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    • 专利摘要:
    "Process for Producing Expandable Pelletized Material and Moldable Foam Molded Parts, Expandable Pelletized Material, Use of Expandable Pelletized Material, Polymer Blend, and Foam" The invention relates to a method for producing expandable pellets containing polylactic acid comprising: (a) melt and mix the components: (i) between 5 and 99,9% by weight, based on the total weight of polylactic acid components (i) to (iii), (ii) between 0 and 49,9% by weight; weight, relative to the total weight of components i) to iii), of at least one other polymer, iii) between 0.1 and 2% by weight, relative to the total weight of components i) to iii), of a diepoxide or (iv) from 0 to 10% by weight of one less additive, (b) mixing (v) from 3 to 7% by weight, based on the total weight of the components of (iv), of an organic blowing agent, polymer melt by means of a static or dynamic mixer at least 40 c, c) discharging the mixture through a hole extruder plate having a maximum diameter at the extruder plate outlet of 1.5 mm, and d) granulating the melt comprising blowing agent directly behind the extruder. underwater extruder plate at a pressure between 1 and 20 bar (100 to 2,000 kpa). The invention also relates to expandable granules comprising polylactic acid obtainable according to said method and to special expandable granules comprising polylactic acid, and from 3 to 7% by weight of an organic blowing agent, preferably, n-pentane, and particularly preferably isopentane. The invention also relates to a preferred method for producing expandable granules containing polylactic acid and a blowing agent with a low volumetric density.
    公开号:BR112012017449B1
    申请号:R112012017449-5
    申请日:2011-01-06
    公开日:2019-10-29
    发明作者:Füssl Andreas
    申请人:Basf Se；
    IPC主号:
    专利说明:

    PROCESSES TO PRODUCE EXPANSIBLE PELLETIZED MATERIAL AND MOLDABLE FOAM MOLDED PIECES, EXPANSIBLE PELLETIZED MATERIAL, USE OF EXPANDABLE PELLETIZED MATERIAL, POLYMER MIXTURE, AND FOAM [1] The invention relates to a process to produce expandable pelletized material that comprises expandable pelletized material comprising the following steps:
    a) melt and mix to incorporate the following components: i) from 50 to 99.9% by weight, based on the total weight of components of ia iii, polylactic acid, ii) from 0 to 49.9% by weight, based on the total weight of ia iii components, one or more additional polymers, iii) from 0.1 to 2% by weight, based on the total weight of ia iii components, a diepoxide or polyepoxide, and iv) from 0 to 10% by weight, based on the total weight of ia iii components, one or more additives,
    b) mix to incorporate v) from 3 to 7% by weight, based on components from i to iv), of an organic blowing agent in the polymer melt by means of a static or dynamic mixer at a temperature of at least 140 ° C,
    c) discharge through an extruder plate with holes, whose diameter at the exit of the extruder plate is a maximum of 1.5 mm, and
    d) pelletize the melting mass comprising blowing agent directly downstream of the extruder plate, and underwater, at a pressure in the range of 1 to 20 bar (100 to 2,000 kPa).
    [2] The invention further relates to expandable pelletized material which comprises polylactic acid and which is obtainable by means of said process, and also to specific expandable pelletized material which comprises polylactic acid and which presents a proportion of 3 to 7% by weight an organic blowing agent, preferably n-pentane, or a mixture of n-pentane and isopentane (this mixture is also
    Petition 870190090495, of 12/09/2019, p. 9/55
    2/36 called s-pentane) and, particularly preferably, isopentane. The invention further relates to a preferred process for producing expandable pelletized material which comprises blowing agent and which comprises polylactic acid, and which has low volumetric density.
    [3] Processes for producing expandable pelletized material comprising polylactic acid (moldable foams which comprise polylactic acid) have been described in general terms in WO 01/012706, but there is no mention of the specific polylactic acid mixture (see components of i) to iv ) in step a) or the advantageous mode of operation via underwater pressurized pelletizing (see steps c) to e) of the invention). There are wide ranges in which this process does not provide reproducible moldable foams and, in particular, does not prevent premature foaming of the expandable pelletized material.
    [4] WO 08/130226 describes a complicated multistage process to produce expandable pelletized material that comprises polylactic acid, with the polylactic acid beads being coated and then post-impregnated with carbon dioxide, or the beads are post-impregnated with dioxide carbon and then coated. Post-impregnation with carbon dioxide leads to pre-foamed beads, and this completely changes the technology for further processing of moldable foams.
    [5] It was an object of the present invention that provides a simple process that can give good results in the production of expandable pelletized material that comprises polylactic acid and that presents small pellet size and uniform distribution of pellet sizes.
    [6] Thus, the process described in the introduction was verified.
    [7] The process of the invention is described in more detail below.
    [8] The polymer comprising polylactic acid and which is produced in step a) is generally a mixture of:
    i) 50 to 98.9% by weight, based on the total weight of components i to iii, polylactic acid,
    Petition 870190090495, of 12/09/2019, p. 10/55
    3/36 ii) from 1 to 49.9% by weight, based on the total weight of components of ia iii, at least one polyester based on aliphatic and / or aromatic dicarboxylic acids, and on aliphatic dihydroxy compound, iii ) from 0.1 to 2% by weight, based on the total weight of components of ia iii, of a copolymer comprising epoxy groups and based on styrene, acrylate, and / or methacrylate, and iv) from 0 to 10 % by weight, based on the total weight of components of ia iii, one or more additives.
    [9] It is preferable that the polymer comprising polylactic acid is made up of a mixture comprising:
    i) from 50 to 98.9% by weight, particularly from 70 to 94.9% by weight based on the total weight of components of ia iii, polylactic acid, ii) from 1 to 44.9% by weight, particularly from 5 to 29.9% by weight based on the total weight of components of ia iii, at least one polyester based on aliphatic dicarboxylic acids and aliphatic dihydroxy compound or polyalkylene succinate-co-terephthalate derivative, iii) 0, 1 to 2% by weight, in particular 0.1 to 1% by weight based on the total weight of components of ia iii, of a copolymer comprising epoxy groups and based on styrene, acrylate, and / or methacrylate, and iv) from 0.1 to 2% by weight, based on the total weight of ia iii components, of a nucleating agent.
    [10] It is particularly preferable that the PM 'polymer comprising polylactic acid is made up of a mixture comprising:
    i) from 60 to 98.9% by weight, particularly from 65 to 79.9% by weight based on the total weight of components i to iii, of polylactic acid,
    Petition 870190090495, of 12/09/2019, p. 11/55
    Ii) from 1 to 39.9% by weight, particularly from 20 to 34.9% by weight based on the total weight of components i to iii, of at least one polyester based on:
    a) from 90 to 99.5 mol%, based on components from a to b, of succinic acid;
    b) from 0.5 to 10 mol%, based on components from a to b, of one or more C8-C20 dicarboxylic acids, preferably selected from terephthalic acid, azelaic acid, sebacic acid, and / or brassic acid ;
    c) from 98 to 102 mol%, based on components from a to b, of 1,3-propanediol or 1,4-butanediol;
    iii) from 0.1 to 2% by weight, in particular from 0.1 to 1% by weight based on the total weight of components of ia iii, of a copolymer comprising epoxy groups and based on styrene, acrylate, and / or methacrylate, and iv) from 0 to 1% by weight, and preferably from 0.1 to 1% by weight, based on the total weight of components of ia iii, of a nucleating agent.
    [11] As shown by inventive example 14, the last mentioned PM 'polymer comprising polylactic acid can be used to produce expandable pelletized material and, from this, foams with improved heat resistance, improved mechanical properties, and low density. Therefore, it is also preferred the PM 'polymer comprising polylactic acid and the foams produced therefrom.
