(Co)polyamides obtainable from 1,4-cyclohexanedicarboxylic acid and a diamine of formula H.SUB.2.N-(CH.SUB.2.).SUB.2.-O-(CH.SUB.2.).SUB.2.-O-(CH.SUB.2.).SUB.2.-NH.SUB.2

Abstract

The present invention relates to (co)polyamides comprising at least 60 mol. % of recurring units of formula (I): (I). The present invention also relates to polymer compositions comprising such (co)polyamides, as well as articles comprising the same and methods of using said articles in high temperature applications requiring sufficient swelling or deformation upon exposure to moisture, such as for example oil and gas extraction processes (e.g. fracturing balls), or as support materials used to print three-dimensional (3D) parts. ##STR00001##

Claims

1. A (co)polyamide for use as a support material for 3D printing comprising at least 60 mol. % of recurring units of formula (I): ##STR00012##

2. The (co)polyamide of claim 1, wherein the (co)polyamide is a condensation product of a mixture comprising: 1,4-cyclohexanedicarboxylic acid of formula (II): ##STR00013## and a diamine of formula (III):
H.sub.2N(CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.2NH.sub.2(III).

3. The (co)polyamide of claim 2, wherein the (co)polyamide is the condensation product of the mixture further comprising one diacid (DA) selected from the group consisting of adipic acid, sebacic acid, isophthalic acid, terephthalic acid, 5-hydroxyisophthalic acid, and 5-sulfophthalic acid.

4. The polyamide of claim 2, wherein the (co)polyamide is the condensation product of the mixture further comprising one diamine (NN) selected from the group consisting of 1,4-diaminobutane, 1,5-diamonopentane, 1,6-diaminohexane, 1,10-diaminedecane, H.sub.2N(CH.sub.2).sub.3O(CH.sub.2).sub.2O(CH.sub.2).sub.3NH.sub.2, and m-xylylene diamine.

5. The (co)polyamide of claim 4, wherein the diamine (NN) is of formula (IV):
H.sub.2N(CH.sub.2).sub.3O(CH.sub.2).sub.2O(CH.sub.2).sub.3NH.sub.2(IV).

6. The (co)polyamide of claim 2 comprising a molar ratio n.sub.diacid/n.sub.diamine ranging from 0.8 to 1.2.

7. The (co)polyamide of claim 1, wherein the (co)polyamide has a melting point of at least 260 C., as determined according to ASTM D3418.

8. The (co)polyamide of claim 1, wherein the (co)polyamide has a water uptake at saturation, by immersion in water at 23 C. of at least 2 wt. %.

9. The (co)polyamide of claim 1, wherein the (co)polyamide has a solubility in water of at least 50 wt. % at a concentration of 5 g/L, at 110 C., under atmospheric pressure.

10. The (co)polyamide of claim 1, wherein the number average molecular weight M.sub.N of the (co)polyamide ranges from 1,000 to 40,000 g/mol, as determined by GPC.

11. A (co)polyamide composition comprising: at least one (co)polyamide according to claim 1, and at least one component selected from the group consisting of reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, and mixtures thereof.

12. An article comprising the (co)polyamide of claim 1.

13. The article of claim 12, provided in a dry state, having a moisture content of less than 0.5 wt. %, with respect to a total weight of the support material.

14. A support material to print 3D parts comprising the article of claim 12.

15. Polymer fibers or carbon fibers coated with the article of claim 12.

16. The article of claim 13 having a moisture content of less than 0.2 wt. %, with respect to the total weight of the support material.

Description

EXAMPLES

(1) Raw Materials

(2) Jeffamine EDR-148 polyetheramine, 2,2-(ethylenedioxy)bis(ethylamine), presenting the following formula:
H.sub.2N(CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.2NH.sub.2

(3) Jeffamine EDR-176 polyetheramine, ethylene glycol bis(3-aminopropyl)ether, presenting the following formula:
H.sub.2N(CH.sub.2).sub.3O(CH.sub.2).sub.2O(CH.sub.2).sub.3NH.sub.2

(4) Jeffamine D-230 polyetheramine, poly(propylene glycol) bis(2-aminopropyl ether) presenting the following formula:

(5) ##STR00011##

(6) in which x is 2.5.

(7) Terephthalic acid (Flint Hills Resources)

(8) 1,4-cyclohexanedicarboxylic acid (Eastman Chemical Products)

(9) Adipic acid (Koch Industries)

(10) Sebacic acid (Aldrich Chemical Company)

(11) Isophthalic acid (Flint Hills Resources)

(12) 5-hydroxyisophthalic acid (Aldrich Chemical Company)

(13) 5-sulfoisophthalic acid, sodium salt (Aldrich Chemical Company)

(14) 5-sulfoisophthalic acid, monolithium salt (Aldrich Chemical Company)

(15) (Co)polyamides Preparation

(16) All of the (co)polyamides C1-C3 and 1-8 were prepared according to a similar process in an electrically-heated reactor equipped with a stirrer and a distillate line equipped with a pressure regulation valve. For composition 1, the reactor was charged with 9.08 g (0.053 mol) of 1,4-cyclohexane dicarboxylic acid, 7.86 g (0.053 mol) of 2,2-(ethylenedioxy)bis(ethylamine), 0.0052 g H.sub.3PO.sub.3 and 11 g of deionized water. The reactor was sealed, the pressure release valve was set to 17 bar and the reaction mixture was heated to 260 C. in 45 minutes. Pressure was incrementally reduced to atmospheric pressure while increasing internal temperature to 300 C. The reaction mixture was kept at 300 C. for 15 min and then cooled down to 200 C. within 1 hour and then to room temperature.

