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CN-115768816-B - High melting temperature soluble semi-crystalline polyamides

CN115768816BCN 115768816 BCN115768816 BCN 115768816BCN-115768816-B

Abstract

The present invention relates to (co) polyamides comprising at least 85 mole% (mol.%) of recurring units (R PA ) of formula (I) the invention also relates to polymer compositions comprising such (co) polyamides, as well as articles comprising them and methods of using the articles in high temperature applications such as oil and gas extraction processes (e.g. frac balls) or as support materials for printing three-dimensional (3D) parts, which require sufficient swelling or deformation when exposed to moisture.

Inventors

  • T. Hershek
  • N.J. Singletree

Assignees

  • 索尔维特殊聚合物美国有限责任公司

Dates

Publication Date
20260505
Application Date
20210616
Priority Date
20200629

Claims (20)

  1. 1. A (co) polyamide comprising recurring units (R PA ) selected from the group consisting of: -a unit (R PA 1 ) having the formula: Wherein p and q are the same or different from each other and are independently an integer of 3 to 9, R H is monovalent C 1 -C 6 alkyl, and -A unit (R PA 2 ) having the formula selected from the group consisting of: -a unit having the formula: Wherein r and s are the same or different from each other and are independently an integer of 1 to 3; -a unit having the formula: Wherein r and s are the same or different from each other and are independently an integer of 1 to 3; wherein the (co) polyamide is semi-crystalline and has an amorphous phase and a crystalline phase, thereby yielding a detectable melting point, as determined by differential scanning calorimetry according to ASTM D3418; And wherein the (co) polyamide is a homo-polyamide essentially comprising 100 mol% of recurring units (R PA ), or is a copolyamide comprising at least 95 mol% of recurring units (R PA ), the proportion of recurring units being given relative to the total moles of recurring units of the (co) polyamide, wherein the expression "essentially" means that in addition to the recurring units listed less than 1 mol% of terminal groups, impurities, defects and other spurious units relative to the total moles of recurring units may also be present in the (co) polyamide.
  2. 2. The (co) polyamide according to claim 1, wherein in unit (R PA 1 ), wherein p and q are the same or different from each other, independently are integers of 4 to 6.
  3. 3. The (co) polyamide according to claim 1, wherein in unit (R PA 1 ), each of p and q is 6.
  4. 4. The (co) polyamide according to claim 1, wherein the units (R PA 1 ) have the formula: And R BH is C 1 -C 3 alkyl.
  5. 5. The (co) polyamide according to claim 1, wherein the unit (R PA 2 ) is a unit having the formula: Wherein r and s are the same or different from each other and are independently integers of 1 to 3.
  6. 6. The (co) polyamide according to claim 5, wherein the units (R PA 2 ) have the formula: 。
  7. 7. The (co) polyamide according to any one of claims 1 to 6, comprising up to 5 mol% of recurring units other than those of formula (F) below, relative to the total moles of recurring units of the (co) polyamide: (F), -wherein E is a group having any one of formula (I N 1 ) or (I N 2 ): (I N 1 ) (I N 2 ) wherein R alk is a monovalent C 1 -C 12 hydrocarbon radical which may contain one or more heteroatoms, each of R alk 1 and R alk 2 , which are identical or different from each other, is a bond or a divalent C 1 -C 12 hydrocarbon radical which may contain one or more heteroatoms, provided that R alk 1 and R alk 2 are not simultaneously bonds and together with the nitrogen atom to which they are attached form a heterocyclic mononuclear or polynuclear group, and -N1 and n2 are integers, identical to or different from each other; These repeat units are different from those of formula (F), which correspond to any one of the following formulas: -NR” H -R 1 -C(O)- (II) -NR’” H -R 2 -NR'" H -C(O)-R 3 -C(O)-(III) Wherein R " H and R'" H are the same or different from each other and are each H or hydrocarbyl groups, and R 1 、R 2 、R 3 are the same or different from each other, are divalent hydrocarbyl groups, and may be aliphatic, alicyclic, cycloaliphatic, aromatic, or combinations thereof, wherein R 1 、R 2 、R 3 may contain one or more heteroatoms selected from the group consisting of O, N, S, P.
  8. 8. The (co) polyamide according to any one of claims 1 to 6, having a number average molecular weight M N ranging from 1 to 50 000 g/mol, as determined by Gel Permeation Chromatography (GPC) following ASTM D5296 specifications with reference to a substantially monodisperse polystyrene standard.
  9. 9. The (co) polyamide according to any one of claims 1 to 6, having a crystallinity such that its heat of fusion is at least 5J/g when measured by differential scanning calorimetry according to ASTM D3418.
  10. 10. The (co) polyamide of claim 9 having a crystallinity such that its heat of fusion is at least 10J/g when measured by differential scanning calorimetry according to ASTM D3418.
  11. 11. The (co) polyamide of claim 9 having a crystallinity such that its heat of fusion is at least 15J/g when measured by differential scanning calorimetry according to ASTM D3418.
  12. 12. The (co) polyamide according to any one of claims 1-6, having a melting point of at least 250 ℃, as determined according to ASTM D3418.
  13. 13. A process for preparing a polyamide (a) according to any one of claims 1 to 12, which comprises thermally polycondensing a monomer mixture of one or more than one 1, 4-cyclohexanedicarboxylic acid [ acid (CHDA) ] (or derivatives thereof) and a diamine component consisting of one or more than one diamine (or derivatives thereof) of any one of the following formulae: [ amine (N N 1 ) ] Wherein R alk ° is monovalent C 1 -C 6 alkyl, n1 and n2 are the same or different from each other and are, at each occurrence, an integer from 3 to 9; 1, 4-bis (aminoalkyl) piperazine [ amine (N N 2 ) ], wherein aminoalkyl is a group selected from aminomethyl, aminoethyl, and aminopropyl; and possibly additionally at least one mixture selected from: -a mixture (M1) comprising at least one diacid [ acid (DA) ] (or a derivative thereof) and at least one diamine [ amine (NN) ] (or a derivative thereof), wherein (i) the acid (DA) is not an acid (CHDA) and/or (ii) the amine (NN) is neither an amine (N N 1 ) nor an amine (N N 2 ); -a mixture (M2) comprising at least one lactam [ lactam (L) ]; A mixture (M3) comprising at least one aminocarboxylic acid [ amino Acid (AN) ] and Combinations thereof, as described above.
  14. 14. The method of claim 13, wherein the molar ratio n Diacid(s) /n Diamines in the monomer mixture is in the range from 0.8 to 1.2.
  15. 15. The method of claim 14, wherein the molar ratio n Diacid(s) /n Diamines in the monomer mixture is in the range from between 0.9 and 1.1.
  16. 16. The method of claim 14, wherein the molar ratio n Diacid(s) /n Diamines in the monomer mixture is in the range from between 0.95 and 1.05.
  17. 17. The method of claim 14, wherein the molar ratio n Diacid(s) /n Diamines in the monomer mixture is in the range from between 0.98 and 1.02.
  18. 18. A composition (C) comprising at least one (co) polyamide according to any one of claims 1 to 12 and further comprising at least one component selected from the group consisting of reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, crosslinking agents and antioxidants.
  19. 19. Composition (C) according to claim 18, comprising at least one (co) polyamide according to any one of claims 1 to 12, and further comprising at least one reinforcing filler chosen from fibrous fillers.
  20. 20. The composition (C) of claim 19, wherein the reinforcing filler is selected from glass fibers and carbon fibers.