    [12] Component i) preferably comprises polylactic acid with the following property profile:
    • melt volume ratio of 0.5 to 15 ml / 10 minutes, preferably 1 to 9 ml / 10 minutes, particularly preferably 2 to 8 ml / 10 minutes (MVR at 190 ° C using 2.16 kg according
    Petition 870190090495, of 12/09/2019, p. 12/55
    5/36 with ISO 1133) • melting point below 180 ° C • glaze transition temperature (Tg) above 40 ° C • water content less than 1000 ppm • residual monomer (lactide) content less than 0, 3% • molecular weight above 50,000 daltons.
    [13] Examples of preferred polylactic acids are the following from NatureWorks®: Ingeo® 2002 D, 4032 D, 4042 D and 4043 D, 8251 D, 3251 D, and in particular 8051 D, and also 8052 D. NatureWorks 8051 D and 8052 D are NatureWorks polylactic acids, being products with the following properties: Tg: 65.3 ° C, Tm: 153.9 ° C, MVR: 6.9 [ml / 10 minutes], M w : 186 000, Mu : 107 000. In addition, these products have a slightly higher acidity index.
    [14] Polylactic acids which have proved to be particularly advantageous for producing the expandable pelletized material of the invention have MVR of 5 to 8 ml / 10 minutes according to ISO 1133 [190 ° C / 2.16 kg].
    [15] Polylactic acids which are particularly advantageous have the MVR range indicated above and / or have a low temperature crystallization onset rate in the range of 80 ° C to 125 ° C, preferably 90 ° C to 115 ° C, and particularly preferably from 95 ° C to 105 ° C, measured by differential scanning calorimetry (DSC), at a heating rate of 20K / min (measuring range -60 ° C at 220 ° C; Mettler DSC 30 using a TC15 / TA controller, Mettler-Toledo AG).
    [16] It has been found that, under the conditions indicated above, most types of polylactic acid obtainable on the market have a low-crystallization onset temperature below 80 ° C. Comparison of NatureWorks® 8051 D, 8052D Polylactic Acids (PLAs)
    Petition 870190090495, of 12/09/2019, p. 13/55
    6/36 and 4042D (PLAs) will clearly show (see table) the different crystallization behavior of the pelletized material produced therefrom. The table shows DSC measurements on expandable pelletized material of two types of PLA, which were nucleated with 0.3% by weight of talc and loaded with 5.7% by weight of n-pentane respectively as a blowing agent.
    Table: DSC data for a heating rate of 20K / min (measuring range from -60 ° C to 220 ° C)
    Example Tg(glazed transition temp) Starting Tc Tc(low temperature crystallization) Tm(fusion point) PLA 4042 D 42.4 ° C 71.8 ° C 82.5 ° C 155.6 ° C PLA 8051 D 41.1 ° C 94.7 ° C 106.9 ° C 147.6 ° C
    [17] The crystalline content of the expandable pelletized material after the production process is generally only a few percent; the material is, therefore, predominantly amorphous. A higher temperature of initiation of crystallization at low temperature in the region of 80 ° C to 125 ° C, preferably from 90 ° C to 115 ° C, and, particularly preferably, from 95 ° C to 105 ° C, favors steam defoaming. Types of PLAs, such as NatureWorks® 8051D and 8052D, provide an ideal balance between the trend towards crystallization and foaming behavior in the expandable pelletized material.
    [18] Component ii consists of aliphatic or semi-aromatic (aliphatic-aromatic) polyesters.
    [19] As mentioned, purely aliphatic polyesters are advantageous as component ii). Aliphatic polyesters are polyesters derived from C2-C12 aliphatic alkanediols and aliphatic C4C36 alkanedicarboxylic acids, e.g. e.g., polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), polybutylene succinate sebacate (PBSSe), polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe) , or corresponding polyesteramides. Polyesters
    Petition 870190090495, of 12/09/2019, p. 14/55
    7/36 aliphatics are marketed by Showa Highpolymers as Bionolle, and by Mitsubishi as GSPla. EP08165370.1 describe relatively recent developments.
    [20] The intrinsic viscosities of aliphatic polyesters are generally 150 to 320 cm 3 / g, preferably 150 to 250 cm 3 / g, according to DIN 53728.
    [21] MVR (mass melt volume rate) is generally 0.1 to 70 cms 3/10 min, preferably from 0.8 to 70 cm 3/10 min and in particular from 1 to 60 cm3 / 10 min, according to EN ISO 1133 (190 C, 2.16 kg body weight).
    [22] acidity indices are generally 0.01 to 1.2 mg KOH / g, preferably 0.01 to 1.0 mg KOH / g, and particularly preferably 0.01 to 0 , 7 mg KOH / g, according to DIN EN 12634.
    [23] Semi-aromatic polyesters, which are also advantageous as component ii), consist of aliphatic diols and aliphatic dicarboxylic acids, as well as aromatics. Among the advantageous semi-aromatic polyesters are linear, non-extended chain polyesters (WO 92/09654). Particularly advantageous partners in a mixture are aliphatic / aromatic polyesters derived from butanediol, terephthalic acid, and C4-C18 aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, submeric acid, azelaic acid, sebacic acid, and brassic acid (for example, as described in WO 2006/097353 to 56). It is preferable to use semi-aromatic polyesters of extended and / or branched chain as component ii. The latter are known from the descriptions mentioned below in the introduction: WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, which are incorporated herein by reference. It is also possible to use a mixture of different semi-aromatic polyesters.
    [24] Biodegradable aromatic aliphatic-polyesters ii are particularly advantageous for the process of the invention to produce
    Petition 870190090495, of 12/09/2019, p. 15/55
    8/36 moldable foams, with these polyesters comprising:
    a) 40 to 70 mol%, based on components from a to b, one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid, and brassylic acid;
    b) from 60 to 30 mol%, based on components from a to b, of a terephthalic acid derivative;
    c) from 98 to 102 mol%, based on components from a to b, of a C2-C8 alkylenediol or C2-C6 oxyalkylenediol;
    d) from 0.00 to 2% by weight, based on the total weight of components from a to c, of a chain extender and / or crosslinking agent selected from the group consisting of: a di- or polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, peroxide, and carboxylic anhydride, and / or an alcohol at least trihydrous, or a carboxylic acid at least tri-functional.
    [25] Aliphatic-aromatic polyesters ii used preferably comprise:
    a) from 50 to 65 mol%, and in particular 58 mol% based on components from a to b, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, azelaic acid, brassylic acid, and preferably adipic acid, particularly preferably sebacic acid;
    b) from 50 to 35 mol%, and in particular 42 mol% based on components from a to b, of a terephthalic acid derivative;
    c) from 98 to 102 mol%, based on components from a to b, of 1,4-butanediol, and
    d) from 0 to 2% by weight, preferably from 0.01 to 2% by weight, based on the total weight of components from a to c, a chain extender and / or crosslinker selected from the group consisting of of: a polyfunctional isocyanate, isocyanurate, oxazoline, carboxylic anhydride, as anhydride
    Petition 870190090495, of 12/09/2019, p. 16/55
    9/36 maleic, or epoxide (in particular an epoxidated poly (meth) acrylate, and / or an alcohol at least trihydrous, or a carboxylic acid at least tri-functional.
    [26] Aliphatic dicarboxylic acids which are preferably advantageous are succinic acid, adipic acid, and particularly preferably sebacic acid. An advantage of polyesters that comprise succinic acid and that comprise sebacic acid is that they can also be obtained in the form of renewable raw material.
    [27] Polyesters ii used preferably comprise:
    a) from 90 to 99.5 mol%, based on components from a to b, of succinic acid;
    b) from 0.5 to 10 mol%, based on components from a to b, of one or more C8-C20 dicarboxylic acids, and
    c) from 98 to 102 mol%, based on components from a to b, of 1,3-propanediol or 1,4-butanediol.
