CA1080875A - Blends of trans-1,4 polymers and poly (epsilon-caprolactone) - Google Patents
Blends of trans-1,4 polymers and poly (epsilon-caprolactone)Info
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- CA1080875A CA1080875A CA263,579A CA263579A CA1080875A CA 1080875 A CA1080875 A CA 1080875A CA 263579 A CA263579 A CA 263579A CA 1080875 A CA1080875 A CA 1080875A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Abstract
ABSTRACT OF THE DISCLOSURE
Blends of trans-1,4 polymers of C4-C5 conjugated diolefinic compounds and poly(epsilon-caprolactone) have improved properties and are suitable for use in medical casts or, when vulcanized, as golf balls covers.
Blends of trans-1,4 polymers of C4-C5 conjugated diolefinic compounds and poly(epsilon-caprolactone) have improved properties and are suitable for use in medical casts or, when vulcanized, as golf balls covers.
Description
7~
This invention is directed to polymeric blends having improved properties, specifically to blends of trans-1,4 polymers of C4 - C5 conjugated diolefinic compounds with polymers of caprolactone.
One naturally occurring polymer of a trans-1,4 conjugated diolefinic compound is the polymer of isoprene known as balata or gutta percha~ Thîs polymer has enjoyed a varîety of uses over the years including use in submarine cables and golf ball covers. The polymer is relatively high - 10 in cost and the supply is irregular. Because of this, it has been extensiveIy replaced by a synthetic trans-1,4-polyisoprene which is available on a more regular supply basis and is of ~, ';
uniform composition, not needing the clean up and purifîcation steps necessary with balata. Trans-1,4 polybutadiene is also available as a synthetic polymer which has generally simîlar characterîstîcs to those'of trans-1,4-polyîsoprene. Another - s~nthetic polymer whîch'also possesses' certain of the'same ~ -characteristics îs trans-1,4 polyc~Loroprene.
A characteristic common to these'polymers is that they all have'a high level of crystallinity which leads to good strength properties in the'polymer at normal temperatures and easy processing of tEe polymer at temperatures near or above the crystallîne melting point. Further, these polymers are all vulcanizable, due'to the presence of unsaturatîon alone or in combination with an active chlorine group~ The raw '' polymer, or the raw polymer compounded with conventional compounding ingredients wit~'t~e exception of vulcanization agents, may be used in a wîde'variety of applîctations where strength at amb;ent temperature'is important~ Such'applications include medical casts, ad~esives-and moldable s~eets~ The `
w lcanized polym~r may be used where hardness and a greater degree of permanence of shape is required such as in a golf ball cover.
PlY(epsilon-caprolactone~ is a cyclic ester polymer which may be generally described as containing a major pro-portion of units of structure ~ (CH2~5 C ~
wherein p is not less than 100 and not more than about 3,000.
This particular polymer is crystalline and has a relatively high strength. However, it cannot be vulcanized due to the absence of unsaturatIon în the polymer. Because of the low crystalline melting point ~about 60C) it has a low upper temperature'service'l;mît~ Uses proposed for this polymer include formable'toy applicatîons, casts and household repair products.
We'have now discovered that bIends of trans-1,4 polymers of C4 - C5 conjugated diolefinic compounds and po~y(epsilon-caprolactone~ possess useful properties which would not be predîctable'based on the'properties of the indivîdual polymers of the'bIend~ We'have found, for example, that such blends yield improved medical casts in the non~
vulcanized state and provide împroved golf ball covers when vulcanized.
It is an object of this invention to provide blends having împroved propertîes comprising a trans-1,4 polymer of C4 - C5 conjugated diolefinic compounds and poly(epsilon-caprolactone~, the proportions of the polymers~in the blend being from about 98 parts to a~out S0 parts by weight of the .
v~
trans~l,4 polymer and from about 2 to about 50 parts by weight of the polyCepsilon-capro].actone).
It is a further o~ject of this invention to provide blends having improved properties comprising trans-1,4 polymer of C~ - C5 conjugated diolefinic compounds and poly(epsilon-caprolactone) additionally containing from about 10 to about 30 parts by weight per 100 parts by weight of the polymeric blend of at least one fine particle size filler, the proportions of the polymers in the ~lends ~eing from about 85 parts to about 60 parts by weight of the trans-1,4 polymer and from about 15 to about 40 parts by weight of the poly(epsilon-caprolactone).
