阅读说明：本技术 聚(芳基醚砜)和聚二甲基硅氧烷的共聚物 (Copolymers of poly (aryl ether sulfone) and polydimethylsiloxane ) 是由 K·奈尔 J·波里诺 S·乔尔 D·B·托马斯 于 2019-10-21 设计创作，主要内容包括：本发明涉及聚(芳基醚砜)(PAES)和聚二甲基硅氧烷(PDMS)的共聚物(P1),并且涉及通过熔融氢化硅烷化制备该共聚物(P1)的方法。(The present invention relates to copolymers (P1) of poly (aryl ether sulfone) (PAES) and Polydimethylsiloxane (PDMS) and to a process for preparing the copolymers (P1) by melt hydrosilylation.)

1. A solvent-free process for preparing a copolymer (P1) having the formula (L):

wherein

Each R₁Independently selected from the group consisting of: 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 sulfonate, aryl, thioether, carboxylic acid, ester, amide, imide, amide,Alkyl phosphonates, amines and quaternary amines;

-each i is independently selected from 0 to 4;

-T is selected from the group consisting of: bond, -CH₂-；-O-；-SO₂-；-S-；-C(O)-；-C(CH₃)₂-；-C(CF₃)₂-；-C(＝CCl₂)-；-C(CH₃)(CH₂CH₂COOH)-；-N＝N-；-R_aC＝CR_b-, wherein R_aAnd R_bEach independently of the others is hydrogen or C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl; - (CH)₂)_m-and- (CF)₂)_m-, where m is an integer from 1 to 6; a linear or branched aliphatic divalent group having up to 6 carbon atoms; and combinations thereof;

-n_pand n_rMolar% of each repeating unit p and r, respectively;

the repeating units p and r are arranged in a block manner, in an alternating manner, or randomly;

-5≤n_p<100；

-5≤n_r<100；

-q₁and q is₂Independently varying between 2 and 14 (inclusive),

the method comprises reacting a poly (aryl ether sulfone) (PAES) polymer (P0) comprising:

-a repeating unit p having formula (N):

and

-at least one terminal group having formula (M):

wherein R is₁I and T are as described above, and s varies between 0 and 12 (inclusive);

and a compound having the formula (I):

wherein m varies between 1 and 200;

wherein the compound (I)/polymer (P0) molar ratio is 0.5:1 and 1: 0.5;

optionally in the presence of a metal-based catalyst;

the reaction is carried out at a temperature ranging from 150 ℃ to 450 ℃.

2. The method of claim 1, wherein T is selected from the group consisting of: bond, -SO₂-and-C (CH)₃)₂-。

3. The method of any one of claims 1 to 2, wherein 50 ≦ n_p<100。

4. The method of any one of claims 1 to 3, wherein q is₁And q is₂Equal to 2.

5. The method of any one of claims 1 to 4, wherein for each R of formulas (L), (M), and (N), R₁And i is zero.

6. The process as claimed in any of claims 1 to 5, which is carried out in a stirred reactor, extruder or kneader.

7. The process of any one of claims 1 to 6, carried out in the presence of at least one metal-based catalyst selected from the group consisting of platinum-based catalysts, rhodium-based catalysts and ruthenium-based catalysts.

8. The method of claim 7, wherein the catalyst is platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane or chloroplatinic acid.

9. The process of any one of claims 1 to 8, which is carried out in the presence of at least one free radical generator.

10. The method of claim 9, wherein the free radical generator is benzoyl peroxide.

11. A copolymer (P1) obtained by the process according to any one of claims 1 to 10.

12. A method for manufacturing a three-dimensional object with an additive manufacturing system, the method comprising a step comprising printing a layer of the three-dimensional object from a part material comprising the copolymer (P1) of claim 11.

13. Use of the copolymer of claim 11 as Hot Melt Adhesive (HMA).

Technical Field

The present disclosure relates to a solvent-free process for preparing copolymers of poly (aryl ether sulfone) (PAES) and Polydimethylsiloxane (PDMS) (P1) by melt hydrosilylation (addition of-Si-H groups to carbon-carbon double bonds). The invention also relates to a copolymer (P1) obtainable by such a process and the use of this copolymer as part material for 3D printing, as hot melt adhesive for moulding/overmolding applications and for the automotive, smart device and semiconductor industries.

Background

Poly (aryl ether sulfone) (PAES) polymers belong to the group of high performance thermoplastics and are characterized by high heat distortion resistance, good mechanical properties, excellent hydrolysis resistance and inherent flame retardancy. Versatile and useful PAES polymers have many applications in the electronics, electrical industry, medicine, general engineering, food processing, and 3D printing.

