CA2187625A1 - Easily degradable star-block copolymers - Google Patents
Easily degradable star-block copolymersInfo
- Publication number
- CA2187625A1 CA2187625A1 CA002187625A CA2187625A CA2187625A1 CA 2187625 A1 CA2187625 A1 CA 2187625A1 CA 002187625 A CA002187625 A CA 002187625A CA 2187625 A CA2187625 A CA 2187625A CA 2187625 A1 CA2187625 A1 CA 2187625A1
- Authority
- CA
- Canada
- Prior art keywords
- star
- block copolymer
- polycaprolactone
- polylactide
- lactide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
Abstract
Star-bloc copolymers containing polycaprolactone and polylactide blocks of limited molecular weight are tough, easily degradable polymers. Such copolymers, which are noncrystalline and have glass transition temperatures near or below room temperature, are useful in many packaging and other applications.
Description
~ wo ssl29200 2 1 8 7 6 2 .~ ' 14 ~ITLE
E~SILY DEGRADABLE STAR-BLOCR COPOLYMERS
FIFT n OF TTIF TNVENTION
Disclosed herein 2re easLly hydro- and 5 bio~ rA~T~hle stsr-block copolymers of caprolactone and lactlde. Even though of relatlvely low molecular weight, the copolymers are tough elastomer-llke materials .
TFr~TNIr2T. Bp~rp~r~RollNr) Polymers, particularly thermoplastics, are in theory recyclable, but are often not recycled because of the cost of collecting, sorting and purifylng the recycled plastics. Therefore, most plastics and other polymers such as elastomers, are disposed of with other trash, such as in lAn-lf~llc, where they are very chemically stable, and degrade min~r'lly. One way of reducing the amount of stable polymers in landfills and the llke ls to produce polymers which are degradable, as by hydrolysis, biodegradation, or like processes.
It is known that under the proper conditions, polylactlde ls blodegradable, and polymers C~ntA~n~n~
this repeat unit have been considered desirable for this reason. However, most polylactide polymers are plastics, that ls thelr glass transition temperature ~Tg) is above room temperature, and they may be crystalline. Polymers which contain lactide repeat units but yet have elastomeric-like properties would also be desirable.
~.S. Patent 5,210,108 describes foam made from 2 star shaped polymer containing lactide repeat units.
The foams produced are rigid, not elastomeric.
D ~. Gri jpma, et al., MAkrom~l . Cht~m . FA~id Commun., vol. 14, p. 155-;61 (1992) report the synthesis of star block copolymers having polylactide blocks and trimethylene carbonate or A mixture of trimethylene W0 95129200 ~ ` r~J,~ 14 z carbonate and another lactone block. These copolymers have polylactide ~rg ' s of 50-55C .
SUMMA~Y OF TE~F INVF:NTION
This invention concerns, a star-block copolymer, 5 consisting essentially of, a core, 3 to about 20 inner arms of polycaprolactone which are bound to said core, and polylactide outer arms bound to said inner arms, and provided that:
said polylactide is at least 50% by weight of0 said copolymer;
said polycaprolactone is about 10% to about 50% by weight of said copolymer;
said polycaprolactone and said polylactide do not crystallize upon melt processing; and said polylactide has a glass transition temperature of less than 35C.
DETATT c OF T~F. INVENTION
The inst2nt copolymer is a star-block copolymer which contains polycaprolactone and polylactide blocks.
The copolymer also contains a core, which is often the "starting point" for the copolymer. The core is originally a multi-functional material usually containing the same number of functional groups as arms which the star copolymer is meant to have. By functional group in this instance is meant a group which either by itself, or by a reaction of the group, forms a site for the initiation of one copolymer chain (an arm of the star). In this case it will initiate the polymerization of caprolactone.
Suitable functional groups for the core include hydroxyl, amino, and sulfhydryl. These may be used in standard ways to initiate the polymerization of caprolactone. For instance, a catalyst such as stannous octoate may be used. Such polymerizations are described 35 in European Patent Application 117, 538, which is hereby 218762~
WO 95/29200 ~ r~ 014 3 I.
Lncluded by reference. The polymerization mzy ~e done neat (no solvent) or with a solvent pre3ent.
The polysaprolactone herein i5 formed from epsilon-caprolactone, which i5 the monomer. The polycapro-lactone forms the "inner arm" of the copolymer herein.
An inner arm is the polymer which is attached or bonded J to the core. Since the Tg of polycaprolactone is quite low (below 0C) this property does not generally affect the rigidity of the product of the invention. ~owever, 10 polycaprolactone does partially crystallize if the molecular weight is hlgh enough. Therefore, the molecular weight of the polycaprolactone blocks should be low enough so that such cryst~ 7~t~on does not take place upon melt processng. A useful molecular weight 15 range for the polycaprolactone inner arm is a number average molecular weight of about 800 to about 4000. It is preferred if the polycaprolactone is about 10% to about 40% by weight of the copolymer, more preferred if it Ls about 15% to about 30%, and especially preferred 20 i~ it is about 18~ to about 22% by weight of the copolymer .
