U.S. patent application number 10/948978 was filed with the patent office on 2005-03-31 for transparent thermoplastic blend of a cycloolefin copolymer and a thermoplastic polyurethane.
Invention is credited to Ludlow, James M. III.
Application Number | 20050070665 10/948978 |
Document ID | / |
Family ID | 34381239 |
Filed Date | 2005-03-31 |
United States Patent
Application |
20050070665 |
Kind Code |
A1 |
Ludlow, James M. III |
March 31, 2005 |
Transparent thermoplastic blend of a cycloolefin copolymer and a
thermoplastic polyurethane
Abstract
A blend of a cycloolefin copolymer and a thermoplastic urethane
having similar indices of refraction is transparent. The
cycloolefin copolymer is derived from norbornene and other monomers
such that it has a processing range compatible with the
thermoplastic urethane. The urethane component preferably has a
polyether intermediate. A thermoplastic urethane compatibilizing
agent is utilized desirably having a hydrocarbon intermediate
portion. The compositions can be made to have desirable electrical
dissipative properties for static control applications.
Inventors: |
Ludlow, James M. III;
(Sagamore Hills, OH) |
Correspondence
Address: |
NOVEON IP HOLDINGS CORP.
9911 BRECKSVILLE ROAD
CLEVELAND
OH
44141-3247
US
|
Family ID: |
34381239 |
Appl. No.: |
10/948978 |
Filed: |
September 24, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60506426 |
Sep 26, 2003 |
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Current U.S.
Class: |
525/131 |
Current CPC
Class: |
C08L 23/0823 20130101;
C08L 65/00 20130101; C08L 65/00 20130101; C08L 2666/20 20130101;
C08L 2666/20 20130101; C08L 2666/06 20130101; C08L 75/08 20130101;
C08L 75/08 20130101; C08L 23/0823 20130101 |
Class at
Publication: |
525/131 |
International
Class: |
C08L 075/04 |
Claims
What is claimed is:
1. A clear thermoplastic composition, comprising: a blend of
cycloolefin copolymer and a thermoplastic polyurethane, said
cycloolefin copolymer and said thermoplastic polyurethane,
independently, having an index of refraction of from about 1.48 to
about 1.58.
2. A clear thermoplastic composition according to claim 1, wherein
said cycloolefin copolymer is derived from at least one polycyclic
olefin monomer and from at least one acylic 1-olefin monomer and
wherein the amount of said acylic 1-olefin monomer is from about 45
to about 85 mole percent based upon the total moles of said acylic
1-olefin monomer and said polycyclic olefin monomer.
3. A clear thermoplastic composition according to claim 2, wherein
said composition according to ASTM D-1003 has a light transmission
of at least about 65% and a haze value of about 32% and less, and
wherein said thermoplastic polyurethane is derived from a) an
intermediate made from an alkylene oxide monomer having from 2 to
about 6 carbon atoms or from a polyester intermediate made from a
dicarboxylic acid having from 4 to about 15 carbon atoms and from a
glycol having from 2 to about 12 carbon atoms, b) a polyisocyanate
having the formula R(NCO).sub.n where n is from about 2 to about 4
and wherein R is an aliphatic, an aromatic, or combinations thereof
having a total of from 2 to about 30 carbon atoms, and c) a diol
having from 2 to about 10 carbon atoms.
4. A clear thermoplastic composition according to claim 3, wherein
said polycyclic olefin monomer is norbornene or tetracyclododecene,
wherein said acylic 1-olefin monomer is ethylene or propylene,
wherein said alkylene oxide is ethylene oxide or propylene oxide,
wherein said ester intermediate is derived from succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic
acid, sebacic acid, dodecanedioic acid, isophthalic acid,
terephthalic acid, cyclohexane acid, and combinations thereof and
from a glycol including, ethylene glycol, propylene-1,2-glycol,
1,3-propanediol, butylene-1,3-glycol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-- diol,
2,2-diethylene-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene
glycol, dodecamethylene glycol, and combinations thereof, wherein
said polyisocyanate is a diisocyanate comprising
4,4'-methylenebis-(phenyl isocyanate) (MDI); isophorone
diisocyanate (IPDI), m-xylylene diisocyanate (XDI), toluene
diisocyanate, phenylene-1,4-diisocyanate,
naphthalene-1,5-diisocyanate, 1,4-cyclohexyl diisocyanate (CHDI),
decane-1,10-diisocyanate,
diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanat- e,
dicyclohexylmethane-4,4'-diisocyanate, and
cyclohexyl-1,4-diisocyanate, or combinations thereof, and wherein
said diol is ethylene glycol, diethylene glycol, propylene glycol,
dipropylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,3-butane
diol, 1,5-pentane diol, 1,4-cyclohexane-dimethanol, neopentyl
glycol, hydroquinone di(hydroxyethyl)ether and
2-methyl-1,3-propanediol, or combinations thereof.
5. A clear thermoplastic composition according to claim 4, wherein
said cycloolefin copolymer, and said thermoplastic polyurethane,
independently, have an index of refraction of from about 1.50 to
about 1.56, and wherein said thermoplastic composition according to
ASTM D-1003 has a light transmission of at least about 80% and a
haze value of about 27% and less.
6. A clear thermoplastic composition according to claim 5, wherein
said cycloolefin copolymer is derived from norbornene and from
ethylene, wherein the amount of said ethylene is from about 60 to
about 70 mole percent based upon the total number of moles of said
ethylene and said norbornene, wherein said alkylene oxide is
ethylene oxide, wherein said diisocyanate is MDI, and wherein said
diol is butane diol.
7. A clear thermoplastic composition according to claim 6, wherein
said cycloolefin copolymer, and said thermoplastic polyurethane,
independently, have an index of refraction of from about 1.52 to
about 1.54, and wherein said thermoplastic composition according to
ASTM D-1003 has a light transmission of at least about 82% and a
haze value of about 22% and less.
8. A clear thermoplastic composition according to claim 1,
including a compatibilizing agent, wherein said compatibilizing
agent comprises a thermoplastic polyurethane derived from a
diisocyanate, a diol, and a substantially hydrocarbon intermediate
containing at least 20 carbon atoms between non-carbon atoms in the
intermediate backbone, or said intermediate is derived from one or
more dienes having a total of from 4 to 8 carbon atoms.
9. A clear thermoplastic composition according to claim 3,
including a compatibilizing agent, wherein said compatibilizing
agent comprises a thermoplastic polyurethane derived from a
diisocyanate, a diol, and a substantially hydrocarbon intermediate
containing at least 20 carbon atoms between non-carbon atoms in the
intermediate backbone, or said intermediate is derived from one or
more dienes having a total of from 4 to 8 carbon atoms, wherein at
least 80% of the initial carbon to carbon double bonds in said
intermediate have been saturated, wherein said diisocyanate is
ethylene diisocyanate; toluene diisocyanate; methylene
bis-(4-phenylisocyanate) (MDI); isophorone diisocyanate;
hexamethylene diisocyanate; naphthalene diisocyanate; cyclohexylene
diisocyanate; diphenylmethane-3,3' dimethoxy-4,4'-diisocyanate,
meta-tetramethylxylene diisocyanate (m-TMXD 1),
paratetramethylxylene diisocyanate (p-TMXD 1), m-xylylene
diisocyanate (XDI), decane-1,10-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, and combinations thereof,
and wherein said diol is ethylene glycol, 1,3-propane diol, 2,3- or
1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, hydroquinone
bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexanedimethanol, and combinations
thereof.
10. A clear thermoplastic composition according to claim 7,
including from about 0.25 to about 8 parts by weight of a
compatibilizing agent per 100 parts by weight of said thermoplastic
urethane and said cycloolefin copolymer, wherein said
compatibilizing agent, wherein said compatibilizing agent comprises
a thermoplastic polyurethane having a hydrocarbon intermediate
derived from one or more dienes having a total of from 4 to 8
carbon atoms wherein at least 90% of the initial carbon to carbon
double bonds have been saturated, wherein said diisocyanate is MDI,
and wherein said diol is neopentyl glycol.
11. An optical film or coating, comprising the composition of claim
1.
12. An optical film or coating, comprising the composition of claim
8.
13. An electrostatic dissipating thermoplastic composition,
comprising: a cycloolefin copolymer, an electrostatic dissipating
thermoplastic composition, and a compatibilizing agent.
14. An electrostatic dissipating thermoplastic composition of claim
13 wherein said electrostatic dissipating composition contains a
polymer selected from the group consisting of thermoplastic
polyurethane, polyether amide, polyether ester, copolymer of
ethylene oxide and propylene oxide, and copolymer of ethylene oxide
and epichlorohydrin.
15. An electrostatic dissipating thermoplastic composition
according to claim 13, wherein said cycloolefin copolymer is
derived from at least one polycyclic olefin monomer and at least
one acyclic 1-olefin monomer, said polycyclic olefin monomer having
the formula 6wherein each R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6, independently, are the same or different, and
is a hydrogen atom or a hydrocarbon radical, and wherein said
acylic 1-olefin has the formula 7wherein each R.sup.7, R.sup.8,
R.sup.9, and R.sup.10, independently, are the same or different,
and is a hydrogen atom or a C.sub.6-C.sub.10 aryl group or a
C.sub.1-C.sub.8 alkyl group, and wherein said electrostatic
dissipating composition has a surface resistivity of from about
1.times.10.sup.6 to about 1.times.10.sup.12 ohm/square.
16. An electrostatic dissipating thermoplastic composition
according to claim 15, wherein said electrostatic dissipating
thermoplastic composition comprises a thermoplastic polyurethane
derived from one or more cyclic ether monomers, at least one
diisocyanate, and at least one diol, wherein said cyclic ether
monomer has the formula 8wherein each R.sub.1, R.sub.2, R.sub.3,
R.sub.4, and R.sub.5, independently, is a hydrogen atom, an
unsubstituted or substituted alkyl, cycloalkyl, cycloalkenyl, aryl,
aralkyl or alkaryl, and wherein said substituents which can be
substituted within the foregoing are OR.sub.6, SR.sub.6, CN or a
halogen, where R.sub.6 is hydrogen, alkyl, cycloalkyl,
cycloalkenyl, aryl, aralkyl, alkaryl, or carboxyl, and n is 0, 1,
2, or 4, and wherein said compatibilizing agent comprises a
thermoplastic polyurethane derived from a diisocyanate, a diol, and
a substantially hydrocarbon intermediate containing at least 20
carbon atoms between non-carbon atoms in the intermediate backbone
or a hydrocarbon intermediate derived from one or more dienes
having a total of from 4 to 8 carbon atoms.