    [28] Polyesters ii used particularly preferably include:
    a) from 90 to 99.5 mol%, based on components from a to b, of succinic acid;
    b) from 0.5 to 10 mol%, based on components from a to b, of terephthalic acid, azelaic acid, sebacic acid, and / or brassylic acid;
    c) from 98 to 102 mol%, based on components from a to b, of 1,3-propanediol or 1,4-butanediol, and
    d) from 0.01 to 5% by weight, based on the total weight of components from a to c, of a chain extender and / or crosslinking agent selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide (in particular an epoxidated poly (meth) acrylate), an alcohol at least trihydrous, or a carboxylic acid at least tri-functional.
    Petition 870190090495, of 12/09/2019, p. 17/55
    10/36 [29] The described polyesters ii are synthesized by the processes described in WO-A 92/09654, WO-A 96/15173, or, preferably, in WO-A 09/127555, and WO-A 09 / 127556, preferably in a two-stage reaction cascade. Derivatives of dicarboxylic acid are first reacted with a diol in the presence of a transesterification catalyst, resulting in a pre-polyester. The intrinsic viscosity (IV) of said prepolyester is generally 50 to 100 ml / g, preferably 60 to 80 ml / g. The commonly used catalysts comprise zinc catalysts, aluminum catalysts, and in particular titanium catalysts. An advantage of titanium catalysts, such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT) over tin catalysts, antimony catalysts, cobalt catalysts, and lead catalysts frequently used in the literature, an example being dioctanate of tin, is that when residual amounts of the catalyst or a product formed from the catalyst are retained in the product they are less toxic. This is particularly important in the case of biodegradable polyesters, because they can pass directly into the environment via the compounding process.
    [30] Polyesters ii are then produced in a second stage using the processes described in WO-A 96/15173 and EP-A 488 617. The prepolyester is reacted with chain extenders d), for example with diisocyanates or polymethacrylates containing epoxide, in a chain extension reaction that gives an IV polyester of 50 to 450 ml / g, preferably 80 to 250 ml / g.
    [31] The process generally uses from 0.01 to 2% by weight, preferably from 0.1 to 1.0% by weight, and particularly preferably from 0.1 to 0.3% by weight, with based on the total weight of components from a to c, a crosslinking agent (d ') and / or chain extender (d) selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide,
    Petition 870190090495, of 12/09/2019, p. 18/55
    11/36 peroxide, carboxylic anhydride, at least trihydric alcohol, or at least tribasic carboxylic acid. Chain d extenders that can be used are isocyanates, isocyanurates, oxazolines, carboxylic anhydride, or polyfunctional epoxides, and in particular difunctional.
    [32] Chain extenders, and also alcohols or carboxylic acid derivatives having at least three functional groups, can also be interpreted as d 'crosslinking agents. Particularly preferred compounds have three to six functional groups. Examples that can be mentioned are: tartaric acid, citric acid, malic acid; trimethylolpropane, trimethylolethane; pentaerythritol; polyethertrioles and glycerol, trimethic acid, trimellitic acid, trimellitic anhydride, pyromelitic acid, and pyromelitic dianhydride. Polyols, such as trimethylolpropane, pentaerythritol, and in particular glycerol, are preferred. Using components d and d 'it is possible to build biodegradable polyesters with a structural viscosity. The rheological behavior of the melting masses improves; biodegradable polyesters are easier to process. The compounds d act by reducing the viscosity under shear, i.e. the viscosity at relatively high shear rates is reduced.
    [33] The average arithmetic molar mass (Mn) of the polyesters ii is generally in the range of 5000 to 100,000 g / mol, in particular in the range of 10,000 to 75,000 g / mol, preferably in the range of 15,000 to 38,000 g / mol, while its average weight molar mass (Mw) is generally 30,000 to 300,000 g / mol, preferably 60,000 to 200,000 g / mol, and its Mw / Mn ratio is 1 to 6, preferably from 2 to 4. The intrinsic viscosity is 50 to 450 g / ml, preferably 80 to 250 g / ml (measured in odichlorobenzene / phenol (50/50 weight ratio)). The melting point is in the range of 85 to 150 ° C, preferably in the range of 95 to 140 ° C.
    [34] The indicated polyesters can have hydroxy and / or carboxy terminal groups in any desired ratio. Polyesters
    Petition 870190090495, of 12/09/2019, p. 19/55
    12/36 mentioned can also be modified in their terminal groups. As an example, therefore, OH terminal groups can be acid-modified via reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromelitic acid, or pyromelitic anhydride. Polyesters are preferred with acid levels below 1.5 mg KOH / g.
    [35] Biodegradable polyesters ii may comprise additional ingredients which are known to the person skilled in the art, but which are not essential to the invention. For example, additional materials conventional in plastics technology, such as stabilizers; nucleating agents; lubricants and release agents, such as stearates (in particular calcium stearate); plasticizers, such as citrus esters (in particular tributyl acetyl citrate), glycerol esters, such as triacetylglycerol, or ethylene glycol derivatives, surfactants, such as polysorbates, palmitates, or laurates; waxes, such as beeswax or beeswax ester; antistatic agent, UV absorber, UV stabilizer; anti-fog agents, or dyes. The used concentrations of the additives are 0 to 5% by weight, in particular 0.1 to 2% by weight, based on the polyesters of the invention. The amount of plasticizers comprised in the polyesters of the invention can be from 0.1 to 10% by weight.
    [36] Component iii) is described in more detail below.
    [37] Epoxides are, in particular, a copolymer based on styrene, acrylate, and / or methacrylate, and which contains epoxy groups. Units carrying epoxy groups are preferably glycidyl (meth) acrylates. Copolymers which have been shown to be advantageous have a proportion of glycidyl methacrylate greater than 20% by weight, particularly preferably greater than 30% by weight, and particularly preferably greater than 50% by weight, based on the copolymer. The epoxy equivalent weight (EEW) in these polymers is. preferably from 150 to
    Petition 870190090495, of 12/09/2019, p. 20/55
    13/36
    3000 g / equivalent and particularly preferably 200 to 500 g / equivalent. The average molecular weight (weight average) Mw of the polymers is preferably 2000 to 25,000, in particular 3000 to 8000. The average molecular weight (arithmetic) M n of the polymers is preferably 400 to 6000 , in particular from 1000 to 4000. Polydispersity (Q) is generally 1.5 to 5. Copolymers of the type indicated above containing epoxy groups are marketed by way of example by BASF Resins BV as Joncryl® ADR. Joncryl® ADR 4368 is particularly advantageous as a chain extender.
    [38] Component iv is, in particular, one or more of the following additives: stabilizer, nucleating agent, lubricant and release agent, surfactant, wax, antistatic agent, anti-fog agent, dye, pigment, UV absorber, stabilizer UV, or other plastic additives. It is particularly preferable as indicated above to use 0.5 to 1% by weight, based on components i and ii, of a nucleating agent.
    [39] Nucleating agent is in particular talc, chalk, charcoal black, graphite, calcium stearate or zinc stearate, poly-D-lactic acid, N, N'-ethylenebis-12-hydroxystearamide, or polyglycolic acid. Talc is particularly preferred as a nucleating agent.
    [40] The blowing agent can be interpreted as an additional component v.
    [41] The polymer melt mass comprising blowing agent generally comprises a total proportion of 2 to 10% by weight, preferably 3 to 7% by weight, based on the polymer melt mass comprising blowing agent, of one or more blowing agents homogeneously dispersed. Advantageous blowing agents are the physical blowing agents conventionally used in EPS, e.g. aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers, amides, or halogenated hydrocarbons. It is preferable to use isobutane,
    Petition 870190090495, of 12/09/2019, p. 21/55
    14/36 n-butane, n-pentane, and in particular isopentane. Mixtures of n-pentane and isopentane are additionally preferred.