When caprolactone is polymerized, the end group is normally a hydroxyl group, which can be used to help initiate the polymerization of lactide. Therefore, the 25 lactide polymer block becomes bound (attached) to the end of the polycaprolactone block, and herein this is called the outer arm. Lactide in the D, L, or meso forms, or any combination thereof, may be used to form the polylactide block. Lactide homopolymer is semi-30 crystalline, and has a Tg of about 55-60C. Therefore the polylactide block should be small enough (low in molecular weight) so that the Tg is 35C or less, preferably 30C or less. A typical useful ranse of polylactide block sizes is about 1, 000 to about 12, 000 35 in number average molecular weight, but this will var~
~187625 WO 95t29200 . ~ ~
somewhat with the size of the pQlycaprQlactone block.
It is preferred that the number average molecular weight of eQch polylactide block is abQut 3, 000 Qr more. It is also preferred if the pQlylactide is at least 70% by weight of the copolymer.
The pQlylactide blQck is fQrmed by the pQlymerization of lactide itself. This polymerization can be carried out in a number Qf ways, but it is usually dQne with a catalyst. Stannou3 octoate is a useful catalyst, but preferred catalysts are selected rare earth metal r~ oun~c, such as those disclosed in U.S. Patents 5,028,667 and 5,292,859, which are both hereby ;n~lu~d by reference. The catalysts disclosed in the latter patent are especially preferred. These polymerizatiQns are carried out neat or with solvent present, but neat (no solvent present) pQlymerizations are preferred. ~olymerization temperatures are not critical, and 0C to abQut 200CC is a cQnvenient range.
The polymerization of the caprolactone and lactide can be done in sequential steps in the same reactor, or the polycaprolactone ~attached tQ the cQre) star polymer may be isolated and then mixed with lactide to be polymerized to iorm the final copQlymer.
The star-block cQpQlymers herein have 3 to 20 arms, preferably 3 to 10 arms, more preferably 3 to 6 arms, and especially preferably 4 arms.
The cQpolymers described herein are relatively tough, elastomeric-like materials that are suitable fQr many uses. Among these uses are liquid food packaging, such as milk pouches, juice pouches, coatings fQr coated board for refrigerated li~uids, and processed meat wrap;
dry fQod packaging such as the outer w~ap for boxed foods, as part of a multilayer packaging film, and as the cQating Qn cQated bQard for frozen foods; coating for coated board for fast food, such as for drink cups;
21~62~
~ Wo 95/29200 . ~1ll 14 other consumer products such as non-woven absor~ants for diapers, soft pliable baclcsheet for diapers, film overwrap for toiletries and personal care productsi agricultural products such as mulch film; medical 5 products such as pliable wound dressings and low modulus surgical implants; as a toughening additive for other polymers, such as polymers used for foams or blow molding and a modifier for polymer to be spun into fibers for improved elongation and tenacLty; and other 10 uses such as adhesives, film overwrap for animal feed supplements, and artiflcial snow. The copolymer dLsclosed herein is particularly useful in these applications because of its biodegradability, toughn~ss, tear strength and soft feel.
~he copolymers herein should not be crystalline, i.e., should not have a melting transition of greater than 3 J/g when tested by Differential Scanning calorimetry (see test for Tg below) upon melt processing. The sample for such a test is prepared by 20 in~ection molding some of the copolymer in question into a 3 . 2 mm thick plaque, with the mold temperature being about 10C, and the copolymer having a melt temperature (exiting the screw barrel) of about 150C.
~olecular weight measurements herein are made by 25 Gel Permeation Chromatography using polystyrene standards. The average molecular weight of a polylactide outer arm is the number average molecular weight of the copolymer times the weight fraction of polylactide in the copolymer divided by the nominal 30 number of arms in the copolymer. Similarly, the average molecular weight of the polycaprolactone inner arm is the number average molecular weight of the copolymer times the weight ~raction of polycaprolactone in the copolymer divided by the nominal number of arms in the 35 copolymer.
WO 95l29200 ~1816 2 ~ . F~ J.,9~ ~ ~q The glass transition temper2ture (Tg) of the copolymer ~particularly the polylactide blocks) is measured by the following procedure. About 0.5 g of copolymer is dissolved in 5 mL of methylene chloride and 5 the resulting solution is added dropwise to 50 mL of rapidly stirred methanol (this is done to remove any free lactide in the copolymer, which acts as a plasticizer). The precipitated fluff is collected via i'iltration and/or rlprAnt~t; ~n and dried in vacuo at room 10 temperature. lH-NMR at 300 ~Hz is used to verify that no residual lactide remains in the copolymer.
Dlfferential Sr~nn~nr~ Calorimetry ~DSC) is performed using a TA Instruments 2100 analyzer, with a 5-10 mg sample in a covered, sealed, standard aluminum pan. The 15 heating rate is 10C/min. The Tg is taken as the midpoint of the step transition. It is preferred if the Tg of the polylactide in the copolymer is 30C or less.
In the f ollowing examples, Mn is number average molecular weight and Mw is weight average molecular 20 weight.
~T'NT'R~T. AN~T.YTI~ri~T, DET~.rT.':
Molecular weights were measured using size exclusion chromatography (SEC, GPC) in THF solvent at 25C using polystyrene calibration standards. Residual 25 lactide monomer and total caprolactone contents are measured using lH-NMR at 300 MHz. Physical properties were measured using a Laboratory Microsystems tester at 9.1 kg full scale load range and a crosshead speed oi 5.1 cm per minute. The reported values are the mean of 30 at least five determinations. Film samples (0 . 025-0 . 050 mm in thickness) were prepared by compression molding at 150 to 180C and a pressure of ~rom 6.9 to 39.5 MPa depending on the flow characteristics of the individual polymer sample.
