanurate foam formulations
can contain surfactants, antioxidants, diluents such as low
viscosity liquid C.sub.1-4 halocarbon and/or halohydrocarbon
diluents in which the halogen content is 1-4 bromine and/or
chlorine atoms can also be included in the compositions of this
invention. Non-limiting examples of such diluents include
bromochloromethane, methylene chloride, ethylene dichloride,
ethylene dibromide, isopropyl chloride, n-butyl bromide, sec-butyl
bromide, n-butyl chloride, sec-butyl chloride, chloroform,
perchloroethylene, methyl chloroform, and carbon tetrachloride.
[0060] It should be noted that these and other ingredients that can
be used in the polyurethane or polyisocyanurate foam formulations
of the present invention, and the proportions and manner in which
they are used are reported in the literature. See for example:
Herrington and Hock, Flexible Polyurethane Foams, The Dow Chemical
Company, 1991, 9.25 9.27 or Roegler, M "Slabstock Foams"; in
Polyurethane Handbook; Oertel, G., Ed.; Hanser Munich, 1985, 176
177 or Woods, G. Flexible Polyurethane Foams, Chemistry and
Technology; Applied Science Publishers, London, 1982, 257 260,
which is hereby incorporated by reference in its entirety, and U.S.
patent application Ser. No. 11/569,210, which has already been
incorporated herein by reference.
[0061] The above description is directed to several embodiments of
the present invention. Those skilled in the art will recognize that
other means, which are equally effective, could be devised for
carrying out the spirit of this invention. It should also be noted
that preferred embodiments of the present invention contemplate
that all ranges discussed herein include ranges from any lower
amount to any higher amount. For example, when discussing the
second reaction conditions, these ranges can include temperatures
in the range of from about 75.degree. C. to about 100.degree. C.,
90.degree. C. to about 180.degree. C., 100.degree. C. to about
260.degree. C., 150.degree. C. to about 180.degree. C., etc. The
following examples will illustrate the present invention, but are
not meant to be limiting in any manner.
EXAMPLES
[0062] In the following Examples, the notation "Wt % in Crude"
indicates the amount of each component in the ester product
recovered from the reactor, and is thus based on the total weight
of the product recovered from the reactor. "Normalized wt %"
indicates the amount of each component calculated by dividing the
"Wt % in Crude" values by the "Normalization Factor", thus
indicating the amount of each component in relation to the
alkylated triaryl phosphate ester.
Example 1
Comparative
[0063] A reaction flask was purged with nitrogen. 15.3g (0.1 mole)
of phosphorous oxychloride ("POCl.sub.3") followed by 13.6 g(0.1
mole) of ortho-isopropylphenol ("OIP"). The mixture was heated to
about 110.degree. C. for 10 hours under agitation. The content of
the flask were analyzed via .sup.1H-NMR and it was discovered that
greater than 50mol. % of the OIP was unreacted. The content of the
flask were also analyzed via .sup.31P-NMR, and the molar ratio of
2-isopropylphenyl dichlorophosphate to bis-(2-isopropylphenyl)
chlorophosphate bis to tris-(2-isopropylphenyl) phosphate was found
to be 40.8:22.6:5.0.
Example 2
Comparative
[0064] A reaction flask was purged with nitrogen. 15.3 g (0.1 mole)
of phosphorous oxychloride ("POCl.sub.3") followed by 13.6 g(0.1
mole) of ortho-isopropylphenol ("OIP") was then added to the flask
over a 30 minute period. The mixture was heated to 195.degree. C.
for 5 hours under agitation. The content of the flask were analyzed
via Proton NMR, and the presence of unreacted OIP in the flask
detected by this analysis indicated that the reaction was
incomplete. The content of the flask were then heated to
250.degree. C. for 3 hours under agitation until no OIP was
detected. The content of the flask were analyzed via .sup.31P-NMR,
and the molar ratio of 2-isopropylphenyl dichlorophosphate to
bis-(2-isopropylphenyl) chlorophosphate bis to
tris-(2-isopropylphenyl) phosphate was found to be
56.2:28.7:2.8.
Example 3
Example 1 Extracted from U.S. Pat. No. 4,139,487--Comparative
[0065] Phenol (65.2 parts) and a mixture of meta- and
para-isopropyl phenols (47.9 parts) were mixed with phosphorus
oxychloride (51 parts; that is a 5% excess of phenolic reactants).
Powdered anhydrous magnesium chloride (0.5 part) was added to
catalyze the reaction. The reaction mixture was rapidly heated to
130.degree. C. and then slowly to 230.degree. C. over a period of
about 2 hours, after which there was no further appreciable
evolution of hydrogen chloride. Completion of the reaction was
checked by titration tests on the crude product which was then
distilled under vacuum to give a fraction of recovered phenols, a
small intermediate fraction and a main ester fraction (88% of crude
product) boiling at 205.degree. C.-225.degree. C. at 1 mm. of
mercury.
[0066] The composition of the recovered phenolic fraction was shown
by analysis to be substantially the same as that of the phenolic
feedstock mixture, indicating that there had been no appreciable
separation of the components due to preferential esterification,
which was verified by hydrolyzing a portion of the main ester
fraction and analyzing the recovered phenols. The distilled
phosphate ester had a satisfactory color, content of oxidizable
impurities and acidity and was not therefore further purified. The
viscosity of the distilled phosphate ester was 30 cs at 25.degree.
C. and the specific gravity (25.degree. C./25.degree. C.) was
1.169. The constitution of the distilled phosphate ester is
indicated in Table 2, below. The wt. % is based on the total weight
of the distilled phosphate ester.
TABLE-US-00002 TABLE 2 Component wt. % Triphenylphosphate 30
Mono-(isopropylphenyl) diphenyl phosphate 44 Bis-(isopropylphenyl)
phenyl phosphate 22 Tris-(isopropylphenyl) phosphate 4 Total
100
[0067] The distilled phosphate esters had a calculated carbon
number of 21 and containing 33 mole-percent of the isopropylphenyl
group.
