• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a novel type of sacrificial polymer or support material for 3D printing, comprising a block copolymer consisting of: at least one elastomeric block, partially or totally hydrophilic, having a Tg of less than 30 ° C. and comprising at least one hydrophilic monomer, and at least one water-soluble thermoplastic block having a Tg greater than 30 ° C and comprising at least one monomer having a carboxyl group, said copolymer being extrudable and granular, said copolymer being partially or totally soluble in water or in water. aqueous medium, and the mass proportion of the thermoplastic block being greater than 50% of the weight of said copolymer.
    公开号:FR3030529A1
    申请号:FR1463192
    申请日:2014-12-23
    公开日:2016-06-24
    发明作者:Rabi Inoubli；Sylvain Bourrigaud
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates generally to the field of three-dimensional printing (or 3D printing) of an object. This technology makes it possible to additively manufacture (in English: "additive manufacturing" or AM) a real object from a virtual object. It is based on the cutting of the 3D virtual object in 2D strips of very thin thickness. These thin strips are deposited one by one by fixing them on the previous ones, which reconstitutes the real object. Among the materials constituting the object, there are plastic materials (including acrylonitrile butadiene styrene (or ABS) and polylactic acid (or PLA)), wax, metal, plaster of Paris or ceramics. Examples of additive techniques are the deposition of fused deposition (FDM) and laser sintering (laser sintering).
    [0002] Molten filament deposition modeling is a mechanical technique that consists in melting a filament of synthetic material (generally ABS or PLA type plastic) through an extrusion nozzle heated to a temperature of between 160 and 270 ° C. A molten filament, of a diameter of the order of a tenth of a millimeter, comes out. This wire is deposited online and is sticking by re-fusion on what has been filed beforehand. This technique makes it possible to create parts made of good material, having mechanical, thermal and stability characteristics identical to injected thermoplastic parts. This technique also has an important advantage concerning the support structure necessary for the production of the parts, since this construction support is in most cases constituted in a different material than that constituting the created object, material which is eliminated from said object. when the construction process of the latter is finished. According to an alternative embodiment, the material used as a support for the production of 3D objects is a polymer, also called sacrificial polymer. The present invention thus relates, more specifically, to a new type of sacrificial polymer or support material for 3D printing, comprising a new block copolymer.
    [0003] BACKGROUND ART Certain 3D polymer printing techniques, such as digital manufacturing systems ("digital manufaturing systems"), require the use of a sacrificial polymer to "support" the polymer of the object to be produced. to print. This technique and the characteristics of this sacrificial polymer are described in WO2010 / 045147. According to this document, the main characteristics of this sacrificial polymer must be: solubility in an aqueous medium (most often alkaline); a creep relaxation transition temperature (directly linked to the glass transition temperature Tg, according to the measurement protocol described in US Pat. No. 5,866,058) of the order of that of the polymer to be printed (or of one of the fractions of the polymer to be printed). For example, for ABS printing, the Tg of the sacrificial polymer should be at least 120 ° C; an ability to be compounded with additives allowing the improvement of the mechanical properties. The support material described in WO2010 / 045147 contains a copolymer and a polymeric impact modifier. According to one embodiment, said copolymer comprises monomeric units carrying a carboxyl group and monomeric units comprising a phenyl group. According to another embodiment, the support material is formed of a first copolymer and a second copolymer. The first copolymer comprises monomeric units carrying a carboxyl group, monomeric units comprising a phenyl group and monomeric units comprising carboxylate ester groups. The second copolymer comprises a plurality of epoxy-terminated carboxylate ester groups. Examples 1-15 describe the use as a support material of a mixture of copolymer and impact modifier, said copolymer being based on butyl acrylate, styrene and methacrylic acid. The partial anhydrification of the acid functions allows it to reach Tg of the order of 120 ° C (measured by DSC) and thus to be able to print polymers such as ABS. The system used in this patent is derived from the compounding of the copolymer with a shock additive Elvaloy® type (Du Pont) and / or Lotader® (Arkema). During the preliminary compounding step, the impact modifier reacts, via the epoxy functions, with the acid functions of said copolymer.