~ W0 95l29200 2 1 ~ 7~ 2 S r~ 014 F:xAMPT ~ 1 Synthe~is of 14~ Caorolactone 4-~rm StAr ~lork Polylactlde Seven g polycaprolactone tetrol ~Lot ~17360-10 from Union Carbide, Mn 7240), 41.3 g L-Lactide and 1.7 g of D, L-Lactide were charged under argon to a carefully dried Helicone~l9 C2V mixer ~Atlantic Research Corp. ), held at 164C. After 10 minutes stirring, 0 . 657 mL of a 0.45 M solution ~140 Solvent 66/3 from Unocal, hereafter referred to as AMSCO 140) of La ~2, 2, 6, 6-tetramethyl-heptane-3, 5-dionate) 3-bis ~ethoxyet~ylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and ryuenched into water. Lactide conversion and caprolactone content by lH-nmr were 92 . 4, and 11% respectively, and Tg was 27C.
Mn was 40, 000 and Mw/Mn was 1.4 . Tensile strength, 96 elongation and modulus ~hereafter referred to as TEM) were 103 MPa, 137~i, 448 M~a, respectively, as measured on a compression molded film.
EXAM~T ~ 2 Synthe~lc of 10% C~orolActrne 3--Arm StAr Elock PolylActide Five g polycaprolactone triol ~Lot ~16874-95 from Union Carbide, Mn 5260), 43.2 g L-Lactide and 1.8 g of 25 D, L-Lactide were charged under argon to a carefully dried Helicone~ C2V mixer (Atlantic P~esearch Corp . ), held at 164C . After 10 minutes stirring, 0 . 687 mL of a 0.45 M solution ~AMSCO 140) of La~2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis ~ethoxy-ethylether) catalyst 30 was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and r~uenched into water. Tg was 19C. Mn was 39, 000, and Mw/Mn was 1.6. T~M -- 3.5 MPa, 210~, 82.7 MPa.
.
~18762a W0 95l29200 ; ~ ~ P~ 4 E~r~PL~ 3 Synth~qis of 20% (';~rol ;~ctone 3-~rm St~r ;310ck Polyl~--tide Ten g polycaprolactone triol (Lot ~t16874-95 from Union Carbide, Mn 5260), 38 . 4 g L-Lactide and 1. 6 g of D,L-Lactide were charged under argon to a carefully dried TTel 1 rrn~$ C2V mixer (Atlantic Research Corp . ), held at 167C . After 10 minutes stirring, 0. 615 mL of a 0.45 M solution (AMSCO 140) of La(2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and rluenched into water. Tg was 20C. Mn was 63, 000 and Mw/Mn was 1.2. TEM = 3.5 MPa, 123%, 110 MPa.
Ex~SPL~ 4 - S~nth~qiq of 20% ~rol~ctrne 4-,~rm St P r Rl ork Polyl ~rti-l~
Ten g polycaprolactone tetrol (Lot 1~17360-lO from Union Carbide, Mn 7240), 38.4 g L-Lactide and 1.6 g of 20 D,L-Lactide were charged under argon to a carefully dried Helicone$ C2V mixer (Atlantic Research Corp. ), held at 161C . After lO minutes stirring, 0 . 615 mL of a 0.45 M solution (AMSCO 140) of La(2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst 25 was added via syringe. A~ter 15 minutes, the pale yellow, viscous polymer melt was drained and riuenched into water. Tg was 10C. Mn was 36, 400 and Mw/Mn was 1.3. TEM = 11.7 MPa, 247%, 303 MPa.
Ex~MPT ~ 5 G1 ~qq Tran~ition vs . C~ osition Study Polycaprolactone tetrol (# arms=4; Lot ~17360-10 from Union Carbide, Mn 7240) and lactide in varying amounts were charged to flame-dried Pyrex~D test tubes in a nitrogen filled glove-box, capped with rubber septa, ~-nd heated in a vapor bath at 140 or 166C. After SUB~llUrE SHEE~ (RUL~ 2~) ~ Wo 95/29200 2 1 8 7 6 2 a ~ ~IIL 14 allowing 5 minutes for the molten monomer mixture to come to temperature, La(2,2,6,6-tetramethylheptane-3,5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via long-needle microsyringe with vigorous shalcing. When -. 5 the polymerization was complete, as evidenced by high vLscosity, a small sample was removed and quenched into water and dried. The polymers were then dissolved at room temperature in dichloromethane and precipitated with r~pid stirring into 5 volumes of methanol, in order to remove residual lactide monomers. The compositions and analytical results are shown below.
TeD~I Catalyst R:~n Mn Tg Sample ~ l~cdde % CLI ~L) ('C) (GPC)
E~SILY DEGRADABLE STAR-BLOCR COPOLYMERS
FIFT n OF TTIF TNVENTION
Disclosed herein 2re easLly hydro- and 5 bio~ rA~T~hle stsr-block copolymers of caprolactone and lactlde. Even though of relatlvely low molecular weight, the copolymers are tough elastomer-llke materials .
