U.S. patent application number 13/333273 was filed with the patent office on 2012-05-17 for ketal compounds and uses thereof.
This patent application is currently assigned to SEGETIS, INC.. Invention is credited to Vivek BADARINARAYANA, Brian D. MULLEN, Tara J. MULLEN, Marc D. SCHOLTEN, Chunyong WU.
Application Number | 20120122745 13/333273 |
Document ID | / |
Family ID | 43386859 |
Filed Date | 2012-05-17 |
United States Patent
Application |
20120122745 |
Kind Code |
A1 |
MULLEN; Brian D. ; et
al. |
May 17, 2012 |
KETAL COMPOUNDS AND USES THEREOF
Abstract
Various esterified alkyl ketal ester or hydroxyalkyl ketal ester
products are useful as components of organic polymer compositions.
The ketal esters are produced in certain transesterifications
between alkyl ketal esters and/or hydroxyalkyl ketal esters and
polyols, aminoalcohols, polyamines and/or polycarboxylic acids. The
products are excellent plasticizers for a variety of organic
polymers, notable poly(vinyl chloride) plastisols. The products are
also very good lubricants for many lubrication applications.
Inventors: |
MULLEN; Brian D.; (Delano,
MN) ; WU; Chunyong; (Plymouth, MN) ; MULLEN;
Tara J.; (Delano, MN) ; SCHOLTEN; Marc D.;
(Saint Paul, MN) ; BADARINARAYANA; Vivek; (Saint
Louis Park, MN) |
Assignee: |
SEGETIS, INC.
Golden Valley
MN
|
Family ID: |
43386859 |
Appl. No.: |
13/333273 |
Filed: |
December 21, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US2010/039554 |
Jun 22, 2010 |
|
|
|
13333273 |
|
|
|
|
61219098 |
Jun 22, 2009 |
|
|
|
Current U.S.
Class: |
508/308 ;
252/182.28; 521/88; 524/108; 549/370; 549/375; 549/448;
549/454 |
Current CPC
Class: |
C07D 407/12 20130101;
C10M 129/70 20130101; C10M 2207/044 20130101; C08K 5/1575 20130101;
C07D 317/30 20130101; C10M 129/20 20130101; C08K 5/1515 20130101;
C08K 5/1565 20130101 |
Class at
Publication: |
508/308 ;
549/448; 549/454; 549/375; 549/370; 524/108; 521/88;
252/182.28 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C07D 317/30 20060101 C07D317/30; C07D 319/06 20060101
C07D319/06; C08K 5/1575 20060101 C08K005/1575; C09K 3/00 20060101
C09K003/00; C08L 27/06 20060101 C08L027/06; C08L 67/04 20060101
C08L067/04; C08L 31/04 20060101 C08L031/04; C08L 69/00 20060101
C08L069/00; C07D 407/12 20060101 C07D407/12; C08K 5/1565 20060101
C08K005/1565 |
Claims
1. A compound having a structure corresponding to structure I
##STR00031## wherein a is from 0 to 12; b is 0 or 1; each R.sup.1
is independently hydrogen, a hydrocarbyl group, or a substituted
hydrocarbyl group; each R.sup.2, R.sup.3, and R.sup.4 are
independently methylene, alkylmethylene, or dialkylmethylene; x is
at least 1, y is 0 or a positive number and x+y is at least 2;
R.sup.6 is a hydrocarbyl group or a substituted hydrocarbyl group;
and each Z is independently --O--, --NH-- or --NR-- where R is a
hydrocarbyl group or a substituted hydrocarbyl group.
2. The compound of claim 1, wherein each Z is --O--.
3. The compound of claim 1, where y is from 0 to 2, x is at least
2.
4. The compound of claim 1, wherein all a are 2, and all R.sup.1
are methyl.
5. The compound of claim 4, where y is 0 and x is 2.
6. The compound of claim 4, wherein y is 1 and x is 1.
7. A compound of claim 1 which has the structure ##STR00032##
8. A compound of claim 1 which has the structure: ##STR00033##
9. A compound of claim 1, wherein R.sup.6 contains one or more
ether or ester groups.
10. A compound of claim 1, wherein R.sup.6 is C.sub.2-C.sub.6
alkyl.
11. A mixture comprising two or more compounds of claim 1.
12. A composition comprising the compound of claim 1 and an organic
polymer.
13. A composition comprising a mixture of claim 11 and a
polymer.
14. The composition of claim 12, which has a glass transition
temperature at least 5.degree. C. lower than a glass transition
temperature of the polymer.
15. The composition of claim 12, which has a glass transition
temperature at least 30.degree. C. lower than a glass transition
temperature of the polymer.
16. The composition of claim 12, wherein the compound or mixture
constitutes from 0.1 to 90% of the combined weight of the compound
or mixture and the polymer.
17. The composition of claim 12, wherein the polymer is a
thermoplastic.
18. The composition of claim 12, wherein the polymer is a
thermoset.
19. The composition of claim 12, wherein the polymer comprises a
poly(vinyl chloride), polyhydroxyalkanoate, a poly(lactic acid), a
polystyrene, a polyurethane, a polyurea, a polyurea-urethane, a
polycarbonate, an acrylic polymer, a styrene-acrylic polymer, a
vinyl-acrylic polymer, an ethylene-vinyl acetate polymer, a
polyester, a polyamide, a polyether, a polybutadiene, an
acrylonitrile-butadiene-styrene copolymer, a
styrene-butadiene-styrene copolymer, a polyvinyl acetate, an
elastomer, or homopolymers thereof, or random, graft, or block
copolymers thereof, or blends or mixtures thereof.
20. The composition of claim 12, wherein the composition forms a
dispersed phase in a latex, a dispersion, or an emulsion.
21. The composition of claim 12, wherein the compound is melt
blended or solution blended with the polymer.
22. The composition of claim 12, wherein the composition is a
plastisol.
23. The composition of claim 22, wherein at least a portion of the
compound is in a liquid phase of the plastisol.
24. The composition of claim 12, further comprising one or more
crosslinkers, adjuvants, colorants, antifouling agents, tougheners,
solvents, fillers, metal particulates, odor scavenging agents,
lubricants, thermal stabilizers, light stabilizers including UV
stabilizers, flame retardant additives, pigments, blowing agents,
processing aids, impact modifiers, coalescing solvents, antioxidant
or a combination of any two or more thereof.
25. The composition of claim 12, further comprising one or more
additives selected from the group consisting of dialkyl phthalates,
trimethyl pentanyl diisobutyrate, dialkyl isophthalates, dialkyl
terephthalates, alkyl benzyl phthalates, dialkyl adipates, trialkyl
trimellitates, alkylyl trialkyl citrates, dialkyl azelates, dialkyl
glutarates, dialkyl sebacates, dialkyl cyclohexanedicarboxylates,
esters of pentaerythritol, esters of glycerol, fatty acid
triglycerides, esters of fatty acids, glycol dibenzoates,
epoxidized soybean oil, and mixtures thereof.
26. An article comprising the composition of claim 12.
27. A process for plasticizing a polymer comprising melt or
solution blending a polymer and a plasticizing amount of at least
one compound of claim 1.
28. The process of claim 27, wherein compound constitutes from 0.1
to 90% of the combined weights of the compound and the polymer.
29. A method for making an ester or amide compound according to
claim 1 comprising: a. contacting reagents comprising (A) one or
more alkylketal esters having the structure ##STR00034## (B) a
catalyst and (C) a polyol having the structure R.sup.6(OH).sub.t or
a polyamine having the structure R.sup.6(NRH).sub.t or
R.sup.6(NH.sub.2).sub.t where R is a hydrocarbyl or substituted
hydrocarbyl group and b. effecting a reaction to form an alcohol
and a compound of claim 1, wherein t=x+y and R.sup.20 is a
hydrocarbyl group or substituted hydrocarbyl group having up to 36
carbon atoms.
30. The method of claim 29, wherein reagent (C) is a polyol having
the structure R.sup.6(OH).sub.t.
31. The method of claim 30, wherein t is 2 and the mole ratio of
the alkyl ketal ester to the polyol is in a range of 2:1 to
10:1.
32. A method of making a compound of claim 1 comprising: a.
reacting a compound comprising a structure corresponding to
##STR00035## with a polyol comprising a structure corresponding to
R.sup.6(OH).sub.t to form water and a compound comprising a
structure corresponding to ##STR00036## b. adding a compound
comprising a structure corresponding to ##STR00037## and c.
effecting a reaction to form water and a compound having a
structure corresponding to claim 1, wherein a, b, R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.6 are as defined in claim 1, x is at
least 1, y is zero or a positive number and t=x+y.
33. A lubricant composition comprising an antioxidant and at least
one compound of claim 1.
34. A method of lubricating at least two contacting surfaces, the
method comprising introducing the lubricant composition of claim 33
between the two contacting surfaces.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of and claims priority to
Patent Cooperation Treaty Application No. PCT/US2010/039554, filed
Jun. 22, 2010, which claims the benefit of U.S. Provisional Patent
Application No. 61/219,098, filed 22 Jun. 2009, the entire contents
of both applications being incorporated herein by reference in
their entirety.
DETAILED DESCRIPTION
[0002] New chemical compositions based on 1,2- and 1,3-alkanediol,
and 1,2- and 1,3-alkanetriol ketals of oxocarboxylate esters are
disclosed, as are uses of these compositions as plasticizers for
organic polymers and a lubricant.
[0003] The 1,2-propanediol ketals of oxocarboxylate esters are
known. For example, the 1,2-propanediol ketal of ethyl levulinate
is disclosed at
http://www.thegoodscentscompany.com/data/rwl597311.html, and the
1,2-propanediol ketal of ethyl acetoacetate is disclosed in U.S.
Patent Publication No. 2006/0165622. Other ketals of
oxocarboxylates include those based on various 1,2-alkanediols such
as ethylene glycol, or those based on 1,3-alkanediols, such as
1,3-propanediol or 1,3-butanediol.
[0004] International Patent Publication No. WO 2009/032905 and U.S.
Patent Publication No. 2008/0242721 disclose the reaction products
of triols, such as glycerol, 1,1,1-trimethylolpropane, or
1,1,1-trimethylolethane, with esters of various oxocarboxylates
including alkyl levulinates, alkyl acetoacetates, and alkyl
pyruvates. These compounds all feature one free hydroxyl group and
one carboxylate ester, acid, or salt per molecule.
[0005] A number of known plasticizer compounds are derived from
non-renewable, petroleum or natural gas derived feedstocks.
Phthalate esters, particularly, dioctyl phthalate ester,
di(2-ethylhexyl) phthalate ester, and diisononyl phthalate ester
are industrially significant plasticizers useful for plasticizing
many formulations; more common formulations include those
containing poly(vinyl chloride) (PVC). Recent regulatory pressure
has targeted phthalates (United States Environmental Protection
Agency Report: Phthalates Action Plan-Dec. 30, 2009) for
replacement due to the risks associated with their use. Plasticizer
replacements are needed to plasticize formulations without the risk
to humans, animals and the environment.
[0006] There is a need to provide plasticizers based on
non-phthalates, or, more generally, from non-petroleum feedstocks.
It is desirable that such materials be synthesized economically in
large volumes. A number of lubricating fluids are based on mineral
oils that present potential environmental hazards. These
formulations have been widely used for many decades. Some demanding
lubricant applications include metal working which requires high
performance metalworking fluids containing chlorinated paraffins.
Recently however, the use of chlorinated paraffins has been
questioned due to hazards to workers and the environment. Previous
attempts to use non-chlorinated replacements have failed in
metalworking requiring high performance lubricating and extreme
pressure/anti-wear properties.
[0007] There is a need for high performance, economical,
environmentally safe lubricating fluids based on renewable biomass
feedstocks. It is desirable that such lubricants be readily
available, cost-effective, and non-hazardous for delivering key
lubricating/anti-wear properties.
SUMMARY
[0008] This invention is in one aspect a compound having a
structure corresponding to structure I
##STR00001##
wherein a is from 0 to 12; b is 0 or 1; each R.sup.1 is
independently hydrogen, a hydrocarbyl group, or a substituted
hydrocarbyl group; each R.sup.2, R.sup.3, and R.sup.4 are
independently methylene, alkylmethylene, or dialkylmethylene, x is
at least 1, y is 0 or a positive number and x+y is at least 2;
R.sup.6 is a hydrocarbyl group or a substituted hydrocarbyl group
and each Z is independently --O--, --NH-- or --NR-- where R is a
hydrocarbyl group or a substituted hydrocarbyl group.
[0009] In another aspect, the invention is a mixture comprising at
least two different compounds according to structure I.
