POLYMERS, COMPOSITIONS AND METHOD FOR MANUFACTURING AN ARTICLE BY 3D PRINTING

Abstract

The present invention relates to poly(aryl ether) polymers which can for example be used in lithographic processes for the photofabrication of three-dimensional (3D) articles. The invention further relates to compositions including these poly(aryl ether) polymers. Still further, the invention relates to lithographic methods to form 3D articles or objects that incorporate the aforementioned polymer compositions.

Claims

1. A poly(aryl ether) (PAE) polymer (P1) comprising: recurring units R.sub.PAES and/or recurring units R.sub.PAEK, wherein recurring units R.sub.PAES are according to formula (M): ##STR00024## recurring units R.sub.PAEK are selected from the group consisting of units of formulas (J-A) to (J-D): ##STR00025## at least one group of formula (L1) to (L4): ##STR00026## wherein each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.xC═CR.sub.y—, where each R.sub.x and R.sub.y, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m and —(CF.sub.2).sub.m with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof; Ar is a tetravalent aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; Ar′ is a trivalent aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; each R.sub.2 is independently H or an alkyl; each Y is independently selected from the group consisting of: O—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k being from 1 to 20; and R.sub.4 being H or an alkyl; O—(CH.sub.2).sub.p—Ar—CR.sub.5═CHR.sub.6 or O—(CH.sub.2).sub.p—OAr—CR.sub.5═CHR.sub.6, wherein p is from 0 to 20; Ar comprises one or two aromatic or heteroaromatic rings; R.sub.5 and R.sub.6 are H, an alkyl, a phenyl or a COOR.sub.7 with R.sub.7 being H or an alkyl; O—(CH.sub.2).sub.q—CH═CHR.sub.8 with q being from 0 to 20; and R.sub.8 being H or an alkyl; O—(CH.sub.2).sub.r—O—CH═CHR.sub.9 with r being from 0 to 20; and R.sub.9 being H or an alkyl; ##STR00027##  with s being from 0 to 20; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k and R.sub.4 as above-defined, O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.p—Ar—CR.sub.5═CHR.sub.6, with p, Ar, R.sub.5 and R.sub.6 as above-defined, O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.p—OAr—CR.sub.5═CHR.sub.6 with p, Ar, R.sub.5 and R.sub.6 as above-defined, O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.q—CH═CHR.sub.8, with q and R.sub.8 as above-defined, O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.r—O—CH═CHR.sub.9, with r and R.sub.9 as above-defined, ##STR00028##  with s as above-defined, wherein R.sub.a, R.sub.b, and R.sub.c are independently H or an alkyl.

2. The PAE polymer (P1) of claim 1, wherein the recurring units R.sub.PAES and/or recurring units R.sub.PAEK are in blocks comprising at least two recurring units.

3. The PAE polymer (P1) of claim 1, comprising at least 50 mol. % (based on the total number of moles in the polymer) of recurring units of formula (M) in which T is selected from the group consisting of a bond, —SO.sub.2— and —C(CH.sub.3).sub.2—.

4. The PAE polymer (P1) of claim 1, wherein Y is O—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k being from 2 to 6 and R.sub.4 being H or CH.sub.3.

5. The PAE polymer (P1) of claim 1, wherein the PAE polymer (P1) has a number average molecular weight (Mn) (as measured by gel permeation chromatography (GPC) using N,N dimethyl formamide (DMF) as a mobile phase, with polystyrene standards) of: less than 100,000 g/mol; and/or more than 1,000 g/mol.

6. A formulation (F), comprising: the PAE polymer (P1) of claim 1; and one solvent; optionally one photoinitiator; optionally one blocker.

7. The formulation (F) of claim 6, wherein: the solvent is selected from the group consisting of chlorobenzene, chloroform, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and sulfolane; the photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone (DMPA), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and/or the blocker is selected from the group consisting of avobenzone and 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene.

