`
`PCT
`
`WORLD INTELLECTUAL PROPERTY ORGANIZATlON
`International Bureau
`
`
`
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`(51) International Patent Classification 6 3
`(11) International Publication Number:
`WO 97/11106
`C08G 63/199
`
`(43) International Publication Date:
`
`27 March 1997 (27.03.97)
`
`PCT/US96/ 14873
`(21) International Application Number:
`(22) International Filing Date:
`17 September 1996 (17.09.96)
`
`(81) Designated States: AU, BR, CA, CN, IL, JP, KR, MX, NO,
`NZ, European patent (AT, BE, CH, DE, DK, ES, FI, FR,
`GB, GR, IE, IT, LU, MC, NL, PT, SE).
`
`Published
`With international search report.
`Before the expiration of the time limit for amending the
`claim and to be republished in the event of the receipt of
`amendments.
`
`(30) Priority Data:
`08/531,495
`
`21 September 1995 (21.09.95)
`
`US
`
`(71) Applicant: EASTMAN CHEMICAL COMPANY [US/US];
`100 North Eastman Road, Kingsport, TN 37660 (US).
`
`(72) Inventors: HOFFMAN, Douglas, Claire; 1016 Timberidge
`Trail, Kingsport, TN 37660 (US). PECORINI, Thomas.
`Joseph; 208 Remington Court, Kingsport, TN 37663 (US).
`DICKERSON, James, Palmer;
`28 Willowbrook Drive,
`Kingsport, TN 37660 (US). DeLOACH, Joseph, Alexander;
`596 A A Deakins, Jonesborough, TN 37659 (US).
`
`(74) Agent: BOSHEARS, Betty, Joy; PO. Box 511, Kingsport, TN
`37662-5075 (US).
`
`
`
`(54) Title: POLYESTER MOLDING COMPOSITIONS
`
`(57) Abstract
`
`This invention relates to a molded object prepared from a copolyester having an inherent viscosity of 0.4 to 1.1 dL/g, wherein the acid
`component comprises repeat units from 90 to 40 mole % terephthalic acid and from 10 to 60 mole % of one or more additional dibasic acids
`selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic
`acid, and stilbenedicarboxylic acid; wherein the glycol component comprises repeat units from 1,4-cyclohexanedimethanol.
`
`
`
`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the PCT on the front pages of pamphlets publishing international
`applications under the PCT.
`
`Viet Nam
`
`United Kingdom
`Georgia
`Guinea
`Greece
`Hungaw
`Ireland
`Italy
`Japan
`Kenya
`Kyrgystan
`Democratic People‘s Republic
`of Korea
`Republic of Korea
`Kazakhstan
`Liechtenstein
`Sri Lanka
`Liberia
`Lithuania
`Luxembourg
`Latvia
`Monaco
`Republic of Moldova
`Madagascar
`Mali
`Mongolia
`Mauritania
`
`AM
`AT
`AU
`BB
`BE
`BF
`BG
`BJ
`BR
`BY
`CA
`CF
`CG
`CH
`CI
`CM
`CN
`CS
`CZ
`DE
`DK
`EE
`ES
`Fl
`FR
`GA
`
`Armenia
`Austria
`Australia
`Barbados
`Belgium
`Burkina Faso
`Bulgaria
`Benin
`Brazil
`Belarus
`Canada
`Central African Republic
`Congo
`Switzerland
`Cote d’Ivoire
`Cameroon
`China
`Czechoslovakia
`Czech Republic
`Germany
`Denmark
`Estonia
`Spain
`Finland
`France
`Gabon
`
`Malawi
`Mexico
`Niger
`Netherlands
`Norway
`New Zealand
`Poland
`Portugal
`Romania
`Russian Federation
`Sudan
`Sweden
`Singapore
`Slovenia
`Slovakia
`Senegal
`Swaziland
`Chad
`Togo
`Tajikistan
`Trinidad and Tobago
`Ukraine
`Uganda
`United States of America
`Uzbekistan
`
`
`
`
`
`WO 97/11106
`
`PCT/US96/l 4873
`
`POLYESTER MOLDING COHPOSITIONS
`
`This invention relates to certain molded objects
`
`comprising poly(1,4—cyclohexylenedimethylene
`
`terephthalate) copolyesters which have improved
`
`toughness, clarity and stress crack resistance.
`
`Background of the Invention
`
`Various polymeric materials have been widely used
`
`over the past 60 years for molding toothbrushes,
`
`tool
`
`handles, windshield scrapers, steering wheels, hair
`
`brushes, cutlery, eyeglass frames and the like.
`
`In many
`
`of these applications,
`
`the molded part must be clear,
`
`tough,
`
`impact resistant, stress crack resistant,
`
`hydrolysis resistant as well as having a pleasing feel
`
`and appearance.