    [42] The amount of blowing agent added is selected in such a way that the expansion capacity oc of the expandable pelletized material, defined as volumetric density before the pre-foaming process, is from 500 to 800 kg / m 3 and, preferably, from 580 to 750 kg / m 3 , and its volumetric density after the pre-foaming process is at most 125 kg / m 3 , preferably from 8 to 100 kg / m 3 .
    [43] When using filters, volumetric densities in the range of 590 to 1200 g / 1 can rise as a function of the nature and quantity of the charge.
    [44] The following materials can also be added to the polymer melt mass, together or with spatial separation: additives, nucleating agents, fillers, plasticizers, flame retardants, soluble and insoluble organic and / or inorganic pigments and dyes, being examples IR absorbers [infrared], p. eg, carbon black, graphite, or aluminum powder, for example, with auxiliary mixers or extruders. The amounts generally added of the dyes and pigments are in the range of 0.01 to 10% by weight, preferably in the range of 1 to 5% by weight. To obtain a homogeneous and microdispersed distribution of the pigments within the polymer, it may be advantageous, particularly in the case of polar pigments, to use a dispersing agent, e.g. e.g., organosilanes, epoxidized polymers, or grafted polymers of maleic anhydride. Mineral oils, or phthalates, are preferred plasticizers, and the amounts used of these can be from 0.05 to 10% by weight, based on the polymer.
    [45] To produce the expandable pelletized material of the invention, the blowing agent is incorporated by mixing in the polymer melt. The process comprises the following steps: A) melt production, B) mixing, C) transport, and D) pelletizing. Each of
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    15/36 said stages can be performed with the devices or combinations of devices known in the processing of plastics. Static or dynamic mixers are advantageous for the incorporation-by-mixing process, with extruders being examples. The polymer melt can be produced directly via the melt mass of pelleted polymeric material. If necessary, the temperature of the melting mass can be reduced with the use of a cooler. Examples of methods that can be used for pelletizing are underwater pressurized pelletizing, and pelletizing using rotary blades and sprayed liquid cooling for temperature control. Examples of advantageous device arrangements for conducting the process are:
    i) extruder - static mixer - cooler - pelletizer ii) extruder - pelletizer.
    [46] The arrangement may additionally include an auxiliary extruder for the introduction of additives, e.g. eg solids or additional materials that are sensitive to heat.
    [47] The temperature at which the polymer melt comprising blowing agent is transported through the extruder plate is generally in the range of 140 to 300 ° C, preferably in the range of 160 to 240 ° C.
    [48] The extruder plate is heated to at least the temperature of the polymer melt comprising blowing agent. It is preferable that the temperature of the extruder plate is in the range of 20 to 100 ° C above the temperature of the polymer melt comprising blowing agent. This inhibits the formation of polymer deposits within the extruder plates and ensures that pelletizing is problem-free.
    [49] To obtain pelletizable pellet sizes, the diameter (D) of the holes in the extruder plate at the outlet of the extruder plate should be in the range of 0.1 to 2 mm, preferably in the range of 0.1 to 2 mm 1.2 mm, so
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    16/36 particularly preferable in the range of 0.1 to 0.8 mm. Even after swelling of the extrudate, this allows controlled adjustment of pellet sizes below 2 mm, particularly in the range of 0.2 to 1.4 mm.
    [50] The swelling of the extrudate can be affected not only by the distribution of molecular weights, but also by the geometry of the extruder plate. The extruder plate preferably has holes with an L / D [length / diameter] ratio of at least 2, with the length (L, length) corresponding to that region of the extruder plate where the diameter is at most diameter (D) at the extruder plate outlet. The L / D ratio is preferably in the range of 3 to 20.
    [51] The diameter (E) of the holes at the entrance of the extruder plate should generally be at least twice as large as the diameter (D) at the exit of the extruder plate.
    [52] An embodiment of the extruder plate has holes with a conical inlet and an inlet angle α less than 180 °, preferably in the range of 30 to 120 °. In another embodiment, the extruder plate has holes with a conical outlet and an outlet angle β less than 90 °, preferably in the range of 15 to 45 °. To produce controlled distributions of pellet sizes in the polymers, the extruder plate can be equipped with holes of different discharge diameter (D). The various embodiments of the extrusion plate geometry can also be combined together.
    [53] A preferred process for producing expandable pelletized material comprising polylactic acid comprises the following steps:
    a) melt and mix to incorporate components i) from 50 to 99.9% by weight of polylactic acid, ii) from 0 to 50% by weight of one or more additional polymers, iii) from 0.1 to 2% by weight of a diepoxide or polyepoxide, and iv) 0 to 3% by weight of one or more additives,
    b) mixing to incorporate an organic blowing agent in the polymer melt optionally by means of a mixer
    Petition 870190090495, of 12/09/2019, p. 24/55
    17/36 static or dynamic at a temperature of at least 140 ° C, preferably from 180 to 260 ° C, and optional cooling of the polymer melt comprising blowing agent to a temperature of 120 to 160 ° C by means of of an intervening cooling device, before unloading,
    c) discharge through an extruder plate with holes, whose diameter at the exit of the extruder plate is a maximum of 1.5 mm, and
    d) pelletize the melting mass comprising blowing agent directly downstream of the extruder plate, and underwater, at a pressure in the range of 1 to 20 bar (100 to 2,000 kPa).
    [54] In addition, it has been found that by lowering the temperature to 5 to 20 ° C during the underwater pelletizing process, expandable pellets are obtained that comprise polylactic acid and have defined cavities with an average diameter in the range of 0.1 to 50 μηι. The average diameter of the pelleted material is generally in the range of 0.1 to 2 mm, with 50 to 300 cavities / mm 2 of cross-sectional area. Reducing the temperature during the underwater pelletizing process can reduce the volumetric density to the range of 580 to 750 kg / m 3 and, preferably, from 580 to 720 kg / m 3 . The expandable pelletized material produced in this way and comprising polylactic acid has, in addition, longer shelf life. It can still be foamed without difficulty after a period of weeks.
    [55] The following preferred procedure can also be used to achieve a reduction in volumetric density and increase the shelf-life of expandable pelletized material comprising polylactic acid:
    a) melt and mix to incorporate components i) from 50 to 99.9% by weight, based on the total weight of components of ia iii, polylactic acid, ii) from 0 to 49.9% by weight, based on total weight of ia iii components, one or more additional polymers, iii) from 0.1 to 2% by weight, based on the total weight of ia iii components, of a diepoxide or polyepoxide,
    Petition 870190090495, of 12/09/2019, p. 25/55
    18/36 and iv) 0.1 to 5% by weight, based on the total weight of components i to iii, of a nucleating agent,
    b) mix to incorporate v) from 1 to 7% by weight, based on the total weight of components from iv iv, an organic blowing agent and iv) from 0.01 to 5% by weight of a co-agent blowing - selected from the group of nitrogen, carbon dioxide, argon, helium, and mixtures thereof - into the polymer melt optionally by means of a static or dynamic mixer at a temperature of at least 140 ° C,
    c) discharge through an extruder plate with holes, whose diameter at the exit of the extruder plate is a maximum of 1.5 mm, and
    d) pelletize the melting mass comprising blowing agent directly downstream of the extruder plate, and underwater, at a pressure in the range of 1 to 20 bar (100 to 2,000 kPa).
    [56] Using volatile liquid-gaseous blowing agents (vi) that form cavities, it is possible to establish, in the expandable pelletized material, a cellular structure that can improve the subsequent foaming procedure and it is possible to control the size of the cells.
    [57] Nucleanting agents iv) and blowing agents v) advantageous are the materials described above.
    [58] The process for establishing said cavity morphology can also be called pre-nucleation, the cavities being formed, in essence, by the blowing co-agent vi).