It is a still further objective of this invention to provide polymeric blends suitable for use as golf ball covers comprising trans-1,4 polyisoprene and poly(epsilon-caprolactone~ wherein the amount of trans-1,4 polyisoprene is :~
from about 80 pa~ts to about 65 parts by weig~t and the amount of poly(epsilon-caprolactone) is from about 20 to about 35 parts by weight, the blend having a melt flow index under a load of lOkg of about 0.75 to about 2.0g per 10 minutes~
- In t~e blends of thls- invention, suitable trans-1,4 polymers of C4 - C5 conjugated d;olefinic compounds are the trans-1,4 polymers of butadiene, isoprene and chloroprene.
The trans-1,4 content of these polymers is suitably at least about 7S~, and preferably at least about 85%, of the unsatuxa-tion in the polymer. A preferred polymer is trans-1,4-poly-lsoprene which contains at least 85% trans-1,4 units and has at least 10%, preferably 20% to 401O~ crystallinity at room temperature Cthat is abbut 20 to 30C.2 as measured by X-ray diffraction The pol~Cepsilon--~aprolactone~ used in the blends of this invention contains repeat units of the structure ~o (C~2)5-B~ . ' where p is at least 100 and not more than about 3,000, and has a melting point of 60C and a density at 20C of about 1.15g/cc.
The fine particle size'fillers which may be used in the blends of this invention are preferably selected from silica, titanium dioxide'and diatomaceous earth or mixtures thereof. The preferred silica has a particle size of about 0.25 microns or less and is normally a precipitated silica. -The preferred titanium dioxide has an average particle size of about 0.3 microns and the'diatomaceo~s earth has an average particle size between about 1 and 10 microns depending on the particular grade'used. The'filler may be present in the ~ `
blends at a concentration of from about 10 to about 30 parts ~ ~' by weight per 100 parts by weight of the polymeric blend and - prefer~bly is present at 20 to 30 parts by weight. Mixtures ' of the fillers may also be'used, especîally of silica and ~ ~' titanium dioxide. ;'~
In the blends of this invention suitable for use as golf ball covers, the'polymeric blend as hereinbefore described `
may be mixed with natural rubber in the proportion of poly-meric blend about 80 parts by weight and natural rubber'about 20 parts by weight. To this may, for example, be added about 5 to 25 parts by weight of titanium dioxide and about 2 to 10 parts by weigh~ of zinc oxide~' A su;table curing system may include about 0.5 to 1 5 parts by weight of elementary sulphur and optionally additional organo-sulphur compounds ....
well known in the art as accelerators in amounts of about 0.1 to about 0.25 parts by weight. When formed over the core o~ the golf ball, such a cover may be cured, for example, by heating at about 100F [38C3 for about 5 days. The art of curing golf ball covers containing trans-1,4-polyisoprene is well known in the industry.
It is surprising that the trans-1,4 polymer and the poly(epsilon-caprolactone) are compatible, that the blend is vulcanizable and that there appears to be a synergistic effect on the properties of the blends. It is especially surprising that a hydrocarbon polymer such as trans-1,4-polyisoprene should be compatible with a polar polymer such as poly(epsilon-caprolacton~) and that the blend does not exhibit two separate phases, each phase having the melting point of the major component of that phase. The poly(epsilon-caprolactone) is very sticky above its melting point and cannot readily be handled at temperatures above 60C, but when allowed to cool it hardens very rapidly and has a very short working time, eliminating any prolonged molding. On the other hand, trans-1,4-polyisoprene handles quite readily even at temperatures above about 65C, the melting point of the crystals, and when allowed to cool hardens fairly slowly, thereby allowing a reasonable working time for molding. Additionally, the trans-1,4-polyisoprene retains its property of self adherence during the cooling stage and while it is workable, whereas the poly(epsilon-caprolactone) is not self adherent beyond its very short working time, which is a serious disadvantage in the preparation of medical casts. The blends of this inven-tion exhibit a range of properties which permit them to be used in a wider range of end uses than is possible for either - :
polymer in the bl~nd or, alternatively, improves the sui~ability for certain end uses.
The invention is exemplified by the following examples wherein all parts are parts by weight unless otherwise specified.
Example 1 The blends of composition shown in Table I were mixed in a Brabender mixer (Brabender is a registered Trade Mark) at 70C for 5 minutes, the rotor being operated at 160 rpm and the mixing chamber being kept under nitrogen. The trans~
polyisoprene has a Mooney value (ML ~ 4 at 100C) of 64 and a crystallinity of about 27% when measured by an X-ray method at room temperature. The poly(epsilon-caprolactone) was too fluid at 100C for a Mooney measurement; the material was obtained from Union Carbide Corporation identified as PCL-700.
The properties of the blends that were measured were the Shore C Hardness, the melt flow index (ASTM-D-1238-65T at 100C), ~ooney (ML 1 + 4 at 100C), stress-strain and the adherence ~o itself of the partially cooled blend.
Blend Nos. 1 and 5 are controls showing the properties of the trans-1,4-polyisoprene and of poly(epsilon-caprolactone).