[0010] In another aspect, the invention is a compound having a
structure according to structure II
##STR00002##
each R.sup.1 is independently hydrogen, a hydrocarbyl group, or a
substituted hydrocarbyl group;
[0011] each R.sup.2, R.sup.3, and R.sup.4 are independently
methylene, alkylmethylene, or dialkylmethylene; R.sup.5 is hydrogen
or
##STR00003##
R.sup.6 is a hydrocarbyl group or a substituted hydrocarbyl group;
each R.sup.14 and R.sup.15 are independently hydrogen, a
hydrocarbyl, or a substituted hydrocarbyl group; each Z is
independently --O--, --NH-- or --NR-- where R is a hydrocarbyl
group or a substituted hydrocarbyl group, each a and each e is
independently from 0 to 12; each b and each f is independently 0 or
1; each i is zero or one; each j is zero to 100; w is from 1 to
100; x is at least 1, y is 0 or a positive number and z is zero or
a positive number provided that z is at least one when R.sup.5 is
hydrogen.
[0012] In another aspect, the invention is a mixture comprising at
least two different compounds according to structure II.
[0013] In still another aspect, the invention is a compound having
a structure according to structure III
##STR00004##
wherein a is from 0 to 12; b is 0 or 1; i is 0 or 1; each R.sup.1
is independently hydrogen, a hydrocarbyl group, or a substituted
hydrocarbyl group; each R.sup.2, R.sup.3, and R.sup.4 is
independently methylene, alkylmethylene, or dialkylmethylene, each
R.sup.7 and each R.sup.8 are independently hydrogen, a hydrocarbyl,
or a substituted hydrocarbyl group; each R.sup.23 is a hydrocarbyl
group or substituted hydrocarbyl group having between 1 and 12
carbon atoms; c is from 0 to 12; d is 0 or 1; and n is a number
from 1 to 100.
[0014] In another aspect, the invention is a mixture comprising at
least two different compounds according to structure III.
[0015] In another aspect, the invention is a compound having a
structure corresponding to IV
##STR00005##
wherein each e is independently from 0 to 12; each f is
independently 0 or 1; each i is independently 0 or 1; each R.sup.10
is independently a hydrocarbyl group or a substituted hydrocarbyl
group; each R.sup.14 and each R.sup.15 are independently hydrogen,
a hydrocarbyl, or a substituted hydrocarbyl group; R.sup.12 is a
covalent bond, a hydrocarbyl group or a substituted hydrocarbyl
group; w is a number from 1 to 100, v is a number from 0 to 100 and
s is at least one.
[0016] In another aspect, the invention is a mixture comprising at
least two compounds of structure IV.
[0017] In still another aspect, the invention is mixture of two or
more compounds selected from compounds of structure I, compounds of
structure II, compounds of structure III and compounds of structure
IV.
[0018] The invention in other aspects is a composite comprising a
compound of structure I, structure II or structure III or structure
IV, or any combination of two or more thereof, and a polymer.
[0019] The invention is also a process for plasticizing a polymer
comprising melt or solution blending a polymer and a plasticizing
amount of at least one compound of structure I, at least one
compound of structure II, at least compound of structure III, at
least one compound of structure IV or a mixture of two or more of
compounds having structures I, II, III IV or V.
[0020] In yet another aspect, the invention is a method for making
an ester or amide compound according to structure I comprising:
a. contacting reagents comprising (A) one or more alkylketal esters
having the structure
##STR00006##
(B) a catalyst and (C) a polyol having the structure
R.sup.6(OH).sub.t or a polyamine having the structure
R.sup.6(NRH).sub.t or R.sup.6(NH.sub.2).sub.t where R is a
hydrocarbyl or substituted hydrocarbyl group and b. effecting a
reaction to form an alcohol and a compound of claim 1, wherein
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6, Z, a, b, x, y and z
are as defined above, t=x+y and R.sup.20 is a hydrocarbyl group or
substituted hydrocarbyl group having up to 36 carbon atoms.
[0021] The invention is also making an ester compound of structure
II comprising:
a. contacting reagents comprising (1) one or more alkylketal esters
having the structure
##STR00007##
(2) one or more hydroxyalkyl ketal esters having the structure
##STR00008##
(3) a catalyst and (4) a polyol having the structure
R.sup.6(OH).sub.t or a polyamine having the structure
R.sup.6(NRH).sub.t or R.sup.6(NH.sub.2).sub.t where R is a
hydrocarbyl or substituted hydrocarbyl group; and b. effecting a
reaction to form an alcohol and a compound of structure II, wherein
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6, R.sup.14, R.sup.15, Z,
a, b, e, f, i, j, w, x, y, z and n are as defined above, t=x+y+z,
R.sup.20 and R.sup.21 are each independently a hydrocarbyl group or
substituted hydrocarbyl group having up to 12 carbon atoms and
R.sup.5 is hydrogen or
##STR00009##
[0022] The invention is in another aspect a method for making an
ester compound of structure III comprising:
a. contacting reagents comprising (1) one or more alkylketal ester
having the structure
##STR00010##
(2) one or more hydroxyalkyl ketal esters having the structure
##STR00011##
and (3) a catalyst; and b. effecting a reaction to form an alcohol
and a compound of structure III, wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.7, R.sup.8, R.sup.23, a, b, c, d and n are as
defined above, and R.sup.20 and R.sup.21 are each independently a
hydrocarbyl group or substituted hydrocarbyl group having up to 12
carbon atoms.
[0023] The invention is in still another aspect a method of making
an ester comprising contacting reagents comprising (1) one or more
hydroxyalkyl ketal esters having the structure
##STR00012##
(2) a full or partial ester of a polycarboxylic acid, and (3) a
catalyst; and effecting a reaction to form the ester compound and
an alcohol, wherein e is from 0 to 12; f is 0 or 1, i is zero or 1,
each R.sup.10 is independently a hydrocarbyl group or a substituted
hydrocarbyl group; each R.sup.14 and each R.sup.15 are
independently hydrogen, a hydrocarbyl, or a substituted hydrocarbyl
group.
[0024] In another aspect, the invention is a method of making a
compound of structure I comprising:
a. reacting a compound comprising a structure corresponding to
##STR00013##
with a polyol comprising a structure corresponding to
R.sup.6(OH).sub.t in the presence of a catalyst to form water and a
compound comprising a structure corresponding to
##STR00014##
b. adding a compound comprising a structure corresponding to
##STR00015##
and c. effecting a reaction to form water and a compound having a
structure corresponding to claim 1, wherein a, b, R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.6 are as defined in claim 1, x is at
least 1, y is zero or a positive number and t=x+y.
[0025] The invention is also a lubricant composition comprising an
antioxidant and a compound having structure I, II, III, IV or a
mixture of two or more such compounds. The invention is also a
method for lubricating at least two contacting surfaces, the method
comprising introducing the lubricant composition of claim 70
between the two contacting surfaces.
[0026] The structure I products correspond to a reaction product of
a polyol, aminoalcohol or polyamine and certain 1,2- and/or
1,3-alkanediol ketal of an oxocarboxylate esters, although the
invention is not limited to any particular preparation method. 1,2-
and 1,3-alkanediols ketals of oxocarboxylate esters are sometimes
referred to herein as "alkylketal esters". Up to one mole of alkyl
ketal ester can be reacted per equivalent of hydroxyl groups or
amino groups provided by the polyol, aminoalcohol or polyamine. The
polyol, aminoalcohol or polyamine is most preferably difunctional,
but polyols, aminoalcohols and polyamines having more than two
hydroxyl and/or amino groups can be used.
[0027] The values of x and y in structure I will depend on the
number of hydroxyl groups or amino groups on the polyol,
aminoalcohol or polyamine, the number of moles of the alkyl ketal
ester per mole of the polyol, aminoalcohol or polyamine, and the
extent to which the reaction is taken towards completion. Higher
amounts of the alkyl ketal ester favor lower values for y and
higher values of x.
[0028] In structure I, y is preferably from 0 to 2 and x is
preferably at least 2. All a in structure I are preferably 2, and
all R.sup.1 are preferably methyl. In some embodiments of structure
I, all Z are --O--, y is 0 and x is 2; these products correspond to
a reaction of two moles of an alkyl ketal ester and one mole of a
diol. In some other embodiments, all Z are --O--, y is 1 and x is
1; these products correspond to the reaction of one mole of the
alkyl ketal ester and one mole of a diol.
[0029] When Z is --O--, R.sup.6 corresponds to the residue, after
removal of hydroxyl groups, of a polyol having the structure
R.sup.6(OH).sub.t, where t=x+y. No two hydroxyl groups should be
bonded to the same carbon atom. Suitable polyols include alkane
diols such as ethane diol, 1,2-propane diol, 1,3-propane diol,
1,4-butane diol, 1,5-pentane diol and 1,6-hexane diol,
1,4-cyclohexanediol, glycerine, trimethylolpropane,
trimethylolethane, pentaerythritol, erythritol, sucrose,
isosorbide, sorbitol, bisphenol-A, 2,3-dibromobutene-1,4-diol,
1,4-benzene dimethanol, 1,4-benzenediol (hydroquinone),
2-butyne-1,4-diol, 3-hexyne, 3,5-diol and other alkyne-containing
polyols such as those marked under the Surfynol.TM. brand name by
Air Products and Chemicals. Other suitable polyols contain ether
groups; these include glycol ethers such as diethylene glycol,
triethylene glycol, dipropylene glycol, tripropylene glycol. Other
suitable ether-containing polyols include hydroxyl-terminated
polyethers such as poly(ethylene oxide), poly(propylene oxide),
ethylene oxide-propylene oxide copolymers and polymers of
tetramethylene glycol; these may have molecular weights of up to
6000, preferably up to 1000 and more preferably up to 150. The
polyol may contain ester linkages; these polyols include those
formed by condensation or step-growth polymerization of diols and
dicarboxylic acids (or their derivatives), including a polyester of
diethylene glycol and phthalic acid or phthalic anhydride. The
R.sup.6 group preferably contains from 2 to 24, especially from 2
to 12 or from 2 to 6 carbon atoms.
[0030] When all Z are --NR-- or --NH--, R.sup.6 corresponds to the
residue, after removal of amino groups, of a polyamine having the
structure R.sup.6(NRH).sub.t or R.sup.6(NH.sub.2).sub.t where
t=x+y. No two amino groups should be bonded to the same carbon
atom. Examples of suitable polyamines include hydrazine,
ethane-1,2-diamine, 1,6-hexanediamine, but-2-ene-1,4-diamine,
Metformin, butane-1,4-diamine, propane-1,2-diamine, piperazine,
2,2,4-trimethyl-1,6-hexanediamine,
2,4,4-trimethyl-1,6-hexanediamine, benzene-1,3-diamine,
2-methylbenzene-1,3-diamine, 4-chlorobenzene-1,3-diamine, and
polyoxyalkyleneamines having two amine groups, such as those sold
under the trade name JEFFAMINE.RTM., (Huntsman Corp.; Salt Lake
City, Utah), diamines such as those sold under the trade name
ELASTAMINE.RTM. (Huntsman Corporation), phenylene diamine,
methylene bis(aniline), diethyltoluenediamine and the like.
[0031] When the Z groups in structure I include at least one --O--
and at least one --NH-- or --NR-linkage, R.sup.6 corresponds to the
residue, after removal of hydroxyl and primary or secondary amino
groups, of an aminoalcohol, where the combined number of hydroxyl,
primary and secondary amino groups is equal to x+y. Examples of
suitable aminoalcohols include 2-aminoethanol, 3-aminopropan-1-ol,
isopropanolamine, 2-aminopropan-1-ol, 2-aminobutan-1-ol,
2-amino-3-methylbutan-1-ol, 2-amino-4-methylpentan-1-ol,
6-aminohexan-1-ol, 1-amino-3-chloropropan-2-ol,
7-aminobicyclo[2.2.2]octan-8-ol, 2-aminopyridin-3-ol,
2-amino-4-phenylphenol, 5-aminonaphthalen-1-ol, and
4-(4-aminophenyl)phenol.
[0032] In structures I-IV herein, a "substituted" hydrocarbon or
hydrocarbyl group may contain any substituents that do not react
with carboxylate groups, hydroxyl groups or amino groups under the
conditions of the reactions that form the various products of
structures I-IV. Therefore, the substituents should exclude groups
such as hydroxyl, primary or secondary amino, mercapto, carboxylic
acid or salts or esters thereof, carboxylic acid halides, sulfur-
or phosphorus-containing acids, isocyanates and the like. In
addition, the substituent groups also should not otherwise
interfere with the reactions that form the various products of
structures I-IV. Suitable substituents include, carbonyl, halogen,
tertiary amino, ether, sulfone, and the like, among others.
[0033] Some specific compounds according to structure I include
those having the structure
##STR00016##
or the structure
##STR00017##
particularly in which R.sup.6 is --(CH.sub.2)--.sub.m wherein m is
from 2 to 18, especially 2, 3, 4 or 6. Compounds according to
structure I can be prepared in a transesterification or
ester-aminolysis reaction between the corresponding polyol,
aminoalcohol or polyamine and the corresponding alkyl ketal ester.
