New block copolymers

Abstract

A block copolymer contains at least a block (P1) and a block (P2). The block (P1) is obtained or obtainable by reaction of a triblock copolymer having the structure A-B-A′, where block B is selected from polyethers or polyesters and blocks A and A′ are identical or different, and at least one polymer (PM) selected from polyesters and polyethers. The block (P2) is selected from polyamides and polyesters. A process can be used for producing the inventive block copolymer, a shaped article can be made containing the inventive block copolymer, and the inventive block copolymer can be used for producing a shaped article.

Claims

1. A block copolymer, comprising at least: a block (P1) obtained or obtainable by reacting a triblock copolymer having a structure A-B-A′, where block B is selected from the group consisting of polyethers and polyesters, and block A and block A′ are identical or different, and at least one polymer (PM) selected from the group consisting of polyesters and polyethers, and a block (P2) selected from the group consisting of polyamides and polyesters.

2. The block copolymer as claimed in claim 1, wherein block B and the at least one polymer (PM) are selected from the group consisting of polyethers.

3. The block copolymer as claimed in claim 1, wherein the triblock copolymer is used in an amount within a range from 20% to 80% by weight based on a sum of the amount of the triblock copolymer and of the at least one polymer (PM).

4. The block copolymer as claimed in claim 1, wherein block B is selected from the group consisting of polyethers and the at least one polymer (PM) is selected from the group consisting of polyethers.

5. The block copolymer as claimed in claim 1, wherein block B is selected from the group consisting of polytetramethylene oxides and polytrimethylene oxides.

6. The block copolymer as claimed in claim 5, wherein a number-average molecular weight Mn of a polytetramethylene oxide is within a range from 500 to 3500 g/mol.

7. The block copolymer as claimed in claim 1, wherein block B is selected from the group consisting of polyesters and the at least one polymer (PM) is selected from the group consisting of polyesters.

8. The block copolymer as claimed in claim 1, wherein block A, or block A′, or block A and block A′ are selected from the group consisting of polycaprolactones.

9. The block copolymer as claimed in claim 1, wherein the triblock copolymer is a poly-ε-caprolactone polyol obtainable or obtained by reaction of ε-caprolactone and a starter molecule selected from the group consisting of α-hydro-ω-hydroxypoly(oxytetramethylene)diols.

10. The block copolymer as claimed in claim 1, wherein a number-average molecular weight Mn of the at least one polymer (PM) is within a range from 500 to 3500 g/mol.

11. The block copolymer as claimed in claim 1, wherein a number-average molecular weight of the at least one polymer (PM) is within a range from 80% to 120% of the a number-average molecular weight of the triblock copolymer.

12. The block copolymer as claimed in claim 1, wherein block (P2) is a polyamide block obtained or obtainable by reaction of one selected from the group consisting of aliphatic, semiaromatic, and aromatic polyamides.

13. The block copolymer as claimed in claim 1, wherein block (P2) is a polyester block obtained or obtainable by reaction of one selected from the group consisting of polybutylene terephthalates and polyethylene terephthalates.

14. A process for producing a block copolymer, the process comprising: reacting a composition comprising a triblock copolymer A-B-A′ and at least one polymer (PM) selected from the group consisting of polyesters and polyethers, to obtain a block copolymer, wherein the block copolymer comprises at least a block (P1) and a block (P2), wherein the block (P1) is obtained or obtainable by reaction of the triblock copolymer having the structure A-B-A′, where block B is selected from the group consisting of polyethers and polyesters and block A and block A′ are identical or different, and the at least one polymer (PM), and wherein the block (P2) is selected from the group consisting of polyamides and polyesters.

15. A shaped article, comprising the block copolymer as claimed in claim 1.

16. A foamed pellet material, comprising the block copolymer as claimed in claim 1.

17. The foamed pellet material as claimed in claim 16, wherein an average diameter of particles is within a range from 0.5 to 20 mm.

18. A shaped article, composed of the foamed pellet material as claimed in claim 16.

19. A method, comprising: molding the block copolymer as claimed in claim 1, to produce a shaped article.

20. The shaped article as claimed in claim 15, wherein the shaped article is at least partly in a form of a foam or particle foam.