Uses for trans-l,~-polyisoprene and for the blends of this invention require the polymer to possess a balance of various properties including flow, hardness and strength.
The results in Table I show that the blends of this invention possess a suitable range of such properties depending on the composition of the blend.
.
.. . . . . . ..
TABLE I
Blend No.: 1 2 3 4 5 (Control) Trans-1,4-poly- :
isoprene lO0 90 75 50 Poly(epsilon-cap-rolacetone) - 10 25 50 100 Shore C Hardness 72 72 75 78 85 M.F.l. g/lO mins. 0.15 0.26 0.78 4.66 12.7 Mooney (ML 1 + 4 at 100C) 64 40 20 10 Self-Adherence Yes Yes Yes Yes No Tensi~e Strength .
Kg/cm 428 385 247 113 372 300% Modulus Kg/cm~ 216 223 183 95 139 Elongation % 495 450 379 320 770 :
20.
~ .. ..
., - - - ,. . . .
The trans-1,4-polyisoprene and the blends of this invention exhibit a working time o:E about 4 to 5 minutes during which time the surface will readily adhere to itself when lightly contacted, whereas the poly(epsilon-caprolactone) exhibits a working time of only about 1 minute after which it does not exhibit self-adherence.
Example 2 Blends were prepared of trans-1,4-polyisoprene, poly(epsilon-caprolactone) and fine particle silica available as Hisil 233 (Hisil is a registered Trade Mark). The amount of each component in the blends is shown in Table II. The mixing was done on a two-roll rubber mill, with the rolls maintained at about 70C for sufficient time to achieve good dispersion of all the components. The properties of the ' blends are shown in Table II, blend numbers 21, 24 and 27 being controls outside the scope of this invention.
TABLE II
Blend No. 21 22 23 24 25 26 27 (Control) (Control) (Control) Trans-1,4 100 85 75 - 75 62;5 - j polyiso-prene Poly(epsi-~ lon-capro-lac~one) - 15 25 100 25 37.5100 Hi Sil 15 15 15 15 25 25 25 Flexural stren~th Kg/cm 114112 123 198135 144222 Flexural Modul~us Kg/cmJ 305027903025 51854000 44807200 Hardness Shore C 77 77 77 87 80 8490 ! . ~ .
~ 7 Exampl'e'3 Blends o~ trans-1,4-polyisoprene and poly(epsilon-caprolactone) were prepared and then further compounded and evaluated as golf ball covers. The blends were prepared, in the ratios shown in Table III, by mill mixing at about 70C.
Portions of each blend were then compounded, in the recipe shown in Table III under Compound composition, such as to be suita~le for subsequent use as golf ball covers. The melt flow index and stress-strain characteristics were determined for these compounds. Samples of these compounds, in sheet form, were immersed in a 5 wt. % solution of dibutyl xanthogen disulphide in acetone for lO:minutes, removed, surface material s~aken off and stored in an air chamber for 3 days at 45C in order to cause w lcanization to occur.
~he` stress-strain properties of the vulcanizates were determined; Further samples of the compounds were molded over pre-formed wound golf ball centres to produce covered golf balls which were then vulcanized by the same immersion and storag2'procedure'as above. The golf balls so produced were found to have good resilience, excellent click and excellent cut res;stance.
. .
TABLE II~
Experiment No. 31 32 33 A. Polymer blend composition - parts by weight Trans-1,4-polyisoprene80 75 70 . .
Poly(epsilon-capro-lactone) 20 25 30 Melt flow index g/10 minutes 0.71 0.97 1.86 B~ Compound`composition -parts by weight Polymer blend 80 80 80 Natural rubber 20 20 20 TItanium dioxide 20 20 20 Zînc oxide 3 3 3 Sulphur DBA
Melt flow index g/10 mînutes 1.32 1.60 2.52 Tensile strength Kg/cm2 335 280 265 -300% Modulus Kg/cm2 210 205 190 Elongation % 450 390 405 ~ ~
.. - ' :
C. Vulcanizate properties .;
Tensile strength :
Kg/cm2 215 185 150 300% Modulus Kg/cm2 125 120 110 Elongation /O 475 420 390
This invention is directed to polymeric blends having improved properties, specifically to blends of trans-1,4 polymers of C4 - C5 conjugated diolefinic compounds with polymers of caprolactone.
