COPOLYAMIDES OBTAINABLE FROM 4-(AMINOMETHYL)BENZOIC ACID

Abstract

The present invention relates to copolyamides comprising 4-(aminomethyl)benzoic acid (4-AMBa). The present invention also relates to polymer compositions comprising such copolyamides, as well as articles comprising the same and methods of using said articles to prepare windows, clear containers for cosmetic products packaging or glass frames & lenses. The present invention also relates to the use of the copolyamide, as such or in a composition of matter, for the manufacture of three-dimensional objects using an additive manufacturing system, for example an extrusion-based manufacturing system.

Claims

1. A copolyamide, having the following formula (I) : ##STR00002## wherein: n.sub.x and n.sub.y are respectively the moles % of each recurring units x and y ; recurring units x and y are arranged in blocks, in alternation or randomly; n.sub.x+n.sub.y=100%; 5%<n.sub.x<90%; R.sub.1 is selected from the group consisting of a bond, a C.sub.1-C.sub.15 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; and R.sub.2 is selected from the group consisting of a C.sub.1-C.sub.20 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl.

2. The copolyamide of claim 1, wherein R.sub.1 is selected from the group consisting of a C.sub.4-C.sub.10 alkyl and a C.sub.6-C.sub.12 aryl, optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl, and/or R.sub.2 is selected from the group consisting of a C.sub.4-C.sub.12 alkyl and a C.sub.6-C.sub.12 aryl, optionally comprising one or more heteroatoms.

3. The copolyamide of claim 1, wherein the copolyamide is the condensation product of a mixture comprising from 5 mol. % to 90 mol.% of 4-(aminomethyl)benzoic acid (4-AMBa) or derivative thereof, and at least one dicarboxylic acid component or derivative thereof, and at least one diamine component.

4. The copolyamide of claim 1, wherein the copolyamide is the condensation product of a mixture comprising: from 5 mol. % to 90 mol. % of 4-(aminomethyl)benzoic acid (4-AMBa) or derivative thereof, a dicarboxylic acid component selected from the group consisting of adipic acid, azelaic acid, sebacic acid, dodecanedioic, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4′-bibenzoic acid, 5-hydroxyisophthalic acid, 5-sulfophthalic acid, and mixture thereof, and a diamine component selected from the group consisting of 1,4-diaminobutane, 1,5-diamonopentane, 2-methyl-1,5diaminopentane, hexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctoane, 1,10-diaminedecane, H.sub.2N—(CH.sub.2).sub.3—O—(CH.sub.2).sub.2—O(CH.sub.2).sub.3—NH.sub.2, m-xylylene diamine, p-xylylene, 1,3-bis(aminomethyl)cyclohexane and mixture thereof.

5. The copolyamide of claim 1, wherein the copolyamide is the condensation product of a mixture comprising : from 5 mol. % to 90 mol. % of 4-(aminomethyl)benzoic acid (4-AMBa) or derivative thereof, 4-(aminomethyl)benzoic acid(4-AMBa)—a dicarboxylic acid component selected from the group consisting of adipic acid, sebacic acid, terephthalic acid, isopthalic acid and mixture thereof, and a diamine component selected from the group consisting of hexamethylenediamine, m-xylylene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,10-decamethylene diamine and mixture thereof

6. The copolyamide of claim 1, wherein the copolyamide is such that : 50%<n.sub.x<90%.

7. The copolyamide of claim 1, wherein the copolyamide is such that: 5%<n.sub.x<85%.

8. The copolyamide of claim 1, wherein the copolyamide has a glass transition temperature of at least 100° C., as determined according to ASTM D3418.

9. A copolyamide composition (C), comprising: at least one copolyamide according to claim 1, at one least one of components selected from the group consisting of reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

10. An article comprising the copolyamide of claim 1.

11. Transparent or semi-transparent articles comprising the copolyamide of claim 1.

12. Windows, clear containers for cosmetic products packaging or glass frames and lenses comprising the article of claim 10.

13. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising: providing a part material comprising the copolyamide of claim 1, and printing layers of the three-dimensional object from the part material.

14. A filament for use in the manufacture of three-dimensional objects comprising the copolyamide of claim 1.

15. The method of claim 13, wherein the additive manufacturing system is an extrusion-based additive manufacturing system.

16. An article comprising the composition (C) of claim 9.

17. Transparent or semi-transparent articles comprising the composition (C) of claim 9.

18. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising : providing a part material comprising the composition (C) of claim 9, and printing layers of the three-dimensional object from the part material.

19. A filament for use in the manufacture of three-dimensional objects comprising the composition (C) of claim 9.

Description

EXAMPLES

Raw Materials

[0105] 4-AMBa : 4-(aminomethyl)benzoic acid monomer (Sigma-Aldrich)

[0106] 3-AMBa : 3-(aminomethyl)benzoic acid monomers, obtained by the process described in patent application WO 2017/097220, from biobased furfural derivatives (5 carbon atoms over 8 carbon atoms are from biobased sources).

[0107] Isophthalic acid (Flint Hills Resources)

[0108] Hexamethylenediamine (Ascend Performance Materials)

[0109] 1,3-bis(aminomethyl)cyclohexane (Mitsubishi Gas Company)

Copolyamides Preparation

[0110] Synthesis of Ex 1 and 2: The molar equivalent amounts of 1,4-AMBA, hexamethylenediamine and isophthalic (Table 1) acid were charged into the agitated reactor and added with DI water (30 wt %). Phosphorous acid (120 ppm equivalent P) was used as an additive in the polymerization. The mixture was agitated and heated to 310° C. The steam generated was released and the reacting mixture was further heated at this temperature for another 60 minutes at ambient pressure. Vacuum was applied for 10 minutes before the heating was turned off. The formed polymer was discharged and analyzed for its thermal properties.

[0111] Synthesis of Ex 3: The molar equivalent amounts of 1,4-AMBA, 1,3-bis(aminomethyl)cyclohexane and isophthalic acid (Table 1) were charged into the agitated reactor and added with DI water (30 wt %). Phosphorous acid (120 ppm equivalent P) was used as an additive in the polymerization. The mixture was agitated and heated to 310° C. The steam generated was released and the reacting mixture was further heated at this temperature for another 60 minutes at ambient pressure. Vacuum was applied for 10 minutes before the heating was turned off. The formed polymer was discharged and analyzed for its thermal properties.

[0112] Synthesis of Ex 4: The polymerization was conducted using a jacketed 300-ml reactor equipped with a distillation line, a pressure regulation valve, an agitator and a discharge valve. The vessel was charged with 61.00 g 1,4-AMBA, 31.57 g HMD, 44.69 g isophthalic acid, 0.047 g sodium acetate, 0.123 g NaH2PO2.H2O and 59 g deionized water. The reactor was purged 3 times with nitrogen (5 bars) and sealed under a nitrogen atmosphere. The regulation valve was set at 17.5 bars and the reaction mixture was heated to 220° C. in about 50 minutes under stirring. The reaction mixture was further heated up to 280° C. during an additional 70 minutes, while the regulation valve maintained a plateau pressure of 17.5 bars. The pressure was then reduced down to 2 bars in about 25 minutes. The polymer was then discharged from the reactor, drawn, cooled in a water bath and pelletized.

[0113] Synthesis of Ex 5: The polymerization was performed using a jacketed 7.5 L autoclave reactor equipped with a distillation line, a pressure regulation valve and an agitator. The vessel was charged with 1193 g of 1,4-AMBA, 598.6 g of HMD, 856.6 g of isophthalic acid, 0.9119 g sodium acetate, 2.356 g NaH2PO2.H20 and 1140 g deionized water. The polymerization steps described for Ex 3 were followed with the exception of the reactor pressure at discharge. Three identical charges were polymerized with slightly varying discharge pressures of 3.5, 2.7 and 2.5 bars. The combined product was dried to a moisture content of 1550 ppm. The polymer was processed through twin screw extrusion using a Leistritz 18 mm extruder in order to increase molecular weight. Zone temperatures from the hopper to the die were 220, 290, 290, 290, 290 and 300° C. A vacuum of 26 inches of Hg was applied at zone 5. Polymer Ex 4 was produced at a screw speed of 120 rpm and a throughput rate of 3.3 lb/hr. Ex 5 and pre-polymer molecular weight data are reported in Table 2.

