U.S. patent application number 10/233066 was filed with the patent office on 2003-10-02 for infusion of cyclic olefin resins into porous materials.
Invention is credited to Cruce, Christopher J., Filice, Gary W., Giardello, Michael A., Stephen, Anthony R., Trimmer, Mark S..
Application Number | 20030186035 10/233066 |
Document ID | / |
Family ID | 23228397 |
Filed Date | 2003-10-02 |
United States Patent
Application |
20030186035 |
Kind Code |
A1 |
Cruce, Christopher J. ; et
al. |
October 2, 2003 |
Infusion of cyclic olefin resins into porous materials
Abstract
The present invention relates to novel compositions comprising
porous materials infused with polymers obtained from metathesis
reactions, for example ROMP derived polymers and ADMET derived
polymers. The invention further relates to cyclic olefin monomer
formulations, including ruthenium or osmium carbene metathesis
catalysts, useful for the infusion of porous materials. Also
disclosed are methods for preparing the porous materials infused
with cyclic olefin resin formulations.
Inventors: |
Cruce, Christopher J.;
(Poway, CA) ; Filice, Gary W.; (Moorpark, CA)
; Giardello, Michael A.; (Pasadena, CA) ; Stephen,
Anthony R.; (South Pasadena, CA) ; Trimmer, Mark
S.; (Monrovia, CA) |
Correspondence
Address: |
Pillsbury Winthrop LLP
Intellectual Property Group
Suite 2800
725 South Figueroa Street
Los Angeles
CA
90017-5406
US
|
Family ID: |
23228397 |
Appl. No.: |
10/233066 |
Filed: |
August 30, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60316290 |
Aug 30, 2001 |
|
|
|
Current U.S.
Class: |
428/292.4 ;
473/567 |
Current CPC
Class: |
C04B 41/63 20130101;
C04B 41/4857 20130101; C04B 41/4857 20130101; C04B 41/009 20130101;
C08J 9/42 20130101; C08L 97/02 20130101; C04B 41/4521 20130101;
C08L 2666/26 20130101; C08L 2666/22 20130101; C08L 2666/02
20130101; C08L 23/02 20130101; C04B 28/02 20130101; C08J 2423/00
20130101; C08K 5/098 20130101; C08L 2666/06 20130101; C08L 23/02
20130101; C08L 65/00 20130101; C08L 97/02 20130101; C04B 41/009
20130101; C08L 79/02 20130101; Y10T 428/249925 20150401; C08K
5/5425 20130101; C08K 3/01 20180101; C08L 23/02 20130101; C08L
97/02 20130101; C08K 3/01 20180101; C04B 2111/27 20130101; C08L
79/02 20130101 |
Class at
Publication: |
428/292.4 ;
473/567 |
International
Class: |
D21J 001/00; A63B
059/06 |
Claims
What is claimed is:
1. A composition comprising a porous material infused with a
metathesis-derived polyolefin.
2. The composition of claim 1, further comprising a coupling
agent.
3. The composition of claim 2, wherein the coupling agent is
selected from the group consisting of organotitanates,
organozirconates, and silanes.
4. The composition of claim 1 wherein the porous material is
selected from the group consisting of a non-organic material and an
organic material.
5. The composition of claim 1, wherein the porous material is
selected from the group consisting of wood, cement, concrete,
open-cell and reticulated foams and sponges, papers, cardboards,
felts, ropes and braids of natural or synthetic fibers, sintered
materials, unglazed porous ceramics, compacted free standing metal
powder objects, porous concrete aggregates, wood, wood products,
and cellulosic materials.
6. The composition of claim 1, wherein the metathesis-derived
polyolefin is selected from the group consisting of a ROMP polymer
and an ADMET polymer.
7. The composition of claim 1, wherein the metathesis-derived
polyolefin is prepared from one or more olefin monomers selected
from the group consisting of norbornenes, cyclopropenes,
cyclobutenes, benzocyclobutenes, cyclopentenes, cyclopentadiene
oligomers, cyclohexenes, cycloheptenes, cyclooctenes,
cyclooctadienes, norbornadienes, [2.2.1]bicycloheptenes, and
[2.2.2]bicyclooctene, cyclohexenylnorbornenes, and norbornene
dicarboxylic anhydrides.
8. The composition of claim 1, wherein the metathesis-derived
polyolefin is polydicyclopentadiene.
9. The composition of claim 1, wherein the metathesis-derived
polyolefin is polymerized using a ruthenium or osmium metal carbene
catalyst.
10. The composition of claim 1, wherein the metathesis-derived
polyolefin is polymerized using a catalyst selected from the group
consisting of a catalyst of the formula: 4wherein: M is ruthenium
or osmium; n is an integer between 0-5; L, L.sup.1 and L.sup.2 are
each independently any neutral electron donor ligand; R and R.sup.1
are each independently hydrogen or any hydrocarbyl or silyl moiety;
X and X.sup.1 are each independently any anionic ligand; Y is any
noncoordinating anion; and Z and Z.sup.1 are each independently any
linker selected from the group consisting of --O--, --S--,
--NR.sup.2--, --PR.sup.2--, --P(.dbd.O)R.sup.2--, --P(OR.sup.2)--,
--P(.dbd.O)(OR.sup.2)--, --C(.dbd.O)--, --C(.dbd.O)O--,
--OC(.dbd.O)--, --OC(.dbd.O)O--, --S(.dbd.O)--, or
--S(.dbd.O).sub.2--.
11. A method for preparing a polyolefin-infused porous material
comprising: mixing an olefin monomer resin formulation with a
metathesis catalyst to form a catalyzed resin formulation, infusing
the mixture into the porous material, and curing the catalyzed
resin formulation within said porous material.
12. The method of claim 11 wherein the porous material is selected
from the group consisting of wood, cement, concrete, open-cell and
reticulated foams and sponges, papers, cardboards, felts, ropes or
braids of natural or synthetic fibers, and sintered materials.
13. The method of claim 11, wherein the olefin monomer resin
formulation comprises an olefin monomer selected from the group
consisting of norbornenes, cyclopropenes, cyclobutenes,
benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers,
cyclohexenes, cycloheptenes, cyclooctenes, cyclooctadienes,
norbornadienes, [2.2.1]bicycloheptenes, and [2.2.2]bicyclooctene,
cyclohexenylnorbornenes, and norbornene dicarboxylic
anhydrides.
14. The method of claim 11, wherein the olefin monomer resin
formulation comprises dicyclopentadiene.
15. The method of claim 11, wherein the olefin monomer resin
formulation includes a coupling agent.
16. The method of claim 11, wherein the coupling agent is selected
from the group consisting of organotitanates, organozirconates, and
silanes.
17. The method of claim 11, wherein the metathesis catalyst is a
ruthenium or osmium metal carbene complex.
18. The method of claim 11, wherein the wherein the metathesis
catalyst is selected from the group consisting of a catalyst of the
formula: 5wherein: M is ruthenium or osmium; n is an integer
between 0-5; L, L.sup.1 and L.sup.2 are each independently any
neutral electron donor ligand; R and R.sup.1 are each independently
hydrogen or any hydrocarbyl or silyl moiety; X and X.sup.1 are each
independently any anionic ligand; Y is any noncoordinating anion;
and Z and Z.sup.1 are each independently any linker selected from
the group consisting of --O--, --S--, --NR.sup.2--, --PR.sup.2--,
--P(.dbd.O)R.sup.2--, --P(OR.sup.2)--, --P(.dbd.O)(OR.sup.2)--,
--C(.dbd.O)--, --C(.dbd.O)O--, --OC(.dbd.O)--, --OC(.dbd.O)O--,
--S(.dbd.O)--, or --S(.dbd.O).sub.2--.
19. A method for preparing a polyolefin-infused wood object
comprising: spraying the wood object with a cleaning and wetting
high-pressure water spray; drying the object, wherein the drying is
performed by heat and vacuum; infusing the object with a mixture of
an olefin monomer resin formulation and a metathesis catalyst under
pressure; curing the catalyzed resin formulation within the wood
object; and post-curing the polyolefin-infused wood object.
20. An article of manufacture comprising a porous material infused
with a metathesis-derived polyolefin.
21. The article of manufacture of claim 20, wherein the article is
selected from the group consisting of golf tees, golf clubs,
weighted golf club heads, golf club shafts, golf club gradient
shafts, basketball backboards, tennis rackets, squash rackets,
racquetball rackets, badminton rackets, snow boards, surfboards,
boogie board, skis, backboards, sleds, toboggans, baseball bats,
cricket bats, hockey sticks, pool cues, archery bows, archery
arrows, rifle butts, polo mallets, croquet mallets, tent stakes,
piers, docks, posts, decking, hulls, oars, propellers, rudders,
keels, masts, boat fascia, kayaks, canoes, ferro-cement boats,
hand-tool handles, knife handles, ladders, wood flooring panels,
deck lumber, treated concrete or cinder blocks, door and window
frames, office furniture, concrete bridge decks, parking structure
ramps, post-tensional beams and slabs, treated concrete pipes and
channel liners for aggressive and acidic fluids, sewer pipes,
containment structures, pavers, stone consolidation, plaster or
concrete ornamental objects, and pre-cast concrete objects.
22. The article of manufacture of claim 20, wherein the article is
a baseball bat.
Description
[0001] This application claims the benefit of co-pending U.S.
Provisional Patent Application Serial No. 60/316,290, filed Aug.
30, 2001, the contents of which are incorporated herein by
reference.
BACKGROUND
[0002] The invention is directed generally to methods and systems
for the infusion of cyclic olefin resins into free standing porous
materials, together with ring opening metathesis polymerization
(ROMP) catalysts to effect the polymerization of such olefins
within the porous materials to yield specific composite structures
and novel derivatives.