`
`Plasticized cellulose acetate propionate (CAP)
`
`compositions have been used successfully in the past for
`
`toothbrush handles.
`
`Such compositions have good
`
`clarity, sparkle and overall appearance. However,
`
`design changes in toothbrush handles to increase the
`
`bristle density has led to cracking in certain brushes.
`
`The cracks which occur during bristle insertion are a
`
`result of insufficient weld—line strength.
`
`Increased
`
`plasticizer concentrations improve the weld—line
`
`strength but this leads to decreased stiffness which can
`
`result in inadequate bristle retention.
`
`Certain rigid polyurethane materials have been
`
`evaluated in this application but this polymer is
`
`difficult to mold, and the urethane linkages in the
`
`polymer chain can hydrolyze in the presence of moisture
`
`during molding.
`
`Polyester materials such as poly(ethylene
`
`terephthalate)
`
`(PET) and poly(1,4-
`
`cyclohexylenedimethylene terephthalate)
`
`(PCT) have many
`
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`WO 97/11106
`
`PCT/U896” 4873
`
`desirable properties for molded parts but these polymers
`
`are readily crystallizable and provide hazy or opaque
`objects when molded in thick parts. Modification of PET
`
`polymers with high levels of glycol components other
`
`tough molded parts
`than ethylene glycol provide clear,
`but they tend to stress crack in the presence of certain
`
`toothpaste solutions containing mint oil.
`
`For example, U. S. Patent 2,901,466 (1959) assigned
`to Eastman Kodak Company describes a wide range of
`linear polyesters and polyesteramides derived from 1,4—
`cyclohexanedimethanol
`(CHDM). Many of the compositions
`are readily crystallizable and molded parts are hazy or
`
`opaque. Thus,
`objects.
`
`they are not suitable for clear, molded
`
`There is a need in the art, therefore, for molding
`compositions which have visual clarity and which have
`
`improved molding and physical property requirements.
`
`Summary of the Invention
`
`This invention relates to molded objects prepared
`
`from a copolyester having an inherent viscosity of 0.4
`
`to 1.1 dL/g,
`
`wherein the acid component comprises repeat
`
`units from 90 to 40 mole % terephthalic acid and
`
`from 10 to 60 mole % of one or more additional
`
`dibasic acids selected from the group consisting of
`isophthalic acid, cyclohexanedicarboxylic acid,
`
`naphthalenedicarboxylic acid, diphenyldicarboxylic
`acid, and stilbenedicarboxylic acid; and,
`
`wherein the glycol component comprises repeat
`
`units from 1,4—cyclohexanedimethanol.
`
`These molded objects have the advantage of having
`improved clarity and stress crack resistance.
`They also
`have good physical properties including strength,
`stiffness,
`impact resistance and hydrolysis resistance.
`
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`W0 97/] l l 06
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`PCT/U596“ 4873
`
`Brief Description of the Drawings
`
`Fig. 1 — illustrates the molded plaques used to
`
`determine chemical resistance
`
`5
`
`Fig. 2 —
`
`illustrates the testing apparatus used to
`
`determine stress crack resistance
`
`Description of the Invention
`
`It has been found that certain PCT copolyesters are
`
`10
`
`highly suitable for molding clear,
`
`tough, stress crack
`
`resistant parts.
`
`The molded objects are prepared from a copolyester
`
`having an inherent viscosity of 0.4 to 1.1 dL/g,
`
`where the acid component comprises repeat
`
`15
`
`units from 90 to 40 mole %, preferably 85 to 52
`
`mole %, more preferably, 83 to 52 mole %
`
`terephthalic acid and from 10 to 60 mole %,
`
`preferably 15 to 48 mole, preferably 17 to 48 mole
`
`%, of one or more additional dibasic acids selected
`
`20
`
`from the group consisting of isophthalic acid,
`
`cyclohexanedicarboxylic acid,
`
`naphthalenedicarboxylic acid, diphenyldicarboxylic
`
`acid, and stilbenedicarboxylic acid;
`
`_
`
`where the glycol component comprises repeat
`
`25
`
`units from 1,4—cyclohexanedimethanol, preferably 80
`
`to 100 mole % 1,4—cyclohexanedimethanol, more
`
`preferably, 85 to 100 mole %, even more preferably
`
`90 to 100 mole %, and even more preferably 95 to
`
`100 mole %.
`
`30
`
`When using the cyclohexanedicarboxylic acids,
`
`they may be in the cis or trans forms or as Gig/trans
`
`isomer mixtures.
`
`The lower alkyl esters, such as the
`
`methyl esters, may be used instead of the dibasic acids
`
`in preparing the molding compositions of this invention.
`
`
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`W0 97/11 106
`
`PCT/US96/l4873
`
`When cyclohexanedicarboxylic acid is used, 1,3~ and
`
`l,4—cyclohexanedicarboxylic acid are preferred. When
`
`naphthalenedicarboxylic acid is used, 2,6—, 2,7—, 1,4—
`
`and 1,S—naphthalenedicarboxylic acid are preferred.
