WO2000049065A1 - Addition of treatment agents to solid phase polymerization processes - Google Patents
Addition of treatment agents to solid phase polymerization processes Download PDFInfo
- Publication number
- WO2000049065A1 WO2000049065A1 PCT/US2000/003980 US0003980W WO0049065A1 WO 2000049065 A1 WO2000049065 A1 WO 2000049065A1 US 0003980 W US0003980 W US 0003980W WO 0049065 A1 WO0049065 A1 WO 0049065A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- solid state
- polymerization
- state polymerization
- treatment agent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
Definitions
- This invention concerns a process for the addition of volatile materials, such as catalysts or treatment agents, to prepolymers prior to or during solid state polymerization processes and the subsequent solid state polymerization process.
- volatile materials such as catalysts or treatment agents
- the volatile materials having completed their function, may be removed from the polymer during or after the solid state polymerization process.
- the present invention adds the catalyst or other treatment agent as a gas or dissolved in a liquid, which improves the contact of the polymer, typically in the form of a particle or a pastille, with the catalyst or treatment material and, if the agent is sufficiently volatile, also facilitates removal of the agent from the system.
- the agent is then removed easily from the system after contact with the polymer by the inert gas sweep employed in solid state polymerization processes and the resulting polymerization product is substantially free of catalyst or treatment agent.
- This invention provides a process for the addition of volatile treatment agents to a solid state polymerization in a condensation polymerization process comprising: a) establishing a recirculating gas flow over polymer particles undergoing solid state polymerization; b) introducing a volatile treatment agent into said recirculating gas flow; and c) contacting said polymer particles with said volatile treatment agent under solid phase polymerization conditions.
- This invention further provides a process for the addition of volatile treatment agents to a solid state polymerization in a condensation polymerization process comprising: a) contacting polymer particles with a solution of a volatile treatment agent in a suitable solvent; b) removing said solvent to yield polymer particles coated with or containing said treatment agent; c) subjecting said polymer particles to solid state polymerization in the presence of a gas flow.
- This invention may be used with additive materials such as catalysts, treatment agents, catalyst deactivators, nucleating agents, antioxidants, ultraviolet stabilizing agents, plasticizers, thermal stabilizers, comonomers, tinting agents and barrier property enhancers.
- additive materials such as catalysts, treatment agents, catalyst deactivators, nucleating agents, antioxidants, ultraviolet stabilizing agents, plasticizers, thermal stabilizers, comonomers, tinting agents and barrier property enhancers.
- it is desirable to remove the additive material after contact with the polymer although in some embodiments herein the additive is incorporated into the polymer as part of the final product.
- the process of the present invention applies to the polymerization of polymers where the polymerization process is subject to catalysis or other treatment.
- Suitable polymer types include polyesters, polyamides and polycarbonates, including homopolymers and copolymers of these various polymer types.
- the polymer to which the process of the present invention is applied typically has a degree of polymerization in the range of from 5 to 25. In working with these polymers it has been customary to introduce the catalyst species into the melt phase of the polymerization process followed by solidification and crystallization.
- a catalyst or treatment material effective in solid state polymerization is introduced into the solid state polymerization stage via a gas stream that is introduced to, and vented from, the solid state polymerizer. It is also within the scope of the present invention to introduce the catalyst or treatment agent via a gas stream introduced to a preheater or conditioner vessel upstream of the solid phase polymerizer.
- the catalyst or treatment material must be sufficiently volatile, i.e., it has a high enough vapor pressure, to be introduced via the gas stream, and, optionally, to also be removed via the gas stream.
- the amount of catalyst remaining in the subject polymer may be substantially reduced.
- This offers potential utility both in polymer purity and stability.
- residual catalyst lends itself to polymer instability, especially during the course of post-polymerization treatment steps or uses that involve exposure to elevated temperatures.
- the additive may be introduced by use of a solution of the additive in a suitable solvent, followed by removal of said solvent.