Example 4
Example 2 Extracted from U.S. Pat. No. 4,139,487--Comparative
[0068] Phenol (32.6 parts) and a mixture of meta- and
para-isopropyl phenols (95.8 parts) were mixed with phosphorus
oxychloride (51 parts) and anhydrous magnesium chloride (0.6 part)
as catalyst. Reaction and purification were carried out as in
Example 1 (Example 3 herein) and the main ester fraction (89% by
weight of the crude product) distilled at 207-230.degree. C. at 1
mm of mercury. As in Example 1(Example 3 herein) the product
required no further purification and had a viscosity of 58 cs at
25.degree. C. and a specific gravity (25.degree. C./25.degree. C.)
of 1.123.
[0069] Analysis of the mixed ester indicated it to possess the
following constitution (Table 3) (wt %). The wt. % is based on the
total weight of the distilled phosphate ester.
TABLE-US-00003 TABLE 3 Component wt. % Triphenylphosphate 4
Mono-(isopropylphenyl) diphenyl phosphate 19 Bis-(isopropylphenyl)
phenyl phosphate 52 Tris-(isopropylphenyl) phosphate 25 Total
100
[0070] The mixed phosphate esters had a carbon number of 24 and
contained 66 mole-percent of the isopropylphenyl group.
Example 5
[0071] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated phenyl
phosphate began. A 150 g charge of the mixture (1.1 mole of
reactive isopropylated phenols prepared via ortho alkylation of
phenol with propylene and AlCl.sub.3), described in Table 4 below
was combined with 640 g (4.17 mole) of POCl.sub.3 and 1.5 grams of
tetrabutyl ammonium bromide in a reactor. The mixture was heated
under constant agitation to about 114.degree. C. and refluxed at
that temperature until evolution of HCl ceased, thus indicating the
formation of the intermediate product. Excess POCl.sub.3 was
recovered from the intermediate product (95% of theoretical amount)
by first heating it at atmospheric pressure to about 130.degree. C.
and then heating it to about 135.degree. C. at 1 mmHg. Heating of
the reactor's content was discontinued, the reactor's content
allowed to cool, and the reactor charged with 0.3 g of MgCl.sub.2
and 188 g of phenol (2.0 mole, 99.6%).
[0072] After the addition of the MgCl.sub.2 and phenol, the
temperature of the reactor's content was increased to about
110.degree. C., and the reaction mixture in the reactor was then
heated from about 110 to about 130.degree. C. over a period of
about 3 hours under agitation. .sup.31P-NMR indicated complete
conversion of the mono aryl dichlorophosphate and about a 55/45
mixture of the diaryl to triaryl intermediate and the alkylated
triaryl phosphate ester product.
[0073] An additional 0.9 g of MgCl.sub.2 was then added to the
reactor and the reaction was conducted for an additional 4 hours,
during which moderate HCl evolution was observed, until HCl
evolution ceased. After HCl evolution ceased, 12.00 g of fresh
phenol (0.13 mole, 99.6%) was charged to the reactor and the
reaction was run with a nitrogen sparge at 130.degree. C. until
complete (about 2 hrs). Pressure was reduced to 10 mmHg and
unreacted phenol removed overhead at 130.degree. C. The alkylated
triaryl phosphate ester thus produced was analyzed, and the
alkylated triaryl phosphate ester was found to have the
characteristics outlined in Table 5, below. Normalized, or relative
weight percents, are based on the total weight of phenol and the
alkylated triaryl phosphate ester as is indicated in the table.
TABLE-US-00004 TABLE 4 AlCl.sub.3 o-Alkylation IPS Mixture wt % in
Normalized Component Crude wt % phenol 0.53 0.55 OIP 82.50 85.05
PIP 8.03 8.28 2,6-DIP 4.87 5.02 2,4-DIP 1.03 1.06 TIP 0.04 0.04
Normalization 97.00 100.00 Factor (%)
TABLE-US-00005 TABLE 5 Formula Wt % in Normalized Component Weight
Crude wt % TPP 326.28 0.18 0.20 2-IPP + 3-IPP + 4-IPP 368.36 84.49
94.39 2,4 DDP + DTPP (1) 410.44 0.82 0.92 DTPP (2,3) 410.44 3.91
4.37 TTPP 452.52 0.11 0.12 Normalization Factor 89.51 100.00
Example 6
[0074] Unless otherwise indicated, the reactants were added to the
autoclave under constant agitation and the autoclave content
remained under this agitation until recovery of the isopropylated
phenols began.
[0075] A 2.0-liter Parr autoclave was charged with 50 grams of dry
Amberlyst.RTM. 15 and 1200 g (12.75 mole) of molten Phenol
(Mallinckrodt, 99.6% loose crystals). The autoclave was sealed,
purged with N.sub.2 and heated to 110.degree. C. The headspace of
the autoclave was vented to atmospheric pressure and then purged
with a 10-gram charge of propylene. Propylene, 190 g (4.5 mole),
was then fed to the autoclave over a 90-minute period. The feed was
such that the autoclave pressure varied from 80-30 psig during the
addition. The reaction temperature was maintained from 110 to
118.degree. C. for an additional hour, and the autoclave content
then cooled to 70.degree. C. The autoclave content was then allowed
to settle for 30 minutes prior to transferring (positive N.sub.2
pressure through dip leg) to a nitrogen purged storage bottle.
[0076] A second 1000 g (10.6 mole) charge of molten phenol was made
to the autoclave containing the IP's/Amberlyst.RTM. 15 heel. The
propylation reaction was repeated with 156 g (3.7 mole) of
propylene. The combined decanted reaction mixture from the first
and second molten phenol additions was then fractionally distilled
(1 atmosphere). The light cut (typically 93% phenol, 7% OIP) was
returned to the autoclave with make-up phenol and again propylated.
