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WO2000039172A1 - Procede d'obtention d'un poly(alkylene carbonate) de poids moleculaire moindre a partir d'un poly(alkylene carbonate) de poids moleculaire eleve - Google Patents

Procede d'obtention d'un poly(alkylene carbonate) de poids moleculaire moindre a partir d'un poly(alkylene carbonate) de poids moleculaire eleve Download PDF

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Publication number
WO2000039172A1
WO2000039172A1 PCT/US1999/031130 US9931130W WO0039172A1 WO 2000039172 A1 WO2000039172 A1 WO 2000039172A1 US 9931130 W US9931130 W US 9931130W WO 0039172 A1 WO0039172 A1 WO 0039172A1
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Prior art keywords
poly
thε
molecular weight
carbonate
hydroxy
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PCT/US1999/031130
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English (en)
Inventor
Joseph G. Sant'angelo
Xiaomao Chen
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PAC Polymers Inc
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PAC Polymers Inc
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Publication of WO2000039172A1 publication Critical patent/WO2000039172A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08G64/42—Chemical after-treatment

Definitions

  • the invention resides in the chemical arts. It relates to the art of synthetic resins, and more particularly to poly( alkylene carbonates) .
  • Poly(alkylene carbonates) are thermoplastic homopoly ers and copolymer ⁇ of alkylene carbonates.
  • the alkylene moiety of the monomeric units of these polymers has two-eight carbons .
  • Embodiments of these polymers are disclosed in such U.S. Patents as 3,585,168 of Inoue et al . , (normally solid homopolymers), 4,763,715 of Cannarsa et al . , (normally solid random copolymers), and 4,665,136 of Santangelo et al . , (normally solid block coploymer ⁇ ). The disclosures of these patents are incorporated by reference.
  • each alkylene carbonate monomeric unit in the random and block polymers can vary, but generally is in the range of 10-90 mole % of each polymer.
  • specific poly( alkylene carbonates) include poly(ethylene carbonate), poly(propylene carbonate), poly(cyclohexylene carbonate), random copolymer of ethylene carbonate and propylene carbonate, random copolymer of propylen ⁇ carbonate and cyclohexene carbonate, block copolymer of ethylene carbonate and propylene carbonate, and block copolymer of propylene carbonate and cyclohexene carbonate.
  • Poly(alkylene carbonates) are made by a process which, for ease of reference, is referred to herein as the zinc catalyst process.
  • a mixture of carbon dioxide and one or more than one alkylene oxide is reacted with a catalyst such as a zinc dicarboxylate to form a reaction mixture containing a homopolymer (in the case of one alkylene oxide) or a random copolymer (in the case of more than one alkylene oxide).
  • a catalyst such as a zinc dicarboxylate
  • a mixture of the above reaction mixture, carbon dioxide and another alkylene oxide, or more than one alkylene oxide, are reacted with or without added catalyst to form another reaction mixture, but one containing a block copolymer product.
  • One or more than one such additional reaction steps can be performed as desired.
  • the polymerization reaction conditions, and polymer recovery and work-up steps are disclosed in the above cited patents.
  • the homo- and copolymers thus obtained are amorphous, and are normally solid, that is, shaped articles of them maintain their shapes under the force of gravity at temperatures up to at least about 120°C.
  • Their weight average molecular weights generally are in the range from about 50,000 to about 800,00.
  • the zinc catalyst process does not appear to be capable of making alkylene carbonate homo- and copolymer products predominate in homo- and copolymers of weight average molecular weight generally in the range from about 1,000 to about 50,000.
  • poly(alkylene carbonates) is as sacrificial binders in the manufacture of articles from ceramic and metal powders. See, for example, the U.S. Patents 4,814,370 and 4,882,110 of Kramer et al . , and the U.S. Patent 5,089,070 of
  • the poly( alkylene carbonate) functions as a binder of the powder until the shaped "green" articles thereof are sintered to fuse together the ceramic or metallic particles.