Alternatively, compounds according to structure I can be prepared
by reacting an oxocarboxylic acid with the polyol, aminoalcohol or
polyamine to form an ester or amide, and then ketalizing the
resulting product with a 1,2- or 1,3-alkane diol such as ethylene
glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,
1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol,
1,3-hexanediol, and the like. Ketalization is conveniently
performed according to the methods described in International
Patent Publication No. WO 2009/048874, or U.S. Patent Publication
No. 2008/0242721.
[0034] A mixture of products is commonly obtained from the
synthesis process. For example, it is common for the reaction
product to contain a mixture of materials having various values of
x and y. It is preferred that no more than 25 mole percent of the
product represents compounds in which y is 1 or greater. In
especially preferred cases in which the starting polyol is a diol,
it is preferred that at least 75 mole of the product is species in
which x is 2 and y is zero.
[0035] Compounds corresponding to structure II correspond to the
reaction product of a polyol of the structure R.sup.6(OH).sub.t, an
amino alcohol or a polyamine having the structure
R.sup.6(NRH).sub.t or R.sup.6(NH.sub.2).sub.t, in which t=x+y+z,
one or more alkyl ketal esters having the structure
##STR00018##
and one or more triol ketals of an oxocarboxylate ester having the
structure
##STR00019##
wherein the variables are as defined before. R.sup.6 is as
described above with respect to structure I. Ketals of triols with
oxocarboxylate esters are sometimes referred to herein as
"hydroxyalkyl ketal esters". Some examples of useful alkylketal
ester starting materials include the 1,2-propane diol ketal of
ethyl levulinate, the 1,3-propane diol ketal of propyl levulinate,
1,2-propane diol ketal of butyl levulinate, 1,3-propane diol ketal
of ethyl levulinate and 1,2-ethane diol ketal of ethyl levulinate.
Some examples of useful hydroxyalkyl ketal ester starting materials
include the 1,2-glycerol ketal of methyl levulinate, 1,2-glycerol
ketal of ethyl levulinate, 1,2-glycerol ketal of methyl
acetoacetate, and 1,2-glycerol ketal of ethyl acetoacetate. Useful
methods for making such alkyl ketal esters and hydroxyalkyl ketal
esters are described in U.S. Patent Publication No. 2008/0242721
and International Patent Publication No. WO 2009/048874, which are
incorporated herein by reference in their entirety.
[0036] The values of j, w, x, y and z in structure II will depend
on factors including the number of hydroxyl or amino groups on the
polyol, aminoalcohol or polyamine, the number of moles of alkyl
ketal ester per mole of the polyol, aminoalcohol or polyamine, the
number of moles of the hydroxyalkyl ketal ester per mole of the
polyol, aminoalcohol or polyamine, and the extent to which the
reaction is taken towards completion. Higher amounts of the alkyl
ketal ester favor lower values for y. Higher amounts of the
hydroxyalkyl ketal ester favor lower values of y, and higher values
of x and z and/or higher values of j and w.
[0037] When j or w is greater than 1 in structure II, some amount
of self-condensation ("oligomerization") of the hydroxyalkyl ketal
ester has taken place.
[0038] In some embodiments of the structure II compound, R.sup.5
is
##STR00020##
and (a) j=0, z is at least one and w is from 1 to 15, (b) z=0, x=1
and w is from 1 to 15 or (c) z=0, x is greater than 1 and w is from
1 to 15. In some other embodiments of the structure II compound,
R.sup.5 is hydrogen, j is from 0 to 15 and z is at least one. In
some embodiments of the structure II compound, including those
specific embodiments just mentioned, each Z is --O--.
[0039] In structure II, including the specific embodiments
mentioned in the preceding paragraph, a and all e preferably are 2,
all R.sup.1 and R.sup.8 preferably are methyl and R.sup.14 is
preferably an alkyl group, especially one having up to 4 carbon
atoms. R.sup.6 in any of the foregoing embodiments may include
ether or ester groups.
[0040] Compounds according to structure II can be prepared in a
transesterification reaction between the corresponding polyol,
aminoalcohol or polyamine, the corresponding alkyl ketal ester and
the corresponding hydroxyalkyl ketal ester. In some embodiments,
all three of these materials are combined and reacted in a single
step to form the structure II material. In other embodiments, the
compound is formed in a one-pot process in which the reagents are
added sequentially; in such a case the hydroxyalkyl ketal ester may
be starve-fed to the reaction to minimize oligomerization.
[0041] In other embodiments, the polyol, aminoalcohol or polyamine
and hydroxyalkyl ketal ester are reacted first to form an
intermediate, which is then reacted with the alkyl ketal ester. In
still other embodiments, when the value of j and/or w in structure
II is greater than 1, the hydroxyalkyl ketal ester can be
oligomerized in a preliminary step, and the oligomerized material
is then reacted with the other starting materials or with an
intermediate formed by reaction of the polyol, aminoalcohol and/or
polyamine and the alkyl ketal ester. Oligomerization of the
hydroxyalkyl ketal ester also can be performed at the same time
that the hydroxyalkyl ketal ester reacts with the other starting
materials.
[0042] Again, a mixture of products is commonly obtained from the
synthesis process. For example, it is common for the reaction
product to contain a mixture of materials having various values of
j, w, x, y and z.
[0043] The structure III compounds correspond to certain reaction
product of an alkyl ketal ester having the structure
##STR00021##
wherein the variables are as defined before, and a hydroxyalkyl
ketal ester having the structure
##STR00022##
where again the variables are as defined before. Suitable alkyl
ketal esters include those described above with respect to
structure I. Suitable hydroxyalkyl ketal esters include those
described above with respect to structure II.
[0044] In structure III, n is preferably from 1 to 15, a and all c
are preferably 2, R.sup.1 and R.sup.8 are preferably methyl and
R.sup.23 is preferably an alkyl or phenyl group. As with structure
II, a value of n greater than 1 indicates that some oligomerization
of the hydroxyalkyl ketal ester has occurred, n is more preferably
from 1 to 2 and may be 1. The structure III compound is a 1:1
reaction product of the starting materials when n is 1. An example
of a compound according to structure III is
##STR00023##
wherein R.sup.23 is as defined above.
[0045] Compounds according to structure III can be prepared in a
transesterification reaction between the corresponding alkyl ketal
ester and the corresponding hydroxyalkyl ketal ester. The values of
n in structure III will depend on the relative number of moles of
the alkyl ketal ester and hydroxyalkyl ketal ester, and the extent
to which the reaction is continued. Higher amounts of the
hydroxyalkyl ketal ester favor higher values of n. When n is
greater than 1, indicating that the hydroxyalkyl ketal ester has
oligomerized, it is possible to perform the oligomerization
reaction separately, in a preliminary step. Alternatively, the
oligomerization can be performed at the same time as the reaction
with the alkyl ketal ester. If oligomerization is to be minimized
or prevented, the hydroxyalkyl ketal ester may be starve-fed to the
alkyl ketal ester under reaction conditions.
[0046] Compounds according to structure IV correspond to reaction
products of transesterification reaction between a full or partial
polycarboxylic acid ester compound and one or more hydroxyalkyl
ketal esters as described above.
[0047] The full or partial polycarboxylic acid ester compound is a
material that contains more than one carboxyl group per molecule,
at least one of which is esterified, preferably with a hydrocarbyl
or substituted hydrocarbyl group having up to 12 carbon atoms,
especially up to 6 carbon atoms. If all of the carboxyl groups are
esterified, the polycarboxylic ester compound is said to be a full
ester. A partial ester is one in which only a portion of the
carboxyl groups are esterified; the remaining carboxyl groups may
be in the acid or salt form. In some embodiments, the
polycarboxylic acid ester may contain from 2 to 8 carboxylic acid
or carboxylic acid groups, but preferably it contains from 2 to 4
such groups and more preferably is a monoester or a diester of a
dicarboxylic acid.
[0048] The full or partial ester can be represented by the
structure R.sup.12--(COOX).sub.n, where R.sup.12 is as defined
before, n=1+s, and X is hydrocarbyl or substituted, hydrogen or a
monovalent cation, further provided that at least one X is
hydrocarbyl or substituted hydrocarbyl. It is preferred that all X
are hydrocarbyl or substituted hydrocarbyl.
[0049] Examples of full or partial polycarboxylic acid esters
suitable for forming the reaction product corresponding to IV
include monoesters and diesters of dicarboxylic acids in which
R.sup.12 is a covalent bond, divalent alkyl (especially those of
the form --(CH.sub.2).sub.k-- where k is from 1 to 20, especially 2
to 10), divalent alkenyl (especially the cis or trans form of
--CH.dbd.CH--), divalent alkynyl, phenylene, substituted phenylene,
and the like. Examples of suitable full or partial carboxylic acid
esters include various esters of oxalic, malonic, adipic, sebacic,
azealic, maleic, fumaric, butandoic, succinic, dodecanoic and
octadecandioic acids. In some embodiments, suitable diesters
include diethyl adipate, diethyl sebacate, diethyl succinate,
dimethyl adipate, dibutyl adipate, dioctyl adipate,
dioctyl-phthalate, and butyl-benzyl phthalate. Suitable
hydroxyalkyl esters include those described above with respect to
structure II.
[0050] In structure IV, the values of w, s and v will depend on
factors including the number of carboxylic acid or carboxylic acid
ester groups on the full or partial carboxylic acid ester, the
number of moles of hydroxyalkyl ketal ester per mole of the full or
partial carboxylic acid ester, and the extent to which the reaction
is taken towards completion. Higher amounts of the hydroxyalkyl
ketal ester favor higher values of w, s and v. s is preferably from
1 to 7, more preferably from 1 to 3 and most preferably 1. w and v
may each be from 1 to 100, preferably from 1 to 10. In some
embodiments, w and v are each 1. In other embodiments, w+v is at
least 3. In still other embodiments, v=0. When w=1, v=0 and s=1,
the product corresponds to a 1:1 reaction product of the
hydroxyalkyl ketal ester and a dicarboxylic acid mono- or diester.
When w=v=s=1, the product corresponds to a 2:1 reaction product of
the hydroxyalkyl ketal ester and a dicarboxylic acid mono- or
diester. When either or both of w and v are greater than 1, the
molecular weight of the structure IV material may range from about
200 to 40,000 daltons, but is preferably from 300 to 3000
daltons.
[0051] In structure IV, the value of each e is preferably 1 or 2,
each R.sup.14 is preferably methyl and each R.sup.15 is preferably
alkyl having up to 3 carbon atoms. Each R.sup.10 is preferably
Ci-.sub.1-8 alkyl, more preferably C.sub.2-4 alkyl.
[0052] Specific examples of useful compounds of structure IV
include,
##STR00024## ##STR00025##
wherein h=0 to 34, preferably 2, 3, 4 or 6 and each R.sup.10 is
independently C.sub.1-C.sub.12 alkyl, preferably C.sub.1-C.sub.4
alkyl, or aromatic or alkyl aromatic of up to 12 carbon atoms.
[0053] Compounds according to structure IV can be prepared in a
transesterification reaction between the corresponding full or
partial polycarboxylic acid ester and the corresponding
hydroxyalkyl ketal ester. In some embodiments, the materials are
combined and reacted in a single step to form the structure IV
material. In other embodiments, when the value of n in structure IV
is greater than 1, the hydroxyalkyl ketal ester can be oligomerized
in a preliminary step, and the oligomerized material is then
reacted with the full or partial polycarboxylic acid ester.
Oligomerization of the hydroxyalkyl ketal ester also can be
performed at the same time that material reacts with the full or
partial polycarboxylic acid ester. As before, oligomerization of
the hydroxyalkyl ketal ester can be minimized or prevented by
starve-feeding the material into the reaction under reaction
conditions.
[0054] In some embodiments, a stoichiometric excess of hydroxyalkyl
ketal ester is employed with respect to the full or partial
polycarboxylic acid ester in order to form a reaction product
having structure IV. In some cases, about two equivalents of
hydroxyalkyl ketal ester are employed per mole of carboxylate ester
in one or more transesterification reactions. In other embodiments,
greater than about 2 and up to 100 equivalents of hydroxyalkyl
ketal ester are employed per equivalent of the polycarboxylic acid
ester in the reaction to form compound IV. This mole ratio may be
between about 2.1 to 50:1 or about 2.2-5:1. In still other
embodiments, less than a 2:1 molar ratio of hydroxyalkyl ketal
ester to full or partial polycarboxylic acid ester is used,
although higher ratios can be used if the reaction is not taken to
full conversion. In some other embodiments, where a 1:1 reaction
product of the hydroxyalkyl ketal ester and the full or partial
polycarboxylic acid ester is desired, about 1 to 10 equivalents of
polycarboxylic acid ester is employed per mole of hydroxyalkyl
ketal ester.
