# US 11,299,626 B2 · Use of a prepolymer in transparent thermoplastic compositions, compositions comprising same and uses thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,626 B2 - Document ID: US11299626B2 - Status: Granted - Kind: B2 - Application number: 15/759,009 - Filed: 2016-09-20 - Published: 2018-10-11 - Granted: 2022-04-12 - Earliest claimed: 2015-09-22 - Assignees: Arkema France - Applicants: Arkema France - Inventors: Yves Deyrail; Mathieu Sabard; Philippe Blondel; René-Paul Eustache - Web page: https://patentgrep.com/patent/US11299626B2 ## CPC - C08L 77/02: Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08L77/10 takes precedence) - C08G 69/36: derived from amino acids, polyamines and polycarboxylic acids - C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The invention relates to the use of at least one prepolymer in a composition which includes: a matrix of at least one transparent semi-crystalline polyamide, and optionally at least one additive, for improving the crystallisation kinetics and reducing the warping of the composition while preserving or improving the transparency properties thereof as well as the mechanical properties thereof, in comparison with the same composition without a prepolymer, wherein the composition does not contain a nucleating agent. ## Claims ### Claim 1 A method for improving the crystallization kinetics and limiting the warping of a composition, wherein said method comprises a step of dry blending at least one prepolymer having a number-average molecular mass of from 1000 to 10 000 g/mol into a composition to form a prepolymer-polyamide, wherein said prepolymer is a monofunctional acid or monofunctional amine wherein the composition comprises: a matrix comprising at least one semicrystalline transparent polyamide, and optionally at least one additive, wherein the composition possesses a crystallization half-time at 164° C. as measured according to ISO 11357-7:2013 that is from 6 to 8 minutes, wherein the warpage of the composition is limited to a change in elongation that is from 0 to 0.5% after 60 minutes after being heated at 90° C., wherein the transparency properties and the mechanical properties of the composition are either improved or conserved, when compared with the same composition that is free of the prepolymer, wherein the composition is also free of nucleating agent. ### Claim 2 (depends on 1) The method according to claim 1, wherein said at least one semicrystalline transparent polyamide has a transmittance >75% (measured at a wavelength of 560 nm and for a plate thickness of 2 mm). ### Claim 3 (depends on 1) The method according to claim 1, wherein said prepolymer-polyamide comprises said matrix constituted of said at least one semicrystalline transparent polyamide in a proportion of from 60 to 99.95% by weight; said prepolymer in a proportion of 0.05% to 20% by weight; wherein the weight proportion of the semicrystalline transparent polyamide matrix and that of the prepolymer is, respectively, from 60% to 99.9% and from 40% to 0.1%, relative to the sum of the semicrystalline transparent polyamide and the prepolymer weights; and said additive in a weight proportion of 0 to 20%; wherein the sum of the semicrystalline transparent polyamide, of the prepolymer and optionally of the additive weight are equal to 100%. ### Claim 4 (depends on 1) The method according to claim 1, wherein said matrix comprises at least one semicrystalline transparent homopolyamide. ### Claim 5 (depends on 4) The method according to claim 4, wherein said at least one semicrystalline transparent homopolyamide is of formula X.Y, selected from the group consisting of P.12, B.12, and mixtures thereof. ### Claim 6 (depends on 1) The method according to claim 1, wherein said matrix comprises of at least one semicrystalline transparent copolyamide. ### Claim 7 (depends on 6) The method according to claim 6, wherein said at least one semicrystalline transparent copolyamide has formula A/X.Y; and wherein the molar proportion of unit A in said semicrystalline transparent copolyamide A/X.Y is from 91% to less than 100%, “A” being chosen from a unit obtained from at least one aminocarboxylic acid, a unit obtained from at least one branched aminocarboxylic acid and a unit obtained from at least one lactam, “X.Y” being a repeating unit obtained from the polycondensation of at least one cycloaliphatic amine or from at least one linear or branched aliphatic diamine or from at least one arylamine and from at least one dicarboxylic acid comprising from 4 to 36 carbon atoms. ### Claim 8 (depends on 7) The method according to claim 7, wherein the molar proportion of unit A in the copolyamide A/X.Y is from 95% to less than 100%. ### Claim 9 (depends on 7) The method according to claim 7, wherein the unit A is selected from PA11 or PA12, and wherein the unit X.Y is a homopolyamide comprising a cycloaliphatic diamine. ### Claim 10 (depends on 1) The method according to claim 1, wherein the prepolymer is compatible with the polyamide. ### Claim 11 (depends on 1) The method according to claim 1, wherein the prepolymer is an aliphatic polyamide, wherein the aliphatic polyamide is selected from the group consisting of PA6, PA11, PA12, PA11/6, PA6/12 and blends thereof. ### Claim 12 (depends on 1) The method according to claim 1, wherein the weight proportion of the prepolymer is from 0.1% to 20%, relative to the weight of the composition. ### Claim 13 (depends on 1) The method according to claim 1, wherein the weight proportion of the prepolymer is from 1% to 30% relative to the weight of the prepolymer-polyamide. ### Claim 14 (depends on 1) The method according to claim 1, wherein the prepolymer comprises PA11. ### Claim 15 (depends on 1) The method according to claim 1, wherein the at least one additive is selected from the group consisting of core-shell type, stabilizers, dyes, plasticizers, flame retardants, fibers, fillers and mixtures thereof. ### Claim 