`
`5
`
`The molded objects of the invention, may comprise
`
`up to 10 mole % of even further additional dibasic
`
`acids. These dibasic acids may be selected from one or
`
`more of the group consisting of aromatic dicarboxylic
`acids, aliphatic dicarboxylic acids, and cycloaliphatic
`dicarboxylic acids, each preferably having 4 to 40
`
`10
`
`carbon atoms. More specifically,
`
`these additional
`
`dibasic acids can be selected from one or more of the
`
`group consisting of phthalic acid, cyclohexanediacetic
`
`acid, succinic acid, glutaric acid, adipic acid, azelaic
`
`15
`
`acid, sebacic acid,
`
`isophthalic acid,
`
`cyclohexanedicarboxylic acid, naphthalenedicarboxylic
`
`acid, diphenyldicarboxylic acid, and
`
`stilbenedicarboxylic acid.
`
`Preferred additional carboxylic acids are selected
`
`20
`
`from the group consisting of isophthalic acid,
`
`cyclohexanedicarboxylic acid, naphthalenedicarboxylic
`
`acid, diphenyldicarboxylic acid, and
`
`stilbenedicarboxylic acid.
`
`Even more preferred
`
`25
`
`additional dibasic acids include isophthalic acid,
`~cyclohexanedicarboxylic acid and naphthalenedicarboxylic
`acid.
`
`The glycol component may contain up to 20 mole % of
`
`one or more additional aliphatic or alicyclic glycols,
`
`preferably containing 2 to 20 carbon atoms. These
`
`30
`
`additional glycols may be selected from the group
`
`consisting of ethylene glycol, diethylene glycol,
`
`triethylene glycol, propanediol, butanediol,
`
`pentanediol, hexanediol, neopentyl glycol and
`
`tetramethylcyclobutanediol. Ethylene glycol is
`
`35
`
`particularly preferred.
`
`
`
`
`
`WO 97/11106
`
`PC17US96H4873
`
`Very small amounts (less than 1.5 mole%) of certain
`
`branching agents such as trimellitic anhydride,
`
`trimellitic acid, pyromellitic dianhydride,
`
`trimesic
`
`acid, hemimellitic acid, glycerol,
`
`trimethylolpropane,
`
`pentaerythritol, 1,2,4—butanetriol, 4,2,6-hexanetriol,
`
`sorbitol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane,
`
`dipentaerythritol and the like may be used.
`
`The copolyesters of this invention are readily
`
`prepared using melt phase or solid state
`
`10
`
`polycondensation procedures well known in the art.
`
`They
`
`may be made by batch or continuous processes.
`
`Examples
`
`of these processes can be found in U.S. Patent Nos.
`
`4,256,861, 4,539,390, and 2,901,466 and include
`
`preparation by direct condensation or by ester
`
`15
`
`interchange.
`
`Specifically,
`
`the polymers of this invention may be
`
`prepared according to the methods described in United
`
`States Patent 2,901,466. However,
`
`the preparation of
`
`the polymers of this invention is not particularly
`
`20
`
`limited to the method described in United States Patent
`
`2,901,466. This patent discloses interchange reactions
`
`as well as polymerization build—up processes. Briefly,
`
`a typical procedure consists of at least two distinct
`
`stages;
`
`the first stage, known as ester—interchange or
`
`esterification,
`
`is conducted under an inert atmosphere
`
`at a temperature of 150 to 250°C for 0.5 to 8 hours,
`
`preferably from 180 to 240°C for 1 to 4 hours.
`
`The
`
`glycols, depending on their reactivities and the
`
`specific experimental conditions employed, are commonly
`
`used in molar excesses of 1.05 — 2.5 per total moles of
`
`acid-functional monomers.
`
`The second stage, referred to
`
`as polycondensation,
`
`is conducted under reduced pressure
`
`at a temperature of 230 to 350°C, preferably 265 to
`
`325°C, and more preferably 270 to 300°C for 0.1 to 6
`
`hours, preferably 0.25 to 2 hours. Stirring or
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`W0 97/] l 106
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`PCT/US96/l4873
`
`appropriate conditions are used in both stages to ensure
`adequate heat transfer and surface renewal of the
`
`The reactions of both stages are
`. reaction mixture.
`facilitated by appropriate catalysts, especially those
`well—known in the art, such as alkoxy titanium
`
`5
`
`compounds, alkali metal hydroxides and alcoholates,
`salts of organic carboxylic acids, alkyl tin compounds,
`metal oxides, and so forth.
`
`Suitable copolyesters will have inherent viscosity
`(I.V.) values of about 0.4 to about 1.1 dL/g.