[0055] As before, a mixture of products is commonly obtained from
the synthesis process. For example, it is common for the reaction
product to contain a mixture of materials having various values of
w, v and s. In some embodiments, a mixture of products is obtained,
which includes species in which w and s are 1 and v is zero, as
well as species in which w, s and v are all 1. In some embodiments,
at least 75 wt. %, more preferably at least 85 wt. %, of such a
mixture is the species in which w, s and v are all 1. In other
embodiments, such a mixture contains no more than 10 wt. % or no
more than 5 wt. % of the mixture is the species in which w, s and v
are all 1.
[0056] Certain compounds according to structures I-IV may exist as
optical and/or geometrical isomers. In such cases, any of the
isomers are suitable.
[0057] The transesterification reactions that are used to form the
compounds of structures I-IV can be carried out in the presence of
an inert solvent, such as hexane, toluene, dichlorobenzene and the
like. In other embodiments the reaction is carried out neat. In
some embodiments, the reaction is performed at temperature and
pressure conditions such that the condensation coproduct, i.e., an
alcohol in most cases but water in some cases, evaporates from the
reaction mixture, wherein the vapor is condensed and thereby
removed. In some embodiments, a temperature between about
60.degree. C. and 300.degree. C. is employed; in other embodiments,
a temperature of about 100.degree. C. to 250.degree. C. is
employed; in still other embodiments, a temperature of about
160.degree. C. to 240.degree. C. is employed to accomplish the
reaction. In some embodiments, pressure in the reaction vessel is
lowered to below atmospheric pressure to assist in the removal of
the condensation by-product, i.e., the alcohol or water. In some
embodiments, nitrogen is sparged or swept through the reaction
mixture to assist in the removal of the coproduct alcohol.
[0058] The various reactions described above are typically
performed in the presence of a catalyst. While the choice of
catalyst employed in the reactions is not particularly limited
within the scope of the disclosure, a preferred set of embodiments
employs metallic catalysts, for example, a catalyst based on
titanium, aluminum, zirconium, or tin, such as titanium
tetraisopropoxide (Ti(OiPrM), or tin (II) octanoate, or organic
zirconates. Other suitable catalysts are, for example, organic
titanates and zirconates marketed under Tyzor.RTM. brand by DuPont
deNemours and Co. of Wilmington, Del. In some embodiments, more
than one species of catalyst is used; thus, blends of one or more
catalysts such as those mentioned above may be used in a mixture to
catalyze the formation of compounds of structures I-IV.
[0059] In some embodiments, catalysts such as inorganic bases,
including sodium methoxide, sodium ethoxide, calcium acetate, and
potassium methoxide, can be used. Organo-ammonium and
organo-phosphonium catalysts can be used, such as
tetramethylammonium hydroxide, tetrabutyl phosphonium hydroxides
and acetates Strong acid catalysts, including camphorsulfonic acid
or sulfuric acid can be used in ketalization and esterification
reactions. Catalysts are used in amounts suitable to catalyze the
reaction. In embodiments, the amount of organometallic catalyst
employed is about 5 to 50,000 ppm based on the weight of the total
weight of reagents, or about 10 to 500 ppm based on the total
weight of reagents.
[0060] In some embodiments, the catalyst is incorporated into, or
onto, or covalently bound to, a solid support material. Resin
beads, membranes, porous carbon particles, zeolite materials, and
other solid support materials may be functionalized with catalytic
moieties that are, in embodiments, covalently bound or strongly
sorbed to one or more surfaces of the solid support. In some
embodiments, it is desirable to deactivate the catalyst after the
reaction is complete. Deactivation is useful in embodiments, for
example, where distillation or a high temperature process or
application is to be employed. Deactivation is accomplished by any
convenient technique; the method is not particularly limited by the
method of deactivation. Examples of deactivating materials include
phosphite compounds such as water, and phenol based compounds such
as IRGAFOS.RTM. 168 and PEP-Q.RTM., or IRGANOX.RTM. MD 1024
(BASF.RTM.; Ludwigshafen am Rhein, Germany), and carboxylic acids
such as salicylic acid and the like.
[0061] The various synthesis reactions described herein can be
carried out batch wise or in continuous mode, depending on
equipment, scale, and other reaction parameters. The reaction
vessel may be made of any suitable material. In some embodiments,
the reagents are dried before addition of catalyst, using any
convenient technique. In embodiments, drying is accomplished by
warming the reaction vessel to about 60.degree. C.-110.degree. C.
and applying a vacuum of 5-20 Torr for at least about an hour; in
other embodiments a dry inert gas, such as nitrogen or argon, is
swept continuously through the vessel instead of applying a vacuum.
The reagents are, in some embodiments, analyzed for water content
prior to addition of catalyst to the vessel. In other embodiments,
the reagents are dried separately prior to addition to the reaction
vessel and are introduced to the vessel by a closed system, such as
by pipes or tubes, which does not entrain water or air during
introduction of the reagents to the vessel.
[0062] The catalyst may be added batchwise or in continuous fashion
to the vessel. In embodiments, during the addition of catalyst, the
reagents are at the same temperature as employed during drying. In
other embodiments the reagents are preheated to a targeted
temperature, for example in the ranges specified above, prior to
addition of the catalyst. After catalyst addition, in some
embodiments, a vacuum is employed to remove any air that has become
entrained during the addition. In other embodiments, the catalyst
is introduced to the vessel by a closed system, such as by pipes or
tubes that do not entrain water or air during introduction of the
reagents to the vessel. The reaction is, in embodiments, carried
out under an inert gas blanket or an inert gas sparge, and agitated
using any convenient means of agitation.
[0063] In embodiments, the reaction is complete in less than about
2 hour; in other embodiments the reaction is complete between about
1 hour and 12 hours; in still other embodiments the reaction is
complete in about 2 to 8 hours. In some embodiments, the limiting
reagent in the reaction is metered in gradually by employing an
addition funnel, metered pump, or another apparatus known in the
industry. Metering of a reagent is, in embodiments, initiated after
or during addition of the catalyst and is particularly useful where
the reaction is accomplished in a continuous process.
[0064] If desired, the crude reaction product can be purified using
any convenient techniques, one of which is distillation. A
distillation may be performed under reduced pressure or with the
aid of nitrogen sparging. It is preferred to perform the
distillation in a way that minimizes heat history. Therefore, this
step is preferably performed below temperatures at which
degradation, color formation, or another side reaction occurs, or
if such temperatures are used, the distillation should be performed
to minimize the exposure time of the product to such temperatures.
In some embodiments, it is desirable to maintain temperatures at or
below 200.degree. C. during purification. In other embodiments, it
is desirable to maintain temperatures at or below 175.degree. C.
during purification. Techniques such as wiped film evaporation,
falling film evaporation, and membrane pervaporization are useful.
Purification is carried out either with or without prior
deactivation of the catalyst.
[0065] In some cases, in which mixtures of reaction products are
obtained, it may be desirable to separate one or more of those
reaction products from the mixture of reaction products, in order
to obtain a product that is enriched in (or even consists of) a
specific compound or mixture of compound. This can be performed by
any suitable technique, including distillation, solvent extraction,
chromatographic methods, and the like.
[0066] Compounds according to structures I-IV are useful components
in compositions that also contain an organic polymer. A very wide
range of organic polymers is useful, depending of course on
particular applications. The organic polymer may be thermoset or
thermoplastic.
[0067] Many compounds according to structure I-VI have Hildebrand
Solubility Parameters ("HSP") of at least 12 (MPa).sup.1/2, quite
typically from 12 to 20 MPa).sup.1/2. Such compounds tend to be
quite compatible with organic polymers having Hildebrand Solubility
Parameters ("HSP") of about 16 (MPa).sup.1/2 or greater, therefore
preferred compositions are those in which the organic polymer has a
Hildebrand Solubility Parameters ("HSP") of about 16 (MPa).sup.1/2
or greater. The good compatibility of these tends to make the
compound of structure I-IV difficult to extract from the
composition, and also makes the composition less likely to exude or
leach the plasticizer material.
[0068] Extractability in various extractants such as hexanes, soapy
water, and mineral oil can be evaluated according to the ASTM D
1239 procedure; weight losses on this test are preferably no
greater than 2% and still more preferably no greater than 1% for
preferred compositions of the invention. Migration of a plasticizer
from an article causes increased exposure of the plasticizer to the
environment. The increased exposure can cause adhesive failure,
cracking of materials in contact with the article, and
contamination of fluids in contact with the article. Additionally,
migration out of the articles can lead to stiffening, loss of
performance and increase in T.sub.g.
[0069] Some examples of suitable organic polymers include
poly(vinyl chloride), poly(vinylidene chloride),
polyhydroxyalkanoates, poly(lactic acid), polystyrene,
polycarbonates, polyurethanes or ureas, acrylic polymers,
styrene-acrylic polymer, vinyl-acrylic polymers, ethylene-vinyl
acetate polymers, polyesters, polyamides, polyethers,
acrylonitrile-butadiene-styrene polymers, styrene-butadiene-styrene
polymers, polyvinyl acetate, poly(vinyl butyrate), polyketal esters
and copolymer thereof, cellulosics, thermoplastic elastomers, or
random, graft, or block copolymers thereof or mixtures thereof.
[0070] Compounds according to structures I-IV are generally
renewable bio-based feedstocks, wherein "bio-based" is used as
defined in ASTM D6866. As such, these compounds offer opportunities
to replace petroleum-based products such as plasticizer with
bio-based materials. Such a bio-based compound can be blended with
a bio-based organic polymer to form a polymer composition which is
also bio-based. One such polymer is poly(lactic acid), or PLA.
Compounds according to any of structures I-IV are good plasticizers
for PLA. Compounds I-IV often have high permanence in PLA compared
to other compatible plasticizers. The compound according to
structures I-IV may be incorporated into an organic polymer
composition using any suitable technique such as mechanical
blending or compounding, melt blending, solution blending and the
like. When the organic polymer is a thermoset, the compound may be
blended into one or more precursor materials, which are
subsequently cured or otherwise polymerized to form the
thermosetting polymer.
[0071] A composition containing a compound according to any of
structures I-IV and an organic polymer may take the form of a
homogeneous blend, a dispersion of one component into the other,
or, in some cases, that of a continuous liquid phase into which the
organic polymer is dispersed in the form of polymer particles. The
mixture of the compound according to any of structures I-IV and the
organic polymer may form the disperse phase in an emulsion or
dispersion in another material, which serves as a continuous liquid
phase, as is the case with a latex.
[0072] The relative amounts of the compound of structures I-IV and
the organic polymer may vary considerably. In various embodiments,
the organic polymer may constitute from 10 to 99.9%, from 30 to
96%, from 65 to 90% or from 40 to 60% of the combined weight of
polymer and compound of structure I-IV.
[0073] Compounds according to structures I-IV often perform a
plasticizing function when blended with organic polymers. When a
compound of structures I-IV is to perform such a function, it is
preferably liquid at room temperature or, if a solid at room
temperature, it has a glass transition temperature and/or softening
temperature below room temperature, often 0.degree. or -20.degree.
C. Plasticization is indicated by a reduction in T.sub.g of the
composition, compared to that of the neat organic polymer, and or a
softening or flexibilizing effect, as indicated by a reduction in
Shore hardness and/or a lowered flexural modulus, respectively.
Typically, the combination the organic polymer and the compound of
any of structure I-IV will have a T.sub.g of at least 5.degree. C.
lower at least 15.degree. C. lower, at least 30.degree. C. lower,
or at least 50.degree. C. lower than a T.sub.g of the neat polymer,
as measured by DSC according to ASTM D3418 or other DSC method. A
useful general procedure is as follows: The sample is evaluated on
a TA Q200 instrument with refrigerated cooling and TA Thermal
Advantage software (TA Instruments; New Castle, Del.), or
equivalent, using a ramp rate of 20.degree. C./min. Samples are
ramped from room temperature to 210.degree. C. followed by a rapid
quench. Samples are then reheated to 210.degree. C. at a rate of
20.degree. C./min. Glass transition temperature is measured on the
second scan.
[0074] When used to perform a plasticizing function, a compound of
any of structure I-IV preferably have viscosities less than about
500 centipoise (cP) at 25.degree. C. The viscosity may be from
about 1 cP to 250 cP; or about 50 cP to 200 cP at 25.degree. C. Low
viscosity provides ease of compounding into one or more polymer
compositions without, for example, preheating or addition of
diluents or solvents to lower viscosity and enables the creation of
pastes such as plastisols.