21. The shaped article as claimed in claim 15, wherein the shaped article is a part of a shoe sole, a mattress, a seat cushion, an underlay, a grip, a protective film, a component in automobile interiors and exteriors, a gymnastics mat, a body protector, a trim element in automobile construction, a sound insulator, a vibration damper, a cushioning, a bicycle saddle, a toy, a tire or part of a tire, a covering for a track and field surface, a sports hall or a pathway, a damping layer or a damping core in a sandwich element, or a packaging.

22. The shaped article as claimed in claim 15, wherein the shaped article is an injection-molded, extruded and pressed article, a hose, a cable or part of a cable, an elevator belt or drive belt, a conveyor belt, a hose, part of a shoe, a film, a nonwoven, a fiber, a ski shoe or part of a ski shoe, a ski film, a plug, a damping element, a housing, or a molding for the electricals industry, automotive industry, mechanical engineering, 3D printing, medicine, consumer goods, or sports articles.

Description

EXAMPLES

1. Production of PCL500-PTHF1000-PCL500

[0216] The triblock PCL500-PCL1000-PCL500 was obtained by ring-opening polymerization of 100 percent by weight of caprolactone based on an initially charged hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 1000 g/mol in the presence of 10 ppm of titanium tetrabutoxide (TTB) at 180° C.

2. Comparative Example 1: TPC Production via DMT and PTHF2000

[0217] Dimethyl terephthalate (100 mol %) was reacted in the presence of a threefold excess of butane-1,4-diol (300 mol %) and hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (16.1 mol %) in a steel reactor in the presence of tetrabutyl orthotitanate as catalyst and 0.5% Irganox 1010 for 90 minutes at 165° C., standard pressure, and an atmosphere of nitrogen, while methanol was distilled off. The reaction temperature was then increased gradually to 210° C. After approx. 1 h the reaction temperature was increased to 250° C. and the excess butane-1,4-diol distilled off under reduced pressure (˜20 Pa).

[0218] The synthesis was stopped as soon as a melt flow rate (MFR) of 5 cm.sup.3/10 min at 190° C./2.16 kg was achieved. Extrusion of the product afforded lenticular pellets.

3. Example 1: TPC Production Via MIT and PTHF2000/PCL500-PTHF1000-PCL500 (1:2)

[0219] Dimethyl terephthalate (100 mol %) was reacted in the presence of a threefold excess of butane-1,4-diol (300 mol %), hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (5.4 mol %), and a hydroxy-terminated PCL500-PTHF1000-PCL500 having a number-average molecular weight Mn of 2.000 g/mol (10.7 mol %) in a steel reactor in the presence of tetrabutyl orthotitanate as catalyst and 0.5% Irganox 1010 for 90 minutes at 165° C., standard pressure, and an atmosphere of nitrogen, while methanol was distilled off. The reaction temperature was then increased gradually to 210° C. After approx. 1 h the reaction temperature was increased to 250° C. and the excess butane-1,4-diol distilled off under reduced pressure (˜20 Pa).

[0220] The synthesis was stopped as soon as a melt flow rate (MFR) of 5 cm.sup.3/10 min at 190° C./2.16 kg was achieved. Extrusion of the product afforded lenticular pellets.

4. Comparative Example 2: TPC Production Via Terephthalic Acid and PTH52000

[0221] Terephthalic acid (100 mol %) was reacted in the presence of an excess of butane-1,4-diol (250 mol %) and hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (16.1 mol %) in a steel reactor in the presence of tetrabutyl orthotitanate as catalyst and 0.5% Irganox 1010 for 90 minutes at 165° C., standard pressure, and an atmosphere of nitrogen, while methanol was distilled off. The reaction temperature was then increased gradually to 210° C. After approx. 1 h the reaction temperature was increased to 250° C. and the excess butane-1,4-diol distilled off under reduced pressure (˜20 Pa).

[0222] The synthesis was stopped as soon as a melt flow rate (MFR) of 5 cm.sup.3/10 min at 190° C./2.16 kg was achieved. Extrusion of the product afforded lenticular pellets.