`Such
`values are obtained in'a 60/40 phenol/tetrachlorethane
`
`solution containing 0.5 grams (g) of polymer in 100
`milliliters (mL) of solution.
`It is preferred that the
`
`Preferred copolyesters must have glass transition
`temperatures (Tg) of at least 70°C as determined by
`Differential Scanning Calorimetry (Dsc) and a
`crystallization half—time of at least 1 minute as
`
`10
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`15
`
`measured by a small angle laser light scattering
`technique.
`
`20
`
`25
`
`30
`
`The technique for determining the crystallization
`haze half—times consists primarily in following the
`increase in depolarization of plane—polarized light by
`the polyester.
`The method used in this invention is
`primarily that shown in "A New Method for Following
`Rapid Rates of Crystallization", I. Poly (hexamethylene
`adipamide), J. H. Magill, Polymer, Vol. 2, page 221—233
`(1961) with the exception that Magill uses a polarizing
`microscope as the source of light and light—collection
`lenses.
`In measuring the crystallization half-times of
`
`the present invention, a helium—neon laser [with a small
`angle light scattering technique (SALS)] was used as was
`shown by Adams and Stein in J. Polymer Sci. A2, Vol.
`6
`(1962).
`
`
`
`WC 97/1 1106
`
`PCT/U896“ 4873
`
`Crystallization half—times are measured at the time
`
`in which the transmitted intensity is half of the
`
`maximum intensity achieved.
`
`The method used is generally as follows:
`
`(1) Melt the sample to remove existing
`
`crystallinity;
`
`(2) Crystallize the sample polyester at a pre—
`
`determined temperature;
`
`(3) Record the transmitted light intensity plotted
`
`versus time;
`
`(4)
`
`Find the time at which the transmitted
`
`intensity is half of the maximum intensity
`achieved.
`
`The above procedure is repeated at different
`
`temperatures until a minimum value for the
`
`crystallization half—time can be measured.
`"Minimum
`value" refers to the lowest measurable point on a curve
`
`plotted using the temperature data and corresponding
`
`crystallization half—time data.
`
`The term "crystallization haze half—time as
`
`measured from the melt phase" as defined herein is the
`
`procedure as describe above.
`
`It is preferred that the molded objects of the
`
`_invention have a crystallization haze half—time of
`
`greater than 1 minute, preferably greater than 3
`
`minutes, and more preferably greater than 5 minutes.
`
`When the molded objects of the invention have
`
`crystallization haze half—times as described,
`
`they are
`
`generally visually clear for regions of a molded object
`
`having a thickness of from 1 to 11.5 mm, preferably 3 to
`11.5."
`
`It is also preferable that molded objects prepared
`from the blends of the invention have a diffuse
`
`transmittance value of less than about 60%, more
`
`preferably,
`
`less than about 40%, and more preferably,
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`PCT/US96/l 4873
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`less than about 20% as determined by ASTM Method D1003.
`
`When the diffuse transmittance value is less than about
`
`60%,
`
`the molded objects are visually clear.
`
`Also, the molded objects of the invention
`
`demonstrate improved stress cracking.resistance as
`
`determined for test specimens which are 0.32 centimeters
`
`thick under a flexural load with 1.4% strain and with
`
`2.7% strain and as demonstrated more fully in the
`
`following Examples.
`
`This stress cracking resistance testing is
`
`preferably performed in the presence of a f1aVorant.
`
`More preferably,
`
`the flavorant is a mint oil.
`
`0f the
`
`possible mint oils, it is preferable that the mint oil
`
`is either peppermint oil or Spearmint oil.
`
`The stress cracking resistance measurements used in
`
`the invention are also preferably performed in the
`
`presence of a toothpaste solution comprising water and a
`
`toothpaste containing greater than 0.6 weight % mint oil
`
`or, more specifically,
`in the presence of peppermint oil
`directly as described more fully in the following
`Examples.
`
`other ingredients may be used in the toothpaste
`solutions including glycerine, sodium bicarbonate,
`
`_water, hydrated silicate, polyethylene glycol, sodium
`
`laural sulfate, sodium laural sarcosinate, sodium
`
`pyrophosphates, sodium phosphates, sorbitol, sodium
`
`benzoate, sodium saccharin, xantham gum, cellulose gum,
`flavorants, sodium saccharin, FD&C blue #1 and FD&C
`
`yellow #10, FD&C red 30, 1—hydroxy—2—propanone,
`
`3—
`
`octanol, 4—methyl—1—(1—methy1ethyl)cyclohexene,
`
`pulegone, dodecanol, 3—phenyl—2—propenal, dodecanol,
`eugenol and titanium dioxide.
`
`Flavorants useful in performing the tests of the
`
`invention include peppermint oil, curly mint oil, anise
`
`oil, Japanese anise oil, caraway oil, eucalyptus oil,
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`PCT/US96/l 4873
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`fennel oil, cinnamon
`
`oil, clove oil, geranium oil, sage
`
`oil, pimento oil,
`
`thyme oil, and majoram oil.
