EP3041877A1 - Blends of thermoplastic polyurethanes and rubbers and process for producing same - Google Patents
Blends of thermoplastic polyurethanes and rubbers and process for producing sameInfo
- Publication number
- EP3041877A1 EP3041877A1 EP14758515.2A EP14758515A EP3041877A1 EP 3041877 A1 EP3041877 A1 EP 3041877A1 EP 14758515 A EP14758515 A EP 14758515A EP 3041877 A1 EP3041877 A1 EP 3041877A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubbers
- rubber
- blends
- nitrile
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000005060 rubber Substances 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 28
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 82
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 29
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- -1 polyacetates Polymers 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229920000034 Plastomer Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229920003244 diene elastomer Polymers 0.000 claims description 6
- 229920005555 halobutyl Polymers 0.000 claims description 6
- 125000004968 halobutyl group Chemical group 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 239000005061 synthetic rubber Substances 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229920003049 isoprene rubber Polymers 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000012963 UV stabilizer Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 15
- 229920002959 polymer blend Polymers 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical class O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- SBYYCRLQTMFKSE-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene Chemical compound CC1=C(C)C(CN=C=O)=C(C)C(C)=C1CN=C=O SBYYCRLQTMFKSE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VIOMIGLBMQVNLY-UHFFFAOYSA-N 4-[(4-amino-2-chloro-3,5-diethylphenyl)methyl]-3-chloro-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C(=C(CC)C(N)=C(CC)C=2)Cl)=C1Cl VIOMIGLBMQVNLY-UHFFFAOYSA-N 0.000 description 1
- LKHVCEWNPKEPBT-UHFFFAOYSA-N 4-[(4-amino-3-methoxyphenyl)methyl]-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC(CC=2C=C(OC)C(N)=CC=2)=C1 LKHVCEWNPKEPBT-UHFFFAOYSA-N 0.000 description 1
- FLNVGZMDLLIECD-UHFFFAOYSA-N 4-[(4-amino-3-methyl-5-propan-2-ylphenyl)methyl]-2-methyl-6-propan-2-ylaniline Chemical compound CC1=C(N)C(C(C)C)=CC(CC=2C=C(C(N)=C(C)C=2)C(C)C)=C1 FLNVGZMDLLIECD-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- KZTROCYBPMKGAW-UHFFFAOYSA-N 4-[[4-amino-3,5-di(propan-2-yl)phenyl]methyl]-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=C(N)C(C(C)C)=CC(CC=2C=C(C(N)=C(C(C)C)C=2)C(C)C)=C1 KZTROCYBPMKGAW-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- GMKSMTJXIGEYLX-UHFFFAOYSA-N n,n'-bis(2-ethyl-6-methylphenyl)methanediamine Chemical compound CCC1=CC=CC(C)=C1NCNC1=C(C)C=CC=C1CC GMKSMTJXIGEYLX-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- the invention relates to the field of chemistry and relates to blends of thermoplastic polyurethanes and rubbers, as can be used, for example, for applications in which good mechanical properties, good tear and abrasion resistance, good damping properties, high chemical resistance are required, such as for rollers and roll covers in the printing, textile, paper and graphic industry, industrial wheels, bumpers, pump impellers or drive belts, and a method for their manufacture.
- polymer blends are mixtures of chemically different polymers, the chemical diversity of the polymers causing their non- and partial miscibility. Polymer blends are characterized by their chemical structure, the conformation of their chain molecules in the molecular range and their morphology in the order of molecular structure.
- Polymer blends can have improved mechanical and tribological properties compared to the individual polymers, since in this case the properties of the polymer blends result from the combination of the properties of the polymers involved (Ott, KH, et al .: Kunststoffhandbuch, Polymerblends, 1, Carl Hanser Verlag, 1993 ).
- polymer blends are defined as a macroscopically homogeneous mixture of two or more different polymers. They are usually produced by intensive mechanical mixing of molten polymers, resulting in a homogeneous material. When the melt cools, the polymer chains remain finely divided, thus ensuring that the property profile of the blend is a permanent superposition of the properties of the individual polymers (Wikipedia, keyword polymer blend).
- compositions of polyurethanes and rubbers are known in the art.
- thermoplastic polyurethane elastomer blend which is composed of at least 30 to at most 40% by volume of a polyurethane component and at least 60 to at most 70% by volume of a nitrile rubber and has a Shore A hardness from about 55 to 70 with added plasticizer.
- the polyurethane component contains at least 50% by weight of polyisocyanate and the nitrile rubber component contains about 34% by mol of acrylonitrile.
- thermoplastic polyurethane having a glass transition temperature of less than 60 ° C and a rubbery material from the group of rubbers, thermoplastic elastomers, thermoplastic vulcanizates and plastomers, which has a glass transition temperature of less than -20 ° C have.
- the weight ratio of the thermoplastic polyurethane to the rubber is at most 50:50.
- thermoplastic polymer blend comprising polyvinyl chloride, polyether urethane and a butadiene-acrylonitrile copolymer, wherein the mixture 65 to 80 parts by weight of the polyvinyl halide resin having a specific viscosity of 0.28 to 0.4, 5 bis 25 parts by weight of an unhardened aliphatic hydrocarbon-diene-aliphatic nitrile rubber copolymer having a Mooney viscosity of 47 to 70 and 5 to 25 parts by weight of a polyether polyurethane having a 350 ° F melt index of 0 to 100.
- the plasticizer is a mixture consisting of 25% to 75% of an ester plasticizer and 75% to 25% of a viscous liquid reaction product of a polyurethane elastomer with an amine, wherein the ester plasticizer has general compatibility with the rubber and the Polyurethane reaction product, dioctyl phthalate, dibutyl phthalate, Dioctyladipat and Dioctylsebacat has.
- US Pat. No. 4,374,192 discloses an electrophotographic developer consisting of coated carrier particles together with toner particles, the coating consisting of a mixture of a butadiene-acrylonitrile rubber.
- the blend contains 20% to 40% by weight of acrylonitrile and a polyurethane elastomer and is soluble in organic solvents.
- thermoplastic polymer blends have insufficient physical properties. It is also disadvantageous that known processes for producing thermoplastic polymer blends are energy-consuming and expensive.
- the object of the present invention is to provide blends of thermoplastic polyurethanes and rubbers which have improved physical properties and a simple energy and inexpensive process for their preparation.
- thermoplastic polyurethanes and rubbers consist of rubber or a rubber mixture and 5 to 80 wt .-%, based on the blend, of one or more thermoplastic polyurethanes which are homogenized in the rubber or in the rubber mixture, and wherein in the contact areas between gums or rubber compounds and polyurethanes gearing the materials together.
- rubbers or rubber mixtures synthetic rubbers, natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl, nitrile-butadiene rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof, advantageously vulcanized rubbers or rubber compounds.
- thermoplastic polyurethanes advantageously up to 70 wt .-%, based on the blend, thermoplastic polyurethanes present.
- At least one rubber or a rubber mixture is homogenized, after homogenization of which 5 to 80% by weight precursors of polyurethanes, based on the blend, are added and homogenized, the precursors
- Monomers of one or more polyisocyanates, macroglycols and chain extenders are monomers of one or more polyisocyanates, macroglycols and chain extenders.
- Synthetic rubbers natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof are advantageously used as rubbers or rubber mixtures.
- diene rubbers and / or hydrogenated diene rubbers are diene rubbers and / or hydrogenated diene rubbers, in particular nitrile rubbers, such as nitrile-butadiene rubbers, carboxylated nitrile-butadiene rubbers, hydrogenated nitrile-butadiene rubbers, hydrogenated carboxylated nitrile-butadiene rubbers, nitrile-isoprene rubbers. Rubbers, butadiene rubbers and / or styrene-butadiene rubbers can be used.
- nitrile rubbers such as nitrile-butadiene rubbers, carboxylated nitrile-butadiene rubbers, hydrogenated nitrile-butadiene rubbers, hydrogenated carboxylated nitrile-butadiene rubbers, nitrile-isoprene rubbers. Rubbers, butadiene rubbers and / or styrene-butad
- polyisocyanates used are aliphatic, aromatic, cycloaliphatic and / or araliphatic polyisocyanates, in particular diisocyanates.
- macroglycols are used based on polyolefins, polycarbonates, polyacetates, polysiloxanes, polycaprolactones, Polyesters, polyethers and / or block copolymers of polyester and polyether or mixtures thereof.
- amine-based compounds multifunctional compounds containing isocyanate-reactive hydrogen atoms, diols, diamine and / or mixtures of these materials are used as chain extenders.
- the prepolymer is prepared by mixing and reacting polyisocyanate (s) and macroglycol (s).
- vulcanizing agents such as sulfur compounds, accelerated sulfur compounds, peroxides, hydrogen peroxide coagens compounds, phenolic resins, catalysts, plasticizer oils, organic fillers, inorganic fillers, antioxidants, plasticizers, UV stabilizers , Flame retardants and / or additives used.
- homogenization and vulcanization are realized in an internal mixer, a rolling mill and / or an extruder.
- thermoplastic polyurethanes and rubbers by a process which have improved physical properties and can be prepared simply, as well as energy and inexpensively.
- the blends according to the invention consist of thermoplastic polyurethanes and rubbers, wherein in the blends 5 to 80 wt .-%, based on the blend, of one or more thermoplastic polyurethanes are present which are homogenized in the rubber or in the rubber mixture, and in the contact areas between rubber or rubber compounds and polyurethanes gearing the materials together.
- rubbers or rubber mixtures are advantageously vulcanized rubbers or vulcanized rubber mixtures, synthetic rubbers, natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl, nitrile-butadiene rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof.
- the blend contains up to 70% by weight of thermoplastic polyurethanes which are homogenized in the rubber or in the rubber mixture and have toothings of the materials with one another in the contact regions between rubber or rubber mixtures and polyurethanes.
- the blends according to the invention are prepared by a process in which at least one rubber or a rubber mixture is homogenized. Subsequently, 5 to 80 wt .-% precursors of polyurethanes, based on the blend, are added and homogenized with the rubber or the rubber mixture. These precursors are
- Monomers of one or more polyisocyanates, macroglycols and chain extenders are monomers of one or more polyisocyanates, macroglycols and chain extenders.
- a prepolymer of polyisocyanate (s) and macroglycol (s) is prepared by mixing and reactive reaction and added together with at least one chain extender to the rubber or rubber mixture.
- the resulting polymer blend is advantageously subjected to a vulcanization process of the rubber or the rubber mixture.
- the prepolymer prepared from polyisocyanates and macroglycols
- the monomers of polyisocyanates and macroglycols can be used together with the chain extender for the in-situ formation of thermoplastic polyurethane in the rubber directly.
- in-situ synthesized polyurethane is formed by the addition of the precursors during mixing with the rubber or the rubber mixture, which forms an improved homogenization and in the contact areas of polyurethane and rubber, a toothing of the materials what to improved properties of the blend according to the invention, such as an improved modulus of elasticity, increased breaking stress, elongation at break and hardness with reduced abrasion behavior leads.
- the blend according to the invention has an isocyanate index of 90 to 110.
- the isocyanate index is understood to mean the percentage ratio of isocyanate groups to isocyanate-reactive hydrogen atoms in the blend.
- thermoplastic polyurethanes and rubbers can be produced with advantageous properties when the Polyurethane precursors / precursors of a prepolymer of polyisocyanate (s) and macroglycol (s) and chain extenders or monomers of polyisocyanate (s) and macroglycol (s) and chain extenders are synthesized in-situ during homogenization and advantageously vulcanization of the rubbers to thermoplastic polyurethanes ,
- Organic polyisocyanates used according to the invention are advantageously aliphatic, aromatic, cycloaliphatic and araliphatic polyisocyanates, especially diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-disocyanates, tetramethyl-m-xylylene diisocyanate, tetramethyl-p-xylylene diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanates, preferably 4,4'-diphenylmethane diisocyanate, optionally with isomers of diphenylmethane diisocyanate.
- the polyisocyanate used according to the invention may also be a compound having reactive isocyanate side groups, as is known in polyurethane technology.
- macroglycols also called polyols, which are based on polyolefins, polycarbonates, polyacetates, polysiloxanes, preferably polycaprolactone, polyesters, polyethers, block copolymers of polyester / polyethers and the like, and mixtures thereof.
- Saturated and / or unsaturated polyols can also be used according to the invention.
- Chain extenders which may advantageously be used are multifunctional and in particular diisocyanate-reactive hydrogen-containing compounds, preferably diols and more preferably diamines or a mixture of different types.
- the amine-based chain extenders, preferably diamines may be selected from the following classes of compounds: 4,4'-methylenedianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-methylenebis (2-methoxyaniline), bis (4-amino-2-chloro-3,5-diethylphenyl) -methane, 4,4'-methylenebis (2-6-diethylaniline), 4,4'-methylenebis (2-methyl-aniline), 4,4 Methylene-bis (2-6-dimethyl-aniline), 4,4'-methylenebis (2-isopropyl-6-methyl-aniline), 4,4'-methylenebis (2,6-diisopropylaniline) , Diethyl
- the rubber component may be selected from any conventional rubbers known in the art. From polar rubbers such as nitrile-butadiene rubber, carboxylated nitrile-butadiene rubber, hydrogenated nitrile-butadiene rubber, hydrogenated carboxylated nitrile-butadiene rubber, nitrile-isoprene rubber, acrylate rubber, chloroprene rubber, halobutyl rubber, Polyurethane rubber and the like; also from non-polar rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber and the like, or also from mixtures of different rubbers.
- the rubber component may also consist of thermoplastic elastomers, thermoplastic vulcanizates, plastomers or other rubbery materials.
- the rubber component of this invention are, in particular, diene rubbers, hydrogenated diene rubbers, preferably nitrile rubber, and advantageously nitrile-butadiene rubber.
- the rubber component is preferably crosslinked by conventional vulcanization or electron beam induced vulcanization.
- Typical crosslinkers are sulfur compounds, accelerated sulfur compounds, peroxides, hydrogen peroxide-coagens compounds, phenolic resins, and / or combinations thereof.
- Auxiliaries and additives typical of polyurethane and rubber technology can also be used. This includes the use of compatibilizers, such as surfactants, to adjust the interfacial tension between the polyurethane and rubber phases.
- compatibilizers such as surfactants
- the in situ process of the present invention can be accomplished using conventional internal mixers, rolling mills or extruders known in the art.
- the process according to the invention is also particularly advantageous since highly reactive and high molecular weight amine-based chain extenders can be used without the use of a catalyst in order to obtain the blend according to the invention, which consists of a matrix of rubber in which polyurethane is distributed in finely dispersed form. It is advantageous that with the diamine content of the chain extender in the in-situ synthesized thermoplastic polyurethanes, a significant mechanical reinforcement of the blend is achieved.
- the inventive method allows a high degree of flexibility in the adaptation of the soft and hard segments of the in-situ synthesized thermoplastic polyurethanes and leads to significantly improved physical properties, in particular in tensile and abrasion resistance.
- nitrile-butadiene rubber 100 g are kneaded in a heated internal mixer (Haake Rheomix 600P) at 120 ° C. and 60 rpm for 5 minutes. following 8.2 g of prepolymer (methylene diphenyl diisocyanates, polyester-based prepolymer, with 8.54 wt .-% isocyanates) and 2.9 g of 4,4 '- (m-phenylene diisopropylidene) anilines are pre-mixed as a chain extender and added to the mixing in the rubber and the components. 5 Minutes mixed at 120 ° C. The added starting materials have an isocyanate index of 100.
- prepolymer methylene diphenyl diisocyanates, polyester-based prepolymer, with 8.54 wt .-% isocyanates
- 4,4 '- (m-phenylene diisopropylidene) anilines 5 Minutes mixed at 120 ° C.
- the resulting mixture is then mixed on a rolling mill (Servitec Polymix 1 1 OL) for 10 minutes with 5 g of zinc oxides, 2 g of stearic acid, 1, 7 g of N-cyclohexyl-2-benzothiazolylsulfenamid (CBS) and 2 g of sulfur and then on a Heating press vulcanized at a temperature of 150 ° C and a pressure of 15 MPa.
- a rolling mill Server Polymix 1 1 OL
- CBS N-cyclohexyl-2-benzothiazolylsulfenamid
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Abstract
Description
Blends aus thermoplastischen Polyurethanen und Kautschuken und Verfahren zu ihrer Herstellung Blends of thermoplastic polyurethanes and rubbers and process for their preparation
Die Erfindung bezieht sich auf das Gebiet der Chemie und betrifft Blends aus thermoplastischen Polyurethanen und Kautschuken, wie sie beispielsweise für Anwendungen eingesetzt werden können, bei denen gute mechanische Eigenschaften, gute Reiß- und Abriebfestigkeiten, gute Dämpfungseigenschaften, hohe Chemikalienbeständigkeiten erforderlich sind, wie für Walzen und Walzenbezüge in der Druck-, Textil-, Papier- und grafischen Industrie, Industrie-Räder, Stoßstangen, Pumpenlaufräder oder Treibriemen, und ein Verfahren zu ihrer Herstellung. The invention relates to the field of chemistry and relates to blends of thermoplastic polyurethanes and rubbers, as can be used, for example, for applications in which good mechanical properties, good tear and abrasion resistance, good damping properties, high chemical resistance are required, such as for rollers and roll covers in the printing, textile, paper and graphic industry, industrial wheels, bumpers, pump impellers or drive belts, and a method for their manufacture.
Das Interesse der anwendungsorientierten Polymerforschung orientiert sich auch auf die Kombination an sich bekannter Polymere, um deren Eigenschaften miteinander kombinieren zu können. Das Ergebnis solcher Kombinationen sind sogenannte Polymerblends. Als Polymerblends werden Mischungen chemisch unterschiedlicher Polymere bezeichnet, wobei die chemische Verschiedenheit der Polymere deren Nicht- und Teilmischbarkeit bedingt. Polymerblends sind charakterisiert durch ihren chemischen Aufbau, die Konformation ihrer Kettenmoleküle im molekularen Bereich und ihren als Morphologie bezeichneten Ordnungszustand im übermolekularen Bereich. Die beim Mischen von verschiedenen Polymeren entstehenden Polymerblends können verbesserte mechanische und tribologische Eigenschaften gegenüber den einzelnen Polymeren aufweisen, da sich hierbei die Eigenschaften der Polymerblends aus der Kombination der Eigenschaften der beteiligten Polymere ergeben (Ott, K.H., et.al.: Kunststoffhandbuch, Polymerblends, 1 , Carl Hanser Verlag, 1993). The interest of application-oriented polymer research is also based on the combination of polymers known per se in order to be able to combine their properties with one another. The result of such combinations are so-called polymer blends. Polymer blends are mixtures of chemically different polymers, the chemical diversity of the polymers causing their non- and partial miscibility. Polymer blends are characterized by their chemical structure, the conformation of their chain molecules in the molecular range and their morphology in the order of molecular structure. The resulting from the mixing of different polymers Polymer blends can have improved mechanical and tribological properties compared to the individual polymers, since in this case the properties of the polymer blends result from the combination of the properties of the polymers involved (Ott, KH, et al .: Kunststoffhandbuch, Polymerblends, 1, Carl Hanser Verlag, 1993 ).
Mischungen mehrerer Polymere werden als Polymerblends bezeichnet. Diese sind als makroskopisch homogene Mischung von zwei oder mehr verschiedenen Polymeren definiert. Hergestellt werden sie meist durch intensive mechanische Vermischung von geschmolzenen Polymeren, wobei sich ein homogenes Material ergibt. Beim Abkühlen der Schmelze bleiben die Polymerketten fein verteilt und sorgen so dafür, dass das Eigenschaftsprofil des Blends eine auf Dauer erhalten bleibende Überlagerung der Eigenschaften der einzelnen Polymere ist (Wikipedia, Stichwort Polymerblend). Mixtures of several polymers are called polymer blends. These are defined as a macroscopically homogeneous mixture of two or more different polymers. They are usually produced by intensive mechanical mixing of molten polymers, resulting in a homogeneous material. When the melt cools, the polymer chains remain finely divided, thus ensuring that the property profile of the blend is a permanent superposition of the properties of the individual polymers (Wikipedia, keyword polymer blend).
Aus dem Stand der Technik sind zahlreiche Zusammensetzungen aus Polyurethanen und Kautschuken bekannt. Numerous compositions of polyurethanes and rubbers are known in the art.
Bekannt aus der US 5376723 ist ein thermoplastischer Polyurethan-Elastomer- Blend, welcher sich aus mindestens 30 bis höchstens 40 Vol.-% einer Polyurethan- Komponente und mindestens 60 bis höchstens 70 Vol.-% eines Nitrilkautschuks zusammensetzt und eine Shore-A-Härte von etwa 55 bis 70 bei zugesetztem Weichmacher aufweist. Dabei beinhaltet die Polyurethan-Komponente mindestens 50 Gew.-% Polyisocyanat und die Nitril-Kautschuk-Komponente etwa 34 Mol-% Acrylnitril. Known from US Pat. No. 5,377,623 is a thermoplastic polyurethane elastomer blend which is composed of at least 30 to at most 40% by volume of a polyurethane component and at least 60 to at most 70% by volume of a nitrile rubber and has a Shore A hardness from about 55 to 70 with added plasticizer. In this case, the polyurethane component contains at least 50% by weight of polyisocyanate and the nitrile rubber component contains about 34% by mol of acrylonitrile.
Aus der US 6291587 ist ein Komposit bekannt, dass aus einem harten thermoplastischen Polyurethan mit einer Glasübergangstemperatur von weniger als 60°C und einem gummiartigen Material aus der Gruppe der Kautschuke, thermoplastischen Elastomeren, thermoplastischen Vulkanisaten und Piastomeren, die eine Glasübergangstemperatur von weniger als -20°C aufweisen. Das Gewichtsverhältnis des thermoplastischen Polyurethans zum Kautschuk beträgt dabei höchstens 50:50. From US 6291587 a composite is known that consists of a hard thermoplastic polyurethane having a glass transition temperature of less than 60 ° C and a rubbery material from the group of rubbers, thermoplastic elastomers, thermoplastic vulcanizates and plastomers, which has a glass transition temperature of less than -20 ° C have. The weight ratio of the thermoplastic polyurethane to the rubber is at most 50:50.
Weiterhin bekannt aus der US 3678129 ist ein thermoplastischer Polymerblend, beinhaltend Polyvinylchlorid, Polyetherurethan und ein Butadien-Acrylnitril-Copolymer, wobei die Mischung 65 bis 80 Gew.-Teile des Polyvinylhalogenidharzes mit einer spezifischen Viskosität von 0,28 bis 0,4, 5 bis 25 Gew.-Teile eines ungehärteten aliphatischen Kohlenwasserstoff-Dien-aliphatischen Nitril Kautschuk-Copolymers mit einer Mooney Viskosität von 47 bis 70 sowie 5 bis 25 Gew.-Teile eines Polyether- Polyurethan mit einem 350° F Schmelzindex von 0 bis 100 aufweist. Further known from US 3678129 is a thermoplastic polymer blend comprising polyvinyl chloride, polyether urethane and a butadiene-acrylonitrile copolymer, wherein the mixture 65 to 80 parts by weight of the polyvinyl halide resin having a specific viscosity of 0.28 to 0.4, 5 bis 25 parts by weight of an unhardened aliphatic hydrocarbon-diene-aliphatic nitrile rubber copolymer having a Mooney viscosity of 47 to 70 and 5 to 25 parts by weight of a polyether polyurethane having a 350 ° F melt index of 0 to 100.
Auch bekannt aus US 4143092 ist ein Verfahren zur Modifizierung der Härte eines Acrylnitril-Kautschuks, bei dem beim Mischen eines Gummi-Präpolymers mit einem Härter die Menge an Weichmacher zugegeben wird, um die Härte des gehärteten Kautschuks auf die gewünschte Härte der Kautschuk-Mischung einzustellen. Hierbei ist der Weichmacher eine Mischung, bestehend aus 25% bis 75% eines Ester- Weichmachers und 75% bis 25% eines viskosen flüssigen Reaktionsproduktes aus einem Polyurethan-Elastomer mit einem Amin, wobei der Ester-Weichmacher allgemeine verträgliche Eigenschaften mit dem Kautschuk und dem Polyurethan- Reaktionsprodukt, Dioctylphthalat, Dibutylphthalat, Dioctyladipat und Dioctylsebacat aufweist. Also known from US 4143092 is a method for modifying the hardness of an acrylonitrile rubber, in which, when mixing a rubber prepolymer with a curing agent, the amount of plasticizer is added to adjust the hardness of the cured rubber to the desired hardness of the rubber compound , Here, the plasticizer is a mixture consisting of 25% to 75% of an ester plasticizer and 75% to 25% of a viscous liquid reaction product of a polyurethane elastomer with an amine, wherein the ester plasticizer has general compatibility with the rubber and the Polyurethane reaction product, dioctyl phthalate, dibutyl phthalate, Dioctyladipat and Dioctylsebacat has.
Weiterhin ist aus der US 4374192 ein elektrofotografischer Entwickler bekannt, bestehend aus beschichteten Trägerteilchen gemeinsam mit Tonerpartikeln, wobei die Beschichtung aus einer Mischung eines Butadien-Acrylnitril-Kautschuks besteht. Die Mischung beinhaltend 20% bis 40 Gew.-% Acrylnitril und ein Polyurethan- Elastomer und ist in organischen Lösungsmitteln löslich. Furthermore, US Pat. No. 4,374,192 discloses an electrophotographic developer consisting of coated carrier particles together with toner particles, the coating consisting of a mixture of a butadiene-acrylonitrile rubber. The blend contains 20% to 40% by weight of acrylonitrile and a polyurethane elastomer and is soluble in organic solvents.
Bekannt ist auch die Synthese von Polyurethan durch die gleichzeitige Umsetzung von Hydroxyl-terminierten Polybutadien, Toluoldiisocyanat und dem Vernetzer 1 ,1 ,1 - Trimethylolpropan in Lösung, welche Nitril-Butadien-Kautschuk, Schwefel und Füllstoff enthält (Desai, S.; et al: J. Macromol. Sei. 2001 , 38, 71 1 -729). Also known is the synthesis of polyurethane by the simultaneous reaction of hydroxyl-terminated polybutadiene, toluene diisocyanate and crosslinker 1, 1, 1-trimethylolpropane in solution containing nitrile-butadiene rubber, sulfur and filler (Desai, S., et al : J. Macromol, Sci., 2001, 38, 71 1 -729).
Ebenfalls bekannt ist die Herstellung von Mischungen aus selbstsynthetisierten Polyurethan-Ionomeren und Nitril-Butadien-Kautschuk durch ein Schmelzmischverfahren. Hierbei werden die Mischungen mit Schwefelvernetzern vulkanisiert und gleichzeitig durch Triisocyanat vernetzt (Dimitrievski, I.: Adv. Poly. Blends & Alloys, 1993, 4,19-29). Also known is the preparation of blends of self-synthesized polyurethane ionomers and nitrile butadiene rubber by a melt blending process. Here, the mixtures are vulcanized with sulfur crosslinkers and simultaneously crosslinked by triisocyanate (Dimitrievski, I .: Adv. Poly. Blends & Alloys, 1993, 4, 19-29).
Weiterhin bekannt ist die Herstellung einer Mischung von Polyurethan- Prä kursorsystemen, bestehend aus kristallinen Polyol- und Polyisocyanat- Verbindungen und Peroxid härtbaren hydrierten Nitril-Butadien-Kautschuk (Sebenik, U., et.al.: Appl. Poly.Sci. 2012, 125, E41 -E48; Karger-Kocsis, J. et al;, Wear 2010, 268, 464-472). Dabei wird eine gleichzeitige Reaktion des Polyurethan-Präkursor nach Deblockierung der Polyisocyanatverbindung und die Vernetzung des hydrierten Nitril-Butadien-Kautschuk während des Vulkanisationsvorganges erreicht. Also known is the preparation of a mixture of polyurethane precursor systems consisting of crystalline polyol and polyisocyanate compounds and peroxide-curable hydrogenated nitrile-butadiene rubber (Sebenik, U., et al .: Appl. Poly.Sci. 125, E41-E48; Karger-Kocsis, J. et al; Wear 2010, 268, 464-472). This is a simultaneous reaction of the polyurethane precursor achieved after deblocking of the polyisocyanate compound and the crosslinking of the hydrogenated nitrile-butadiene rubber during the vulcanization process.
Weiterhin bekannt ist die Herstellung von Polyurethan-Silica-Hybrid-Netzwerken und Acrylnitril-Butadien-Kautschuk durch Schmelzmischen. Hierbei wird eine Reaktion von Isocyanat-terminierten Präpolymeren mit den Hydroxylgruppen auf Silica- Oberflächen vorgeschlagen, welche bei der Vernetzung des Nitril-Butadien- Kautschuks auftritt (Tan, J.H.: eXPRESS Poly. Lett. 2012, 6, 588-600). Also known is the production of polyurethane-silica hybrid networks and acrylonitrile-butadiene rubber by melt blending. Herein, a reaction of isocyanate-terminated prepolymers with the hydroxyl groups on silica surfaces is proposed, which occurs in the crosslinking of the nitrile-butadiene rubber (Tan, J.H .: eXPRESS Poly. Lett. 2012, 6, 588-600).
Nachteile des Standes der Technik sind, das bekannte thermoplastische Polymerblends unzureichende physikalische Eigenschaften aufweisen. Auch ist es nachteilig, dass bekannte Verfahren zum Herstellen von thermoplastischen Polymerblends energie- und kostenaufwendig sind. Disadvantages of the prior art are that known thermoplastic polymer blends have insufficient physical properties. It is also disadvantageous that known processes for producing thermoplastic polymer blends are energy-consuming and expensive.
Die Aufgabe der vorliegenden Erfindung besteht darin, Blends aus thermoplastischen Polyurethanen und Kautschuken anzugeben, die verbesserte physikalische Eigenschaften aufweisen und ein einfaches energie- und kostengünstiges Verfahren zu ihrer Herstellung. The object of the present invention is to provide blends of thermoplastic polyurethanes and rubbers which have improved physical properties and a simple energy and inexpensive process for their preparation.
Die Aufgabe wird durch die in den Ansprüchen angegebene Erfindung gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche. The object is achieved by the invention specified in the claims. Advantageous embodiments of the invention are the subject of the dependent claims.
Die erfindungsgemäßen Blends aus thermoplastischen Polyurethanen und Kautschuken bestehen aus Kautschuk oder einer Kautschukmischung und 5 bis 80 Gew.-%, bezogen auf den Blend, von einem oder mehreren thermoplastischen Polyurethanen, welche homogenisiert im Kautschuk oder in der Kautschukmischung vorliegen, und wobei in den Kontaktbereichen zwischen Kautschuk oder Kautschukmischungen und Polyurethanen Verzahnungen der Materialien miteinander vorliegen. The blends of thermoplastic polyurethanes and rubbers according to the invention consist of rubber or a rubber mixture and 5 to 80 wt .-%, based on the blend, of one or more thermoplastic polyurethanes which are homogenized in the rubber or in the rubber mixture, and wherein in the contact areas between gums or rubber compounds and polyurethanes gearing the materials together.
Vorteilhafterweise sind als Kautschuke oder Kautschukmischungen, synthetische Kautschuke, Naturkautschuke, Acrylat-, Chloropren-, Halogenbutyl-, Polyurethan-, Isopren-, Butyl-, Nitril-Butadien-Kautschuke, thermoplastische Elastomere, thermoplastische Vulkanisate und/oder Plastomere oder deren Mischungen, vorteilhafterweise vulkanisierte Kautschuke oder Kautschukmischungen, vorhanden. Ebenfalls vorteilhafterweise sind bis 70 Gew.-%, bezogen auf den Blend, thermoplastische Polyurethane vorhanden. Advantageously, as rubbers or rubber mixtures, synthetic rubbers, natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl, nitrile-butadiene rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof, advantageously vulcanized rubbers or rubber compounds. Likewise advantageously up to 70 wt .-%, based on the blend, thermoplastic polyurethanes present.
Bei dem erfindungsgemäßen Verfahren zur Herstellung von Blends aus thermoplastischen Polyurethanen und Kautschuken wird mindestens ein Kautschuk oder eine Kautschukmischung homogenisiert, wobei nach der Homogenisierung 5 bis 80 Gew.-% Präkursoren von Polyurethanen, bezogen auf den Blend, zugegeben und homogenisiert werden, wobei die Präkursoren In the process according to the invention for producing blends of thermoplastic polyurethanes and rubbers, at least one rubber or a rubber mixture is homogenized, after homogenization of which 5 to 80% by weight precursors of polyurethanes, based on the blend, are added and homogenized, the precursors
- ein oder mehrere Präpolymere aus Polyisocyanat(en) und Makroglykol(en) und mindestens ein Kettenverlängerer sind, one or more prepolymers of polyisocyanate (s) and macroglycol (s) and at least one chain extender,
und/oder and or
Monomere eines oder mehrerer Polyisocyanate, Makroglykole und Kettenverlängerer. Monomers of one or more polyisocyanates, macroglycols and chain extenders.
Vorteilhafterweise werden als Kautschuke oder Kautschukmischungen synthetische Kautschuke, Naturkautschuke, Acrylat-, Chloropren-, Halogenbutyl-, Polyurethan-, Isopren-, Butyl-Kautschuke, thermoplastische Elastomere, thermoplastische Vulkanisate und/oder Plastomere oder deren Mischungen eingesetzt. Synthetic rubbers, natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof are advantageously used as rubbers or rubber mixtures.
Ebenfalls vorteilhafterweise werden als Kautschuke oder Kautschukmischungen Dienkautschuke und/oder hydrierte Dienkautschuke, insbesondere Nitrilkautschuke, wie Nitril-Butadien-Kautschuke, carboxylierte Nitril-Butadien-Kautschuke, hydrierte Nitril-Butadien-Kautschuke, hydrierte carboxylierter Nitril-Butadien-Kautschuke, Nitril- Isopren-Kautschuke, Butadien-Kautschuke und/oder Styrol-Butadien-Kautschuke eingesetzt werden. Also advantageously used as rubbers or rubber mixtures are diene rubbers and / or hydrogenated diene rubbers, in particular nitrile rubbers, such as nitrile-butadiene rubbers, carboxylated nitrile-butadiene rubbers, hydrogenated nitrile-butadiene rubbers, hydrogenated carboxylated nitrile-butadiene rubbers, nitrile-isoprene rubbers. Rubbers, butadiene rubbers and / or styrene-butadiene rubbers can be used.
Weiterhin vorteilhafterweise werden als Polyisocyanate aliphatische, aromatische, cycloaliphatische und/oder araliphatische Polyisocyanate, insbesondere Diisocyanate, eingesetzt. Further advantageously, the polyisocyanates used are aliphatic, aromatic, cycloaliphatic and / or araliphatic polyisocyanates, in particular diisocyanates.
Und auch vorteilhafterweise werden Makroglykole eingesetzt basierend auf Polyolefinen, Polycarbonaten, Polyacetaten, Polysiloxanen, Polycaprolactonen, Polyestern, Polyethern und/oder Blockcopolymeren aus Polyester und Polyether oder Mischungen davon. And also advantageously, macroglycols are used based on polyolefins, polycarbonates, polyacetates, polysiloxanes, polycaprolactones, Polyesters, polyethers and / or block copolymers of polyester and polyether or mixtures thereof.
Vorteilhaft ist es auch, wenn als Kettenverlängerer Amin-basierte Verbindungen, multifunktionale, Isocyanat-reaktive Wasserstoffatome enthaltende Verbindungen, Diole, Diamin und/oder Mischungen dieser Materialien eingesetzt werden. It is also advantageous if amine-based compounds, multifunctional compounds containing isocyanate-reactive hydrogen atoms, diols, diamine and / or mixtures of these materials are used as chain extenders.
Weiterhin vorteilhaft ist es, wenn das Prapolymer durch Mischung und reaktive Umsetzung von Polyisocyanat(en) und Makroglykol(en) hergestellt wird. It is furthermore advantageous if the prepolymer is prepared by mixing and reacting polyisocyanate (s) and macroglycol (s).
Ebenfalls vorteilhaft ist es, wenn Vulkanisationsmittel, Vernetzer und/oder Hilfs- und Zusatzstoffe, wie Schwefelverbindungen, beschleunigte Schwefelverbindungen, Peroxide, Wasserstoffperoxid-Koagens-Verbindungen, Phenolharze, Katalysatoren, Weichmacheröle, organische Füllstoffe, anorganische Füllstoffe, Antioxidantien, Weichmacher, UV-Stabilisatoren, Flammschutzmittel und/oder Additive, eingesetzt werden. It is also advantageous if vulcanizing agents, crosslinking agents and / or auxiliaries and additives, such as sulfur compounds, accelerated sulfur compounds, peroxides, hydrogen peroxide coagens compounds, phenolic resins, catalysts, plasticizer oils, organic fillers, inorganic fillers, antioxidants, plasticizers, UV stabilizers , Flame retardants and / or additives used.
Und auch vorteilhaft ist es, wenn 5 - 80 Gew.-%, bezogen auf den Blend, an Präpolymer aus Polyisocyanat(en) und Makroglykol(en), zusammen mit Kettenverlängerern zugegeben und homogenisiert werden. It is also advantageous if 5-80% by weight, based on the blend, of prepolymer of polyisocyanate (s) and macroglycol (s), together with chain extenders, are added and homogenized.
Von Vorteil ist es auch, wenn die Homogenisierung und Vulkanisation in einem Innenmischer, einem Walzwerk und/oder einem Extruder realisiert werden. It is also advantageous if the homogenization and vulcanization are realized in an internal mixer, a rolling mill and / or an extruder.
Mit der erfinderischen Lösung wird es erstmals möglich, einen Blend aus thermoplastischen Polyurethanen und Kautschuken mit einem Verfahren bereitzustellen, die verbesserte physikalische Eigenschaften aufweisen und einfach sowie energie- und kostengünstig hergestellt werden können. With the inventive solution, it becomes possible for the first time to provide a blend of thermoplastic polyurethanes and rubbers by a process which have improved physical properties and can be prepared simply, as well as energy and inexpensively.
Die erfindungsgemäßen Blends bestehen dabei aus thermoplastischen Polyurethanen und Kautschuken, wobei in den Blends 5 bis 80 Gew.-%, bezogen auf den Blend, von einem oder mehreren thermoplastischen Polyurethanen vorhanden sind, die homogenisiert im Kautschuk oder in der Kautschukmischung vorliegen, und in den Kontaktbereichen zwischen Kautschuk oder Kautschukmischungen und Polyurethanen Verzahnungen der Materialien miteinander vorliegen. The blends according to the invention consist of thermoplastic polyurethanes and rubbers, wherein in the blends 5 to 80 wt .-%, based on the blend, of one or more thermoplastic polyurethanes are present which are homogenized in the rubber or in the rubber mixture, and in the contact areas between rubber or rubber compounds and polyurethanes gearing the materials together.
Die erfindungsgemäß vorhandenen Kautschuke oder Kautschukmischungen sind vorteilhafterweise vulkanisierte Kautschuke oder vulkanisierte Kautschukmischungen, synthetische Kautschuke, Naturkautschuke, Acrylat-, Chloropren-, Halogenbutyl-, Polyurethan-, Isopren-, Butyl-, Nitril-Butadien- Kautschuke, thermoplastische Elastomere, thermoplastische Vulkanisate und/oder Plastomere oder deren Mischungen. The present invention rubbers or rubber mixtures are advantageously vulcanized rubbers or vulcanized rubber mixtures, synthetic rubbers, natural rubbers, acrylate, chloroprene, halobutyl, polyurethane, isoprene, butyl, nitrile-butadiene rubbers, thermoplastic elastomers, thermoplastic vulcanizates and / or plastomers or mixtures thereof.
Vorteilhafterweise sind im Blend bis 70 Gew.-% an thermoplastischen Polyurethanen vorhanden, welche homogenisiert im Kautschuk oder in der Kautschukmischung vorliegen und in den Kontaktbereichen zwischen Kautschuk oder Kautschukmischungen und Polyurethanen Verzahnungen der Materialien miteinander aufweisen. Advantageously, the blend contains up to 70% by weight of thermoplastic polyurethanes which are homogenized in the rubber or in the rubber mixture and have toothings of the materials with one another in the contact regions between rubber or rubber mixtures and polyurethanes.
Erfindungsgemäß hergestellt werden die erfindungsgemäßen Blends durch ein Verfahren, bei dem mindestens ein Kautschuk oder eine Kautschukmischung homogenisiert wird. Nachfolgend werden 5 bis 80 Gew.-% Präkursoren von Polyurethanen, bezogen auf den Blend, zugegeben und mit dem Kautschuk oder der Kautschukmischung homogenisiert. Diese Präkursoren sind According to the invention, the blends according to the invention are prepared by a process in which at least one rubber or a rubber mixture is homogenized. Subsequently, 5 to 80 wt .-% precursors of polyurethanes, based on the blend, are added and homogenized with the rubber or the rubber mixture. These precursors are
- ein oder mehrere Präpolymere aus Polyisocyanat(en) und Makroglykol(en) und mindestens ein Kettenverlängerer, one or more prepolymers of polyisocyanate (s) and macroglycol (s) and at least one chain extender,
und/oder and or
Monomere eines oder mehrerer Polyisocyanate, Makroglykole und Kettenverlängerer. Monomers of one or more polyisocyanates, macroglycols and chain extenders.
Vorteilhafterweise wird ein Präpolymer aus Polyisocyanant(en) und Makroglykol(en) durch Mischung und reaktive Umsetzung hergestellt und zusammen mit mindestens einem Kettenverlängerer dem Kautschuk oder der Kautschukmischung zugegeben. Advantageously, a prepolymer of polyisocyanate (s) and macroglycol (s) is prepared by mixing and reactive reaction and added together with at least one chain extender to the rubber or rubber mixture.
Durch das erfindungsgemäße Verfahren wird durch Additionsreaktionen der Isocyanatgruppen aus den Präkursoren, also den Präpolymeren aus Polyisocyanaten und Makroglykolen oder aus den Monomeren von Polyisocyanaten und Makroglykolen, und den Amingruppen des Kettenverlängerers während des Mischens und Homogenisierens das thermoplastische Polyurethan in-situ in dem Kautschuk synthetisiert. By the method according to the invention by addition reactions of the isocyanate groups from the precursors, so the prepolymers of polyisocyanates and macroglycols or from the monomers of polyisocyanates and macroglycols, and the amine groups of the chain extender during the Mixing and homogenizing the thermoplastic polyurethane synthesized in-situ in the rubber.
Anschließend wird der so entstandene Polymerblend vorteilhafterweise einem Vulkanisationsprozess des Kautschuks oder der Kautschukmischung unterworfen. Anstatt des Präpolymers, hergestellt aus Polyisocyanaten und Makroglykolen, können zur in-situ Bildung von thermoplastischem Polyurethan im Kautschuk auch direkt die Monomere von Polyisocyananten und Makroglykolen gemeinsam mit dem Kettenverlängerer eingesetzt werden. Subsequently, the resulting polymer blend is advantageously subjected to a vulcanization process of the rubber or the rubber mixture. Instead of the prepolymer, prepared from polyisocyanates and macroglycols, the monomers of polyisocyanates and macroglycols can be used together with the chain extender for the in-situ formation of thermoplastic polyurethane in the rubber directly.
Vorteilhaft wird mit dem erfindungsgemäßen Verfahren erreicht, dass sich durch die Zugabe der Präkursoren während des Mischens mit dem Kautschuk oder der Kautschukmischung in-situ synthetisiertes Polyurethan bildet, welches eine verbesserte Homogenisierung und in den Kontaktbereichen von Polyurethan und Kautschuk eine Verzahnung der Materialien ausbildet, was zu verbesserten Eigenschaften des erfindungsgemäßen Blends, wie beispielweise ein verbesserter E- Modul, erhöhte Bruchspannung, Bruchdehnung und Härte bei verringertem Abriebverhalten führt. Advantageously, it is achieved with the method according to the invention that in-situ synthesized polyurethane is formed by the addition of the precursors during mixing with the rubber or the rubber mixture, which forms an improved homogenization and in the contact areas of polyurethane and rubber, a toothing of the materials what to improved properties of the blend according to the invention, such as an improved modulus of elasticity, increased breaking stress, elongation at break and hardness with reduced abrasion behavior leads.
Der erfindungsgemäße Blend weist einen Isocyanat-Index vom 90 bis 1 10 auf. Unter dem Isocyanat-Index wird das prozentuale Verhältnis von Isocyanat-Gruppen zu Isocyanat-reaktiven Wasserstoffatomen im Blend verstanden. The blend according to the invention has an isocyanate index of 90 to 110. The isocyanate index is understood to mean the percentage ratio of isocyanate groups to isocyanate-reactive hydrogen atoms in the blend.
Die meisten Polymere sind auf molekularer Ebene nicht mischbar, was sich aus thermodynamischen Gründen ergibt. Im Ergebnis einer Mischung unterschiedlicher Polymere entstehen meist mehrphasige Systeme, wobei im Allgemeinen in einer Matrix des einen Reaktionspartners Domänen des anderen Polymers entstehen. Die Auswahl des Polymerisationsverfahrens und damit der physikalisch-chemischen Mischung der beiden Phasen haben entscheidenden Einfluss auf die meist nur geringen Grenzflächenspannungen zwischen den einzelnen Phasen und die Mikrostruktur des meist grobdispersiven Blends. Most polymers are immiscible at the molecular level, which results from thermodynamic reasons. As a result of a mixture of different polymers, mostly multiphase systems are formed, generally resulting in a matrix of one reactant domains of the other polymer. The choice of the polymerization process and thus the physical-chemical mixture of the two phases have a decisive influence on the usually only small interfacial tensions between the individual phases and the microstructure of the usually coarsely dispersible blend.
Mit der erfinderischen Lösung konnte überraschend herausgefunden werden, dass Blends aus thermoplastischen Polyurethanen und Kautschuken mit vorteilhaften Eigenschaften hergestellt werden können, wenn die Polyurethanvorläufer/Präkursoren von einem Präpolymer aus Polyisocyanat(en) und Makroglykol(en) und Kettenverlangerer oder von Monomeren von Polyisocyanat(en) und Makroglykol(en) und Kettenverlangerer in-situ während des Homogenisierens und vorteilhafterweise des Vulkanisierens der Kautschuke zu thermoplastischen Polyurethanen synthetisiert werden. With the inventive solution it has surprisingly been found that blends of thermoplastic polyurethanes and rubbers can be produced with advantageous properties when the Polyurethane precursors / precursors of a prepolymer of polyisocyanate (s) and macroglycol (s) and chain extenders or monomers of polyisocyanate (s) and macroglycol (s) and chain extenders are synthesized in-situ during homogenization and advantageously vulcanization of the rubbers to thermoplastic polyurethanes ,
Besonders vorteilhaft ist es, dass im Gegensatz zum bekannten Stand der Technik einerseits keine kostenintensiven Lösungsmittel eingesetzt werden müssen und auf die vorherige Herstellung von Polyurethan verzichtet werden kann. It is particularly advantageous that, in contrast to the known state of the art, on the one hand, no cost-intensive solvents have to be used and the prior production of polyurethane can be dispensed with.
Erfindungsgemäß eingesetzte organische Polyisocyanate sind vorteilhafterweise aliphatische, aromatische, cycloaliphatische und araliphatische Polyisocyanate, vor allem Diisocyanate, wie Hexamethylendiisocyanat, Isophorondiisocyanat, 4,4'- Disocyanate, Tetramethyl-m-Xylyloldiisocyanat, Tetramethyl-p-Xylyloldiisocyanat, Toluoldiisocyanat, Xyloldiisocyanat, Phenylendiisocyanate, vorzugsweise 4,4'- Diphenylmethan-diisocyanat, gegebenenfalls mit Isomeren von Diphenylmethan- diisocyanat. Das erfindungsgemäß eingesetzte Polyisocyanat kann auch eine Verbindung mit reaktiven Isocyanat-Seitengruppen sein, wie es in der Polyurethan- Technik bekannt ist. Organic polyisocyanates used according to the invention are advantageously aliphatic, aromatic, cycloaliphatic and araliphatic polyisocyanates, especially diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-disocyanates, tetramethyl-m-xylylene diisocyanate, tetramethyl-p-xylylene diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanates, preferably 4,4'-diphenylmethane diisocyanate, optionally with isomers of diphenylmethane diisocyanate. The polyisocyanate used according to the invention may also be a compound having reactive isocyanate side groups, as is known in polyurethane technology.
Weiterhin erfindungsgemäß werden vorteilhafterweise Makroglycole eingesetzt, auch Polyole genannt, die auf Polyolefinen, Polycarbonaten, Polyacetaten, Polysiloxanen, vorzugsweise Polycaprolacton, Polyestern, Polyethern, Blockcopolymeren aus Polyester / Polyether und dergleichen, und Mischungen davon basieren. Auch gesättigte und/oder ungesättigte Polyole können erfindungsgemäß eingesetzt werden. Furthermore, according to the invention, it is advantageous to use macroglycols, also called polyols, which are based on polyolefins, polycarbonates, polyacetates, polysiloxanes, preferably polycaprolactone, polyesters, polyethers, block copolymers of polyester / polyethers and the like, and mixtures thereof. Saturated and / or unsaturated polyols can also be used according to the invention.
Als Kettenverlängerer (chain extender) können vorteilhafterweise multifunktionale und insbesondere Di-lsocyanat-reaktiven Wasserstoff enthaltende Verbindungen, vorzugsweise Diole und mehr bevorzugt Diamine oder eine Mischung von verschiedenen Typen eingesetzt werden. Die Amin-basierten Kettenverlängerer, vorzugsweise Diamine können aus folgenden Substanzklassen ausgewählt werden: 4,4'-Methylendianilin, o-Phenylendiamin, m-Phenylendiamin, p-Phenylendiamin, 4,4'- Methylen-bis-(2-methoxyanilin), bis (4-Amino-2-chlor-3 ,5-diethylphenyl)-methan, 4,4'-Methylen-bis (2-6-diethylanilin), 4,4'-Methylen-bis (2-methyl-anilin), 4,4'- Methylen-bis (2-6-Dimethyl-anilin), 4,4'-Methylen-bis (2-isopropyl-6-methyl-anilin), 4,4'-Methylen-bis (2,6-Diisopropyl-anilin), Diethyl-toluol-diamin, 4,4'Diamino-diphenyl- sulfon, 3,3'-Diannino-diphenyl-sulfon, 4,4 -Methylen-bis-(2-chlor-anilin), Trimethylen- bis-(4-amino-benzoat), Methylen-bis (2-ethyl-6-methyl-anilin), 3,5-Dimethyl-thio-2 ,4- toluol-diamin, 3,5-Dimethylthio-2,6-Toluylen-diannin, 3,5-diethyltoluol 2,6-Diamin, 3,5- Diethyltoluol-2,4-diamin, Naphthalin-1 ,8-diamin, 2,4-toluylendiamin, 2,6 Toluylendiamin, 3,4-Toluylendiamin, Benzidin und seine Derivate, 1 ,3-bis (3-amino- phenoxy) benzol, 4,4'-Diamino-diphenylether, Diamino-dihydroxyl-sulfon, 4,4'-(p- Phenylendiisopropyliden)-dianilin, 4,4'-(m-Phenylendiisopropyliden) dianilin. Auch sekundäre Amin-Kettenverlängerer und Komplexverbindungen mit verzögerter Wirkung von Kettenverlängerer mit blockierten Hydroxylgruppen und/oder Amin- Funktionalitäten können zur Herstellung der erfindungsgemäßen Blends eingesetzt werden. Chain extenders which may advantageously be used are multifunctional and in particular diisocyanate-reactive hydrogen-containing compounds, preferably diols and more preferably diamines or a mixture of different types. The amine-based chain extenders, preferably diamines, may be selected from the following classes of compounds: 4,4'-methylenedianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-methylenebis (2-methoxyaniline), bis (4-amino-2-chloro-3,5-diethylphenyl) -methane, 4,4'-methylenebis (2-6-diethylaniline), 4,4'-methylenebis (2-methyl-aniline), 4,4 Methylene-bis (2-6-dimethyl-aniline), 4,4'-methylenebis (2-isopropyl-6-methyl-aniline), 4,4'-methylenebis (2,6-diisopropylaniline) , Diethyl-toluenediamine, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4-methyl-bis (2-chloroaniline), trimethylene bis (4 amino-benzoate), methylene-bis (2-ethyl-6-methyl-aniline), 3,5-dimethyl-thio-2, 4-toluene-diamine, 3,5-dimethylthio-2,6-toluene-diannine , 3,5-diethyltoluene 2,6-diamine, 3,5-diethyltoluene-2,4-diamine, naphthalene-1,8-diamine, 2,4-toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine, benzidine and its derivatives, 1, 3-bis (3-aminophenoxy) benzene, 4,4'-diamino-diphenyl ether, diamino-dihydroxyl-sulfone, 4,4 '- (p-phenylenediisopropylidene) -dianiline, 4,4' - (m-phenylenediisopropylidene) dianiline. Secondary amine chain extenders and complex-action complex compounds of chain extenders with blocked hydroxyl groups and / or amine functionalities can also be used to prepare the blends of the invention.
Die Kautschukkomponente kann aus beliebigen herkömmlichen Kautschuken, welche in der Technik bekannt sind, ausgewählt werden. Aus polaren Kautschuken wie Nitril-Butadien-Kautschuk, carboxyliertem Nitril-Butadien-Kautschuk, hydriertem Nitril-Butadien-Kautschuk, hydriertem carboxylierten Nitril-Butadien-Kautschuk, Nitril- Isopren-Kautschuk, Acrylat-Kautschuk, Chloropren-Kautschuk, Halogenbutyl- Kautschuk, Polyurethan-Kautschuk und dergleichen; ebenso aus nicht-polaren Kautschuken wie Naturkautschuk, Isopren-Kautschuk, Butadien-Kautschuk, Styrol- Butadien-Kautschuk, Butyl-Kautschuk und dergleichen, oder auch aus Mischungen verschiedener Kautschuke. Die Kautschukkomponente kann auch aus thermoplastischen Elastomeren, thermoplastischen Vulkanisaten, Plastomeren oder anderen gummiartigen Materialien bestehen. The rubber component may be selected from any conventional rubbers known in the art. From polar rubbers such as nitrile-butadiene rubber, carboxylated nitrile-butadiene rubber, hydrogenated nitrile-butadiene rubber, hydrogenated carboxylated nitrile-butadiene rubber, nitrile-isoprene rubber, acrylate rubber, chloroprene rubber, halobutyl rubber, Polyurethane rubber and the like; also from non-polar rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber and the like, or also from mixtures of different rubbers. The rubber component may also consist of thermoplastic elastomers, thermoplastic vulcanizates, plastomers or other rubbery materials.
Die Kautschukkomponente dieser Erfindung sind insbesondere Dienkautschuke, hydrierte Dienkautschuke, vorzugsweise Nitrilkautschuk und vorteilhafterweise Nitril- Butadien-Kautschuk. The rubber component of this invention are, in particular, diene rubbers, hydrogenated diene rubbers, preferably nitrile rubber, and advantageously nitrile-butadiene rubber.
Die Kautschukkomponente wird vorzugsweise durch herkömmliche Vulkanisation oder auch Elektronenstrahl induzierte Vulkanisation vernetzt. The rubber component is preferably crosslinked by conventional vulcanization or electron beam induced vulcanization.
Typische Vernetzer, wie in der Technik bekannt, sind Schwefelverbindungen, beschleunigte Schwefelverbindungen, Peroxide, Wasserstoffperoxid-Koagens- Verbindungen, Phenolharze und/oder Kombinationen davon. Hilfs- und Zusatzstoffe, welche typisch für die Polyurethan- und Kautschuk- Technologie sind, können ebenfalls verwendet werden. Dies schließt die Verwendung von Kompatibilisierungsmitteln, wie z.B. grenzflächenaktive Substanzen, ein, um die Grenzflächenspannung zwischen den Phasen Polyurethan und Kautschuk anzupassen. Eingeschlossen sind auch Katalysatoren, Weichmacheröle, organische und anorganische Füllstoffe, Antioxidantien, Weichmacher, UV-Stabilisatoren, Flammschutzmittel und andere als Additiv geeignete Stoffe für die erfindungsgemäßen Mischungen. Typical crosslinkers, as known in the art, are sulfur compounds, accelerated sulfur compounds, peroxides, hydrogen peroxide-coagens compounds, phenolic resins, and / or combinations thereof. Auxiliaries and additives typical of polyurethane and rubber technology can also be used. This includes the use of compatibilizers, such as surfactants, to adjust the interfacial tension between the polyurethane and rubber phases. Also included are catalysts, processing oils, organic and inorganic fillers, antioxidants, plasticizers, UV stabilizers, flame retardants and other substances suitable as additives for the mixtures according to the invention.
Das erfindungsgemäße in-situ-Verfahren kann unter Verwendung von herkömmlichen Innenmischern, Walzwerken oder Extrudern erfolgen, welche in der Technik bekannt sind. The in situ process of the present invention can be accomplished using conventional internal mixers, rolling mills or extruders known in the art.
Besonders vorteilhaft ist das erfindungsgemäße Verfahren auch deshalb, da hochreaktive und hochmolekulare Amin-basierte Kettenverlängerer ohne Einsatz eines Katalysators eingesetzt werden können, um den erfindungsgemäßen Blend zu erhalten, welcher aus einer Matrix aus Kautschuk besteht, in dem Polyurethan feindispers verteilt vorliegt. Dabei ist es von Vorteil, dass mit dem Diamingehalt des Kettenverlängerers in den in-situ synthetisierten thermoplastischen Polyurethanen eine signifikante mechanische Verstärkung des Blends erreicht wird. The process according to the invention is also particularly advantageous since highly reactive and high molecular weight amine-based chain extenders can be used without the use of a catalyst in order to obtain the blend according to the invention, which consists of a matrix of rubber in which polyurethane is distributed in finely dispersed form. It is advantageous that with the diamine content of the chain extender in the in-situ synthesized thermoplastic polyurethanes, a significant mechanical reinforcement of the blend is achieved.
Darüber hinaus ermöglicht das erfindungsgemäße Verfahren eine hohe Flexibilität bei der Anpassung der weichen und harten Segmentanteile der in-situ synthetisierten thermoplastischen Polyurethane und führt zu deutlich verbesserten physikalischen Eigenschaften, insbesondere in Zug-und Abriebfestigkeit. In addition, the inventive method allows a high degree of flexibility in the adaptation of the soft and hard segments of the in-situ synthesized thermoplastic polyurethanes and leads to significantly improved physical properties, in particular in tensile and abrasion resistance.
Nachfolgend wird die Erfindung an zwei Ausführungsbeispielen näher erläutert: The invention will be explained in more detail below with reference to two exemplary embodiments:
Beispiel 1 example 1
100 g Nitril-Butadien-Kautschuk wird in einem beheizten Innenmischer (Haake Rheomix 600P) bei 120 °C und 60 U/min für 5 Minuten geknetet. Nachfolgend werden 8.2 g an Präpolymer (Methylendiphenyldiisocyanate, Polyester basiertes Präpolymer, mit 8.54 Gew.-% Isocyanate) und 2.9 g 4,4'-(m-Phenylen- diisopropyliden)aniline als Kettenverlangerer vorgemischt und zum Mischen in den Kautschuk aufgenommen und die Komponenten 5 Minuten bei 120 °C gemischt. Durch die zugegebenen Ausgangsstoffe ist ein Isocyanat-Index von 100 eingestellt. Die erhaltene Mischung wird anschließend auf einem Walzwerk (Servitec Polymix 1 1 OL) für 10 Minuten mit 5 g Zinkoxide, 2 g Stearinsäure, 1 ,7 g N-Cyclohexyl-2- benzothiazolylsulfenamid (CBS) und 2 g Schwefel eingemischt und nachfolgend auf einer Heizpresse bei einer Temperatur von 150 °C und einem Druck von 15 MPa vulkanisiert. 100 g of nitrile-butadiene rubber are kneaded in a heated internal mixer (Haake Rheomix 600P) at 120 ° C. and 60 rpm for 5 minutes. following 8.2 g of prepolymer (methylene diphenyl diisocyanates, polyester-based prepolymer, with 8.54 wt .-% isocyanates) and 2.9 g of 4,4 '- (m-phenylene diisopropylidene) anilines are pre-mixed as a chain extender and added to the mixing in the rubber and the components. 5 Minutes mixed at 120 ° C. The added starting materials have an isocyanate index of 100. The resulting mixture is then mixed on a rolling mill (Servitec Polymix 1 1 OL) for 10 minutes with 5 g of zinc oxides, 2 g of stearic acid, 1, 7 g of N-cyclohexyl-2-benzothiazolylsulfenamid (CBS) and 2 g of sulfur and then on a Heating press vulcanized at a temperature of 150 ° C and a pressure of 15 MPa.
Mechanische Eigenschaften des hergestellten Blends (NBR/PU 90/10) im Vergleich zu reinem NBR werden in Tabelle 1 gezeigt. Mechanical properties of the produced blend (NBR / PU 90/10) compared to pure NBR are shown in Table 1.
Tabelle 1 : Table 1 :
Beispiel 2 Example 2
Eine weitere Nitrilkautschukmischung mit in-situ synthetisiertem thermoplastischen Polyurethane gemäß Beispiel 1 jedoch mit 80/20 Gewichtsverhältnis wurde mit demselben Verfahren wie nach Beispiel 1 hergestellt. Tabelle 2 gibt die physikalischen Kenngrößen dieses Blends an. Tabelle 2: Another Nitrilkautschukmischung with in-situ synthesized thermoplastic polyurethane according to Example 1 but with 80/20 weight ratio was prepared by the same method as in Example 1. Table 2 gives the physical characteristics of this blend. Table 2:
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013217661.9A DE102013217661B4 (en) | 2013-09-04 | 2013-09-04 | Process for producing blends of thermoplastic polyurethanes and rubbers and blends produced therewith |
| PCT/EP2014/068245 WO2015032681A1 (en) | 2013-09-04 | 2014-08-28 | Blends of thermoplastic polyurethanes and rubbers and process for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3041877A1 true EP3041877A1 (en) | 2016-07-13 |
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| EP14758515.2A Withdrawn EP3041877A1 (en) | 2013-09-04 | 2014-08-28 | Blends of thermoplastic polyurethanes and rubbers and process for producing same |
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| Country | Link |
|---|---|
| US (1) | US10450445B2 (en) |
| EP (1) | EP3041877A1 (en) |
| JP (1) | JP2016529376A (en) |
| KR (1) | KR20160056906A (en) |
| DE (1) | DE102013217661B4 (en) |
| WO (1) | WO2015032681A1 (en) |
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| WO2019124502A1 (en) * | 2017-12-22 | 2019-06-27 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
| DE102018204884A1 (en) * | 2018-03-29 | 2019-10-02 | SchäferRolls GmbH & Co. KG | Process for the preparation of a polyurethane and a polyurethane produced or preparable by the process |
| FR3086950B1 (en) * | 2018-10-09 | 2020-12-25 | Hutchinson | RUBBER COMPOSITION FOR DYNAMIC APPLICATIONS, ITS PREPARATION PROCESS, PRODUCTS INCORPORATED AND USES |
| US11377552B2 (en) | 2019-01-04 | 2022-07-05 | Basf Se | Hard-phase-modified thermoplastic polyurethane |
| EP3741912A1 (en) * | 2019-05-22 | 2020-11-25 | Valmet Technologies Oy | Roll for manufacture of a fibrous web and method for making it |
| CN111763417A (en) * | 2020-06-30 | 2020-10-13 | 江阴久盛科技有限公司 | Nano titanium dioxide filled thermoplastic polyurethane/chloroprene rubber blend composite material and preparation method thereof |
| CN112708255A (en) * | 2020-12-24 | 2021-04-27 | 广州机械科学研究院有限公司 | Low-temperature-resistant elastomer rubber composition and application thereof |
| FI20216016A1 (en) * | 2021-09-30 | 2023-03-31 | Valmet Technologies Oy | Belt |
| CN114395246B (en) * | 2021-12-20 | 2024-02-23 | 绍兴市聚成新材料科技股份有限公司 | Dynamically vulcanized silica gel modified polyurethane and preparation method thereof |
| CN115403837B (en) * | 2022-10-11 | 2024-04-05 | 无锡二橡胶股份有限公司 | Production formula of high-speed spinning high-count differential fiber drafting rubber roller |
| CN117946343A (en) * | 2024-01-27 | 2024-04-30 | 广州佳沐体育发展有限公司 | Lockable plastic throwing court ground material |
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- 2014-08-28 EP EP14758515.2A patent/EP3041877A1/en not_active Withdrawn
- 2014-08-28 KR KR1020167008878A patent/KR20160056906A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2015032681A1 (en) | 2015-03-12 |
| DE102013217661A1 (en) | 2015-03-05 |
| JP2016529376A (en) | 2016-09-23 |
| US20160194483A1 (en) | 2016-07-07 |
| DE102013217661B4 (en) | 2023-01-12 |
| KR20160056906A (en) | 2016-05-20 |
| US10450445B2 (en) | 2019-10-22 |
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