  • the sintering step is carried out at temperatures at which the poly(alkylene carbonate) binder thermally decomposes or burns (when the step is done without the exclusion of air) .
  • poly( alkylene carbonates) of lower molecular weights that is, of shorter polymer chain lengths, than poly(alkylene carbonates) of higher molecular weights, and particularly those made by the zinc catalyst process, might be more advantageous as sacrificial binders in ceramic technologies being developed.
  • Poly( alkylene carbonates) of lower molecular weights tend to thermally decompose at lower temperatures and at faster rates than the higher molecular weight alkylene carbonate polymers .
  • the invention hereof provides a process for obtaining a lower molecular weight poly( alkylene carbonate) from a higher molecular weight poly( alkylene carbonate).
  • Specific embodiments of the process enables the production of poly(alkylene carbonates) of weight average molecular weights of about 1,000-50,000 from poly( alkylene carbonates) made by the zinc catalyst process, that is, poly( alkylene carbonates) of weight average molecular weights of about 50,000-800,000.
  • the process comprises:
  • hydroxy material (a) admixing hydroxy material with the higher molecular weight poly( alkylene carbonate), the hydroxy material being selected from the group consisting of water and normally liquid, hydroxy aliphatic compounds;
  • the reaction mixture thus obtained consists essentially of lower molecular weight poly(alkylene carbonate). In most embodiments of the process, lower molecular weight poly(alkylene carbonate) is separated from the reaction mixture.
  • the hydroxy material comprises one or more than one of the members of the recited group.
  • Normally liquid, hydroxy aliphatic compounds are hydroxy aliphatic compounds that at 20-25°C are liquid under atmospheric pressure.
  • Preferred normally liquid, hydroxy aliphatic compounds are mono- and polyhydric alcohols.
  • alkanols having one-six carbons examples of which are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl alcohols, the pentyl alcohols, the h ⁇ xyl alchols the alicyclic alcohols including cyclohexanol and the like, and such polyhydric aliphatic alcohols as glycerol and the like.
  • the quantity of hydroxy material admixed with the physical combination should be about 1-30%, preferably 3-10%, by weight of the higher molecular weight poly( alkylene carbonate).
  • the catalyst material comprises one or more than one catalyst.
  • the catalyst or catalysts include transesterification catalysts and hydrolysis catalysts, such as tributyltin dilaurate and the like.
  • An example of a catalytically effective concentration is 100 parts by weight per million parts by weight of the higher molecular weight poly( alkylene carbonate).
  • the pressure under which the initial mixture of hydroxy material and the higher molecular weight poly( alkylene carbonate), and the resulting reaction mixture, is established and maintained during the treating step is dependent on the temperature or temperatures at which the initial and resulting mixtures are established and maintained. In the above specified general temperature range, a pressure of about 20-200 psi (about 0.1-1.4 MPa) , preferably 50-150 psi (about 0.3-1 MPa) , usually is adequate .
  • Th ⁇ p ⁇ riod of time the high ⁇ r mol ⁇ cular w ⁇ ight poly( alkylene carbonat ⁇ ) is subj ⁇ cted to these conditions is depend ⁇ nt on the number of carbons in the alkyl ⁇ ne moieties of, and the number of monomeric units in, the polymer chains. In general, the higher the molecular weight of a poly(alkylene carbonate) the longer is the time to degrade it at a giv ⁇ n te peratur ⁇ . Also, th ⁇ higher the number of carbon atoms in the alkylene carbonat ⁇ monomeric units of a poly(alkylene carbonate) the higher the t ⁇ mp ⁇ rature should be for its degradation.
  • the range of the period of time is from about five minut ⁇ to about fifty hours.
  • som ⁇ ⁇ mbodim ⁇ nts of th ⁇ proc ⁇ ss p ⁇ riods of ti ⁇ within this range are sel ⁇ ct ⁇ d to r ⁇ sult in lower molecular weight poly(alkyl ⁇ n ⁇ carbonate) that is still solid at 20-25°C.
  • the p ⁇ riod of tr ⁇ atm ⁇ nt tim ⁇ is insuffici ⁇ nt to form more than a quantatively minor amount of alkylene carbonate.