`
`Mint oil may contain several ingredients including,
`
`but not limited to:
`
`limonene, cineole, menthone,
`
`menthol, and carvone.
`
`The copolyesters may be used in clear form or they
`
`may be colored or pigmented with additives or
`
`copolymerizable colorants. Typically useful
`
`copolymerizable colorants are described in U. S. Patents
`
`5,030,703 (1991), 5,102,980 (1992) and 5,194,571 (1993)
`
`all assigned to Eastman Kodak Company,
`
`incorporated
`
`herein by reference.
`Other additives
`
`such as stabilizers, antioxidants,
`
`mold release agents,
`
`fillers and the like may also be
`
`used if desired.
`
`Polymer blends may be used.
`
`The copolyesters of this invention are easy to mold
`
`into desired shapes 5
`
`uch as toothbrush handles, hair
`
`brush handles,
`
`ice sc
`
`rapers, cutlery or cutlery handles,
`
`10
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`
`tool handles, automot
`
`ive steering wheels, eyeglass
`
`20
`
`frames and the like.
`
`This invention can be further
`
`illustrated by the fo
`
`llowing examples of preferred
`
`embodiments thereof,
`
`although it will be understood that
`
`these examples are in
`
`cluded merely for purposes of
`
`25
`
`_illustration and are
`the invention unless
`
`not intended to limit the scope of
`
`otherwise specifically indicated.
`
`The starting material
`
`5 are commercially available unless
`
`otherwise indicated.
`
`otherwise stated.
`
`Percentages are by weight unless
`
`
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`WO 97/11106
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`PCT/US96/l4873
`
`I.
`
`PREPARATION OF COPOLYESTERS AND MOLDED OBJECTS
`
`Example 1 — Comparative — Preparation of Copolyesters
`
`containing terephthalatel ethylene glycol and 3 mole%
`
`1.4—cyclohexanedimethanol
`
`A 5000 mL stainless steel reactor equipped with an
`
`agitator shaft, nitrogen inlet, and an outlet to allow
`
`for removal of volatile materials was charged with 679.7
`
`grams (3.5 mole) of dimethyl terephthalate (DMT), 427.8
`
`grams (6.9 mole) of ethylene glycol
`
`(EG), 16.4 grams
`
`(0.11 mole) of 1,4—cyclohexanedimethanol
`
`(CHDM)
`
`(70 %
`
`trans isomer/30 % cis isomer) and 1.35 mL of a 3.30%
`
`(W/V) solution of titanium (IV)
`
`isopropoxide in n—
`
`butanol.
`
`The reactor was purged with nitrogen and
`
`heated to 200°C under a slow nitrogen sweep with
`
`agitation and held for one hour.
`
`The reactor
`
`temperature was raised to 220°C and held for two hours.
`
`The temperature was raised to 280°C and the nitrogen
`
`purge was removed and a vacuum was applied such that a
`
`vacuum of < 0.5 mm was attained over a 30 minute period.
`
`The reactor was stirred under vacuum for one hour.
`
`The
`
`vacuum was then displaced with a nitrogen atmosphere and
`
`_the polymer was extruded through an opening in the
`
`bottom of the reactor.
`
`The extruded rod was cooled in
`
`The recovered polymer
`an 5°C water bath and pelletized.
`pellets had an inherent viscosity of 0.70 deciliters
`
`(dL)/g according to ASTM D3835—79.
`
`The diol component
`
`of the polymer consisted of 96 mole% EG,
`
`3 mole% CHDM
`
`and 1 mole% diethylene glycol
`
`(DEG) as measured by gas
`
`chromatography on a hydrolyzed sample.
`
`A glass
`
`transition temperature (Tg) of 78°C and a melting point
`(Tm) of 248°C were measured by DSC (differential
`
`scanning calorimetry) analysis.
`
`The crystallization
`
`haze half—time as measured from the melt phase was 0.8
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`PCT/US96/l4873
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`minutes.
`
`The sample was dried at 150°C in a
`
`dehumidifier drier for about 4 hours and injection
`
`molded into clear plaques that were 7.5 centimeters (cm)
`
`square and 0.32 cm thick. Located approximately 1 cm
`
`from the plaque edge was an area 1.L cm by 0.6 cm which
`
`contains twelve holes approximately 0.1 cm in diameter
`
`as shown in Figure 1. This area of the plaque was used
`
`to simulate the head of a toothbrush into which bristles
`
`would be inserted.