One naturally occurring polymer of a trans-1,4 conjugated diolefinic compound is the polymer of isoprene known as balata or gutta percha~ Thîs polymer has enjoyed a varîety of uses over the years including use in submarine cables and golf ball covers. The polymer is relatively high - 10 in cost and the supply is irregular. Because of this, it has been extensiveIy replaced by a synthetic trans-1,4-polyisoprene which is available on a more regular supply basis and is of ~, ';
uniform composition, not needing the clean up and purifîcation steps necessary with balata. Trans-1,4 polybutadiene is also available as a synthetic polymer which has generally simîlar characterîstîcs to those'of trans-1,4-polyîsoprene. Another - s~nthetic polymer whîch'also possesses' certain of the'same ~ -characteristics îs trans-1,4 polyc~Loroprene.
A characteristic common to these'polymers is that they all have'a high level of crystallinity which leads to good strength properties in the'polymer at normal temperatures and easy processing of tEe polymer at temperatures near or above the crystallîne melting point. Further, these polymers are all vulcanizable, due'to the presence of unsaturatîon alone or in combination with an active chlorine group~ The raw '' polymer, or the raw polymer compounded with conventional compounding ingredients wit~'t~e exception of vulcanization agents, may be used in a wîde'variety of applîctations where strength at amb;ent temperature'is important~ Such'applications include medical casts, ad~esives-and moldable s~eets~ The `
w lcanized polym~r may be used where hardness and a greater degree of permanence of shape is required such as in a golf ball cover.
PlY(epsilon-caprolactone~ is a cyclic ester polymer which may be generally described as containing a major pro-portion of units of structure ~ (CH2~5 C ~
wherein p is not less than 100 and not more than about 3,000.
This particular polymer is crystalline and has a relatively high strength. However, it cannot be vulcanized due to the absence of unsaturatIon în the polymer. Because of the low crystalline melting point ~about 60C) it has a low upper temperature'service'l;mît~ Uses proposed for this polymer include formable'toy applicatîons, casts and household repair products.
We'have now discovered that bIends of trans-1,4 polymers of C4 - C5 conjugated diolefinic compounds and po~y(epsilon-caprolactone~ possess useful properties which would not be predîctable'based on the'properties of the indivîdual polymers of the'bIend~ We'have found, for example, that such blends yield improved medical casts in the non~
vulcanized state and provide împroved golf ball covers when vulcanized.
It is an object of this invention to provide blends having împroved propertîes comprising a trans-1,4 polymer of C4 - C5 conjugated diolefinic compounds and poly(epsilon-caprolactone~, the proportions of the polymers~in the blend being from about 98 parts to a~out S0 parts by weight of the .
v~
trans~l,4 polymer and from about 2 to about 50 parts by weight of the polyCepsilon-capro].actone).
It is a further o~ject of this invention to provide blends having improved properties comprising trans-1,4 polymer of C~ - C5 conjugated diolefinic compounds and poly(epsilon-caprolactone) additionally containing from about 10 to about 30 parts by weight per 100 parts by weight of the polymeric blend of at least one fine particle size filler, the proportions of the polymers in the ~lends ~eing from about 85 parts to about 60 parts by weight of the trans-1,4 polymer and from about 15 to about 40 parts by weight of the poly(epsilon-caprolactone).
It is a still further objective of this invention to provide polymeric blends suitable for use as golf ball covers comprising trans-1,4 polyisoprene and poly(epsilon-caprolactone~ wherein the amount of trans-1,4 polyisoprene is :~
from about 80 pa~ts to about 65 parts by weig~t and the amount of poly(epsilon-caprolactone) is from about 20 to about 35 parts by weight, the blend having a melt flow index under a load of lOkg of about 0.75 to about 2.0g per 10 minutes~
- In t~e blends of thls- invention, suitable trans-1,4 polymers of C4 - C5 conjugated d;olefinic compounds are the trans-1,4 polymers of butadiene, isoprene and chloroprene.
The trans-1,4 content of these polymers is suitably at least about 7S~, and preferably at least about 85%, of the unsatuxa-tion in the polymer. A preferred polymer is trans-1,4-poly-lsoprene which contains at least 85% trans-1,4 units and has at least 10%, preferably 20% to 401O~ crystallinity at room temperature Cthat is abbut 20 to 30C.2 as measured by X-ray diffraction The pol~Cepsilon--~aprolactone~ used in the blends of this invention contains repeat units of the structure ~o (C~2)5-B~ . ' where p is at least 100 and not more than about 3,000, and has a melting point of 60C and a density at 20C of about 1.15g/cc.