  • a batch mode trial run be made at a t ⁇ mperature in the treat ⁇ nt t ⁇ mperature range, and under pressur ⁇ sufficient to keep the hydroxy mat ⁇ rial in th ⁇ r ⁇ action mixture, that is, keep it liquid, and during the run periodically withdraw a sample of th ⁇ reaction mixture for analysis of the lower mol ⁇ cular weight poly( alkylene carbonate) content and alkylen ⁇ carbonat ⁇ (s) content th ⁇ r ⁇ of.
  • lower mol ⁇ cular w ⁇ ight poly( alkyl ⁇ n ⁇ carbonat ⁇ ) is isolated from the reaction mixture. This can be done by cooling the reaction mixture to room te p ⁇ ratur ⁇ (20-25°C). Regardless of wheth ⁇ r th ⁇ low ⁇ r mol ⁇ cular w ⁇ ight poly( alkyl ⁇ n ⁇ carbonate) is solid or liquid at this temperature, it is not in solution in the hydroxy material. It is either a solid or a liquid immiscible with the hydroxy material. In a broad sens ⁇ , it and th ⁇ hydroxy mat ⁇ rial ar ⁇ segregated.
  • Henc ⁇ after cooling the reaction mixture to the indicated temperature, lower molecular weight poly(alkylen ⁇ carbonat ⁇ ) product is separated by conventional ways and means for separating solids from liquids, or separating immiscible liquids.
  • Such ways and m ⁇ ans included ⁇ filtration (wh ⁇ n th ⁇ product is solid), d ⁇ cantation, c ⁇ ntrifugation, ⁇ vaporation of hydroxy material by the application of heat, vacuum, or both, and the like.
  • Th ⁇ process of the invention can b ⁇ practiced in batch mod ⁇ or in continuous mod ⁇ .
  • conv ⁇ ntional equipment appropriate for the mod ⁇ is ⁇ mployed.
  • the preferred practice includes carrying out the admixing and treatm ⁇ nt st ⁇ ps with good, constant mixing action.
  • the degrad ⁇ d polymer product of th ⁇ proc ⁇ ss usually compris ⁇ s not only low ⁇ r molecular weight poly(alkyl ⁇ ne carbonate), but also alkyl ⁇ n ⁇ carbonat ⁇ , or alkyl ⁇ n ⁇ carbonates if the higher molecular weight poly( alkylene carbonat ⁇ ) had differ ⁇ nt alkyl ⁇ n ⁇ carbonat ⁇ monom ⁇ ric units.
  • Th ⁇ conc ⁇ ntration of th ⁇ alkyl ⁇ n ⁇ carbonate(s) is dep ⁇ ndent on the length of time the polymeric material is subj ⁇ ct ⁇ d to th ⁇ abov ⁇ ⁇ l ⁇ vated temp ⁇ ratur ⁇ and pressure conditions.
  • This alkylen ⁇ carbonat ⁇ (s) cont ⁇ nt can b ⁇ of advantag ⁇ as a plasticiz ⁇ r of th ⁇ low ⁇ r molecular weight poly(alkylen ⁇ carbonat ⁇ ) when it is normally solid, and the d ⁇ graded polymer product alone or with other mat ⁇ rial is extruded, injection molded or the like.
  • th ⁇ alkyl ⁇ n ⁇ carbonat ⁇ (s) cont ⁇ nt in whol ⁇ or in part is s ⁇ parated from the lower molecular weight poly(alkylene carbonate) by extraction with a solvent (for example, ethanol) for the alkylene carbonate(s) content.
  • a solvent for example, ethanol
  • the lower molecular weight poly( alkylene carbonate) thus obtain ⁇ d has utility as a sacrificial bind ⁇ r in th ⁇ manufactur ⁇ of articl ⁇ s from c ⁇ ramic, m ⁇ tallic and glass powd ⁇ rs in those instances wher ⁇ it is d ⁇ ired or requir ⁇ d that the binder thermally decompos ⁇ or burn at a t ⁇ mp ⁇ ratur ⁇ substantially lower than the thermal decomposition or burning temp ⁇ ratur ⁇ of th ⁇ high ⁇ r mol ⁇ cular w ⁇ ight poly(alkyl ⁇ n ⁇ carbonate) .
  • the hydroxyl oieti ⁇ th ⁇ r ⁇ of can b ⁇ reacted with an alkenylacyl halid ⁇ (for ⁇ xampl ⁇ , acryloyl chlorid ⁇ ) or an alk ⁇ nyl carboxylic acid (for ⁇ xampl ⁇ , m ⁇ thacrylic acid) to form functional group ⁇ that, with th ⁇ aid of a conv ⁇ ntional chemical initiator, can be cro ⁇ -linked with molecular energizing radiation ⁇ uch a ⁇ light.
  • the thus functionalized, low ⁇ r mol ⁇ cular w ⁇ ight poly( alkyl ⁇ n ⁇ carbonate) is useful as a n ⁇ gativ ⁇ r ⁇ sist in photolithography.
  • th ⁇ hydroxy material consisted of wat ⁇ r, th ⁇ quantity of which was 15% by w ⁇ ight of th ⁇ copolym ⁇ r, th ⁇ tr ⁇ atm ⁇ nt temp ⁇ ratur ⁇ was 190°C, and th ⁇ treatment time was 5 hours.
  • Th ⁇ ⁇ xpr ⁇ s ⁇ ion excludes an unrecit ⁇ d substanc ⁇ at a conc ⁇ ntration suffici ⁇ nt to substantially adversely affect th ⁇ e ⁇ sential prop ⁇ rties and characteri ⁇ tics of th ⁇ composition of att ⁇ r b ⁇ ing defined, whil ⁇ p ⁇ rmitting th ⁇ presence of one or mor ⁇ than one unrecited substance at a concentration or conc ⁇ ntrations insuffici ⁇ nt to substantially adversely aff ⁇ ct said ⁇ ss ⁇ ntial properties and charcteristics .