- polymer particles are contacted with the treatment agent, then after solvent removal, the coated polymer particles are subjected to solid state polymerization in the presence of a vapor sweep. If the agent is sufficiently volatile, and the solid state polymerization is sufficiently lengthy, the additive may be completely removed by the vapor sweep leading to the same potential advantages as described above for vapor state addition of volatile agents.
- additives such as catalysts, treatment agents, catalyst deactivators, nucleating agents, antioxidants, ultraviolet stabilizing agents, plasticizers, thermal stabilizers, co-monomers, tinting agents and barrier property enhancers may be contacted with the polymer in the solid state polymerizer.
- catalyst additives useful herein include the following: benzene- sulfonic acid, methanesulfonic acid triflic acid (trifluoromefhanesulfonic acid), toluene sulfonic acids, especially p-toluene sulfonic acid, other volatile Bronsted and Lewis acids, tetra isopropoxy titanate and tri butoxy antimonate. Volatile Bronsted acids are preferred.
- Bronsted acids are generally not useful in conventional solid state polymerization processes of polyesters due to excessive dialkylene glycol formation.
- Certain grades of polyester, such as for the bottle resin market are typically polymerized to high molecular weight in the melt phase, i.e., to -0.65 IV, and then subjected to post-polymerization solid phasing to raise the molecular weight even further to levels needed for bottle resins or for industrial fibers.
- Example 4 shows that the process of the present invention can be used to increase rates of this post polymerization solid phasing.
- Viscosities reported below were obtained with a Viscotek Forced Flow Viscometer. Polyesters were dissolved in trifluoroacetic acid/methylene chloride. The viscosity data reported have been correlated to the intrinsic viscosity in 60/40 wt % phenol/tetrachloroethane following ASTM D4603-96.
- the pastilles treated with the C6H5SO3H catalyst analyzed for 1068 ppm S before solid phase polymerization and 145 ppm S after solid phase polymerization.
- a sample of these pastilles after solid phase polymerization was subjected to a vacuum oven at 110°C for 16 hours which further reduced their sulfur content to 15 ppm S.
- a sample of these pastilles after solid phase polymerization was melted under vacuum for 60 minutes, which reduced their sulfur content to 130 ppm S.
- the polyethylene terephthalate oligomer used in this experiment contained 275 ppm Sb catalyst, had 2 mole % isophthalic acid comonomer, and possessed a degree of polymerization of 20.
- the pastilles weighed 16 mg/particle on average.
- the end group composition was 225 meq/kg of carboxyl groups with essentially all of the remainder being hydroxyl groups.
- Fifteen grams of this oligomer was solid-phase polymerized using dry nitrogen at 230°C which had been passed over 3 grams of benzene sulfonic acid.
- the catalyst is added in the gas phase in this experiment.
- the total polymerization time was 24 hours. This sample is designated A in the table below.
- sample B in the table below.
- the table shows the intrinsic viscosity versus time.
- EXAMPLE 4 This example demonstrates the addition of catalyst after melt phase polymerization as a means of enhancing the rate of subsequent solid phase polymerization.
- Crystar® Merge 3934 polyethylene terephthalate is a typical commercial grade high molecular weight polyester prepared in a melt process using antimony trioxide as catalyst. It is obtainable from E. I. du Pont de Nemours and Company, Wilmington, DE.
- the polymer used was in the form of pellets that had been first crystallized by heating to 160°C for 5 hours. Fifteen gram aliquots of these pellets were soaked for 3 minutes in a solution consisting of 5.0 g of benzene sulfonic acid in 100 mL of methylene chloride.
- Example 2 The procedure of Example 2 was repeated except with a pre-polymer low in acid end groups and rich in ethylene glycol end groups.
- This oligomer had an initial acid end group concentration of 77 meq/kg and an initial ethylene glycol end group concentration of 552 meq/kg.
- the control had an acid end group concentration of 225 meq/kg, with the remaining end groups being ethylene glycol end groups.
- the inherent viscosity as a function of time in solid stating is tabulated below. These data show that solid-phase polymerization is faster at these lower ethylene glycol end group concentrations.