17. An electrostatic dissipating thermoplastic composition
according to claim 16, wherein said cycloolefin copolymer is
derived from norbornene or tetracyclododecene, wherein said acylic
1-olefin monomer is ethylene or propylene, wherein said
electrostatic dissipating thermoplastic polyurethane cyclic ether
monomer is a cycloalkyl having from 3 to 8 ring carbon atoms,
wherein said diisocyanate is 1,4-diisocyanatobenzene (PPDI),
4,4'-methylenebis(phenyl isocyanate) (MDI),
4,4'-methylenebis(3-methoxy phenyl isocyanate), isophorone
diisocyanate (IPDI) 1,5-naphthalene diisocyanate (NDI),
phenylene-1,4-diisocyanate, toluene diisocyanate (TDI), m-xylene
diisocyanate (XDI), 1,4-cyclohexyl diisocyanate (CHDI),
1,10-diisocyanatonaphthylene, and 4,4'-methylenebis-(cyclohexyl
isocyanate) (H.sub.12 MDI), and wherein said glycol chain extender
is ethylene glycol, 1,3-propanediol, propylene glycol,
1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol,
diethylene glycol, 1,4-cyclohexane dimethanol, neopentyl glycol,
hydroquinone bis(2-hydroxyethyl) ether, or combinations
thereof.
18. An electrostatic dissipating thermoplastic composition
according to claim 17, wherein said cycloolefin copolymer is
derived from norbornene and ethylene, wherein the amount of said
ethylene monomer is from about 45% to about 85 mole % based upon
the total moles of said ethylene and said norbornene monomers, and
wherein said compatibilizing agent diisocyanate is ethylene
diisocyanate; toluene diisocyanate; methylene
bis-(4-phenylisocyanate) (MDI); isophorone diisocyanate;
hexamethylene diisocyanate; naphthalene diisocyanate; cyclohexylene
diisocyanate; diphenylmethane-3,3' dimethoxy-4,4'-diisocyanate,
meta-tetramethylxylene diisocyanate (m-TMXD1),
paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene
diisocyanate (XDI), decane-1,10-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, and combinations thereof,
and wherein said compatibilizing agent diol is ethylene glycol,
1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol,
1,6-hexane diol, hydroquinone bis(2-hydroxyethyl)ether,
1,4-cyclohexanediol, diethylene glycol, dipropylene glycol,
1,4-cyclohexanedimethanol, and combinations thereof.
19. An electrostatic dissipating thermoplastic composition
according to claim 18, wherein said electrostatic dissipating
thermoplastic urethane cycloalkyl is ethylene oxide, wherein said
diisocyanate is MDI and wherein said diol is butane diol, wherein
said electrostatic dissipating thermoplastic polyurethane has a
surface resistivity of from about 1.times.10.sup.8 to about
1.times.10.sup.10 ohm/square, and wherein the amount of said
compatibilizing agent is from about 0.25 to about 8 parts by weight
per 100 parts by weight of said cycloolefin copolymer and said
electrostatic dissipating thermoplastic urethane.
20. An electrostatic dissipating thermoplastic composition
according to claim 19, wherein the amount of said ethylene monomer
in said cycloolefin copolymer is from about 55 to about 80 mole %
based upon the total moles of said ethylene and said norbornene
monomers, wherein said compatibilizing agent intermediate is
derived from butadiene, wherein said diisocyanate is MDI and
wherein said diol is neopentyl glycol.
21. An electrostatic dissipating thermoplastic composition
according to claim 20, wherein said composition comprises
co-continuous phases of said cycloolefin copolymer and said
electrostatic dissipating thermoplastic urethane.
22. An electronic or semi-conductor packaging material comprising
the composition of claim 13.
23. An electronic or semi-conductor packaging material comprising
the composition of claim 17.
24. An electronic or semi-conductor packaging material comprising
the composition of claim 20.
25. An electronic or semi-conductor packaging material comprising
the composition of claim 14.
26. A hard disc drive component or packaging material comprising
the composition of claim 13.
27. A hard disc drive component or packaging material comprising
the composition of claim 16.
28. A hard disc drive component or packaging material comprising
the composition of claim 20.
29. A hard disc drive component or packaging material comprising
the composition of claim 14.
30. A compatibilized polymer blend, comprising: a cycloolefin
copolymer, a thermoplastic polyurethane, and a compatibilizing
agent.
31. A compatibilized polymer blend according to claim 30, wherein
said cycloolefin copolymer is derived from at least one polycyclic
olefin monomer and from at least one acylic 1-olefin monomer and
wherein the amount of said acylic 1-olefin monomer is from about 45
to about 85 mole percent based upon the total moles of said acylic
1-olefin monomer and said polycyclic olefin monomer, wherein said
thermoplastic polyurethane is derived from a) an intermediate made
from an alkylene oxide monomer having from 2 to about 6 carbon
atoms or from a polyester intermediate made from a dicarboxylic
acid having from 4 to about 15 carbon atoms and from a glycol
having from 2 to about 12 carbon atoms, b) a polyisocyanate having
the formula R(NCO).sub.n where n is from about 2 to about 4 and
wherein R is an aliphatic, an aromatic, or combinations thereof
having a total of from 2 to about 30 carbon atoms, and c) a diol
having from 2 to about 10 carbon atoms, and wherein said
compatibilizer comprises a thermoplastic polyurethane derived from
a diisocyanate, a diol, and a substantially hydrocarbon
intermediate containing at least 20 carbon atoms between non-carbon
atoms in the intermediate backbone, or said intermediate is derived
from one or more dienes having a total of from 4 to 8 carbon
atoms.
32. A compatibilized polymer blend according to claim 31, wherein
said polycyclic olefin monomer is norbornene or tetracyclododecene,
wherein said acylic 1-olefin monomer is ethylene or propylene;
wherein said alkylene oxide is ethylene oxide or propylene oxide,
wherein said ester intermediate is derived from succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic
acid, sebacic acid, dodecanedioic acid, isophthalic acid,
terephthalic acid, cyclohexane acid, and combinations thereof and
from a glycol including, ethylene glycol, propylene-1,2-glycol,
1,3-propanediol, butylene-1,3-glycol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-- diol,
2,2-diethylene-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene
glycol, dodecamethylene glycol, and combinations thereof; wherein
said thermoplastic polyurethane polyisocyanate is a diisocyanate
comprising 4,4'-methylenebis-(phenyl isocyanate) (MDI); isophorone
diisocyanate (IPDI), m-xylylene diisocyanate (XDI), toluene
diisocyanate, phenylene-1,4-diisocyanate,
naphthalene-1,5-diisocyanate, 1,4-cyclohexyl diisocyanate (CHDI),
decane-1,10-diisocyanate, diphenylmethane-3,3'-dimet-
hoxy-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and
cyclohexyl-1,4-diisocyanate, or combinations thereof, and wherein
said thermoplastic polyurethane diol is ethylene glycol, diethylene
glycol, propylene glycol, dipropylene glycol, 1,4-butane diol,
1,6-hexane diol, 1,3-butane diol, 1,5-pentane diol,
1,4-cyclohexane-dimethanol, neopentyl glycol, hydroquinone
di(hydroxyethyl)ether and 2-methyl-1,3-propanediol, or combinations
thereof; and wherein said compatibilizing agent intermediate is
derived from one or more dienes having a total of from 4 to 8
carbon atoms, wherein at least 80% of the initial carbon to carbon
double bonds in said intermediate have been saturated, wherein said
compatibilizing agent diisocyanate is ethylene diisocyanate;
toluene diisocyanate; methylene bis-(4-phenylisocyanate) (MDI);
isophorone diisocyanate; hexamethylene diisocyanate; naphthalene
diisocyanate; cyclohexylene diisocyanate; diphenylmethane-3,3'
dimethoxy-4,4'-diisocyan- ate, meta-tetramethylxylene diisocyanate
(m-TMXD1), paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene
diisocyanate (XDI), decane-1,10-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, and combinations thereof,
and wherein said compatibilizing agent diol is ethylene glycol,
1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol,
1,6-hexane diol, hydroquinone bis(2-hydroxyethyl)ether,
1,4-cyclohexanediol, diethylene glycol, dipropylene glycol,
1,4-cyclohexanedimethanol, and combinations thereof.
33. A compatibilized polymer blend according to claim 32, wherein
said cycloolefin copolymer is derived from norbornene and from
ethylene, wherein the amount of said ethylene is from about 60 to
about 70 mole percent based upon the total number of moles of said
ethylene and said norbornene; wherein said thermoplastic
polyurethane alkylene oxide is ethylene oxide, wherein said
diisocyanate is MDI, and wherein said diol is butane diol; and
wherein said compatibilizing agent hydrocarbon intermediate derived
from one or more dienes having a total of from 4 to 8 carbon atoms
wherein at least 90% of the initial carbon to carbon double bonds
have been saturated, wherein said diisocyanate is MDI, and wherein
said diol is neopentyl glycol.
Description
FIELD OF INVENTION
[0001] The present invention relates to a transparent blend of a
thermoplastic elastomer such as a polyurethane based inherently
dissipative polymer (TPU-IDP), a cycloolefin copolymer, and
desirably a compatibilizing agent. More specifically, the present
invention relates to a clear blend wherein the indices of
refraction of the thermoplastic polyurethane and the cycloolefin
are similar. The present invention also relates to blends of
thermoplastic polyurethanes (TPU) and cycloolefin copolymer which
are not transparent and to other inherently dissipative polymers
and cycloolefin copolymers.