This decantation and distillation process was continued through 8
runs.
[0077] The concentrated crude IP's was distilled at 1 atmosphere to
produce 3300 g of material. The analysis of which is reported in
Table 5, below. The material was separated via distillation into a
light cut (2200g, 93% phenol and 7% OIP), which was combined with
(2200 g) fresh phenol and subsequently used as the alcohol of the
second step to make IPP crude in Examples 7, 8 and 10-13 below.
After recovery of unreacted phenol, through the eight runs a total
of 2500 g of phenol had been reacted with 1200 g of propylene to
yield 3300 g of IPs suitable for use in making low TPP IPP. This
material is described in Table 6 and was used as the alkylated
phenol of the first step in Examples 7-13 below.
TABLE-US-00006 TABLE 6 Molecular IPPP Crude Component Weight (wt %)
Phenol 94.11 0.35 2-isopropylphenol (OIP) 136.19 59.48
4-isopropylphenol (PIP) 136.19 29.76 2,6-diisopropylphenol
(2,6-DIP) 178.27 4.25 2,4-diisopropylphenol (2,4-DIP) 178.27 5.83
2,4,6-triisopropylphenol (2,4,6-TIP) 220.35 0.32
Example 7
[0078] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated phenyl
phosphate began.
[0079] A 475 g (3.34 mole of reactive isopropylated phenols) sample
of the material described in Table 5, above, was combined with 795
g (5.19 mole) of POCl.sub.3 and 3.56 grams (0.33 mole %) of
tetrabutyl ammonium bromide. The mixture was heated to 114.degree.
C. and refluxed at that temperature until evolution of HCl slowed.
The temperature was gradually increased to 135.degree. C. and left
at that temperature until HCl evolution ceased. The excess
POCl.sub.3 was recovered in vacuo, stripping to an end point of
135.degree. C. and <1.0 mmHg.
[0080] After the removal of excess POCl.sub.3 was complete, the
reactor was allowed to cool. The reactor was then charged with 3.26
g of MgCl.sub.2 (1.0 mole %) and heated to 110.degree. C. To the
reactor was fed 629.1 g (6.69 moles) of a mixture comprising phenol
(96.3 wt %) and 2-isopropylphenol (3.7 wt %), recycled from the
final light cut of IP's preparation described above (Example 6)
with concomitant heating of the reactor's content from 110.degree.
C. to 135.degree. C. over a 3 hour period. Within one hour after
the completion of the feed, .sup.31P-NMR analysis indicated
complete conversion of the monoaryl dichlorophosphate to triaryl
phosphates. The pressure was reduced to 10 mmHg and unreacted
phenol partially removed overhead at 140.degree. C.
[0081] The alkylated triaryl phosphate ester thus produced was
analyzed, and the alkylated triaryl phosphate ester was found to
have the characteristics outlined in Table 7, below. Normalized or
relative weight percents are based on the total weight of phenol
and the alkylated triaryl phosphate ester as is indicated in the
table.
TABLE-US-00007 TABLE 7 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.86 0.98 2-IPP + 3-IPP +
4-IPP 368.36 77.90 88.37 2,4 DDP + DTPP (1) 410.44 6.50 7.37 DTPP
(2,3) 410.44 2.53 2.87 TTPP 452.52 0.36 0.41 Normalization Factor
88.15 100.00
Example 8
[0082] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0083] A 470 g sample of the material described in Table 5, above,
was combined with 571 g (3.73 mole) of POCl.sub.3 recycled from
previous Examples and 6.15 grams (0.58 mole %) of tetrabutyl
ammonium bromide in a reactor. The mixture was heated to
118.degree. C. and refluxed at that temperature until evolution of
HCl slowed. The temperature was gradually increased to 135.degree.
C. and left at that temperature until HC1 evolution ceased. The
excess POCl.sub.3 was recovered in vacuo, stripping to an end point
of 135.degree. C. and <1.0 mmHg. The reactor was allowed to
cool, and then charged with 5.5 g of MgCl.sub.2 (1.75 mole %) and
heated to 110.degree. C. To the reactor was fed 622.5 g (6.61
moles) of a phenol/2-isopropylphenol mixture comprising 96.3 wt %
phenol and 3.7 wt % 2-isopropylphenol, with concomitant gradual
increased heating from 110.degree. to 135.degree. C. over a 3-hour
period.
[0084] Within one hour after the completion of the
phenol/2-isopropylphenol mixture feed, .sup.31P-NMR analysis
indicated complete conversion of the monoaryl dichlorophosphate to
triaryl phosphates. The pressure of the reactor was reduced to 10
mmHg and unreacted phenol partially removed overhead at 140.degree.
C. The alkylated triaryl phosphate ester was recovered from the
reactor and analyzed, and the alkylated triaryl phosphate ester was
found to have the characteristics outlined in Table 8, below.
Normalized or relative weight percents are based on the total
weight of phenol and the alkylated triaryl phosphate ester as is
indicated in the table.
TABLE-US-00008 TABLE 8 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.58 0.66 2-IPP + 3-IPP +
4-IPP 368.36 76.49 86.72 2,4 DDP + DTPP (1) 410.44 7.04 7.98 DTPP
(2, 3) 410.44 3.35 3.80 TTPP 452.52 0.74 0.84 Normalization Factor
88.20 100.00
Example 9
[0085] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0086] A 246 g sample of the material described in Table 5, above,
was combined with 800 g (5.22 mole) of POCl.sub.3 and 2.56 grams
(0.46 mole %) of tetrabutyl ammonium bromide. The mixture was
heated to 114.degree. C. and refluxed at that temperature until
evolution of HCl slowed. The temperature was gradually increased to
135.degree. C. and held at that temperature until HCl evolution
ceased. The excess POCl.sub.3 was recovered in vacuo stripping to
an end point of 135.degree. C. and <1.0 mmHg.