5. Example 2: TPC Production Via Terephthalic Acid and PTHF2000/PCL500-PTHF1000-PCL500 (1:2)

[0223] Terephthalic acid (100 mol %) was reacted in the presence of an excess of butane-1,4-diol (250 mol %), hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (5.4 mol %), and a hydroxy-terminated PCL500-PTHF1000-PCL500 having a number-average molecular weight Mn of 2000 g/mol (10.7 mol %) in a steel reactor in the presence of tetrabutyl orthotitanate as catalyst and 0.5% Irganox 1010 for 90 minutes at 165° C., standard pressure, and an atmosphere of nitrogen, while methanol was distilled off. The reaction temperature was then increased gradually to 210° C. After approx. 1 h the reaction temperature was increased to 250° C. and the excess butane-1,4-diol distilled off under reduced pressure (˜20 Pa).

[0224] The synthesis was stopped as soon as a melt flow rate (MFR) of 5 cm.sup.3/10 min at 190° C./2.16 kg was achieved. Extrusion of the product afforded lenticular pellets.

6. Comparative Example 3: TPA Production via PA6 and PTHF2000

[0225] ε-Caprolactam (100 mol %), terephthalic acid (6.3 mol %), and deionized water (27.8 mol %) were stirred in a steel reactor for 2 h at 260° C. and 3 bar pressure. The pressure was then gradually lowered to 5000 Pa and stirring continued for a further 2 h.

[0226] After a further 2 h, hydroxy-terminated polytetramethylene oxide having, a number-average molecular weight Mn of 2000 g/mol (3.15 mol %), propane-1,3-diol (4.8 mol %), and tetraisopropyl orthotitanate as catalyst were added to the reaction mixture and this was stirred for 1 h at 240° C. and 2 bar pressure. Excess propane-1,3-diol was then distilled off over a period of 1 h by lowering the pressure to ˜20 Pa and raising the temperature to 250° C.

7. Example 3: TPA Production via PA6 & PTHF2000/PCL500-PTHF1000-PCL500

[0227] ε-Caprolactam (100 mol %), terephthalic acid (6.3 mol %), and deionized water (27.8 mol %) were stirred in a steel reactor for 2 h at 260° C. and 3 bar pressure. The pressure was then gradually lowered to 5000 Pa and stirring continued for a further 2 h.

[0228] After a further 2 h, hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (1.1 mol %), hydroxy-terminated PCL500-PTHF1000-PCL500 having a number-average molecular weight Mn of 2000 g/mol (2.05 mol %), propane-1,3-diol (4.8 mol %), and tetraisopropyl orthotitanate as catalyst were added to the reaction mixture and this was stirred for 1 h at 240° C. and 2 bar pressure. Excess propane-1,3-diol was then distilled off over a period of 1 h by lowering the pressure to ˜20 Pa and raising the temperature to 250° C.

8. Comparative Example 4: TPA Production Via PA12 with PTHF2000

[0229] Laurolactam (100 mol %) and decanedicarboxylic acid (26 mol %) were heated in a steel reactor to 280° C. under nitrogen for 2 h. To this was then added hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (26.5 mol %), After stirring at 280° C. for 1 h, the temperature was lowered to 270° C. and stirring continued for a further 5 hours under a nitrogen atmosphere and a further 8 h under a vacuum of 90 mbar.

[0230] The synthesis was stopped as soon as a melt flow rate (MFR) of 12 g/10 min at 235° C./1.00 kg was achieved. Extrusion of the product afforded lenticular pellets.

9. Example 4: TPA Production via PA12 & PTHF2000/PCL500-PTHF1000-PCL500

[0231] Laurolactam (100 mol %) and decanedicarboxylic acid (26 mol %) were heated in a steel reactor to 280° C. under nitrogen for 2 h. To this were then added hydroxy-terminated polytetramethylene oxide having a number-average molecular weight Mn of 2000 g/mol (8.83 mol %) and a hydroxy-terminated PCL500-PTHF1000-PCL500 having a number-average molecular weight Mn of 2000 g/mol (17.7 mol %). After stirring at 280° C. for 1 h, the temperature was lowered to 270° C. and stirring continued for a further 5 hours under a nitrogen atmosphere and a further 8 h under a vacuum of 90 mbar.

[0232] The synthesis was stopped as soon as a melt flow rate (MFR) of 12 g/10 min at 235° C./1.00 kg was achieved. Extrusion of the product afforded lenticular pellets.

10. DSC Analysis

[0233] Injection molding was used to produce injection-molded sheets having a thickness of 2 mm, which were then subjected to heat treatment at 100° C. for 20 h. After the test specimen had been dried at 100° C. for 10 min, the first heating run of a DSC measurement was then measured from −60 to 240° C. at a heating rate of 20° C./min.