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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)
- Polyesters Or Polycarbonates (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002359082A CA2359082A1 (en) | 1999-02-17 | 2000-02-17 | Addition of treatment agents to solid phase polymerization processes |
EP00913488A EP1155064B1 (en) | 1999-02-17 | 2000-02-17 | Addition of treatment agents to solid phase polymerization processes |
DE60017366T DE60017366T2 (en) | 1999-02-17 | 2000-02-17 | ADDITION OF TREATMENT AGENTS IN SOLID PHASE POLYMERIZATION PROCEDURES |
AT00913488T ATE286933T1 (en) | 1999-02-17 | 2000-02-17 | ADDING TREATMENT AGENTS IN SOLID PHASE POLYMERIZATION PROCESSES |
JP2000599801A JP4463430B2 (en) | 1999-02-17 | 2000-02-17 | Addition of treatment agent to solid-state polymerization method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12039399P | 1999-02-17 | 1999-02-17 | |
US60/120,393 | 1999-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000049065A1 true WO2000049065A1 (en) | 2000-08-24 |
Family
ID=22389979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/003980 WO2000049065A1 (en) | 1999-02-17 | 2000-02-17 | Addition of treatment agents to solid phase polymerization processes |
Country Status (8)
Country | Link |
---|---|
US (1) | US6180756B1 (en) |
EP (1) | EP1155064B1 (en) |
JP (1) | JP4463430B2 (en) |
AT (1) | ATE286933T1 (en) |
CA (1) | CA2359082A1 (en) |
DE (1) | DE60017366T2 (en) |
ES (1) | ES2234578T3 (en) |
WO (1) | WO2000049065A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6342578B1 (en) | 2000-12-06 | 2002-01-29 | Arteva North America S.A.R.L. | Copolyester with high carboxyl end groups and a method for making |
EP1705201A1 (en) * | 2005-03-24 | 2006-09-27 | Giuliano Cavaglia' | Reactive atmosphere for continuous and/or discontinuous solid phase polymerisation of polyester and method of application of said atmosphere |
US7244792B2 (en) | 2002-03-20 | 2007-07-17 | Agarwal Uday S | Process for making a modified thermoplastic polyester |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1323747A1 (en) * | 2001-12-19 | 2003-07-02 | Borealis Technology Oy | Production of olefin polymerisation catalysts |
TW200615298A (en) * | 2004-10-04 | 2006-05-16 | Shell Int Research | Process for producing polytrimethylene rephthalate |
MX2009000462A (en) * | 2006-07-11 | 2009-03-03 | Wellman Inc | Composite solid phase polymerization catalyst. |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2503000A1 (en) * | 1974-02-07 | 1975-08-21 | Gen Electric | POLYMERIZATION OF POLY(1,4-BUTYLENE TEREPHTHALATE) IN THE SOLID STATE |
WO1994015991A1 (en) * | 1993-01-04 | 1994-07-21 | Eastman Chemical Company | Production of polyesters and polyester articles having good clarity |
US5523361A (en) * | 1995-08-31 | 1996-06-04 | Shell Oil Company | Process for crystallizing polyethylene naphthalate |
EP0717061A2 (en) * | 1994-12-16 | 1996-06-19 | Sinco Engineering S.P.A. | Process for the solid state polycondensation of polyester resins |
EP0807655A1 (en) * | 1996-02-15 | 1997-11-19 | Council Of Scientific And Industrial Research | Preparation of aromatic polyesters |
EP0807656A1 (en) * | 1995-02-03 | 1997-11-19 | Idemitsu Petrochemical Co., Ltd. | Process for producing polycarbonates |
EP0908483A1 (en) * | 1997-09-16 | 1999-04-14 | Council of Scientific and Industrial Research | A process for the preparation of poly (ester-carbonate)s |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4150215A (en) | 1978-02-13 | 1979-04-17 | The Goodyear Tire & Rubber Company | Process for preparing catalyst-free polyester |