[0087] The reactor was allowed to cool and then charged with 2.96 g
of MgCl.sub.2 (1.8 mole %) and heated to 110.degree. C. 622.5 g
(6.61 moles) of Phenol (99.6%) was fed to the reactor while
gradually and simultaneously increasing the temperature of the
reactor's content from 110.degree. to 135.degree. C. over a 3-hour
period. Within one hour after the completion of the feed, P-31 NMR
analysis indicated complete conversion of the monoaryl
dichlorophosphate to triaryl phosphates. The pressure was reduced
to 10 mmHg and unreacted phenol partially removed overhead at
140.degree. C.
[0088] The alkylated triaryl phosphate ester was recovered from the
reactor and analyzed, and the alkylated triaryl phosphate ester was
found to have the characteristics outlined in Table 9, below.
Normalized or relative weight percents are based on the total
weight of phenol and the alkylated triaryl phosphate ester as is
indicated in the table.
TABLE-US-00009 TABLE 9 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.54 0.61 2-IPP + 3-IPP +
4-IPP 368.36 80.41 91.23 2,4 DDP + DTPP (1) 410.44 5.27 5.98 DTPP
(2, 3) 410.44 1.80 2.04 TTPP 452.52 0.12 0.14 Normalization Factor
88.14 100.00
Example 10
[0089] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0090] A 462 g charge of the material described in Table 5, above,
was combined with 1000 g (6.52 mole) of a 1:2 mix of fresh and
recycled POCl.sub.3 and 3.8 grams (1.23 mole %) of MgCl.sub.2. The
mixture was heated initially to 85.degree. C., and at that
temperature, evolution of HCl was apparent. The temperature of the
mixture was gradually increased to 135.degree. C. and held at that
temperature until HCl evolution ceased. The excess POCl.sub.3 was
recovered in vacuo, stripping to an end point of 135.degree. C. and
50 mmHg. Toluene (2.times.100 g) was charged (subsurface) to the
hot reactor, and the toluene was then stripped to the ending
conditions of 140.degree. C. and 50 mmHg.
[0091] The reactor was allowed to cool, and after cooling to
110.degree. C., 612 g (6.5 moles) of a phenol/2-isopropylphenol
mixture comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol,
was fed to the reactor while gradually increasing the temperature
of the reactor's content from 110.degree. to 135.degree. C. over a
3-hour period. Within one hour after the end of the
phenol/2-isopropylphenol mixture feed, .sup.31P-NMR analysis
indicated complete conversion of the monoaryl dichlorophosphate to
triaryl phosphates. The pressure of the reactor was reduced to 10
mmHg and unreacted phenol removed overhead at 140.degree. C.
[0092] The alkylated triaryl phosphate ester was recovered from the
reactor and analyzed, and the alkylated triaryl phosphate ester was
found to have the characteristics outlined in Table 10, below.
Normalized or relative weight percents are based on the total
weight of phenol and the alkylated phenyl phosphate as is indicated
in the table.
TABLE-US-00010 TABLE 10 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.73 0.80 2-IPP + 3-IPP +
4-IPP 368.36 78.69 85.82 2,4 DDP + DTPP (1) 410.44 7.64 8.33 DTPP
(2, 3) 410.44 3.97 4.33 TTPP 452.52 0.66 0.72 Normalization Factor
91.69 100.00
Example 11
[0093] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0094] A 231.5 g (1.63 mole of reactive isopropylated phenols)
sample of the material described in Table 5, above, was combined
with 750 g (3.01 mole) of a mix 1:2 mix of fresh and recycled
POCl.sub.3 and 2.6 grams (1.20 mole %) of AlCl.sub.3. The mixture
was heated initially to 80.degree. C., and at that temperature,
evolution of HCI was apparent. The temperature of the reactor's
content was gradually increased to 135.degree. C. and held at that
temperature until HCl evolution ceased.
[0095] Excess POCl.sub.3 was recovered in vacuo stripping to an end
point of 135.degree. C. and 50 mmHg. Toluene (2.times.100 g) was
then charged (subsurface) to the hot reactor, and the toluene was
then stripped to the ending conditions of 140.degree. C. and 50
mmHg. The reactor's content was allowed to cool to 110.degree. C.,
and 305 g (3.25 moles) of a phenol/2-isopropylphenol mixture
comprising 96.3 wt % phenol and 3.7 wt % 2-isopropylphenol, was fed
to the reactor while gradually increasing the temperature of the
reactor's content from 110.degree. C. to 135.degree. C. over a
3-hour period. Foaming was very problematic throughout the phenol
feed. Within one hour after the end of the feed, .sup.31P-NMR
analysis indicated complete conversion of the monoaryl
dichlorophosphate to triaryl phosphates. The pressure was reduced
to 50 mmHg and unreacted phenol partially removed overhead at
140.degree. C.
[0096] The alkylated triaryl phosphate ester phosphate was
recovered from the reactor and analyzed, and the alkylated triaryl
phosphate ester was found to have the characteristics outlined in
Table 11, below. Normalized or relative weight percents are based
on the total weight of phenol and the alkylated triaryl phosphate
ester as is indicated in the table.
