Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on 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
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof

Definitions

• This invention relates to polyester blends, more particularly to blends of hydroxy-functional polyesters, and to processes for preparing the same.
• Hydroxy-functional polyesters are known in the art and are described, for example, in U.S. Patents 5,496,910; 5,171 ,820 and 5,138,022. Blends of hydroxy-functional polyesters with other thermoplastic polyesters are also known, as described in Japanese Patents Shotsugan Kokai 62-25151 and 62-15255. These are immiscible blends which may require compatibilizers to maximize adhesion between phases to insure acceptable physical properties, as described in Japanese Patents Shotsugan Kokai 64-210454. Miscible blends of hydroxy-functional polyesters with thermoplastic polyesters, such as poly(ethylene terephthalate) (PET) are described in U.S. Patent 5,134,201. However, these hydroxy- functional polyesters and blends thereof are not suitable for certain applications, such as hot-melt adhesives, adhesive tackifiers, plasticizers, heat-curable adhesives and heat- curable coatings.
• PTT poly(ethylene terephthalate)
• the present invention is a composition comprising a blend of a hydroxy-functional polyester and a polyalkylene oxide, a polyester polyol or an aliphatic polyester.
• the blends of the present invention can be used as hot-melt adhesives, adhesive tackifiers, plasticizers, heat-curable adhesives and heat-curable coatings. Some of these materials are biodegradable and are therefore suitable for application to compostable end-products.
• the hydroxy-functional polyester which can be employed in the practice of the present invention is a poly(hydroxy ester) or a poly(hydroxy ester ether) having repeating units represented by the formula:
• R is a divalent organic moiety which is primarily hydrocarbon;
• R 3 is:
• R 4 is:
• R 2 and R 6 are independently divalent organic moieties which are primarily hydrocarbon;
• R 5 is hydrogen or alkyl and n is from 0 to 100.
• R 1 , R 2 and R 6 are independently alkylene, cycloalkylene, alkylenearylene, alkyleneoxyalkylene, poly(alkyleneoxyalkylene), alkyleneamidealkylene, poly(alkyleneamidealkylene), alkylenethioalkylene, poly(alkylenethioalkylene), alkylenesulfonylalkylene, poly(alkyienesulfonylalkylene), arylene, dialkylenearylene, diaryleneketone, diarylenesulfone, diarylene oxide, alkylidene-diaryiene, diarylene sulfide, or a combination of these moieties, optionally substituted with at least one hydroxyl group.
• R 1 is methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethyiene, octamethylene, nonamethylene, decamethylene, dodecamethylene, 1 ,4-cyclohexylene, 1 ,3-cyclohexylene or 1 ,2-cyclohexylene, optionally substituted with at least one hydroxyl group; and R 2 and R 6 are independently methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethyiene, octamethylene, nonamethylene, decamethylene, dodecamethylene, 1 ,4-cyclohexylene, 1 ,3-cyclohexylene or 1 ,2-cyclohexylene, optionally substituted with at least one hydroxyl group.
• R 1 and R 6 are represented by the formula:
• R 2 is represented by the formula:
• R 7 is independently hydrogen or methyl and x and y are independently 0 to 100.
• R 1 and R 6 are independently m-phenylene, p- phenylene or 2,6-naphthalene;
• R 2 is independently m-phenylene, p-phenylene, naphthalene, diphenylene-isopropylidene, sulfonyldiphenylene, carbonyldiphenylene, oxydiphenylene or 9,9-fluorenediphenylene;
• R 5 is hydrogen;
• R 7 is independently hydrogen or methyl.
• the hydroxy-functional polyesters can be prepared by reacting dicarboxylic acids and diglycidyl ethers or diglycidyl esters at conditions sufficient to yield hydroxy ester ether or hydroxy ester linkages.
• dicarboxylic acids and diglycidyl ethers or diglycidyl esters at conditions sufficient to yield hydroxy ester ether or hydroxy ester linkages.
• Polyalkylene oxides which can be used in the practice of the present invention include those polymers comprising polymerized EO units with an average molecular weight of from 100 to 8,000,000, preferably from 400 to 1 ,000,000 and most preferably from 1 ,000 to 100,000.
• Preferred polyalkylene oxides are poly(ethylene oxide), poly(propylene oxide) poly(ethylene-co-propylene oxide), poly(butyiene oxide) and poly(tetrahydrofuran).
• the most preferred polyalkylene oxide is poly(ethylene oxide).
• the aliphatic polyesters which can be used in the practice of the present invention include polymers having the following repeat units:
• R 8 and R 9 are independently an alkylene moiety such as ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethyiene, octamethylene, methylmethylene, methylethylene, 1-methylpropylene, 2-methylpropylene, 2,2-dimethylpropylene, ethylmethylene, or ethylethylene;