[0003] A wide variety of both natural and synthetic structural
materials have a porous nature. Common examples include wood,
cement and concrete, open-cell foams and sponges, paper and
cardboard, and various sintered materials. The porosity of these
materials may be an unintended consequence of their mode of origin
or may be a deliberate design feature. Depending upon the intended
use of a given material, such porosity may offer advantages such as
decreased weight, absorbency, breathability, or unique conductivity
or insulative characteristics. However, for many applications,
porosity can also lead to problems such as decreased mechanical
performance and durability. As a common example, water or moisture
routinely enters and exits the pores of porous materials. Aside
from affecting the resulting mechanical properties of the material,
this moisture often also accelerates degradation by chemical and/or
mechanical action.
[0004] Many types of treatments have been devised to try to protect
and improve the performance of porous materials. Paints and other
coatings are often applied for surface protection but yield little
improvement of mechanical performance. A variety of chemical agents
can be impregnated into porous materials as preservatives,
fire-retardants, water-repellents, or biocides, albeit generally to
the detriment of mechanical strength and toughness. In addition,
most of these agents slowly leach away over time, diminishing their
effectiveness and creating environmental issues. Polymeric
impregnants potentially alleviate some of these issues but can be
difficult to apply, especially with microporous materials. The
viscosities of thermoplastic, and even many thermoset, resins are
very high, making impregnation and wetting of porous materials very
difficult. Low-viscosity thermoset resins, which would be easier to
infuse, typically form brittle polymers upon cure. In addition,
thermoset resin chemistries may be incompatible with moieties
present in the interstices or surfaces of porous materials (porous
materials have very high surface areas) and are quite often
susceptible to hydrolysis, thereby limiting their long-term
durability.
[0005] Low-viscosity thermoset resins yielding tough,
moisture-resistant polymers would seem to be ideal candidates for
infusion into porous materials as protectants and mechanical
performance enhancers. Such polymers may be obtained by the
ring-opening metathesis polymerization (ROMP) of cyclic olefin
monomers. The resulting ROMP polymers possess non-hydrolyzable
hydrocarbon backbones and are generally very tough. ROMP, however,
typically depends upon transition metal catalysts that are
extremely sensitive to air, moisture, and functional groups that
may be present in the monomers or the porous materials. Thus, ROMP
polymers are not commonly considered as candidate impregnants for
porous materials.
[0006] Recently, however, certain ruthenium and osmium carbene
compounds have been identified as effective catalysts for ROMP even
in the presence of air, water, and most functional groups. Examples
of such metathesis catalysts have been previously described in, for
example, U.S. Pat. Nos. 5,312,940; 5,969,170; 5,917,071; 5,977,393;
6,111,121; 6,211,391, 6,225,488 and 6,306,987 and PCT Publications
WO 98/39346, WO 99/00396, WO 99/00397, WO 99/28330, WO 99/29701, WO
99/50330, WO 99/51344, WO 00/15339, WO 00/58322, WO 00/71554 and WO
02/14376, the disclosures of each of which are incorporated herein
by reference. Surprisingly, it has now also been found that these
catalysts enable ROMP of cyclic olefin monomers that have been
infused into a variety of porous materials including, for example,
such highly functional materials as wood and concrete.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows a preferred method of infusing baseball bats
with DCPD resin.
DETAILED DESCRIPTION
[0008] The present invention encompasses novel compositions
comprising porous materials infused with polymers obtained from
metathesis reactions, for example ROMP derived polymers and ADMET
derived polymers. Another embodiment of the invention is cyclic
olefin monomer formulations, including ruthenium or osmium carbene
metathesis catalysts, useful for the infusion of porous materials.
A further embodiment of the invention includes methods for
preparing the porous materials infused with cyclic olefin resin
formulations. Other embodiments of the present invention are
specific composite structures and articles fabricated from porous
materials infused with cyclic olefin polymers.
[0009] A number of catalysts have been developed recently for
initiating olefin metathesis reactions, including ring-opening
metathesis polymerization (ROMP) of cyclic olefins, ring-closing
metathesis (RCM) of dienes to form ring-closed products, acyclic
diene metathesis polymerization (ADMET), depolymerization of
unsaturated polymers to form the depolymerized products, synthesis
of telechelic polymers by reaction of a cyclic olefin with a
functionalized olefin, and synthesis of cyclic olefins by
self-metathesis of an acyclic olefin or cross-metathesis of two
acyclic oletins.
[0010] Any suitable metathesis catalyst may be used. Preferred
metathesis catalysts include, but are not limited to, neutral
ruthenium or osmium metal carbene complexes that possess metal
centers that are formally in the +2 oxidation state, have an
electron count of 16, are penta-coordinated, and are of the general
formula I. Other preferred metathesis catalysts include, but are
not limited to, cationic ruthenium or osmium metal carbene
complexes that possess metal centers that are formally in the +2
oxidation state, have an electron count of 14, are
tetra-coordinated, and are of the general formula II. Still other
preferred metathesis catalysts include, but are not limited to,
neutral ruthenium or osmium metal carbene comlexes that possess
metal centers that are formally in the +2 oxidation state, have an
electron count of 18, are hexa-coordinated, and are of the general
formula III. 1
[0011] wherein:
[0012] M is ruthenium or osmium;
[0013] n is an integer between 0-5;
[0014] L, L.sup.1 and L.sup.2 are each independently any neutral
electron donor ligand;
[0015] R, and R.sup.1 are each independently hydrogen or any
hydrocarbyl or silyl moiety;
[0016] X and X.sup.1 are each independently any anionic ligand;
[0017] Y is any noncoordinating anion;
[0018] Z and Z.sup.1 are each independently any linker selected
from the group nil, --O--, --S--, --NR.sup.2--, --PR.sup.2--,
--P(.dbd.O)R.sup.2--, --P(OR.sup.2)--, --P(.dbd.O)(OR.sup.2)--,
--C(.dbd.O)--, --C(.dbd.O)O--, --OC(.dbd.O)--, --OC(.dbd.O)O--,
--S(.dbd.O)--, or --S(.dbd.O).sub.2--; and
[0019] wherein any two or more of X, X.sup.1, L, L.sup.1, L.sup.2,
Z, Z.sup.1, R, R.sup.1, and R.sup.2 may be optionally joined
together to form a multidentate ligand and wherein any one or more
of X, X.sup.1, L, L.sup.1, L.sup.2, Z, Z.sup.1, R, and R.sup.1 may
be optionally linked chemically to a solid or glassy support.
[0020] In preferred embodiments of these catalysts, L, L.sup.1 and
L.sup.2 are each independently selected from the group consisting
of phosphine, sulfonated phosphine, phosphite, phosphinite,
phosphonite, arsine, stibine, ether, amine, amide, imine,
sulfoxide, carbonyl, carboxyl, isocyanide, nitrosyl, pyridine,
quinoline, thioether, and nucleophilic carbenes of the general
formula IV or V: 2
[0021] wherein:
[0022] A is either carbon or nitrogen;
[0023] R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are each
independently hydrogen or any hydrocarbyl moiety, except that in
the case where A is nitrogen R.sup.5 is nil;
[0024] Z.sup.2 and Z.sup.3 are each independently any linker
selected from the group nil, --O--, --S--, --NR.sup.2--,
--PR.sup.2--, --P(.dbd.O)R.sup.2--, --P(OR.sup.2)--,
--P(.dbd.O)(OR.sup.2)--, --C(.dbd.O)--, --C(.dbd.O)O--,
--OC(.dbd.O)--, --OC(.dbd.O)O--, --S(.dbd.O)--, or
--S(.dbd.O).sub.2--, except that in the case where A is nitrogen
Z.sup.3 is nil; and
[0025] Z.sup.2, Z.sup.3, R.sup.4, and R.sup.5 together may
optionally form a cyclic optionally substituted with one or more
moieties selected from the group consisting of C.sub.1-C.sub.10
alkyl, C.sub.1-C.sub.10 alkoxy, aryl, and a functional group
selected from the group consisting of hydroxyl, thiol, thioether,
ketone, aldehyde, ester, ether, amine, imine, amide, nitro,
carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,
carboalkoxy, carbamate, and halogen.
[0026] In more preferred embodiments, L and L.sup.1 are each a
phosphine of the formula PR.sup.7R.sup.8R.sup.9, where R.sup.7,
R.sup.8, and R.sup.9 are each independently any hydrocarbyl moiety,
particularly aryl, primary C.sub.1-C.sub.10 alkyl, secondary alkyl
or cycloalkyl. In even more preferred embodiments, L and L.sup.1
are selected from the group consisting of --P(cyclohexyl).sub.3,
--P(cyclopentyl).sub.3, --P(isopropyl).sub.3, --P(butyl).sub.3, and
--P(phenyl).sub.3. These phosphines are commonly referred to by
their abbreviated designations: PCy.sub.3, PCp.sub.3,
P(i-Pr).sub.3, PBu.sub.3, and PPh.sub.3, respectively.
[0027] In the most preferred embodiments, L is a phosphine and
L.sup.1 is a nucleophilic carbene of the general formula III.
Preferably, L is selected from the group consisting of
--P(cyclohexyl).sub.3, --P(cyclopentyl)3, --P(isopropyl).sub.3,
--P(butyl).sub.3, and --P(phenyl).sub.3 and L.sup.1 is selected
from the group consisting of structures VI, VII, or VIII (wherein m
is an integer between 0 and 5): 3
[0028] The ligand L.sup.1 of structure VII is commonly referred to
as "IMES" in the case where m=3. The saturated variant of structure
VI is similarly referred to as "s-IMES" in the case where m=3.
[0029] In other preferred embodiments, L is a phosphine or a
nucleophilic carbene of the general formula IV and L.sup.1 and
L.sup.2 are each independently a pyridine or substituted pyridine
ligand or L.sup.1 and L.sup.2 together form a chelating bispyridine
or phenanthroline ligand, either of which may be substituted or
unsubstituted.