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  • Chemical & Material Sciences (AREA)
  • General 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)

Abstract

L'invention porte sur un procédé de réduction du poids moléculaire d'un poly(alkylène carbonate) normalement solide consistant à soumettre un mélange dudit poly(alkylène carbonate) normalement solide et d'un matériau hydroxy (liquide à la température ambiante et à la pression atmosphérique), puis à le chauffer sous une pression suffisante pour maintenir liquide le matériau hydroxy jusqu'à la dégradation totale de la quasi totalité du poly(alkylène carbonate) en un poly(alkylène carbonate) présentant le poids moléculaire réduit désiré. Le matériau hydroxy est choisi parmi de l'eau, du glycérol et d'autres composés hydroxy aliphatiques normalement liquides. Le poly(alkylène carbonate) de poids moléculaire réduit s'obtient par refroidissement du mélange réactif à la température ambiante, puis séparation du produit ainsi ségrégué du matériau hydroxy du mélange.
PCT/US1999/031130 1998-12-30 1999-12-29 Procede d'obtention d'un poly(alkylene carbonate) de poids moleculaire moindre a partir d'un poly(alkylene carbonate) de poids moleculaire eleve Ceased WO2000039172A1 (fr)

Applications Claiming Priority (2)

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US11423898P 1998-12-30 1998-12-30
US60/114,238 1998-12-30

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WO2000039172A1 true WO2000039172A1 (fr) 2000-07-06

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7858204B2 (en) 2006-05-25 2010-12-28 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering
USRE42329E1 (en) 2002-07-24 2011-05-10 Lucas-Milhaupt, Inc. Flux cored preforms for brazing
EP2557104A1 (fr) 2011-08-12 2013-02-13 Basf Se Procédé de fabrication de polyalkylène de carbonate de bas poids moléculaire
US9095937B2 (en) 2006-05-25 2015-08-04 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of making and using same
US9157134B2 (en) 2009-10-26 2015-10-13 Lucas-Milhaupt, Inc. Low silver, low nickel brazing material
US9314862B2 (en) 2013-05-30 2016-04-19 Lucas-Milhaupt, Inc. Process for flux coating braze preforms and discrete parts
US9731383B2 (en) 2014-07-09 2017-08-15 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of using same
US10744601B2 (en) 2015-08-07 2020-08-18 Bellman-Melcor Development, Llc Bonded brazing ring system and method for adhering a brazing ring to a tube

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3585168A (en) * 1968-09-21 1971-06-15 Shohei Inoue Process for producing copolymer of epoxide and carbon dioxide
US4665136A (en) * 1986-04-07 1987-05-12 Air Products And Chemicals, Inc. Process for producing novel block alkylene polycarbonate copolymers
US4763715A (en) * 1987-12-14 1988-08-16 Arco Chemical Company Process for preparing polycarbonate terpolymer foam suitable for lost foam casting

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3585168A (en) * 1968-09-21 1971-06-15 Shohei Inoue Process for producing copolymer of epoxide and carbon dioxide
US4665136A (en) * 1986-04-07 1987-05-12 Air Products And Chemicals, Inc. Process for producing novel block alkylene polycarbonate copolymers
US4763715A (en) * 1987-12-14 1988-08-16 Arco Chemical Company Process for preparing polycarbonate terpolymer foam suitable for lost foam casting

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE42329E1 (en) 2002-07-24 2011-05-10 Lucas-Milhaupt, Inc. Flux cored preforms for brazing
USRE44343E1 (en) 2002-07-24 2013-07-09 Lucas-Milhaupt, Inc. Flux cored preforms for brazing
US7858204B2 (en) 2006-05-25 2010-12-28 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering
US9095937B2 (en) 2006-05-25 2015-08-04 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of making and using same
US10071445B2 (en) 2006-05-25 2018-09-11 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of making and using same
US9157134B2 (en) 2009-10-26 2015-10-13 Lucas-Milhaupt, Inc. Low silver, low nickel brazing material
EP2557104A1 (fr) 2011-08-12 2013-02-13 Basf Se Procédé de fabrication de polyalkylène de carbonate de bas poids moléculaire
US9314862B2 (en) 2013-05-30 2016-04-19 Lucas-Milhaupt, Inc. Process for flux coating braze preforms and discrete parts
US9731383B2 (en) 2014-07-09 2017-08-15 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of using same
US10744601B2 (en) 2015-08-07 2020-08-18 Bellman-Melcor Development, Llc Bonded brazing ring system and method for adhering a brazing ring to a tube

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