While PAES polymers have many advantages and good physical properties, it is sometimes necessary to adjust these properties to improve performance in specific applications. Modification of properties can be achieved by combining two polymer molecules to make a copolymer with a combination of the inherent properties of each individual molecule.

Polydimethylsiloxane (PDMS) is a thermally stable material and can be used in a variety of applications in polymer and material science. PDMS has one of the lowest glass transition temperatures (Tg well below 0 ℃), which makes it an attractive material that can be incorporated into high temperature materials such as PAES polymers.

Hydrosilylation coupling reactions have been studied to produce multi-block copolymers of PDMS with Polyethersulfone (PSU). However, one major difficulty is the high incompatibility of these polymers and the identification of conventional reaction solvents. Sulfone polymers have low solubility in the solvent in which the PDMS molecules are dissolved, which limits the formation of high molecular weight copolymers, as characterized by high melt viscosity. For example, while PDMS has good solubility in chloroform, poly (biphenyl ether sulfone) polymer (PPSU) has limited solubility in chloroform.

The article by Auman B.C. et al (Polymer [ polymers ]1987,28,1407-1417) describes Pt-catalyzed hydrosilylation of Polyethersulfone (PSU) with PDMS in dilute solutions of chlorobenzene, which is then concentrated as the reaction proceeds (known as the dilute-concentrate method). However, the process described by Auman et al does not allow to obtain copolymers of high molecular weight.

The present invention provides a solvent-free process for preparing PAES and PDMS copolymers with high melt viscosity.

Disclosure of Invention

One aspect of the present disclosure relates to a solvent-free process for preparing a copolymer (P1) having the formula (L):

wherein

Each R₁Independently selected from the group consisting of: 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 phosphonates, alkyl phosphonates, amines and quaternary amines;

-each i is independently selected from 0 to 4;

-T is selected from the group consisting of: bond, -CH₂-；-O-；-SO₂-；-S-；-C(O)-；-C(CH₃)₂-；-C(CF₃)₂-；-C(＝CCl₂)-；-C(CH₃)(CH₂CH₂COOH)-；-N＝N-；-R_aC＝CR_b-, wherein R_aAnd R_bEach independently of the others is hydrogen or C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl; - (CH)₂)_m-and- (CF)₂)_m-, where m is an integer from 1 to 6; a linear or branched aliphatic divalent group having up to 6 carbon atoms; and combinations thereof;

-n_pand n_rMolar% of each repeating unit p and r, respectively;

the repeating units p and r are arranged in a block manner, in an alternating manner, or randomly;

-5≤n_p<100；

-5≤n_r<100；

-q₁and q is₂Independently varying between 2 and 14 (inclusive),

the method comprises reacting a poly (aryl ether sulfone) (PAES) polymer (P0) comprising:

-a repeating unit p having formula (N):

and

-at least one terminal group having formula (M):

wherein R is₁I and T are as described above, and s varies between 0 and 12 (inclusive);

and a compound having the formula (I):

wherein m varies between 1 and 200;

wherein the compound (I)/polymer (P0) molar ratio is 0.5:1 and 1: 0.5;

optionally in the presence of a metal-based catalyst;

at a temperature ranging from 150 ℃ to 450 ℃.

The invention also relates to the copolymer (P1) obtained by this process.

The invention also relates to a method for manufacturing a three-dimensional object with an additive manufacturing system, the method comprising a step comprising printing a layer of the three-dimensional object from a part material comprising the copolymer of the invention.

The invention also relates to the use of the copolymers according to the invention as hot-melt adhesives (HMAs).

Drawings

FIG. 1 shows a Transmission Electron Microscope (TEM) micrograph of the copolymer (P1-A) of example 1.

Detailed Description

The present invention relates to a process for the preparation of a copolymer (P1) which is a copolymer of poly (aryl ether sulfone) (PAES) and Polydimethylsiloxane (PDMS) by hydrosilylation (also referred to herein as melt hydrosilylation) in the absence of any solvent. The copolymers can be used, for example, as part materials in additive manufacturing processes, as well as in the automotive, smart device, and semiconductor industries. It can also be used as a hot melt adhesive for molding or overmolding applications. More details regarding the application of copolymer (P1) are given below.

The invention also relates to a copolymer obtainable by this process, and the use of this copolymer notably for 3D printing.

The prior art processes are carried out in a solvent; however, the low solubility of highly incompatible PAES and PDMS polymers in solvents limits the molecular weight increase of the copolymer. This is mainly due to the limited solubility of PAES in the solvents that dissolve PDMS (e.g. chloroform). The process of the present invention is solvent-free, meaning that the solubility of the polymer is not a limiting factor in the preparation of higher molecular weight copolymers. In addition, the solvent-less process of the present invention avoids the necessity of post-reaction purification steps.