    [0004] The applicant has now found that it is possible to prepare a block copolymer acting alone as a support material, said block copolymer having the properties required to fulfill this function (namely a solubility in aqueous medium and a glass transition temperature Tg of the high majority phase, preferably greater than 120 ° C) without it being necessary to mix it in advance with an additive. SUMMARY OF THE INVENTION According to a first object, the invention relates to a support material for an additive system for the digital production of objects, said support material consisting of a block copolymer consisting of: at least one elastomeric block, partially or totally hydrophilic composition, having a Tg lower than 30 ° C and comprising at least one hydrophilic monomer, and - at least one water-soluble thermoplastic block having a Tg greater than 30 ° C and comprising at least one monomer having a carboxyl group.
    [0005] Typically, the mass proportion of the thermoplastic block (s) is greater than 50%, preferably greater than 60% by weight of said copolymer. This confers on the block copolymer a thermoplastic character. The block copolymer according to the invention is extrudable and granulable. According to one embodiment, the elastic shear modulus G 'is greater than 0.1 MPa at the cutting temperature, which gives it a granular character. Indeed, it is known to those skilled in the art that below a certain level of modulus, it is difficult to granulate a polymer including underwater cutting. This modulus limit could be related to the values presented by the Dahlquist criterion since below this limit, even using anti-caking agents, the elastomeric nature of the polymer will not be able to avoid caking problems. In addition, said copolymer is partially or completely soluble in water or in aqueous medium. According to one embodiment, said copolymer is soluble in an alkaline medium having a pH greater than 8 and preferably greater than 10. Advantageously, the mass ratio of the carboxyl functions in the diblock copolymer ranges from 5 to 30%, preferably from 10 to 20% relative to the weight of said copolymer.
    [0006] The invention also relates to a process for preparing said block copolymer by controlled radical polymerization. Another object of the invention is a method for manufacturing objects by an additive system for digital manufacturing (or 3D printing), which uses as support material the block copolymer according to the invention. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 represents a diagram illustrating the solubility of the diblock copolymers according to the invention in an aqueous medium, measured in terms of weight loss of the copolymer as a function of time. FIG. 2 represents a diagram illustrating the variation of the elastic modulus G 'of a copolymer according to the invention as a function of the temperature. DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. According to a first aspect, the invention relates to a support material for an additive digital object manufacturing system, said support material consisting of a copolymer block copolymer formed of at least a first elastomeric block and at least a second block thermoplastic. The first block is an elastomeric block having a Tg of less than 30 ° C and comprising at least one hydrophilic monomer. By "monomer" is meant any monomer polymerizable or copolymerisable radical. The term "monomer" covers mixtures of several monomers.