    [59] The blowing co-agent vi) that forms the cavities differs from the blowing agent v) effective in terms of solubility in the polymer. In the production process, blowing agent v) and blowing co-agent vi) are first completely dissolved in the polymer at a sufficiently high pressure. The pressure is then reduced, preferably within a short period, and the solubility of the blowing co-agent vi) is thus reduced. Therefore, phase separation occurs in the polymer matrix, and produces
    Petition 870190090495, of 12/09/2019, p. 26/55
    19/36 if a pre-nucleated structure. The effective blowing agent v) remains dissolved mainly in the polymer, because it has a higher solubility and / or lower diffusion rate. It is preferable to reduce the temperature at the same time as reducing the pressure, to prevent excessive nucleation of the system and to reduce the extent of the blowing agent escape v) effective by diffusion. This is achieved by using blowing co-agent vi) in conjunction with ideal pelletizing conditions.
    [60] It is preferable that at least 80% by weight of the blowing co-agent F) escape within 24 h from the expandable thermoplastic beads during storage at 25 ° C, atmospheric pressure, and 50% relative humidity. The solubility of the blowing co-agent F) in the expandable thermoplastic beads is preferably below 0.1% by weight.
    [61] The amount of blowing co-agent F) used that is added during the pre-nucleation process should, in all cases, exceed maximum solubility under prevailing process conditions. Therefore, it is preferable to use blowing co-agents vi) which have low, but sufficient, solubility in the polymer. These include, in particular, gases such as nitrogen, carbon dioxide, air, and noble gases, particularly nitrogen, whose solubility decreases in many polymers at low temperatures and pressures. However, it is also possible to use other liquid additives.
    [62] It is particularly preferable to use inert gases, such as nitrogen and carbon dioxide. Characteristics of both gases, in addition to their physical properties, are low costs, good availability, ease of handling, and non-reactive or inert behavior. For example, polymer degradation is unlikely to occur in the presence of the two gases. The gases themselves are obtained from the atmosphere, and therefore their effect on the environment is also neutral.
    [63] The amount of blowing co-agent used vi) here
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    20/36 should: (a) be small enough to dissolve at the prevailing melt temperatures and prevailing melt pressures prevalent during the melt impregnation process prior to the pelletizing process; (b) be high enough to demix the polymer under pelletizing water pressure and pelletizing temperature, and cause nucleation. In a preferred embodiment, at least one of the blowing agents used is gaseous at room temperature and under atmospheric pressure.
    [64] It is particularly preferable to use talcum powder as a nucleating agent iv) in combination with nitrogen as a blowing co-agent vi).
    [65] Equipment that can be used for the transportation and storage of expandable pelletized material consists inter alia of metal drums and octagonal packaging. When using drums, a factor to be considered is that the release of blowing co-agents (vi) can sometimes cause an increase in pressure in the drum. Preferably used packaging means are, therefore, open packages, such as octagonal packages or drums that allow depressurization by permeation of the gas out of the drum. Particularly preferred here are drums that allow escape of the blowing co-agent vi) by means of diffusion to minimize or prevent the escape of the effective blowing agent
    v) through diffusion. This is possible, by way of example, by selecting a suitable sealing material for the blowing agent and, respectively, the blowing co-agent vi). The permeability of the sealing material with respect to the blowing co-agent vi) is preferably greater by at least a factor of 20 than the permeability of the sealing material with respect to the blowing agent v).
    [66] The pre-nucleation process, for example, by adding small amounts of nitrogen and carbon dioxide, can establish
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    21/36 a cell morphology within the expandable pelletized material comprising blowing agent. The average cell size in the center of the pearl here may be greater than in the peripheral regions, and the density in the peripheral regions of the pearls may be greater. Losses of blowing agent are therefore minimized as much as possible.
    [67] The pre-nucleation process can achieve a cell size distribution and a markedly better cell size reduction after the pre-foaming process. The amount of blowing agent required to achieve minimum volumetric density is also less, and the material has improved shelf life. Small amounts of nitrogen or carbon dioxide added to the melt can dramatically reduce pre-defoaming times with a constant blowing agent content, or they can dramatically reduce blowing amounts with constant defoaming times and minimal foam densities. In addition, the pre-nucleation process improves product homogeneity and process stability.
    [68] The re-impregnation of the pelletized polymeric material of the invention with blowing agents can also be markedly faster than with pelletized material of identical constitution, but with compact structure, i.e. non-cellular. Firstly, the diffusion times are shorter and, secondly, by analogy with directly impregnated systems, quantities of blowing agent required for the foaming process are shorter.
    [69] Finally, the pre-nucleation process can reduce the blowing agent content required to obtain a certain density, and thus can reduce the release times during the production of a molded part or block. Thus, it is possible to reduce the costs of further processing and improve the quality of the product.
    [70] The pre-nucleation process principle can be used
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    22/36 only for suspension technology, but also for fusion impregnation technology to produce expandable beads. It is preferred to apply it in the melt extrusion process in which the addition of blowing co-agents vi) is pelletized by means of pressure-assisted underwater pelletizing after unloading the melt loaded with blowing agent. The microstructure of the pelletized material can be controlled as described above by selecting the pelletizing parameters and the blowing co-agent vi).
    [71] With the use of relatively large amounts of blowing co-agent vi), for example, in the range of 1 to 10% by weight, based on the melt mass of polymer comprising blowing agent, it is possible to decrease the temperature of melting or the viscosity of the melting mass and thus significantly increase the flow. This can also provide a non-aggressive method of incorporating thermally labile additives, such as flame retardants, into the polymer melt. There is no change resulting from the constitution of expandable thermoplastic beads, because the blowing co-agent in essence escapes during the melt extrusion process. It is preferable to use CO2 to make use of this effect. In the case of N2, the effects on viscosity are less. Nitrogen is therefore used mainly to establish the desired cell structure.
    [72] The liquid-filled chamber for pelletizing the expandable thermoplastic polymer beads is preferably operated at a temperature in the range of 20 to 80 ° C, particularly preferably in the range of 30 to 60 ° C.
    [73] In order to minimize thermal degradation of polylactic acid, it is additionally advantageous at all stages of the process to minimize the amount of mechanical and thermal energy introduced. The average shear rates in the thread channel should be small, and it is preferred to keep the shear rates below 250 / s., Preferably below
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    23/36
    100 / s., And at temperatures below 260 ° C, and also with residence times in the range of 2 to 10 minutes in stages c) and d). Residence times are generally 1.5 to 4 minutes in the absence of a cooling step, and generally 5 to 10 minutes if a cooling step is provided. The polymer melt can be transported and discharged using pressurizing pumps, e.g. gear pumps.
    [74] To improve processability, the finished expandable pelletized material can be coated with glycerol ester, with antistatic agents, or with anti-fouling agents.
    [75] The expandable pelletized material of the invention has relatively little encrustation when compared to pelletized material which comprises plasticizers with low molecular weight, and has reduced loss of pentane during storage.
    [76] In a first step, hot air or steam can be used to pre-foam the expandable pelletized material of the invention to provide beads having density in the range of 8 to 100 kg / m 3, and in a second step, the material may be cast in a closed mold resulting in molded parts made up of pearls.
    [77] Surprisingly, foam beads have markedly higher crystallinity than expandable pelletized material. Crystallinity can be determined with the aid of differential thermal analysis (DSC). The crystalline content of the expandable pelleted material after the production process is generally a few percent - the material therefore becoming predominantly amorphous - while the crystallinity of the foamed pearls is markedly higher: from 8 to 40%, and, associated with this, they exhibit markedly higher heat resistance. Surprisingly, this effect is markedly more pronounced when
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    24/36 polymers used comprising polylactic acid comprise from 1 to 49.9% by weight and preferably from 1 to 29.9% by weight of an aliphatic or semi-aromatic polyester (component ii) than for a polymer that comprises polylactic acid, but which does not comprise component ii. Component ii) appears to have a nucleating effect on the polymer comprising polylactic acid. It is interesting to note that the foaming process provides high crystallinity of the foam beads without any damage to the foaming behavior of the expandable pelletized material.