[0030] Relating to R and R.sup.1-R.sup.9, examples of hydrocarbyl
moieties include, but are not limited to, the group consisting of
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, aryl,
heteroaryl, aralkyl, or arylalkyl. Examples of silyl moieties
include, but are not limited to, the group consisting of
tri(hydrocarbyl)silyl, tri(hydrocarbyloxy)silyl, or mixed
(hydrocarbyl)(hydrocarbyloxy)silyl. Optionally, each of the R,
R.sup.1 or R.sup.2 substituent groups may be substituted with one
or more hydrocarbyl or silyl moieties, which, in turn, may each be
further substituted with one or more groups selected from a
halogen, a C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, and
phenyl. Moreover, any of the catalyst ligands may further include
one or more functional groups. Examples of suitable functional
groups include but are not limited to: hydroxyl, thiol, thioether,
ketone, aldehyde, ester, ether, amine, imine, amide, nitro,
carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,
carboalkoxy, carbamate, and halogen. In addition, any or all of R,
R.sup.1 and R.sup.2 may be joined together to form a bridging or
cyclic structure.
[0031] In preferred embodiments of these catalysts, the R
substituent is hydrogen and the R.sup.1 substituent is selected
from the group consisting C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20
alkenyl, aryl, alkaryl, aralkyl, trialkylsilyl, and trialkoxysilyl.
In even more preferred embodiments, n equals 0, 1 or 2 and the
R.sup.1 substituent is phenyl, t-butyl or vinyl, optionally
substituted with one or more moieties selected from the group
consisting of C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy,
phenyl, and a functional group. In especially preferred
embodiments, n equals 0 or 1 and R.sup.1 is phenyl, t-butyl, or
vinyl substituted with one or more moieties selected from the group
consisting of chloride, bromide, iodide, fluoride, --NO.sub.2,
--NMe.sub.2, methyl, methoxy and phenyl.
[0032] In preferred embodiments of these catalysts, X and X.sup.1
are each independently hydrogen, halide, or one of the following
groups: C.sub.1-C.sub.20 alkyl, aryl, C.sub.1-C.sub.20 alkoxide,
aryloxide, C.sub.3-C.sub.20 alkyldiketonate, aryldiketonate,
C.sub.1-C.sub.20 carboxylate, arylsulfonate, C.sub.1-C.sub.20
alkylsulfonate, C.sub.1-C.sub.20 alkylthiol, aryl thiol,
C.sub.1-C.sub.20 alkylsulfonyl, or C.sub.1-C.sub.20 alkylsulfinyl.
Optionally, X and X.sup.1 may be substituted with one or more
moieties selected from the group consisting of C.sub.1-C.sub.10
alkyl, C.sub.1-C.sub.10 alkoxy, and aryl which in turn may each be
further substituted with one or more groups selected from halogen,
C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, and phenyl. In more
preferred embodiments, X and X.sup.1 are halide, benzoate,
C.sub.1-C.sub.5 carboxylate, C.sub.1-C.sub.5 alkyl, phenoxy,
C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.5 alkylthiol, aryl thiol,
aryl, and C.sub.1-C.sub.5 alkyl sulfonate. In even more preferred
embodiments, X and X.sup.1 are each halide, CF.sub.3CO.sub.2,
CH.sub.3CO.sub.2, CFH.sub.2CO.sub.2, (CH.sub.3).sub.3CO,
(CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO,
MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate. In the
most preferred embodiments, X and X.sup.1 are each chloride,
bromide, or iodide. In addition, the X and X.sup.1 together may
comprise a bidentate ligand.
[0033] Y may be derived from any tetracoordinated boron compound or
any hexacoordinated phosphorus compound. Preferred boron compounds
include BF.sub.4.sup.-, BPh.sub.4.sup.-, and fluorinated
derivatives of BPh.sub.4.sup.-. Preferred phosphorous compounds
include PF.sub.6.sup.- and PO.sub.4.sup.-. The noncoordinating
anion may be also any one of the following: ClO.sub.4.sup.-,
SO.sub.4.sup.-, NO.sub.3.sup.-, OTeF.sub.5.sup.-,
F.sub.3CSO.sub.3.sup.-, H.sub.3CSO.sub.3.sup.-, CF.sub.3COO.sup.-,
PhSO.sub.3.sup.-, or (CH.sub.3)C.sub.6H.sub.5SO.sub.3.- sup.-. Y
may be also derived from carboranes, fullerides, and
aluminoxanes.
[0034] The catalyst:olefin monomer ratio in the invention is
preferably between about 1:5 and about 1:1,000,000. More
preferably, the catalyst:olefin ratio is between about 1:100 and
about 1:100,000 and, most preferably, is between about 1:1,000 and
about 1:30,000. Particularly preferred metal catalysts include, but
are not limited to: (PCy.sub.3).sub.2Cl.sub.2Ru.dbd.CHPh,
(PCy.sub.3).sub.2Cl.sub.2Ru.dbd.CH-- -CH.dbd.CMe.sub.2,
(PCy.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHCMe.sub.3,
(PCy.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHSiMe.sub.3,
(PCy.sub.3)(s-IMES)Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2,
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2,
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHPh,
(PCp.sub.3)(s-IMES)Cl.sub.2Ru- .dbd.CH--CH.dbd.CMe.sub.2,
(PPh.sub.3)(s-IMES)Cl.sub.2Ru.dbd.C.dbd.CHCMe.s- ub.3,
(PPh.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHSiMe.sub.3,
(P(i-Pr).sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHPh,
(PPh.sub.3)(s-IMES)Cl.sub- .2Ru.dbd.C.dbd.CHSiMe.sub.3,
(PBu.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHPh,
(PPh.sub.3)(s-IMES)Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2,
(PCy.sub.3)(s-IMES)Cl.sub.2Ru.dbd.C.dbd.CHPh,
(PCp.sub.3)(s-IMES)Cl.sub.2- Ru.dbd.C.dbd.CHPh,
(PBu.sub.3)(s-IMES)Cl.sub.2Ru.dbd.C.dbd.CHPh,
(PCy.sub.3)(s-IMES)Cl.sub.2Ru.dbd.CHPh,
(PBu.sub.3)(s-IMES)Cl.sub.2Ru.dbd- .CH--CH.dbd.CMe.sub.2,
(PCy.sub.3)(IMES)Cl.sub.2Ru.dbd.CHPh,
(PPh.sub.3).sub.2Cl.sub.2Ru.dbd.C.dbd.CHCMe.sub.3,
(PCy.sub.3)(IMES)Cl.sub.2Ru.dbd.C.dbd.CHCMe.sub.3,
(PCp.sub.3)(IMES)Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2,
(PBu.sub.3)(IMES)Cl.sub.2Ru.dbd.C.dbd.CHPh,
(s-IMES)(C.sub.5H.sub.5N).sub- .2Cl.sub.2Ru.dbd.CHPh, and
(s-IMES)(3-Br--C.sub.5H.sub.4N).sub.2Cl.sub.2Ru-
.dbd.CH--CH.dbd.CMe.sub.2.
[0035] The inventive formulation resins include any olefin monomer
and metathesis catalyst. The olefin monomers may be used alone or
mixed with each other in various combinations to adjust the
properties of the olefin monomer composition. For example, mixtures
of cyclopentadiene oligomers offer a reduced melting point and
yield cured olefin copolymers with increased mechanical strength
and stiffness relative to pure poly-DCPD. As another example,
incorporation of COD, norbornene, or alkyl norbornene comonomers
tend to yield cured olefin copolymers that are relatively soft and
rubbery. The polyolefin resins of the invention are amenable to
thermosetting and are tolerant of various additives, stabilizers,
rate modifiers, hardness and/or toughness modifiers, viscosity
modifiers, adhesion or coupling agents, and fillers.
[0036] Any suitable cyclic olefin monomer can be used with the
present invention. Within the scope of this invention, olefin
monomers for infusion include at least one of all "tight"
cycloolefins as described in U.S. Pat. No. 6,001,909; and at least
one of all cycloolefins as described in U.S. Pat. No. 5,840,238 and
U.S. Pat. No. 5,922,802; and at least one of all Diels-Alder
adducts as described in U.S. Pat. No. 6,100,323. The most preferred
olefin monomer for use in the invention is dicyclopentadiene
(DCPD). Various DCPD suppliers and purities may be used such as
Lyondell 108 (94.6% purity), Velsicol UHP (99+ % purity), Cymetech
Ultrene.RTM. (97% and 99% purities), and Hitachi (99+ % purity).
High-purity grades of DCPD, such as Ultrene.RTM. 99, are preferred.
In certain preferred formulations, the DCPD resin may optionally
contain other cyclopentadiene oligomers, including trimers,
tetramers, pentamers, and the like. Such oligomers may be
introduced into DCPD by heat treatment of DCPD as described in U.S.
Pat. No. 4,899,005 to Lane (et al.) and U.S. Pat. No. 4,751,337 to
Espy (et al.). The oligomer content may be controlled by varying
the heat treatment conditions or by blending oligomer mixtures of
known composition with DCPD until the desired oligomer
concentration is obtained. Advantages of using such oligomer
mixtures include decreased melting point of the monomer mixture and
increased mechanical properties and glass transition temperature of
the cured resin.