    [0007] Tg is the glass transition temperature of a polymer measured by DSC according to ASTM E1356. The Tg of a monomer is also referred to as the Tg of the homopolymer having a number average molecular weight Mn of at least 10,000 g / mol, obtained by radical polymerization of said monomer. Said hydrophilic monomer is advantageously chosen from: acrylic acid, methacrylic acid, polyethylene glycol (meth) acrylate, dimethyl acrylamide copolymerized with an acrylic of Tg <0 ° C such as butyl acrylate, esters of acrylic or methacrylic acids, such as methyl, ethyl, butyl, 2-ethylhexyl, octyl acrylate, acrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, isoprene, acrylates or methacrylates, butadiene. The second block is a thermoplastic block having a Tg greater than 30 ° C, preferably between 50 ° C and 250 ° C. It comprises at least one monomer having a carboxyl group. This monomer is preferably chosen from: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, diacrylic acid, dimethylfumaric acid, citraconic acid, vinylbenzoic acid, acrylamidoglycolic acid of formula CH2 = CHCONHCH (OH) COOH, diallyl maleate of formula C3H5-OO2-CH = CH-OO2-C3H5, tert-butyl (meth) acrylate, carboxylic anhydrides bearing a vinyl bond, as well as their salts; and their mixtures. It is understood that for the esters mentioned above, these will be, after polymerization, hydrolyzed to give the units bearing -CO2H functions. hydroxyalkyl (meth) acrylates and (meth) acrylamides in which the alkyl group comprises 2 to 4 carbon atoms, in particular 2-hydroxyethyl methacrylate (55 ° C.), 2-hydroxypropyl methacrylate and methacrylate; 4-hydroxybutyl, dimethylacrylamide, N- (2-hydroxypropyl) (meth) acrylamide; acrylates and methacrylates of polyethylene glycol or of glycol substituted or unsubstituted on their terminal function by alkyl, phosphate, phosphonate or sulphonate groups. With the hydrophilic monomer which comprises carboxyl functions which are capable of establishing hydrogen bonds with the water molecules, the thermoplastic block is water-soluble or water-dispersible. A polymer is said to be "water-soluble" if it is soluble in water (that is, if it forms a clear solution), at least 5% by weight, at 25 ° C. Said thermoplastic block is especially soluble in running water or basic water.
    [0008] A polymer is said to be "hydrodispersible" if it forms at a concentration of 5%, at 25 ° C., a stable suspension of fine, generally spherical particles. The average particle size constituting said dispersion is less than 1 .mu.m and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering. According to one embodiment, the block copolymer consists of an elastomeric block and a thermoplastic block. The hydrophilic thermoplastic block is rigid at ambient temperature and constitutes the majority phase of the block copolymer according to the invention. The diblock copolymer according to the invention has an elastic shear modulus G 'greater than 108 Pa at room temperature, which shows that, according to the Dahlquist tack criterion, it does not have a tacky character. According to a second aspect, the invention relates to a process for the preparation of the diblock copolymer described above. According to one embodiment, this diblock copolymer is obtained by controlled or living radical polymerization. Controlled radical polymerization makes it possible to reduce the reactions of the growing radical species, in particular the termination stage, reactions which in the conventional polymerization interrupt the growth of the polymer chain irreversibly and without control of the termination reactions. To solve this problem and to reduce the probability of termination reactions, it has been proposed to use "dormant" radical species, in the form of a low dissociation energy bond, capable of blocking and restarting the polymerization at will. As a result, periods of growth of active radical species and periods of growth arrest are obtained as required. This alternation leads to an increase in the average molecular weight according to the progress of the reaction while controlling its progress. This control can result in a narrower molecular weight distribution (lower polymolecularity index) than in a conventional radical and, above all, in synthesizing block copolymers by restarting the polymerization with a new monomer from a species. dormant polymer. In principle, any living radical polymerization process compatible with the choice of monomers can be used to prepare a block copolymer. A preferred method is controlled radical polymerization in the presence of a nitroxide mediator, since it makes it possible to polymerize a wide variety of monomers, in particular acrylic monomers and acrylic monomers functionalized by means of carboxyl groups. It is possible for this purpose to use, for example, the processes which use, as stable free radicals, nitroxides such as SG1 or its alkoxyamine derivatives as described in patent EP 0 970 973 and applications WO 00/49027 and WO 2005 / 082945. A preferred controlled radical polymerization initiator is the alkoxyamine of the following formula (I): ## STR1 ## In which: R1 and R3, which may be identical or different, represent a linear or branched alkyl group having a number of carbon atoms ranging from 1 to 3; R 2 represents a hydrogen atom, a linear or branched alkyl group having a number of carbon atoms ranging from 1 to 8, a phenyl group, an alkali metal such as Li, Na, K, an ammonium ion; such as NH4 +, NHBu3 +; preferably R1 and R3 being CH3 and R2 being H, the abbreviation "Bu" meaning the butyl group. An alkoxyamine usable for designing the diblock copolymers of the invention, referred to as BlocBuilder, has the following formula (II), wherein the abbreviation "Et" signifies an ethyl group: 20 0 OH EtO- / 1 The polymerization generally takes place in several stages according to the following general scheme: in a first step, the polymerization of the first monomer or mixture of hydrophilic monomers is carried out to form a macroinitiator or precursor; in a second step, the polymerization of the second block consisting of a monomer or a mixture of monomers comprising at least one monomer having a carboxyl group at the end of the macroinitiator is carried out. The use of this process allows the synthesis of the diblock copolymers according to the invention in solution, in suspension, in bulk, in organic solvent or in emulsion, which then makes it possible to obtain the products in the form of an aqueous latex comprising a stable emulsion in water of these copolymers. The organic solvent, when it is necessary for carrying out a polymerization mode, may be chosen from toluene, xylene, chloroform, ethyl acetate, methyl ethyl ketone, dioxane, tetrahydrofuran or dimethylformamide.