• Preferred aliphatic polyesters are polycaprolactone, poly(lactic acid), poly(hydroxybutyrate), poly(hydroxybutyrate valerate), poly(butylene succinate) and poly(butylene adipate).
• the hydroxy-functional polyesters are blended with the polyalkylene oxides, polyester polyol or aliphatic polyester by conventional dry blending methods using conventional means such as a barrel mixer, or a tumble mixer or by melt blending in an appropriate apparatus, such as a Banbury type internal mixer, rubber mill, single or twin screw extruder or compounder.
• the amount of the polyalkylene oxide, polyester polyol or aliphatic polyester most advantageously blended with the hydroxy-functionalized polyether is dependent on a variety of factors including the specific polymers used in making the blends, as well as the desired properties of the products resulting from the blends. Typical amounts can range from 1 to 95 weight percent of the blend.
• the polyalkylene oxide, polyester polyol or aliphatic polyester is used in an amount of from 5 to 70 weight percent, more preferably from 10 to 50 weight percent and, most preferably, from 15 to 30 weight percent of the blend.
• the following examples are for illustrative purposes only and are not intended to limit the scope of this invention. Unless otherwise indicated, all parts and percentages are by weight.
• a poly(hydroxy ester ether) (PHEE) was synthesized by allowing adipic acid to polymerize with bisphenol A-diglycidyl ether according to the method described in U.S. Patent 5,171 ,820.
• PHEE poly(hydroxy ester ether)
• the blends were compression molded between sheets made of tetrafluoroethylene fluorocarbon polymers in a 5 by 9 by 0.35 cm mold cavity at a temperature of 80°C and pressure of 100 psi, and the resulting plaques were cut into standard tensile specimens and their mechanical properties determined. The results are shown in Table II.
• Moldings of the blends in Examples 1-6 and Comparative Example A were immersed in water at 25°C for 350 hours, and water uptake into the samples was determined as percent weight gain (Table II).
• films of the blends were cast from solutions in tetrahydrofuran onto glass plates. Contact angles of water droplets placed on the films were measured and are listed in Table II. Increasing wettability of the films are as indicated by decreasing contact angle.
• the resin was pressed into a 1/8 inch (thickness) by 1 inch (diameter) circular disk mold at 80°C.
• the circular disk resin was cooled down to room temperature and released from the mold and then vacuum dried overnight at 25 °C.
• the vacuum-dried resin disk was weighed and the weight (W1 ) recorded.
• the disk was then placed into a 2 ounce glass bottle filled with 0.3 weight percent of sodium azide in deionized water solution. After 2 weeks immersion in the aqueous solution, the disk was weighed and the weight (W2) recorded.
• the water uptake was calculated as the percentage of weight gain over the initial dry weight.
• Binary mixtures of the poly(hydroxy ester ether) derived from bisphenol A diglycidyl ether and 1 ,4-cyclohexanedicarboxylic acid and poiycaprolactone, poly(lactic acid) or a commercial blend of poiycaprolactone and starch were prepared by mixing in the melt state in a Brabender roller mixer. First, the blend of desired amounts of two polymers was quickly fed into the mixing bowl of the mixer that was preheated to the desired temperature (180°C for blends with poiycaprolactone; 200°C for blends with poly(lactic acid); and 160°C for the blends with the commercial Bioplast resin).
• the mixing blades were set at a low speed, but after the chamber was completely full, the lid was closed and the speed increased.
• the temperature of the chamber initially decreased by 10°C to 20°C, but it regained its original level in 4 to 5 minutes.
• the melt-blended mixtures were then compression molded between tetrafluoroethylene-coated plates to form films or rectangular bars for tensile and dynamic mechanical testing. All of the blend samples were also conditioned in the constant temperature room (50 percent relative humidity and 23°C) for at least 24 hours before they were tested. The results of the tests are shown in Tables 111 and IV.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 1997
  • 1997-12-15 WO PCT/US1997/022892 patent/WO1998029511A1/en not_active Application Discontinuation
  • 1997-12-15 EP EP97954103A patent/EP0950079A1/de not_active Withdrawn
  • 1997-12-15 JP JP53004998A patent/JP2001507737A/ja active Pending
  • 1997-12-30 AR ARP970106254A patent/AR011322A1/es unknown

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