16 (depends on 1) The method according to claim 1, wherein the prepolymer is selected from the group consisting of monoNH2 prepolymer, and monoacid prepolymer. ### Claim 17 A composition comprising: from 60 to 99.95% by weight of at least one semicrystalline transparent copolyamide; from 0.05% to 20% by weight of at least one prepolymer with a number-average molecular mass from 1000 to 15 000 g/mol, wherein said prepolymer is a monofunctional acid or monofunctional amine the weight proportion of the semicrystalline transparent copolyamide is from 60% to 99.95 and the weight proportion of the prepolymer is from 40% to 0.1%, relative to the sum of the weight of the transparent semicrystalline copolyamide and the weight of the prepolymer; from 0 to 20% by weight of one or more additives; wherein the composition is free of nucleating agent and is free of impact modifier, wherein the composition is formed by dry blending the at least one semicrystalline transparent copolyamide, the at least one prepolymer and the one or more additives together, and wherein the composition has improved crystallization kinetics and reduced warpage and the same or improved transparency properties and the same or improved mechanical properties, when compared with the same composition free of prepolymer. ### Claim 18 (depends on 17) The composition according to claim 17, wherein the semicrystalline transparent copolyamide is of formula A/X.Y, and wherein the molar proportion of unit A in the copolyamide A/X.Y is from 91% to less than 100%, “A” being chosen from a unit obtained from at least one aminocarboxylic acid, a unit obtained from at least one branched aminocarboxylic acid and a unit obtained from at least one lactam, “X.Y” being a repeating unit obtained from the polycondensation of at least one cycloaliphatic amine or from at least one linear or branched aliphatic diamine or from at least one arylamine and from at least one dicarboxylic acid comprising from 4 to 36 carbon atoms. ### Claim 19 (depends on 18) The composition according to claim 18, wherein the molar proportion of unit A in the copolyamide A/X.Y is from 95% to less than 100%. ### Claim 20 (depends on 18) The composition according to claim 18, wherein the unit A is selected from PA11 or PA12, and the unit X.Y is a homopolyamide comprising a cycloaliphatic diamine. ### Claim 21 (depends on 17) The composition according to claim 17, wherein the prepolymer is compatible with the polyamide. ### Claim 22 (depends on 17) The composition according to claim 17, wherein the prepolymer has a number-average molecular mass from 1000 to 10 000 g/mol. ### Claim 23 (depends on 17) The composition according to claim 17, wherein the weight proportion of prepolymer is from 0.1% to 20% relative to the total weight of the composition. ### Claim 24 (depends on 17) The composition according to claim 17, wherein the weight proportion of prepolymer is from 1% to 30% relative to the total weight of the prepolymer and the polyamide. ### Claim 25 (depends on 17) The composition according to claim 17, wherein the prepolymer comprises PA11. ### Claim 26 (depends on 17) The composition according to claim 17, wherein the one or more additives are selected from the group consisting of stabilizers, dyes, plasticizers, flame retardants, fibers and fillers. ### Claim 27 (depends on 1) A method for the manufacture of articles wherein the method comprises at least one step of extrusion, injection or molding of a composition formed from the method according to claim 1. ### Claim 28 (depends on 27) The method according to claim 27, wherein the articles are selected from sports shoes, and the method comprises injection. ### Claim 29 A process for preparing a composition, wherein the process comprises a step of dry blending a prepolymer with at least one semicrystalline transparent polyamide and optionally at least one additive, wherein said at least one semicrystalline transparent polyamide is present in a proportion of from 60% to 99.95% by weight, relative to the sum of the weights of the polyamide and the prepolymer; wherein said prepolymer is a monofunctional acid or monofunctional amine, said prepolymer being present in a proportion of 0.05% to 20% by weight, relative to the sum of the weights of polyamide and the prepolymer, said additive being in a proportion by weight of 0 to 20%; the sum of the weights of the polyamide, the prepolymer and optionally the additive being equal to 100%, said composition being free of nucleating agent, whereby said composition has improved crystallization kinetics and reduced warpage and the same or improved transparency properties and the same or improved mechanical properties, when compared with the same composition free of prepolymer. ### Claim 30 (depends on 1) The method according to claim 1, wherein said matrix comprises of at least one semicrystalline transparent copolyamide, wherein the at least one semicrystalline transparent copolyamide has formula A/X.Y/Z; and wherein the molar proportion of unit A in said semicrystalline transparent copolyamide A/X.Y/Z is from 91% to less than 100%, “A” being chosen from a unit obtained from at least one aminocarboxylic acid, a unit obtained from at least one branched aminocarboxylic acid and a unit obtained from at least one lactam, “X.Y” being a repeating unit obtained from the polycondensation of at least one cycloaliphatic amine or from at least one linear or branched aliphatic diamine or from at least one arylamine and from at least one dicarboxylic acid comprising from 4 to 36 carbon atoms, and “Z” being a unit that is similar to but different from A or a unit that is similar to but different from X.Y. ### Claim 31 (depends on 1) The method according to claim 1, wherein the at least one semicrystalline transparent polyamide is mixed with a PEBA. ### Claim 32 (depends on 1) The method of claim 1, wherein the compositions comprises at least one core-shell type modifier additive.