CA1133643A - High gloss smooth molded articles from filled pet compositions - Google Patents
High gloss smooth molded articles from filled pet compositionsInfo
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- CA1133643A CA1133643A CA322,518A CA322518A CA1133643A CA 1133643 A CA1133643 A CA 1133643A CA 322518 A CA322518 A CA 322518A CA 1133643 A CA1133643 A CA 1133643A
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/40—Glass
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Polyethylene terephthalate resin compositions contain-ing filler or reinforcing agent, a selected sodium or potassium salt of a hydrocarbon acid or a salt of a selected organic polymer containing pendant carboxyl groups, and a selected low molecular weight organic ester, ketone, sulfone, sulfoxide, nitrile or amide. Articles molded from the compositions have high gloss when molded at temperatures below 110°C.
Polyethylene terephthalate resin compositions contain-ing filler or reinforcing agent, a selected sodium or potassium salt of a hydrocarbon acid or a salt of a selected organic polymer containing pendant carboxyl groups, and a selected low molecular weight organic ester, ketone, sulfone, sulfoxide, nitrile or amide. Articles molded from the compositions have high gloss when molded at temperatures below 110°C.
Description
AD-4940-A 11~3~'~3 TITLE
PRODUCT AND PROCESS
FIELD OF THE INVENTION
This invention relates to polyethylene terephthalate resins useful in molding applications.
More particularly, this invention relates to polyethylene terephthalate resins containing an inorg~nic reinforclng or ~iller material.
B~CKGROUND
It is desirable to enhance the strength o~ articles molded ~rom polyethylene terephthalate resin by employing a reinforcing materialJ such as glass fibers, asbestos ~ibers or other fibrous mineral materials with a coupling agent, in the resin. Furthermore, it is sometimes sufficient to merely increase the modulus by use of a filler, such aæ beads or a mineral of low aspect ratio, in the resin. However, heretofore, it was necessary to use very high mold temperatures, on the order o~ 130C, to obtain molded articles from such reinforced or filled resins which had a glossy surface . . .
. ~ , - .
. . .
. --:: ~ :
36'~3 and which were not rough in texture. If these high mold temperatures were not employed, the molded articles had a rough surface with poor gloss. It is believed that the crystallization rate of poly-ethylene terephthalate is too slow below about 130Cto result in a molded article having good surface characteristics.
While good surface characteristics can be obtained at molding temperatures of 130C or more, the use of such temperatures is not pxactical in the molding field, for most molds are heated with water and attain temperatures of only about 85-110C.
A few molding devices employ heating means such as oil to reach temperatures higher than 85-110C but these generally are inconvenient to use and still either do not generally reach such temperatures or reach them unevenly because of inadequate coring. Because of these heating problems, it has proven commercially unattractive to employ these high temperature molding devices with reinforced or filled polyethylene terephthalate resins.
SUMMARY OF THE INVENTION
It is desirable to provide a reinforced or filled polyethylene terephthalate resin that can be molded at mold temperatures below about 110C to produce a molded article having a smooth and glossy surface. The reinforced or filled polyethylene terephthalate resins of this invention achieve the foregoing by having incorpor-ated therein 1) a sodium or potassium salt of a selected hy~rocarhon acid or a sodium or potassium salt of a selected organic polymer containing pendant carboxyl groups and 2) a selected low molecular weight organic ester, ketone, sulfone, 11336~3 sulfoxide nitrile or amideO
Specific~lly the resins of this invention are compositions consisting essentially of:
A. polyethylene terephthalate having an lnherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a material selected from a sodium or potassium salt of a hydrocarbon aci~ containin~
between about 7 and 25 carbon atoms or a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups said material present in an amount sufficient to provide a ~H~j~HC ra~io of less than 0.25 to a mixture of components A B and C;
-D. a compound present in an amount sufficient to provide a Tpk at least 4C lower than the Tpk of a mixture of components A B and C
said compound being selected from a) organic esters selected from the product of an aromatic carboxylic acid of 7-11 carbon atoms containing at }east 1 carboxyl group per aromatic nucleus and an alcohol selected from ~hose of the formula (HOCH2tXR wherein x is 1 2 25 or 3 and R is a hydrocarbon radical of 2-15 carbon atoms (preferably 2-10 carbon atoms) or those of the formula HO~Rn0tyRn wherein y is a cardinal number between 1 ~ud 15 and preferably between 2 and 8 : R~ is a hydrocarbon radical of 2-15 carbon atoms (preferably 2-8 carbon atoms~ and R ' is -H or a . hydrocarbon radical of 2-20 carbon atoms (preferably
PRODUCT AND PROCESS
FIELD OF THE INVENTION
This invention relates to polyethylene terephthalate resins useful in molding applications.
More particularly, this invention relates to polyethylene terephthalate resins containing an inorg~nic reinforclng or ~iller material.
B~CKGROUND
It is desirable to enhance the strength o~ articles molded ~rom polyethylene terephthalate resin by employing a reinforcing materialJ such as glass fibers, asbestos ~ibers or other fibrous mineral materials with a coupling agent, in the resin. Furthermore, it is sometimes sufficient to merely increase the modulus by use of a filler, such aæ beads or a mineral of low aspect ratio, in the resin. However, heretofore, it was necessary to use very high mold temperatures, on the order o~ 130C, to obtain molded articles from such reinforced or filled resins which had a glossy surface . . .
. ~ , - .
. . .
. --:: ~ :
36'~3 and which were not rough in texture. If these high mold temperatures were not employed, the molded articles had a rough surface with poor gloss. It is believed that the crystallization rate of poly-ethylene terephthalate is too slow below about 130Cto result in a molded article having good surface characteristics.
While good surface characteristics can be obtained at molding temperatures of 130C or more, the use of such temperatures is not pxactical in the molding field, for most molds are heated with water and attain temperatures of only about 85-110C.
A few molding devices employ heating means such as oil to reach temperatures higher than 85-110C but these generally are inconvenient to use and still either do not generally reach such temperatures or reach them unevenly because of inadequate coring. Because of these heating problems, it has proven commercially unattractive to employ these high temperature molding devices with reinforced or filled polyethylene terephthalate resins.
SUMMARY OF THE INVENTION
It is desirable to provide a reinforced or filled polyethylene terephthalate resin that can be molded at mold temperatures below about 110C to produce a molded article having a smooth and glossy surface. The reinforced or filled polyethylene terephthalate resins of this invention achieve the foregoing by having incorpor-ated therein 1) a sodium or potassium salt of a selected hy~rocarhon acid or a sodium or potassium salt of a selected organic polymer containing pendant carboxyl groups and 2) a selected low molecular weight organic ester, ketone, sulfone, 11336~3 sulfoxide nitrile or amideO
Specific~lly the resins of this invention are compositions consisting essentially of:
A. polyethylene terephthalate having an lnherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a material selected from a sodium or potassium salt of a hydrocarbon aci~ containin~
between about 7 and 25 carbon atoms or a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups said material present in an amount sufficient to provide a ~H~j~HC ra~io of less than 0.25 to a mixture of components A B and C;
-D. a compound present in an amount sufficient to provide a Tpk at least 4C lower than the Tpk of a mixture of components A B and C
said compound being selected from a) organic esters selected from the product of an aromatic carboxylic acid of 7-11 carbon atoms containing at }east 1 carboxyl group per aromatic nucleus and an alcohol selected from ~hose of the formula (HOCH2tXR wherein x is 1 2 25 or 3 and R is a hydrocarbon radical of 2-15 carbon atoms (preferably 2-10 carbon atoms) or those of the formula HO~Rn0tyRn wherein y is a cardinal number between 1 ~ud 15 and preferably between 2 and 8 : R~ is a hydrocarbon radical of 2-15 carbon atoms (preferably 2-8 carbon atoms~ and R ' is -H or a . hydrocarbon radical of 2-20 carbon atoms (preferably
2-12 carbon atoms); or b) organic ketones of the formula RCR .
c) organic sulfones of the formula RSOOR
d) organic sulfoxides of the formula R2SO
e) organi~ nitriles of the formula RCN or .
-.
: -:
. : :
. ~ .
~133~ *3 o f) organic amides of the formula RCNR'R or Jol RSONR'R
wherein in formulas b) through f) each R can be the same as or different from any other R and i8 a hydro-carbyl group of 1-25 carbon atoms, while in the formulas in f) R~ is hydrogen or a hydrocarbyl group of 1-25 carbon atoms.
DESCRIPTION OF T B INVENTION
The polyethylene terephthalate em~loyed herein is one which has an inherent viscosity of at least O.4. The polyethylene terephthalate preferably has an upper limit on inherent viscosity of about 1.2.
Inherent viscosity is measured at 30C using 0.5 g of polyethylene terephthalate per 100 ml of a liquid that is a mixture, at a 3:1 ratio by volume, of methylene chloride and trifluoroacetic acid i.e. using the proce-dure of ASTM D-2857. me polyethylene terephthalate can contain minor amounts of other comonomers such as diethylene glycol or glutaric acid.
The reinforcing or filler material employed herein include glass fibers, glass beads, aluminum silicate, asbestos, mica and the like, or combina-tions thereof as for example a mixture of mica andglass fibers.
Materials present in an amount sufficient to cause the compositions of the inventi~n to have a ~HH/~HC ratio of less than 0.25 (component C defined - 30 above~ include the sodium or potassium salts of hydro-carbon carboxylic acids containing between 7 and 25 carbon atoms, preferably more than 12 carbon atoms. Representative of these acids (which are fatty acids) are stearic, pelargonic, and behenic acid. These materials also include the sodium or potassium salts of carboxyl containing organic poly-mers, such as copolymers of olefins and acrylic or ~33Çi'~3 methacrylic acids, or copolymers of aromatic olefins and maleic anhydride. Preferably these materials include the sodium or potassium salt of ~tearlc acid; the sodium or potassium salt of ethylene/
methacrylic acid copolymers (including both wholly or partially neutralized salts e.g., at least about 30%
neutralized), the sodium salt of styrene/maleic anhydride copolymers (including both wholly or partially neutralized salts e.g., at least about 30~ neutralized) and sodium versatate. In the co-polymers listed above the olefin or aromatic olefin moiety ordinarily comprises 50-98 percent by weight of the copolymer, and preferably 80-98 percent. An especially preferred material is the sodium salt of ethylene/methacrylic acid copolymer. The copolymers may be prepared by conventional high pressure polymerization technology.
Preferred o'rganic esters of component D
recited above are those in which the aromatic carboxylic acids are hydrocarbon acids containing 1-3 carboxyl groups and the alcohols are aliphatic.
In other words, the R groups in the alcohols are alkyl or alkylene depending upon the particular R group.
Preferably also when the carboxylic acids contain two 25 or more carboxyl groups, the carboxyl groups are all reacted to form ester (COO) linkages, that is, there will be no free carboxylgroups present in the ester. Preferably, all the hydroxyl groups of the alcohols will also be reacted to form ester (COO) linkages, that is, there will be no free hydroxyl groups present in the ester.
A preferred class of esters are those in which the acid is benzoic acid, and the alcohol is (HOCH2)2-R' wherein R' is alkylene of 4-6 carbon atoms (preferably neopentyl glycol) or HO(R"OtyH wherin R" is ethylene or propylene, and y is 2 or 3.
:
11~3~3 Preferred ketones, sulfanes, sulfoxides, nitriles and amides are those in which the R
groups in the formulas provided further above for these organic compounds are aryl groups of 6-10 carbon atoms or alkyl groups of 1-10 carbon atoms.
Specific compounds within these definitions are listed following (The number in parenthesis after each compound is the number of degrees centigrade that 1 percent by weight of the compound present (based on polyethylene terephthalate) in the reinforced or filled polyethylene terephthalate lower the Tpk):
dibenzoate of neopentyl glycol (2.0), dibenzoate of triethylene glycol (3.0), dibenzoate of di-ethyleneglycol (3.2), dibenzoate of dipropylene glycol (3.0), tris-2-ethyl hexyl trimellitate (2.5), phenyl benzoate (3.0), trimethylolethane tribenzoate (1.53), dioctylphthalate (1.3), diisodecyl phthalate (0.8)/ benzophenone (2.5), 4-fluorobenzo-phenone (1.9), diphenyl sulfone (2.8), N-ethyl-o,p-toluene gulfonamide (2.3), tolyl sulfoxide (2.6),lauryl nitrile (2.9), and erucyl nitrile (2.3).
Components (C) and (D) in the compositions of this invention aid in o~taining molded articles of high sur~ace gloss at molding temperatures below 110C by increasing the rate of crystallization of polyethylene terephthalate. Component (C) is believed to primarily aid in increasing the rate of crystallization while component (D) is believed to primarily improve the mobility of the polyethylene terephthalate in its supercooled state by re-ducing the viscosity in such state. Both are necessary to obtain the high gloss found in the articles molded from the composition.
The amount of component (C) present in the compositions of this invention is an amount which il33643 will result in a ~HH/~HC ratio of the composition less than 0.25. To find the ~H~/~HC ratio, poly-ethylene terephthalate is molded at 70C into 1/16"
thick bars. The bars are heated and at between 95C and 120C an exotherm (termed aHH) is recorded on a differential scanning calormeter (DSC) cell attached to a Du Pont 900 Differential Thermal Analysis (DTA) device. The bar is heated to 290 (which is above its melting point) and the melted sample cooled at 10C/minute. Another exotherm at between about 200-220C (termed ~Hc) is the exotherm recorded on freezing of the sample. It has been found that the ~H/~HC ratio is a convenient method of measuring the degree of crystallization.
The Tpk of the composition of this invention is the temperature at which heat evolves most rapidly during the heating cycle recited in the previous paragraph. As stated earlier the amount of component (D) present in the composition of this invention is an amount which lowers the Tpk of the composition by at least 4C over that of an identical composition that does not contain component (D).
The upper limits on the amounts of components C and D are not critical. However, physical properties may become adversely affected as amounts increase. In general, the upper amount employed for any one component will usually be about 12 percent by weight based on weight polyethylene terephthalate, while the lower limit will be about 1 percent. For the preferred component (C) salts of ethylene/methacrylic acid copolymer the upper limit on the amount present will be about 12 percent by weight based on weight of polyethylene terephthalate while the lower limit will be about 0.5 percent, but preferably an amount within the range of 1-5 percent will be used.
.:
:,, '
c) organic sulfones of the formula RSOOR
d) organic sulfoxides of the formula R2SO
e) organi~ nitriles of the formula RCN or .
-.
: -:
. : :
. ~ .
~133~ *3 o f) organic amides of the formula RCNR'R or Jol RSONR'R
wherein in formulas b) through f) each R can be the same as or different from any other R and i8 a hydro-carbyl group of 1-25 carbon atoms, while in the formulas in f) R~ is hydrogen or a hydrocarbyl group of 1-25 carbon atoms.
DESCRIPTION OF T B INVENTION
The polyethylene terephthalate em~loyed herein is one which has an inherent viscosity of at least O.4. The polyethylene terephthalate preferably has an upper limit on inherent viscosity of about 1.2.
Inherent viscosity is measured at 30C using 0.5 g of polyethylene terephthalate per 100 ml of a liquid that is a mixture, at a 3:1 ratio by volume, of methylene chloride and trifluoroacetic acid i.e. using the proce-dure of ASTM D-2857. me polyethylene terephthalate can contain minor amounts of other comonomers such as diethylene glycol or glutaric acid.
The reinforcing or filler material employed herein include glass fibers, glass beads, aluminum silicate, asbestos, mica and the like, or combina-tions thereof as for example a mixture of mica andglass fibers.
Materials present in an amount sufficient to cause the compositions of the inventi~n to have a ~HH/~HC ratio of less than 0.25 (component C defined - 30 above~ include the sodium or potassium salts of hydro-carbon carboxylic acids containing between 7 and 25 carbon atoms, preferably more than 12 carbon atoms. Representative of these acids (which are fatty acids) are stearic, pelargonic, and behenic acid. These materials also include the sodium or potassium salts of carboxyl containing organic poly-mers, such as copolymers of olefins and acrylic or ~33Çi'~3 methacrylic acids, or copolymers of aromatic olefins and maleic anhydride. Preferably these materials include the sodium or potassium salt of ~tearlc acid; the sodium or potassium salt of ethylene/
methacrylic acid copolymers (including both wholly or partially neutralized salts e.g., at least about 30%
neutralized), the sodium salt of styrene/maleic anhydride copolymers (including both wholly or partially neutralized salts e.g., at least about 30~ neutralized) and sodium versatate. In the co-polymers listed above the olefin or aromatic olefin moiety ordinarily comprises 50-98 percent by weight of the copolymer, and preferably 80-98 percent. An especially preferred material is the sodium salt of ethylene/methacrylic acid copolymer. The copolymers may be prepared by conventional high pressure polymerization technology.
Preferred o'rganic esters of component D
recited above are those in which the aromatic carboxylic acids are hydrocarbon acids containing 1-3 carboxyl groups and the alcohols are aliphatic.
In other words, the R groups in the alcohols are alkyl or alkylene depending upon the particular R group.
Preferably also when the carboxylic acids contain two 25 or more carboxyl groups, the carboxyl groups are all reacted to form ester (COO) linkages, that is, there will be no free carboxylgroups present in the ester. Preferably, all the hydroxyl groups of the alcohols will also be reacted to form ester (COO) linkages, that is, there will be no free hydroxyl groups present in the ester.
A preferred class of esters are those in which the acid is benzoic acid, and the alcohol is (HOCH2)2-R' wherein R' is alkylene of 4-6 carbon atoms (preferably neopentyl glycol) or HO(R"OtyH wherin R" is ethylene or propylene, and y is 2 or 3.
:
11~3~3 Preferred ketones, sulfanes, sulfoxides, nitriles and amides are those in which the R
groups in the formulas provided further above for these organic compounds are aryl groups of 6-10 carbon atoms or alkyl groups of 1-10 carbon atoms.
Specific compounds within these definitions are listed following (The number in parenthesis after each compound is the number of degrees centigrade that 1 percent by weight of the compound present (based on polyethylene terephthalate) in the reinforced or filled polyethylene terephthalate lower the Tpk):
dibenzoate of neopentyl glycol (2.0), dibenzoate of triethylene glycol (3.0), dibenzoate of di-ethyleneglycol (3.2), dibenzoate of dipropylene glycol (3.0), tris-2-ethyl hexyl trimellitate (2.5), phenyl benzoate (3.0), trimethylolethane tribenzoate (1.53), dioctylphthalate (1.3), diisodecyl phthalate (0.8)/ benzophenone (2.5), 4-fluorobenzo-phenone (1.9), diphenyl sulfone (2.8), N-ethyl-o,p-toluene gulfonamide (2.3), tolyl sulfoxide (2.6),lauryl nitrile (2.9), and erucyl nitrile (2.3).
Components (C) and (D) in the compositions of this invention aid in o~taining molded articles of high sur~ace gloss at molding temperatures below 110C by increasing the rate of crystallization of polyethylene terephthalate. Component (C) is believed to primarily aid in increasing the rate of crystallization while component (D) is believed to primarily improve the mobility of the polyethylene terephthalate in its supercooled state by re-ducing the viscosity in such state. Both are necessary to obtain the high gloss found in the articles molded from the composition.
The amount of component (C) present in the compositions of this invention is an amount which il33643 will result in a ~HH/~HC ratio of the composition less than 0.25. To find the ~H~/~HC ratio, poly-ethylene terephthalate is molded at 70C into 1/16"
thick bars. The bars are heated and at between 95C and 120C an exotherm (termed aHH) is recorded on a differential scanning calormeter (DSC) cell attached to a Du Pont 900 Differential Thermal Analysis (DTA) device. The bar is heated to 290 (which is above its melting point) and the melted sample cooled at 10C/minute. Another exotherm at between about 200-220C (termed ~Hc) is the exotherm recorded on freezing of the sample. It has been found that the ~H/~HC ratio is a convenient method of measuring the degree of crystallization.
The Tpk of the composition of this invention is the temperature at which heat evolves most rapidly during the heating cycle recited in the previous paragraph. As stated earlier the amount of component (D) present in the composition of this invention is an amount which lowers the Tpk of the composition by at least 4C over that of an identical composition that does not contain component (D).
The upper limits on the amounts of components C and D are not critical. However, physical properties may become adversely affected as amounts increase. In general, the upper amount employed for any one component will usually be about 12 percent by weight based on weight polyethylene terephthalate, while the lower limit will be about 1 percent. For the preferred component (C) salts of ethylene/methacrylic acid copolymer the upper limit on the amount present will be about 12 percent by weight based on weight of polyethylene terephthalate while the lower limit will be about 0.5 percent, but preferably an amount within the range of 1-5 percent will be used.
.:
:,, '
3 ti t 3 In addition to the components discussed hereinabove, the compositions of this invention may contain additives commonly employed with poly-ester resins, such as colorants, mold release agents, antioxidants, ultraviolet light stabilizers, flame retardants and the like. Additives which improve physical properties, such as tensile strength and elongation can also be employed; such additives include epoxy compounds (e.g., an epoxy compound formed from bisphenol-A and epichlorohydrin) present in amounts of from 0.1-L.5 percent by weight based on weight of composition.
The compositions of this invention are prepared by blending the components together by any convenient means. Neither temperature nor pressure are critical. For example, the poly-ethylene terephthalate can be mixe-d dry in any suitable blender or tumbler with components B, C
and D and the mix~ure melt-extruded. The ~xtrudate can be chopped and mixed with reinforcing agent and then this mixture melt extruded. More con-veniently, all the components can be mixed dry in any suitable blender or tumbler and the mixture then melt extruded.
The following Examples describe the best mode of carrying out the in~ention. The ~HH/~HC
ratio and the Tpk were determined as described above, while the gloss of molded sample was measured with a Gardner Multi Angle Gloss (P~odel GG-9095) set a~ a selected degree angle set forth in the Examples.
Example l A dry blend of 92.57 percent by weight of dry polyethylene terephthalate having an inherent viscosity of about 0.5 to 0.6, 1 percent 113~ 3 by weight sodium stearate, 5 percent by weight benzophenone, and 1.43 percent by weight N-stearyl erucamide (a mold release additive~ was extruded through a 28 mm twin screw extruder at a melt temperature of approximately 264~C. The chopped strands from the extruded melt were dried at about 110C for 16 hours in a vacuum oven. The dried chopped strands were dry mixed with sufficient OCF 419AA glass fiber (chopped to 3/16") to make 30 percent glass fiber by weight and extruded through a 2-stage single screw extruder at about 264C melt temperature. The AHH/~HC ratio was 0.06 and the Tpk was 12 less than the same composition but without the benzophenone present. The extruded strands were cooled and chopped and then dried at about 110C for 16 hours in a vacuum - oven. The dried chopped strands were molded in a 6 Z- injection molding machine at approximately 290C, with a fast ram, 20 seconds injection forward time, and 20 seconds mold close ~ime and a 95C
cavity temperature. Gloss of the molded article was very good. As determined with a Gardner Multi Angle Gloss Meter,(Model GG-90~5) set at a twenty degree angle the gloss registered 23. At a 70 cavity temperature gloss measured in the same manner was 5.
EXAMPLES 2 TO 15 AND COMPARISONS A TO ~
In the Examples and comparisons which follow, the procedure generally employed to make compositions of this invention is as follows:
Dry polyethylene terephthalate having an inherent viscosity c about 0.5-0.65 was mixed manually with glass fiber as specified in the tables below and with ethylene/methacrylic acid copolymer (85/15 by weight) which had been : .: .
1133t~ ~3 60 percent neutralized with sodium (which is component C herein) in an amount specified in the tables below and with the component D specified in the tables. Other additives may be present to improve strength of molded articles or to improve mold release properties. These additives, if present, are specified in the tables.
The resulting mixture was then extruded through a two-stage two inch single screw extruder at a melt temperature of 285~C and at a vaccum of 28 inches. The extruded strand was cut and the resulting resin pellets dried at 110C in a vacuum oven for about 16 hours. The resin pellets were then molded into tumblers that were 9.2 cm high, 7.5 cm in diameter at the top, 5.5 cm in diameter at the bottom and which had a wall thic~ness of 0.19 cm. Melt temperature in the molding machine was 295C; while the surface temperature of the mold was 85C. Cycle times and release pressures are recited in the tables.
Gloss was measured at an angle of 60 by theGardner Multi Angle Gloss Meter (Model GG-9095) several times for each sample. Gloss was measured around the circumference of the tumbler, at one-third the way down from the top. Pressure needed to release the tumbler was also measured by recording the air pressure necessary to move the ejector. The tables record the highest and the lowest gloss figures obtained in all the gloss tests performed on the sample. The t~bles also record the visual surface appearance of the molded tumblers.
In the tables, percent amount of components C and D are based on weight of poly-ethylene terephthalate employed. Percent amount of filler or reinforcing agent and other additives 1:1336~1t3 are based on weight of mixture that is to be extruded.
In the tables, component D is identified by a single letter. The letters represent the specific component D as follows:
A - Dibenzoate of neopentyl glycol B - Lauryl nitrile C - Dibenzoate of dipropylene glycol D - Erucyl nitrile E - Benzophenone F - Trioctyl trimellitate G - Diphenyl sulfone H - N-ethyl-o,p-toluene sulfonamide I - Dibenzoate of diethylene glycol The reinforcing or filler material employed is identified in tables by two letters.
The letters represent the specific materials as follows:
AA - OCF 277B glass fiber BB - Mica (Suzorite* A60) platelets CC - OCF 419AA glass fiber The other additives are identified by letter as follows:
X - epoxy formed from bisphenol A and epichlorohydrin Y - tetrakis [methylene (3,5-di-tert-butyl-
The compositions of this invention are prepared by blending the components together by any convenient means. Neither temperature nor pressure are critical. For example, the poly-ethylene terephthalate can be mixe-d dry in any suitable blender or tumbler with components B, C
and D and the mix~ure melt-extruded. The ~xtrudate can be chopped and mixed with reinforcing agent and then this mixture melt extruded. More con-veniently, all the components can be mixed dry in any suitable blender or tumbler and the mixture then melt extruded.
The following Examples describe the best mode of carrying out the in~ention. The ~HH/~HC
ratio and the Tpk were determined as described above, while the gloss of molded sample was measured with a Gardner Multi Angle Gloss (P~odel GG-9095) set a~ a selected degree angle set forth in the Examples.
Example l A dry blend of 92.57 percent by weight of dry polyethylene terephthalate having an inherent viscosity of about 0.5 to 0.6, 1 percent 113~ 3 by weight sodium stearate, 5 percent by weight benzophenone, and 1.43 percent by weight N-stearyl erucamide (a mold release additive~ was extruded through a 28 mm twin screw extruder at a melt temperature of approximately 264~C. The chopped strands from the extruded melt were dried at about 110C for 16 hours in a vacuum oven. The dried chopped strands were dry mixed with sufficient OCF 419AA glass fiber (chopped to 3/16") to make 30 percent glass fiber by weight and extruded through a 2-stage single screw extruder at about 264C melt temperature. The AHH/~HC ratio was 0.06 and the Tpk was 12 less than the same composition but without the benzophenone present. The extruded strands were cooled and chopped and then dried at about 110C for 16 hours in a vacuum - oven. The dried chopped strands were molded in a 6 Z- injection molding machine at approximately 290C, with a fast ram, 20 seconds injection forward time, and 20 seconds mold close ~ime and a 95C
cavity temperature. Gloss of the molded article was very good. As determined with a Gardner Multi Angle Gloss Meter,(Model GG-90~5) set at a twenty degree angle the gloss registered 23. At a 70 cavity temperature gloss measured in the same manner was 5.
EXAMPLES 2 TO 15 AND COMPARISONS A TO ~
In the Examples and comparisons which follow, the procedure generally employed to make compositions of this invention is as follows:
Dry polyethylene terephthalate having an inherent viscosity c about 0.5-0.65 was mixed manually with glass fiber as specified in the tables below and with ethylene/methacrylic acid copolymer (85/15 by weight) which had been : .: .
1133t~ ~3 60 percent neutralized with sodium (which is component C herein) in an amount specified in the tables below and with the component D specified in the tables. Other additives may be present to improve strength of molded articles or to improve mold release properties. These additives, if present, are specified in the tables.
The resulting mixture was then extruded through a two-stage two inch single screw extruder at a melt temperature of 285~C and at a vaccum of 28 inches. The extruded strand was cut and the resulting resin pellets dried at 110C in a vacuum oven for about 16 hours. The resin pellets were then molded into tumblers that were 9.2 cm high, 7.5 cm in diameter at the top, 5.5 cm in diameter at the bottom and which had a wall thic~ness of 0.19 cm. Melt temperature in the molding machine was 295C; while the surface temperature of the mold was 85C. Cycle times and release pressures are recited in the tables.
Gloss was measured at an angle of 60 by theGardner Multi Angle Gloss Meter (Model GG-9095) several times for each sample. Gloss was measured around the circumference of the tumbler, at one-third the way down from the top. Pressure needed to release the tumbler was also measured by recording the air pressure necessary to move the ejector. The tables record the highest and the lowest gloss figures obtained in all the gloss tests performed on the sample. The t~bles also record the visual surface appearance of the molded tumblers.
In the tables, percent amount of components C and D are based on weight of poly-ethylene terephthalate employed. Percent amount of filler or reinforcing agent and other additives 1:1336~1t3 are based on weight of mixture that is to be extruded.
In the tables, component D is identified by a single letter. The letters represent the specific component D as follows:
A - Dibenzoate of neopentyl glycol B - Lauryl nitrile C - Dibenzoate of dipropylene glycol D - Erucyl nitrile E - Benzophenone F - Trioctyl trimellitate G - Diphenyl sulfone H - N-ethyl-o,p-toluene sulfonamide I - Dibenzoate of diethylene glycol The reinforcing or filler material employed is identified in tables by two letters.
The letters represent the specific materials as follows:
AA - OCF 277B glass fiber BB - Mica (Suzorite* A60) platelets CC - OCF 419AA glass fiber The other additives are identified by letter as follows:
X - epoxy formed from bisphenol A and epichlorohydrin Y - tetrakis [methylene (3,5-di-tert-butyl-
4-hydroxyhydrocinnamate)] methane * denotes trade mark .
.
,... . ' ~ ,- ~
1133~3 TABLE I
AMOUNT OF COMPONENT FILLER OT~ER ADDI-COMPONENT D AND AND TIVES
EXAMPLE C !~) AMOUNT (%) AMOUNT(%) PRESENT(%~
2 5.8 A(5.7) AA(25)X(0.6) Y(0.3) 3 5.8 A(5.4) AA(35)X(0.55) Y(0.25) 4 5.9 A(5.4) AA(55)X(0.5) Y(0.18)
.
,... . ' ~ ,- ~
1133~3 TABLE I
AMOUNT OF COMPONENT FILLER OT~ER ADDI-COMPONENT D AND AND TIVES
EXAMPLE C !~) AMOUNT (%) AMOUNT(%) PRESENT(%~
2 5.8 A(5.7) AA(25)X(0.6) Y(0.3) 3 5.8 A(5.4) AA(35)X(0.55) Y(0.25) 4 5.9 A(5.4) AA(55)X(0.5) Y(0.18)
5.7 A(5.3) BB(30)NONE
6 5.8 A(5.6) CC(25)NONE
7 6.1 A(11.6) CC(25)NONE
8- 5.6 B(2.8) CC(25)NONE
9 5.8 C~5.7) AA(25)X(0.6) Y(0.3) 5.8 D(4.3) CC(2S)SA2~E
11 2.1 E(5.1) CC(25)NONE
12 5.7 F(3.7) CC(25)NONE
13 5.8 G(5.3) CC(25)NONE
14 5.8 H(5.3) CC(25)NONE
5.7 I(3.7) ` CC(25) NONE
.
~:
~ ....... . .. .
.
--1~33643 GLOSS AS
MOLDED(low-RELEASE est value/ MOLDED
QHH/ CYCLE PRESSURE highest SURFACE
Ex. ~H~ aTpk TIME (psi) value) APPEARANCE
, . . . _ 2 0.16 -11 10/15 920 61/67 very smooth 3 0.16 -10 10/10 940 52/60 very smooth 4 0.16 -10 10/13 70 24/42 very smooth
11 2.1 E(5.1) CC(25)NONE
12 5.7 F(3.7) CC(25)NONE
13 5.8 G(5.3) CC(25)NONE
14 5.8 H(5.3) CC(25)NONE
5.7 I(3.7) ` CC(25) NONE
.
~:
~ ....... . .. .
.
--1~33643 GLOSS AS
MOLDED(low-RELEASE est value/ MOLDED
QHH/ CYCLE PRESSURE highest SURFACE
Ex. ~H~ aTpk TIME (psi) value) APPEARANCE
, . . . _ 2 0.16 -11 10/15 920 61/67 very smooth 3 0.16 -10 10/10 940 52/60 very smooth 4 0.16 -10 10/13 70 24/42 very smooth
10 5 0.16 -10 i0/30 370 27/32 very smooth 6 0.16 -11 10/15 1060 62/69 very smooth 7 0.16 -24 10/15 1080 58/62 smooth all over 8 0.16 -8.1 10/15 720 63/67 smooth all over 9 0.16 -17 10/10 970 55/65 very smooth 0.16 -10 1~/15 440 51/54 very smooth
11 0.16 -13 10/15 1730 56/63 very smooth
12 0.16 -9.3 10/15 1150 14/40 smooth
13 0.16 -15 10/20 1230 24/58 very smooth
14 0.16 -12 10/25 1290 20/40 smooth 0.16 -12 10/15 1430 64/70 very smooth all over .. . ..
, . . ' ' ' . :
.
.
. In the following comparisons, the same general procedure was employed as was usefl in the preceding examples, and the tables which follow contain the same column headings as the tables above. Component C was varied in the comparisons and is listed for each comparison.
COMPONENT COMPONENT ADDITIVES
COMPARISON C t~) D (%) FILLER ~%) .
A NONE A~5.4) AA(25) X(0.6) Y(0 3) Talc(0.7) B Material NONE CC(25) N-stearyl Used in Erucamide Examples Mold Re-2-15(5.5) lease Agent(0.9) C NONE E(10) CC(25) NONE
D Sodium NONE CC(25) Methyl Stearate Stearate (0.5) (0.53) E Material A(1.4)* CC(25) NONE
Used in Examples 2-15(5.5) F Material E(5.0) CC(25) NONE
Used in Examples 2-15(0.35)*
* Amount is too small 113361~3 TABLE~ 3 (Continued) RELEASE GLOSS MOLDED
CYCLE PRESSURE lowest/ SURFACE
5 ~H /~H ~ TIME (PSi3 hlqhest APPEARANCE
--H --c A About Not 10/15 2150 29/38 very rough 0.4 Measured B Not 0 1~/30 144013/23moderately 10 Measured rough surface C About Not 10/30 had to 36/47rough 0.5 Measured spray surface mold D Not Not 10/25 159016/23very rough Measured Measured surface E 0.16 -3 10/30 17909/18 smooth to moderately rough F About Not Sticking/ Spray 5/8 very rough 5 0.45 Measured No molding cycle established Although gloss values for some of the experiments in Table 3 is in the range of gloss values found for some of the Examples in Table 2, the surface roughness is not acceptable in the experiments of the Comparisons.
, . . ' ' ' . :
.
.
. In the following comparisons, the same general procedure was employed as was usefl in the preceding examples, and the tables which follow contain the same column headings as the tables above. Component C was varied in the comparisons and is listed for each comparison.
COMPONENT COMPONENT ADDITIVES
COMPARISON C t~) D (%) FILLER ~%) .
A NONE A~5.4) AA(25) X(0.6) Y(0 3) Talc(0.7) B Material NONE CC(25) N-stearyl Used in Erucamide Examples Mold Re-2-15(5.5) lease Agent(0.9) C NONE E(10) CC(25) NONE
D Sodium NONE CC(25) Methyl Stearate Stearate (0.5) (0.53) E Material A(1.4)* CC(25) NONE
Used in Examples 2-15(5.5) F Material E(5.0) CC(25) NONE
Used in Examples 2-15(0.35)*
* Amount is too small 113361~3 TABLE~ 3 (Continued) RELEASE GLOSS MOLDED
CYCLE PRESSURE lowest/ SURFACE
5 ~H /~H ~ TIME (PSi3 hlqhest APPEARANCE
--H --c A About Not 10/15 2150 29/38 very rough 0.4 Measured B Not 0 1~/30 144013/23moderately 10 Measured rough surface C About Not 10/30 had to 36/47rough 0.5 Measured spray surface mold D Not Not 10/25 159016/23very rough Measured Measured surface E 0.16 -3 10/30 17909/18 smooth to moderately rough F About Not Sticking/ Spray 5/8 very rough 5 0.45 Measured No molding cycle established Although gloss values for some of the experiments in Table 3 is in the range of gloss values found for some of the Examples in Table 2, the surface roughness is not acceptable in the experiments of the Comparisons.
Claims (11)
1. A composition consisting essentially of:
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a material selected from a sodium or potassium salt of a hydrocarbon acid containing between about 7 and 25 carbon atoms, or a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said material present in an amount sufficient to provide a .DELTA.HH/.DELTA.Hc ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount sufficient to provide a Tpk at least 4°C lower than the Tpk of a mixture of components A, B and C, said compound being selected from a) organic esters selected from the product of an aromatic carboxylic acid of 7-11 carbon atoms containing at least 1 carboxyl group per aromatic nucleus, and an alcohol selected from those of the formula (HOCH2?XR' wherein x is l, 2 or 3 and R' is a hydrocarbon radical of 2-15 carbon atoms or those of the formula HO?R"O?yR"' wherein y is a cardinal number between 1 and 15, R"
is a hydrocarbon radical of 2-15 carbon atoms, and R"' is -H or a hydrocarbon radical of 2-20 carbon atoms, b) organic ketones of the formula R?R, c) organic sulfones of the formula RSOOR, d) organic sulfoxides of the formula R2SO, e) organic nitriles of the formula RCN, or f) organic amides of the formula R?NR'R or R?ONR'R;
wherein in formulas b) through f) each R can be the same as, or different from, any other R and is a hydrocarbyl group of 1-25 carbon atoms, while in the formulas in f) R' is hydrogen or a hydrocarbyl group of 1-25 carbon atoms.
A. polyethylene terephthalate having an inherent viscosity of at least about 0.4;
B. between about 10 and about 60 percent by weight reinforcing or filling material;
C. a material selected from a sodium or potassium salt of a hydrocarbon acid containing between about 7 and 25 carbon atoms, or a sodium or potassium salt of an organic polymer which contains pendant carboxyl groups, said material present in an amount sufficient to provide a .DELTA.HH/.DELTA.Hc ratio of less than 0.25 to a mixture of components A, B and C;
D. a compound present in an amount sufficient to provide a Tpk at least 4°C lower than the Tpk of a mixture of components A, B and C, said compound being selected from a) organic esters selected from the product of an aromatic carboxylic acid of 7-11 carbon atoms containing at least 1 carboxyl group per aromatic nucleus, and an alcohol selected from those of the formula (HOCH2?XR' wherein x is l, 2 or 3 and R' is a hydrocarbon radical of 2-15 carbon atoms or those of the formula HO?R"O?yR"' wherein y is a cardinal number between 1 and 15, R"
is a hydrocarbon radical of 2-15 carbon atoms, and R"' is -H or a hydrocarbon radical of 2-20 carbon atoms, b) organic ketones of the formula R?R, c) organic sulfones of the formula RSOOR, d) organic sulfoxides of the formula R2SO, e) organic nitriles of the formula RCN, or f) organic amides of the formula R?NR'R or R?ONR'R;
wherein in formulas b) through f) each R can be the same as, or different from, any other R and is a hydrocarbyl group of 1-25 carbon atoms, while in the formulas in f) R' is hydrogen or a hydrocarbyl group of 1-25 carbon atoms.
2. The composition of Claim 1 wherein Component C is the sodium or potassium salt of an organic polymer which contains pendant carboxyl groups.
3. The composition of Claim 1 wherein Component C is the sodium or potassium salt of a copolymer of an olefin and acrylic or methacrylic acid.
4. The composition of Claim 1 wherein Component C is the sodium salt of a copolymer of ethylene and methacrylic acid in which at least 30%
of the carboxyl groups are neutralized with sodium.
of the carboxyl groups are neutralized with sodium.
5. The composition of Claim 1 wherein Component D is an organic ester selected from the organic esters defined in Claim 1.
6. The composition of Claims 2, 3 or 4 wherein Component D is an organic ester selected from the product of an aromatic hydrocarbon carboxylic acid of 7-11 carbon atoms containing 1-3 carboxyl groups per aromatic nucleus, and an alcohol selected from those of the formula (HOCH2?xR' wherein x is 1, 2 or 3 and R' is alkyl of 2-10 carbon atoms when x is 1 and R' is alkylene of 2-10 carbon atoms when x is 2 or 3, or those of the formula HO?R''O?yR"' wherein y is a cardinal number of between 1 and 8, R"
is alkylene of 2-8 carbon atoms and R"' is -H.
is alkylene of 2-8 carbon atoms and R"' is -H.
7. The composition of Claims 2, 3 or 4 wherein Component D is an ester selected from the product of benzoic acid and an alcohol of the formula (HOCH2?2R' wherein R' is alkylene of 4-6 carbon atoms or HO(R"O?yH wherein R" is ethylene or propylene and y is 2 or 3.
8. The composition of Claims 1, 3 or 5 wherein Component B is glass fiber.
9. The composition of Claims 1, 3 or 5 wherein Component B is glass fiber and which con-tains 0.1 to 1.5 percent by weight of an epoxy compound.
10. The composition of Claims 1, 3 or 5 wherein Component B is mica.
11. The composition of Claims 1, 3 or 5 wherein Component B is a mixture of glass fibers and mica.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88221978A | 1978-02-28 | 1978-02-28 | |
| US882,219 | 1978-02-28 | ||
| US06/000,631 US4352904A (en) | 1978-02-28 | 1979-01-05 | Molding resins |
| US000,631 | 1979-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133643A true CA1133643A (en) | 1982-10-12 |
Family
ID=26667908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA322,518A Expired CA1133643A (en) | 1978-02-28 | 1979-02-27 | High gloss smooth molded articles from filled pet compositions |
Country Status (15)
| Country | Link |
|---|---|
| AU (1) | AU521662B2 (en) |
| BE (1) | BE874468A (en) |
| BR (1) | BR7901204A (en) |
| CA (1) | CA1133643A (en) |
| CH (1) | CH644618A5 (en) |
| DD (1) | DD142199A5 (en) |
| DE (1) | DE2907729C2 (en) |
| ES (1) | ES478146A1 (en) |
| FR (1) | FR2418254A1 (en) |
| GB (1) | GB2015014B (en) |
| IT (1) | IT1207176B (en) |
| LU (1) | LU80979A1 (en) |
| NL (1) | NL173537C (en) |
| RO (1) | RO78442A (en) |
| SE (1) | SE430168B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223113A (en) | 1976-11-23 | 1980-09-16 | Bayer Aktiengesellschaft | Polyester compositions which crystallize rapidly |
| ATE7396T1 (en) | 1979-09-21 | 1984-05-15 | Imperial Chemical Industries Plc | RAPIDLY CRYSTALLIZABLE COMPOSITION BASED ON A BLOCK COPOLYESTER. |
| CA1166781A (en) * | 1979-11-19 | 1984-05-01 | Peter Bier | Process for injection molding a rapidly crystallizing polyethylene terephthalate composition at reduced mold temperatures |
| EP0031201A3 (en) * | 1979-12-12 | 1981-07-15 | Imperial Chemical Industries Plc | Fast crystallising polyester compositions |
| GB2075032B (en) | 1980-04-28 | 1983-07-27 | Teijin Ltd | Polyethylene terephthalate resin compositions |
| US4338243A (en) | 1980-05-07 | 1982-07-06 | E. I. Du Pont De Nemours And Company | Polyethylene terephthalate blends |
| EP0041315A1 (en) * | 1980-05-29 | 1981-12-09 | E.I. Du Pont De Nemours And Company | Polyethylene terephthalate molding blends and molded articles thereof |
| US4351758A (en) | 1980-08-06 | 1982-09-28 | Celanese Corporation | Polyester blends |
| US4444931A (en) * | 1980-08-06 | 1984-04-24 | Celanese Corporation | Polyester blends |
| US4425457A (en) | 1980-08-06 | 1984-01-10 | Celanese Corporation | High gloss polyethylene terephthalate reinforced resin compositions |
| US4483955A (en) * | 1980-08-06 | 1984-11-20 | Celanese Corporation | High gloss polyethylene terephthalate reinforced resin compositions |
| US4316866A (en) | 1980-09-26 | 1982-02-23 | R. Martin & Associates | Process and apparatus involving a cutting wire spooling system for cutting brick and tile |
| US4351757A (en) * | 1980-10-24 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Molding material of polyethylene terephthalate and alkai metal salt of C30 -C54 substantially aliphatic carboxylic acid |
| US4357268A (en) | 1980-12-29 | 1982-11-02 | Allied Corporation | Nucleation agents for crystalline polymers |
| DE3276178D1 (en) * | 1981-01-30 | 1987-06-04 | Teijin Ltd | Polyester resin composition |
| DE3110906A1 (en) * | 1981-03-20 | 1982-10-14 | Akzo Gmbh, 5600 Wuppertal | HYDROPHILE POLYESTER MATERIAL |
| US4349503A (en) | 1981-05-15 | 1982-09-14 | Allied Corporation | Polyester compositions containing sodium nitrite |
| US4486561A (en) * | 1981-08-21 | 1984-12-04 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
| US4539352A (en) * | 1981-08-21 | 1985-09-03 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
| US4368285A (en) * | 1981-12-07 | 1983-01-11 | Dart Industries Inc. | Fast crystallizing polyethylene terephthalate containing neopentyl dibenzoate |
| JPS58117246A (en) * | 1981-12-28 | 1983-07-12 | Daicel Chem Ind Ltd | Polyester composition |
| US4378444A (en) * | 1982-05-12 | 1983-03-29 | E. I. Du Pont De Nemours And Company | Molding material |
| WO1983004038A1 (en) * | 1982-05-13 | 1983-11-24 | Ethyl Corporation | Polyester composition |
| US4533679A (en) * | 1982-06-28 | 1985-08-06 | Mobay Chemical Corporation | Reinforced polyester composition having an improved strength |
| GB2124637A (en) * | 1982-08-03 | 1984-02-22 | Bip Chemicals Ltd | Polyethylene terephthalate moulding compositions |
| US4425470A (en) | 1982-08-06 | 1984-01-10 | E. I. Du Pont De Nemours And Company | Alkali metal salts of low molecular weight polyethylene terephthalate as nucleating agents for polyethylene terephthalates |
| US4429067A (en) | 1982-10-27 | 1984-01-31 | E. I. Du Pont De Nemours And Company | Polyethylene terephthalate molding compositions |
| EP0109123B1 (en) * | 1982-11-11 | 1987-03-25 | Akzo N.V. | Thermoplastic block copolyester resin composition containing a nucleating agent and an accelerator |
| US4548996A (en) * | 1984-01-09 | 1985-10-22 | Monsanto Company | Hot melt adhesive compositions |
| US4581410A (en) * | 1984-01-09 | 1986-04-08 | Monsanto Company | Hot melt adhesive compositions |
| DE3585935D1 (en) * | 1984-02-24 | 1992-06-04 | Du Pont | REINFORCED THERMOPLASTIC POLYESTER COMPOSITIONS. |
| DE3532033A1 (en) * | 1985-09-09 | 1987-03-19 | Hoechst Ag | QUICK CRYSTALIZING POLYESTER MATERIALS AND METHOD FOR THE PRODUCTION THEREOF |
| IT1197798B (en) * | 1986-08-01 | 1988-12-06 | Montefibre Spa | QUICK CRYSTALLIZATION POLYESTER COMPOSITIONS |
| EP0288398A3 (en) * | 1987-04-23 | 1989-08-09 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Fiber-reinforced polyester of improved strength |
| US4908428A (en) * | 1987-07-27 | 1990-03-13 | Montefibre S.P.A. | Quick-crystallizing polyester composition |
| US5554120A (en) * | 1994-07-25 | 1996-09-10 | Advanced Cardiovascular Systems, Inc. | Polymer blends for use in making medical devices including catheters and balloons for dilatation catheters |
| US5849846A (en) * | 1994-07-25 | 1998-12-15 | Advanced Cardiovascular Systems, Inc. | Balloons for medical catheters |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6608999A (en) * | 1965-11-20 | 1967-02-27 | ||
| US3639527A (en) * | 1967-09-05 | 1972-02-01 | Hoechst Ag | Polyester-ionic copolymer thermoplastic moulding compositions |
| US3533994A (en) * | 1968-02-20 | 1970-10-13 | Fmc Corp | Stabilized polyesters |
| US3516957A (en) * | 1968-04-29 | 1970-06-23 | Eastman Kodak Co | Thermoplastic polyester composition containing organic ester mold release agent |
| DE2014770B2 (en) * | 1969-04-01 | 1978-07-20 | Mitsubishi Rayon Co. Ltd., Tokio | Polyethylene terephthalate molding compound and nucleating agent |
| BE757093A (en) * | 1969-10-06 | 1971-04-06 | Hoechst Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON POLYESTERS |
| JPS4914564A (en) * | 1972-05-22 | 1974-02-08 | ||
| JPS4928640A (en) * | 1972-07-13 | 1974-03-14 | ||
| GB1485841A (en) * | 1974-02-22 | 1977-09-14 | Ici Ltd | Polyester composition |
| AU500523B2 (en) * | 1975-12-08 | 1979-05-24 | General Electric Company | Thermoplastic molding composition |
-
1979
- 1979-01-30 SE SE7900801A patent/SE430168B/en unknown
- 1979-02-23 BR BR7901204A patent/BR7901204A/en unknown
- 1979-02-26 FR FR7904843A patent/FR2418254A1/en active Granted
- 1979-02-26 AU AU44592/79A patent/AU521662B2/en not_active Ceased
- 1979-02-27 DD DD79211257A patent/DD142199A5/en unknown
- 1979-02-27 BE BE0/193708A patent/BE874468A/en not_active IP Right Cessation
- 1979-02-27 CA CA322,518A patent/CA1133643A/en not_active Expired
- 1979-02-27 CH CH192879A patent/CH644618A5/en not_active IP Right Cessation
- 1979-02-27 ES ES478146A patent/ES478146A1/en not_active Expired
- 1979-02-27 IT IT7920606A patent/IT1207176B/en active
- 1979-02-28 NL NLAANVRAGE7901605,A patent/NL173537C/en not_active IP Right Cessation
- 1979-02-28 LU LU80979A patent/LU80979A1/en unknown
- 1979-02-28 RO RO7996741A patent/RO78442A/en unknown
- 1979-02-28 DE DE2907729A patent/DE2907729C2/en not_active Expired
- 1979-02-28 GB GB7907034A patent/GB2015014B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2418254A1 (en) | 1979-09-21 |
| DE2907729C2 (en) | 1982-08-26 |
| NL173537C (en) | 1988-08-16 |
| DD142199A5 (en) | 1980-06-11 |
| BE874468A (en) | 1979-08-27 |
| RO78442A (en) | 1982-03-24 |
| AU521662B2 (en) | 1982-04-22 |
| LU80979A1 (en) | 1979-09-07 |
| FR2418254B1 (en) | 1981-01-30 |
| ES478146A1 (en) | 1980-01-16 |
| CH644618A5 (en) | 1984-08-15 |
| IT1207176B (en) | 1989-05-17 |
| DE2907729A1 (en) | 1980-01-10 |
| NL173537B (en) | 1983-09-01 |
| GB2015014B (en) | 1982-09-08 |
| IT7920606A0 (en) | 1979-02-27 |
| SE430168B (en) | 1983-10-24 |
| AU4459279A (en) | 1980-01-03 |
| BR7901204A (en) | 1979-10-02 |
| GB2015014A (en) | 1979-09-05 |
| SE7900801L (en) | 1979-08-29 |
| NL7901605A (en) | 1979-08-30 |
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