    [78] The pelletized material produced by the process of the invention shows high biodegradability together with good foaming properties.
    [79] For the purposes of the present invention, a substance or mixture of substances falls within the biodegradable characteristic if that substance or mixture of substances has a percentage degree of biodegradation of at least 90% according to DIN EN 13432.
    [80] Biodegradability generally leads to the decomposition of pelletized material or foams produced therefrom in an appropriate and demonstrable life span. Degradation can occur through an enzymatic, hydrolytic, or oxidative pathway, and / or via exposure to electromagnetic radiation, such as UV radiation, and, in most cases, can be provided predominantly via exposure to microorganisms, such as bacteria, yeasts, fungi, and algae. Biodegradability can be quantified as an example by mixing polyester with compound and storing this for a particular period. As an example, according to DINEN 13432, CO 2 free air is passed through a matured compound during the compounding process, and the compound is subjected to a defined temperature profile. Biodegradability here is defined as a percentage degree of biodegradation considering the
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    25/36 ratio of the pure amount of CO 2 released from the sample (after subtracting the amount of CO2 released by the sample without compost) to the maximum amount of CO2 that can be released from the sample (calculated from the carbon content of the sample). Biodegradable pelletized material usually shows marked signs of degradation in just a few days of compost formation, examples being fungal growth, fissure, and perforation.
    [81] Other methods for determining biodegradability are described by way of example in ASTM D5338 and ASTM D6400-4.
    Examples
    Materials used:
    Component i:
    i- l: Aliphatic polyester, polylactide from Natureworks® 8051D by NatureWorks.
    Component ii:
    ii- 1: To produce the ii-1 polyester, 87.3 kg of dimethyl terephthalate, 80.3 kg of adipic acid, 117 kg of 1,4-butanediol, and 0.2 kg of glycerol were mixed together with 0.028 kg of tetrabutil orthotitanate (TBOT), with a molar ratio between the alcohol component and the acid components being 1.30. The reaction mixture was heated to a temperature of 180 ° C and reacted for 6 h at this temperature. The temperature was then increased to 240 ° C, and the excess dihydroxy compound was removed by vacuum distillation over a period of 3 h. Then 0.9 kg of hexamethylene diisocyanate was introduced in a dosed manner into the mixture at 240 ° C within a period of 1 h.
    [82] The melting point of the resulting ii-1 polyester was 119 ° C, its molar mass (M n ) being 23,000 g / mol (corresponds to Ecoflex® FBX 7011, produced by BASF SE).
    ii-2: To produce the ii-2 polyester, 14.89 kg of acid
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    26/36 sebacic, 165.18 kg of succinic acid, 172.5 kg of 1,4-butanediol, and 0.66 kg of glycerol were mixed with 0.031 kg of tetrabutil orthotitanate (TBOT) in a polycondensation tank of 450 liters, with the molar ratio of alcohol to acid components being 1.30. The reaction mixture was heated to an internal temperature of 200 ° C, with the removal of water by means of distillation, and the said temperature was maintained for 1 h. The temperature was then increased to an internal temperature of about 250-260 ° C, and at the same time the excess 1,4-butanediol was removed by distillation, with the application of vacuum (final vacuum of about 320 mbar ( 0.3 kPa to 2kPa). The polycondensation process was terminated by cooling to about 180-200 ° C once the desired final viscosity has been reached, and the pre-polyester has the chain extended with 1.5 kg of hexamethylene diisocyanate for 1 h at 240 ° C, and pelletized.
    [83] The molar mass (Mn) of the resulting ii-2 polyester was 37,000 g / mol.
    Component iii:
    iii- 1: Joncryl® ADR 4368 CS from BASF SE.
    Component iv:
    iv- 1: Chinatalc HP 325 from Luzenac
    Component v:
    v- 1: Blowing agent: isopentane v- 2: Blowing agent: n-pentane
    Component vi:
    vi- 1: Blowing co-agent: nitrogen (N2) vi-2: Blowing co-agent: carbon dioxide (CO2) [84] The proportions correspond to% by weight and are based on 100% by weight of polymer (ia iii components)
    Inventive example 1 [85] 5.7 parts of isopentane (component v-1) have been incorporated
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    27/36 by mixing, in an extruder (Leistritz 18 mm), to a melt consisting of 79.6 parts of i-1, 20 parts of component ii-1, 0.4 parts of component iii-1 , and 0.3 part of component iv-1, at a melting temperature of 200 ° C to 220 ° C. The quantities indicated in parts are based on the total number of components i-1, ii-1, and iii-1.
    [86] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)) (water temperature 40 ° C). The average particle size was 1.4 mm. The density of the impregnated pelletized material (raw pearls) was 742 kg / m 3 .
    [87] A steam flow was used to pre-foam the pelleted material. The volumetric density of the foamed beads of the pelleted material was 32 kg / m 3 . After 16 weeks it was no longer possible to foam the pellets of pelleted material.
    Inventive example 2 [88] 5.7 parts of isopentane (component v-1) were incorporated by mixing a melting mass consisting of 99.6 parts of component i-1, 0.4 part of component iii- 1, and 0.3 part of component iv-1, at a melting temperature of 200 ° C to 220 ° C.
    [89] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1,200 kPa)). The average particle size was 1.4 mm.
    [90] A steam flow was used to pre-foam the pelleted material. The volumetric density of the foamed beads of the pelleted material was 99 kg / m 3 .
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    28/36
    Comparative example 3 [91] 5.7 parts of isopentane were incorporated by mixing a melt consisting of 100 parts of component i-1 and 0.3 parts of component iv-1 at a melting temperature from 200 ° C to 220 ° C.
    [92] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1,200 kPa)). The average particle size was 1.4 mm.
    [93] A steam flow was used to pre-foam the pelleted material. The volumetric density of the foamed beads of the oelotized material was 117 kg / m 3 .
    Ex. I-1 component [arts] Component ii-1 [arts] Component iii-1 [arts] Component iv-1 [arts] Component v-1 [arts] Minimum volumetric density [kg / m 3 ] E.g. inv. 1 79.6 20 0.4 0.3 5.7 32 E.g. inv. 2 99.60.4 0.3 5.7 99 Ex. Comp. 3 100 0.3 5.7 117
    [94] The mixture of inventive examples 1 and 2 differs from that of comparative example 3 in the mixture of component iii.
    [95] For evaluation of inventive example 1 and comparative example
    3, the defoaming time and densities of the molded parts were measured. The corresponding ability of the foamed pearls to melt resulting in foam blocks was also qualitatively assessed.
    Examples Molded part density Fusion E.g. inv. 1 42 kg / m 3 ++ Ex. Comp. 3 180 kg / m 3 -
    Caption: ++ very good + good weak
    - - very weak [96] These experiments were conducted by analogy with inventive example 1, but on a Leistritz 27 mm extruder.
    Inventive example 4 [97] 5.7 parts of isopentane (component v-1) have been incorporated
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    29/36 by mixing a melting mass consisting of 79.6 parts of component i-1, 20 parts of component ii-1, 0.4 parts of iii-1, and 0.3 parts of iv- 1, at a melting temperature of 200 ° C to 220 ° C. The quantities indicated in parts are based on the entire quantity of components i-1, ii1, and iii-1.
    [98] The molten mass was transported at a flow rate of 10.0 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.8 mm). The compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (9 bar (900 kPa)). The average particle size was 1.4 mm.
    [99] A steam flow was used to pre-foam the pelleted material. The minimum volumetric density of the foamed beads of the pelleted material was 54 kg / m 3 .
    Inventive example 5 [100] 5.7 parts of a 50/50 mixture of component v-1 and component v-2 were incorporated by mixing into a melt consisting of 79.6 parts of i-1, 20 parts ii-1, 0.4 part iii-1, and 0.3 part iv-1, at a melting temperature of 200 ° C to 220 ° C. The quantities indicated in parts are based on the total number of components i-1, ii-1, and iii-1. The melt was transported at a flow rate of 10.0 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.8 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (9 bar (900 kPa)). The average particle size was 1.4 mm.