In addition, the reaction proceeds at a fast reaction rate and a short reaction time. This is a low cost process and results in high yields. Furthermore, masterbatches with different resins can be made in a single step.

The inventors have shown that the solvent-free process of the present invention allows for the production of high viscosity copolymers.

The hydrosilylation process of the present invention is solvent-free, which means that the process is carried out in the melt, in the absence of a solvent or in the presence of a limited amount of a solvent. For example, the process of the present invention can be carried out in the presence of less than 5 wt.%, e.g., less than 4 wt.%, less than 2 wt.%, or less than 1 wt.% (based on the total weight of the reaction mixture) of a solvent. According to an embodiment, the hydrosilylation process of the present invention is solvent-free, carried out in the absence of a solvent selected from the group consisting of: anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, or alternatively, in the presence of a limited amount of one of these solvents (as detailed above).

The reaction can be carried out in a device made of a material inert to the polymer. In this case, it is feasible to select the apparatus so as to provide sufficient contact of the polymer and in which the volatile reaction products are removed. Suitable equipment includes stirred reactors, extruders and kneaders, for example mixing kneaders from List AG or BUSS. The use of a mixing kneader can be used notably for the preparation of solvent-free PPSU for reasons that may be longer than the residence time in the extruder.

Copolymer (P1)

The copolymer (P1) of the invention is according to the following formula (L):

wherein

Each R₁Independently selected from the group consisting of: 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: bond, -CH₂-；-O-；-SO₂-；-S-；-C(O)-；-C(CH₃)₂-；-C(CF₃)₂-；-C(＝CCl₂)-；-C(CH₃)(CH₂CH₂COOH)-；-N＝N-；-R_aC＝CR_b-, wherein R_aAnd R_bEach independently of the others is hydrogen or C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl; - (CH)₂)_m-and- (CF)₂)_m-, where m is an integer from 1 to 6; a linear or branched aliphatic divalent group having up to 6 carbon atoms; and combinations thereof;

-n_pand n_rMolar% of each repeating unit p and r, respectively;

the repeating units p and r are arranged in a block manner, in an alternating manner, or randomly;

-5≤n_p<100；

-5≤n_r<100；

-q₁and q is₂Independently vary between 2 and 14 (inclusive).

More specifically, the present invention relates to copolymers of PAES and PDMS, such as diblock, triblock or multiblock copolymers. The copolymers (P1) of the present invention can be used directly or in the form of compositions of matter for melt processing (e.g. melt blending, molding, extrusion), or solution processing (e.g. 3D printing processes), and can also be used as compatibilizers for high molecular weight homolog blends thereof or as high temperature adhesives.

The copolymer (P1) of the present invention may have the following structure:

PAES-b-(PDMS-b-PAES-b)_g-PAES

wherein

G varies from 0 to 20, for example from 0 to 10, and

b is

-O-(CH₂)_q1-Si(CH₃)₂-O-or

-O-(CH₂)_q2-Si(CH₃)₂-O-

Wherein q is₁And q is₂As defined above, the above-mentioned,

for example b is-O- (CH)₂)₂-Si(CH₃)₂-O-。

As detailed below, depending on the nature of T, the PAES block of copolymer (P1) may be, for example, poly (biphenyl ether sulfone) (PPSU), Polysulfone (PSU), or Polyethersulfone (PES). The copolymer (P1) may notably comprise different PAES blocks, such as PPSU blocks and PES blocks. According to this embodiment, the block copolymer (P1) may have the following structure:

PPSU-b-(PDMS-b-PES)_g’-(PDMS-b-PPSU)_g”-PES

wherein

-g' and g "vary from 0 to 20, e.g. from 0 to 10, and

wherein b, q₁And q is₂As defined above.

According to an embodiment, R at each position in formula (L)₁Independently selected from the group consisting of: a C1-C12 moiety optionally containing one or more than one heteroatom; sulfonic acid and sulfonate ester groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.

According to an embodiment, for each R of formula (L)₁And i is zero. In other words, according to this embodiment, the repeating unit p is unsubstituted.

According to an embodiment of the invention, the PAES block polymer is such that T is selected from the group consisting of: bond, -SO₂-and-C (CH)₃)₂-。

According to yet another embodiment of the present invention, the PAES block polymer comprises repeating units selected from the group consisting of: formulA (N-A), (N-B) or (N-C):

according to another embodiment of the present invention, the PAES block polymer comprises at least 50 mol.% (based on the total moles in the PAES polymer) of recurring units of formulA (N-A), (N-B) and/or (N-C).