TFr~TNIr2T. Bp~rp~r~RollNr) Polymers, particularly thermoplastics, are in theory recyclable, but are often not recycled because of the cost of collecting, sorting and purifylng the recycled plastics. Therefore, most plastics and other polymers such as elastomers, are disposed of with other trash, such as in lAn-lf~llc, where they are very chemically stable, and degrade min~r'lly. One way of reducing the amount of stable polymers in landfills and the llke ls to produce polymers which are degradable, as by hydrolysis, biodegradation, or like processes.
It is known that under the proper conditions, polylactlde ls blodegradable, and polymers C~ntA~n~n~
this repeat unit have been considered desirable for this reason. However, most polylactide polymers are plastics, that ls thelr glass transition temperature ~Tg) is above room temperature, and they may be crystalline. Polymers which contain lactide repeat units but yet have elastomeric-like properties would also be desirable.
~.S. Patent 5,210,108 describes foam made from 2 star shaped polymer containing lactide repeat units.
The foams produced are rigid, not elastomeric.
D ~. Gri jpma, et al., MAkrom~l . Cht~m . FA~id Commun., vol. 14, p. 155-;61 (1992) report the synthesis of star block copolymers having polylactide blocks and trimethylene carbonate or A mixture of trimethylene W0 95129200 ~ ` r~J,~ 14 z carbonate and another lactone block. These copolymers have polylactide ~rg ' s of 50-55C .
SUMMA~Y OF TE~F INVF:NTION
This invention concerns, a star-block copolymer, 5 consisting essentially of, a core, 3 to about 20 inner arms of polycaprolactone which are bound to said core, and polylactide outer arms bound to said inner arms, and provided that:
said polylactide is at least 50% by weight of0 said copolymer;
said polycaprolactone is about 10% to about 50% by weight of said copolymer;
said polycaprolactone and said polylactide do not crystallize upon melt processing; and said polylactide has a glass transition temperature of less than 35C.
DETATT c OF T~F. INVENTION
The inst2nt copolymer is a star-block copolymer which contains polycaprolactone and polylactide blocks.
The copolymer also contains a core, which is often the "starting point" for the copolymer. The core is originally a multi-functional material usually containing the same number of functional groups as arms which the star copolymer is meant to have. By functional group in this instance is meant a group which either by itself, or by a reaction of the group, forms a site for the initiation of one copolymer chain (an arm of the star). In this case it will initiate the polymerization of caprolactone.
Suitable functional groups for the core include hydroxyl, amino, and sulfhydryl. These may be used in standard ways to initiate the polymerization of caprolactone. For instance, a catalyst such as stannous octoate may be used. Such polymerizations are described 35 in European Patent Application 117, 538, which is hereby 218762~
WO 95/29200 ~ r~ 014 3 I.
Lncluded by reference. The polymerization mzy ~e done neat (no solvent) or with a solvent pre3ent.
The polysaprolactone herein i5 formed from epsilon-caprolactone, which i5 the monomer. The polycapro-lactone forms the "inner arm" of the copolymer herein.
An inner arm is the polymer which is attached or bonded J to the core. Since the Tg of polycaprolactone is quite low (below 0C) this property does not generally affect the rigidity of the product of the invention. ~owever, 10 polycaprolactone does partially crystallize if the molecular weight is hlgh enough. Therefore, the molecular weight of the polycaprolactone blocks should be low enough so that such cryst~ 7~t~on does not take place upon melt processng. A useful molecular weight 15 range for the polycaprolactone inner arm is a number average molecular weight of about 800 to about 4000. It is preferred if the polycaprolactone is about 10% to about 40% by weight of the copolymer, more preferred if it Ls about 15% to about 30%, and especially preferred 20 i~ it is about 18~ to about 22% by weight of the copolymer .
When caprolactone is polymerized, the end group is normally a hydroxyl group, which can be used to help initiate the polymerization of lactide. Therefore, the 25 lactide polymer block becomes bound (attached) to the end of the polycaprolactone block, and herein this is called the outer arm. Lactide in the D, L, or meso forms, or any combination thereof, may be used to form the polylactide block. Lactide homopolymer is semi-30 crystalline, and has a Tg of about 55-60C. Therefore the polylactide block should be small enough (low in molecular weight) so that the Tg is 35C or less, preferably 30C or less. A typical useful ranse of polylactide block sizes is about 1, 000 to about 12, 000 35 in number average molecular weight, but this will var~
~187625 WO 95t29200 . ~ ~
somewhat with the size of the pQlycaprQlactone block.
It is preferred that the number average molecular weight of eQch polylactide block is abQut 3, 000 Qr more. It is also preferred if the pQlylactide is at least 70% by weight of the copolymer.
The pQlylactide blQck is fQrmed by the pQlymerization of lactide itself. This polymerization can be carried out in a number Qf ways, but it is usually dQne with a catalyst. Stannou3 octoate is a useful catalyst, but preferred catalysts are selected rare earth metal r~ oun~c, such as those disclosed in U.S. Patents 5,028,667 and 5,292,859, which are both hereby ;n~lu~d by reference. The catalysts disclosed in the latter patent are especially preferred. These polymerizatiQns are carried out neat or with solvent present, but neat (no solvent present) pQlymerizations are preferred. ~olymerization temperatures are not critical, and 0C to abQut 200CC is a cQnvenient range.