BACKGROUND OF THE INVENTION
[0002] Inherently dissipative polymers (IDPs) are a class of
polyether elastomers which have inherent volume resistivity in the
1.times.10.sup.5 to 1.times.10.sup.12 ohm-cm. Examples include
polyethylene oxide-based polyether urethanes, polyether amides and
polyether esters, and copolymers of ethylene oxide such as ethylene
oxide/propylene oxide or ethylene oxide/epichlorohydrin. IDPs are
used in alloys with other thermoplastics as a means to impart a
level of conductivity sufficient to render the plastics static
dissipative (surface and volume resistivities in the
1.times.10.sup.5 to 1.times.10.sup.12 range). For example, U.S.
Pat. No. 5,574,104 relates to polymer compositions comprising a
polyether polyurethane IDP which can be blended with one or more
base polymers. The subject blends have useful static dissipative
properties and exceptional cleanliness, making them suitable for
handling of sensitive electronic components and devices. However,
the blends are generally not transparent.
[0003] U.S. Pat. No. 6,140,405 relates to a low molecular weight
polyether oligomer which is modified with a salt, preferably
containing lithium, during a chain extension reaction of the
polyether oligomer to form IDP products such as polyurethanes,
polyether amide block copolymers and polyether-ester block
copolymers. The reaction product polymers exhibit lower surface and
volume resistivities and static decay times, relative to other
IDPs, yet are free of excessive amounts of extractable anions,
particularly chlorine, nitrate, phosphate and sulfate.
[0004] U.S. Pat. Nos. 4,332,919, 4,302,558 and 4,384,078 describe
inherently dissipative acrylic polymers made by a core/shell
process. This class of IDP polymers is transparent, but suffers
from high resistivity, slow static decay times and high off-gassing
of volatile impurities, making it less desirable for sensitive
electronic handling applications.
[0005] U.S. Pat. No. 6,225,407 relates to a polymer blend
comprising one or more cycloolefin copolymers and one or more types
of core-shell particles or one or more copolymers which are
composed to some extent of rubbers with low glass transition
temperatures, or a combination of one or more types of core-shell
particles and of one or more copolymers which are composed to some
extent of rubbers with low glass transition temperatures.
[0006] U.S. Pat. No. 6,054,533 relates to a compatibilized blend of
a thermoplastic elastomer and a polyolefin. The compatibilizer is a
thermoplastic polyurethane formed by the reaction of a
substantially hydrocarbon intermediate such as a polybutadiene
polyol, a diisocyanate such as MDI, and an amine or diol chain
extender such as neopentyl glycol. The compatibilizer has high
amounts of soft segments therein and imparts improved properties to
blends of a thermoplastic elastomer and polyolefin such as good
impact resistance, good tensile strength, good tear resistance, and
good delamination resistance. These compositions are not
transparent.
SUMMARY OF THE INVENTION
[0007] Transparent thermoplastic blends are formed from a
thermoplastic urethane and a cycloolefin copolymer such as
norbornene-ethylene. The thermoplastic urethane desirably has a
polyether intermediate and the cycloolefin copolymer has a
processing temperature range which is compatible with the
thermoplastic urethane. The norbornene-ethylene copolymers
generally contain at least about 50 mole % ethylene and have a Tg
of less than about 150.degree. C. The indices of refraction of both
components are similar so that a transparent blend is produced
which can be utilized in various applications requiring
transparency such as in electronic and semi-conductor packaging,
clean room components and articles, hard disc drive components and
packaging, optical devices and films, and the like. A
compatibilizing agent desirably is also utilized which can be a
thermoplastic polyurethane having a hydrocarbon intermediate.
[0008] Blends of cycloolefin copolymers and thermoplastic
polyurethanes (TPU) are also provided which have excellent physical
properties and can be made to have electrical dissipative
properties by the selection of the TPU. The cycloolefin copolymers
are also blended with other inherently dissipative polymers
(non-TPU) to give electrical dissipative properties. Examples of
other IDP polymers which are blended with the cycloolefin
copolymers include polyether amides, polyether esters, copolymers
of ethylene oxide and propylene oxide, and copolymers of ethylene
oxide and epichlorohydrin.
DETAILED DESCRIPTION
[0009] The thermoplastic polyurethane (TPU) of the present
invention can be conventional TPUs which generally have poor
electrostatic dissipating properties or other TPUs which are an
inherently dissipative polymer (TPU-IDP).
Conventional TPU
[0010] Suitable typical or conventional TPUs which are utilized as
a blend polymer are made by reacting a hydroxyl terminated
polyester intermediate, or preferably a hydroxyl terminated
polyether; at least one polyisocyanate; and one or more chain
extenders. The hydroxyl terminated polyester intermediate polymer
is generally a linear polyester having a number average molecular
weight of from about 300 to about 10,000 and preferably from about
500 to about 5,000. The molecular weight is determined by assay of
the terminal functional groups. The polymers are produced by (1) an
esterification reaction of one or more glycols with one or more
dicarboxylic acids or anhydrides or (2) by transesterification
reaction, i.e., the reaction of one or more glycols with esters of
dicarboxylic acids. Mole ratios generally in excess of more than
one mole of glycol to acid are preferred so as to obtain linear
chains having a preponderance of terminal hydroxyl groups.
[0011] A suitable reaction for the formation of a polyester
intermediate also includes a ring opening polymerization which can
utilize various lactones such as epsilon-caprolactone and can be
initiated with a bifunctional initiator such as diethylene
glycol.
[0012] The dicarboxylic acids of the polyester intermediate can be
aliphatic, cycloaliphatic, aromatic, or combinations thereof.
Suitable dicarboxylic acids which may be used alone or in mixtures
generally have a total of from 4 to about 15 carbon atoms and
include: succinic, glutaric, adipic, pimelic, suberic, azelaic,
sebacic, dodecanedioic, isophthalic, terephthalic, Cyclohexanoic,
and the like. Anhydrides of the above dicarboxylic acids such as
phthalic anhydride, tetrahydrophthalic anhydride, or the like, can
also be used. Adipic acid is the preferred acid. The glycols which
are reacted to form a desirable polyester intermediate can be
aliphatic, aromatic, or combinations thereof, and have a total of
from 2 to about 12 carbon atoms, and include ethylene glycol,
propylene-1,2-glycol, 1,3-propanediol, butylene-1,3-glycol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
2,2-dimethylpropane-1,3-- diol, 2,2-diethylene-1,3-diol,
1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene
glycol, and the like. 1,4-butanediol is the preferred glycol.
[0013] The preferred polyether polyol intermediates are derived
from a diol or polyol having a total of from 2 to 15 carbon atoms,
for example, an alkyl diol or glycol which is reacted with an ether
comprising an alkylene oxide having from 2 to 6 carbon atoms,
typically ethylene oxide or propylene oxide or mixtures thereof.
For example, hydroxyl functional polyether can be produced by first
reacting propylene glycol with propylene oxide followed by
subsequent reaction with ethylene oxide. Primary hydroxyl groups
resulting from ethylene oxide are more reactive than secondary
hydroxyl groups and thus are preferred. Useful commercial polyether
polyols include poly(ethylene glycol) comprising ethylene oxide
reacted with ethylene glycol, poly(propylene glycol) comprising
propylene oxide reacted with propylene glycol,
poly(propylene-ethylene glycol) comprising propylene oxide and
ethylene oxide reacted with propylene glycol, poly(tetramethylene
ether glycol) comprising water reacted with tetrahydrofuran
(PTMEG), glycerol adduct comprising glycerol reacted with propylene
oxide, trimethylopropane adduct comprising trimethylolpropane
reacted with propylene oxide, pentaerythritol adduct comprising
pentaerythritol reacted with propylene oxide, and similar hydroxyl
functional polyethers. The various polyether intermediates
generally have a number average molecular weight, as determined by
assay of the terminal functional groups of from about 200 to about
10,000 and preferably from about 500 to about 5,000.
[0014] The desired thermoplastic polyurethane (blend polymer) is
made from the above-noted intermediate such as a hydroxyl
terminated polyester or polyether which is further reacted with a
polyisocyanate, preferably a diisocyanate, along with extender
glycol. Examples of suitable diisocyanates generally have the
formula R(NCO).sub.n wherein n equals 2, 3, or 4 with 2 being
highly preferred. Mixtures of various polyisocyanates can also be
utilized and thus need not be an integer. R is an aliphatic, an
aromatic, or combinations thereof having a total of from 2 to about
30 carbon atoms with from about 6 or about 8 to about 15 being
preferred. Examples of suitable diisocyanates include non-hindered
aromatic diisocyanates such as: 4,4'-methylenebis-(phenyl
isocyanate) (MDI); isophorone diisocyanate (IPDI), m-xylylene
diisocyanate (XDI), toluene diisocyanate,
phenylene-1,4-diisocyanate, naphthalene-1,5-diisocy- anate, as well
as non-hindered cyclic aliphatic diisocyanates such as
1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate,
diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate,
dicyclohexylmethane-4,4- '-diisocyanate, and
cyclohexyl-1,4-diisocyanate. MDI is highly preferred.
[0015] Examples of suitable extender glycols (i.e., chain
extenders) are lower aliphatic or short chain glycols having from
about 2 to about 10 carbon atoms and include for instance ethylene
glycol, diethylene glycol, propylene glycol, dipropylene glycol,
1,4-butane diol (highly preferred), 1,6-hexane diol, 1,3-butane
diol, 1,5-pentane diol, 1,4-cyclohexane-dimethanol, neopentyl
glycol, hydroquinone di(hydroxyethyl)ether and
2-methyl-1,3-propanediol. Amine chain extenders are avoided
inasmuch as they generally do not result in good properties.
[0016] While a two-step reaction can be utilized such as reacting
the intermediate with generally an equivalent weight amount of a
diisocyanate and subsequently chain extending the same, the
one-shot process is preferred. That is, the one or more
intermediates, the one or more diisocyanates, and the one or more
chain extenders are added to a reaction vessel and heated in the
presence of a suitable catalyst to a temperature above about
100.degree. C. and usually above about 125.degree. C. Inasmuch as
the reaction is exothermic, the reaction temperature increases to
about 200.degree. C. to about 260.degree. C. or about 290.degree.