TABLE-US-00011 TABLE 11 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.65 0.72 2-IPP + 3-IPP +
4-IPP 368.36 75.00 82.53 2,4 DDP + DTPP (1) 410.44 8.13 8.95 DTPP
(2, 3) 410.44 5.96 6.56 TTPP 452.52 1.14 1.25 Normalization Factor
90.88 100.00
Example 12
[0097] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0098] A 197.2 g (1.39 mole of reactive isopropylated phenols)
sample of the material described in Table 5, above, was combined
with 640 g (4.17 mole) of POCl.sub.3 and 4.0 grams (3.64 mole %) of
pyridine (dried over molecular sieves) in a reactor. The mixture
was heated to 114.degree. C. and refluxed at that temperature until
evolution of HCl slowed. The temperature was then gradually
increased to 135.degree. C. with distillation of POCl.sub.3 and
held at that temperature until HCl evolution ceased. The remaining
excess POCl.sub.3 was recovered in vacuo stripping to an end point
of 135.degree. C. and 50 mmHg. During the POCl.sub.3 strip, some
pyridine-HCl was observed in the overhead and in the recycle
POCl.sub.3 Toluene (2.times.100 g) was charged (subsurface) to the
hot reactor. Toluene was stripped to the ending conditions of
140.degree. C. and 50 mmHg. The reactor's content was allowed to
cool to 110.degree. C., and 278 g (2.78 moles) of a
phenol/2-isopropylphenol mixture comprising 96.3 wt % phenol and
3.7 wt % 2-isopropylphenol, was fed to the reactor while gradually
increasing the temperature of the reactor's content from
110.degree. to 135.degree. C. over a 3-hour period. Within one hour
after the end of the feed, .sup.31P-NMR analysis indicated complete
conversion of the monoaryl dichlorophosphate to triaryl phosphates.
The pressure was reduced to 10 mmHg and unreacted phenol removed
overhead at 140.degree. C.
[0099] The alkylated triaryl phosphate ester was recovered from the
reactor and analyzed, and the alkylated phenyl phosphate was found
to have the characteristics outlined in Table 12, below. Normalized
or relative weight percents are based on the total weight of phenol
and the alkylated triaryl phosphate ester as is indicated in the
table.
TABLE-US-00012 TABLE 12 Wt % in Normalized Major Components FW
Crude wt % TPP 326.28 0.52 0.61 2-IPP + 3-IPP + 4-IPP 368.36 76.90
89.53 2,4 DDP + DTPP (1) 410.44 6.21 7.23 DTPP (2, 3) 410.44 2.15
2.50 TTPP 452.52 0.11 0.13 Normalization Factor 85.89 100.00
Example 13
[0100] Unless otherwise indicated, the reactants were added to the
reactor under constant agitation and the reactor's content remained
under this agitation until recovery of the alkylated triaryl
phosphate ester began.
[0101] A fully jacketed 2000 ml dry round bottom flask was used as
a reactor in this example. It was equipped with an overhead
stirrer, thermometer, oil jacketed addition funnel and an efficient
condenser/takeoff head. The reactor was vented through a
Drierite.RTM. column to a caustic scrubber. 1100 g (7.17 mole) of
POCl.sub.3 (comprised of 2:1 mix of recycle and fresh POCl.sub.3),
530 g (3.74 mole of reactive IPPs) of a mixture of isopropylated
phenols comprised of 59.48 wt % OIP, 29.76 wt % PIP, 5.83 wt %
2,4-DIP and 6.0 g (2 mole % relative to reactive IPP's charged) of
pyridine were charged to the reactor. The reactor's content was
heated to 113.degree. C. (oil jacket temperature 124.degree. C.).
HCl evolution initiated at 80.degree. C. and became much more
apparent at 105.degree. C. After 90 minutes at 113.degree. C. HCl
evolution slowed. The jacket temperature was increased to
135.degree. C., within an additional 60 minutes the pot temperature
had reached 127.degree. C., HCl Evolution was essentially complete,
and pyridine.HCl separated as an oil suspended in the reaction
mixture (the resulting turbidity seems to be a good visual indictor
of the reaction endpoint).
[0102] The reactor jacket temperature was increased to 145.degree.
C. and the valve on the take off head was opened to the receiver,
and POCl.sub.3 was collected for recycle. Distillation of
POCl.sub.3 was facilitated with a slow nitrogen purge through the
reactor headspace. Once the pot temperature reached 135.degree. C.
and POCl.sub.3 distillation had slowed, the reactor pressure was
gradually reduced (max vacuum 50 mmHg) until the theoretical amount
of POCl.sub.3 was collected (495 g, [95% of Theory] of POCl.sub.3
was thus recovered). During the distillation pyridine.HCl formed in
the overheads, but caused no operational problems. The last trace
of POCl.sub.3 was removed via the addition and stripping with 300
ml of toluene (ending conditions 135.degree. C. 50 mmHg). An
aliquot was removed for analysis; .sup.31P-NMR analysis indicated a
97.4:2.6 relative ratio of ArOCl.sub.2PO:(ArO).sub.2CIPO as well as
verified complete removal of POCl.sub.3.
[0103] 3.5 g (0.98 mole % relative to IPPS) of MgCl.sub.2 were then
charged to the reactor and left to stir at 140.degree. C. under a
stream of nitrogen for 1 hr. A second aliquot was removed for
analysis, and .sup.31P-NMR indicated this second aliquot had a
97.2:2.8 relative ratio of ArOCl.sub.2PO:(ArO).sub.2ClPO. Phenol
(706 g, 96.3 wt % Phenol, 3.7 wt % 2-isopropylphenol, 7.4 mole
total phenols) was then charged to the oil jacketed addition
funnel, from which it was gradually fed over a 75-minute period to
the reactor. During this addition, HCl evolution was extremely
vigorous. The reaction appeared to be complete after 170 minutes
total reaction time. Conversion as measured by .sup.31P-NMR was
99.3%. An additional 23 g charge of the phenol mixture described
above was made. After an additional 30 minutes the nearly water
white mixture (density=1.09, 1370 g total reaction mass, 1378 g
Theory) was transferred to a wash kettle.