The polymerization of the caprolactone and lactide can be done in sequential steps in the same reactor, or the polycaprolactone ~attached tQ the cQre) star polymer may be isolated and then mixed with lactide to be polymerized to iorm the final copQlymer.
The star-block cQpQlymers herein have 3 to 20 arms, preferably 3 to 10 arms, more preferably 3 to 6 arms, and especially preferably 4 arms.
The cQpolymers described herein are relatively tough, elastomeric-like materials that are suitable fQr many uses. Among these uses are liquid food packaging, such as milk pouches, juice pouches, coatings fQr coated board for refrigerated li~uids, and processed meat wrap;
dry fQod packaging such as the outer w~ap for boxed foods, as part of a multilayer packaging film, and as the cQating Qn cQated bQard for frozen foods; coating for coated board for fast food, such as for drink cups;
21~62~
~ Wo 95/29200 . ~1ll 14 other consumer products such as non-woven absor~ants for diapers, soft pliable baclcsheet for diapers, film overwrap for toiletries and personal care productsi agricultural products such as mulch film; medical 5 products such as pliable wound dressings and low modulus surgical implants; as a toughening additive for other polymers, such as polymers used for foams or blow molding and a modifier for polymer to be spun into fibers for improved elongation and tenacLty; and other 10 uses such as adhesives, film overwrap for animal feed supplements, and artiflcial snow. The copolymer dLsclosed herein is particularly useful in these applications because of its biodegradability, toughn~ss, tear strength and soft feel.
~he copolymers herein should not be crystalline, i.e., should not have a melting transition of greater than 3 J/g when tested by Differential Scanning calorimetry (see test for Tg below) upon melt processing. The sample for such a test is prepared by 20 in~ection molding some of the copolymer in question into a 3 . 2 mm thick plaque, with the mold temperature being about 10C, and the copolymer having a melt temperature (exiting the screw barrel) of about 150C.
~olecular weight measurements herein are made by 25 Gel Permeation Chromatography using polystyrene standards. The average molecular weight of a polylactide outer arm is the number average molecular weight of the copolymer times the weight fraction of polylactide in the copolymer divided by the nominal 30 number of arms in the copolymer. Similarly, the average molecular weight of the polycaprolactone inner arm is the number average molecular weight of the copolymer times the weight ~raction of polycaprolactone in the copolymer divided by the nominal number of arms in the 35 copolymer.
WO 95l29200 ~1816 2 ~ . F~ J.,9~ ~ ~q The glass transition temper2ture (Tg) of the copolymer ~particularly the polylactide blocks) is measured by the following procedure. About 0.5 g of copolymer is dissolved in 5 mL of methylene chloride and 5 the resulting solution is added dropwise to 50 mL of rapidly stirred methanol (this is done to remove any free lactide in the copolymer, which acts as a plasticizer). The precipitated fluff is collected via i'iltration and/or rlprAnt~t; ~n and dried in vacuo at room 10 temperature. lH-NMR at 300 ~Hz is used to verify that no residual lactide remains in the copolymer.
Dlfferential Sr~nn~nr~ Calorimetry ~DSC) is performed using a TA Instruments 2100 analyzer, with a 5-10 mg sample in a covered, sealed, standard aluminum pan. The 15 heating rate is 10C/min. The Tg is taken as the midpoint of the step transition. It is preferred if the Tg of the polylactide in the copolymer is 30C or less.
In the f ollowing examples, Mn is number average molecular weight and Mw is weight average molecular 20 weight.
~T'NT'R~T. AN~T.YTI~ri~T, DET~.rT.':
Molecular weights were measured using size exclusion chromatography (SEC, GPC) in THF solvent at 25C using polystyrene calibration standards. Residual 25 lactide monomer and total caprolactone contents are measured using lH-NMR at 300 MHz. Physical properties were measured using a Laboratory Microsystems tester at 9.1 kg full scale load range and a crosshead speed oi 5.1 cm per minute. The reported values are the mean of 30 at least five determinations. Film samples (0 . 025-0 . 050 mm in thickness) were prepared by compression molding at 150 to 180C and a pressure of ~rom 6.9 to 39.5 MPa depending on the flow characteristics of the individual polymer sample.
~ W0 95l29200 2 1 ~ 7~ 2 S r~ 014 F:xAMPT ~ 1 Synthe~is of 14~ Caorolactone 4-~rm StAr ~lork Polylactlde Seven g polycaprolactone tetrol ~Lot ~17360-10 from Union Carbide, Mn 7240), 41.3 g L-Lactide and 1.7 g of D, L-Lactide were charged under argon to a carefully dried Helicone~l9 C2V mixer ~Atlantic Research Corp. ), held at 164C. After 10 minutes stirring, 0 . 657 mL of a 0.45 M solution ~140 Solvent 66/3 from Unocal, hereafter referred to as AMSCO 140) of La ~2, 2, 6, 6-tetramethyl-heptane-3, 5-dionate) 3-bis ~ethoxyet~ylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and ryuenched into water. Lactide conversion and caprolactone content by lH-nmr were 92 . 4, and 11% respectively, and Tg was 27C.