C. wherein the various components react with one another. The
catalysts are conventional and include tin catalysts such as
stannous octolate, dibutyl tin dilaurate, dibutyl tin dioctate as
well as other metal carboxylate compounds. On a mole basis, the
amount of extender glycol for each mole of the polyol intermediate
is from about 0.1 to about 3.0, desirably from about 0.2 to about
2.0 and preferably from about 0.5 to about 1.5 moles. Inasmuch as
amine chain extenders are not desired, the amount thereof is low,
for example about 0.5 moles or less, desirably 0.2 moles or less,
and preferably 0.1 moles or less and most preferably nil, that is
none at all. On a mole basis, the high molecular weight
polyurethane polymer produced by the one-shot process comprises
from about 0.96 to about 1.04 and preferably from about 0.98 to
about 1.02 moles of the diisocyanate for every 1.0 total moles of
both the chain extender and the intermediate, e.g., polyester or
polyether.
[0017] As noted, the preferred intermediate is a polyether, while
MDI is the preferred isocyanate and 1,4-butane diol is the
preferred chain extender.
[0018] The above conventional thermoplastic polyurethanes as well
as the below TPU-IDPs are generally clear and have an index of
refraction of from about 1.48 to about 1.58, desirably from about
1.50 to about 1.56 and preferably from about 1.52 to about
1.54.
TPU-IDP
[0019] Often, as noted above, it is desirable to use a
thermoplastic polyurethane based inherently dissipative polymer,
TPU-IDP, composition which can contain an electrostatic dissipating
agent. The TPU-IDP composition comprises a low molecular weight
polyether oligomer having two reactive moieties which is reacted
with a non-hindered diisocyanate and also with a chain extender,
generally simultaneously, (i.e. a one-shot polymerization
process).
[0020] The polyether oligomer of the TPU-IDP composition generally
is derived from one or more copolymerizable cyclic ether monomers
having the formula: 1
[0021] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are
independently hydrogen, unsubstituted or substituted alkyl,
cycloalkyl, cycloalkenyl, aryl, aralkyl or alkaryl, and wherein the
substituents which can be substituted within the foregoing are
OR.sub.6, SR.sub.6, CN or halogens, where R.sub.6 is hydrogen,
alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, or
carboxyl, and further wherein the reactive moieties are OH,
NH.sub.2, or NHR.sub.6, and n is 0, 1, 2, or 4. The reaction of the
low molecular weight oligomer with a diisocyanate will furnish a
polymer having melt indices from 0.05 to 110 grams per ten minutes.
The preferred melt index range of the polymer will be from about
1.0 to 65 grams/10 minutes. In general, the melt index is
determined according to ASTM D-1238 Procedure A at a barrel
temperature of 190.degree. C. and an 8,700 gram piston load.
[0022] In a preferred embodiment the low molecular weight oligomer
employed is a polymer of cyclic ether monomers having the formula:
2
[0023] In a more preferred embodiment the low molecular weight
oligomer employed is a polymer of cyclic ether monomers wherein
R.sub.1, R.sub.2 and R.sub.3 are hydrogen and R.sub.4 is H,
CH.sub.3, or CH.sub.2 X wherein X is a halogen, OR.sub.6, or
COOR.sub.6, and R.sub.6 is defined herein-above.
[0024] The most preferred cyclic ether is ethylene oxide.
[0025] In an alternative embodiment the low molecular weight
polyether oligomer is end capped with ethylene oxide thereby
providing an oligomer which will have two primary moieties.
[0026] The alkyl groups of the above cyclic ether formulas can have
from 1 to 6 carbon atoms, be straight or branched chain and may be
unsubstituted or substituted. The alkenyl groups can have from 1 to
6 carbon atoms, be straight or branched chain, have 1 or 2 double
bonds and be unsubstituted or substituted.
[0027] The cycloalkyl and cycloalkenyl groups can have from 3 to 8
ring carbon atoms and from 1 to 3 rings. The cycloalkenyl groups
can have 1 or 2 double bonds.
[0028] The aryl groups can have from 6 to 10 ring carbon atoms and
one or two rings.
[0029] Useful polyether oligomers are linear polymers having the
general formula: 3
[0030] wherein X+1 is the number of repeating ether units, each M
is a reactive moiety, n is 0,1,2, or 4 and R.sub.1, R.sub.2,
R.sub.3, R.sub.4 and R.sub.5 are as defined hereinabove. The most
common M is the OH group. For the subject invention X+1 is at least
4 and between 4 and about 250. On a molecular weight basis, the
useful range of polyether oligomers have a number average molecular
weight from about 200 to about 10,000 and preferably from about 500
to about 5,000. A highly preferred oligomer is polyethylene glycol.
Commercially available polyethylene glycols useful in this
invention are typically designated as polyethylene glycol 600,
polyethylene glycol 1,450, and polyethylene glycol 4,000.
[0031] The polyether oligomer can be a homopolymer or a copolymer
of two or more copolymerizable monomers. Some examples of
comonomers are ethylene oxide, propylene oxide, 1,2-butylene oxide,
epichlorohydrin, allyl glycidyl ether, n-butyl glycidyl ether,
glycidyl acrylate, glycidyl methacrylate, 2-ethylhexyl glycidyl
ether, tetrahydrofuran, or styrene oxide.
[0032] In accordance with the present invention, the low molecular
weight polyether oligomer intermediate and the non-hindered
diisocyanate are co-reacted simultaneously in a one-shot
polymerization process at a temperature above about 100.degree. C.
and usually about 120.degree. C., whereupon the reaction is
exothermic and the reaction temperature is increased to about
200.degree. C. to about 285.degree. C.
[0033] The glycol chain extender can be any diol (i.e., glycol) or
combination of diols, containing 2 to 10 carbon atoms, such as
ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol,
1,4-cyclohexane dimethanol, neopentyl glycol, hydroquinone
bis(2-hydroxyethyl) ether, or any aliphatic or aromatic molecule
containing two reactive hydroxyl groups. The preferred chain
extender is 1,4-butanediol.
[0034] The hydroxyl terminated polyols described above can be
blended with a glycol chain extender before the blend is reacted
with a polyisocyanate or the polyol and the chain extender can be
brought to the reaction zone simultaneously. Less desired, the
polyol can be reacted with the diisocyanate, and then the
prepolymer is reacted with the chain extender. Stabilizers such as
antioxidants can be added prior to the reaction or during the
reaction.
[0035] The amount of glycol chain extender is generally from about
0 or about 0.1 to about 35 moles and desirably from about 0 or
about 0.1 to about 20 moles for every mole of low molecular weight
polyether oligomer. Generally, the number of moles of diisocyanate
per total of the number of moles of the low molecular weight
polyether oligomer plus the number of moles of chain extender is
from about 0.95 to about 1.06 and preferably from about 0.97 to
about 1.03.
[0036] In an alternative procedure two or more of the polyether
oligomers can be reacted with a diisocyanate to furnish an oligomer
dimer or trimer. These dimers or trimers can then be chain extended
under similar conditions to form the high molecular weight polymer.
This procedure can be used to produce a high molecular weight chain
extended polymer with varying polyisocyanate groups.
[0037] Conventional diisocyanate or polyisocyanate type components
are molecules having two functional groups (reactive sites) which
will react with the reactive moieties of the polyethers.
[0038] The reactive moieties typically occur at the ends of the
polyether oligomers as a result of routine synthesis, however the
reactive moieties can be located at locations other than the ends.
The reactive moieties most useful for the present invention are OH,
NH.sub.2 and NHR.sub.6. In a preferred form the reactive moieties
are OH, NH.sub.2 or NHR.sub.6 and are on primary carbon atoms. The
most preferred reactive moiety is OH.
[0039] Any conventional diisocyanate can be used, either aliphatic
or aromatic. The polyisocyanates generally have the formula
R(NCO).sub.n wherein n is 2, 3, or 4, or mixtures of
polyisocyanates wherein n need not be an integer and preferably is
about 2. R is an aliphatic, aromatic, or combinations thereof
having a total of from 2 to about 30 carbon atoms with from 6 or
about 8 to about 15 carbon atoms being preferred. In a preferred
embodiment diisocyanates are utilized. Suitable diisocyanates
include, for example, 1,4-diisocyanatobenzene (PPDI),
4,4'-methylenebis(phenyl isocyanate) (MDI),
4,4'-methylenebis(3-methoxy phenyl isocyanate), isophorone
diisocyanate (IPDI) 1,5-naphthalene diisocyanate (NDI),
phenylene-1,4-diisocyanate, toluene diisocyanate (TDI), m-xylene
diisocyanate (XDI), 1,4-cyclohexyl diisocyanate (CHDI),
1,10-diisocyanatonaphthylene, and 4,4'-methylenebis-(cyclohexyl
isocyanate) (H.sub.12 MDI). The most preferred diisocyanate is
MDI.
[0040] Preferred TPU-IDP compositions thus contain a polyether
intermediate which is polyethyleneoxide glycol, a diisocyanate
which preferably is MDI and a chain extender which preferably is
butane diol. Preferred TPU-IDP compositions are also set forth in
U.S. Pat. No. 5,574,104 which is hereby fully incorporated by
reference.
[0041] The TPU-IDP compositions can contain a small amount of a
salt such as an electrostatic dissipating agent and such
compositions are generally preferred. The salt can generally be
added to any existing TPU-IDP composition such as those set forth
herein above which is hereby fully incorporated by reference.
[0042] Accordingly, it is an important aspect of the present
invention to utilize an effective amount of a salt, a salt complex
or a salt compound formed by the union of a metal ion with a
non-metallic ion or molecule. These salts are preferably added
during the one-shot polymerization process. While the exact
mechanism of attachment and/or attraction of the salt to the
TPU-IDP reaction product is not completely understood, the salt
unexpectedly improves the surface and volume resistivities of the
resulting polymer without the presence of unacceptably high levels
of extractable anions. Moreover, the static decay times remain in
an acceptable range. Examples of salts useful in the subject
invention include but are not limited to: LiClO.sub.4, LiN(CF.sub.3
SO.sub.2).sub.2, LiPF.sub.6, LiAsF.sub.6, LiI, LiBr, LiSCN,
LiSO.sub.3CF.sub.3, LiNO.sub.3, LiC(SO.sub.2 CF.sub.3).sub.3,
Li.sub.2 S, and LiMR4 where M is Al or B, and R is a halogen, alkyl
or aryl group. The preferred salt is LiN(CF.sub.3SO.sub.2).sub.2,
which is commonly referred to as lithium trifluoromethane
sulfonimide. The effective amount of the selected salt added to the
one-shot polymerization is at least about 0.10 parts to about 10
parts by weight based on 100 parts by weight of the TPU-IDP
composition, desirably at least about 0.25 parts to about 7 parts
by weight and preferably at least about 0.75 parts to about 5 parts
by weight.