[0104] After the nearly water white mixture was charged to the wash
kettle, 350 g of a Na.sub.2CO.sub.3/HNa.sub.2PO.sub.4 solution
(pH=9 density=1.15) was charged to the wash kettle. The content of
the wash kettle were then stirred at 88.degree. C. for 5 minutes
and then allowed to settle for a period of 20 minutes. The bottom
milky (suspended MgCO.sub.3) aqueous layer was removed (226 g,
pH=7.5-8.0) from the wash kettle, and the resulting crude IPPP was
washed for an additional 5 minutes with a second aliquot
(90.degree. C., 200 g) of the Na.sub.2CO.sub.3/HNa.sub.2PO.sub.4
solution. A second phase was removed from the bottom of the reactor
to yield a 195 g less turbid yet still milky aqueous solution
having a pH of 10. 530 g of a dilute H.sub.3PO.sub.4 solution, 0.56
wt %, H.sub.3PO.sub.4, based on the solution, was then charged to
the reactor, and the bottom turbid product layer was collected
(1357 g). The aqueous phase was removed (pH=3.5, 610 g), and the
product layer was placed in a reactor and sparged with nitrogen at
95.degree. C. to remove water, thus yielding an 1335 g of an
alkylated phenyl phosphate. The alkylated triaryl phosphate ester
was recovered from the reactor and analyzed, and the alkylated
triaryl phosphate ester was found to have the characteristics
outlined in Table 13, below. Normalized or relative weight percents
are based on the total weight of phenol and the alkylated phenyl
phosphate as is indicated in the table.
TABLE-US-00013 TABLE 13 Molecular Wt % in Normalized Major
Components Weight Crude wt % TPP 326.28 0.47 0.53 2-IPP + 3-IPP +
4-IPP 368.36 77.51 87.79 2,4 DDP + DTPP (1) 410.44 7.10 8.04 DTPP
(2, 3) 410.44 3.05 3.45 TTPP 452.52 0.16 0.18 Normalization Factor
88.29 100.00
Example 14
[0105] The crude alkylated triaryl phosphate ester recovered from
Examples 7-12 were combined and washed with a
Na.sub.2CO.sub.3/HNa.sub.2PO.sub.4 having the concentrations and in
the same manner described in Example 13, above. That material was
then combined with the crude product from Example 13. The total
mixture was then distilled under a reduced pressure (<2 mmHg)
nitrogen atmosphere. During the distillation, the "forerun" (6 wt %
of the total mixture, based on the mixture) was collected between
180-218.degree. C. The "product cut" (92 wt % of the total of the
total mixture, based on the mixture) was collected between
118.5-235.degree. C. The undistilled bottoms represented the last 2
wt %, based on the mixture, of the total mass of the mixture. The
forerun was analyzed by HPLC, which found 13.2 wt % phenol, 0.7 wt
% 4-isopropylphenol, 13.0 wt % 2-isopropylphenol, 7.0 wt %
2,6-diisopropylphenol, 0.0 wt % TPP, 2.3 wt % monoisopropylphenyl
diphenyl phosphates, 0.2 wt % diisopropylated triaryl phosphates,
and 0.02 wt % triisopropylated triaryl phosphate. The product cut
was also analyzed for purity and physical properties; the results
are presented in the Table 14, below. All weight percents are
absolute and are based on the total mass of that which is being
analyzed.
TABLE-US-00014 TABLE 14 Analysis Flashed Product HPLC Wt %
Triphenyl Phosphate 0.71 Isopropylphenyl diphenyl phosphates 87.21
Diisopropylated triaryl phosphates 11.44 Triisopropylated triaryl
phosphates 0.64 Acid Number 0.11 mg KOH/g APHA Color 28.00 Density
(20.degree. C.) 1.1689 g/ml Flash Point (Cleveland Open Cup)
222.degree. C. Moisture 19.2 ppm Wt % Phosphorus (NMR) 8.34 [Al]
<0.11 ppm [Mg] <0.0018 ppm [Na] <0.6 ppm Kinetic Viscosity
(25.degree. C.) 52.91 cSt
[0106] Thus, as illustrated in Table 14, our product, on average,
is 10% higher in Phosphorous than those produced in the
comparatives examples above, and is also 10% less viscous than the
products of the comparative examples.
Example 15
[0107] A 5-liter reactor was equipped with an addition funnel,
thermal well and distillation apparatus. The distillation apparatus
was vented to a caustic scrubber through a Drierite.RTM. column.
The reactor was purged with N.sub.2 and charged with 3886 g (25.34
mole) of recycled POCl.sub.3 and 6.37 g (0.53 mole %) of
MgCl.sub.2. The content of the reactor was heated to 85.degree. C.
A redistilled 67:1:32 blend (1725 g, 12.67 mole) of OIP (Aldrich))
MIP (Aldrich) and PIP (Aldrich) was fed to the reactor over a
3-hour period. During the feed the reaction temperature was
gradually increased to 130.degree. C. After 4 hours total reaction
time distillation of POCl.sub.3 was initiated. The reactor pressure
was decreased gradually as the rate of POCl.sub.3 distillation
decreased. Distillation was continued to an ending condition of
140.degree. C. and 50 mmHg. Toluene was then charged
(2.times.250ml) and stripped at 140.degree. C. (50 mmHg).
Phosphorus NMR of the stripped reaction mixture verified the
complete removal of POCl.sub.3 and indicted a 100:4.2 relative
ratio of ArOPOCl.sub.2:(ArO).sub.2POCl.
[0108] The content of the reactor was cooled to 130.degree. C.
Molten phenol (99.6%), 2362 g (25.1 mole) was feed to the reactor
over a 5-hour period. Towards the end of the feed the reaction
temperature was increased to 150.degree. C. Phosphorus NMR analysis
of the reactor's content confirmed complete reaction within 1-hour
of the end of the feed. The content of the reactor was transferred
under N.sub.2 to a 5-liter storage bottle, 4547 g. HPLC analysis is
Tabulated below. Normalized or relative weight percents are based
on the total weight of phenol and the alkylated triaryl phosphate
ester as is indicated in Table 15, below.