According to yet another embodiment of the present invention, the PAES block polymer comprises at least 50 mol.% (based on the total moles in the polymer) of recurring units selected from the group consisting of: formulA (N-A), (N-B) and (N-C), wherein for each R₁And i is zero.

According to another embodiment of the present invention, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, at least 99 mol.% or all of the recurring units in the PAES block polymer are recurring units p having the formulA (L) or the formulae (N-A), (N-B) and (N-C).

According to an embodiment, the PAES block polymer has a Tg ranging from 90 ℃ to 250 ℃, preferably from 170 ℃ to 240 ℃, more preferably from 180 ℃ to 230 ℃, as measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418.

According to an embodiment, the PAES block polymer is poly (biphenyl ether sulfone) (PPSU) having at least 50 mol.% (based on the total moles in the polymer) of recurring units of formula (N-C); for example, according to this embodiment, the PAES block polymer is a PPSU having at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, at least 99 mol.% of recurring units having the formula (N-C). According to another embodiment, all of the recurring units in the PAES block polymer are recurring units of the formula (N-C), e.g., wherein for each R₁And i is zero.

Poly (biphenyl ether sulfone) polymers (PPSU) are polyarylene ether sulfones containing a biphenyl moiety. Poly (biphenyl ether sulfone) is also known as polyphenylsulfone (PPSU) and results, for example, from the condensation of 4,4 '-dihydroxybiphenyl (bisphenol) and 4,4' -dichlorodiphenyl sulfone.

The poly (biphenyl ether sulfone) (PPSU) can be prepared by any method known in the art. It can be produced, for example, by condensation of 4,4 '-dihydroxybiphenyl (bisphenol) and 4,4' -dichlorodiphenyl sulfone in the presence of a base. The reaction of the monomer units proceeds via nucleophilic aromatic substitution while eliminating one hydrogen halide unit as a leaving group. It should be noted, however, that the structure of the resulting poly (biphenyl ether sulfone) does not depend on the nature of the leaving group.

PPSU is available from Solvay Specialty Polymers USA as Solvay Specialty Polymers, L.L.C.)PPSU is commercially available.

According to an embodiment, the copolymer (P1) is according to formula (L-C):

wherein R is₁、i、q₁、q₂、n_pAnd n_rAs described above.

According to a preferred embodiment, the copolymer (P1) is according to formula (L-C'):

wherein q is₁、q₂、n_pAnd n_rAs mentioned above, preferably wherein both q1 and q2 are equal to 2 and preferably wherein 50. ltoreq. np<100。

According to an embodiment, the PAES block polymer is A Polysulfone (PSU) polymer having at least 50 mol.% (based on the total moles in the PAES polymer) of recurring units of formulA (N-A); for example, according to this embodiment, the PAES block polymer is PSU having at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, at least 99 mol.% of recurring units having the formulA (N-A). According to another embodiment, all of the PAES block polymersThe repeating unit is A repeating unit having the formulA (N-A), for example wherein for each R₁And i is zero.

According to an embodiment, the copolymer (P1) is according to formula (L-a):

wherein R is₁、i、q₁、q₂、n_pAnd n_rAs described above.

PSU is available from Sorvv Special polymers, Inc., USA asPSU is available.

According to embodiments, the PAES block polymer is a Polyethersulfone (PES) polymer having at least 50 mol.% (based on total moles in the PAES polymer) of recurring units having the formula (N-B); for example, according to this embodiment, the PAES block polymer is PES having at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, at least 99 mol.% of recurring units having the formula (N-B). According to another embodiment, all the recurring units in the PAES block polymer are recurring units (R) having the formula (N-B)_PES) For example wherein for each R₁And i is zero.

According to an embodiment, the copolymer (P1) is according to formula (L-B):

wherein R is₁、i、q₁、q₂、n_pAnd n_rAs described above.

PES is obtained from Sorvv Special polymers, Inc. of America asPES is available.

According to embodiments of the invention, the PAES block polymer has a number average molecular weight (Mn) of less than about 25,000g/mol, less than about 18,000g/mol, or less than about 17,000g/mol as measured by Gel Permeation Chromatography (GPC) using methylene chloride as the mobile phase with polystyrene standards.

According to embodiments of the invention, the PAES block polymer has a number average molecular weight (Mn) of not less than about 1,000g/mol or not less than about 2,000g/mol as measured by Gel Permeation Chromatography (GPC) using methylene chloride as the mobile phase with polystyrene standards.

According to an embodiment of the invention, the PDMS block has a temperature of from 1x10 at 25 ℃²To 2.5x10⁶Centistokes (1 to 2.5 m)²In seconds) viscosity μ.