[0043] In accordance with another important feature of the present
invention, it has been discovered that the amount of salt utilized
can be unexpectedly lowered when the salt is added in conjunction
with an effective amount of a co-solvent and that lower surface and
volume resistivities are obtained. That is, the polyether polyol
intermediate is considered to be a solvent. Examples of co-solvents
suitable for this purpose include but are not limited to ethylene
carbonate, propylene carbonate, dimethyl sulfoxide, tetramethylene
sulfone, tri- and tetra ethylene glycol dimethyl ether, gamma
butyrolactone, and N-methyl-2-pyrrolidone. Ethylene carbonate is
preferred. Although the addition of one of the co-solvents is
optional, in some applications lower amounts of the salt may be
desirable. The effective amount of co-solvent required to achieve
the desired result of lower salt usage while still attaining the
desired properties in the TPU-IDP, is at least about 0.10 parts to
about 20 parts by weight based on 100 parts of the TPU-IDP,
preferably at least about 0.50 parts to about 15 parts, and most
preferably at least about 1.0 parts to about 7 parts by weight.
[0044] The TPU-IDP composition also has small amounts of impurities
such as anions therein. For example the total amount of extractable
anions of chlorine anions, nitrate anions, phosphate anions, and
sulfate anions, is generally less than about 8,000 parts, desirably
less than about 7,000 parts, and preferably less than about 6,000
parts by weight per one billion total parts by weight of total
extractable solution; generally the parts by weight of extracted
chlorine anions per billion parts by weight of total extractable
solution is less than about 1,000 parts, desirably less than about
700 parts, and preferably less than about 350 by weight; generally
the parts by weight of extractable nitrate ions per billion parts
by weight of extractable solution is less than about 100 parts,
desirably less than about 90 parts, and preferably less than about
75 parts by weight; generally the parts by weight of extractable
phosphate ions per billion parts by weight of extractable solution
is less than about 6,000 parts, desirably less than about 5,500
parts, and preferably less than about 5,000 parts by weight; and
generally the parts by weight of extractable sulfate ions per
billion parts by weight of extractable solution is less than about
1,000 parts, desirably less than about 750 parts, and preferably
less than about 500 parts by weight per billion parts by weight.
The extractable ions, etc., was determined by placing an 8.times.2
cm sample in 10 ml of water for 60 minutes at 80.degree. C. The ion
content was analyzed via ion chromatography. Hence, the above
results are reported by parts per billion per total extracted
water.
[0045] The use of lithium salts either alone or in association with
a solvent is described in detail in U.S. Pat. No. 6,140,405 which
is hereby fully incorporated by reference.
[0046] The electrostatic dissipative compositions of the present
invention which preferably are thermoplastic urethanes have good
surface resistivity and volume resistivity as measured by ASTM
D-257 For example, the above TPU-IDP compositions whether or not
they contain a lithium salt generally have a surface resistivity of
from about 1.times.10.sup.6 to about 1.times.10.sup.12 ohm/square,
desirably from about 1.times.10.sup.7 to about 1.times.10.sup.11
ohm/square and preferably from about 1.times.10.sup.8 to about
1.times.10.sup.10 ohm/square and a volume resistivity of from about
1.times.10.sup.6 to about 1.times.10.sup.12 ohm-centimeter,
desirably from about 1.times.10.sup.7 to about 1.times.10.sup.11
ohm-centimeter and preferably from about 1.times.10.sup.9 to about
5.times.10.sup.10 ohm-centimeter.
[0047] IDP polymers other than TPU-IDP, as described above, may be
used in the blends of this invention. IDP polymers such as
polyether amides (commercially available as Pebax.RTM. from
Atofina), polyether esters, copolymers of ethylene oxide and
propylene oxide, and copolymers of ethylene oxide and
epichlorohydrin may be used. The most preferred IDP is a TPU-IDP as
described above, especially if a transparent blend is desired.
COC
[0048] The cycloolefin copolymers of the present invention are
prepared by polymerizing from 0.1% to 99.9% by weight, based on the
total amount of the monomers, of at least one polycyclic olefin of
the formula I and/or II 4
[0049] where each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 are identical or different and are a hydrogen atom or a
hydrocarbon radical, where the same radicals in the different
formulae may have a different meaning; and from 0.1 to 99% by
weight, based on the total amount of the monomers, of at least one
acyclic 1-olefin of the formula III 5
[0050] wherein each R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are
identical or different and are a hydrogen atom or a hydrocarbon
radical, preferably a C.sub.6-C.sub.10-aryl radical or a
C.sub.1-C.sub.8 alkyl radical, with ethylene or propylene being
preferred.
[0051] Preference is given to cycloolefins of the formulae I or II
where each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 are
identical or different and are a hydrogen atom or a hydrocarbon
radical, in particular a (C.sub.6-C.sub.10)-aryl radical or a
(C.sub.1-C.sub.8)-alkyl radical, where the same radicals in the
different formulae may have a different meaning.
[0052] Particularly preferred polycyclic olefins are norbornene and
tetracyclododecene, where these can optionally have
C.sub.1-C.sub.6-alkyl substitution. They are preferably
copolymerized with ethylene.
[0053] The amount of the one or more acyclic one-olefin monomers is
generally from about 0.1% to about 99%, desirably from about 45% to
about 85%, more desirably from about 55% to about 80%, and
preferably from about 60% to about 70 mole % based upon the total
number of moles of said one or more acyclic one-olefin monomers and
said one or more polycyclic olefin monomers of Formulas I and/or
II.
[0054] The novel polymer blend is characterized in that the
cycloolefin copolymer(s) present are prepared by the process
described below. The process for preparing the cycloolefin
copolymers present in the novel polymer blend is described in
detail in DE-A-196 52 340, which is expressly incorporated herein
by way of reference.
[0055] The process according to the invention for preparing a
cycloolefin copolymer encompasses the polymerization of at least
one polycyclic olefin monomer with at least one acyclic 1-olefin,
in the presence of a catalyst system. The catalyst system to be
used for preparing the cycloolefin copolymer present in the novel
polymer blend comprises at least one transition metal compound.
Preference is given to the use of one or more metallocenes as
transition metal compound.
[0056] The polymerization is carried out in the liquid cycloolefin
itself or in a cycloolefin solution. The pressure is usually above
1 bar.
[0057] The catalyst system to be used in preparing the cycloolefin
copolymer present in the novel polymer blend may moreover comprise
one or more cocatalysts.
[0058] The catalyst system to be used for preparing the cycloolefin
copolymer present in the novel polymer blend is a high-activity
catalyst for olefin polymerization. Preference is given to using a
metallocene and a cocatalyst. It is also possible to use mixtures
of two or more metallocenes, particularly for preparing reactor
blends or polyolefins with a broad or multimodal molar mass
distribution.
[0059] The process for preparing the cycloolefin copolymer present
in the novel polymer blend, and also the catalyst system to be used
for this process, are described in detail in DE-A-1 96 52 340,
which is expressly incorporated herein by way of reference.
[0060] The cocatalyst present in the catalyst system to be used for
preparing the cycloolefin copolymer present in the novel polymer
blend preferably comprises an aluminoxane.
[0061] Examples of the metallocenes to be used according to the
invention are:
isopropylene(1-indenyl)(3-isopropylcyclopentadienyl)zirconium
dichloride,
diphenylmethylene(1-indenyl)(3-isopropylcyclopentadienyl)zirc-
onium dichloride,
methylphenylmethylene(1-indenyl)(3-isopropylcyclopentadi-
enyl)zirconium dichloride,
isopropylene(1-indenyl)(3-tert-butylcyclopentad- ienyl)zirconium
dichloride, diphenylmethylene(1-indenyl)(3-tert-butylcyclo-
pentadienyl)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-tert--
butylcyclopentadienyl)zirconium dichloride,
isopropylene(4,5,6,7-tetrahydr-
o-1-indenyl)(3-isopropylcyclopentadienyl)-zirconium dichloride,
diphenylmethylene(4,5,6,7-tetrahydro-1-indenyl)(3-isopropylcyclopentadien-
yl)zirconium dichloride,
methylphenylmethylene(4,5,6,7-tetrahydro-1-indeny-
l)(3-isopropylcyclopentadienyl)zirconium dichloride,
isopropylene(1-indenyl)(3-trimethylsilylcyclopentadienyl)zirconium
dichloride,
diphenylmethylene(1-indenyl)(3-trimethylsilylcyclopentadienyl-
)zirconium dichloride,
methylphenylmethylene(1-indenyl)(3-trimethylsilylcy-
clopentadienyl)-zirconium dichloride,
isopropylene(4,5,6,7-tetrahydro-1-in-
denyl)(3-tert-butylcyclopentadienyl)-zirconium dichloride,
diphenylmethylene(4,5,6,7-tetrahydro-1-indenyl)(3-tert-butylcyclopentadie-
nyl)zirconium dichloride,
methylphenylmethylene(4,5,6,7-tetrahydro-1-inden-
yl)(3-tert-butylcyclopentad ienyl)zirconium dichloride,
isopropylene(4,5,6,7-tetrahydro-1-indenyl)(3-trimethylsilylcyclopentadien-
yl)-zirconium dichloride,
diphenylmethylene(4,5,6,7-tetrahydro-1-indenyl)(-
3-trimethylsilylcyclopentadienyl)zirconium dichloride,
methylphenylmethylene(4,5,6,7-tetrahydro-1-indenyl)(3-trimethylsilylcyclo-
pe ntadienyl)zirconium dichloride.