[0075] In certain embodiments, at least a portion of compound I-IV
is in a liquid phase of the plastisol. As used herein, the term
"plastisol" means a flowable suspension of polymer particles in a
plasticized emulsion that forms a solid, flexible, plasticized
polymer product with the addition of heat. A preferred polymer
phase is polyvinylchloride) although other polymer particles can be
used. A plastisol in accordance of the invention may contain from
10 to 90% by weight of a compound of structure I-IV. Polymer
plastisols are, in embodiments, poured into a mold or onto a
surface where the subsequent addition of heat causes the suspension
to form a solid, flexible mass. In such embodiments, it is
important for the plasticizer to cause "fusing", which means for
the purposes of discussion that the polymer particle boundaries of
the plastisol are broken by the effect of the plasticizer, causing
mixing of the polymer on a molecular scale, wherein the effect
persists to the solid state. Compounds according to structures I-IV
are often function well as "fast fusing plasticizers," which means
that they shorten the time required for the polymer particle
boundaries of the plastisol to be broken and mixing to occur, lower
the temperature required for the polymer particle boundaries of the
plastisol to be broken and mixing to occur, or both.
[0076] Plastisols in accordance with the invention are useful in
the production of sheet stock or films, flooring, tents,
tarpaulins, coated fabrics such as automobile upholstery, in car
underbody coatings, in moldings and other consumer products.
Plastisols are also used in medical uses such as blood bags and
multilayered sheets and films, tubing, footwear, fabric coating,
toys, flooring products and wallpaper. Plastisols typically contain
40 to 200 parts by weight, more typically 50 to 150 parts by
weight, more typically 70 to 120 parts by weight, more typically 90
to 110 parts by weight of plasticizer per 100 parts of dispersed
polymer particles. PVC plastisols are usually made from PVC that
has been produced by emulsion polymerization.
[0077] In certain embodiments, compounds according to structures
I-IV are contained in a PVC plastisol composition containing from
40 to 200 parts by weight, or 50 to 150 parts by weight, or 70 to
120 parts by weight, or 90 to 110 parts by weight of the compound
per 100 parts of PVC.
[0078] Such plastisol compositions tend to have stable viscosities;
their viscosities tend to increase less than about 200% over a
period of 14 days when stored at a temperature between about
20.degree. C. to 25.degree. C., or less than about 100%, preferably
less than 70% and more preferably less than 50% when stored at a
temperature of between about 20.degree. C. to 25.degree. C. for
five days.
[0079] In another embodiment of the present disclosure, a process
for the production of flexible PVC articles is provided, whereby a
layer is formed from a plastisol containing from 40 to 200 parts by
weight, or 50 to 150 parts by weight, or 70 to 120 parts by weight,
or 90 to 110 parts by weight of a plasticizer composition
containing one or more of compounds I-IV per 100 parts by weight of
PVC, and subsequently fusing the layer by the application of heat.
A plastisol in accordance with the invention may further contain
one or more additional plasticizers such as diethylene glycol
dibenzoate, butyl benzyl phthalate, dibutyl phthalate, diisononyl
phthalate, diisodecyl phthalate, other dialkyl phthalates,
dipropylene glycol dibenzoate, such as the phenyl cresyl esters of
pentadecyl sulfonic aromatic sulfonic acid esters available from
Bayer AG of Leverkusen, Germany as MESAMOLL.TM., citrates such as
tributylacetyl citrate, tri-2-ethylhexyl phosphate, trioctyl
phosphate such as 2-ethylhexyl-isodecyl phosphate, di-2-ethylhexyl
phenyl phosphate, triphenyl phosphate and tricresyl phosphate and
the like.
[0080] In general, polymer compositions in accordance with the
invention may further include one or more crosslinkers, adjuvants,
colorants, antifouling agents, tougheners, solvents, fillers, metal
particulates, odor scavenging agents, lubricants, thermal
stabilizers, light stabilizers including UV stabilizers, flame
retardant additives, pigments, blowing agents, processing aids,
impact modifiers, coalescing solvents, or a combination
thereof.
[0081] The useful, optional additives include, but are not limited
to, trimethyl pentanyl diisobutyrate, dialkyl isophthalates,
dialkyl terephthalates, alkyl benzyl phthalates, dialkyl adipates,
trialkyl trimellitates, alkylyl trialkyl citrates, dialkyl
azelates, dialkyl glutarates, dialkyl sebacates, dialkyl
cyclohexanedicarboxylates, dialkyl sulfonates, esters of
pentaerythritol, esters of glycerol, esters of fatty acids, glycol
dibenzoates, epoxidized soybean oil, any of the additives described
in International Patent Application Nos. PCT/US08/79337 or
PCT/US09/40841, or a mixture of any of these additional additives.
One or more of the alkyl, dialkyl, or trialkyl groups are, in
embodiments, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl, n-decyl, n-undecyl, n-dodecyl, capryl, cyclohexyl,
2-ethylhexyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl,
isononyl, isodecyl, isoundecyl, or a mixture thereof. In
embodiments, the alkylyl is acetyl or n-butyryl. In embodiments,
the glycol is ethylene glycol, propylene glycol, diethylene glycol,
or dipropylene glycol. The additional additives are present, in
embodiments, as a blend with one or more of the compounds I-IV.
[0082] Still more, optional materials that may be present in a
polymer composition of the invention include, for example, one or
more solvents (including coalescing solvents), crosslinkers,
colorants (dyes or pigments), antifouling agents (such as
antifungal, antibacterial, or antiviral agents), tougheners,
tackifiers, additional polymers, fillers, diluents, viscosity
modifying agents, metal particulates, odor scavenging agents,
adjuvants, lubricants, heat stabilizers, light stabilizers
including UV stabilizers, flame retardant additives, blowing
agents, processing aids, impact modifiers, or a combination
thereof. The additional materials impart various elements of
functionality to the composition, the nature of which depend on the
intended use of the composition, for example in one or more
articles as will be described below.
[0083] Polymer compositions of the invention are useful to form a
variety of articles. An "article" as used herein is an item with a
discrete shape, such as a tube, a film, a sheet, or a fiber, that
incorporates one or more compositions of the disclosure; in some
embodiments, the article may have its origin in a composition that
undergoes a transformation, such as solidification or evaporation
of one or more solvents, to result in the final article. In some
embodiments, an article is substantially formed from a polymer
composition of the invention; in other embodiments, the polymer
composition of the invention forms only one part, such as one
layer, of an article.
[0084] An article can be formed from a polymer composition of the
invention by a wide range of fabrication methods, including for
example, coating, casting, extrusion, coextrusion, profile
extrusion, blow molding, thermoforming, injection molding,
coinjection molding, reaction injection molding, milling, or
weaving. Where the polymer includes PVC, for example, the article
is, in some embodiments, a casing, a pipe, a cable, a wire
sheathing, a fiber, a woven fabric, a nonwoven fabric, a film, a
window profile, a floor covering, a wall base, an automotive item,
a medical item, a toy, a packaging container, a screw closure or
stopper adapted for a bottle, a gasket, a sealing compound, a film,
a synthetic leather item, an adhesive tape backing, or an item of
clothing. In some embodiments, the casing is a casing for an
electrical device. In some embodiments, the medical item is medical
tubing or a medical bag. In some embodiments, the film is a roofing
film, a composite film, a film for laminated safety glass, or a
packaging film.
[0085] In some embodiments, the packaging container is a food or
drink container. In some embodiments, the sealing compound is for
sealed glazing. In some embodiments, the automotive item is seat
upholstery, an instrument panel, an arm rest, a head support, a
gear shift dust cover, a seat spline, a sound-deadening panel, a
window seal, a landau top, a sealant, a truck tarpaulin, a door
panel, a cover for a console and glove compartment, a trim
laminating film, a floor mat, a wire insulation, a side body
molding, an underbody coating, a grommet, or a gasket.
[0086] In some embodiments, the article comprises two or more
layers and the compound of any of structures I-IV constitutes or is
contained within at least one layer. In another embodiment, the
article comprises a composition containing one or more compounds
I-IV in at least one layer. In some such embodiments, the other of
the two adjacent layers contains a plasticizer that doesn't have a
structure corresponding to compounds I-IV; the plasticizers
include, in various embodiments, other additives. Some examples of
such additives include dialkyl phthalates, trimethyl pentanyl
diisobutyrate, dialkyl isophthalates, dialkyl terephthalates, alkyl
benzyl phthalates, dialkyl adipates, trialkyl trimellitates,
alkylyl trialkyl citrates, dialkyl azelates, dialkyl glutarates,
dialkyl sebacates, dialkyl cyclohexanedicarboxylates, esters of
pentaerythritol, esters of glycerol, fatty acid triglycerides,
esters of fatty acids, glycol dibenzoates, epoxidized soybean oil,
and mixtures thereof.
[0087] Certain polymer compositions in accordance with the
invention are useful as adhesives, including as adhesive films or
adhesive coatings. Such adhesives may include, for example, a
poly(vinyl acetate) or vinyl acetate copolymer emulsion.
[0088] In some embodiments, the compounds I-IV are useful as
plasticizers in nail polish formulations. In another embodiment,
compounds I or II can be used as solvents and/or cosolvents in
these formulations. Polymers useful in nail polish formulations
include nitrocellulose, tosylamide-formaldehydes and the like.
[0089] Compounds according to any of structures I-IV are also
useful as lubricants or as a component of a lubricant composition.
In some embodiments, a blend or mixture of two or more such
compounds are useful as lubricants or as components of a lubricant
composition. The lubricant typically includes at least one
antioxidant, which typically will constitute from 0.1 to 5,
especially from 0.1 to 2% by weight of the lubricant composition.
The lubricant is applied between two contacting surfaces to provide
lubricating performance between the two surfaces.
[0090] Lubricants in accordance with the invention are useful as,
for example, such as compressor fluids, industrial oils (antiwear,
circulating, compound, cotton picker, cylinder, edge coat seal,
electrical, biodegradable lubricants), engine oils, automatic
transmission fluids, automotive gear lubricants, metalworking
fluids, and R&O turbine oils. Compounds I-IV of the present
disclosure can be used as a blend with one or more other
lubricants, such as, for example, one or more mineral oils,
polyalphaolefins, dibasic esters, polyol esters, alkylated
aromatics, polyalkylene glycols, phosphate esters, vegetable oils
and the like. Lubricant formulations can further include antiwear
and extreme pressure agents, corrosion and rust inhibitors,
detergents, dispersants, friction modifiers, pour point
depressants, seal swell agents, viscosity modifiers, antifoam
agents, metal deactivators, and the like, pour point of the product
of Example 5 is evaluated according to (Foaming
Characteristics--Sequences I, II and II), and ASTM D97,
respectively.
[0091] Compounds I-IV useful as lubricants or in lubricant
formulations preferably have a pour point, as measured according to
ASTM D97, of no higher than 0.degree. C., preferably no higher than
-20.degree. C. The compounds preferably exhibit excellent
resistance to foaming, as indicated by ASTM D892 IP 146, and
preferably exhibit foam volumes of less than 1 mL after both 5 and
10 minutes of blowing on that test. Low foaming can give a better
lubricating film and steady oil pressure during extensive
operations. Further, low foam lubricants can lead to better
performance in high performance oil pump systems with high volume
or pressure.
[0092] The following examples further elucidate and describe the
compounds of the disclosure and applications thereof without
limiting the scope thereof. All parts and percentages are by weight
unless otherwise indicated.
EXAMPLE 1
[0093] A 250 mL 3-neck round bottom flask is charged with 32.8 g
(0.15 mol) of the glycerin ketal of ethyl levulinate (Et-LGK)
(98.2%), and 91.0 g (0.45 mol) of the 1,2-propylene glycol ketal of
ethyl levulinate (Et-LPK) (0.14% ethyl levulinate and no detectable
propanediol). The contents of the flask are stirred under vacuum (6
torr) and heated to 110.degree. C. and 9.7 .mu.L of a titanium
tetra-isopropoxide is added into the flask. A nitrogen purge is
maintained and the contents of the flask are heated to 230.degree.
C. during which time a liquid condensate forms. The reaction
mixture is cooled to 110.degree. C., and distillation of a second
liquid is accomplished using reduced pressure of about 4 torr.
[0094] The reaction mixture is allowed to cool to ambient
temperature when no further distillate is collected. The product is
a mixture of compounds corresponding to structure III in which a
and c are 2, b is 0, d is 0, i is 1, R.sup.1 and R.sup.8 are
methyl, R.sup.3 is CH(CH.sub.3), R.sup.4 is methylene, R.sup.7 is
hydrogen and R.sup.23 is ethyl. The value of n is 1 for about 48.6%
of the material, 2 for 26.8% of the material, 3 for 12.2% of the
material and 4 for 8.2% of the material. The product contains 4.3%
of residual Et-LGK and Et-LPK.