8. A process for preparing the PAE polymer (P1) of claim 1, comprising: a) providing a PAE polymer (P0) of formula R.sub.nR.sub.mN—P—NR.sub.nR.sub.m, wherein P comprises recurring units R.sub.PAES and/or recurring units R.sub.PAEK, wherein recurring units R.sub.PAES are according to formula (M): ##STR00029## recurring units R.sub.PAEK are selected from the group consisting of units of formulas (J-A) to (J-D): ##STR00030## wherein each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each R.sub.n and R.sub.m is independently H or an alkyl; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.xC═CR.sub.y—, where each R.sub.x and R.sub.y, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m and —(CF.sub.2).sub.m with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof. b) reacting the PAE polymer (P0) with a compound of formula (I), (II), (III) or (IV): ##STR00031## wherein: Ar is a tetravalent aromatic moiety, selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; Ar′ is a trivalent aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; X is Cl, Br, F or I; each Y is independently selected from the group consisting of: O—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k being from 1 to 20; and R.sub.4 being H or an alkyl, O—(CH.sub.2).sub.p—Ar—CR.sub.5═CHR.sub.6 or O—(CH.sub.2).sub.p—OAr—CR.sub.5═CHR.sub.6, wherein p is from 0 to 20; Ar comprises one or two aromatic or heteroaromatic rings; R.sub.5 and R.sub.6 are H, an alkyl, a phenyl or a COOR.sub.7 with R.sub.7 being H or an alkyl, O—(CH.sub.2).sub.q—CH═CHR.sub.8 with q being from 0 to 20; and R.sub.8 being H or an alkyl; O—(CH.sub.2).sub.r—O—CH═CHR.sub.9 with r being from 0 to 20; and R.sub.9 being H or an alkyl; ##STR00032##  with s being from 0 to 20; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k and R.sub.4 as above-defined; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.p—Ar—CRs═CHR.sub.6, with p, Ar, R.sub.5 and R.sub.6 as above-defined; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.p—OAr—CRs═CHR.sub.6 with p, Ar, R.sub.5 and R.sub.6 as above-defined; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.q—CH═CHR.sub.8, with q and R.sub.8 as above-defined; O.sup.−, NR.sub.aR.sub.bR.sub.cH.sup.+—(CH.sub.2).sub.r—O—CH═CHR.sub.9, with r and R.sub.9 as above-defined; ##STR00033##  with s as above-defined; wherein R.sub.a, R.sub.b, and R.sub.c are independently H or an alkyl, in the presence of a polar aprotic solvent and an organic base.

9. The process of claim 8, wherein the solvent is selected from the group consisting of chlorobenzene, chloroform, N-methylpyrrolidone (NMP), N,Ndimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and sulfolane, and the organic base is selected from the group consisting of pyridine and alkylamine.

10. A process for preparing the PAE polymer (P1) of claim 1, comprising: a) providing a PAE polymer (P0) of formula R.sub.nR.sub.mN—P—NR.sub.nR.sub.m, wherein P comprises recurring units R.sub.PAES and/or recurring units R.sub.PAEK, wherein recurring units R.sub.PAES are according to formula (M): ##STR00034## recurring units R.sub.PAEK are selected from the group consisting of units of formulas (J-A) to (J-D): ##STR00035## wherein each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each R.sub.n and R.sub.m is independently H or an alkyl; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.xC═CR.sub.y—, where each R.sub.x and R.sub.y, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m and —(CF.sub.2).sub.m with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof. b) reacting the PAE polymer (P0) with a compound of formula (V), (V), (VI) or (VIII): ##STR00036## wherein: Ar is a tetravalent aromatic moiety, selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; Ar′ is a trivalent aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; X is OH, Cl, Br, F or I; c) reacting the polymer obtained in step b) with a compound selected from the group consisting of: NR.sub.aR.sub.bR.sub.c—(CH.sub.2).sub.k—O—CO—CH═CHR.sub.4, with k and R.sub.4 as above-defined, NR.sub.aR.sub.bR.sub.c—(CH.sub.2).sub.p—Ar—CR.sub.5═CHR.sub.6, with p, Ar, R.sub.5 and R.sub.6 as above-defined, NR.sub.aR.sub.bR.sub.c—(CH.sub.2).sub.p—OAr—CR.sub.5═CHR.sub.6 with p, Ar, R.sub.5 and R.sub.6 as above-defined, NR.sub.aR.sub.bR.sub.c—(CH.sub.2).sub.q—CH═CHR.sub.8, with q and R.sub.8 as above-defined, NR.sub.aR.sub.bR.sub.c—(CH.sub.2).sub.r—O—CH═CHR.sub.9, with r and R.sub.9 as above-defined, ##STR00037##  with s as above-defined, wherein R.sub.a, R.sub.b, and R.sub.c are independently H or an alkyl.