TABLE-US-00015 TABLE 15 Major Molecular Wt % in Normalized
Components Weight Crude wt % Phenol 94.11 4.10 4.35 TPP 326.28 0.10
0.11 2-IPP + 3-IPP + 4-IPP 368.36 85.90 91.09 DTPP 410.44 4.20 4.45
TTPP 452.52 0.00 0.00 Normalization Factor 94.30
[0109] A 5-liter glycol jacketed baffled reactor was charged with
500 g of 11% aqueous Na.sub.2CO.sub.3 and 2065 g of the alkylated
triaryl phosphate ester of Table 13. The mixture was briefly
stirred at 85-92.degree. C. and then left to phase separate. The
bottom aqueous layer was removed along with a clear rag layer of
intermediate density. The wash procedure was repeated through 4
washes. In order to completely remove the suspended rag layer,
comprised primarily of sodium and magnesium phenoxide, 2000 ml of
Toluene was added. The IPP/toluene mixture was then washed with tap
water (2.times.500 ml ).
[0110] To the same 5-liter glycol jacketed baffled reactor was
charged with 540 g of 4% aqueous NaOH, 2478 g of the crude product
mixture and 1750 g of Toluene. The mixture was briefly stirred at
45-50.degree. C. and then warmed to 65.degree. C. without stirring.
The resulting bottom aqueous layer was removed along with the
suspended Mg(OH).sub.2 suspended within it. A second wash was
conducted at 65.degree. C. with 608 g of 1% NaOH. The product
mixture was then washed at 85.degree. C. with 532 g of tap water
(resulting aqueous cut pH=10). The IPP/toluene mixture was
contaminated with a fine suspension of trace Mg(OH).sub.2. This was
removed by washing at 90.degree. C. with 514 g of 0.7%
H.sub.3PO.sub.4 (resulting aqueous cut pH=3.5). A final 212 g tap
water wash (90.degree. C.) resulted in an aqueous phase with
pH=4.5.
[0111] The washed and stripped IPP-crude from the two separate
work-up procedures above was combined. The mixture was heated to
180.degree. C. and sparged with nitrogen to remove trace toluene,
moisture and phenol. An analytical sample (500 g) was removed for
the analyses reported in Table 16, below. The balance of the
material was combined with the product from Example 16 and later
flash distilled at 1 mmHg and 220-240.degree. C. (see example 17
for final product analyses). All weight percents are absolute and
are based on the total mass of that which is being analyzed
(indicated in the table).
TABLE-US-00016 TABLE 16 Analysis Stripped Crude Product HPLC Wt %
Phenol 0.81 Triphenyl Phosphate 0.15 Isopropylphenyl diphenyl
phosphates 94.1 Diisopropylated triaryl phosphates 4.58
Triisopropylated triaryl phosphates 0.45 Acid Number 0.45 mg KOH/g
APHA Color 149.00 Density (20.degree. C.) 1.1725 g/ml Flash Point
(Cleveland Open Cup) 229.degree. C. Moisture 46 ppm Wt % Phosphorus
(NMR) 8.40 [Al] <2.0 ppm [Mg] <0.90 ppm [Na] 1.2 ppm Kinetic
Viscosity (25.degree. C.) 47.81 cSt
Example 16
[0112] A 5-liter reactor was equipped with an addition funnel,
thermal well and distillation apparatus. The distillation apparatus
was vented to a caustic scrubber through a Drierite.RTM. column.
The reactor was purged with N.sub.2 and charged with 3385 g (22.08
mole) of recycled POCl.sub.3 and 8.90 g (0.85 mole %) of
MgCl.sub.2. The content of the reactor was heated to 85.degree. C.
A redistilled 67:32:1 blend (1503.3 g, 11.04 mole) of OIP
(Aldrich), PIP (Aldrich) and MIP (Aldrich) was fed to the reactor
over a 3-hour period. During the feed the reaction temperature was
gradually increased to 130.degree. C. After 4 hours total reaction
time distillation of POCl.sub.3 was initiated. The reactor pressure
was decreased gradually as the rate of POCl.sub.3 distillation
decreased. Distillation was continued to an ending condition of
150.degree. C. and 50 mmHg. Toluene was then charged (2.times.250
ml) and stripped at 150.degree. C. (50 mmHg). Phosphorus NMR of the
stripped reaction mixture verified the complete removal of
POCl.sub.3 and indicted a 100:4 relative ratio of
ArOPOCl.sub.2:(ArO).sub.2POCl.
[0113] The content of the reactor was cooled to 130.degree. C.
Molten phenol (99.6%), 1984.97 g (20.75 mole) was fed to the
reactor over a 5-hour period. Toward the end of the feed the
reaction temperature was increased to 150.degree. C. Phosphorus NMR
analysis of the reactor's content confirmed the completion of the
reaction within 1-hour of the end of the feed. The content of the
reactor was transferred under N.sub.2 to a 5-liter storage bottle,
3847 g. HPLC analysis of the content is in Table 175, below.
Normalized or relative weight percents are based on the total
weight of phenol and the alkylated triaryl phosphate ester as is
indicated in the table.
TABLE-US-00017 TABLE 17 Major Molecular Wt % in Normalized
Components Weight Crude wt % Phenol 94.11 2.29 2.30 TPP 326.28 0.15
0.15 2-IPP + 3-IPP + 4-IPP 368.36 92.4 92.98 DTPP 410.44 4.50 4.53
TTPP 452.52 0.04 0.04 Normalization Factor 99.38
[0114] A 5-liter glycol jacketed baffled reactor was charged with
650 g of tap water, 1750 ml of toluene and 1915 g of the crude
product mixture of Table 15. The mixture was briefly stirred at
from 85 to 92.degree. C. and then left to phase separate. The
bottom aqueous layer was removed along with a turbid rag layer of
intermediate density. The organic layer was washed (2.times.1000 g)
with 2% aqueous NaOH at 85.degree. C. and then washed (4.times.800
g) with tap water until a neutral pH of the wash water was
achieved. The above process was repeated with the balance of the
crude material (1897 g). The washed crude product mixtures were
combined and transferred to a third reactor where toluene, and
moisture were removed in vacuo, ending conditions 180.degree. C.
and 1 mmHg. An analytical sample was found to have the
characteristics listed in Table 18, below. All weight percents are
absolute and are based on the total mass of that which is being
analyzed. The balance of the material left after analysis was
combined with the product from Example 15 and later flash distilled
at 1 mmHg and 220-240.degree. C. (see example 17 for final product
analyses).