EXAMPLE 2
[0095] A 250 mL 3-neck round bottom flask is charged with 18.02 g
(0.2 mol) of 1,4-butanediol ((BDO) Sigma Aldrich Company, St.
Louis, Mo.) and 121.35 g (0.6 mole) of ethyl-LPK (Et-LPK) (0.14%
ethyl levulinate and no detectable propanediol). The contents of
the flask are stirred at a pressure of 6 torr while heating to
90.degree. C. Then 3.22 .mu.L of a titanium tetra-isopropoxide is
added into the flask. A nitrogen purge is maintained and the
contents of the flask are heated to 200.degree. C. for 3 hours,
during which time a condensate forms. The reaction mixture is
allowed to cool to 110.degree. C., and distillation of a second
liquid is accomplished under reduced pressure of about 7 torr. The
reduced pressure is maintained until no further distillate is
collected. The flask is allowed to cool to ambient temperature and
the pressure is equilibrated to atmospheric pressure.
[0096] The reaction product contains about 87.2% of the compound
corresponding to
##STR00026##
about 1.1% of the compound corresponding
##STR00027##
wherein R.sup.6 is --(CH.sub.2).sub.4-- and about 0.6% of
ethyl-LPK. The product also contains some oligomerized
materials.
EXAMPLES 3-4 AND COMPARATIVE SAMPLE 1
[0097] The product of Example 1 is pre-mixed with poly(vinyl
chloride) ((PVC), M.sub.n=55,000, Mw=97,000) at 50 parts
plasticizer per hundred parts PVC. The premix is separately blended
for 10 minutes in a twin screw extruder operated at 165.degree.
C.-170.degree. C. under a continuous nitrogen (N2) purge to form
Example 3. Example 4 is made in the same manner, except that the
product of Example 2 replaces the product of Example 1.
[0098] Shore A Hardness of the resulting blends is measured
according to ASTM D 2240. T.sub.g is measured using standard DSC
techniques. Example 3 has a T.sub.g of -9.7.degree. C. and a Shore
A hardness of 81.5. Example 4 has a T.sub.g of -8.0.degree. C. and
a Shore A hardness of 78.8. The PVC by itself has a T.sub.g of
67.2.degree. C.
EXAMPLE 5
[0099] A 5-gallon Parr Model 4557 reactor (Parr Instrument Co.,
Moline, Ill.) is charged with 12.74 kg (63 moles) of Et-LPK and
1.89 kg (20.97 moles) 1,4-butanediol (Sigma-Aldrich Company; St.
Louis, Mo.). The contents of the reactor are stirred at 50 rpm at a
pressure of 52 torr; the recirculating chiller is operating at
-10.degree. C. and the high temperature circulator is operating at
70.degree. C. The reaction mixture is purged with dry nitrogen for
about 16 hours. Then, a vacuum of 4-5 Torr is applied to the
reactor for about 2 hours. 0.358 g (1.26 mmoles) titanium (IV)
isopropoxide (Sigma-Aldrich Company, St. Louis, Mo.) is admixed
with 4 mL of Et-LPK and added to the reactor. The reaction mixture
is purged for about 20 minutes with dry nitrogen followed by the
high temperature circulator set at 200.degree. C.
[0100] The contents of the reactor are heated to about 200.degree.
C. for 3 hours, during which time a condensate is collected. At
about 97.2% conversion, the reactor is cooled with an applied
vacuum of 20-25 torr, by reducing the high temperature circulator
set point to 200.degree. C. Distillation is continued by applying a
vacuum of about 5 Torr to the reactor until condensate formation is
discontinued. The contents of the reactor are analyzed by GC-FID.
Distillation is then restarted and continued as described above
until subsequent analysis reveals that the concentration of
ethyl-LPK is less than about 1.0%. When distillation is complete,
the reactor is cooled to ambient temperature.
[0101] The reaction product contains about 90.77% of a material
according to structure I in which a is 2, b is 0, x is 1, y is 1,
R.sup.1 is --CH.sub.3, R.sup.3 is CH(CH.sub.3), R.sup.4 is
methylene, R.sup.6 is --(CH.sub.2).sub.4--, and each Z is
--O--.
EXAMPLE 6
[0102] A 5-gallon reactor is charged with 12.54 kg (62 moles)
Et-LPK, 3.38 kg (15.48 moles) of Et-LGK, and 2.95 g IRGAFOS.RTM.
168 (Ciba AG, Basel, Switzerland). The contents of the reactor are
stirred at 50 rpm at a pressure of 52 torr with the recirculating
chiller set to -10.degree. C.; the high temperature circulator
operating at 70.degree. C. overnight for about 16 hours. A vacuum
of 4-5 torr is applied to the reactor for about 2 hours. 0.358 g
(1.26 mmoles) titanium (IV) isopropoxide is admixed with 4 mL of
Et-LPK and added to the reactor. The reaction mixture is then
purged for about 20 minutes with dry nitrogen and the high
temperature circulator set at 200.degree. C.
[0103] The contents of the reactor are heated to about 200.degree.
C. for 6 hours, and a condensate is collected. After the reaction
has reached about 99.0% conversion Et-LPK AN Et-LGK distilled off
until their combined concentration is less than 1%. When
distillation is complete, the reactor is cooled to ambient
temperature. The product is a mixture of compounds according to
structure III in which a and c are 2, b is 0, d is 0, i is 1,
R.sup.1 and R.sup.8 are methyl, R.sup.3 is CH(CH.sub.3), R.sup.4 is
methylene, R.sup.7 is hydrogen and R.sup.23 is ethyl. Species in
which n is 1, 2, 3 or greater than 3 respectively constitute
49.60%, 28.35%, 13.01% and 8.32% of the composition.
EXAMPLES 7-8
[0104] 100 parts of a suspension grade PVC powder (Type 2095
Georgia Gulf Corporation, Atlanta, Ga.) are blended with 2.5 parts
of a stabilizer (ThermChek-SP 175, Ferro Corporation, Cleveland,
Ohio) and then with 5 parts of epoxidized soybean oil.
[0105] The resulting mixture is then blended with 50 parts of the
product of Example 5 to form Example 7. Blending is performed on an
orbital mixer for about 5 minutes. The mixture is transferred into
the feed hopper of a 27 mm BRABENDER.RTM. (model #DR2051) PolySpede
twin-screw extruder (CW. BRABENDER.RTM. Instruments, Inc., South
Hackensack, N.J.). The material is extruded at 150.degree. C. with
a screw speed of 65 rpm through a 2 mm rod die. The material is
cooled by a water bath and fed into a Brabender pelletizer.
[0106] Example 8 is prepared in the same way, using the product
from Example 6 instead of the product of Example 5.
[0107] Pelletized extrudates are fed into a Nissei injection
molding machine (Model #PS04E5A; Nissei-America, Inc., Gahanna,
Ohio). ASTM D638-90 Type I tensile bars are injection molded at the
following conditions: 165.degree. C. set temperature for heating
zones 1-3, 165.degree. C. set temperature for the injection nozzle,
25.degree. C. mold temperature, 25% screw speed, 53 mm shot size,
5% back pressure, 1.17 second mold fill time and 9 second recovery
time, followed by 15 seconds cooling before removing the tensile
bar from the mold.
[0108] Plasticizer loadings in the molded tensile bars are
determined using weight loss data from thermogravimetric analysis
(TGA) using a TA Q50 with TA Thermal Advantage software (TA
Instruments; New Castle, Del.). Analysis is carried out by
equilibrating the samples at 30.degree. C. followed by a
temperature ramp of 10.degree. C./min to 600.degree. C. The results
of analysis, labeled "Actual Wt. % Plasticizer" are shown in Table
1.
[0109] Glass transition temperature (T.sub.g) of the pelletized
extrudates is determined by following ASTM D-3418, employing a TA
Q200 instrument with refrigerated cooling and TA Thermal Advantage
software. Homogeneous samples in a range of about 5 and 15 mg are
placed in a T-zero pan and crimped with a T-zero lid. T.sub.g
values are shown in Table 1.
[0110] Shore A hardness testing is carried out at the ends of the
molded tensile bars, where the outer width is wider than the gauge
width with a Durometer Type A (Instron, Norwood, Mass.) as
specified by ASTM D2240. except that the sample thickness of the
molded tensile bars in the area of testing is 3.2 mm; readings are
taken after 15 seconds. An average of ten readings is taken per
sample and reported in Table 1.
[0111] Extraction of soluble materials is carried out in both
hexanes and a 1% solution of soap in water. Hexane (Fisher
Scientific, Waltham, Mass.) was used as received. The 1% soap water
solution is made using deionized water and IVORY.RTM. soap shavings
(Procter and Gamble Co., Cincinnati, Ohio). Five molded tensile
bars are tested and the average value is recorded for each.
Pre-extraction and post-extraction mass measurements are obtained
on the molded tensile bars. The molded tensile bars are completely
immersed (hanging in the container) in the extraction media at
ambient temperature. After 24 hours of immersion, the samples are
removed from the extraction media; the soap solution samples are
rinsed with deionized water before being allowed to dry. All
samples are air dried for 24 hours before post-extraction mass is
measured. The weight loss of the samples is reported in Table
1.
TABLE-US-00001 TABLE 1 Wt. % Wt. % loss, Actual Wt. % loss, 24 hr
in 1% Plasticizer T.sub.g, Shore A 24 hr in soap Example
(TGA)/Source (.degree. C.) Hardness hexane solution 7 30 (Ex. 5) 5
89 0 0 8 33 (Ex. 6) 7 93 0 0
EXAMPLES 9-12
[0112] Examples 9-12 are separately made, all in the following
manner 250 ml 4-neck round bottom flask is charged with 43.62 g
(0.2 mol) of Et-LGK, and 80.90 g (0.4 mol) diethyl adipate (DEA),
followed by the addition of 0.0063 g Irgafos.RTM. 168 (Ciba
Corporation; Florham Park, N.J.). The contents of the flask are
stirred under a nitrogen blanket at 60.degree. C. 12 .mu.l
(microliters) of Ti(isopropoxide).sub.4 is added to the flask. The
contents of the flask are heated to 110.degree. C., degassed for
about 5 minutes at 3-5 torr, and back-filled with nitrogen. The
reaction mixture is heated to 230.degree. C. and a condensate is
distilled from the reaction until completion. The flask is cooled
to ambient temperature. The reaction mixtures are purified by
vacuum distillation to remove residual starting materials.
[0113] The products in each case are mixtures of compounds
according to structure IV, in which e is 2, f is 0, i is 1,
R.sup.10 is ethyl, R.sup.12 is --(CH.sub.2).sub.4--, R.sup.14 is
methyl and R.sup.15 is hydrogen. Each of Examples 9-12 contains
species in which s is 1, v is 0 and w is 1, species in which s is
1, v is 0 and w is 2 or s is 1, v is 1 and w is 1 and species in
which s is 1, v>1 and w>2. They all contain unreacted
starting materials. The relative amounts of those species are
indicated in Table 2.
TABLE-US-00002 TABLE 2 s is 1, v is 0 s is 1, and w is 2 or s is 1,
Unreacted v is 0 s is 1, v is 1 v > 1 and starting Example w is
1, % and w is 1, % w > 1, % materials, % 9 49 23 28 0.4 10 58 23
18 1.5 11 42 25 32 1.2 12 48 18 8 24
EXAMPLE 13
[0114] A 500 mL 4-neck round bottom flask is charged with 191.91 g
(0.95 mol) DEA and 62.30 g (0.24 mol) of the trimethylolpropane
ketal of ethyl levulinate (Et-LTMPK). Et-LTMPK is synthesized
according to the procedure outlined in WO 2007/062118. The reaction
mixture is heated to 60.degree. C. with a nitrogen purge for 12
hrs. 16 .mu.L of TPT is added to the flask, followed by heating the
mixture to 110.degree. C. At 110.degree. C., a vacuum of 20 torr is
applied for 5 min and backfilled with nitrogen, and the reaction
temperature is increased to 230.degree. C. A liquid condensate is
collected with the temperature gradually increasing to 260.degree.
C. After about 3 hours, the contents of the flask are cooled to
ambient temperature.
[0115] The product corresponds to structure IV in which e is 2, f
is 1, i is 1, R.sup.10 is ethyl, R.sup.12 is --(CH.sub.2).sub.4--,
R.sup.14 is methyl and R.sup.15 is ethyl. Example 13 contains 54.6%
of species in which s is 1, v is 0 and w is 1, 11.2% of species in
which s is 1, v is 0 and w is 2 or s is 1, v is 1 and w is 1 and
3.2% of species in which s is 1, v>1 and w>2.