    [101] A steam flow was used to pre-foam the pelleted material. The minimum volumetric density of the foamed beads of the pelleted material was 74 kg / m 3 .
    Inventive example 6
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    30/36 [102] 5.7 parts of n-pentane (component v-2) were incorporated by mixing a melt consisting of 79.6 parts of i-1, 20 parts of ii-1, 0.4 part of iii-1, and 0.3 part of iv-1, at a melting temperature of 200 ° C to 220 ° C. The quantities indicated in parts are based on the total number of components i-1, ii-1, and iii-1.
    [103] The molten mass was transported at a flow rate of 10.0 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.8 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (9 bar (900 kPa)). The average particle size was 1.4 mm.
    [104] A steam flow was used to pre-foam the pelleted material. The minimum volumetric density of the foamed pearls of the
    material pelletized was 94 kg / m 3 . Example I-1 component [arts] Component ii-1 [arts] Component iii-1 [arts] Component iv-1 [arts] ComponentV [arts] Minimum volumetric density [kg / m 3 ] E.g. inv. 4 79.6 20 0.4 0.3 5.7 componentv-1 54 E.g. inv. 5 79.6 20 0.4 0.3 5.7 component v-1 (50%) component v-2 (50%) 74 Inv. Ex 6 79.6 20 0.4 0.3 5.7 componentv-2 94
    [105] The concentration of blowing agent and components of ia iv is the same as in inventive examples 4 to 6. Surprisingly, the expansion behavior is better in inventive example 4 than in inventive examples 5 and 6, this being the case. is determined from the lowest minimum volumetric density of the beads after full defoaming. This represents a clear advantage through the use of isopentane as a blowing agent compared to the use of n-pentane in this system. Inventive example 7 [106] 5.7 parts of isopentane (component v-1) and 0.5 parts of carbon dioxide (vi-2) were incorporated by mixing a
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    31/36 a melting mass consisting of 79.6 parts of component i-1, 20 parts of component ii-1, 0.4 parts of component iii-1, and 0.3 parts of component iv-1, at a melting temperature from 200 ° C to 220 ° C. The amounts indicated in parts are based on the total amount of components i-1, ii-1, and iii-1.
    [107] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)) (water temperature 40 ° C). The average particle size was 1.4 mm. The density of the impregnated pelletized material (raw pearls) was 664 kg / m 3 .
    [108] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 30 kg / m 3 . The minimum volumetric density of the foamed beads of the pelleted material was still 41 kg / m 3 after 16 weeks.
    Inventive example 8 [109] 5.7 parts of isopentane (component v-1) and 0.1 part of nitrogen (vi-1) were added by mixing in an extruder (Leistritz, 18 mm) to a melt consisting of 79.6 parts of component i-1, 20 parts of component ii-1, 0.4 parts of component iii1, and 0.3 parts of component iv-1, at a melting temperature of 200 ° C to 220 ° C. The amounts indicated in parts are based on the total amount of components i-1, ii-1, and iii-1.
    [110] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)) (water temperature 40 ° C). The average particle size was 1.4 mm. The density of the impregnated pelletized material (pearls
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    32/36 gross) was 650 kg / m 3 .
    [111] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 36 kg / m 3 . The minimum volumetric density of the foamed beads of the pelleted material was still 38 kg / m 3 after 16 weeks.
    Inventive example 9 [112] 5.7 parts of isopentane (component v-1) were incorporated by mixing in an extruder (Leistritz, 18 mm) into a melt consisting of 79.6 parts of component i-1, 20 parts of component ii-1, 0.4 parts of component iii-1, and 0.3 parts of component iv-1, at a melting temperature of 200 ° C to 220 ° C. The amounts indicated in parts are based on the total amount of components i-1, ii-1, and iii-1.
    [113] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)) (water temperature 20 ° C). The average particle size was 1.4 mm. The density of the impregnated pelletized material (raw pearls) was 700 kg / m 3 .
    [114] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 52 kg / m 3 . The minimum volumetric density of the foamed beads of the pelleted material was still 126 kg / m 3 after 16 weeks
    Table:
    Inventive examples Comp. i-1 [arts] Comp. ii-1 [arts] Comp. iii-1 [arts] Comp. iv-1 [arts] Comp.V [arts] Comp.vi [arts] Minimum volumetric density [kg / m 3 ] E.g. inv. 7 79.6 20 0.4 0.3 5.7v-1 0.5vi-2 30 E.g. inv. 8 79.6 20 0.4 0.3 5.7v-1 0.1vi-1 36 E.g. inv. 9 79.6 20 0.4 0.3 5.7v-152 E.g. inv. 1010 ° C 79.6 20 0.4 0.3 5.7v-134
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    33/36
    Inventive example 10 [115] 5.7 parts of isopentane (component v-1) were incorporated by mixing in an extruder (Leistritz, 18 mm) into a melt consisting of 79.6 parts of component i-1, 20 parts of component ii-1, 0.4 parts of component iii-1, and 0.3 parts of component iv-1, at a melting temperature of 200 ° C to 220 ° C. The amounts indicated in parts are based on the total amount of components i-1, ii-1, and iii-1.
    [116] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)) (water temperature 10 ° C). The average particle size was 1.4 mm. The density of the impregnated pelletized material (raw pearls) was 680 kg / m 3 .
    [117] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 34 kg / m 3 . The minimum volumetric density of the foamed beads of the pelleted material was still 77 kg / m 3 after 16 weeks.
    Inventive example 11 [118] 5.7 parts of isopentane (component v-1) were incorporated by mixing in an extruder (Leistritz, 18 mm) into a melt consisting of 69.6 parts of component i-1, 30 parts of component ii-2, 0.4 parts of component iii-1, and 0.3 parts of component iv-1, at a melting temperature of 200 ° C to 220 ° C. The amounts indicated in parts are based on the total amount of components i-1, ii-2, and iii-1.
    [119] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar
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    34/36 (1200 kPa)). The average particle size was 1.4 mm.
    [120] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 43 kg / m 3 .
    Inventive example 12 [121] 5.7 parts of isopentane (component v-1) and 0.05 parts of nitrogen (vi-1) were incorporated by mixing into a melt consisting of 69.7 parts of component i-1, 30 parts of component ii-2, 0.3 parts of component iii-1, and 0.3 parts of component iv1, at a melting temperature of 200 ° C to 220 ° C.
    [122] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)). The average particle size was 1.4 mm.
    [123] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was 64 kg / m 3 .
    Inventive example 13 [124] 5.7 parts of isopentane (component v-1) and 0.1 part of nitrogen (vi-1) were incorporated by mixing into a melt consisting of 69.7 parts of component i-1, 30 parts of component ii-2, 0.3 parts of component iii-1, and 0.3 parts of component iv1, at a melting temperature of 200 ° C to 220 ° C.
    [125] The melt was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)). The average particle size was 1.4 mm.
    Petition 870190090495, of 12/09/2019, p. 42/55
    35/36 [126] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was kg / m 3 .
    Inventive example 14 [127] 5.7 parts of isopentane (component v-1) and 0.5 parts of carbon dioxide (vi-2) were incorporated by mixing into a melt consisting of 69.7 parts component i-1, 30 parts component ii-2, 0.4 part component iii-1, and 0.3 part component iv-1, at a melting temperature of 200 ° C to 220 ° C.
    [128] The molten mass was transported at a flow rate of 3.5 kg / h through the extruder plate with a hole (diameter of the extruder plate 0.65 mm). Compact pelletized material with narrow size distribution was produced with the aid of pressurized underwater pelletizing (12 bar (1200 kPa)). The average particle size was 1.4 mm.