According to embodiments of the invention, the PDMS block has a number average molecular weight (Mn) of less than 35,000g/mol, less than 30,000g/mol, or less than 25,000g/mol, calculated based on the AJ Barry equation: log μ (cSt) ═ 1.00+0.0123(Mn)^0.5。

According to embodiments of the present invention, the PDMS block polymer has a number average molecular weight (Mn) of at least 1,000g/mol, at least 2,000g/mol or at least 3,000g/mol as calculated based on the above equation.

In the formula (L), n_pAnd n_rIn mol% for each repeating unit p and r, respectively. The repeating units p and r are arranged in a block manner, in an alternating manner, or randomly. The copolymer (P1) comprises at least the repeating units P and r, but may also comprise further repeating units. The copolymer (P1) comprises at least 5 mol.% of the repeating unit P and at least 5 mol.% of the repeating unit P. In other words, 5 ≦ n_p<100 and 5. ltoreq. n_r<100。

According to an embodiment of the invention, the copolymer (P1) comprises at least 10 mol.% of recurring units P, such as at least 20 mol.%, at least 30 mol.%, at least 40 mol.%, at least 50 mol.%, at least 60 mol.%, or at least 70 mol.%, based on the total moles in the copolymer (P1).

According to another embodiment of the present invention, the copolymer (P1) comprises at least 10 mol.%, such as at least 15 mol.%, at least 20 mol.%, at least 25 mol.%, at least 30 mol.%, at least 35 mol.%, or at least 40 mol.% of recurring units r, based on the total moles in the copolymer (P1).

According to another embodiment of the present invention, the copolymer (P1) comprises from 5 to 85 wt.%, for example from 10 to 60 wt.% or from 20 to 40 wt.% of PDMS block, based on the total weight of the copolymer. The copolymer of the present invention (P1) may notably comprise from 30 to 50 wt.% of a block copolymer having an Mn ranging from 4,000 to 10,000g/mol, based on the total weight of the copolymer. Alternatively, the copolymer of the present invention (P1) may comprise from 5 to 40 wt.% of a block copolymer having an Mn ranging from 15,000 to 25,000g/mol, based on the total weight of the copolymer.

The PDMS content of the block copolymers of the present invention can be varied by varying the molecular weight of the PDMS block used for melt hydrosilylation.

According to an embodiment of the invention, n_p+n_r100. According to this example, the copolymer (P1) consists essentially of the repeating units P and r.

In the formula (L), q₁And q is₂Independently varying between 2 and 14. According to the embodiment, q₁And q is₂Independently between 2 and 12, for example between 2 and 11. Preferably, q is₁And q is₂Are equal. Preferably, q is₁And q is₂Equal to 2 or 11.

Process for preparing copolymer (P1)

The present invention notably provides a solvent-free process for preparing the copolymer (P1) starting from a functionalized poly (aryl ether sulfone) (PAES), herein referred to as a functionalized PAES polymer (P0). The PAES polymer is functionalized with reactive functional groups at least one end of the PAES polymer, preferably at both ends of the PAES polymer. The functional group is introduced to at least one chain end of the PAES polymer, and the resulting intermediate may then be further used to synthesize a block copolymer by solution chemistry or chemical reaction carried out in the melt phase (e.g., reactive extrusion). The chain end functionality of the polymer (P0) is reactive and can therefore be used to efficiently prepare the copolymer (P1).

More sureAccording to the invention, the PAES polymer is functionalized with a functional group, which is of the formula CH, in order to obtain a PAES polymer (P0)₂＝CH-(CH₂)_s-alpha-olefins, wherein s varies between 0 and 12.

These functional groups are introduced as a post-polymerization modification of at least one end of a PAES polymer chain (e.g., at both ends of the PAES polymer chain), e.g., as a PPSU, PES, or PSU as defined above.

According to the present invention, a functionalized PAES polymer (P0) comprises:

-a repeating unit p having formula (N):

and

-at least one terminal group having formula (M):

wherein

Each R₁Independently selected from the group consisting of: 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 (inclusive);

-T is selected from the group consisting of: bond, -CH₂-；-O-；-SO₂-；-S-；-C(O)-；-C(CH₃)₂-；-C(CF₃)₂-；-C(＝CCl₂)-；-C(CH₃)(CH₂CH₂COOH)-；-N＝N-；-R_aC＝CR_b-, wherein R_aAnd R_bEach independently of the others is hydrogen or C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl; - (CH)₂)_m-and- (CF)₂)_m-, where m is an integer from 1 to 6; straight or branched chain having the highest degree of branchingAn aliphatic divalent group of up to 6 carbon atoms; and combinations thereof; and is

S varies between 0 and 12 (limits included).