[0062] Another possible embodiment of the process according to the
invention uses a salt-type compound of the formula R.sub.x
NH.sub.4-X BR'.sub.4 or of the formula R.sub.3 PHBR'.sub.4 as
cocatalyst instead of or in addition to an aluminoxane.
[0063] Here, x=1, 2 or 3, R=alkyl or aryl, identical or different,
and R'=aryl, which may also have been fluorinated or partially
fluorinated. In this case the catalyst is composed of the reaction
product of a metallocene with one of the compounds mentioned
(EP-A-0 277 004).
[0064] Any solvent added to the reaction mixture is a common inert
solvent, such as an aliphatic or cycloaliphatic hydrocarbon, a
gasoline fraction or hydrogenated diesel oil fraction, or
toluene.
[0065] The metallocenes are preferably used in the form of their
racemates. The metallocene is preferably used at a concentration,
based on the transition metal, of from 10.sup.-1 to 10.sup.-8 mol,
preferably from 10.sup.-2 to 10.sup.-7 mol, particularly preferably
from 10.sup.-3 to 10.sup.-7 mol, of transition metal per dm.sup.3
of reactor volume. The aluminoxane is used at a concentration of
from 10.sup.-4 to 10.sup.-1 mol, preferably from 10.sup.-4 to
2.10.sup.-2 mol, per dm.sup.3 of reactor volume, based on the
aluminum content. In principle, however, higher concentrations are
also possible.
[0066] While the cycloolefin copolymers can have glass transition
temperatures of up to 250.degree. C., preferably they have a
processing temperature range such that it is compatible with the
TPU polymer or the TPU-IDP polymer. Suitable cycloolefin copolymers
for blending with a TPU or TPU-IDP polymer generally have a Tg of
from about minus 25.degree. C. to about 150.degree. C., desirably
from about 50.degree. C. to about 125.degree. C., and preferably
from about 60.degree. C. to about 115.degree. C.
[0067] The COCs suitable for the purposes of the invention have
viscosity numbers (determined in decalin at 135.degree. C.) of from
25 to 200 ml/g, preferably from 40 to 120 ml/g, particularly
preferably from 40 to 100 ml/g.
[0068] The cycloolefin copolymers have a particular structure,
which has been described in detail in a dissertation by J. Ruchatz,
Dusseldorf 1997.
[0069] Accordingly, the cycloolefin copolymers present in the novel
polymer blend may have sequences of two norbornene units
incorporated one after the other. Two norbornene units also
correspond to the maximum possible sequence length of the
cycloolefin copolymers present in the novel polymer blend.
[0070] The amount of the cycloolefin copolymer is generally from
about 45% to about 90% by weight, desirably from about 60% to about
85% by weight, and preferably from about 70% to about 80% by weight
based upon the total weight of the one or more cycloolefin
copolymers and the one or more TPU, TPU-IDP, and/or other IDP
polymers.
[0071] As noted above, it is an important aspect of the present
invention to produce transparent blends of the cycloolefin polymer
and the thermoplastic urethane. Accordingly, a cycloolefin
copolymer is utilized which generally has an index of refraction of
from about 1.48 to about 1.58, desirably from about 1.50 to about
1.56 and preferably from about 1.52 to about 1.54. The TPU and/or
TPU-IDP have a similar index or refraction so that the blend is
transparent. Generally, the index of the refraction of these two
components are similar and the difference between them is thus are
less than about 0.05, desirably less than about 0.03, and
preferably less than about 0.01. As also noted above, the TPU
component or the TPU-IDP component has an index of refraction of
generally from about 1.48 to about 1.58, desirably from about 1.50
to about 1.56, and preferably from about 1.52 to about 1.54. The
light transmission of the transparent blend for a 125 mil plaque is
desirably greater than 50%, and preferably greater than 75% as
measured according to ASTM D-1003-61.
[0072] Suitable cycloolefin copolymers (COC) are commercially
available under the name Topas.RTM. from Ticona GmbH. The proper
selection of the particular grade of COC will depend on the IDP
polymer being blended with the COC. To obtain a clear blend, the
index of refraction of the COC should be similar to the IDP polymer
used. Also, the melt processing temperatures should be close enough
to achieve proper intimate blending of the polymers. The proper
selection of the COC is determinable by one skilled in the art of
polymers compounding without undue experimentation. Additionally,
the properties of the COC phase and thus the properties of the
present invention can be tailored as needed by combining COC resins
that have different thermal and rheological properties. Since the
COC resins are miscible, properties such as glass transition
temperature and viscosity can be moved by adjusting their
proportions.
Compatibilizing Agent
[0073] The blends of the present invention comprise the
thermoplastic polyurethane (TPU) such as an inherently dissipative
thermoplastic polyurethane (TPU-IDP) composition or polymer, and
the cycloolefin copolymer (COC) such as a copolymer of norbornene
and an olefin. While the two components have similar processing
temperatures and therefore are processable, and also have similar
indices of refraction and therefore are transparent, they are
generally incompatible and accordingly a compatibilizing agent is
utilized to stabilize the blend and to improve properties without
eliminating or significantly reducing its clarity.
[0074] The preferred compatibilizer to make a clear blend of a COC
and a TPU is a thermoplastic polyurethane derived from the reaction
of a substantially hydrocarbon intermediate, a diisocyanate, and a
chain extender. The hydrocarbon intermediate is a low molecular
weight compound or a polymer having hydroxyl (preferred), amine, or
carboxylic acid terminal groups thereon. When the substantially
hydrocarbon intermediate is not solely a hydrocarbon but, e.g., a
polyester, the number of consecutive polymer backbone carbon atoms
between a non-carbon atom such as oxygen, is large, i.e., at least
20 carbon atoms, desirably at least 30 carbon atoms, and preferably
at least 45 carbon atoms to about 60, or about 75, or about 100
carbon atoms. An example of such a substantially hydrocarbon
intermediate, i.e., a long chain polyester polyol Priplast.RTM.
3197 from Unichema. Priplast.RTM. 3197 is a dimerdiol dimerate
prepared from dimerdiol Pripol.RTM. 2033 containing at least 36
carbon atoms and a dimer acid containing about 44 carbon atoms. A
suitable low molecular weight hydrocarbon intermediate is
Pripol.RTM. 2033 from Unichema, a 36 carbon atom dimerdiol.
However, the intermediate is preferably solely a hydrocarbon
intermediate derived from one or more dienes having a total of from
4 to 8 carbon atoms, such as butadiene, isoprene, and the like,
with butadiene being preferred. The number average molecular weight
of the hydrocarbon intermediate is generally from about 300 or
about 500 to about 10,000, desirably from about 1,000 to about
7,500, and preferably from about 2,000 to about 5,000. The
hydrocarbon intermediate can be unsaturated but preferably is
substantially hydrogenated such that at least 80%, desirably at
least about 90% or about 95%, and preferably at least about 98% or
about 99%, and even 100% of the carbon-carbon double bonds in the
intermediate are saturated. Hydrogenation may be carried out
according to any conventional process or manner such as set forth
in U.S. Pat. No. 5,393,843 or 5,405,911, hereby fully incorporated
by reference. When butadiene is utilized, the microstructure of the
resulting polymer can be largely 1,2 structure or 1,4 structure
(e.g., 15 to 85%) with a similar amount (e.g., 35 to 65%) of each
generally being preferred. Examples of hydrocarbon polyols derived
from butadiene include the following:
1 Identification Supplier Description Kraton .RTM. Liquid Shell
Hydroxyl-terminated polybutadiene, L2203 hydrogenated. Approximate
micro-structure: 55% 1,2; 45% 1,4. Polytail .RTM. H Mitsubishi
Hydroxyl-terminated polybutadiene, hydrogenated. Approximate micro-
structure: 21% 1,2; 79% 1,4. Polytail .RTM. HA Mitsubishi
Hydroxyl-terminated polybutadiene, hydrogenated. Approximate micro-
structure: 83% 1,2; 17% 1,4. Krasol .RTM. LBH Kaucuk AG
Hydroxyl-terminated polybutadiene. Approximate microstructure: 65%
1,2; 35% 1,4. Liquiflex .RTM. H Petroflex Hydroxyl-terminated
polybutadiene. Approximate microstructure: 22% 1,2; 78% 1,4.
[0075] Kraton.RTM. L2203 is preferred in the present invention.
[0076] The term "polyol" with respect to a substantially
hydrocarbon polyol intermediate is to be understood to mean that
while preferably the hydrocarbon has two functional hydroxyl end
groups, the same can generally range from about 1.8 to about 2.2
end groups per molecule.
[0077] The isocyanates utilized in the present invention are
preferably diisocyanates and include aliphatic, cycloaliphatic,
aromatic, alkyl-substituted aromatic diisocyanates and the like, as
well as mixtures thereof. Such diisocyanates generally have the
formula R(NCO).sub.n where R is an aliphatic, an aromatic, or
combinations thereof having a total of from 2 to about 30 carbon
atoms with from about 6 or about 8 to about 15 carbon atoms being
preferred, and an n is from 2 to about 4 with 2 being highly
preferred. Representative examples include ethylene diisocyanate;
toluene diisocyanate; methylene bis-(4-phenylisocyanate), that is,
MDI; isophorone diisocyanate; hexamethylene diisocyanate;
naphthalene diisocyanate; cyclohexylene diisocyanate;
diphenylmethane-3,3' dimethoxy-4,4'-diisocyanate,
meta-tetramethylxylene diisocyanate (m-TMXD 1),
paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene
diisocyanate (XDI), decane-1,10-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, as well as combinations
thereof, and the like, with MDI being preferred. It is to be
understood that isomers of the various diisocyanate can also be
used.
[0078] The chain extenders can be either diamines, alkanolamines,
or preferably diols containing a total of from 2 to about 15 carbon
atoms. Examples of chain extenders include ethanolamine, ethylene
diamine, ethylene glycol, 1,3-propane diol, 2,3- or 1,4-butane
diol, 1,5-pentane diol, 1,6-hexane diol, hydroquinone
bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexanedimethanol, and the like, with
2-butyl-2-ethyl-1,3-propane diol (BEPD) being preferred, and
neopentyl glycol being highly preferred.