    [0009] The process of the invention is generally carried out at a pressure ranging from 0.5 to 20 bar and at a temperature ranging from 50 to 180 ° C., and preferably from 90 to 110 ° C. The resulting diblock copolymers have molecular weights and controlled molecular weight distributions. Advantageously, the weight average molecular weight Mit; the diblock copolymer is between 10,000 and 1,000,000 g / mol, preferably between 50,000 and 300,000 g / mol. The number-average molecular weight Mn is preferably between 10,000 and 50,000. The distribution of the molecular weight or polydispersity index Mw / Mn is in general less than 4, advantageously less than 2. The Mit masses; and Mn of the present invention are expressed as polyethylene glycol equivalent and measured by Steric Exclusion Chromatography, SEC, also known as GPC for the abbreviation in English Gel Permeation Chromatography. According to another aspect, the invention relates to a method of manufacturing objects by a digital manufacturing additive system (or 3D printing), which uses as support material the block copolymer according to the invention. Advantageously, this support material is soluble in an aqueous medium, which makes it easy to remove once the printed object. In addition, this support material is compatible for use with materials constituting the object to be manufactured, having a wide range of glass transition temperatures. According to one embodiment, the numerical manufacturing additive system is the deposition of molten filaments. According to another embodiment, the numerical manufacturing additive system is laser sintering.
    [0010] According to one embodiment, the elastomeric block contains butyl acrylate (BA) and methoxypolyethylene glycol methacrylate (MAMPEG) and the thermoplastic block contains butyl acrylate, methacrylic acid (AMA) and styrene (S) forming a diblock copolymer P (BA - MAMPEG) - b - P (BA - S - AMA).
    [0011] EXAMPLES The following examples illustrate the invention without limiting it. EXAMPLE 1 Synthesis of a Copolymer P (BA-MAMPEG) -B-P (BA-S-AMA) The synthesis of this diblock copolymer takes place in two steps: the block P (BA-MAMPEG) in bulk then stripping unreacted monomers 2 'P (BA - S - AMA) block in solvent 1.1. Synthesis of the P block (BA-MAMPEG) The synthesis of this first block is carried out by a mass polymerization process using a reactor type Büro Engineer Reagents: butyl acrylate (BA) 624 g methacrylate methoxypolyethylene glycol (MAMPEG 126 g BlocBuilder® 8.26 g A number-average molecular weight of 27,000 g / mol to 75% conversion is aimed at.
    [0012] The reagents are weighed then mixed with magnetic stirring, then introduced into the reactor by vacuum. The reactor is stirred (250 rpm). The medium is degassed by alternating nitrogen pressure and vacuum. The polymerization is carried out in three temperature stages: 90 ° C for 60 min then 100 ° C for 90 min then 110 ° C - The polymerization time is 345 min. The conversion is followed by dry extracts, samples are taken every hour. Since MAMPEG is not volatile, the conversion of butyl acrylate can be monitored by measuring the level of solid (125 ° C. thermobalance and 125 ° C. vacuum oven).