[0037] Other preferred olefin monomers include cyclooctadiene (COD;
DuPont); cyclooctene (COE); cyclohexenylnorbornene; norbornene;
norbornene dicarboxylic anhydride (nadic anhydride); norbornadiene
(Elf Atochem); and substituted norbornenes including ethylidene
norbornene (ENB), butyl norbornene, hexyl norbornene, octyl
norbornene, decyl norbornene, and the like. Preferably, the
olefinic moieties include mono-or disubstituted olefins and
cycloolefins containing between 3 and 200 carbons. Most preferably,
metathesis-active olefinic moieties include cyclic or multicyclic
olefins, for example, cyclopropenes, cyclobutenes, cycloheptenes,
cyclooctenes, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes,
benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers
including trimers, tetramers, pentamers, and the like;
cyclohexenes. It is also understood that such compositions include
frameworks in which one or more of the carbon atoms carry
substituents derived from radical fragments including halogens,
pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and
arylthiolate, amino, aminoalkyl, and the like, or in which one or
more carbon atoms have been replaced by, for example, silicon,
oxygen, sulfur, nitrogen, phosphorus, antimony, or boron. For
example, the olefin may be substituted with one or more groups such
as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide,
nitro, carboxylic acid, disulfide, carbonate, isocyanate,
phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide,
carboalkoxy, carbamate, halogen, or pseudohalogen. Similarly, the
olefin may be substituted with one or more groups such as
C.sub.1-C.sub.20 alkyl, aryl, acyl, C.sub.1-C.sub.20 alkoxide,
aryloxide, C.sub.3-C.sub.20 alkyldiketonate, aryldiketonate,
C.sub.1-C.sub.20 carboxylate, arylsulfonate, C.sub.1-C.sub.20
alkylsulfonate, C.sub.1-C.sub.20 alkylthio, arylthio,
C.sub.1-C.sub.20 alkylsulfonyl, and C.sub.1-C.sub.20 alkylsulfinyl,
C.sub.1-C.sub.20 alkylphosphate, arylphosphate, wherein the moiety
may be substituted or unsubstituted.
[0038] In the invention, the viscosity of the formulated olefin
monomers (e.g., the olefin monomers combined with any additives,
stabilizers, or modifiers other than density modulators, fillers,
or fibers) is typically less than about 500 centipoise at
temperatures near room temperature (e.g., from about 25-35.degree.
C.). Preferably, the viscosity of the formulated olefin monomers is
less than about 200 centipoise, more preferably is less than about
75 centipoise, and most preferably, is less than about 50
centipoise. In many circumstances, the viscosity is less than 25
centipoise to promote facile infusion. The viscosity of the
formulated olefin monomers can be controlled by selection of the
combination of monomers and additives, stabilizers, and modifiers
used. The viscosity of the formulated resin may be increased or
decreased by varying the temperature or by the use of additives
such as thixotropes, thickeners, or dilutents.
[0039] Preferred hardness modulators include, for example,
elastomeric additives such as polybutadienes, polyisoprenes, and
the like. Polybutadienes and polyisoprenes of various sources, as
well as various number-average molecular weights (M.sub.n) or
weight-average molecular weights (M.sub.w), may be utilized in the
invention as rubber-like hardness modulators. Unexpectedly, the
poly-DCPD resins of the invention allow compositions containing
polybutadiene to be clear rather than opaque. The hardness
modulators of the invention, when added to a polyolefin resin
composition, alter the hardness, toughness and/or surface "feel" of
the composition compared to the unmodified or native polyolefin. In
addition to butadiene and isoprene-based elastomers, other hardness
modulators include plasticizers such as dioctyl phthalate and
various molecular weight hydrocarbon and the like jellies, greases
and waxes, carboxylic acids and salts thereof, and co-monomers such
as norbornene, cyclooctadiene, cyclooctene, cyclohexenylnorbornene,
norbornadiene, cyclopentene and/or methylcyclopentene. The amount
of hardness modulator included in the polyolefin compositions of
the invention is preferably about 0.1%-20% by weight of the olefin
monomer to which it is added. More preferably, the amount of
hardness modulator is about 1%-10% by weight of the olefin monomer
and, most preferably, is about 2.5%-7.5%.
[0040] Especially preferred toughness modulators are rubber
triblock copolymers such as styrene-butadiene-styrene,
styrene-isoprene-styrene, styrene-ethylene/butylenes-styrene,
styrene-ethylene/propylene-styrene, and the like. An example of
such toughness modulators is the commercially available Kraton.TM.
polymers. Other preferred toughness modulators include
polysiloxanes, because the resulting polyolefin compositions
possess significantly increased toughness properties without
significant concomitant losses in heat distortion temperature
(HDT). The amount of toughness modulator included in the polyolefin
compositions of the invention is preferably about 0.1%-10% by
weight of the olefin monomer to which it is added. More preferably,
the amount of toughness modulator is about 0.5%-6% by weight of the
olefin monomer and, most preferably, is about 2%-4%. For example,
poly-DCPD resins containing 3 parts per hundred low molecular
weight (MW) poly(dimethylsiloxane) (Shin Etsu DMF-50) possess
notched Izod impact values in excess of 4 ft.-lb./in. and HDT
values above 130.degree. C. Hardness and toughness modulators are
further described in PCT Publication No. WO 99/60030, the contents
of which are incorporated herein by reference.
[0041] The UV and oxidative resistance of the polyolefin
compositions of the invention may be enhanced by the addition of
various stabilizing additives such as primary antioxidants (e.g.,
sterically hindered phenols and the like), secondary antioxidants
(e.g., organophosphites, thioesters, and the like), light
stabilizers (e.g., hindered amine light stabilizers or HALS), and
UV light absorbers (e.g., hydroxy benzophenone absorbers,
hydroxyphenylbenzotriazole absorbers, and the like). Preferably,
one or more stabilizing additives are included in the polyolefin
resin composition at a level from about 0.01-15 phr. More
preferably, the antioxidant(s) are present at a level of about
0.05-10 phr and, most preferably, 0.1-8 phr. Exemplary primary
antioxidants include, for example, 4,4'-methylenebis
(2,6-di-tertiary-butylphenol) (Ethanox 702.RTM.; Albemarle
Corporation), 1,3,5-trimethyl-2,4,6-tris
(3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330.RTM.;
Albemarle Corporation),
octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate
(Irganox 1076.RTM.; Ciba-Geigy), and pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)(Irganox.RTM.
1010; Ciba-Geigy). Exemplary secondary antioxidants include
tris(2,4-ditert-butylphenyl)phosphite (Irgafos.RTM. 168;
Ciba-Geigy), 1:11 (3,6,9-trioxaudecyl)bis(dodecylthio)propionate
(Wingstay.RTM. SN-1; Goodyear), and the like. Exemplary light
stabilizers and absorbers include
bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylet-
hyl)-4-hydroxyphenyl]methyl]butylmalonate (Tinuvin.RTM. 144 HALS;
Ciba-Geigy), 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol
(Tinuvin.RTM. 328 absorber; Ciba-Geigy),
2,4-di-tert-butyl-6-(5-chloroben- zotriazol-2-yl)phenyl
(Tinuvin.RTM. 327 absorber; Ciba-Geigy),
2-hydroxy-4-(octyloxy)benzophenone (Chimassorb.RTM. 81 absorber;
Ciba-Geigy), and the like. The UV and oxidative resistance of
polyolefin compositions are further discussed in PCT Publication
No. WO 00/46256, the contents of which are incorporated herein by
reference.
[0042] In addition, a suitable rate modifier such as, for example,
triphenylphosphine (TPP), tricyclopentylphosphine,
tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites,
triarylphosphites, mixed phosphites, pyridine, or other Lewis base,
may be added to the olefin monomer to retard or accelerate the rate
of polymerization as required. In the case of TPP rate modifier, it
is preferably included in an amount of about 10-200 mg per 64 g
olefin monomer. More preferably, the amount of TPP is about 20-100
mg per 64 g olefin monomer and, most preferably, is about 30-80 mg
per 64 g olefin monomer. In the case of other rate modifiers, such
as alkylphospines and pyridine, the amount of rate modifier is
preferably about 0.1-50 mg per 64 g olefin monomer, more preferably
about 1-40 mg per 64 g olefin monomer, and most preferably is about
1-30 mg per 64 g olefin monomer. A detailed description of rate
modifiers can be seen in U.S. Pat. No. 5,939,504 and U.S.
application Ser. No. 09/130,586, the contents of each of which are
incorporated herein by reference.
[0043] Also, various pigments or dyes may be included in the
polyolefin resin compositions of the invention for applications
where color is desired. Preferred pigments include Ferro and Dayglo
products, in an amount of about 0.05-2 parts per hundred of
polyolefin resin. The cyclic olefin resin formulation may also
contain coupling agents or adhesion agents that promote bonding
between the walls of the substrate and the infused resin. U.S. Pat.
Nos. 6,040,363 and 6,001,909, the disclosures of which are
incorporated herein by reference, disclose various preferred sizing
or coupling agents useful with cyclic olefin resin formulations.
Especially preferred coupling agents are metathesis active adhesion
agents as disclosed in WO 00/46257, the contents of which are
incorporated herein by reference, and organotitanates and
organozirconates such as the Ken-React.RTM. products available from
Kenrich Petrochemicals, Inc. Especially preferred organotitanates
and organozirconates are those containing olefinic groups that may
react during polymerization to form carbon-carbon chemical bonds
with the resulting polycycloolefin polymer. Examples of such
compounds include tetra(2,2-diallyloxymethyl)butyl
di(ditridecyl)phosphito titanate (Ken-React.RTM. KR 55),
tetra(2,2-diallyloxymethyl)butyl di(ditridecyl)phosphito zirconate
(Ken-React.RTM. KZ 55), and
cyclo[dineopentyl(diallyl)]pyrophosphato dineopentyl(diallyl)
zirconate (Ken-React.RTM. KZ TPP). Especially preferred metathesis
active adhesion agents are olefin-containing silanes such as
allyltrimethoxysilane, butenyltriethoxysilane,
hexenyltriethoxysilane, octenyltriethoxysilane,
norbornenyltriethoxysilane, norbornenylethyltriethoxysilane, and
the like.
[0044] A wide variety of porous materials may be used in the
present invention so long as such materials are pervious to the
unpolymerized cyclic olefin resin formulation and do not contain
chemical groups that are incompatible with the olefin metathesis
catalyst. Such porous materials include but are not limited to
wood, cement, concrete, open-cell and reticulated foams and
sponges, papers, cardboards, felts, ropes or braids of natural or
synthetic fibers, and various sintered materials. Preferred
non-organic materials include unglazed porous ceramics, compacted
free standing metal powder objects, and porous concrete aggregates
such as cinder blocks. Preferred organic materials include wood,
wood products and related cellulosic materials in various forms.