Process for preparing a Polymer (P0)

The process for preparing the poly (aryl ether sulfone) (PAES) polymer (P0) as described above comprises the steps of: reacting a poly (aryl ether sulfone) (PAES) polymer comprising:

-a repeating unit p having formula (N):

and

-at least one terminal group having formula (P):

wherein:

each R₁Independently selected from the group consisting of: 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;

w is O-R or S-R; and is

-R is H, K, Na, Li, Cs or NHQ, wherein Q is a group containing 1 to 10 carbon atoms;

with compounds of the formula (I)

X-(CH₂)_s-CH₂＝CH₂-X (I)

Wherein

-X is Cl, Br or I;

s varies between 0 and 12 (limits included); and is

Wherein the compound (I)/Polymer (PAES) molar ratio is higher than 1, preferably higher than 5, more preferably higher than 10;

optionally in the presence of a base and a polar aprotic solvent, at a temperature ranging from room temperature to 250 ℃, preferably between 70 ℃ and 120 ℃.

Preferably, W in formula (P) is O-R. In other words, the poly (aryl ether sulfone) (PAES) polymer preferably comprises:

-at least one end group of formula (P '), for example two end groups of formula (P'):

wherein R is¹I, T and R are as described above.

According to an embodiment, the aprotic polar solvent is at least one selected from: n-methylpyrrolidone (NMP), N Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), 1, 3-dimethyl-2-imidazolidinone, Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and sulfolane.

According to another embodiment, the base is selected from the group consisting of: sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium carbonate (K)₂CO₃) Potassium tert-butoxide, sodium carbonate (NaCO)₃) Cesium carbonate (Cs)₂CO₃) And sodium tert-butoxide.

The process for preparing the polymer (P0) is described notably in patent application WO 2017/174546 (Soervi Special Polymer, Inc., USA).

Process for preparing copolymer (P1)

A method of preparing a copolymer (P1) comprising reacting a functionalized PAES polymer (P0) with a compound having the formula (I):

wherein m varies between 1 and 200, preferably between 10 and 100, even more preferably between 15 and 50;

wherein the compound (I)/polymer (P0) molar ratio varies between 0.5:1 and 1:0.5, for example between 0.7:1 and 1:0.7 or between 0.8:1 and 1: 0.8;

optionally in the presence of a metal-based catalyst;

a step of reaction at a temperature ranging from room temperature to 400 ℃.

The process is solvent-free. In other words, the process of the invention is carried out without a solvent, for example selected from the group consisting of: anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, or alternatively, in a limited amount of solvent. According to the invention, certain chemical components, such as plasticizers, can be added to the reactor in order to reduce the melt viscosity in the process. Examples of plasticizers are diphenyl sulfone (DPS) or phthalates. The process of the present invention may be carried out in the presence of less than 20 wt.% of a plasticizer, for example less than 15 wt.% or for example less than 10 wt.%.

The process is preferably carried out in an apparatus made of a material inert to the polymer. In this case, it is feasible to select the apparatus so as to provide sufficient contact of the polymer and in which the volatile reaction products are removed. Suitable equipment includes stirred reactors, extruders and kneaders, for example mixing kneaders from List AG or BUSS. The use of mixing kneaders can be used notably for the preparation of the solvent-free copolymer (P1), for reasons which may be longer than the residence time in the extruder. The apparatus may for example operate under the following conditions:

from 5 to 500s^-1Preferably from 10 to 250s^-1In particular from 20 to 100s^-1A shear rate (i.e., the velocity gradient of the kneaded material in the gap between the rotating kneading elements and the wall) within the range, and

a filling level (i.e. the proportion of the volume capacity filled by the starting monomers in the kneader which can be filled with monomers and allows mixing) in the range from 0.2 to 0.8, preferably from 0.22 to 0.7, in particular from 0.3 to 0.7, in particular from 0.35 to 0.64.

According to the examples, the process is carried out in a stirred reactor, extruder or kneader.

The process of the invention is preferably carried out in the presence of a metal-based catalyst, preferably a platinum-based catalyst, such as platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane (Karstedst catalyst) or chloroplatinic acid. Other organometallic catalysts, such as rhodium-based catalysts or ruthenium-based catalysts (grubbs second generation catalysts), for example benzylidene [1, 3-bis (2,4, 6-trimethylphenyl) -2-4 imidazolinidinylidene ] -dichloro- (tricyclohexylphosphine) ruthenium, may also be used.

The process of the present invention may also be carried out in the presence of a free radical generator such as benzoyl peroxide.