    [0013] When the target conversion is reached, the temperature is lowered to 80 ° C. Once the set point is reached we will gradually put the equipment under vacuum, the unreacted monomers will be distilled (recovery in liquid nitrogen traps). It remains about 90 min at 80 ° C and under maximum vacuum, when the distillation is complete, the set point is lowered to 40 ° C. Once this set point is reached, 400 g of ethanol (by depression) are introduced in order to dilute the medium. Allowed to stir for a few hours and at 40 ° C to homogenize the solution. This solution is then recovered. 1.2. Synthesis of Block P (BA - S - AMA) The solvent process is carried out using an ethanol / toluene mixture having a mass ratio of 60/40. 45% of solvent is used relative to the total charge. A mixture BA / S / AMA mass ratio 30/30/40 is introduced. A copolymer P (BA - MAMPEG) - b - P (BA - S - AMA) of mass composition 30/70 with a conversion of the 2nd block is aimed at. 65%.
    [0014] The feed is prepared as indicated below: Block diluted in ethanol: 200 g BA / S / AMA: 104/104 / 138.7 (g) Ethanol / toluene: 138.4 / 161.2 (g) The molar masses (PS equivalents) of this copolymer are as follows: Mw = 93600 g / min Mn = 55100 g / mol Mw = 97300 g / min Ip = 1.77 Example 2 - Measurement of the solubility in aqueous medium of the diblock copolymer P (BA - MAMPEG) - b - P (BA - S -AMA) For the solubility test, a pellet with a diameter of 20 mm and a thickness of lmm is made with a press and under a temperature of 120 ° vs. The pellet is placed in a slightly agitated aqueous medium and measurements of loss of mass are made as a function of time. The results obtained are shown in the attached FIG.
    [0015] Dissolution of the sample is observed with a mass loss rate of the order of 0.25% per minute. Example 3 - Measurement of the elastic shear modulus (G ') by dynamic mechanical analysis (DMA: Dynamic Mecanical Analysis) of the diblock copolymer P (BA - MAMPEG) - b - P (BA - S - AMA) The elastic shear modulus is measured using an ARES rheometer with imposed deformation (TA Instrument). A rectangular bar of dimensions 40 × 10 × 2 mm is prepared by molding. The analysis (temperature sweep at a frequency of 1 Hz) is done on a rectangular torsion type geometry. The variations of modulus G 'as a function of temperature (from -80 ° to 150 ° C.) are shown in FIG. 2. It can be observed that at ambient temperature an elastic modulus G' of approximately 4.108 Pa is measured, which shows a thermoplastic behavior of the copolymer according to the invention.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. Support material for an additive digital object manufacturing system, said support material consisting of a block copolymer consisting of: - at least one elastomeric block, partially or totally hydrophilic, having a Tg of less than 30 ° C and comprising at least one hydrophilic monomer, and at least one water-soluble thermoplastic block having a Tg greater than 30 ° C and comprising at least one monomer having a carboxyl group, said copolymer being extrudable and granular, said copolymer being partially or totally soluble in water or in water. aqueous medium, and the mass proportion of the thermoplastic block being greater than 50% of the weight of said copolymer.
    [0002]
    2. Support material according to claim 1, wherein said hydrophilic monomer is selected from: acrylic acid, methacrylic acid, polyethylene glycol (meth) acrylate, dimethyl acrylamide copolymerized with an acrylic of Tg <0 C, such as butyl acrylate, esters of acrylic or methacrylic acids, such as methyl, ethyl, butyl, 2-ethylhexyl, octyl acrylate, acrylonitrile, vinyl acetate, styrene, acrylates or methacrylates, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, isoprene, butadiene.