Mn was 40, 000 and Mw/Mn was 1.4 . Tensile strength, 96 elongation and modulus ~hereafter referred to as TEM) were 103 MPa, 137~i, 448 M~a, respectively, as measured on a compression molded film.
EXAM~T ~ 2 Synthe~lc of 10% C~orolActrne 3--Arm StAr Elock PolylActide Five g polycaprolactone triol ~Lot ~16874-95 from Union Carbide, Mn 5260), 43.2 g L-Lactide and 1.8 g of 25 D, L-Lactide were charged under argon to a carefully dried Helicone~ C2V mixer (Atlantic P~esearch Corp . ), held at 164C . After 10 minutes stirring, 0 . 687 mL of a 0.45 M solution ~AMSCO 140) of La~2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis ~ethoxy-ethylether) catalyst 30 was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and r~uenched into water. Tg was 19C. Mn was 39, 000, and Mw/Mn was 1.6. T~M -- 3.5 MPa, 210~, 82.7 MPa.
.
~18762a W0 95l29200 ; ~ ~ P~ 4 E~r~PL~ 3 Synth~qis of 20% (';~rol ;~ctone 3-~rm St~r ;310ck Polyl~--tide Ten g polycaprolactone triol (Lot ~t16874-95 from Union Carbide, Mn 5260), 38 . 4 g L-Lactide and 1. 6 g of D,L-Lactide were charged under argon to a carefully dried TTel 1 rrn~$ C2V mixer (Atlantic Research Corp . ), held at 167C . After 10 minutes stirring, 0. 615 mL of a 0.45 M solution (AMSCO 140) of La(2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and rluenched into water. Tg was 20C. Mn was 63, 000 and Mw/Mn was 1.2. TEM = 3.5 MPa, 123%, 110 MPa.
Ex~SPL~ 4 - S~nth~qiq of 20% ~rol~ctrne 4-,~rm St P r Rl ork Polyl ~rti-l~
Ten g polycaprolactone tetrol (Lot 1~17360-lO from Union Carbide, Mn 7240), 38.4 g L-Lactide and 1.6 g of 20 D,L-Lactide were charged under argon to a carefully dried Helicone$ C2V mixer (Atlantic Research Corp. ), held at 161C . After lO minutes stirring, 0 . 615 mL of a 0.45 M solution (AMSCO 140) of La(2,2,6,6-tetramethyl-heptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst 25 was added via syringe. A~ter 15 minutes, the pale yellow, viscous polymer melt was drained and riuenched into water. Tg was 10C. Mn was 36, 400 and Mw/Mn was 1.3. TEM = 11.7 MPa, 247%, 303 MPa.
Ex~MPT ~ 5 G1 ~qq Tran~ition vs . C~ osition Study Polycaprolactone tetrol (# arms=4; Lot ~17360-10 from Union Carbide, Mn 7240) and lactide in varying amounts were charged to flame-dried Pyrex~D test tubes in a nitrogen filled glove-box, capped with rubber septa, ~-nd heated in a vapor bath at 140 or 166C. After SUB~llUrE SHEE~ (RUL~ 2~) ~ Wo 95/29200 2 1 8 7 6 2 a ~ ~IIL 14 allowing 5 minutes for the molten monomer mixture to come to temperature, La(2,2,6,6-tetramethylheptane-3,5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via long-needle microsyringe with vigorous shalcing. When -. 5 the polymerization was complete, as evidenced by high vLscosity, a small sample was removed and quenched into water and dried. The polymers were then dissolved at room temperature in dichloromethane and precipitated with r~pid stirring into 5 volumes of methanol, in order to remove residual lactide monomers. The compositions and analytical results are shown below.
TeD~I Catalyst R:~n Mn Tg Sample ~ l~cdde % CLI ~L) ('C) (GPC)
2.8 7.2 25.6 74 140 36000 25 22.6 7A 2A.3 76 140 38100 23 32.4 7.6 20.4 78 140 42400 25 42.2 7.8 20.5 80 140 46200 28 52.0 8.0 19.7 82 140 45000 30 61.8 8.2 16.7 84 140 51500 34 71.6 8A 14.7 86 140 54400 36 1% CL = wl ~ caprolactone, by IH-nmr ~XAMPLF 6 Synthesi~ of 22~ Ca~1rolactone 4-Arm Star Block Polvl~ctide Eleven g of polycaprolactone tetrol (Lot ~17360-10 from Union Carbide, ~qn 72gO) and 39 g L-Lactide were charged under argon to a carefully dried Helicone~2~ C2V
mixer (Atlantic Research Corp. ), held at 167C. After 10 minutes stirring, 0 . 615 mL of a 0 . 45 M solution (A~SCO 140) of La(2,2,6,6-tetramethylheptane-3,5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
Lactide conversion and caprolactone content by 1H-nmr Wo 9~/29200 2 1 8 7 6 2 5 . ~ I / L~ ~ 14 were 95.1, and 22% respectively, 2nd Tg was 18~C. Mn wa3 34,200 and Mw/Mn was 1.3. TEM ~ 13.1 MPa, 94~, 351 MPa.