The fine particle size'fillers which may be used in the blends of this invention are preferably selected from silica, titanium dioxide'and diatomaceous earth or mixtures thereof. The preferred silica has a particle size of about 0.25 microns or less and is normally a precipitated silica. -The preferred titanium dioxide has an average particle size of about 0.3 microns and the'diatomaceo~s earth has an average particle size between about 1 and 10 microns depending on the particular grade'used. The'filler may be present in the ~ `
blends at a concentration of from about 10 to about 30 parts ~ ~' by weight per 100 parts by weight of the polymeric blend and - prefer~bly is present at 20 to 30 parts by weight. Mixtures ' of the fillers may also be'used, especîally of silica and ~ ~' titanium dioxide. ;'~
In the blends of this invention suitable for use as golf ball covers, the'polymeric blend as hereinbefore described `
may be mixed with natural rubber in the proportion of poly-meric blend about 80 parts by weight and natural rubber'about 20 parts by weight. To this may, for example, be added about 5 to 25 parts by weight of titanium dioxide and about 2 to 10 parts by weigh~ of zinc oxide~' A su;table curing system may include about 0.5 to 1 5 parts by weight of elementary sulphur and optionally additional organo-sulphur compounds ....
well known in the art as accelerators in amounts of about 0.1 to about 0.25 parts by weight. When formed over the core o~ the golf ball, such a cover may be cured, for example, by heating at about 100F [38C3 for about 5 days. The art of curing golf ball covers containing trans-1,4-polyisoprene is well known in the industry.
It is surprising that the trans-1,4 polymer and the poly(epsilon-caprolactone) are compatible, that the blend is vulcanizable and that there appears to be a synergistic effect on the properties of the blends. It is especially surprising that a hydrocarbon polymer such as trans-1,4-polyisoprene should be compatible with a polar polymer such as poly(epsilon-caprolacton~) and that the blend does not exhibit two separate phases, each phase having the melting point of the major component of that phase. The poly(epsilon-caprolactone) is very sticky above its melting point and cannot readily be handled at temperatures above 60C, but when allowed to cool it hardens very rapidly and has a very short working time, eliminating any prolonged molding. On the other hand, trans-1,4-polyisoprene handles quite readily even at temperatures above about 65C, the melting point of the crystals, and when allowed to cool hardens fairly slowly, thereby allowing a reasonable working time for molding. Additionally, the trans-1,4-polyisoprene retains its property of self adherence during the cooling stage and while it is workable, whereas the poly(epsilon-caprolactone) is not self adherent beyond its very short working time, which is a serious disadvantage in the preparation of medical casts. The blends of this inven-tion exhibit a range of properties which permit them to be used in a wider range of end uses than is possible for either - :
polymer in the bl~nd or, alternatively, improves the sui~ability for certain end uses.
The invention is exemplified by the following examples wherein all parts are parts by weight unless otherwise specified.
Example 1 The blends of composition shown in Table I were mixed in a Brabender mixer (Brabender is a registered Trade Mark) at 70C for 5 minutes, the rotor being operated at 160 rpm and the mixing chamber being kept under nitrogen. The trans~
polyisoprene has a Mooney value (ML ~ 4 at 100C) of 64 and a crystallinity of about 27% when measured by an X-ray method at room temperature. The poly(epsilon-caprolactone) was too fluid at 100C for a Mooney measurement; the material was obtained from Union Carbide Corporation identified as PCL-700.
The properties of the blends that were measured were the Shore C Hardness, the melt flow index (ASTM-D-1238-65T at 100C), ~ooney (ML 1 + 4 at 100C), stress-strain and the adherence ~o itself of the partially cooled blend.
Blend Nos. 1 and 5 are controls showing the properties of the trans-1,4-polyisoprene and of poly(epsilon-caprolactone).
Uses for trans-l,~-polyisoprene and for the blends of this invention require the polymer to possess a balance of various properties including flow, hardness and strength.
The results in Table I show that the blends of this invention possess a suitable range of such properties depending on the composition of the blend.
.
.. . . . . . ..
TABLE I
Blend No.: 1 2 3 4 5 (Control) Trans-1,4-poly- :
isoprene lO0 90 75 50 Poly(epsilon-cap-rolacetone) - 10 25 50 100 Shore C Hardness 72 72 75 78 85 M.F.l. g/lO mins. 0.15 0.26 0.78 4.66 12.7 Mooney (ML 1 + 4 at 100C) 64 40 20 10 Self-Adherence Yes Yes Yes Yes No Tensi~e Strength .
Kg/cm 428 385 247 113 372 300% Modulus Kg/cm~ 216 223 183 95 139 Elongation % 495 450 379 320 770 :
20.
~ .. ..
., - - - ,. . . .
The trans-1,4-polyisoprene and the blends of this invention exhibit a working time o:E about 4 to 5 minutes during which time the surface will readily adhere to itself when lightly contacted, whereas the poly(epsilon-caprolactone) exhibits a working time of only about 1 minute after which it does not exhibit self-adherence.