(17) Composition 9 was produced in a jacketed stainless steel reactor equipped with a double helicon ribbon agitator and heated through circulation of Therminol 66. The reactor was charged with 1.876 kg (12.66 mol) 2,2-(ethylenedioxy)bis(ethylamine), 1.525 kg (8.857 mol) 1,4-cyclohexanedicarboxylic acid, 0.555 kg (3.798 mol) adipic acid and 1.726 kg water, purged with nitrogen and heated to 220 C. with the pressure release valve set at 17 bar. After reaching 17 bar and 213 C., the temperature was increased to 280 C. within 100 minutes. The pressure was then reduced to atmospheric and the temperature increased to 295 C. over a period of 35 minutes. Vacuum was introduced over 10 minutes and then the reaction mixture was held at 400 mbar for 20 min. The polymer was discharged and quenched on stainless steel trays cooled on dry-ice to yield 3.3 kg polymer. The solidified polymer was ground and dried under vacuum for 16 h at 90 C. Polymer was molded into rheology discs using a DSM XPlore mini-compounder and micro-molding machine.

(18) Testing

(19) Melting Temperatures (Tm)

(20) The melting temperatures of the various (co)polyamides 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 330 C., followed by a first cool down to 50 C., followed by a second heat up to 330 C. The Tm was determined from the second heat up as the peak temperature on the melting endotherm. The melting temperatures for the (co)polyamides of the invention and comparative examples are tabulated in Tables 1 and 2.

(21) Dissolution/Solubility Test

(22) Solubility was demonstrated by solution transparency or by significant polymer dispersion as a suspension of fine particles.

(23) Solubility testing was carried out in three solvents: distilled water, water supplemented with 0.1 M H.sub.3PO.sub.4 and water supplemented with 0.1 M NaOH. 0.05 g of sample was placed in a scintillation vial equipped with a reflux condenser and magnetic stir bar with 10 mL of one of the three solvents. Stirring was conducted for 30 minutes at room temperature, followed by visual inspection. Then the temperature was increased by 10 C., followed by visual inspection. These steps were repeated until the sample was completely dissolved or until the heating block temperature had reached 110 C. Dissolution was considered complete when the solution was either transparent or cloudy with fine suspended particles.

(24) Results:

(25) TABLE-US-00001 TABLE 1 C1 C2 C3 1 2 3 Diamine EDR-148 1 1 1 0.9 n (mol) EDR-176 1 0.1 D-230 1 Diacid Terephthalic 1 n (mol) acid 1,4-CHDA 1 1 1 0.95 1 Adipic acid Sebacic 0.05 acid T.sub.m ( C.) 251 257 191 311 300 296 T C. Distilled 110 90 Ins 110 100 110 for water (80 disso- wt. %) lution 0.1M H.sub.3PO.sub.4 90 80 70 90 110 100 in given 0.1M NaOH 110 80 90 80 100 80 solvent M.sub.N (g/mol) 7,200 13,000 6,900 10,000 11,000 7,700

(26) Ins means a solubility < to 50 wt. % at 110 C.

(27) TABLE-US-00002 TABLE 2 4 5 6 7 8 9 Di- EDR- 1 1 1 1 1 1 amine 148 n (mol) Diacid 1,4- 0.95 0.95 0.95 0.9 0.85 0.7 n CHDA (mol) Adipic 0.1 0.3 acid Sebacic acid Iso 0.15 phthalic acid 5- 0.05 hydroxy- iso- phthalic acid 5- 0.05 sulfoiso- phthalic acid, sodium salt 5- 0.05 sulfoiso- phthalic acid, mono- lithium salt T.sub.m ( C.) 289 276 282 305 283 265 T C. Distilled 50 60 60 110 70 60 for water (80 disso- wt. %) lution 0.1M 60 50 90 90 40 50 in H.sub.3PO.sub.4 given 0.1M 50 40 50 80 50 25 sol- NaOH vent M.sub.N (g/mol) 8,500 7,300 10,000 11,000 7,700 10,000

(28) The polyamide of C1, prepared from terephtalic acid and EDR-148 presents a solubility of 100% at 5 g/L at 110 C. under atmospheric pressure in distilled water, but a melting point lower than 260 C. The polyamide of C2, prepared from 1,4-CHDA and EDR-176 presents a melting point lower than 260 C. The polyamide of C3, prepared from 1,4-CHDA and D-230 presents a melting point significantly lower than 260 C., and is insoluble in distilled water at 5 g/L at 110 C. under atmospheric pressure. The polyamides C1, C2 and C3 are not adapted to high temperature applications requiring sufficient swelling or deformation upon exposure to moisture, such as for example oil and gas extraction processes (e.g. fracturing balls), or as support materials used to print three-dimensional (3D) parts. The polyamides 1 to 9 on the other hand present both a melting point above 260 C. and sufficient solubility into water (distilled water, water supplemented with 0.1 M H.sub.3PO.sub.4 and water supplemented with 0.1 M NaOH) at 110 C. or even less. The polyamides of examples 1 and 7 were 80 wt. % soluble at 110 C. All of the polyamides of the examples 1-9 are well adapted to the aforementioned applications.