These include but are not limited to monolithic wood objects as
well as laminated wood, plywood, particleboard and chipboard
objects and products. The most preferred porous materials are
various types of wood.
[0045] Portland cement or concrete has an open pore structure that
is interwoven and interconnected. One particular form of cement
called Enhanced Porosity Cement (EPC) uses little or no sand and
has a 20-25% void volume. The markedly porous structure of all
cements and related materials allows for the ready diffusion of
air, other gases and water vapor. This porous structure also
facilitates moisture migration and the wicking of water. Such
processes are capable of incorporating destructive pollutants such
as nitrate, sulfate and chloride salts into the concrete. At
various rates, these salts weaken the concrete structure, promote
rusting of embedded steel reinforcing materials, which expand on
oxidation and promote the formation of hairline cracks and
fissures. Surface water from acid rain and salt water in marine
applications present particularly difficult and corrosive
environment for the use of concrete. Such problems are mitigated by
the use of the infused composites of the present invention.
Catalyzed cyclic olefin monomer formulations effectively infuse
into the pore structure, cracks and fissures of concrete, and
related materials, to provide chemically stable ROMP polymers that
provide a barrier to water, water vapor and dissolved salts as well
as a reduced permeability to corrosive gases such as NO.sub.x and
SO.sub.2. The infused concrete can also exhibit up to a three to
four times increase in compressive strength, flexural strength and
durability along with a 50-100% increase in the modulus of
elasticity. These features, together with reduced permeability to
water, greatly enhance durability to cycles of freezing and
thawing.
[0046] In the practice of the present invention, the high
reactivity and functional group tolerance of the preferred
metathesis catalysts allow for polymerization within the porous
structures of a wide variety of porous materials. These catalysts
are effective at relatively low loading in resins, they operate at
relatively low temperature, and are tolerant of reactive molecules
surface absorbed in the porous structure and reactive functional
groups on such surfaces, as well as such reactive functional groups
in the resin materials. The initiation and polymerization rates of
the cyclic olefin monomers may be controlled over a wide range by
judicious choice of the chemical structure of the preferred
metathesis catalyst and/or the use of rate-modifying additives as
is well known in the art.
[0047] In the practice of the present invention, the low viscosity
of the preferred cyclic olefin resin formulations facilitates the
infusion of the porous materials. For example, DCPD has a much
lower resin viscosity than other polymeric starting materials such
as epoxy resins. The low viscosity of DCPD resins allows for a
greater degree of infusion into porous and microporous structures
characteristic of porous materials such as wood. The high
reactivity of ROMP catalysts together with the low viscosity of the
DCPD resin allows the resins to cure without the extreme
temperatures and pressures required for other polymers derived from
phenols, polyesters, epoxies, resorcinols or ureas that can cause
breakdown of the porous material structure, especially for
sensitive organic substrates such as wood. Unlike many other
resinous materials, polymers derived from metathesis polymerization
of cyclic olefin monomers are stable to hydrolysis and are
insoluble in polar organic solvents and therefore yield infused
products that are stable to leaching and polymer decomposition. The
preferred resins are also compatible with and will accommodate a
variety of additional additives and fillers to impart additional
properties to the infused composites.
[0048] The resulting infused composites are generally tougher,
harder, more dense, and more rigid than the starting porous
substrate alone. For example, in the case of wood, less expensive
softer woods are, therefore, able to replace more expensive harder
woods in various applications such as sporting equipment, tool
handles, furniture, flooring, railings, window frames, stairs,
decking, etc; and marine applications such as boats, piers and
pilings. Such infused and treated wood will be resistant to the
uptake of water and resistant to rot and insect damage. The surface
wear characteristics will be greatly improved for such
applications. In applications in which an optimum level of water
absorbed within the wood must be maintained to prevent further
drying of the wood and cracking, suitably stable ROMP catalysts and
resins are available to use within wood with various amounts of
absorbed water in order to stabilize the wood to loss of such
water.
[0049] The resulting compositions exhibit unique properties of the
composite for the portion of the material that is infused, while
the shape of the final product is determined by that of the
starting free-standing object. Thus the invention allows for a wide
variety of infused products to be manufactured without the use of
complex molds.
[0050] The polyolefin-infused compositions of the invention are
useful in the production of a variety of products in the areas of
sports and recreation equipment, marine infrastructure, and
construction and consumer goods where enhanced mechanical
performance, durability, and/or moisture-resistance are required.
Examples of sports and recreation products and applications
include, but are not limited to, the following: golf tees, clubs
(including weighted club heads), shafts, and gradient shafts (where
the formulation or density varies along the length of the club
shaft); basketball backboards; tennis rackets, squash rackets,
racquetball rackets, and badminton racquets; snow boards,
surfboards, boogie boards, skis, backboards, sleds, toboggans;
baseball and cricket bats; hockey sticks; pool cues; archery bows
and arrows; rifle butts; polo and croquet mallets; and tent stakes.
Examples of marine infrastructure applications include, but are not
limited to, the following: piers, docks, posts, decking, hulls,
oars, propellers, rudders, keels, masts, boat fascia, kayaks,
canoes, and ferro-cement boats. Examples of construction and
consumer goods applications include, but are not limited to, the
following: hand-tool handles, knife handles, ladders, wood flooring
panels, deck lumber, treated concrete or cinder blocks, door and
window frames, office furniture, concrete bridge decks, parking
structure ramps, post-tensional beams and slabs, treated concrete
pipes and channel liners for aggressive and acidic fluids, sewer
pipes, containment structures, pavers, stone consolidation (e.g.,
James R. Clifton, National Bureau of Standards, Technical Note
1118, May 1980, Government Documents C 13.46:1118), plaster or
concrete ornamental objects, and other pre-cast concrete
objects.
[0051] Other porous materials infused with ROMP polymers to provide
new composites with improved physical properties include unglazed
sintered ceramics of all types including but not limited to ceramic
magnets, superconducting ceramic materials, ceramic capacitors, and
capacitors from reconstituted mica paper. Various open cell plastic
foams, including but not limited to those derived from
polyurethane, provide new compositions with a wide variety of
applications. Graphite foams with continuous porous structures have
a variety of novel applications as heat sinks and in thermal
management technology. This material has the thermal conductivity
of aluminum with approximately 20% of its weight. However
applications of graphite foam are limited by the inherently brittle
and friable nature of this material and corresponding incidental
damage in use. Infusing ROMP polymers into graphite foam provide an
effective means to ruggedize the structures and objects as formed
and to yield new composites.
[0052] A variety of processing techniques, dependent upon the
nature of the porous substrate and the cyclic olefin resin
formulation, may be utilized to prepare the resin-infused
composites of the present invention. For highly porous materials,
it may be sufficient to place the porous substrate in a container
and simply pour in the formulated resin. For medium-porosity
materials, a simple dipping or soaking process may be feasible. For
low-porosity or microporous materials, pressure or a combination of
vacuum and pressure may be required to get the formulated resin to
completely permeate the porous substrate. This may be accomplished
by variations of standard processing techniques such as
resin-transfer molding (RTM) or vacuum-assisted RTM (VARTM or
SCRIMP@, Seemann Composite Resin Infusion Molding Process). If a
mold or container is required, such mold may be constructed of
various materials including, for example, aluminum, teflon, delrin,
high- and low-density polyethylenes (HDPE and LDPE, respectively),
silicone, epoxy, aluminum-filled epoxy, polyurethane and
aluminum-filled polyurethane, plaster, polyvinylchloride (PVC), and
various alloys of stainless steel. The mold temperature is
preferably about 20-150.degree. C., more preferably about
30-100.degree. C., and most preferably about 40-60.degree. C. The
infused part or article of the invention may also be subjected to a
post-cure heating step. Preferably, the post-cure involves heating
to about 60-200.degree. C. for about 10 minutes-3 hours. More
preferably, the post-cure involves heating to about 80-160.degree.
C. for about 30 minutes-2 hours and, and most preferably, heating
to about 140.degree. C. for about 1 hour.
[0053] In the case of microporous substrates such as wood or
concrete, use of a vacuum/pressure process is preferred to achieve
good infusion with the cyclic olefin resin formulation. The vacuum
process helps to remove air and water vapor from the pores of the
substrate. After evacuation of the substrate, the resin formulation
is applied and is drawn into the empty pores. Application of
moderate pressure (typically between about 5 and 200 psi and
preferably between about 40-60 psi) helps to push the resin fully
into the pores of the substrate. The time required to fully infuse
the particular article can vary widely based on the shape and pore
structure of the article and the viscosity of the resin formulation
but will typically vary from about 30 seconds to several hours. The
progress of the infusion may be determined and/or controlled by
monitoring the weight of the substrate. Pressure alone may be
effective in the infusion of microporous substrates if their
internal structure and/or the infusion methodology is such that any
gas displaced by the infused resin can escape rather than becoming
pressurized. If pressurization occurs, then the typically
low-viscosity (at least before they are cured) cyclic olefin resin
formulations may be at least partially expelled from the pores of
the substrate upon the release of the externally applied pressure
due to the backpressure exerted by the compressed gasses trapped
within the pores.
[0054] Certain porous substrates may require chemical or mechanical
pretreatment prior to the resin infusion process. For example, the
pores of pre-shaped (e.g., machined) wood billets tend to be at
least partially clogged by sawdust and other particulate impurities
that hinder the ingress of resin during infusion. Careful
mechanical cleaning of the surface of such wood billets with a wire
brush has been found to be an effective, albeit labor intensive,
pretreatment process. Surprisingly, it has been found that a
high-pressure water spray treatment, which may clean and wet an
object, followed by careful drying serves as an excellent
pretreatment method for wood substrates. Although not wishing to be
bound by theory, it is believed that this methodology more deeply
opens the pores of water-swellable substrates such as wood due to
both the mechanical cleaning action of the impinging water droplets
at the surface of the substrate as well as the bulk expansion and
contraction of the substrate during the overall wetting and drying
process. This methodology also has the advantages that it is
amenable to automation and that adhesion or coupling agents, that
will facilitate chemical bonding between the resin and substrate,
can be easily incorporated into the water treatment rather than as
a separate step.