[0079] The amount of the chain extender can be zero (i.e., none)
but desirably is from about 3 to about 30 percent by weight and
preferably from about 6 to about 25 percent by weight based upon
the total weight of chain extender and the substantially
hydrocarbon intermediate utilized in the formation of the
thermoplastic polyurethane compatibilizer. The amount of the chain
extender and intermediate utilized, whether they contain hydroxyl
groups, amine groups, etc., is generally an equivalent excess to
the amount of diisocyanate utilized. That is, the molar ratio of
the diisocyanate to hydrocarbon intermediate and chain extender is
generally from about 0.8 to about 1.05 and desirably from about 0.9
to about 1.01.
[0080] It is a desirable aspect of the present invention to make
the thermoplastic polyurethane compatibilizer by either the random
polymerization method wherein the substantially hydrocarbon
intermediate, the diisocyanate and the chain extender are all added
together at once and polymerized, or by the prepolymer method. The
prepolymer method is preferred where the chain extender is not
soluble in the intermediate as generally is the case. Thus, the
prepolymer method is generally preferred wherein the isocyanate
component is first partially or fully reacted with the hydrocarbon
intermediate or polyol to form an isocyanate-terminated prepolymer.
The same can be achieved by melt-polymerization. The partially or
fully formed prepolymer can then be subsequently reacted with the
chain extender.
[0081] The polymerization of the reactants forming the
thermoplastic compatibilizer of the present invention can generally
be carried out by melt-polymerization in a substantially
solvent-free and preferably completely solvent-free environment.
The hydrocarbon intermediate is heated to a temperature of from
about 80.degree. C. to about 160.degree. C. The diisocyanate, such
as MDI, is added and prepolymer formation commences. After a short
period of time, for example a couple or several minutes whereby
partial or total prepolymers have been formed, the chain extender
is added and the reaction carried out to completion. This method
allows ready reaction of the insoluble chain extender such as
neopentyl glycol with the diisocyanate inasmuch as neopentyl glycol
does not dissolve in the substantially hydrocarbon
intermediate.
[0082] The formation of the compatibilizer is generally carried out
in the presence of small amounts of catalysts such as organo tin
catalysts, e.g., stannous octoate, a preferred catalyst; stannous
oleate; dibutyl tin dioctoate; dibutyl tin dilaurate; and the like.
Other organic catalysts include iron acetylacetonate, magnesium
acetylacetonate, and the like. Tertiary organic amine catalysts,
such as triethylamine, triethylene diamine, and the like, can also
be utilized. The amount of catalyst is generally very small, from
about 25 to about 1,000 parts per million and desirably from about
40 to about 500 PPM by weight based upon the total weight of the
reactants.
[0083] Although various additives and fillers can be utilized as
known to the art and to the literature, such as pigments,
lubricants, stabilizers, antioxidants, anti-static agents, fire
retardants, etc., the same are generally not utilized in the
preparation of the compatibilizer.
[0084] The thermoplastic polyurethane compatibilizer of the present
invention has soft segments as well as hard segments. The soft
segments are generally defined as being solely the hydrocarbon
portion of the intermediate. The hard segments are defined as
everything else, e.g., the reaction of the intermediate terminal
group with the diisocyanate and the reaction of the chain extender
with the diisocyanate. The preferred compatibilizers of the present
invention desirably have high amounts of soft segments such as at
least about 25% or about 35% by weight, desirably from about 45% to
about 90% by weight, and preferably from about 60% to about 80% by
weight based upon the total weight of the thermoplastic
polyurethane compatibilizer excluding any additives, fillers,
etc.
[0085] The thermoplastic polyurethane compatibilizer was prepared
by either the random melt polymerization method or the prepolymer
method. In the random melt polymerization method, the polyol and
chain extender were blended together at about 100.degree. C. to
about 150.degree. C. or about 250.degree. C.
Diphenyl-methanediisocyanate (MDI) was heated separately to about
100.degree. C. to about 150.degree. C. or about 250.degree. C.,
then mixed with the blend. The reactants were vigorously mixed for
3-4 minutes. The polymer melt was discharged into a cooled,
Teflon-coated pan, cured at 70.degree. C. for 1 week, then
granulated. In the prepolymer method, the polyol was heated to
about 100.degree. C. to about 150.degree. C. or about 250.degree.
C. MDI was separately heated to about 100.degree. C. to about
150.degree. C. or about 250.degree. C., then mixed with the polyol
and allowed to react for 1-2 minutes. The chain extender was added,
and the reaction continued for an additional 1.5-3 minutes. The
polymer melt was then treated as described above. The melt index
values were obtained by ASTM D-1238.
[0086] The essentially hydrocarbon intermediate thermoplastic
urethane compatibilizers of the present invention are also
described in detail in U.S. Pat. No. 6,054,533 granted Apr. 25,
2000, and is hereby fully incorporated by reference.
[0087] When using TPU and/or TPU-IDP polymers in the blend with COC
to achieve a transparent blend, other compatibilizing agents can
also be utilized but are generally not preferred inasmuch as they
result in a lower clarity and transmission of light. Such less
desired compatibilizers are known to the literature and to the art
and include block copolymers of styrene-butadiene-styrene
commercially available from Shell Chemical as KRATON.RTM.. Other
compatibilizing agents of the various maleic anhydride grafted
polyolefins such as polypropylene-g-maleic anhydride and
polyethylene-g-maleic anhydride. The proper selection of the
compatibilizing agent will depend on the transparency desired in
the blend. The less desired compatibilizers mentioned above may be
used in a COC blended with TPU or TPU-IDP if less transparency is
desired. The above mentioned less desired compatibilizers can also
be used with COC blended with non TPU based IDPs.
[0088] The amount of the one or more compatibilizing agents of the
present invention is generally low such as from about 0.1 to about
12 parts by weight, desirably from about 0.25 to about 8 parts by
weight and preferably from about 0.5 to about 2 or 3 parts by
weight for every 100 parts by weight of the one or more
thermoplastic urethanes TPUs, and/or TPU-IDPs, and/or other IDP
polymers and the one or more cycloolefin copolymers, COC.
Transparent-Clear Blends
[0089] As mentioned above, the COC may be blended with a TPU,
TPU-IDP or other IDP polymer, and a compatibilizing agent. The
clarity of the blends will depend on the proper selection of the
COC to match the properties of the other polymers in the blend.
Since the most preferred blends are COC blended with TPU and/or
TPU-IDP, a clear blend is described below. The transparent or clear
blends or alloys of the present invention are made by melt
compounding the three components, i.e. the TPU and/or TPU-IDP, the
COC and the compatibilizing agent, in any suitable blender such as
a Banbury.RTM. or as in a twin screw extruder at temperatures of
from about 150.degree. C. to about 250.degree. C. and desirably
from about 190.degree. C. to about 220.degree. C.
[0090] Optical properties are measured by ASTM D-1003 and include
light transmission and haze values. Generally, thermoplastic
compositions are utilized which have a light transmission of at
least about 65% or about 70%, desirably at least about 75% or about
80% and preferably at least about 82%. Suitable haze values are
generally about 32% and less, desirably about 27% or about 22% and
less, and preferably about 8% or about 5% and less. Better optical
properties are obtained when the TPU is not a TPU-IDP. Conversely,
better electrostatic dissipating properties are obtained when an
TPU-IDP is utilized.
[0091] While stabilizers can be utilized, desirably various
additives such as antioxidants, UV inhibitors, lubricants, flame
retardants, and the like are not utilized inasmuch as they reduce
light transmission as well as clarity. If such additives are
utilized, they generally utilize at less than about 10%, desirably
less than about 5%, and preferably less than about 3% by weight and
more preferably none, based upon 100 parts by weight of the TPU
and/or TPU-IDP and the COC components.
[0092] The use of a compatibilizing agent is generally required
because the COC and the TPU phases have a positive free energy of
mixing and are therefore immiscible. The compatibilized form of the
present invention will have several advantages compared to an
uncompatibilized control. By reducing the interfacial tension and
increasing interfacial adhesion, the compatibilizer helps to
stabilize the desired morphology and therefore properties of the
blend. A co-continuous morphology is preferred when the goal is to
achieve electrical properties through the use of a TPU-IDP.
Increased interfacial adhesion improves energy transfer between the
phases. This helps prevent delamination or gross phase separation
when the blend is subjected the shear forces seen during secondary
processes such as injection molding. It also results in increased
impact properties and energy to break.
[0093] The transparent clear blends of the present invention have
several advantages including static dissipative properties, high
flexural modulus and strength, good clarity, low extractable ions,
and the like. A notable improvement of the blend is that is has low
outgassing properties in that as apparent from the data below, very
small amounts of gas are emitted. For example, generally less than
about 10 .mu.g off-gases/gram sample, desirably less than about 5
.mu.g off-gases/gram sample or about 3 .mu.g off-gases/gram sample
and preferably less than about 1 .mu.g off-gases/gram sample. Such
gases include toluene, styrene, methyl methacrylate, and the
like.
[0094] Outgassing is determined by placing a 500 mg sample in a 20
cc vial and heating for 60 minutes at 85 C in a Tekmar.RTM. 7000
headspace analyzer. An aliquot of the headspace was then
automatically removed and injected into a Hewlett Packard.RTM. 5890
Series II GC equipped with a flame ionization detector. A response
factor for decane was measured and used to determine the amount of
all three organic compounds and the total amount in the headspace.
Identification of each compound was by retention time alone. Off
gassing amount is reported in .mu.g off-gases/gram sample.
[0095] The above combination of properties result in a useful
polymeric blend suitable for electronic and semi-conductor
packaging, clean room components and articles, hard disc drive
components and packaging, optical devices, films, or coatings, and
the like. The blend composition can also be utilized in processes
including injection molding, extrusion, thermoforming and the
like.
[0096] The present invention will be better understood by reference
to the following examples which serve to illustrate but not to
limit the invention.