EXAMPLE 14
[0116] A 250 mL 3-neck round bottom flask is charged with 26.63 g
(0.13 mol) of the glycerin ketal of ethyl acetoacetonate
(synthesized according to WO 2007/062118), 105.37 g (0.52 mol)
diethyl adipate, and heated to 60.degree. C. for 12 h under
nitrogen purge, then increasing the temperature to 110.degree. C.
and a pressure of 20 Torr for an additional 2 hours. Then 7.5 .mu.l
of titanium (IV) isopropoxide is added to the flask, and refilled
with nitrogen; the flask is heated to 230.degree. C. for 2.5 hours,
followed by an increase in temperature to 240.degree. C. for an
additional 2 hours. The mixture is cooled to ambient temperature.
The product is purified by distilling off unreacted starting
materials at 8 Torr and 125.degree. C. for about 25 minutes.
[0117] The product corresponds to structure IV in which e is 1, f
is 0, i is 1, R.sup.10 is ethyl, R.sup.12 is --(CH.sub.2).sub.4,
R.sup.14 is methyl and R.sup.15 is hydrogen. Example 14 contains
36.7% of species in which s is 1, v is 0 and w is 1, 19.4% of
species in which s is 1, v is 0 and w is 2 or s is 1, v is 1 and w
is 1 and 31.1% of species in which s is 1, v>1 and w>2.
EXAMPLES 15-16
[0118] A 250 ml 4-neck round bottom flask is charged with 49.08 g
(0.225 mol) of Et-LGK and 78.39 g (0.45 mol) diethyl succinate
((DESU) Sigma Aldrich; St. Louis, Mo.), and heated to 60.degree. C.
under a constant nitrogen purge for 12 hours to dry the starting
materials. 13.5 .mu.l of TPT is added to the reaction flask and the
reaction mixture is heated to 110.degree. C. for 25 minutes,
followed by degassing under a vacuum of 5-8 torr for 5 minutes;
back-filling the flask with nitrogen, and heating to 210.degree. C.
A condensate is collected and monitored to determine the percent
conversion of the reactants to products. The product (Example 15)
corresponds to structure IV in which e is 2, f is 0, i is 1,
R.sup.10 is ethyl, R.sup.12 is --(CH.sub.2).sub.2--, R.sup.14 is
methyl and R.sup.15 is hydrogen. Example 15 contains 52% of species
in which s is 1, v is 0 and w is 1, 30% of species in which s is 1,
v is 0 and w is 2 or s is 1, v is 1 and w is 1 and 17% of species
in which s is 1, v>1 and w>2.
[0119] Example 16 is made in the same manner, except the amount of
Et-LGK is doubled and the reaction time is extended to 45 minutes.
The product corresponds to structure IV in which e is 2, f is 0, i
is 1, R.sup.10 is ethyl, R.sup.12 is --(CH.sub.2).sub.2--, R.sup.14
is methyl and R.sup.15 is hydrogen. Example 16 contains 69% of
species in which s is 1, v is 0 and w is 1, 24% of species in which
s is 1, v is 0 and w is 2 or s is 1, v is 1 and w is 1 and 7% of
species in which s is 1, v>1 and w>2.
EXAMPLES 17-18
[0120] Et-LGK and diethyl sebacate ((DESE), Sigma Aldrich; St.
Louis, Mo.) are reacted similarly in the procedure described for
Examples 15-16 above. The reaction temperature is 230.degree. C.,
the reaction time is 46 minutes for Example 17 and 35 minutes for
Example 18. The ratio of Et-LGK to diethyl sebacate is 2:1 in
Example 17 and 4:1 in
[0121] The Example 17 product corresponds to structure IV in which
e is 2, f is 0, i is 1, R.sup.10 is ethyl, R.sup.12 is
--(CH.sub.2).sub.8--, R.sup.14 is methyl and R.sup.15 is hydrogen.
It contains 45% of species in which s is 1, v is 0 and w is 1, 32%
of species in which s is 1, v is 0 and w is 2 or s is 1, v is 1 and
w is 1 and 21% of species in which s is 1, v>1 and w>2.
[0122] The Example 18 product corresponds to structure IV in which
e is 2, f is 0, i is 1, R.sup.10 is ethyl, R.sup.12 is
--(CH.sub.2).sub.8--, R.sup.H is methyl and R.sup.15 is hydrogen.
It contains 73% of species in which s is 1, v is 0 and w is 1, 20%
of species in which s is 1, v is 0 and w is 2 or s is 1, v is 1 and
w is 1 and 6% of species in which s is 1, v>1 and w>2.
EXAMPLES 19-21
[0123] Examples 19-21 are prepared as follows. 100 parts of a
suspension grade PVC powder type (Type 2095 Georgia Gulf
Corporation) are blended with 2.5 parts of a stabilizer
(ThermChek-SP175), and then with 5 parts of epoxidized soybean oil.
The product of Example 9 is added at a predetermined loading, and
mixed in a Kitchen-aid mixer with a paddle blade for approximately
5 minutes. The powder is transferred into a feed hopper of a 27 mm
Brabender twin-screw extruder at 150.degree. C. All materials are
passed through a 2 mm rod die, and cooled by a water bath and
pelletized. Pelletized material is fed into a Nissei injection
molder, with three heating zones and a nozzle temperature of
165.degree. C. The mold temperature is set at 25.degree. C. The
screw speed is set at 30% with a shot size of 5 mm and a 5% back
pressure is used to fill the mold with a mold fill time of 1.01
sec, and recovery time of 11.5 sec.
[0124] Glass transition temperature is determined for each of
Examples 19-21 according to ASTM D-3418. Tensile properties are
measured according to ASTM D638. Shore A Hardness is measured at 15
seconds (ASTM D2240) on injection molded bars with a 3.2 mm
thickness. Results are as indicated in Table 3.
TABLE-US-00003 TABLE 3 Plasticizer Secant Loading T.sub.g
Elongation Modulus at Shore A Example (phr) (.degree. C.) at Break
(%) 100% (MPa) Hardness 19 30.0 13 204 19.8 98 20 50.0 -16 332 7.9
84 21 70.0 -25 338 4.7 74
[0125] Extractions (described in Examples 7-8) in hexane, soap
water and mineral oil are conducted on each of Examples 19-21
according to ASTM D 1239 with the following modifications. Samples
are not preconditioned, 1.4 L containers are used for extractions,
and 5 replicate samples are immersed in the same container.
Extraction results are presented in Table 4.
TABLE-US-00004 TABLE 4 Plasticizer Weight Loss (%) Loading 1% Soap
in Mineral Example (phr) Hexane Water Oil 19 30 0 0 0 20 50 0.1 0.2
0.1 21 70 0.5 0.5 0.4
EXAMPLES 22-23 AND COMPARATIVE SAMPLE 2
[0126] Poly(lactic acid) (PLA) resin (grade 4060D; Nature Works,
LLC; Minnetonka, Minn.) is dried at 40.degree. C. under vacuum for
4 hours prior to compounding. The PLA is compounded with the
product of Example 12 in a Brabender 3-piece bowl mixer at
210.degree. C. set at 60 rpm. The PLA resin is fed into the bowl
mixer with mixing for 2 minutes, followed by adding the Example 12
product with mixing for an additional 8 minutes. For Example 22,
10% by weight of the Example 12 product is added; for Example 23,
20% by weight of the Example 12 product is added. In Comparative
Sample 2, no plasticizer is added. The compounded samples are dried
under vacuum at 40.degree. C. for 4 hours. A Carver Model 4122
pneumatic heated plate press (Carver, Inc.; Wabash, Ind.) is
preheated to 210.degree. C. Samples are heated without pressure on
a pneumatic heated plate press at 210.degree. C. for 5 minutes,
followed by pressing at 5000 lbs force for 5 minutes. The samples
are quenched in a water bath and allowed to warm to room
temperature. All moldings are transparent water-white films having
a thickness of approximately 0.075 mm.
[0127] Migration of the plasticizer from compounded samples is
measured using the following procedure: 1 inch squares of
compounded melt pressed films are marked with blue, red and black
Sharpie.RTM. markers; the samples are placed in a controlled heat
and humidity chamber at the conditions specified, and changes to
the ink are evaluated after 100 days. Migration behavior on a scale
of 1 to 5 is used (i.e., 1 (none) being no change in the ink, 2
(very slight) being a small change to the ink edges), 3 (slight),
being a running of the ink edges, 4 (clear) being slight oiliness
on the surface to the touch, and 5 (very clear) being visible oil
on the surface). Migration results are reported in Table 5.
[0128] Glass transition temperature (T.sub.g) is determined using
the general procedure described above; results are as reported in
Table 5.
TABLE-US-00005 TABLE 5 Migration Migration Wt. % T.sub.g 40.degree.
C. dry 25.degree. C. and 50% Designation Plasticizer (.degree. C.)
100 days RH 100 days Comp. 2 0 57 NA NA 22 10 39 2 2 23 20 23 2
2
EXAMPLES 24-25 AND COMPARATIVE SAMPLE 3
[0129] 10 parts of Ultra Talc 609 ((Talc) Specialty Minerals;
Bethlehem, Pa.) are premixed with 100 parts of poly(lactic acid)
resin ((PLA) grade 4032D; Nature Works, LLC; Minnetonka, Minn. This
premix is compounded in a Brabender 3-piece bowl mixer at
210.degree. C., and mixed at 60 rpm for 10 minutes to form a talc
filled master batch. The master batch is cooled and ground. The
master batch is dry blended with virgin PLA resin (grade 4021D;
Nature Works, LLC; Minnetonka, Minn.) at ratios such that the dry
blend contains 1% by weight talc. This dry blend is compounded with
the product of Example 12 in the Brabender at 210.degree. C. Glass
transition temperature (T.sub.g) and melting temperature (Tm) are
determined following the procedure outlined in Examples 22-23
above. Cooling crystallization temperature (T.sub.a) is determined
using the following method: samples are ramped at 20.degree. C./min
from room temperature to 210.degree. C. followed by a rapid quench,
a second ramp is then performed from 25.degree. C. to 210.degree.
C. at 20.degree. C./minute followed by a cooling ramp from
210.degree. C. to 25.degree. C. at 10.degree. C./min, cooling
crystallization temperature (T.sub.c) is determined as the
crystallization peak maximum during the cooling scan. Thermal
measurements and migration results are listed in Table 6.
TABLE-US-00006 TABLE 6 Wt. % Migration, Plasti- T.sub.g T.sub.m
Cooling Migration 25.degree. C. and Designation cizer (.degree. C.)
(.degree. C.) T.sub.c (.degree. C.) 40.degree. C. dry 50% RH C3 0
ND 158 81 NA NA 24 10 18 164 76 1 3 25 20 14 161 81 1 1
EXAMPLES 26-33
[0130] Examples 26-33 are prepared as follows. 100 parts of a
suspension grade PVC powder type (Type 2095 Georgia Gulf
Corporation) are blended with 1.5 parts of a stabilizer
(ThermChek-SP175), and then with 2.5 parts of epoxidized soybean
oil. The products of Examples 9, 10, 12, 14-18, respectively are
used as plasticizers in Examples 26-33. Plasticizer is added at 50
phr, and blended by hand prior to feeding into a HAAKE PolyLab
extruder (Thermo Scientific; Waltham, Mass.). The mixture is melt
mixed at 165.degree. C. with co-rotating screws at 150 rpm for 10
minutes. The compounded PVC mixtures are melt pressed in a Carver
Model 4122 pneumatic heated plate press (Carver, Inc.; Wabash,
Ind.) to a thickness of 1 mm at 165.degree. C. Samples are allowed
to heat without pressure for 5 minutes. Pressure is applied and
released stepwise: 1000 lbs force, 2500 lbs force, 4000 lbs force.
Samples are pressed at 5000 lbs force for 1 minute. Samples are
quenched in a water bath and allowed to come to room temperature.
All materials are transparent water-white to light yellow colored
films with no tackiness at the surface.
[0131] Shore A hardness is measured on a stack of films with a
total thickness of 3 mm following the procedure outlined in
Examples 19-21. Hexane extractions are performed on pre-weighed one
inch squares of 1 mm thickness submersed in 6 mL of hexane for 24
hours at room temperature. The samples are then removed, patted
dry, and allowed to equilibrate for 24 hours. Samples are weighed
to determine the % mass loss. Thermal, hardness and extraction
results are listed in Table 7.
TABLE-US-00007 TABLE 7 Shore A Mass Loss in Example Plasticizer
Hardness T.sub.g (.degree. C.) Hexane (%) 26 Example 14 69 -27 6 27
Example 12 79 -4 1 28 Example 15 75 -23 3.6 29 Example 16 78 -16 2
30 Example 17 74 -29 10 31 Example 18 72 -29 9 32 Example 9 77 -17
3 33 Example 10 81 -17 2
EXAMPLES 34-35
[0132] Polyvinyl acetate (PACE 383 Forbo Adhesives) is melt blended
with the product of Example 11 at a 90:10 weight ratio. Viscosity
is measured with a Brookfield RVT viscometer at 20 rpm and
25.degree. C. The resulting plasticized polyvinyl acetate mixture
is designated Example 34. Example 35 is made by melt blending 90
parts of a vinyl acetate ethylene copolymer (Duroset E-200 HV,
Celanese Corporation) with 10 parts of the Example 11 product. The
viscosities of the resulting blends are measured at 25.degree. C.
after blending, and again after 7 days at about 25.degree. C.