Example 2 Blends were prepared of trans-1,4-polyisoprene, poly(epsilon-caprolactone) and fine particle silica available as Hisil 233 (Hisil is a registered Trade Mark). The amount of each component in the blends is shown in Table II. The mixing was done on a two-roll rubber mill, with the rolls maintained at about 70C for sufficient time to achieve good dispersion of all the components. The properties of the ' blends are shown in Table II, blend numbers 21, 24 and 27 being controls outside the scope of this invention.
TABLE II
Blend No. 21 22 23 24 25 26 27 (Control) (Control) (Control) Trans-1,4 100 85 75 - 75 62;5 - j polyiso-prene Poly(epsi-~ lon-capro-lac~one) - 15 25 100 25 37.5100 Hi Sil 15 15 15 15 25 25 25 Flexural stren~th Kg/cm 114112 123 198135 144222 Flexural Modul~us Kg/cmJ 305027903025 51854000 44807200 Hardness Shore C 77 77 77 87 80 8490 ! . ~ .
~ 7 Exampl'e'3 Blends o~ trans-1,4-polyisoprene and poly(epsilon-caprolactone) were prepared and then further compounded and evaluated as golf ball covers. The blends were prepared, in the ratios shown in Table III, by mill mixing at about 70C.
Portions of each blend were then compounded, in the recipe shown in Table III under Compound composition, such as to be suita~le for subsequent use as golf ball covers. The melt flow index and stress-strain characteristics were determined for these compounds. Samples of these compounds, in sheet form, were immersed in a 5 wt. % solution of dibutyl xanthogen disulphide in acetone for lO:minutes, removed, surface material s~aken off and stored in an air chamber for 3 days at 45C in order to cause w lcanization to occur.
~he` stress-strain properties of the vulcanizates were determined; Further samples of the compounds were molded over pre-formed wound golf ball centres to produce covered golf balls which were then vulcanized by the same immersion and storag2'procedure'as above. The golf balls so produced were found to have good resilience, excellent click and excellent cut res;stance.
. .
TABLE II~
Experiment No. 31 32 33 A. Polymer blend composition - parts by weight Trans-1,4-polyisoprene80 75 70 . .
Poly(epsilon-capro-lactone) 20 25 30 Melt flow index g/10 minutes 0.71 0.97 1.86 B~ Compound`composition -parts by weight Polymer blend 80 80 80 Natural rubber 20 20 20 TItanium dioxide 20 20 20 Zînc oxide 3 3 3 Sulphur DBA
Melt flow index g/10 mînutes 1.32 1.60 2.52 Tensile strength Kg/cm2 335 280 265 -300% Modulus Kg/cm2 210 205 190 Elongation % 450 390 405 ~ ~
.. - ' :
C. Vulcanizate properties .;
Tensile strength :
Kg/cm2 215 185 150 300% Modulus Kg/cm2 125 120 110 Elongation /O 475 420 390
Claims (11)
1. As a composition of matter, a blend having improved properties comprising from about 98 to about 50 parts by weight of a trans-1,4 polymer of butadiene or isoprene in which the trans-1,4 content is at least about 75% and from about 2 to about 50 parts by weight of a poly(epsilon-caprolactone).
2. The composition of Claim 1 wherein the poly(epsilon-caprolactone) contains repeat units of the structure where p is at least 100 but not more than 3,000.
3. The composition of Claim 2 in which the trans-1,4 polymer is trans-1,4-polyisoprene.
4. The composition of Claims 1, 2 or 3 in which the trans-1,4 polymer is trans-1,4-polyisoprene containing at least 85% trans-1,4 units and having an X-ray diffraction crystal-linity of at least 10%.
5. The composition of Claim 1 which comprises from about 85 to about 60 parts by weight of the trans-1,4 polymer and from about 15 to about 40 parts by weight of poly(epsilon-caprolactone) and from about 10 to about 30 parts by weight per 100 parts by weight of the polymeric blend of at least one fine particle size filler.
6. The composition of Claim 5 wherein the particle size of the filler is about 0.25 microns or less.
7. The composition of Claim 5 wherein the filler is selected from silica, titanium dioxide, diatomaceous earth or mixtures thereof.
8. The composition of Claims 5, 6 or 7 in which the filler is a mixture of silica and titanium dioxide and is present as 20 to 30 parts by weight per 100 parts by weight of polymeric blend.
9. The composition of claim 1, suitable for use as a golf ball cover, which comprises from about 80 to about 65 parts by weight of trans-1,4 polyisoprene having at least about 75% trans-1,4 content and from about 20 to about 35 parts by weight of poly(epsilon-caprolactone), the polymeric blend having a melt flow index under a load of 10 kg of about 0.75 to about 2.0 g per 10 minutes.