    [129] A steam flow was used to pre-foam the pelleted material. The density of the foamed beads of the pelleted material was kg / m 3 .
    [130] The advantageous constitution of PM 'polymer comprising polylactic acid can be seen from the comparison of inventive examples 1 and 14, which, in essence, differ in terms of component ii.
    E.g. inv. 11 E.g. inv. 12 E.g. inv. 13 E.g. inv. 14 I-1 component 69.6 69.7 69.7 69.6 Component ii-2 30 30 30 30 Component iii-1 0.4 0.3 0.3 0.4 Component iv-1 0.3 0.3 0.3 0.3 Component v-1 5.7 5.7 5.7 5.7 Component vi-2 - 0.05 0.1 - Component vi-2 - - - 0.5 Volumetric density of raw pearls [kg / m 3 ] 765 661 648 720 Minimum volumetric density of foam [kg / m 3 ] 43 40 38 39 Minimum volumetric density of foam [kg / m 3 ] after 6 weeks not foamy 56 38 53
    [131] The raw beads of inventive example 1 and inventive example were pre-foamed and melted resulting in test samples with a comparable molding density of 50 g / 1.
    Petition 870190090495, of 12/09/2019, p. 43/55
    36/36 [132] The test samples of inventive example 14 show better heat resistance in the form of a dimensional stability value less than 1% in contrast to a dimensional stability value greater than 2% in inventive example 1.
    [133] The specimen of inventive example 14 additionally presents better mechanical stability than the specimen of inventive example 1, this being noticeable in terms of greater compressive strength and greater bending energy.
    权利要求:
    Claims (12)
    [1]
    1. Process to produce expandable pelletized material that comprises polylactic acid, characterized by the fact that it comprises the following steps:
    a) melting and incorporation by mixing the following components: i) from 50 to 98.9% by weight, based on the total weight of components of ia iii, polylactic acid, ii) from 1 to 49.9% in weight, based on the total weight of ia iii components, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and aliphatic dihydroxy compounds, iii) from 0.1 to 2% by weight, based on total weight of ia iii components, a copolymer comprising epoxy groups and based on styrene, acrylate and / or methacrylate, and iv) from 0 to 10% by weight, based on the total weight of ia iii components, of one or more additives,
    b) incorporation by mixing v) from 3 to 7% by weight, based on the total weight of components of ia iv, of an organic blowing agent in the polymer melt by means of a static or dynamic mixer at a temperature of at least 140 ° C,
    c) discharge through an extruder plate with holes, whose diameter at the exit of the extruder plate is a maximum of 1.5 mm, and
    d) pelletize the melt comprising blowing agent directly downstream of the extruder plate, and underwater, at a pressure in the range of 1 to 20 bar (100 to 2,000 kPa).
    [2]
    2. Process according to claim 1, characterized by the fact that component i) used in step a) comprises polylactic acid with MVR of 5 to 8 ml / 10 minutes according to ISO 1133 [190 ° C / 2.16 kg ].
    [3]
    Process according to claim 1, characterized in that the component i) used in step a) comprises polylactic acid with a low crystallization onset temperature
    Petition 870190090495, of 12/09/2019, p. 45/55
    2/4 temperature in the range of 80 ° C to 125 ° C, measured using DSC at a heating rate of 20K / min.
    [4]
    Process according to claim 1, characterized in that the organic blowing agent used in step b) comprises isopentane.
    [5]
    Process according to any one of claims 1 to 4, characterized in that the underwater pelletizing process is carried out at a temperature of 5 to 20 ° C.
    [6]
    6. Expandable pelletized material, characterized by the fact that it comprises polylactic acid and has a solids content of 93 to 97% by weight, comprising:
    (i) 50 to 98.9% by weight, based on the total weight of ia iii components, polylactic acid, ii) from 1 to 49.9% by weight, based on the total weight of ia iii components, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds, iii) from 0.1 to 2% by weight, based on the total weight of components of ia iii, of a copolymer comprising epoxy groups and which is based on styrene, acrylate, and / or methacrylate, and iv) from 0 to 10% by weight, based on the total weight of components of ia iii, one or more additives, and a ratio of v) of 3 to 7% by weight of an organic blowing agent.
    [7]
    7. Process for producing moldable foam molded parts, characterized by the fact that it comprises the use of hot air or steam in a first step to pre-foam expandable pelletized material comprising polylactic acid, as defined in claim 6, resulting in pearls foam with density in the range of 8 to 100 kg / m 3 , and, in a second step, melt the materials in a closed mold.
    Petition 870190090495, of 12/09/2019, p. 46/55
    3/4
    [8]
    8. Use of expandable pelletized material, as defined in claim 6, which comprises polylactic acid, characterized by the fact that it is for producing meat, sausage and soup trays, drink glasses, food or beverage packaging, electrical items, or for insulation in the construction industry, or for shock absorption and sound muffling.
    [9]
    9. Polymer mixture PM ', characterized by the fact that it comprises polylactic acid and comprises:
    (i) 60 to 98.9% by weight, based on the total weight of ia iii components, polylactic acid, ii) from 1 to 39.9% by weight, based on the total weight of ia iii components, at least one polyester based on:
    a) from 90 to 99.5 mol%, based on components from a to b, of succinic acid;
    b) from 0.5 to 10 mol%, based on components from a to b, of one or more C8-C20 dicarboxylic acids;
    c) from 98 to 102 mol%, based on components from a to b, of 1,3-propanediol or 1,4-butanediol;
    iii) from 0.1 to 2% by weight, based on the total weight of components of ia iii, from a copolymer comprising epoxy groups and based on styrene, acrylate and / or methacrylate, and iv) from 0 to 1 % by weight, based on the total weight of ia iii components, of a nucleating agent.
    [10]
    Polymer mixture PM 'according to claim 9, characterized in that it comprises polylactic acid and comprises:
    (i) 65 to 79.9% by weight, based on the total weight of ia iii components, polylactic acid, ii) 20 to 34.9% by weight, based on the total weight of ia iii components, at least one polyester based on:
    Petition 870190090495, of 12/09/2019, p. 47/55
    4/4
    a) from 90 to 99.5 mol%, based on components from i to ii, of succinic acid;
    b) from 0.5 to 10 mol%, based on components from i to ii, terephthalic acid, azelaic acid, sebacic acid, and / or brassylic acid;
    c) from 98 to 102 mol%, based on components from i to ii, 1,3-propanediol or 1,4-butanediol;
    iii) from 0.1 to 1% by weight, based on the total weight of components of ia iii, of a copolymer comprising epoxy groups and based on styrene, acrylate and / or methacrylate, and iv) from 0.1 to 1% by weight, based on the total weight of ia iii components, of a nucleating agent.
    [11]
    Expandable pelletized material according to claim 6, characterized in that it comprises polylactic acid and comprises a polymer mixture PM ', as defined in claim 9 or 10, which comprises polylactic acid.
    [12]
    12. Foam, characterized in that it comprises a polymer mixture PM 'as defined in claim 9 or 10, which comprises polylactic acid.
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    同族专利:
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    US20160060417A1|2016-03-03|
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    CA2787222A1|2011-07-21|
    JP6049810B2|2016-12-21|
    AU2011206716A1|2012-08-16|
    US9212270B2|2015-12-15|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B06T| Formal requirements before examination|
    2019-10-15| B09A| Decision: intention to grant|
    2019-10-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/01/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/01/2011, OBSERVADAS AS CONDICOES LEGAIS |
    2019-11-12| B16C| Correction of notification of the grant|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/01/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) REF. RPI 2547 DE 29/10/2019 QUANTO AO ITEM (72) INVENTOR. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10150730|2010-01-14|
    EP10193484|2010-12-02|
    PCT/EP2011/050129|WO2011086030A2|2010-01-14|2011-01-06|Method for producing expandable granulates containing polylactic acid|
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