The reaction temperature of the system is between 150 ℃ and 450 ℃, but can be maintained between 200 ℃ and 400 ℃, preferably between 250 ℃ and 350 ℃ or between 260 ℃ and 320 ℃.

The residence time of the reaction in the mixing apparatus is typically from a few minutes to an hour. For example, the residence time varies between 1 minute and 30 minutes, for example between 2 minutes and 15 minutes.

Composition (C)

The invention also relates to a composition (C) comprising a copolymer (P1) as described above. The composition may also further comprise at least one component selected from the group consisting of: reinforcing agents, photoinitiators, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium stearate or magnesium stearate or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

The composition (C) may also comprise one or more other polymers. Mention may notably be made of Polyaryletherketones (PAEK) or other polyamides (for example polyphthalamides).

The composition (C) may be, for example, in the form of pellets, powder, solution or filaments.

Reinforcing agent

The composition (C) may comprise, for example, from 1 to 30 wt.% of the reinforcing agent, based on the total weight of the composition (C).

These reinforcing agents (also referred to as reinforcing fibers or fillers) may be selected from fibrous and particulate reinforcing agents. Fibrous reinforcing fillers are considered herein to be materials having a length, a width, and a thickness, wherein the average length is significantly greater than both the width and the thickness. Generally, such materials have an aspect ratio (defined as the average ratio between length and the largest of width and thickness) of at least 5, at least 10, at least 20, or at least 50.

The reinforcing filler may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers and wollastonite.

Among the fibrous fillers, glass fibers are preferable; they include chopped strand A-, E-, C-, D-, S-and R-glass fibers as described in the Additives for Plastics Handbook, 2 nd edition, pp.43-48, John Murphy. Preferably, the filler is selected from fibrous fillers. It is more preferably a reinforcing fiber capable of withstanding high temperature applications.

The reinforcing agents may be present in the polymer composition (C) in an amount ranging between 1 wt.% and 30 wt.%, for example between 2 wt.% and 25 wt.%, based on the total weight of the composition (C).

Preparation of composition (C)

The present invention further relates to a process for preparing composition (C) as detailed above, said process comprising melt blending these components, such as copolymer (P1) and reinforcing agent, optionally any other component or additive.

In the context of the present invention, any melt blending method may be used to mix the polymeric and non-polymeric ingredients. For example, the polymeric ingredients and the non-polymeric ingredients may be fed into a melt mixer (such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a banbury mixer), and the addition step may be a one-time addition or a stepwise addition of the ingredients in portions. When the polymeric ingredients and non-polymeric ingredients are added stepwise in batches, a portion of these polymeric ingredients and/or non-polymeric ingredients are added first and then melt-mixed with the remaining polymeric ingredients and non-polymeric ingredients that are added subsequently until a well-mixed composition is obtained. If the reinforcing agent exhibits a long physical shape (e.g., long glass fibers), then tensile extrusion molding may be used to prepare the reinforcing composition.

Applications of

The copolymer (P1) according to the invention or the polymer composition (C) according to the invention can be used in a variety of applications.

Three-dimensional printing-additive manufacturing

The invention also relates to the use of the copolymer (P1) according to the invention or the polymer composition (C) according to the invention for the manufacture of three-dimensional (3D) objects/articles.

All of the above examples relating to copolymer (P1) and the polymer composition (C) apply equally to the manufacture of three-dimensional (3D) objects/articles.

The invention also relates to a method of manufacturing a three-dimensional (3D) article with an additive manufacturing system, the method comprising:

-providing a part material consisting of the above-mentioned copolymer (P1) or polymer composition (C),

-printing a layer of the three-dimensional (3D) article from the part material.

According to an embodiment, the part material is heated to a temperature of at least 200 ℃, at least 250 ℃ or at least 280 ℃ before printing.

According to an embodiment, the printing step comprises irradiating the part material, e.g. irradiating a layer of the part material deposited on the printing surface with UV light. The layer preferably has a size in the range of 10 μm to 300 μm, for example 50 μm to 150 μm.

The UV light may for example be a laser. The irradiation is preferably of sufficient intensity to cause substantial curing of the polymer composition (C), e.g. of a layer of such composition (C). Furthermore, the irradiation is preferably of sufficient intensity to cause adhesion of the layer of the polymer composition (C).

The invention also relates to a 3D object or 3D article obtainable at least in part by the manufacturing process of the invention, using the copolymer (P1) and the polymer composition (C) described herein.

The 3D object or article obtainable by such a manufacturing method may be used in a variety of end applications. Implantable devices, dental prostheses, stents and parts of complex shape in the aerospace industry and parts inside the hood in the automotive industry may be mentioned in particular.