10. A composition suitable for use as a golf ball cover which comprises about 80 parts by weight of the polymeric blend of Claim 9, about 20 parts by weight of natural rubber, about 5 to 25 parts by weight of titanium dioxide, about 2 to 10 parts by weight of zinc oxide and a suitable curing system.
11. The composition of Claim 10 in which the curing system comprises about 0.5 to 1.5 parts by weight of elementary sulphur and optionally about 0.1 to about 0.25 parts by weight of organo-sulphur accelerators.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA263,579A CA1080875A (en) | 1976-10-18 | 1976-10-18 | Blends of trans-1,4 polymers and poly (epsilon-caprolactone) |
| GB41577/77A GB1545979A (en) | 1976-10-18 | 1977-10-06 | Blends of trans-1,4 polymers and poly(epsilon-caprolactone) |
| US05/841,438 US4144223A (en) | 1976-10-18 | 1977-10-12 | Blends of trans-1,4-polymers and poly(epsilon-caprolactone) |
| DE2746114A DE2746114C2 (en) | 1976-10-18 | 1977-10-13 | Polymer blend |
| FR7731212A FR2367792A1 (en) | 1976-10-18 | 1977-10-17 | VERY CRYSTALLINE VULCANIZABLE POLYMER MIXTURE |
| JP12361177A JPS5350252A (en) | 1976-10-18 | 1977-10-17 | Polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA263,579A CA1080875A (en) | 1976-10-18 | 1976-10-18 | Blends of trans-1,4 polymers and poly (epsilon-caprolactone) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1080875A true CA1080875A (en) | 1980-07-01 |
Family
ID=4107072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA263,579A Expired CA1080875A (en) | 1976-10-18 | 1976-10-18 | Blends of trans-1,4 polymers and poly (epsilon-caprolactone) |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4144223A (en) |
| JP (1) | JPS5350252A (en) |
| CA (1) | CA1080875A (en) |
| DE (1) | DE2746114C2 (en) |
| FR (1) | FR2367792A1 (en) |
| GB (1) | GB1545979A (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1111179A (en) * | 1978-02-17 | 1981-10-20 | Eric G. Kent | Polymeric casts |
| DE3220324C2 (en) * | 1981-06-03 | 1994-02-03 | Daicel Chem | Mass containing polycaprolactone |
| US4371652A (en) * | 1981-12-21 | 1983-02-01 | Exxon Research And Engineering Co. | Blend compounds of sulfonated polymers and compositions thereof |
| JPS5996160A (en) * | 1982-11-24 | 1984-06-02 | Daicel Chem Ind Ltd | Polycaprolactone resin composition |
| GB8417872D0 (en) * | 1984-07-13 | 1984-08-15 | Johnson & Johnson | Thermoplastic composition |
| JPS61123641A (en) * | 1984-11-21 | 1986-06-11 | Asahi Chem Ind Co Ltd | Polymeric resin composition |
| US4984803A (en) * | 1989-10-11 | 1991-01-15 | Acushnet Company | Golf ball cover composition |
| JPH0623260B2 (en) * | 1989-11-08 | 1994-03-30 | 工業技術院長 | Microbial degradable thermoplastic resin molding and method for producing the same |
| US5352498A (en) * | 1992-08-19 | 1994-10-04 | The Goodyear Tire & Rubber Company | Package for compounding rubber and compounded rubber |
| US5378531A (en) * | 1993-07-09 | 1995-01-03 | Larson; Peter M. | Gamma radiation treated sheet material for use as orthopedic splints and casts and the like |
| US5885172A (en) | 1997-05-27 | 1999-03-23 | Acushnet Company | Multilayer golf ball with a thin thermoset outer layer |
| US20050070377A1 (en) * | 1997-05-27 | 2005-03-31 | Christopher Cavallaro | Thin-layer-covered multilayer golf ball |
| US6849006B2 (en) | 1997-05-27 | 2005-02-01 | Acushnet Company | Thin, thermoset, polyurethane-covered golf ball with a dual core |
| US6634964B2 (en) | 1997-05-27 | 2003-10-21 | Acushnet Company | Initial velocity dual core golf ball |
| US6486261B1 (en) * | 1998-12-24 | 2002-11-26 | Acushnet Company | Thin-layer-covered golf ball with improved velocity |
| US6913547B2 (en) | 1997-05-27 | 2005-07-05 | Acushnet Company | Thin-layer-covered multilayer golf ball |
| US6465578B1 (en) | 1998-12-24 | 2002-10-15 | Acushnet Company | Low compression, resilient golf balls including an organosulfur catalyst and method for making same |
| US6998445B2 (en) * | 1998-03-26 | 2006-02-14 | Acushnet Company | Low compression, resilient golf balls with rubber core |