TABLE-US-00001 Maximum of an endothermic peak in the TPE range −20° C. to +20° C. Comparative example 1 Yes Example 1 No Comparative example 2 Yes Example 2 No Comparative example 3 Yes Example 3 No Comparative example 4 Yes Example 4 No

11. Production of a Particle Foam from Example 1

[0234] Expanded particles composed of the TPC produced in example 1 were produced using a twin-screw extruder having a screw diameter of 18 mm and a length-to-diameter ratio of 40 connected to a melt pump, a start-up valve with screen changer, a die plate, and an underwater pelletization system. The TPC produced in example 1 was prior to use dried for 3 h at 80° C. so as to obtain a residual moisture content of less than 0.02% by weight.

[0235] The TPC was mixed with 0.1% by weight of talc (Microtalk IT Extra, Mondo Minerals), based on the TPC, and then metered into the twin-screw extruder gravimetrically.

[0236] After metering the materials into the intake of the twin-screw extruder, the molten TPC was mixed with the talc in the twin-screw extruder. After mixing, a mixture of CO.sub.2 and N.sub.2 was added as blowing agent. While passing along the rest of the extruder length, the blowing agent and the polymer melt were mixed with one another, resulting in the formation of a homogeneous mixture. The total throughput of the extruder, comprising the TPC, the talc, and the blowing agents, was 1.75 kg/h.

[0237] The melt mixture was then forced using a gear pump (GP) via a start-up valve with screen changer (SV) into a die plate (DP), cut into pellets in the cutting chamber of the underwater pelletization system (UWP), and transported away with the temperature-controlled and pressurized water and undergoing expansion in the process. A centrifugal dryer is used to ensure separation of the expanded particles from the process water.

[0238] The employed temperatures of the equipment components are listed in Table 2. Table 3 shows the amounts of blowing agent (CO.sub.2 and N.sub.2) used. The amounts stated for the blowing agents are based on the total throughput of polymer.

TABLE-US-00002 TABLE 2 Temperature data of the equipment components Temperature Water Water range in the Temperature Temperature Temperature pressure in temperature extruder range of the range of the range of the the UWP in the UWP (° C.) GP (° C.) SV (° C.) DP (° C.) (bar) (° C.) V1 215-190 190 200 200 15 40 V2 195-170 190 200 200 15 40 V3 195-170 190 200 200 15 40 V4 195-170 190 200 200 15 40 V5 195-170 190 200 200 15 40 V6 195-170 190 200 200 12.5 40 V7 195-170 190 200 200 10 40 V8 195-170 190 200 200 15 45 V9 215-190 190 200 200 15 45 V10 215-190 190 200 200 15 45

TABLE-US-00003 TABLE 3 Amounts of blowing agents added, based on total throughput of TPC from example 1 CO.sub.2 N.sub.2 [% by wt.] [% by wt.] V1 1.75 0.3 V2 1.75 0.3 V3 2 0.3 V4 2.25 0.3 V5 2.5 0.3 V6 2.5 0.3 V7 2.5 0.3 V8 2.5 0.3 V9 2.5 0.3 V10 2.5 0.45

[0239] The resulting bulk densities of the expanded pellets for the individual experiments are listed in Table 4.

TABLE-US-00004 TABLE 4 Measured bulk density of the expanded particles after a storage period of at least 3 h Bulk density (g/l) V1 134 V2 118 V3 133 V4 159 V5 166 V6 172 V7 182 V8 190 V9 192 V10 165

[0240] In addition to processing in the extruder, expanded particles were also produced in the impregnation vessel. For this, the vessel was filled with the solid/liquid phase to a fill level of 80%, the phase ratio being 0.32.

[0241] The solid phase is here the TPC from example 1 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance. After first purging with nitrogen, this mixture in the gas-tight vessel was pressurized with blowing agent (butane) in the amount stated in Table 5, based on the solid phase (TPC from example 1). The vessel was heated while stirring the solid/liquid phase, and at a temperature of 50° C. the mixture was pressurized with a defined amount of nitrogen to a pressure of 8 bar. The mixture was then further heated up to the desired impregnation temperature (IMT). On reaching the impregnation temperature and impregnation pressure, the pressure in the vessel was released via a valve after a specified hold time. The precise production parameters for the experiments and the bulk densities achieved are listed in Table 5.

TABLE-US-00005 TABLE 5 Production parameters and bulk density achieved for the impregnated TPC from example 1 Blowing agent Hold time concentration based on (range IMT amount of solid phase −5° C to IMT IMT Bulk density Name (% by wt.) +2° C.) (min) (° C.) (g/l) V11 24 15 129.5 185 V12 24 8 130 168 V13 24 10 132 113 V14 24 14 134 104

12. Production of a Particle Foam from Example 4

[0242] Expanded particles composed of the TPA produced in example 4 were produced using a twin-screw extruder having a screw diameter of 18 mm and a length-to-diameter ratio of 40 connected to a melt pump, a start-up valve with screen changer, a die plate, and an underwater pelletization system. The IPA produced in example 4 was prior to use dried for 3 h at 80° C. so as to obtain a residual moisture content of less than 0.02% by weight.

[0243] The TPA was mixed with 0.1% by weight of talc (Microtalk IT Extra, Mondo Minerals), based on the TPA, and then metered into the twin-screw extruder gravimetrically.

[0244] After metering the materials into the intake of the twin-screw extruder, the molten TPA was mixed with the talc in the twin-screw extruder. After mixing, a mixture of CO.sub.2 and N.sub.2 was added as blowing agent. While passing along the rest of the extruder length, the blowing agent and the polymer melt were mixed with one another, resulting in the formation of a homogeneous mixture. The total throughput of the extruder comprising the TPA, the talc, and the blowing agents was 1.75 kg/h.

[0245] The melt mixture was then forced using a gear pump (GP) via a start-up valve with screen changer (SV) into a die plate (DP), cut into pellets in the cutting chamber of the underwater pelletization system (UWP), and transported away with the temperature-controlled and pressurized water and undergoing expansion in the process. A centrifugal dryer is used to ensure separation of the expanded particles from the process water.

[0246] The employed temperatures of the equipment components are listed in Table 6. Table 7 shows the amounts of blowing agent (CO.sub.2 and N.sub.2) used. The amounts stated for the blowing agents are based on the total throughput of polymer.

TABLE-US-00006 TABLE 6 Temperature data of the equipment components Temperature Water Water range in the Temperature Temperature Temperature pressure in temperature extruder range of the range of the range of the the UWP in the UWP (° C.) GP (° C.) SV (° C.) DP (° C.) (bar) (° C.) V15 215-190 190 200 200 15 40 V16 195-170 190 200 200 15 40

TABLE-US-00007 TABLE 7 Amounts of blowing agents added, based on total throughput of TPA from example 4 CO.sub.2 N.sub.2 [% by wt.] [% by wt.] V15 1.75 0.3 V16 1.75 0.3

[0247] The resulting bulk densities of the expanded pellets for the individual experiments are listed in Table 8.

TABLE-US-00008 TABLE 8 Measured bulk density of the expanded particles after a storage period of at least 3 h Bulk density (g/l) V15 134 V16 118

[0248] In addition to processing in the extruder, expanded particles were also produced in the impregnation vessel. For this, the vessel was filled with the solid/liquid phase to a fill level of 80%, the phase ratio being 0.32.

[0249] The solid phase is here the TPA from example 4 and the liquid phase is the mixture of water with calcium carbonate and a surface-active substance. After first purging with nitrogen, this mixture in the gas-tight vessel was pressurized with blowing agent (butane) in the amount stated in Table 9, based on the solid phase (TPA from example 4). The vessel was heated while stirring the solid/liquid phase, and at a temperature of 50° C. the mixture was pressurized with a defined amount of nitrogen to a pressure of 8 bar. The mixture was then further heated up to the desired impregnation temperature (IMT). On reaching the impregnation temperature and impregnation pressure, the pressure in the vessel was released via a valve after a specified hold time. The precise production parameters for the experiments and the bulk densities achieved are listed in Table 9.

TABLE-US-00009 TABLE 9 Production parameters and bulk density achieved for the impregnated TPA from example 4 Blowing agent Hold time concentration based on (range IMT amount of solid phase −5° C. to IMT IMT Bulk density Name (% by wt.) +2° C.) (min) (° C.) (g/l) V17 24 11 102.5 192 V18 24 15 103.5 151 V19 24 22 105 113 V20 24 12 107 89 V21 24 17 109 87

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