Hot Melt Adhesive (HMA)

The invention also relates to the use of the copolymer (P1) according to the invention or of the polymer composition (C) according to the invention as hot-melt adhesive (HMA), for example for moulding/overmolding applications, for example for the encapsulation of fragile components, such as electronic circuit boards or strands.

The copolymers (P1) according to the invention or the polymer compositions (C) according to the invention are generally useful in the smart devices and in the automotive and semiconductor industries.

If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that the terminology may become unclear, the description shall take precedence.

The invention will now be illustrated in more detail with reference to the following examples, which are intended to be illustrative only and do not limit the scope of the invention.

Examples of the invention

Raw material

The copolymer (P1) was prepared by melt hydrosilylation and then characterized by NMR, DSC, TEM and melt viscosity.

¹ H NMR

CD for 400MHz Bruker spectrometer₂Cl₂As a solvent measurement¹H NMR spectrum. All spectra were referenced to residual protons in the solvent.

DSC

Glass transition temperature (Tg) and melting point (Tm) — if present, were determined using DSC. DSC experiments were performed using TA instruments Q100. The DSC curve was recorded by heating the sample between 25 ℃ and 320 ℃ at a heating and cooling rate of 20 ℃/min, cooling, reheating and then re-cooling. All DSC measurements were taken under a nitrogen purge. The reported Tg and Tm values are provided using the second heating curve, unless otherwise indicated.

TEM

Tunneling electron microscopy was used to determine the microphase structure of these block copolymers. The detailed information of the TEM instrument is as follows: philips CM12 transmission electron microscope, 20-120kV acceleration voltage range (images taken at 100 kV), LaB6 filament (electron source), images taken with Optronics QuantFire CCD.

Melt viscosity

It is measured according to ASTM-D3835.

Synthesis of PPSU-PDMS copolymer (P1-A)

The functionalized PPSU polymer (P0-a) was prepared according to the method described in published patent application WO 2017/174546 (sovley specialty polymers llc, usa):

copolymer (P1-a) was prepared according to the following method:

10g of olefin-terminated PPSU (P0-A) was mixed with 6.7g of hydride-terminated PDMS (viscosity about 100cst), then 0.02 mol% of a platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex solution (platinum about 2% in xylene) and 2.95mL of t-butyl hydroperoxide solution, 70 wt.% in H2O, were added. The mixture was charged into a melt blender (DSM Xplore 5&15 micro blender, model 2005, held at 300 ℃) for 10 minutes. The molten product is then discharged, yielding a homogeneous, elastic solid material.

TABLE 1

Characterization of PPSU-PDMS copolymer (P1-A)

The material obtained by the aforementioned method was subjected to DSC,¹H NMR, TEM and melt viscosity characterization.¹HNMR was used to determine end group conversion and to confirm the expected bond linkage. DSC is used to determine the glass transition temperature (Tg) and melting point (Tm), if present. TEM is used to determine phase morphology.

As a result:

the copolymer was first analyzed using proton NMR. The material was first dissolved in NMP and then reprecipitated in methanol, dried and then analyzed by proton NMR. The absence of an olefin signal in the final product indicates the formation of a covalent bond between the two blocks. In addition, there are two different signals in the spectrum of the copolymer, which proved to be diagnostically significant in confirming the desired structure formed. 0.8ppm of-Si- (CH)₃)₃The presence of a group indicates the presence of a PDMS block. Second, the presence of aromatic signals at 7.0, 7.6, and 7.8ppm indicated the presence of an aromatic polysulfone block.

A Transmission Electron Microscope (TEM) micrograph of the copolymer of example 1 (fig. 1A) shows the microphase separation between the two incompatible blocks of polysulfone and PDMS. The very small domain size of the PDMS phase (0.5 micron) indicates that a covalently bonded system is formed between the polysulfone and the PDMS.

Copolymer P1-a shows two different thermal events, one at about 210 ℃ corresponding to the glass transition temperature of the polysulfone block and the other melting peak at-44 ℃ corresponding to the melting point of the PDMS block.

TGA analysis of the polymer gave a single step decomposition profile in which thermal degradation began to occur at 494 ℃.

Melt viscosities of starting material P0-A and copolymer P1-A were measured at 350 ℃ using ASTM-D3835.

TABLE 2

	P0-A	P1-A
			Rate (1/s)	Viscosity (Pa-s)	Viscosity (Pa-s)
100	42.5	369.9
			1,000	23.6	174

The significant viscosity increase after reactive blending indicates the presence of the high molecular weight copolymer (P1-A) compared to the starting material (P0-A).