TABLE-US-00018 TABLE 18 Analysis Stripped Crude Product HPLC Wt %
Phenol 407 ppm Triphenyl Phosphate 0.16 wt % Isopropylphenyl
diphenyl phosphates 94.6 wt % Diisopropylated triaryl phosphates
4.6 wt % Triisopropylated triaryl phosphates 0.01 wt % Acid Number
0.05 mg KOH/g APHA Color 221 Wt % Phosphorus (NMR) 8.32 [Al]
<3.6 ppm [Mg] 1.41 ppm [Na] 1.68 ppm
Example 17
[0115] The stripped crude product mixtures from Examples 15 and 16
were combined and flash distilled at from 220 to 240.degree. C. and
vacuum of <1 mmlig. The product thus obtained had the
characteristics presented in the Table 19, below. All weight
percents are absolute and are based on the total mass of that which
is being analyzed in the Table.
TABLE-US-00019 TABLE 19 Analysis Flashed Product HPLC Wt % Phenol
200 ppm Triphenyl Phosphate 0.17 Isopropylphenyl diphenyl
phosphates 94.93 Diisopropylated triaryl phosphates 4.87
Triisopropylated triaryl phosphates 0.02 Acid Number 0.03 mg KOH/g
APHA Color 27.00 Density (20.degree. C.) 1.1729 g/ml Flash Point
(Cleveland Open Cup) 236.degree. C. Moisture 24 ppm Wt % Phosphorus
(NMR) 8.36 [Al] <0.1 ppm [Mg] <0.06 ppm [Na] <0.56 ppm
Kinetic Viscosity (25.degree. C.) 48.74 cSt
Example 18
[0116] A 5-liter reactor was equipped with an addition funnel,
thermal well and distillation apparatus. The distillation apparatus
was vented to a caustic scrubber through a Drierite.RTM. column.
The reactor was purged with N.sub.2 and charged with 900.00 g (5.88
mole) of recycled POCl.sub.3 21.0 g (3.94 mole %) of dry pyridine
and 916.1 g (6.73 mole) of the redistilled 67:32:1 blend of OIP
(Aldrich), PIP (Aldrich) and MIP (Aldrich). The stirred content of
the reactor was heated to 114.degree. C., the temperature at which
HCl evolution began in earnest. During the course of 7 hours the
reaction temperature was gradually increased to 130.degree. C.
After 8 hours of total reaction time a sample was removed and
analyzed by Phosphorus NMR, which indicted a 93.6:18.5 relative
ratio of ArOPOCl.sub.2:(ArO).sub.2POCl.
[0117] The content of the reactor was left to stand overnight and
then again heated to 130.degree. C. with stirring. Molten phenol
(99.6%), 996.46 g (10.59 mole) was fed to the reactor over a 5-hour
period. Toward the end of the feed the reaction temperature was
increased to 170.degree. C., Phosphorus NMR analysis of the
reactor's content confirmed complete reaction within 3-hours after
the end of the feed. The content of the reactor was transferred
under N.sub.2 to a 5-liter storage bottle, 2055 g. HPLC analysis
indicated it had the properties set out in Table 20, below.
Normalized or relative weight percents are based on the total
weight of phenol and the alkylated phenyl phosphate as is indicated
in the table.
TABLE-US-00020 TABLE 20 Major Molecular Wt % in Normalized
Components Weight Crude wt % Phenol 94.11 2.08 2.09 TPP 326.28 0.13
0.13 2-IPP + 3-IPP + 4-IPP 368.36 70.33 70.83 DTPP 410.44 26.16
26.35 TTPP 452.52 0.59 0.59 Normalization Factor 99.29
[0118] A 5-liter glycol jacketed baffled reactor was charged with
650 g of tap water, 1750 ml of toluene and 2055 g of the crude
product mixture. The mixture was briefly stirred at from 85 to
92.degree. C. and then left to phase separate. The bottom aqueous
layer was removed along with a turbid rag layer of intermediate
density. The organic layer was washed (2.times.1000 g) with 2%
aqueous NaOH at 85.degree. C. and then washed (4.times.800 g) with
tap water until a neutral pH of the wash water was achieved. The
washed crude product mixtures were then transferred to a third
reactor where toluene, moisture and phenols were removed in vacuo,
ending conditions 180.degree. C. and 1 mmHg. An analytical sample
was removed and characterized. The results are reported in the
Table 21, below. All weight percents are absolute and are based on
the total mass of that which is being analyzed in the Table.
TABLE-US-00021 TABLE 21 Analysis Flashed Product HPLC Wt % Phenol
0.07 Triphenyl Phosphate 0.14 Isopropylphenyl diphenyl phosphates
72.2 Diisopropylated triaryl phosphates 27.0 Triisopropylated
triaryl phosphates 0.61 Acid Number 0.01 mg KOH/g APHA Color 92 Wt
% Phosphorus (NMR) 8.1%
[0119] The balance of the material in the reactor was flash
distilled at 1 mmHg and 220-240.degree. C. The product thus
obtained was analyzed and found to exhibit the characteristics
presented in Table 22, below. All weight percents are absolute and
are based on the total mass of that which is being analyzed in the
Table.
TABLE-US-00022 TABLE 22 Analysis Flashed Product HPLC Wt % Phenol
<100 ppm Triphenyl Phosphate 0.14 Isopropylphenyl diphenyl
phosphates 72.16 Diisopropylated triaryl phosphates 27.10
Triisopropylated triaryl phosphates 0.61 Acid Number <0.01 mg
KOH/g APHA Color 35 Density (20.degree. C.) 1.1631 Wt % Phosphorus
(NMR) 8.22% Kinetic Viscosity (25.degree. C.) 55.80 cSt
* * * * *