[0055] The following examples are illustrative of the invention and
it is understood that the invention is not limited to the disclosed
embodiments but that various modifications and substitutions can be
made thereto as would be apparent to those skilled in the art.
EXAMPLES
Example 1
Stiffness and Impact Resistance of Low-Grade White Ash
[0056] Several 3"-diameter billets of low-grade (.ltoreq.{fraction
(1/16)}" grain spacing) northern white ash were turned down to
11/8" diameter dowels and cut to lengths of 10-12" (three per
billet, labeled A-C). The stiffness of each specimen was measured
by centering the dowel on a pair of support rods spaced 9 inches
apart. A 50-pound load was applied to the center of the dowel, in
the radial direction of the grain, and the deflection of the dowel
was measured. The impact resistance of each dowel was determined by
centering it on the same 9"-support and dropping a weighted
impactor from increasing heights until sample failure was observed.
The impact resistance is recorded as the maximum impact level and
the sum total of all impacts achieved until failure. The data for
several samples are reported in Table 1.
1TABLE 1 Sample Density Deflection Max. Impact Total Impact Number
(pcf)* (inches) Level (ft .multidot. lb) Energy (ft .multidot. lb)
1B 40.45 0.009 32 114 2B 41.39 0.011 26 96 4B 37.96 0.010 23 70 5B
39.99 0.009 36 200 9B 40.04 0.009 31 150 17B 38.68 0.008 36 199 19B
40.94 0.014 23 91 31B 39.63 0.009 33 129 40B 37.37 0.011 14 42
Averages 39.6 .+-. 1.3 0.010 .+-. 0.002 28 .+-. 7 121 .+-. 51 *pcf
= pounds per cubic foot
Example 2
Stiffness and Impact Resistance of Medium-Grade White Ash
[0057] Two 3"-diameter billets of medium-grade (.gtoreq.1/8" grain
spacing) northern white ash were turned down to 11/8" diameter
dowels and cut to lengths of 10-12" (three per billet, labeled
A-C). The stiffness and impact resistance of each specimen was
measured as in Example 1. The data for several samples are reported
in Table 2. The medium-grade wood exhibits consistently higher
density, stiffness (e.g., lower deflection), and impact resistance
than the low-grade wood.
2TABLE 2 Sample Density Deflection Max. Impact Total Impact Number
(pcf) (inches) Level (ft .multidot. lb) Energy (ft .multidot. lb)
0B 45.60 0.010 50 815 12A 47.50 0.007 42 513 12B 47.86 0.007 42 765
12C 46.23 0.008 42 723 Averages 46.8 .+-. 0.9 0.008 .+-. 0.001 44
.+-. 4 704 .+-. 115
Example 3
Pressure-Treatment of White Ash with DCPD Resin
[0058] A mixture comprising 100 grams of Ultrene.RTM.-99
dicyclopentadiene (BF Goodrich), 3.0 grams of Ethanox.RTM.-702
(Albemarle) primary antioxidant, 0.10 grams of triphenylphosphine
inhibitor, 1.0 grams of Ferro PDI.RTM. Type 34 blue colorant (to
enable improved visualization of the extent of infusion of the
resin into the wood grain), and 0.11 grams of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst was prepared and poured into a cylindrical mold. The
temperature of the resin and mold was 21.degree. C. A low-grade
white ash dowel (1A), as described in Example 1 was placed into the
mold. The mold was sealed and pressurized to 60 psi for one hour.
The pressure was released and the dowel removed from the mold and
heated in an oven at 60.degree. C. for eight hours to cure the
resin. After curing, the surface of the dowel was lightly sanded to
remove excess resin. The sanded dowel was then post-cured in an
oven for one hour at 140.degree. C. The density of the dowel
increased from 40.77 pcf to 45.95 pcf due to the infused resin.
Example 4
Vacuum/Pressure-Treatment of White Ash with DCPD Resin
[0059] A mixture comprising 500 grams of Ultrene.RTM.-99
dicyclopentadiene (BF Goodrich), 15 grams of Ethanox.RTM.-702
(Albemarle) primary antioxidant, 0.5 grams of triphenylphosphine
inhibitor, 5.0 grams of Ferro PDI.RTM. Type 34 blue colorant (to
enable improved visualization of the extent of infusion of the
resin into the wood grain), and 0.55 grams of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst was prepared and poured into a cylindrical mold. The
temperature of the resin and mold was 20.degree. C. A low-grade
white ash dowel (IC), as described in Example 1 was placed into the
mold. The mold was sealed, evacuated to degas the resin and the
pores of the dowel, and then pressurized to 60 psi for one hour.
The pressure was released and the dowel removed from the mold and
heated in an oven at 60.degree. C. for 6.5 hours to cure the resin.
After light sanding to remove excess resin, the dowel was then
post-cured in an oven for one hour at 140.degree. C. The density of
the dowel increased from 40.96 pcf to 49.72 pcf due to the infused
resin. The stiffness of the treated wood also increased as
evidenced by the decrease in the measured deflection from 0.013
inches before treatment to 0.011 inches after treatment.
Example 5
Modified Vacuum/Pressure-Treatment of White Ash with DCPD Resin
[0060] A mixture comprising 100 grams of Ultrene.RTM.-99
dicyclopentadiene (BF Goodrich), 3 grams of Ethanox.RTM.-702
(Albemarle) primary antioxidant, 0.1 grams of triphenylphosphine
inhibitor, 1 gram of Ferro PDI.RTM. Type 34 blue colorant (to
enable improved visualization of the extent of infusion of the
resin into the wood grain), and 0.11 grams of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst was prepared and poured into a cylindrical mold. The
temperature of the resin and mold was 22.degree. C. A low-grade
white ash dowel (40A), as described in Example 1 was placed into
the mold. The mold was sealed, evacuated to degas the resin and the
pores of the dowel, and then pressurized to 60 psi for seven hours.
The pressure was released and the dowel removed from the mold and
heated in an oven at 60.degree. C. for eight hours to cure the
resin. After light sanding to remove excess resin, the dowel was
then post-cured in an oven for one hour at 140.degree. C. The
density of the dowel increased from 37.55 pcf to 45.90 pcf due to
the infused resin. The stiffness of the treated wood also increased
as evidenced by the decrease in the measured deflection from 0.026
inches before treatment to 0.013 inches after treatment.
Example 6
Pressure-Treatment of White Ash with Modified DCPD Resin
[0061] A DCPD resin formulation comprising approximately 3.5% of
trimeric CPD isomers along with smaller amounts of higher oligomers
was prepared by blending 44 grams of Ultrene.RTM.-99 DCPD with 6
grams of CM15T (heat-treated DCPD containing approximately 29%
trimeric CPD and smaller amounts of higher oligomers obtained from
BF Goodrich), 1.5 grams of Ethanox.RTM.-702 (Albemarle) primary
antioxidant, 0.05 grams of triphenylphosphine inhibitor, 0.518
grams of Ferro PDI.RTM. Type 34 blue colorant (to enable improved
visualization of the extent of infusion of the resin into the wood
grain), and 0.062 grams of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst. Thirty grams of this formulation was poured into a
cylindrical mold. The temperature of the resin and mold was
20.degree. C. A low-grade white ash dowel (40C), as described in
Example 1 was placed into the mold. The top 1" of the dowel was not
submersed in the resin. The mold was sealed and then pressurized to
60 psi for seven hours. The pressure was released and the dowel
removed from the mold and heated in an oven at 140.degree. C. for
one hour to cure/post-cure the resin. The density of the dowel
increased from 38.32 pcf to 42.97 pcf due to the infused resin. The
portion of the dowel that was not submersed in the resin appeared
to contain less resin than the rest of the dowel.
Example 7
Impact Resistance of DCPD-Infused White Ash
[0062] The stiffness and impact resistance of the DCPD-infused
white ash dowels of Example 3-Example 6 were measured as described
in Example 1. The data are summarized in Table 3, compared with
untreated samples 1B and 40B from Example 1, and demonstrate the
increased impact performance of the infused wood.
3 TABLE 3 Sample Example Max. Impact Total Impact Number Number
Level (ft .multidot. lb) Energy (ft .multidot. lb) 1A Example 3 36
249 1B Example 1 32 114 1C Example 4 40 406 40A Example 5 36 429
40B Example 1 14 42 40C Example 6 42 513
Example 8
Test to Measure Wood-Resin Adhesion
[0063] The adhesion between resin and wood can be measured using a
1" long wood dowel (1.125" diameter) with a 1/2" diameter hole
drilled down through its center. The specimen can be optionally
conditioned before the desired resin formulation is poured into the
bore and cured into place. The adhesion between the wood and the
resin is then evaluated by determining the force required to push
the cast resin plug out of the bore. A baseline DCPD resin
formulation comprising approximately 3.5% of trimeric CPD isomers
along with smaller amounts of higher oligomers was prepared by
blending 1,759 grams of Ultrene.RTM.-99 DCPD with 241 grams of
CM15T (heat-treated DCPD containing approximately 29% trimeric CPD
and smaller amounts of higher oligomers obtained from BF Goodrich).
Just prior to fabrication of the test specimens, appropriate
quantities of the baseline resin were removed and mixed with 3 phr
Ethanox.RTM.-702 (Albemarle) antioxidant, 0.10 phr
triphenylphosphine moderator, and 0.11 phr of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst. This mixture was poured into the bore and cured for 1
hour at 40.degree. C. to form a solid plug within the wood dowel.
After 5 hours, the specimens were post-cured at 140.degree. C. for
1 hour. Results for a series of 32 different white ash wood
specimens and the baseline DCPD/3.5% trimer resin averaged
808.+-.147 psi.