11. A method for manufacturing a three-dimensional (3D) article with an additive manufacturing system, comprising: providing a formulation (F) according to claim 6, printing layers of the three-dimensional (3D) article from the formulation (F).

12. The method of claim 11, wherein the step of printing comprises irradiating the polymer composition with light, light.

13. A three-dimensional Three dimensional (3D) article or object manufactured, at least in part, by the method of claim 11.

14. The 3D article or object of claim 13, comprising: recurring units R.sub.PAES and/or recurring units R.sub.PAEK, wherein recurring units R.sub.PAES are according to formula (M): ##STR00038## recurring units R.sub.PAEK are selected from the group consisting of units of formulas (J-A) to (J-D): ##STR00039## at least one group of formula (K): ##STR00040## wherein: each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.aC═CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m and —(CF.sub.2).sub.m with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof; and Ar is a tetravalent aromatic moiety, selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms.

15. A method for the manufacture of 3D objects, the method comprising printing the 3D objects, with the polymer (P1) according to claim 1, by stereolithography technology (SLA), ink-jet process, direct ink writing (DIW) or digital light processing (DLP), where the polymer (P1) is printed alone or in a formulation with one solvent, optionally one photoinitiator, and optionally one blocker.

Description

EXAMPLES

[0259] Two PAE polymers (P1) and corresponding PAE polymers (P2) according to the present invention were prepared and characterized.

[0260] Molecular Weight (Mn, Mw, Mz and Mz+1)

[0261] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5μ mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 20 μL of a 0.2 w/v % solution in mobile phase was selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn, weight average molecular weight Mw, higher average molecular weight Mz and Mz+1, were reported.

Example 1. Synthesis of PPSU Polymer (P1-A) and PPSU Polymer (P2-A)

[0262] This example demonstrates the synthesis of a polymer (P1-A), comprising recurring units R.sub.PPSU, poly(biphenyl ether sulfone), according to Scheme 1.

##STR00020##

[0263] Formation of the Reactants Amine-PPSU and PDMA-HEA (I-A)

[0264] The Amine-PPSU was synthetized according to the methods described in (1) B. J. Sundell, K.-s. Lee, A. Nebipasagil, A. Shaver, J. R. Cook, E.-S. Jang, B. D. Freeman, J. E. McGrath, Industrial & Engineering Chemistry Research 2014, 53, 2583-2593. (2) J. Mecham, H. K. Shobha, F. Wang, W. Harrison, J. E. McGrath, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2000, 41, 1388-1389. (3) C. Puglisi, F. Samperi, G. Cicala, A. Recca, C. L. Restuccia, Polymer 2006, 47, 1861-1874. (4) M. W. Muggli, T. C. Ward, C. Tchatchoua, Q. Ji, J. E. McGrath, J. Polym. Sci., Part B: Polym. Phys. 2003, 41, 2850-2860.

[0265] The PDMA-HEA diacid chloride (I-A) (PMDA-HEA-CI, Mw: 455.24 g/mol) was synthesized according to methods reported in the literature. Reference can be made in particular to Hedge et al. “3D Printing All-Aromatic Polyimides using Mask-Projection Stereolithography: Processing the Nonprocessable” (Adv. Mater. 2017, 29).

[0266] Formation of the PPSU Polymer (P1-A)

[0267] A three-neck flask with a gas-inlet and thermocouple was charged with 8.66 g of Amine-PPSU, 0.3 mL of pyridine and 50 mL NMP with overhead stirring. A separate solution of the crude PMDA-HEA-CI (I-A) (0.7556 g, 3.32 mmol) was then dissolved in 40 mL dry NMP and added dropwise over an 1 h while on an ice bath. After complete addition, the mixture was then left stirring at room temperature for 4 h. After mixing, the solution was coagulated into ˜500 mL MeOH and washed 3 times with MeOH with heavy agitation during each wash. Yield 8.4 g.

[0268] Formation of the PPSU Polymer (P2-A)

[0269] This example also demonstrates the synthesis of a PPSU polymer (P2-A), according to Scheme 2.