EXAMPL~ 7 Synth~sis of 24~ Ca~rolactone 4-Arm St~r E~lock Polyl~ct1de Twelve g polycaprolactone tetrol (Lot ~17360-10 from Union Carbide, Mn 7240) and 38 g L-Lactide were charged under argon to a carefully dried Helicone~9 C2V
mixer ~Atlantic Research Corp. ), held at 163C. After lO minutes stirring, 0 . 615 mL of a 0 . 45 M solution (AMSCO 140) of La (2, 2, 6, 6-tetramethylheptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
Lactide conversion and caprolactone content by lE~-nmr were 92.8, and 25% respectively, and Tg was 16C. Mn was 32,200 and Mw/Mn was 1.3. TEM - 9.7 MPa, 84%, 214 MPa.
EXAMPLr 8 Synthosi~ of 20% t'~rol~ctone 4--Arm St~r ~310ck Polylactide Ten g polycaprolactone tetrol (Lot $17360-lO from Union Carbide, Mn 7240) and 40 g L-Lactide were charged under zrgon to a carefully dried E~elicone~D C2V mixer (Atlantic Research Corp. ), held at 167C . After 15 minutes stirring, 0 . 615 mL of a 0 . 45 M solution (AMSCO 140) of La (2, 2, 6, 6-tetramethylheptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
L2ctide conversion and caprolactone content by lEI-nmr were 94.8, and 21~ respectively, and Tg was 23C, Mn was 38,300 and Mw/Mn was 1.4. TEM ~ 14.5 MPa, 316~, 503 MPa.
~O 95/29200 2 1 ~ 7 ~ 2 5 ~ u~ 14 RXP,~rPT.r. 9 Svnth~qi q of 20% Ca~rolActone 4--Arm Star ;310ck Polyl~ctit1~ ~Tin Oc:toate ~t~lyst) One g polycaprolactone tetrol ~Lot 3~17360-10 from 5 Union Carbide, Mn 7240) and 4 g L-Lactide were charged to a flame-dried Pyrex(~) test tube in a nitrogen iilled glove-box, capped with rubber septa, and heated in 2 vapor bath at 166C. After allowing 5 minutes ~or the molten mixture to come to temperature, 37 microliters o~
10 a O . 49 M toluene solution OI' stannous octoate catalyst was added via long-needle microsyringe with vigorous shaking. When the polymerization was complete, as evidenced by high viscosity, a small sample was removed ~nd ~uenched lnto water and dried. Lactide conversion and caprolactone content by lEI-nmr were 94 .3 and 17 . 89 respectively, and Tg was 25C, Mn was 49,100 and ~w/Mn was 1.2.
mixer (Atlantic Research Corp. ), held at 167C. After 10 minutes stirring, 0 . 615 mL of a 0 . 45 M solution (A~SCO 140) of La(2,2,6,6-tetramethylheptane-3,5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
Lactide conversion and caprolactone content by 1H-nmr Wo 9~/29200 2 1 8 7 6 2 5 . ~ I / L~ ~ 14 were 95.1, and 22% respectively, 2nd Tg was 18~C. Mn wa3 34,200 and Mw/Mn was 1.3. TEM ~ 13.1 MPa, 94~, 351 MPa.
EXAMPL~ 7 Synth~sis of 24~ Ca~rolactone 4-Arm St~r E~lock Polyl~ct1de Twelve g polycaprolactone tetrol (Lot ~17360-10 from Union Carbide, Mn 7240) and 38 g L-Lactide were charged under argon to a carefully dried Helicone~9 C2V
mixer ~Atlantic Research Corp. ), held at 163C. After lO minutes stirring, 0 . 615 mL of a 0 . 45 M solution (AMSCO 140) of La (2, 2, 6, 6-tetramethylheptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
Lactide conversion and caprolactone content by lE~-nmr were 92.8, and 25% respectively, and Tg was 16C. Mn was 32,200 and Mw/Mn was 1.3. TEM - 9.7 MPa, 84%, 214 MPa.
EXAMPLr 8 Synthosi~ of 20% t'~rol~ctone 4--Arm St~r ~310ck Polylactide Ten g polycaprolactone tetrol (Lot $17360-lO from Union Carbide, Mn 7240) and 40 g L-Lactide were charged under zrgon to a carefully dried E~elicone~D C2V mixer (Atlantic Research Corp. ), held at 167C . After 15 minutes stirring, 0 . 615 mL of a 0 . 45 M solution (AMSCO 140) of La (2, 2, 6, 6-tetramethylheptane-3, 5-dionate) 3-bis (ethoxy-ethylether) catalyst was added via syringe. After 15 minutes, the pale yellow, viscous polymer melt was drained and quenched into water.
L2ctide conversion and caprolactone content by lEI-nmr were 94.8, and 21~ respectively, and Tg was 23C, Mn was 38,300 and Mw/Mn was 1.4. TEM ~ 14.5 MPa, 316~, 503 MPa.