`
`Example 2 — Comparative — Preparatibn of Copolyester
`
`containing terephthalate, EG and 31 mole% CHDM
`
`The apparatus and procedure set forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 679.5 grams (3.5 mole) DMT,
`
`365.6 grams (5.9 mole) EG, 160.4 grams (1.1 mole) CHDM
`
`and 2.05 mL of a 3.30% (w/v) solution of titanium
`
`10
`
`15
`
`isopropoxide in n—butanol. The diol interchange step
`
`20
`
`was conducted at 200°C for one hour and at 210°C for tw0
`
`hours. The polycondensation step was conducted at a
`
`vacuum of 0.5 mm Hg for one hour. The polymer was
`
`extruded from the bottom of the reactor.
`
`The extruded
`
`25
`
`30
`
`rod was cooled in an 5°C water bath and pelletized.
`
`The
`
`recovered polymer pellets had an inherent viscosity of
`
`0.74 dL/g.
`
`The diol component of the polymer consisted
`
`of 68 mole% EG, 31 mole% CHDM and 1 mole% DEG.
`
`The
`
`amorphous copolymer possessed a T9 of 80°C as determined
`by BBC analysis.
`The crystallization haze half—time as
`
`measured from the melt phase was greater than 1 hour.
`
`The sample was dried at 65°C in a dehumidifier drier for
`
`about 16 hours.
`
`It was injection molded into clear
`
`specimens set forth in Example 1.
`
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`W0 97/11 106
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`Example 3 — Compagative — Preparation of Copolyester
`containing terephthalateI EG and 62 mole% CHDM
`
`The apparatus and procedure set forth in Example 1
`was used.
`The following amounts of reactants were
`
`charged to the reactor: 679.7 grams (3.5 mole) DMT,
`305.6 grams (4.9 mole) EG, 302.5 grams (2.1 mole) CHDM
`and 2.06 mL of a 3.30% (W/V) solution of titanium
`isopropoxide in n—butanol.
`The diol interchange step
`was conducted at 200°C for one hour and at 210°C for two
`
`hours. The polyCondensation step was conducted at a
`
`The polymer was
`vacuum of 0.5 mm Hg for 45 minutes.
`extruded from the bottom of the reactor.
`The extruded
`
`rod was cooled in an 5°C water bath and pelletized.
`
`The
`
`recovered polymer pellets had an inherent viscosity of
`0.72 dL/g.
`The diol component of the polymer consisted
`of 37 mole% EG, 62 mole% CHDM and 1 mole% DEG.
`A T9 of
`82°C and a Tm of 225°C were obtained for the copolymer
`by DSC analysis.
`The crystallization haze half—time as
`
`measure from the melt phase was 28 minutes. The sample
`was dried at 65°C in a dehumidifier drier for about 16
`
`hours and injection molded into clear specimens set
`forth in Example 1.
`
`Example 4 — Comparative — Preparation of Copolyester
`containing terephthalateI EG and 81 mole% CHDM
`
`The apparatus and procedure set forth in Example 1
`was used.
`The following amounts of reactants were
`
`679.2 grams (3.5 mole) DMT,
`charged to the reactor:
`248.1 grams (4.0 mole) EG, 432.9 grams
`(3.0 mole) CHDM
`and 2.38 mL of a 3.30% (w/v) solution of titanium
`isopropoxide in n—butanol.
`The diol interchange step
`was conducted at 200°C for one hour and at 210°C for two
`
`hours. The polycondensation step was conducted at a
`
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`WO 97/11106
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`_13._
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`vacuum of 0.5 mm Hg for 40 minutes.
`
`The polymer was
`
`extruded from the bottom of the reactor, cooled in an
`
`5°C water bath and pelletized.
`
`The recovered polymer
`
`pellets had an inherent viscosity of 0.76 dL/g and the
`
`diol component of the polymer consisted of 18 mole% EG,
`
`A T9 of 87°C and a Tm of
`81 mole% CHDM and 1 mole% DEG.
`257°C were obtained for the copolymer by DSC analysis.
`
`The crystallization haze half—time as measured from the
`
`melt phase was 3 minutes.
`
`The sample was dried at 150°C
`
`10
`
`in a dehumidifier drier for about 4 hours and injection
`
`molded into clear specimens set forth in Example 1.
`
`Example 5 — Comparative — Preparation of Copolyester
`
`containing 95 mole% terephthalate.
`
`5 mole% isophthalate
`
`15
`
`and CHDM
`
`The apparatus and procedure set forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 645.2 grams (3.3 mole) DMT, 34.1
`
`grams (0.2 mole) dimethyl isophthalate (DMI), 555.7
`
`grams (3.9 mole) CHDM and 2.68 mL of a 3.30% (W/V)
`
`solution of titanium isopropoxide in n—butanol.
`
`The
`
`reactor was purged with nitrogen and heated to 300°C
`
`under a slow nitrogen sweep with agitation.
`
`The reactor
`
`temperature was held for 30 minutes and then the
`
`nitrogen purge was removed and a vacuum was applied such
`
`that a vacuum of < 0.5 mm Hg was attained over a 30
`
`minute period.