##STR00021##

[0270] A tube furnace was charged with 600 mg of the PPSU polymer (P1-A) and was purged for 20 min under a flow of N.sub.2. A flow of N.sub.2 kept until the sample was taken out of the furnace. After the purge, the tube was then heated at 250° C. for 17 min. After heating, the tube was allowed to cool to room temperature (˜1.5 h) and the sample was removed from the furnace.

[0271] Characterization of the PPSU polymers (P1-A) and (P2-A) The different polymers were characterized by GPC to determine molecular weights (Mn & Mw) and polydispersity index (PDI). The results are summarized in Table 1.

TABLE-US-00001 TABLE 1 Mw Mn Mw/Mn Mz Mz + 1 Mz/Mw Amine 23,641 7,143 3.31 39,498 51,290 1.67 PPSU PPSU 54,887 18,736 2.93 82,446 102,715 1.5 (P1-A) PPSU 80,222 28,872 2.78 97,603 107,892 1.22 (P2-A)

Example 2. Synthesis of PSU Polymer (P1-B) and PSU Polymer (P2-B)

[0272] This example demonstrates the synthesis of a polymer (P1-B), comprising recurring units R.sub.PSU, polysulfone, according to Scheme 3.

##STR00022##

[0273] Formation of the Reactants Amine-PSU and PDMA-HEA (I-A)

[0274] The Amine-PSU (Ill) was synthetized according to methods described in (1) B. J. Sundell, K.-s. Lee, A. Nebipasagil, A. Shaver, J. R. Cook, E.-S. Jang, B. D. Freeman, J. E. McGrath, Industrial & Engineering Chemistry Research 2014, 53, 2583-2593. (2) J. Mecham, H. K. Shobha, F. Wang, W. Harrison, J. E. McGrath, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2000, 41, 1388-1389. (3) C. Puglisi, F. Samperi, G. Cicala, A. Recca, C. L. Restuccia, Polymer 2006, 47, 1861-1874. (4) M. W. Muggli, T. C. Ward, C. Tchatchoua, Q. Ji, J. E. McGrath, J. Polym. Sci., Part B: Polym. Phys. 2003, 41, 2850-2860.

[0275] The PDMA-HEA diacid chloride (I-A) (PMDA-HEA-CI, Mw: 455.24 g/mol) was synthesized according to methods reported in the literature. Reference can be made in particular to Hedge et al. “3D Printing All-Aromatic Polyimides using Mask-Projection Stereolithography: Processing the Nonprocessable” (Adv. Mater. 2017, 29).

[0276] Formation of the PSU Polymer (P1-B)

[0277] A three-neck flask with a gas-inlet and thermocouple was charged with 7.6322 g of Amine-PSU, 0.2 mL of pyridine and 40 mL dry NMP with overhead stirring. A separate solution of the crude PMDA-HEA-CI (I-A) (0.54 g, 2.37 mmol) was then dissolved in dry 40 mL dry NMP and added dropwise over an 1 h while on an ice bath. After complete addition, the mixture was then left stirring at room temperature for 4 h. After mixing, the solution was coagulated into ˜500 mL MeOH and washed 3 times with MeOH with heavy agitation during each wash. Yield 6.07 g.

[0278] Formation of the PSU Polymer (P2-B)

[0279] This example demonstrates the synthesis of a PSU polymer (P2-B), according to Scheme 4.

##STR00023##

[0280] A tube furnace was charged with 600 mg of the PSU polymer (P1) and was purged for 20 min under a flow of N.sub.2. A flow of N.sub.2 kept until the sample was taken out of the furnace. After the purge, the tube was then heated at 250° C. for 17 min. After heating, the tube was allowed to cool to room temperature (˜1.5 h) and the sample was removed from the furnace.

[0281] Characterization of the PSU Polymers (P1-B) and (P2-B)

[0282] The material obtained by the aforementioned process was characterized by GPC to determine molecular weights (Mn & Mw) and polydispersity index (PDI). The results are summarized in Table 2.

TABLE-US-00002 TABLE 2 Mw Mn Mw/Mn Mz Mz + 1 Mz/Mw Amine-PSU 17,272 5,564 3.1 29,809 40,118 1.73 PSU (P1-B) 29,323 10,275 2.85 47,693 63,283 1.63 PSU (P2-B) 34,896 10,737 3.25 54,273 69,431 1.56