Example 34 exhibits an initial viscosity of 6040 cps and a
viscosity of 6420 cps after 7 days. Example 35 exhibits an initial
viscosity of 5500 cps and a viscosity of 5600 cps after 7 days.
[0133] Dried film properties are observed after applying a 1.6 mil
wet film with a #16 wire wound rod onto glass plates. Glass plates
are submerged in water to determine water resistance. Speed of set
is measured by applying a 1.6 mil wet film with a #16 wire wound
rod to Kraft paper. A second sheet of Kraft paper is applied to the
top of the adhesive film. Set time is evaluated as the time before
fiber tear is observed upon pulling off the top layer of Kraft
paper. All materials have a similar speed of set. Open time is
evaluated by applying a 1.6 mil wet film with a #16 wire wound rod
to Kraft paper. Copy paper is laid over the adhesive film at 5
second intervals. The adhesive layer is allowed to dry overnight.
The paper strips are peeled apart looking for fiber tear. The open
time is defined as the time between laying the wet film, and the
first interval where the fiber tear is observed
[0134] Example 34 forms a tough, flexible film with no surface
tack. Open time is 20 seconds. The films blush quickly and
redisperse in water. Example 35 forms a soft flexible film with
surface tackiness. Open time is 35 seconds. The films blush but do
not redisperse.
[0135] For comparison, Example 34 is repeated twice, substituting a
commercially available plasticizer (Benzoflex.RTM. LA-705 and
Benzoflex.RTM. 50, both from Genovique, Rosemont, Ill.) for the
Example 11 material. Each provides similar results to Example
34.
[0136] As a further comparison, Example 35 is repeated twice,
substituting the Benzoflex.RTM. 50 material or dibutyl phthalate
for the Example 11 product. Again, very similar results are
obtained.
EXAMPLE 36
[0137] Levulinic acid (580.2 g, 5.0 mol), 1,3-propanediol (209.5 g,
2.75 mol), and sulfuric acid (39.5 mg, 22 .mu.L, 50 ppm) are added
to an empty 2-liter, 4-neck round bottom flask with stirring under
nitrogen for 2 hours at 170.degree. C. After 78% of the theoretical
volatiles are collected, the reaction mixture is placed under
reduced pressure. After 48 minutes, 97% of the theoretical
volatiles are collected. The crude reaction mixture is cooled to
room temperature.
[0138] The crude reaction mixture (390.95 g (1.44 mol)) and
1,2-propylene glycol (328.4 g, 4.3 mol; Brenntag) are added to
1-liter, 3-neck round bottom flask and heated to 70.degree. C. with
stirring at 10 torr vacuum for 4 hours. After 4 hours, 85% (44 mL)
of the theoretical volatiles are collected, and propylene glycol
(93.2 g, 1.22 mol) and sulfuric acid catalyst (18 mg, 10 .mu.L) are
added; the reaction mixture is stirred at 80.degree. C. under 8
torr vacuum for an additional 4 hours. The remaining volatiles (100
mL) are collected and the reaction is cooled to room temperature.
The crude product is neutralized with 20 g of dibasic sodium
phosphate and filtered. The neutralized filtrate is purified by
distillation and hexane extraction to yield 297.4 g of a compound
having the structure
##STR00028##
where R.sup.6=--(CH.sub.2).sub.3--.
EXAMPLE 37
[0139] A 100 mL 3-neck round bottom flask is charged with 7.61 g
(0.1 mol) of 1,3-propanediol ((PDO) Sigma Aldrich Company; St.
Louis, Mo.) and 44.50 g (0.22 mol) of Et-LGK. The contents of the
flask are stirred at a pressure of 5 torr with heating to
90.degree. C., and back-filled with nitrogen. 1.56 .mu.L of
titanium tetra-isopropoxide is added to the flask with a nitrogen
purge; the contents of the flask are then heated to 200.degree. C.
After about 2.5 hours, the reaction mixture is allowed to cool to
104.degree. C., and a second liquid is distilled under reduced
pressure at about 5 torr. Reduced pressure is maintained until no
further distillate is collected. The flask is allowed to cool to
ambient temperature and atmospheric pressure.
[0140] The product contains about 80.9% of a compound having the
structure
##STR00029##
and about 3.0% of a compound having the structure:
##STR00030##
where R.sup.6 in each case is --(CH.sub.2).sub.3--.
EXAMPLES 38-39 AND COMPARATIVE SAMPLE 4
[0141] 4.65 g of polylactic acid (PLA) (PLA 6062; NatureWorks LLC,
Minnetonka, Minn.) is fed into a twin screw compounder (Haake
MiniLab II, Thermo Scientific) at 200.degree. C.; the compounding
screws were co-rotating at 150 rpm. 0.35 g of the product from
Example 5 is added drop-wise to the melted PLA in the compounder
and blended for 10 minute; the extrudate is extruded through the
die face and collected. The product is designated Example 38.
Example 39 is made the same way, except that the product of Example
6 is substituted for the product of Example 5. Comparative Sample 4
is made the same way, but without any plasticizer. Comparative
Sample 4 (neat PLA resin) exhibits a T.sub.g of 57.degree. C. and a
T.sub.m of 162.degree. C. Example 38 exhibits a T.sub.g of
549.degree. C. and a T.sub.m of 163.degree. C. Example 39 exhibits
a T.sub.g of 51.degree. C. and a T.sub.m of 163.degree. C.
EXAMPLE 40
[0142] The foaming tendency and pour point of the product of
Example 5 is evaluated according to ASTM D892 IP 146 (Foaming
Characteristics--Sequences I, II and II), and ASTM D97,
respectively. The foam volume (ml) is determined at the end of a 5
minute and a 10 minute blowing period. Foam volumes of 0 ml are
reported in all cases. Pour point is -33.degree. C.
EXAMPLE 41
[0143] A 250 mL 3-neck round bottom flask is charged with Et-LPK
(40.42 g, 0.20 mol), ethylenediamine (67 mL, 1.00 mol), and
ethylene glycol (10 .mu.L). The contents of the flask are heated to
120.degree. C. for 40 minutes, at 130.degree. C. for 15.25 hours,
and at 140.degree. C. for 6.74 hours. The reaction mixture is
cooled to room temperature. The crude product contains 78% of the
1:1 adduct of Et-LPK:ethylenediamine and 12.5% of the 2:1 adduct of
Et-LPK:ethylenediamine.
EXAMPLE 42
[0144] A 3-neck round bottom flask is charged with 1258.28 gm (5.76
moles) Et-LGK, and 198.26 gm (2.2 moles) 1,4-butanediol. The
contents of the flask are heated to 70.degree. C. for 16 hrs, and
backfilled with nitrogen. 73.5 .mu.L (0.25.times.10.sup.3 moles) of
titanium isopropoxide is added to the reaction mixture with a
nitrogen purge; the contents of the flask are heated to 200.degree.
C. for 6 hrs. A condensate is collected, and when 298.9 gm of the
condensate is collected, the reaction is cooled and analyzed by GPC
and .sup.1H NMR. The product is a yellow viscous liquid. The
product is a mixture of compounds that correspond to structure II,
wherein e is 2, f is 0, x is 2, z is zero, R.sup.5 is hydrogen,
R.sup.6 is --(CH.sub.2).sub.4--, R.sup.14 is methyl and R.sup.15 is
hydrogen. The mixture contains about 14% of species having a
molecular weight of about 1375, 13% of species having a molecular
weight of about 894, 21.5% of species having a molecular weight of
about 682, 30% of species having a molecular weight of about 478,
19% of species having a molecular weight of about 303 and a small
amount of residual Et-LGK.
EXAMPLE 43
[0145] A 3-neck round bottom flask is charged with 129.68 gm (0.28
moles) of the reaction product of Example 42 and 170.32 gm (0.84
moles) of ethyl 4-(2-methyl-1, A-dioxolan-5-yl) pentanoate. The
contents of the flask are heated to 70.degree. C. under a nitrogen
purge for 16 hrs. 11 .mu.L (0.37.times.10.sup.3 moles) of titanium
isopropoxide is added to the reaction mixture with a nitrogen
purge; the contents of the flask are heated to 210.degree. C. for
20 hrs. 25.2 g of a condensate is collected and excess monomer is
removed under vacuum at 200.degree. C. for 3 hrs.
[0146] Examples 44-46 and Comparative Sample 4 Plasticizer
migration out of PVC disks into activated carbon is determined
according to ASTM D1203-A4. Tests are performed on 0.5 mm and 1.0
mm thick disks; conditions are 24 hours at 70.degree. C. Butyl
benzyl phthalate is the plasticizer for Comparative Sample 4. The
product of Example 6 is used as the plasticizer in Example 44; the
product of Example 5 is used as the plasticizer in Example 45; and
the product of Example 43 is used as the plasticizer in Example 46.
Loss of mass on this test indicates migration out of the sample;
therefore, smaller absolute values indicate better results. Results
are as reported in Table 8.
TABLE-US-00008 TABLE 8 Mass Change Activated Mass Change Activated
Carbon, wt-%, 0.5 mm Carbon, wt-%, 1.0 mm Plasticizer thick disk;
thick disk; Comparative -2.64 -1.81 Sample 4 Example 44 -1.33 -0.88
Example 45 -1.41 -0.99 Example 46 -0.88 -0.52
EXAMPLES 47-48
[0147] 62.5 wt % of PVC-2095, 1.9 wt % of ThermChek-SP1363, 3.1 wt
% epoxidized soybean oil (ESO), 3.1 wt % ethyl laurate, 1.9 wt %
texanol-isobutyrate, and 27.5 wt % plasticizer ((Example 5) for
Example 47 and (Example 6) for Example 48) are formulated by
blending with a Kitchen-Aid mixer on low speed for 2 min while
slowly adding the plasticizer. Once a paste is formed, the
composition is stirred an additional 5 min. The composition is
de-aerated in a vacuum oven at 40.degree. C. and 25 mm Hg and cast
onto aluminum dishes. The samples are placed on a Carver Model 4122
pneumatic heated plate press at 165.degree. C. Samples are allowed
to heat without pressure for 10 minutes. The samples form a solid
flexible disk.
EXAMPLE 49-52 AND COMPARATIVE SAMPLES 5-6
[0148] 4.65 g of polycarbonate (PC) (Sabic Innovative Plastics,
Lexan 121R) containing the specified amount of glycerol
monostearate (GMS) (Alfa Aesar) or polybutylene terephthalate (PBT)
(Sabic Innovative Plastics, Valox 310) is fed into a twin screw
compounder (Haake MiniLab II, Thermo Scientific) at the specified
temperature; the compounding screws are co-rotating at 100 rpm. A
plasticizer prepared similarly to Examples 9-12 is added drop-wise
via pipette to the melted resin in the compounder and blended for
10 minutes. This plasticizer contains 56% of species in which s is
1, v is 0 and w is 1, 25% of species in which s is 1, v is 0 and w
is 2 or s is 1, v is 1 and w is 1 and 11% of species in which s is
1, v>1 and w>2. The extrudate is extruded through the die
face and collected. Examples are analyzed by DSC and the results
reported in Table 9. Samples of each are run according to the
following profile: 1.sup.st cycle, heat at 10.degree. C./min from
-80.degree. C. to 200.degree. C.; Cool at 10.degree. C./min to
-80.degree. C.; and 2.sup.nd cycle, heat at 10.degree. C./min to
200.degree. C. Tg values are calculated from the second cycle of
the DSC runs.
TABLE-US-00009 TABLE 9 Wt % Compounding Melt Press Plasti- Wt %
Temperature Temperature T.sub.g Example Resin cizer GMS (.degree.
C.) (.degree. C.) (.degree. C.) 49 PC 10 0.13 270 270 105 50 PC
33.3 0.10 270 270 38 51 PBT 10 0 230 235 10 52 PBT 33.3 0 230 235
-66 Comp. 5 PC 0 0 270 270 142 Comp. 6 PBT 0 0 230 235 44
[0149] The present disclosure may suitably comprise, consist of, or
consist essentially of, any of the disclosed or recited elements.
The disclosure illustratively disclosed herein can be suitably
practiced in the absence of any element which is not specifically
disclosed herein. The various embodiments described above are
provided by way of illustration only and should not be construed to
limit the claims attached hereto. It will be recognized that
various modifications and changes may be made without following the
example embodiments and applications illustrated and described
herein, and without departing from the true spirit and scope of the
following claims.
* * * * *
References