`
`The vacuum and temperature was held for
`
`50 minutes.
`
`The polymer was extruded from the bottom of
`
`the reactor.
`
`The extruded rod was cooled in an 5°C
`
`water bath and pelletized.
`
`The recovered polymer
`
`pellets had an inherent viscosity of 0.78 dL/g and the
`
`polymer consisted of 95 mole% terephthalate and 5 mole%
`
`isophthalate as measured by 1H NMR-
`
`A T9 of 92°C and a
`
`Tm of 287°C were obtained for the copolymer by DSC
`
`20
`
`25
`
`30
`
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`_14__
`
`analysis.
`
`The crystallization haze half—time as
`
`measured from the melt phase was 0.5 minutes.
`
`The
`
`sample was dried at 150°C in a dehumidifier drier for
`
`about 4 hours and injection molded into clear specimens
`set forth in Example 1.
`
`Example 6 — Example of the Invention — Preparation of
`
`Copolyester Containing 83 Mole% terephthalateI 17 Mole%
`isophthalate apd CHDM
`
`The apparatus and procedure set forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 577.3 grams (3.0 mole) EMT,
`
`101.9 grams (0.5 mole) DMI, 565.4 grams (3.9 mole) CHDM
`
`and 2.67 mL of a 3.30% (W/V) solution of titanium
`
`The reactor was purged with
`isopropoxide in n—butanol.
`nitrogen and heated to 290°C under a slow nitrogen sweep
`with agitation.
`The reactor temperature was held for 30
`
`minutes and then the nitrogen purge was removed and a
`
`vacuum was applied such that a vacuum of < 0.5 mm Hg was
`attained over a 30 minute period.
`The vacuum and
`
`temperature was held for 43 minutes.
`
`The polymer was
`
`extruded from the bottom of the reactor, cooled in an
`
`_5°C water bath and pelletized.
`
`The recovered polymer
`
`pellets had an inherent viscosity of 0.70 dL/g and the
`
`polymer consisted of 83 mole% terephthalate and 17 mole%
`isophthalate as measured by 1H NMR.
`A Tg of 89°C and a
`Tm of 262°C were obtained for the copolymer by DSC
`
`analysis.
`
`The crystallization haze half—time as
`
`measured from the melt phase was 1.5 minutes.
`
`The
`
`sample was dried at 150°C in a dehumidifier drier for
`
`about 4 hours and injection molded into clear specimens
`set forth in Example 1.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`
`
`
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`WO 97/11106
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`PCT/US96/l 4873
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`_15_
`
`Example 7 — Example of the Invention — Preparation of
`
`Copolyester containing 70 mole% terephthalatel 30 mole%
`
`isophthalate and CHDM
`
`The apparatus and procedure set,forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 476.3 grams (2.5 mole) DMT,
`
`204.1 grams (1.0 mole) DMI, 555.8 grams (3.9 mole) CHDM
`
`and 2.67 mL of a 3.30% (W/v) solution of titanium
`
`isopropoxide in n—butanol. The reactor was purged with
`
`nitrogen and heated to 290°C under a slow nitrogen sweep
`
`with agitation.
`
`The reactor temperature was held for 30
`
`minutes and then the nitrogen purge was removed and a
`
`vacuum was applied such that a vacuum of < 0.5 mm Hg was
`
`attained over a 30 minute period. The vacuum and
`
`temperature was held for 53 minutes.
`
`The polymer was
`
`extruded from the bottom of the reactor.
`
`The extruded
`
`rod was cooled in an 5°C water bath and pelletized.
`
`The
`
`recovered polymer pellets had an inherent viscosity of
`
`0.70 dL/g and the polymer consisted of 70 mole%
`
`terephthalate and 30 mole% isophthalate as measured by
`
`1H NMR.
`
`An amorphous polymer was recovered that had a
`
`Tg of 87°C as measured by DSC.
`
`The crystallization haze
`
`half—time as measured from the melt phase was 6.8
`
`minutes.
`
`The sample was dried at 65°C in a dehumidifier
`
`drier for about 4 hours and injection molded into clear
`
`specimens set forth in Example 1.
`
`Example 8 — Example of the Invention — Preparation of
`
`Copolyester containing 61 mole% terephthalate, 39 mole%
`
`l.4—cyclohexanedicarboxylate and CHDM
`
`The apparatus and procedure set forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 404.7 grams (2.1 mole) DMT,
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`
`
`W0 97/] l l 06
`
`PCT/US96/l 4873
`
`—16—
`
`243.6 grams (1.4 mole) of dimethyl 1,4—
`
`cyclohexanedicarboxylate (DMCD)
`
`(35% trans isomer/65%
`
`cis isomer), 580.4 grams (4.03 mole) of CHDM and 2.65 mL
`
`of a 3.30% (w/v) solution of titanium isopropoxide in n—
`
`butanol.