EXAMPLES
[0097] The ingredients set forth in Tables 1 and 2 (Examples A
through P) were blended in a Werner Pfleiderer.RTM. model ZSK 30
twin screw extruder under the following general conditions:
[0098] Rate: 25-35 lbs/hour
[0099] Rpm: 175
[0100] Temperatures (C):
[0101] Zone 1: 165
[0102] Zone 2: 175
[0103] Zone 3: 185
[0104] Zone 4: 190
[0105] Zone 5: 190
[0106] Zone 6: 185
[0107] Die: 170
[0108] Amps: 40
[0109] Specimens used for physical, electrical, and cleanliness
testing were injection molded.
[0110] Luminous transmittance % was tested on a Perkin Elmer Model
Lambda.RTM. 9 Spectrophotometer. 0.125" thick samples were scanned
from 400-860 m at a rate of 240 nm/min. The light source was a
Tungsen-halogen lamp. Slit width was 2 nm and the reference sample
was air. Percent transmittance is reported at 700 nm.
[0111] Optical properties are determined according to ASTM D-1003
and include light transmission and haze values.
[0112] Clear compositions were made according to the following
recipes shown in Examples A through J wherein the parts listed are
by weight. Additional examples are given in Table 2.
2 TABLE 1 EXAMPLES Ex. A Ex. B Ex. C Ex. D Ex. E DESCRIPTION COC 1/
COC 2/ COC 1/ TPU-IDP TPU-IDP TPU-IDP Alloy Alloy Alloy w/TPU w/TPU
w/Kraton .RTM. COC 1 compatibilizer COC 2 compatibilizer FG-1901X
FORMULATIONS Topas .RTM. 8007 100 74 72 Topas .RTM. 9506 100 74
TPU-IDP 25 25 25 Estane .RTM. 58315 Estane .RTM. 58206 Kraton FG
1901X 3 TPU-compatibilizer 1 1 Molded Samples Plastic Tensile ASTM
D-882-97 Stress @ Yield psi 9450 5810 8820 5120 5200 Elongation @
Yield % 3.18 3.09 3.1 2.99 3.09 Tensile @ Break psi 4320 2860 4510
510 1840 Elongation @ Break % 6.55 37.9 18.1 30.5 51.4 Modulus psi
394000 271000 381000 247000 254000 Energy to break lbs-in 43.7 185
109 118 226 Flex Modulus 397000 266000 370000 232000 237000 ASTM
D-790-95(.5 in/min) Notched IZOD impact 0.43 4.8 0.5 14.2 9.8 ASTM
D256-93a type of break Complete Hinged Complete Partial Hinged
Gardner impact (in lbs/in) 192 1664 192 960 832 Type of failure
Brittle Ductile Brittle Ductile Ductile Glass transition temp. via
78 C. 65 C. DSC Molded Plaques Surface Resistivity (ohm/sq) >E12
7.80E+09 >E12 7.40E+09 7.4E+09 Volume Resistivity >E12
2.60E+10 >E12 2.70E+10 2.50E+10 (Ohm-cm) Delamination? No No No
No No Optical Properties ASTM D-1003 Light transmission % 94.9 85
93.6 86.8 76.9 Haze % 3.6 16.2 4 20.3 25.5 Luminous Transmittance
(%) 78.24 81.2 88.27 79.15 65.08 ASTM D542 1.53 1.53 Index of
refraction EXAMPLES Ex. F Ex. G Ex. H Ex. I Ex. J DESCRIPTION COC
1/ COC 1/ 58315* Alloy 58206** alloy w/TPU w/TPU Estane .RTM.
Estane .RTM. TPU- compatibilizer compatibilizer 58315 58206 IDP
FORMULATIONS Topas .RTM. 8007 79 79 Topas .RTM. 9506 TPU-IDP 100
Estane .RTM. 58315 20 100 Estane .RTM. 58206 20 100 Kraton FG 1901X
TPU-compatibilizer 1 1 Molded Samples Plastic Tensile ASTM D-882-97
Stress @ Yield psi 6490 6870 4120 NA Elongation @ Yield % 3.09 3.13
218 NA Tensile @ Break psi 3330 2090 2760 3410 NA Elongation @
Break % 51.6 40.9 535 396 NA Modulus psi 302000 330000 1940 1840 NA
Energy to break lbs-in 264 223 901 819 NA Flex Modulus 290000
304000 3270 3760 NA ASTM D-790-95(.5 in/min) Notched IZOD impact
0.97 1.1 NA NA NA ASTM D256-93a type of break Hinged Complete NA NA
NA Gardner impact (in lbs/in) 1024 704 NA NA NA Type of failure
Ductile Ductile Glass transition temp. via DSC Molded Plaques
Surface Resistivity (ohm/sq) >E12 >E12 >E12 >E12
2.0E+07 Volume Resistivity >E12 >E12 >E12 >E12 1.0E+07
(Ohm-cm) Delamination? No No No No No Optical Properties ASTM
D-1003 Light transmission % 93 94.3 94.11 89.56 61.1 Haze % 11.9
6.6 5.04 16.91 12.7 Luminous Transmittance (%) 85.66 86.50 89.54
85.25 79.57 ASTM D542 1.53 1.53 1.53 Index of refraction *58315 is
an ether based TPU commercially available from Noveon, Inc. **58206
is an ester based TPU commercially available from Noveon, Inc.
[0113] The data in Table 2 show two commercially known IDP alloys
(Examples K and L). Examples M, N and O show different levels of
TPU-IDP blended with cycloolefin copolymer and a TPU
compatibilizer. Example P is a COC/TPU-IDP blend without a TPU
compatibilizer. The molding results show that the TPU
compatibilizer is necessary to prevent delamination for high shear
processing, such as molding. Delamination is indictive of a lack of
compatibility in polymer blends. Low shear processing, such as
often occurs in extrusion, is not as prone to show
delamination.
3 TABLE 2 EXAMPLES Ex. K Ex. L Ex. M Ex. N Ex. O Ex. P DESCRIPTION
COC 1/ COC 1/ COC 1/ Acrylic TPU-IDP TPU-IDP TPU-IDP Acrylic core/
Alloy Alloy Alloy IDP shell w/TPU w/TPU w/TPU COC/TPU- alloy IDP
compatibilizer compatibilizer compatibilizer IDP Blend FORMULATIONS
Topas .RTM. 8007 79 71.5 64 75 Topas .RTM. 9506 TPU-IDP 20 27.5 35
25 TPU-compatibilizer 1 1 1 ClearStat .RTM. C-37 100 Bayon .RTM.
YM-312 100 Molded Samples Plastic Tensile ASTM D-882-97 Stress @
Yield psi 5990 4580 3590 5200 Elongation @ Yield % 3.11 3.56 5.86
3.05 Tensile @ Break psi 1050 1870 3000 4420 Elongation @ Break %
27.3 21.7 16.9 8.71 Modulus psi 311000 245000 186000 275000 Energy
to break lbs-in 124 74.6 66.3 47 Flex Modulus 265000 189000 146000
247000 ASTM D-790-95 (.5 in/min) Notched IZOD impact 12.1 12.5 2.3
5 ASTM D256-93a type of break Gardner impact (in lbs/in) 320 Type
of failure Ductile Molded Plaques Surface Resistivity 2.5E+10
3.70E+09 6.90E+08 2.2E+10 (ohm/sq) Volume Resistivity 4.9E+10
7.40E+09 8.30E+08 5.4E+10 (Ohm-cm) Delamination? No No No No No
Yes
[0114] The data in Table 3 below is presented to show the low
offgassing of compositions of this invention as compared to two
other commercially available transparent inherently dissipative
polymers. The low offgassing features of the present invention are
important in electronic applications to avoid damaging the
electronic components. The table below shows offgassing results for
Example B of the present invention and two alternate transparent,
static dissipative polymers. The composition of Example B is shown
in Table 1. Example K (comparative) is a blend of an acrylic based
polymer and a polyether amide based IDP. It is commercially
available from Cyro Industries under the tradename ClearStat.RTM.
C-37. Example L (comparative) is an inherently dissipative acrylic
polymer made by a core/shell process. It is commercially available
from Kureha under the tradename Bayon.RTM.. Example B shows lower
total outgassing and lower outgassing of each identified species.
The formulations for Examples K and L are shown in Table 2.
4TABLE 3 EXAMPLE EXAMPLE K EXAMPLE L B (Comparative) (Comparative)
Off Gassing component -- (.mu.g/g) Methyl Methacrylate <0.03
12.65 1.91 Toluene <0.02 75.77 0.08 Styrene <0.02 7 0.15
Total including 1.32 99.4 11.54 unknowns
[0115] Topas is a copolymer of ethylene and norbornene made by
Ticona GmbH. The TPU-IDP, made by Noveon Inc., is a TPU derived
from a polyethylene oxide intermediate, MDI, and butane diol as a
chain extender with a small amount of a lithium salt and prepared
according to U.S. Pat. No. 6,140,405.
[0116] Kraton.RTM. FG-1901X is a maleated
styrene-ethylene/butylene-styren- e triblock copolymer (SEBS-MA).
It contains 28% polystyrene by weight and 2% maleic anhydride.
[0117] TPU compatibilizer is a compatibilizer derived from a
polybutadiene intermediate, MDI, and a neopentyl glycol chain
extender and made according to U.S. Pat. No. 6,054,533.
[0118] As apparent from Table 1, improved optical properties are
obtained when non-electrostatic dissipating thermoplastic urethanes
are utilized, see Examples F and G. However, when a TPU-IDP is
utilized as in Examples B and D, optical properties drop off but
favorable surface resistivity and volume resistivity values are
obtained which are not too conductive and not too resistant.
Examples M, N, and O (Table 2) demonstrate the effect of TPU-IDP
level on surface and volume resistivity. Resistivity decreases with
increasing level of TPU-IDP. Values can be adjusted to the desired
level within the static dissipative range. Tensile strength and
modulus values decrease with increasing TPU-IDP level.
[0119] Improved impact properties (Gardner and notched izod) were
also obtained when compared to the COC whether or not a TPU-IDP was
utilized.
[0120] While in accordance with the Patent Statutes the best mode
and preferred embodiment have been set forth, the scope of the
invention is not limited thereto but rather by the scope of the
attached claims.
* * * * *