Example 9
Silane Treatment of Wood to Improve Wood-Resin Adhesion
[0064] Five white ash wood specimens as described in Example 8 were
soaked in a solution of 2 phr allyltriethoxysilane (Gelest) in 0.6
millimolar aqueous acetic acid for 20 minutes. The specimens were
then dried for 3 hours at 60.degree. C. in an oven. The resin
mixture of Example 8 was poured into the bore and cured for 1 hour
at 40.degree. C. to form a solid plug within the wood dowel. After
5 hours, the specimens were post-cured at 140.degree. C. for 1
hour. Results for these specimens averaged 2,721.+-.176 psi.
Example 10
Acetic Acid Treatment of Wood to Improve Wood-Resin Adhesion
[0065] Two white ash wood specimens as described in Example 8 were
soaked in a solution of 0.6 millimolar aqueous acetic acid for 20
minutes. The specimens were then dried for 3 hours at 60.degree. C.
in an oven. The resin mixture of Example 8 was poured into the bore
and cured for 1 hour at 40.degree. C. to form a solid plug within
the wood dowel. After 5 hours, the specimens were post-cured at
140.degree. C. for 1 hour. Results for these specimens averaged
2,593.+-.11 psi.
Example 11
Water Treatment of Wood to Improve Wood-Resin Adhesion
[0066] Five white ash wood specimens described in Example 8 were
soaked in deionized water for 20 minutes. The specimens were then
dried for 3 hours at 60.degree. C. in an oven. The resin mixture of
Example 8 was poured into the bore and cured for 1 hour at
40.degree. C. to form a solid plug within the wood dowel. Results
for these specimens averaged 2,606.+-.193 psi.
Example 12
Aqueous Isopropanol Treatment of Wood to Improve Wood-Resin
Adhesion
[0067] Two white ash wood specimens as described in Example 8 were
soaked in 50% isopropanol for 20 minutes. The specimens were then
dried for 3 hours at 60.degree. C. in an oven. The resin mixture of
Example 8 was poured into the bore and cured for 1 hour at
40.degree. C. to form a solid plug within the wood dowel. Results
for these specimens averaged 2,526.+-.44 psi.
Example 13
Norbomene Treatment of Wood to Improve Wood-Resin Adhesion
[0068] Two white ash wood specimens as described in Example 8 were
soaked in a solution of 0.2 grams of
mono-methyl-cis-5-norbornene-endo-2,3-dicar- boxylate
(Sigma-Aldrich) in 10 grams of 50% isopropanol for 20 minutes. The
specimens were then dried for 3 hours at 60.degree. C. in an oven.
The resin mixture of Example 8 was poured into the bore and cured
for 1 hour at 40.degree. C. to form a solid plug within the wood
dowel. Results for these specimens averaged 2,308.+-.184 psi.
Example 14
Dependence of Wood-Resin Adhesion on Wood Density
[0069] Two specimens from each of nine different low-density white
ash dowels ranging in density from 35.3 to 39.5 pcf were prepared
as in Example 8. Results of the adhesion test with this series
averaged 718.+-.213 psi. As can be seen in Chart 1, there is little
dependence of the adhesion result on wood density over this density
range.
Example 15
Additives on White Ash Wood-Resin Adhesion
[0070] Specimens as described in Example 8 were prepared using
low-grade white ash wood dowels, within the density range indicated
in Example 14, wherein the resin mixture was modified by the
addition of 1 phr of various titanate and zirconate coupling agents
available from Kenrich Petrochemicals, Inc. The coupling agents
evaluated included isopropyl triisostearoyl titanate
(Ken-React.RTM. KR TTS), tetraoctyl di(ditridecyl)phosphito
titanate (Ken-React.RTM. KR 46B), diallyloxyneopentyl
tri(N-ethylenediaminoethyl) titanate (Ken-React.RTM. LICA 38),
tetra(2,2-diallyloxymethyl)butyl di(ditridecyl)phosphito titanate
(Ken-React.RTM. KR 55), and tetra(2,2-diallyloxymethyl)butyl
di(ditridecyl)phosphito zirconate (Ken-React.RTM. KZ 55). Three
specimens were prepared and tested using each additive, and the
results are summarized in Table 4. The KR 55 and KZ 55 additives,
with metathesis reactive allyl groups, significantly increased
wood-resin adhesion. The LICA 38 additive, although also containing
metathesis reactive allyl groups, gave very poor results,
presumably due to the presence of the basic amine groups which can
poison the metathesis catalysts.
4 TABLE 4 Additive Adhesion Result (psi) KR TTS 960 .+-. 14 KR 46B
844 .+-. 220 LICA 38 253 .+-. 34 KR 55 1,363 .+-. 238 KZ 55 1,480
.+-. 15
Example 16
Wood-Resin Adhesion with White Ash, Pine and Poplar
[0071] Specimens as described in Example 8 were prepared using pine
and poplar along with white ash. Both the standard resin
formulation as well as a modified formulation containing 0.5 phr
Ken-React.RTM. KR 55 coupling agent were used. The results are
summarized in Table 5 and show that these woods behave similarly to
white ash.
5TABLE 5 Adhesion with Standard Adhesion with Modified Wood Type
Resin Resin White Ash 593 .+-. 198 psi 1,543 .+-. 97 psi Pine 862
.+-. 110 psi 1,735 .+-. 220 psi Poplar 755 .+-. 182 psi 1,622 .+-.
184 psi
Example 17
DCPD Resin Uptake By White Ash Baseball Bats
[0072] Resin uptake for a series of ten net-shape white ash bats is
shown in Chart 2. Even though encompassing results involving many
different parameter variations, the data appear to suggest that
less resin can be infused into higher density wood. Although not
totally unexpected, there does, perhaps, appear to be a preferred
weight for the infused wood (around 1,000 grams--a little heavy for
bat application) suggesting that it may be possible to upgrade a
wide range of wood densities to a more consistent final product
density.
[0073] Chart 3 summarizes the results obtained for variations in
infusion time. All of these experiments were performed using
net-shape bats with 60-psi infusion pressure. Data for high-density
(e.g., over 800 grams) and low-density (e.g., under 800 grams) bats
were analyzed separately. The data suggest that infusion occurs
fairly quickly, likely aided by the very low viscosity of the DCPD
resins, although somewhat higher resin loadings might be attained
with extended infusion times.
Example 18
Method of Spray-Washing Baseball Bats Prior to Infusion
[0074] Pre-shaped wood baseball bat blanks, with a cupped end, of
minor grade white ash were weighed and then subjected to a
high-pressure water spray treatment with ordinary municipal tap
water under pressure of approximately 50 PSI across the bat from
the knob to the handle to the barrel of the bat, as the bat was
manually turned in order to completely cover the long axis and
along the grain of the bat for approximately 30 seconds. The cupped
end of the bat barrel and the knob end of the bat and across the
grain of the wood were given particular attention with
approximately 15 seconds of wash. This water spray treatment
appeared to mechanically remove loose material, sand or saw dust
and to open the end grain of the wood. The weight of the bat blanks
before the water treatment varied from approximately 700 to 800
grams and from approximately 725 to 825 grams after the water wash.
Each bat was then allowed to air dry for approximately 24 hours at
ambient temperature and humidity during which the weight of the bat
dropped to a range of approximately 710 to 810 grams. To finish the
drying process, the bats were then placed into an oven at
60.degree. C. for 30 minutes. The oven temperature was then
increased over a five-minute period to 100.degree. C. and
maintained there for an additional 60 minutes. After cooling, the
bats then weighed near or slightly below the original range of
700-800 grams.
Example 19
Method of Infusing Baseball Bats with DCPD Resin
[0075] A goal of the infusion process is to bring each wood bat up
to a weight of 900 grams regardless of the starting weight of the
bat. The stepwise process utilizing the equipment as shown in FIG.
1 achieves this goal using a system of two separate metal chambers
that are connected by high-pressure flexible tubing. One chamber is
used to perform the infusion process (the "Mold") and the other is
used to store the DCPD resin formulation (the "Resin Chamber"). The
process allows a variety of DCPD resin formulations to be
introduced to the free standing porous wooden bat under vacuum in
order to completely coat or cover the bat, followed by raising the
pressure of the liquid resin to facilitate its infusion into voids
of the wood.
[0076] In a typical example, wood bat blanks of low-medium grade
ash and with a cupped end are weighed and then subjected to a
high-pressure water spray treatment as described in Example 18.
After complete drying, each bat is then placed into the Mold of
cylindrical dimensions sufficient to closely and completely enclose
the bat and with a removable end to allow the bat to be placed in
the vessel. The Mold is mounted vertically to allow the bat to be
completely submerged in resin with the removable end at the top of
the cylinder. The removable end of the Mold is equipped with two
valves (V3 and V4) with removable tubing fittings with one to allow
the chamber to be placed under vacuum and the other to allow the
introduction of a gas under pressure to flush the resin from the
chamber. A third pressure fitting and valve (V2) on the bottom of
the Mold allows the introduction of DCPD resin formulations from
the separate Resin Chamber. The Resin Chamber has a removable top
equipped with a dip tube (V1) to allow resin from the bottom of the
chamber to be introduced into the bottom of the infusion chamber
through a flexible pressure tube. Additional valves (V5 and V6) are
used for applying or venting pressure to the resin chamber. The
Resin Chamber may be periodically refilled with freshly mixed DCPD
resin formulation through valve V7.