Description

High melting temperature soluble semi-crystalline polyamides Technical Field The present invention relates to a (co) polyamide as disclosed in claim 1. Background (Co) polyamides with high melting temperatures (e.g. above 300 ℃) are known and described in the literature. Polyamides of this type are notable under the trade name from Sorve specialty Polymer Co., ltd (Solvay Specialty Polymers USA)PPA is known. These polyamides also exhibit low water absorption, which is a useful advantage in many applications, notably because of the strength and stiffness stability that results, even at high levels of humidity. However, in some applications, such as those described below, (co) polyamides that exhibit high melting temperatures, but at the same time have the ability to dissolve when immersed in an aqueous medium, are desired. For example, in fabricating 3D parts by depositing layers of part material, support layers or structures are typically built under overhanging portions or cavities of the 3D part being built, which parts are not supported by the part material itself. The support structure may be constructed using the same deposition techniques that deposit the part material. The host computer generates additional geometry that acts as a support structure for overhanging or free-space segments of the 3D part being formed, and in some cases, for the sidewalls of the 3D part being formed. The support material adheres to the part material during manufacture and can be removed from the finished 3D part when the printing process is completed. In general, soluble/leachable materials are preferred as support materials so that once the 3D part is built, the support part can be dissolved from the final 3D part so that the post-soak and rinse treatments are effective on the recycled part. Unlike supports that can only be removed mechanically, the use of soluble supports allows for increased freedom of part design and maintains the aesthetic appearance of the part surface. Soluble/water swellable and/or printable materials have been described in the art including polyamide support materials. For example, WO 2017/167691 (D3) (sonde specialty polymer, inc. Of america (Solvay Specialty Polymers USA, LLC)) relates to a method for manufacturing a 3D article using a semi-crystalline polyamide as a support material having sufficient water absorption to provide significant swelling and deformation so as to ensure separation from the target 3D part. Among suitable polyamides, mention may be made of polyamides obtainable from polycondensation of certain diacids with certain diamines, among which mention is made of N-methyl-bis-hexamethylene-triamine. Similarly, US2019/0160732 teaches a soluble polyamide useful as support material in 3D printing techniques, containing units derived from hydrophilic monomers, units derived from hydrophobic dicarboxylic acid monomers and units derived from hydrophobic amine monomers, wherein the hydrophilic monomer units may comprise primary amine groups, secondary amine groups, tertiary amine groups, quaternary ammonium salts, oxyethylenes, hydroxyl groups, carboxyl salt groups, phosphate groups, sulfonate groups, or sulfonate groups. Further, WO 2017/167692 (american sorv specialty polymer company of responsibility) teaches (co) polyamides comprising more than 60% mole of recurring units derived from the condensation of 1, 4-cyclohexanedicarboxylic acid and a diamine having the formula H 2N-(CH2)2-O-(CH2)2-O-(CH2)2-NH2, having a melting point of more than 260 ℃ and being endowed with sufficient solubility in water, acidic water or basic water at temperatures of more than 50 ℃, described as suitable as support materials for printing 3D parts. These (co) polyamides may additionally comprise other units, such as units derived from aromatic diacids and/or units derived from aliphatic diamines, among which N, N-bis (3-aminopropyl) methylamine is notably mentioned. However, the choice of water-soluble polymer is still relatively limited and the taught water-soluble polymer materials may not be sufficient to support the printing of certain polymers requiring high processing temperatures, and in some cases, however, the soak/rinse separation technique remains very burdensome, at least because it requires high temperature dissolution of large amounts of wastewater, extensive post-treatment (due to low solubility) to dispose of and/or recover the water-soluble support polymer. As already explained above, in the manufacture of 3D parts in combination with high temperature part materials, such as polysulphones, polyethersulphones, polyphenylsulphones, polyaryletherketones, polyetherimides, polyamideimides, polyphthalamides, polyphenylene sulphide etc., at the higher operating conditions required for the high temperature part materials, it is desirable that the support materials provide vertical and/or lateral support and that the support materials should not soften too much at these higher operating c