~O 95/29200 2 1 ~ 7 ~ 2 5 ~ u~ 14 RXP,~rPT.r. 9 Svnth~qi q of 20% Ca~rolActone 4--Arm Star ;310ck Polyl~ctit1~ ~Tin Oc:toate ~t~lyst) One g polycaprolactone tetrol ~Lot 3~17360-10 from 5 Union Carbide, Mn 7240) and 4 g L-Lactide were charged to a flame-dried Pyrex(~) test tube in a nitrogen iilled glove-box, capped with rubber septa, and heated in 2 vapor bath at 166C. After allowing 5 minutes ~or the molten mixture to come to temperature, 37 microliters o~
10 a O . 49 M toluene solution OI' stannous octoate catalyst was added via long-needle microsyringe with vigorous shaking. When the polymerization was complete, as evidenced by high viscosity, a small sample was removed ~nd ~uenched lnto water and dried. Lactide conversion and caprolactone content by lEI-nmr were 94 .3 and 17 . 89 respectively, and Tg was 25C, Mn was 49,100 and ~w/Mn was 1.2.
Claims (13)
1. A star-block copolymer, consisting essentially of, a core, 3 to about 20 inner arms of polycaprolactone which are bound to said core, and polylactide outer arms bound to said inner arms, and provided that:
said polylactide is at least 50% by weight of said copolymer;
said polycaprolactone is about 10% to about 50% by weight of said copolymer;
said polycaprolactone and said polylactide do not crystallize upon melt processing; and said polylactide has a glass transition temperature of less than 35°C.
said polylactide is at least 50% by weight of said copolymer;
said polycaprolactone is about 10% to about 50% by weight of said copolymer;
said polycaprolactone and said polylactide do not crystallize upon melt processing; and said polylactide has a glass transition temperature of less than 35°C.
2. The star-block copolymer according to Claim 1 wherein a number average molecular weight for each of the inner arms of polycaprolactone is about 800 to about 4000.
3. The star-block copolymer according to Claim 1 wherein the polycaprolactone is about 15% to 30% by weight of the star-block copolymer.
4. The star-block copolymer according to Claim 2 wherein the polycaprolactone is about 18% to about 22%
by weight of the star-block copolymer.
by weight of the star-block copolymer.
5. The star-block copolymer according to Claim 1 wherein a number average molecular weight for each of the polylactide outer arms is about 1,000 to about 12,000.
6. The star-block copolymer according to Claim 5 wherein a number average molecular weight of each of the polylactide outer arms is about 3,000 or more.
7. The star-block copolymer according to Claim 1 wherein the polylactide is at least 70% by weight of the copolymer.
8. The star-block copolymer according to Claim 1 wherein the star-block copolymer has 3 to 10 arms.
9. The star-block copolymer according to Claim 8 wherein the star-block copolymer has 3 to 6 arms.
10. The star-block copolymer according to Claim 9 wherein the star-block copolymer has 4 arms.
11. The star-block copolymer according to Claim 4 wherein the star-block copolymer has 4 arms.
12. The star-block copolymer according to Claim 1 wherein said glass transition temperature is 30°C or less.
13. The star-block copolymer according to Claim 11 wherein said glass transition temperature is 30°C or less.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/230,994 US5399666A (en) | 1994-04-21 | 1994-04-21 | Easily degradable star-block copolymers |
| US08/230,994 | 1994-04-21 |
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| CA002187625A Abandoned CA2187625A1 (en) | 1994-04-21 | 1995-03-13 | Easily degradable star-block copolymers |
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| US (1) | US5399666A (en) |
| EP (1) | EP0756608A1 (en) |
| JP (1) | JPH09512571A (en) |
| CN (1) | CN1146775A (en) |
| AU (1) | AU1988395A (en) |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1232285A (en) * | 1983-02-24 | 1988-02-02 | Linda A. Domeier | Polyester polyols and a process for their production |
| US5028667A (en) * | 1989-09-29 | 1991-07-02 | E.I. Du Pont De Nemours And Company | Yttrium and rare earth compounds catalyzed lactone polymerization |
| US5292859A (en) * | 1992-12-22 | 1994-03-08 | E. I. Du Pont De Nemours And Company | Rare earth metal coordination compounds as lactone polymerization catalysts |
| US5225521A (en) * | 1991-12-31 | 1993-07-06 | E. I. Du Pont De Nemours And Company | Star-shaped hydroxyacid polymers |
| US5210108A (en) * | 1992-07-29 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Degradable foam materials |
-
1994
- 1994-04-21 US US08/230,994 patent/US5399666A/en not_active Expired - Fee Related
-
1995
- 1995-03-13 AU AU19883/95A patent/AU1988395A/en not_active Abandoned
- 1995-03-13 EP EP95912859A patent/EP0756608A1/en not_active Ceased
- 1995-03-13 WO PCT/US1995/003014 patent/WO1995029200A1/en not_active Application Discontinuation
- 1995-03-13 JP JP7527629A patent/JPH09512571A/en active Pending
- 1995-03-13 CN CN95192679A patent/CN1146775A/en active Pending
- 1995-03-13 CA CA002187625A patent/CA2187625A1/en not_active Abandoned
-
1996
- 1996-10-18 FI FI964217A patent/FI964217A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI964217A (en) | 1996-10-18 |
| CN1146775A (en) | 1997-04-02 |
| AU1988395A (en) | 1995-11-16 |
| WO1995029200A1 (en) | 1995-11-02 |
| FI964217A0 (en) | 1996-10-18 |
| US5399666A (en) | 1995-03-21 |
| EP0756608A1 (en) | 1997-02-05 |
| JPH09512571A (en) | 1997-12-16 |
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