[0077] In the infusion process, the mold, containing a bat, and the
resin transfer tube are evacuated through valve V3, with valve V2
open and valves V1 and V4 closed, with a mechanical pump to
approximately 10.sup.-3 atmospheres, which results in removal of
air from the pores of the wood. The vacuum valve V3 is then closed,
and the weighing mechanism is tared. The Mold is then completely
backfilled with resin from the Resin Chamber by opening valves V1
and V5. The infusion pressure is controlled by the pressure of the
inlet gas at valve V5 and is usually 55 psi or more to promote the
infusion of the formulated DCPD resin into the porous structure of
the wood. The total weight of the mold is continuously monitored
until the uptake of resin is sufficient to bring the total weight
of each bat up to a weight of 900 grams. This can be easily
calculated for each bat if the Mold volume and the bat volume and
weight are known. The time that this can take typically varies from
as short as 10 seconds to as long as 7 minutes. Once the desired
amount of resin has been introduced into the Mold, valves V2 and V5
are closed and the pressure is released from the Resin Chamber by
opening pressure release valve V6. After a slight delay, the excess
DCPD resin in the mold is then flushed back into the resin chamber
by opening valves V2 and V4. Once all of the excess resin has been
returned to the Resin Chamber, Valves V1 and V4 and then Valves V2
and V6 are closed. The Mold is then opened, the infused bat is
removed to a curing oven, and the next bat is placed into the Mold
so that the cycle can be repeated. If required, additional DCPD
resin formulation can also be added to the Resin Chamber at this
time.
[0078] The resin curing process is promoted by placing the infused
bat in an oven at 60.degree. C. for 30 minutes, followed by 2 hours
at room temperature, and then a final post-cure at 140.degree. C.
for 1 hour. After cooling back to room temperature, the bat is then
ready for finishing to a commercial product by a final sanding,
painting and/or the addition of graphics, and application of a
polyurethane top-coat for UV protection and improved
appearance.
Example 20
Durability of DCPD-Infused Wood Baseball Bats
[0079] A sampling of pre-shaped but otherwise unfinished wooden
bats were obtained and sorted into three grades according to the
number of grains counted at the knob. Long-standing experience with
baseball bats indicates that lower grain counts correspond to
increased durability. Therefore, high-grade bats had grain counts
of about 16 or less, medium-grade bats had grain counts from about
17 to 28, and low-grade bats had grain counts of about 29 or
greater. Half of the bats were finished normally with a
polyurethane top coat while the other half were infused with DCPD
resin as described in Example 19. Chart 4 shows the number of
"hits-to-failure" for these untreated and DCPD-infused wood bats
relative to the grain count. Obviously, there is considerable
natural variation within wood, but untreated high-grade baseball
bats would typically be expected to exhibit approximately 200-250
hits to failure while low-grade or medium-grade bats would
typically fail after fewer hits. The infused bats typically exhibit
greater durability (usually greater than 300 hits-to-failure) than
comparable untreated bats and allow a much lower grade of wood to
perform as well or better than untreated bats made of high-grade
wood.
Example 21
Dent-Resistance of DCPD-Infused Wood Baseball Bats
[0080] One of the unexpected features of the DCPD-infused wood is
its greater surface "toughness" or its ability to resist denting,
compared to untreated wood. Since surface denting is a significant
contributor to the failure of wooden bats, increased surface
hardness is desirable feature. Chart 5 shows the depth of dents
measured in both untreated and DCPD-infused baseball bats relative
to the number of hits sustained. These measurements were done with
a baseball impinging at 136 miles per hour, 5 inches from the
barrel end and with the wood grain parallel to the point of impact.
The data demonstrate the significant resistance to denting by the
infused wood.
Example 22
Infusion of a Porous Concrete Block
[0081] A DCPD resin formulation comprising approximately 3.5% of
trimeric CPD isomers along with smaller amounts of higher oligomers
was prepared by blending an 88/12 mixture of Ultrene.RTM.-99 DCPD
and CM15T (heat-treated DCPD containing approximately 29% trimeric
CPD and smaller amounts of higher oligomers obtained from BF
Goodrich), with 3 phr of Ethanox.RTM.-702 (Albemarle) primary
antioxidant, 0.1 phr of triphenylphosphine inhibitor, and 0.124 phr
of (PCp.sub.3).sub.2Cl.sub.2R- u.dbd.CH--CH=CMe.sub.2 metathesis
catalyst. This resin mixture was poured over small pieces of porous
concrete block in a mold. The mold was sealed and then pressurized
to 55 psi. The pressure was released and the infused pieces removed
from the mold and allowed to cure overnight at room temperature.
The next day, they were post-cured in an oven at 140.degree. C. for
one hour. Weight measurements indicated about 10% resin pickup by
the concrete block pieces and there was no odor of unpolymerized
DCPD. The infused pieces were normal in appearance but exhibited
increased hydrophobicity.
Example 23
Properties DCPD-Infused Wood
[0082] Samples of birch, cherry, douglas fir, maple, poplar, red
oak, southern yellow pine, and white ash woods were cut into
1".times.1".times.12" rectangular dowels. The cut samples were
washed using pressurized tap water (90 psi) for 1 minute and then
air-dried for 48 hours at room temperature (20-24.degree. C.). The
specimens were further dried in a vacuum oven for 48 hours at room
temperautre and then an additional 48 hours at 40.degree. C. The
weight of each of the dowels after this treatment ranged from 4-6%
less that its starting weight. Once removed from the oven, the
samples were kept under static vacuum at room temperature until
infused. For infusion, a dowel was placed into a
1.25".times.1.25".times.18" chamber, which was then evacuated to a
vacuum of between 25-29 mm Hg (usually about 1 minute). Resin was
then backfilled into the chamber and then pressurized to 40-45 psi
for 2-3 minutes to fully infuse the specimens. At the end of this
cycle, the pressure was released and the resin drained out of the
chamber. The specimen was then moved into a oven and cured at
60.degree. C. for 1 hour and then post-cured at 160.degree. C. for
an additional hour. Four variations were tested for each type of
wood: (a) a control that was washed and dried but not infused; (b)
a baseline resin formulation comprising DCPD with a 10% trimeric
CPD content, 3 phr Ethanox.RTM.-702 antioxidant, 0.2 phr
triphenylphosophine inhibitor, and 0.104 phr of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst; (c) a modified resin formulation comprising DCPD with a
10% trimeric CPD content, 3 phr Ethanox.RTM.-702 antioxidant, 0.2
phr triphenylphosophine inhibitor, 1 phr Ken-React.RTM. KR 55
organotitanate, and 0.104 phr of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst; and (d) a modified resin formulation comprising DCPD with
a 10% trimeric CPD content, 3 phr Ethanox.RTM.-702 antioxidant, 0.2
phr triphenylphosophine inhibitor, 1 phr Ken-React.RTM. KZ TPP
organozirconate, and 0.104 phr of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.- dbd.CMe.sub.2 metathesis
catalyst. The final resin uptake for each specimen is summarized in
Table 6. The flexural properties were tested using a specimen of
each of the woods by a 3-point bending method and are summarized in
Table 7. The compression properties were tested for each piece
parallel to the direction of the grain and are summarized in Table
8. The Shore D hardness was measured for a specimen of each wood
and is summarized in Table 9.
6TABLE 6 Resin Uptake (%) by Each Specimen Treatment (b) Treatment
(c) Treatment (d) i ii i ii i ii birch 23.2 22.2 28.0 29.4 23.0
21.0 cherry 14.0 9.8 18.7 24.8 23.4 11.2 douglas fir 4.7 8.9 5.8
10.0 7.0 5.3 maple 28.7 28.8 24.1 25.2 22.5 25.5 poplar 40.9 42.9
39.5 40.0 40.4 40.2 red oak 20.7 20.4 20.7 20.7 21.5 21.8 southern
yellow pine 41.3 40.0 45.6 42.2 39.2 38.5 white ash 45.2 46.1 47.2
46.0 44.8 45.2
[0083]
7TABLE 7 3-Point Bending Modulus (ksi) for Infused Wood Control
Treatment (b-i) Treatment (c-i) Treatment (d-i) birch 1,240 1,550
1,680 1,640 cherry 1,190 1,330 1,350 1,270 douglas fir 1,000 880
996 1,100 maple 2,100 2,300 2,400 1,700 poplar 1,400 1,700 1,600
1,800 red oak 1,370 1,510 1,410 1,360 southern 860 1,240 1,280
1,480 yellow pine white ash 670 990 850 1,030
[0084]
8TABLE 8 Compression Strength (psi) for Infused Wood Control
Treatment (b-i) Treatment (c-i) Treatment (d-i) birch 9,400 13,600
14,700 13,500 cherry 8,200 10,800 13,400 13,300 douglas fir 7,300
8,700 9,500 9,400 poplar 8,900 14,600 15,400 15,400 red oak 9,300
12,900 13,300 13,400 southern 7,000 13,100 13,700 14,700 yellow
pine white ash 6,700 11,200 14,300 15,000
[0085]
9TABLE 9 Shore D Hardness for Infused Wood Treatment Treatment
Treatment Control (b-ii) (c-ii) (d-ii) birch 68 76 82 82 cherry 65
75 80 77 douglas fir 50 65 65 65 maple 72 82 86 84 poplar 62 80 82
81 red oak 70 75 75 78 southern yellow 50 72 72 72 pine white ash
65 76 76 80
Example 24
Properties DCPD-Infused Cardstock
[0086] A resin formulation comprising DCPD with 10% trimeric CPD
content, 3 phr Ethanox.RTM.-702 antioxidant, 0.2 phr
triphenylphosophine inhibitor, 1 phr Ken-React.RTM. KR 55
organotitanate, and 0.104 phr of
(PCp.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.CMe.sub.2 metathesis
catalyst was applied to pieces of 0.010" thick predried cardstock
cut into a dogbone shape suitable for tensile testing. The resin
appeared to quickly wet into the porous web. The sheet was then
cured for 1 hour at 40.degree. C., 2 hours at room temperature, and
then post-cured for 1 hour at 140.degree. C. Using this
methodology, a series of 6 specimens picked up an average of
3.37.+-.0.54% resin. The dry, but untreated, cardstock exhibited
the following tensile properties: 5,979 psi tensile strength,
313,597 tensile modulus, and 3.60% strain-to-break. The treated
cardstock exhibited the following improved tensile properties:
6,663 psi tensile strength, 375,936 psi tensile modulus, and 3.20%
strain-to-break.
* * * * *