US4294956A (en) * | 1979-08-27 | 1981-10-13 | Union Carbide Corporation | Process for preparing polyarylates in the presence of a diphenyl ether |
US4296232A (en) * | 1979-08-27 | 1981-10-20 | Union Carbide Corporation | Process for preparing polyarylates in the presence of a diphenyl ether compound and a catalyst |
US4418188A (en) * | 1982-09-07 | 1983-11-29 | The Goodyear Tire & Rubber Company | Polyethylene isophthalate having reduced cyclic dimer content and process therefore |
US4447595A (en) * | 1982-09-07 | 1984-05-08 | The Goodyear Tire & Rubber Company | Polyterephthalates and copolymers thereof having high clarity and process for making same |
-
2000
- 2000-02-16 US US09/505,045 patent/US6180756B1/en not_active Expired - Lifetime
- 2000-02-17 AT AT00913488T patent/ATE286933T1/en not_active IP Right Cessation
- 2000-02-17 CA CA002359082A patent/CA2359082A1/en not_active Abandoned
- 2000-02-17 EP EP00913488A patent/EP1155064B1/en not_active Expired - Lifetime
- 2000-02-17 ES ES00913488T patent/ES2234578T3/en not_active Expired - Lifetime
- 2000-02-17 WO PCT/US2000/003980 patent/WO2000049065A1/en active IP Right Grant
- 2000-02-17 JP JP2000599801A patent/JP4463430B2/en not_active Expired - Fee Related
- 2000-02-17 DE DE60017366T patent/DE60017366T2/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2503000A1 (en) * | 1974-02-07 | 1975-08-21 | Gen Electric | POLYMERIZATION OF POLY(1,4-BUTYLENE TEREPHTHALATE) IN THE SOLID STATE |
WO1994015991A1 (en) * | 1993-01-04 | 1994-07-21 | Eastman Chemical Company | Production of polyesters and polyester articles having good clarity |
EP0717061A2 (en) * | 1994-12-16 | 1996-06-19 | Sinco Engineering S.P.A. | Process for the solid state polycondensation of polyester resins |
EP0807656A1 (en) * | 1995-02-03 | 1997-11-19 | Idemitsu Petrochemical Co., Ltd. | Process for producing polycarbonates |
US5523361A (en) * | 1995-08-31 | 1996-06-04 | Shell Oil Company | Process for crystallizing polyethylene naphthalate |
EP0807655A1 (en) * | 1996-02-15 | 1997-11-19 | Council Of Scientific And Industrial Research | Preparation of aromatic polyesters |
EP0908483A1 (en) * | 1997-09-16 | 1999-04-14 | Council of Scientific and Industrial Research | A process for the preparation of poly (ester-carbonate)s |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6342578B1 (en) | 2000-12-06 | 2002-01-29 | Arteva North America S.A.R.L. | Copolyester with high carboxyl end groups and a method for making |
US7244792B2 (en) | 2002-03-20 | 2007-07-17 | Agarwal Uday S | Process for making a modified thermoplastic polyester |
EP1705201A1 (en) * | 2005-03-24 | 2006-09-27 | Giuliano Cavaglia' | Reactive atmosphere for continuous and/or discontinuous solid phase polymerisation of polyester and method of application of said atmosphere |
WO2006100652A1 (en) * | 2005-03-24 | 2006-09-28 | Cavaglia Giuliano | Reactive atmosphere for continuous and/or discontinuous solid phase polymerisation of polyester and method of application of said atmosphere |
Also Published As
Publication number | Publication date |
---|---|
JP2002537425A (en) | 2002-11-05 |
DE60017366D1 (en) | 2005-02-17 |
US6180756B1 (en) | 2001-01-30 |
DE60017366T2 (en) | 2005-12-15 |
CA2359082A1 (en) | 2000-08-24 |
EP1155064A1 (en) | 2001-11-21 |
JP4463430B2 (en) | 2010-05-19 |
ATE286933T1 (en) | 2005-01-15 |
ES2234578T3 (en) | 2005-07-01 |
EP1155064B1 (en) | 2005-01-12 |
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