[0114] Synthesis of CEx 6. The molar equivalent amounts of 1,3-AMBA, hexamethylenediamine and isophthalic acid were charged into the agitated reactor and added with DI water (30 wt %). Phosphorous acid (120 ppm equivalent P) was used as an additive in the polymerization. The mixture was agitated and heated to 300° C. The steam generated was released and the reacting mixture was further heated at this temperature for another 30 minutes and then the reaction was stopped.

Testing

Thermal Transitions (Tg, Tm)

[0115] The glass transition and melting temperatures were measured using differential scanning calorimetry according to ASTM D3418 employing a heating and cooling rate of 20° C/min. Three scans were used for each DSC test: a first heat up to 320° C., followed by a first cool down to 50° C., followed by a second heat up to 340° C. The Tg was determined from the second heat up. The glass transition temperatures are tabulated in Table 1 (invention) below.

TABLE-US-00001 TABLE 1 mol. % Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 4-AMBa 50 70 50 60 60 Isophthalic acid 50 30 50 40 40 Hexamethylenediamine 50 30 40 40 1,3-BAC 50 Tg (° C.) 156 179 198 165 165 Tm (° C.) — — — — —

[0116] In comparison to compositions described in WO2018/229127, the copolyamides with 1,4-AMBA surprisingly exhibit higher Tg.

[0117] Gel permeation chromatography (GPC) was performed on the copolymer of Example 5 employing a WatersModular SEC Instrument, a Waters Alliance 2695 Separation Module, a Waters 2487 Dual Absorbance Detector, a Waters 2414 Refractive Index Detector, a Waters 515 pump and Waters Empower Pro Gel Chromatography Software. The instrument was equipped with two PL gel 10 μm MiniMixe B 250×4.6 mm columns and a guard column The samples were dissolved at 5 to 6 g/L in HFIP containing 0.05 M NaFTA; a sample was injected. Elution was conducted as 40° C. Results were calibrated against a standard having a Mw=27943, Mn=9340, Mw/Mn=2.99. Molecular weight data for inventive copolymer 5 are presented in Table 2.

TABLE-US-00002 TABLE 2 Ex 5 Ex 5 Ex 5 PreP1 PreP2 PreP3 Ex 5 M.sub.n 7.6 7.7 9.6 11.8 M.sub.w 18.8 20.3 30.8 56

Molding and Mechanical Testing

[0118] Molding of copolymer of example 4 was accomplished using a DSM Xplore® Microcompounder and Mini Injection System. Applied temperatures were as follows: barrels at 320° C., melt and wand at 300° C., mold at 130° C. The residence time in the microcompounder was 90 s. Fill, pack and hold times and pressures were 9 s at 6 bar, 1.5 s at 4 bar and 8 s at 4 bar, respectively. ASTM Type V tensile bars were evaluated according to ASTM method D638 using a testing speed of 0.05″/min. The mechanical data for Ex 4 are presented in Table 3.

TABLE-US-00003 TABLE 3 Ex 4 Modulus of Elasticity, GPa (ksi) 3.23 (469) Tensile Elongation @ Break (%) 9.7 Tensile Elongation @ Yield (%) 6.7 Tensile Strength @ Yield, MPa (psi) 105 (15,200)

[0119] In addition to the unexpected high Tg, the copolymers of the invention can be polymerized to molecular weights required for good mechanical properties. The copolymers display useful mechanical properties such as ductility and high tensile strength.