    [0003]
    3. Support material according to one of claims 1 and 2, wherein said monomer having a carboxyl group is selected from: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid , maleic acid, diacrylic acid, dimethylfumaric acid, citraconic acid, vinylbenzoic acid, acrylamidoglycolic acid of formula CH2 = CH-CONHCH (OH) COOH, diallyl maleate of formula C3H5- 0O2-CH = CH-OO2-C3H5, tert-butyl (meth) acrylate, carboxylic anhydrides carrying a vinyl bond, and salts thereof; (meth) acrylates and hydroxyalkyl (meth) acrylamides wherein the alkyl group comprises 2 to 4 carbon atoms, in particular 2-hydroxyethyl methacrylate (55 ° C), 2-hydroxypropyl methacrylate, methacrylate of
    [0004]
    4-hydroxybutyl, dimethylacrylamide, N- (2-hydroxypropyl) (meth) acrylamide; acrylates and methacrylates of polyethylene glycol or of glycol optionally substituted on their terminal function by alkyl, phosphate, phosphonate or sulphonate groups; and their mixtures. 4. Support material according to one of claims 1 to 3 wherein said copolymer consists of an elastomeric block and a thermoplastic block.
    [0005]
    5. Support material according to one of claims 1 to 3 wherein the mass ratio of the carboxyl functions in the diblock copolymer ranges from 5 to 30%, preferably from 10 to 20% relative to the weight of said copolymer.
    [0006]
    6. Support material according to one of claims 1 to 4 wherein the mass proportion of the thermoplastic block being greater than 60% of the weight of said copolymer.
    [0007]
    7. Support material in which the Tg of said thermoplastic block of said block copolymer varies between 50 ° C and 250 ° C.
    [0008]
    8. Support material according to one of claims 1 to 7 wherein said copolymer has the structure: P (BA-MAMPEG) -b-P (BA-S-AMA).
    [0009]
    9. Process for preparing a block copolymer used as a support material according to one of claims 1 to 8 by controlled radical polymerization in the presence of a nitroxide mediator.
    [0010]
    The process according to claim 9 wherein the polymerization initiator is the alkoxyamine of formula II: OH
    [0011]
    11. A method of manufacturing objects by a digital manufacturing additive system which uses as a support material the material according to one of claims 1 to 8.
    [0012]
    12. The method of claim 11 wherein the numerical manufacturing additive system is the deposition of molten filaments.
    [0013]
    13. The method of claim 11 wherein the numerical manufacturing additive system is laser sintering.
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 6 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463192A|FR3030529B1|2014-12-23|2014-12-23|WATER-SOLUBLE BLOCK COPOLYMER AND USE THEREOF AS A MATERIAL SUPPORT FOR 3D PRINTING|FR1463192A| FR3030529B1|2014-12-23|2014-12-23|WATER-SOLUBLE BLOCK COPOLYMER AND USE THEREOF AS A MATERIAL SUPPORT FOR 3D PRINTING|
    EP15823637.2A| EP3237473B1|2014-12-23|2015-12-14|3d-printing process using a water soluble block copolymer as support material|
    JP2017533423A| JP6466583B2|2014-12-23|2015-12-14|Water-soluble block copolymer and its use as a support material for 3D printing|
    PCT/FR2015/053464| WO2016102802A1|2014-12-23|2015-12-14|Water-soluble block copolymer and use thereof as a support material for 3d printing|
    US15/538,271| US10487168B2|2014-12-23|2015-12-14|Water-soluble block copolymer and use thereof as a support material for 3D printing|
    IL253030A| IL253030A|2014-12-23|2017-06-20|Water-soluble block copolymer and use thereof as a support material for 3d printing|
    US16/653,140| US10577447B2|2014-12-23|2019-10-15|Water-soluble block copolymer and use thereof as a support material for 3D printing|
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