| US6458895B1 (en) | 1998-12-24 | 2002-10-01 | Acushnet Company | Low compression, resilient golf balls including elemental catalyst and method for making same |
| US6291592B1 (en) | 1998-12-24 | 2001-09-18 | Acushnet Company | Low compression, resilient golf balls including aromatic catalyst and method for making same |
| US6417278B1 (en) | 1998-03-26 | 2002-07-09 | Acushnet Company | Low compression, resilient golf balls including a cis-to-trans catalyst and method for making same |
| US6162135A (en) | 1998-12-24 | 2000-12-19 | Acushnet Company | Low compression, resilient golf balls including an inorganic sulfide catalyst and methods for making the same |
| US6767294B2 (en) | 2002-09-06 | 2004-07-27 | Callaway Golf Company | Golf ball |
| JP4861036B2 (en) * | 2006-03-31 | 2012-01-25 | リンテック株式会社 | Release sheet and method for producing the same |
| US20080108009A1 (en) * | 2006-11-03 | 2008-05-08 | Cms Dental Aps | Obturation device, material and methodolgy |
| US20090298617A1 (en) * | 2008-05-28 | 2009-12-03 | Bridgestone Sports Co., Ltd. | Golf ball material and golf ball |
| US20100269282A1 (en) * | 2009-04-24 | 2010-10-28 | Euro-Pro Operating, Llc | Shaggy fabric towel steam pocket for a steam appliance |
| US8987405B2 (en) | 2012-01-03 | 2015-03-24 | Nike, Inc. | Golf ball having an over-indexed thermoplastic polyurethane elastomer cover and having a soft feeling when hit |
| US20150065932A1 (en) | 2013-08-27 | 2015-03-05 | Peter M. Larson | Moldable splint and method of using same |
| US11918863B1 (en) | 2020-02-19 | 2024-03-05 | Topgolf Callaway Brands Corp. | Method and system utilizing imaging analysis for golf balls |
| US11058924B1 (en) | 2020-02-19 | 2021-07-13 | Callaway Golf Company | Method and system utilizing imaging analysis for golf balls |
| US11911667B1 (en) | 2020-02-19 | 2024-02-27 | Topgolf Callaway Brands Corp. | Method and system utilizing imaging analysis for golf balls |
| US11911666B1 (en) | 2020-02-19 | 2024-02-27 | Topgolf Callaway Brands Cor. | Method and system utilizing imaging analysis for golf balls |
| US11752396B1 (en) | 2020-02-19 | 2023-09-12 | Topgolf Callaway Brands Corp. | Method and system utilizing imaging analysis for golf balls |
| US11318354B2 (en) | 2020-05-27 | 2022-05-03 | Callaway Golf Company | Method and system for utilizing radio-opaque fillers in multiple layers of golf balls |
| US11185741B1 (en) | 2020-05-27 | 2021-11-30 | Callaway Golf Company | Method and system for utilizing radio-opaque fillers in multiple layers of golf balls |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3528936A (en) * | 1965-12-17 | 1970-09-15 | Polymer Corp | Stabilized compositions of interpolymers of butadiene polymers and polyunsaturated polyesters |
| US3637544A (en) * | 1969-04-01 | 1972-01-25 | Union Carbide Corp | Vulcanized elastomeric blends containing a cyclic ester polymer |
| GB1355956A (en) * | 1970-07-10 | 1974-06-12 | Dunlop Holdings Ltd | Playballs |
| US3701702A (en) * | 1970-08-25 | 1972-10-31 | Uniroyal Inc | Method of free curing rubber |
| US3708331A (en) * | 1970-11-13 | 1973-01-02 | Chase W & Co | Composition for sealing contained sterilized foods |
| CA946088A (en) * | 1971-02-03 | 1974-04-23 | Uniroyal | Golf ball cover |
-
1976
- 1976-10-18 CA CA263,579A patent/CA1080875A/en not_active Expired
-
1977
- 1977-10-06 GB GB41577/77A patent/GB1545979A/en not_active Expired
- 1977-10-12 US US05/841,438 patent/US4144223A/en not_active Expired - Lifetime
- 1977-10-13 DE DE2746114A patent/DE2746114C2/en not_active Expired
- 1977-10-17 FR FR7731212A patent/FR2367792A1/en active Granted
- 1977-10-17 JP JP12361177A patent/JPS5350252A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2746114C2 (en) | 1984-12-13 |
| JPS5350252A (en) | 1978-05-08 |
| US4144223A (en) | 1979-03-13 |
| FR2367792A1 (en) | 1978-05-12 |
| GB1545979A (en) | 1979-05-16 |
| FR2367792B1 (en) | 1981-07-24 |
| DE2746114A1 (en) | 1978-04-20 |
| JPS6143375B2 (en) | 1986-09-27 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |