Patent · US4409167A · A · US
Process for extruding a modified high molecular weight poly(ethylene terephthalate) resin
- (11) Publication number
- US4409167A
- (21) Application number
- 06/332,768
- (22) Filing date
- 1981-12-21
- (30) Priority date
- 1981-01-13
- (43) Publication date
- 1983-10-11
- (45) Date of grant
- 1983-10-11
- (51) IPC
- B29C 48/395; C08G 18/40; C08G 18/42; C08G 63/91
- (52) CPC
- C08G Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds: 63/916, 18/4063, 18/4213
- B29C Shaping or joining of plastics; shaping of material in a plastic state, not otherwise provided for; after-treatment of the shaped products, e.g. repairing: 48/022, 48/07, 48/395
- B29K Indexing scheme associated with subclasses B29B, B29C or B29D, relating to moulding materials or to materials for {moulds, } reinforcements, fillers or preformed parts, e.g. inserts: 2067/00
- (73) Assignee
- EI Du Pont de Nemours and Co
- (72) Inventors
- Robert J. Kolouch; Rudolph H. Michel
- (54) Title
- Process for extruding a modified high molecular weight poly(ethylene terephthalate) resin
- (57) Abstract
Poly(ethylene terephthalate) resin and blends of poly(ethylene terephthalate) resin with other polymers are extruded while being coupled with an organic diisocyanate under conditions where carbon dioxide gas is vented smoothly, as it is formed. The extruder has a number of zones designed to perform specific functions. The temperature in the kneading zone and in the venting zone must be maintained at about 280 DEG -320 DEG C. to bring about rapid reaction and to permit efficient gas evolution and removal without thermally degrading the polymeric material. The extruded article is free of trapped gas bubbles and other imperfections. This process is particularly suitable for making PET billets, which then are stretched to form strapping useful in packaging applications.
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Claims (13)
- A process for extruding a bubble-free article from a polymeric composition selected from the class consisting of: (a) poly(ethylene terephthalate) resin; (b) a uniform blend of poly(ethylene terephthalate) resin with a compatible polymer, the amount of the compatible polymer being at most about 10 weight percent of the blend; and (c) a uniform blend of a poly(ethylene terephthalate) resin with an incompatible polymer and a compatibilizing agent, the total amount of the incompatible polymer and compatibilizing agent being at most about 20 weight percent of the blend; said process comprising: (1) premixing an organic diisocyanate with said polymeric composition or individual components of said composition, in any order, the amount of said diisocyanate being sufficient to increase the melt viscosity of said polymeric composition to the desired level without causing excessive crosslinking; (2) introducing the premix of step (1) into the feed section of a twin-screw extruder having a cold feed section, a hot plastication zone, a kneading zone maintained at an average temperature of about 280° to 320° C., a venting zone maintained at an average temperature of about 280° to 320° C. and at a pressure of less than about 1.33 kPa, a metering zone maintained at an average temperature of about 260° to 280° C., and an extrusion due maintained at an average temperature of about 255° to 265° C., all the temperatures being wall temperatures; and (3) operating the extruder at about 30-120 rpm and at a pressure of about 350 kPa or less to recover the extruded article from the die.
- A process of claim 1 wherein the diisocyanate is methylenebis(p-phenyl isocyanate).
- A process of claim 2 wherein the polymeric composition is poly(ethylene terephthalate).
- A process of claim 1 wherein the polymeric composition is a blend of poly(ethylene terephthalate) with an EPDM elastomer grafted with an unsaturated compound selected from the class consisting of maleic anhydride, maleic acid, fumaric acid, and mono- and diesters of maleic and fumaric acids.
- A process of claim 4 wherein the grafted EPDM elastomer is present in the amount of 4-6% of the total weight of the blend.
- A process of claim 1 wherein the polymeric composition is a blend of poly(ethylene terephthalate) with a compatible polymer, which is present in an amount of at least 3% of the total weight of the blend.
- A process of claim 2 wherein the amount of the diisocyanate is about 0.6-1.1% based on the weight of poly(ethylene terephthalate) resin.
- A process of claim 7 wherein the amount of diisocyanate is 0.7-1% based on the weight of poly(ethylene terephalate) resin.
- A process of claim 8 wherein the amount of diisocyanate is 0.8-0.9% based on the weight of poly(ethylene terephthalate) resin.
- A process of claim 1 wherein the average temperature range within the kneading zone and within the venting zone is about 290°-310° C.
- A process of claim 10 wherein the vent port is maintained at a pressure of about 0.1-0.13 kPa.
- A process of claim 10 wherein the average temperature range within the metering zone is about 270°-280° C.
- A process of claim 10 wherein the feed rate is about one-half of the internal volume per hour.
Description
This is a continuation-in-part of application Ser. No. 224,673 filed Jan. 13, 1981 now abandoned.
Poly(ethylene terephthalate), sometimes abbreviated to PET throughout this disclosure, has many industrial uses, including the manufacture of fibers, films, and shaped articles. PET resins having a low to moderate molecular weight, M n =12,000-16,000, are easy to fabricate in all types of equipment. Higher molecular weight resins, for example, those having M n of about 25,000-45,000, are more difficult to extrude because more energy is required to move the viscous melt throughout the equipment.
A known expedient, that has been used in the past, is to increase the molecular weight of polyester resins directly in the fabricating equipment, for example, by coupling with an organic diisocyanate and crosslinking. Since, however, at the normal PET melt processing temperatures of about 265°-270° C. the intermediate --COOCONH-- group formed by reaction of the isocyanate with the terminal carboxyl groups of the poly(ethylene terephthalate) decomposes with carbon dioxide evolution, the polymer is likely to contain trapped gas bubbles. This naturally is undesirable where a homogeneous and strong material is required. A practical method of extruding various shapes from high molecular weight PET thus is needed.
Citations (11)
- US3553157A
- US3963679A
- US4065532A
- US4022752A
- US3963678A
- US4022863A
- US4055534A
- US4178277A
- US4245081A
- US4261946A
- US4260690A
Record as JSON
{
"publication_number": "US4409167A",
"country": "US",
"kind": "A",
"title": "Process for extruding a modified high molecular weight poly(ethylene terephthalate) resin",
"abstract": "Poly(ethylene terephthalate) resin and blends of poly(ethylene terephthalate) resin with other polymers are extruded while being coupled with an organic diisocyanate under conditions where carbon dioxide gas is vented smoothly, as it is formed. The extruder has a number of zones designed to perform specific functions. The temperature in the kneading zone and in the venting zone must be maintained at about 280 DEG -320 DEG C. to bring about rapid reaction and to permit efficient gas evolution and removal without thermally degrading the polymeric material. The extruded article is free of trapped gas bubbles and other imperfections. This process is particularly suitable for making PET billets, which then are stretched to form strapping useful in packaging applications.",
"claims": [
"1. A process for extruding a bubble-free article from a polymeric composition selected from the class consisting of: (a) poly(ethylene terephthalate) resin; (b) a uniform blend of poly(ethylene terephthalate) resin with a compatible polymer, the amount of the compatible polymer being at most about 10 weight percent of the blend; and (c) a uniform blend of a poly(ethylene terephthalate) resin with an incompatible polymer and a compatibilizing agent, the total amount of the incompatible polymer and compatibilizing agent being at most about 20 weight percent of the blend; said process comprising: (1) premixing an organic diisocyanate with said polymeric composition or individual components of said composition, in any order, the amount of said diisocyanate being sufficient to increase the melt viscosity of said polymeric composition to the desired level without causing excessive crosslinking; (2) introducing the premix of step (1) into the feed section of a twin-screw extruder having a cold feed section, a hot plastication zone, a kneading zone maintained at an average temperature of about 280° to 320° C., a venting zone maintained at an average temperature of about 280° to 320° C. and at a pressure of less than about 1.33 kPa, a metering zone maintained at an average temperature of about 260° to 280° C., and an extrusion due maintained at an average temperature of about 255° to 265° C., all the temperatures being wall temperatures; and (3) operating the extruder at about 30-120 rpm and at a pressure of about 350 kPa or less to recover the extruded article from the die.",
"2. A process of claim 1 wherein the diisocyanate is methylenebis(p-phenyl isocyanate).",
"3. A process of claim 2 wherein the polymeric composition is poly(ethylene terephthalate).",
"4. A process of claim 1 wherein the polymeric composition is a blend of poly(ethylene terephthalate) with an EPDM elastomer grafted with an unsaturated compound selected from the class consisting of maleic anhydride, maleic acid, fumaric acid, and mono- and diesters of maleic and fumaric acids.",
"5. A process of claim 4 wherein the grafted EPDM elastomer is present in the amount of 4-6% of the total weight of the blend.",
"6. A process of claim 1 wherein the polymeric composition is a blend of poly(ethylene terephthalate) with a compatible polymer, which is present in an amount of at least 3% of the total weight of the blend.",
"7. A process of claim 2 wherein the amount of the diisocyanate is about 0.6-1.1% based on the weight of poly(ethylene terephthalate) resin.",
"8. A process of claim 7 wherein the amount of diisocyanate is 0.7-1% based on the weight of poly(ethylene terephalate) resin.",
"9. A process of claim 8 wherein the amount of diisocyanate is 0.8-0.9% based on the weight of poly(ethylene terephthalate) resin.",
"10. A process of claim 1 wherein the average temperature range within the kneading zone and within the venting zone is about 290°-310° C.",
"11. A process of claim 10 wherein the vent port is maintained at a pressure of about 0.1-0.13 kPa.",
"12. A process of claim 10 wherein the average temperature range within the metering zone is about 270°-280° C.",
"13. A process of claim 10 wherein the feed rate is about one-half of the internal volume per hour."
],
"description_excerpt": "This is a continuation-in-part of application Ser. No. 224,673 filed Jan. 13, 1981 now abandoned.\n\nPoly(ethylene terephthalate), sometimes abbreviated to PET throughout this disclosure, has many industrial uses, including the manufacture of fibers, films, and shaped articles. PET resins having a low to moderate molecular weight, M n =12,000-16,000, are easy to fabricate in all types of equipment. Higher molecular weight resins, for example, those having M n of about 25,000-45,000, are more difficult to extrude because more energy is required to move the viscous melt throughout the equipment.\n\nA known expedient, that has been used in the past, is to increase the molecular weight of polyester resins directly in the fabricating equipment, for example, by coupling with an organic diisocyanate and crosslinking. Since, however, at the normal PET melt processing temperatures of about 265°-270° C. the intermediate --COOCONH-- group formed by reaction of the isocyanate with the terminal carboxyl groups of the poly(ethylene terephthalate) decomposes with carbon dioxide evolution, the polymer is likely to contain trapped gas bubbles. This naturally is undesirable where a homogeneous and strong material is required. A practical method of extruding various shapes from high molecular weight PET thus is needed.",
"cpc": [
"C08G 63/916",
"B29C 48/022",
"B29C 48/07",
"B29C 48/395",
"B29K 2067/00",
"C08G 18/4063",
"C08G 18/4213"
],
"ipc": [
"B29C 48/395",
"C08G 18/40",
"C08G 18/42",
"C08G 63/91"
],
"assignees": [
"EI Du Pont de Nemours and Co"
],
"inventors": [
"Robert J. Kolouch",
"Rudolph H. Michel"
],
"filing_date": "1981-12-21",
"publication_date": "1983-10-11",
"grant_date": "1983-10-11",
"priority_date": "1981-01-13",
"application_number": "US-33276881-A",
"family_id": "26918933",
"cited_by_count": 30,
"citations": [
"US3553157A",
"US3963679A",
"US4065532A",
"US4022752A",
"US3963678A",
"US4022863A",
"US4055534A",
"US4178277A",
"US4245081A",
"US4261946A",
"US4260690A"
]
}
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