`
`The reactor was purged with nitrogen and
`
`heated to 220°C for 60 minutes under a slow nitrogen
`
`sweep with sufficient agitation. After raising the
`
`temperature to 290°C the nitrogen purge was removed and
`
`a vacuum was applied such that a vacuum of < 0.5 mm Hg
`
`was attained in 30 min.
`
`The vacuum and temperature was
`
`held for 120 minutes to perform the polycondensation.
`
`The vacuum was then displaced with a nitrogen atmosphere
`
`and the polymer was drained from the bottom of the
`
`reactor, cooled in an 5°C water bath and pelletized.
`
`An
`
`inherent viscosity of 0.70 dL/g was determined for the
`
`recovered polymer.
`
`The polymer contained 61 mole%
`
`terephthalate and 39 mole% 1,4—cyclohexanedicarboxylate
`
`(51% trans isomer/49% cis isomer) as measured by 1H NMR.
`
`A T9 of 72°C and a T5 of 223°C were obtained for the
`
`copolymer by DSC analysis.
`
`The crystallization haze
`
`half—time as measured from the melt phase was 15
`
`minutes.
`
`The sample was dried at 65°C in a dehumidifier
`
`drier for about 4 hours and injection molded into clear
`
`specimens set forth in Example 1.
`
`Example 9 — Example of the Invention — Preparation of
`
`Copolyester containing 52 mole% terephthalateI 48 mole%
`
`l,4—cyclohexanedicarboxylate and CHDM
`
`The apparatus and procedure set forth in Example 1
`was used.
`The following amounts of reactants were
`
`charged to the reactor: 404.7 grams (2.1 mole) of
`
`dimethyl terephthalate (DMT), 243.6 grams (1.4 mole) of
`dimethyl 1,4—cyclohexanedicarboxylate (9S %
`trans
`
`isomer/5 % cis isomer), 580.4 grams (4.03 mole) of CHDM
`
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`
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`
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`WO 97/11106
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`PCT/US96/l4873
`
`and 2.68 mL of a 3.30% (W/V) solution of titanium
`
`isopropoxide in n—butanol.
`
`The reactor was purged with
`
`nitrogen and heated to 290°C under a slow nitrogen sweep
`
`with agitation.
`
`The reactor temperature was held for 30
`
`minutes and then the nitrogen purge was removed and a
`
`vacuum was applied such that a vacuum of < 0.5 mm was
`
`attained over a 30 minute period.
`
`The vacuum and
`
`temperature was held for 53 minutes.
`
`The polymer was
`
`extruded from the bottom of the reactor through an
`
`orifice.
`
`The extruded rod was cooled in an 5°C water
`
`bath and pelletized.
`
`An inherent viscosity of 0.74 dL/g
`
`was determined for the recovered polymer. The polymer
`
`contained 52 mole% terephthalate and 48 mole% 1,4—
`
`cyclohexanedicarboxylate (88% trans isomer/12% cis
`
`isomer) as measured by 1H NMR.
`
`A glass transition
`
`temperature Tg of 78°C and a Tm of 225°C were obtained
`for the polymer by DSC analysis.
`The crystallization
`
`haze half—time as measured from the melt phase was 11.5
`
`minutes.
`
`The sample was dried at 65°C in a dehumidifier
`
`drier for about 4 hours and injection molded into clear
`
`specimens set forth in Example 1.
`
`Example 10 — Example of the Invention — Preparation of
`
`vCopolyester containing 70 mole% terephthalateI 30 mole%
`
`2.6—naphthalenedicarboxylate and CHDM
`
`The apparatus and procedure set forth in Example 1
`
`was used.
`
`The following amounts of reactants were
`
`charged to the reactor: 477.0 grams (2.5 mole) DMT,
`
`203.9 grams (1.0 mole) DMI, 565.4 grams (3.9 mole) CHDM
`
`and 2.67 mL of a 3.30% (W/V) solution of titanium
`
`isopropoxide in n—butanol.
`
`The reactor was purged with
`
`nitrogen and heated to 290°C under a slow nitrogen sweep
`
`with agitation.
`
`The reactor temperature was held for 30
`
`minutes and then the nitrogen purge was removed and a
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`
`
`WO 97/11106
`
`PCT/US96/l4873
`
`vacuum was applied such that a vacuum of < 0.5 mm was
`
`attained over a 30 minute period.
`
`The vacuum and
`
`temperature was held for 43 minutes.
`
`The polymer was
`
`extruded from the bottom of the reactor.
`
`The extruded
`
`rod was cooled in a 5°C water bath and pelletized.
`
`The
`
`recovered polymer pellets had an inherent viscosity of
`0.64 dL/g and the polymer consisted of 70 mole%
`
`terephthalate and 30 mole% naphthalate as measured by
`1H NMR.
`A T9 of 103°C and a Tm of 246°C were obtained
`for the polymer by D
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