GB2170502A - Thermoplastic polymer blends - Google Patents
Thermoplastic polymer blends Download PDFInfo
- Publication number
- GB2170502A GB2170502A GB08530606A GB8530606A GB2170502A GB 2170502 A GB2170502 A GB 2170502A GB 08530606 A GB08530606 A GB 08530606A GB 8530606 A GB8530606 A GB 8530606A GB 2170502 A GB2170502 A GB 2170502A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyamide
- composition according
- weight
- polyolefin
- acid
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 8
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 5
- 229920006345 thermoplastic polyamide Polymers 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims description 38
- 239000004952 Polyamide Substances 0.000 claims description 37
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- 229920000299 Nylon 12 Polymers 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 3
- 150000002978 peroxides Chemical class 0.000 claims 3
- 239000007859 condensation product Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 claims 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims 1
- 229920006017 homo-polyamide Polymers 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 229920006347 Elastollan Polymers 0.000 description 3
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920003698 Grilamid® L 20 G Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- -1 polytetramethylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance 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
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- UCWRHXBFPRXNKA-UHFFFAOYSA-N 2,3-di(ethylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=CC UCWRHXBFPRXNKA-UHFFFAOYSA-N 0.000 description 1
- MUTDXQJNNJYAEG-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(dimethylamino)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)N(C)C MUTDXQJNNJYAEG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 229920003620 Grilon® Polymers 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- QUSSPXNPULRXKG-UHFFFAOYSA-N galleon Natural products O1C(=CC=2)C(OC)=CC=2CCCCC(=O)CCC2=CC=C(O)C1=C2 QUSSPXNPULRXKG-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000002649 leather substitute Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A thermoplastically processable composition comprises a mixture consisting of 5 to 90% by weight of a thermoplastic polyamide, 5 to 90% by weight of a thermoplastic polyurethane, and 5 to 50% by weight of a thermoplastic, activated polyolefin.
Description
SPECIFICATION
Thermoplastic polymer blends
This invention relates to blends of thermoplastic polymers.
Polyamides are exceptionally suited to thermoplastic processing. Many fields of use are known for polyamides, hitherto generally in relation to stiff, stable construction parts. Disadvantages associated with most aliphatic polyamides are insufficient dimensional stability and loss of stiffness during use, as the result of moisture uptake. Their resistance to abrasion is relatively good, but often insufficient for practical demands.
Flexible polyamides have recently become available. The flexibility is achieved by the addition of monomeric plasticisers and also through the formation of segmented polymer structures in which elastomer blocks are introduced between normal polyamide blocks. These generally consist of polytetramethylene oxide with a molecular weight of 600 to 3000.
Monomeric plasticisers can be extracted from polyamides on contact with water or organic solvents.
Segmented polyamides are expensive to prepare, despite being very easily processable. Disadvantages lie with respect to abrasion resistance, elastic resilience and generally with respect to hydrolysis-resistance.
Thermoplastic polyurethanes have a wide spectrum of properties. Their hardness can cover a broad range, from 80 Shore A to 75 Shore D. Their abrasion resistance and their elastic resilience, particularly after annealing, are outstanding. Their low-temperature flexibility and toughness can be partially influenced by choosing suitable amounts of elastomer segments, of which there are three principal kinds:
1. Tetramethylene oxide polyether
2. Poly-w-caprolactone 3. Adipic acid-polyester with ethylene glycol or mixed ethylene glycol/butanediol or hexanediol as diol components
The hard segments are generally based on aromatic diisocyanates, in particular the diphenylmethanediisocyanate-types (MDI) or the isophoronediisocyanate (IPDI) or the toluenediisocyanate (TDI), which are often prereacted with butanediol.The principal disadvantage of the thermoplastic polyurethanes is their poor processability in injection moulding and particularly in extrusion.
The class of polyamides is described, e.g. in the Kunststoff-handbuch, Volume VI (1966), and the class of the polyurethanes in the Kunststoffhandbuch, Volume VII (1983), both published by the Carl Hanser
Verlag, Munich.
There has been no shortage of attempts to combine the properties and the good processability of polyamides with the properties of the thermoplastic polyurethanes.
Org. Coat. Plast. Chem., 40 (1979) 664-668, describes blends of TPUR with a variety of thermoplasts.
Extensive non-compatibility was found with pure polyamide 6, and a partial compatibility with polyamide 12.
The theromplastic PA-TPUR blends described in the patent literature are distinguished by the use of a particular copolyamide of low softening temperature and containing, in generai, dimerised tall oil fatty acid having 36 C atoms. This is the case, for example, in EP-A-0109342, US-A-4384083 and DE-A-2431984, in which such products are generally suitable as melt-adhesives.
Owing to low compatibility, the TPUR proportion is often considerably restricted, e.g. in US-A-4369285 and SU-A-0352915. In FR-A-2207955, JP-A-7278673 and JP-A-7434947, the addition of monomeric plasticizers is described, which,in addition to reducing the stiffness of the final products, improve the plasticity, miscibility and compatibility.
By the choice of soft, low-melting copolyamides, the stiffness, strength and heat-resistance are reduced. The possibility of adding only a little TPUR reduces the possibility of desired standardisation of combinations of properties. Monomeric plasticizers can sweat out during processing or in use, leading to undesirable side-effects.
Blends of polyamide with thermoplastic polyurethane, with a range of miscibility between the polyamide and polyurethane which is as broad as possible, which are easily processable and which allow new combinations of properties, are therefore desired.
It has now been found that a thermoplastically processable composition of:
a) 5-90% by weight of a thermoplastic polyamide
b) 5-90% by weight of a thermoplastic polyurethane
c) 5-50% by weight of a thermoplastic, activated polyolefin has a good thermoplastic processability and
leads to products with new combinations of properties. The compositions are particularly easily processable when the a:b ratio is 0.2-5, when at least 10% by weight of component c) is present.
Suitable polyamides comprise all linear, thermoplastically processable polyamides which have a softening range below about 235"C. Linear aliphatic polyamides such as polyamide 6, polyamide 6.9, po
lyamide 6.10, polyamide 6.12, polyamide 11 and polyamide 12 are particularly suitable.
The polyamide compositions can also comprise copolyamides principally of aliphatic monomers or al
loys of two polyamides. If this involves the use of polyamide 66, a depression in melting point can be achieved, in the case of true alloys, so that the softening temperature is reduced to 2350C and below or, if polyamide 66 is not the principal component, it can be present as a disperse phase, e.g. in the matrix of the other polyamide (for instance polyamide 6), so that the composition is nevertheless processable at 235"C and below. The same is true for mixtures of other, e.g. also amorphous, polyamides.
All types of thermoplastic polyurethanes which, on account of their heat stability, can be processed with polyamides, are suitable. Particularly easily processable compositions are obtained by the use of socalled polyether-polyurethanes. Polyurethanes with polycaprolactone as the soft segment also render easily processable products. It is of particular interest, howoever, that easily processable compositions, with new combinations of properties, are obtained from the hydrolysis-sensitive and poorly processable adipate types by mixture according to the given process.
The so-called activated copolyolefins are copolymers of ethylene with at least one a-olefin with 3 and more carbon atoms, on which organic carboxylic acid or a derivative of a carboxylic acid which has 1 or more -COOH groups or their derivatives is grafted. The grafting should be such that about 0.05-2% by weight acid or its derivative is grafted.
Most preferably, maleic acid anhydride or fumaric acid is used for the grafting. Copolymeres of ethylene with propylene, butene, hexene and octene are used as copolyolefins. Copolyolefins with a predominant proportion of ethylene are usual, but it can also be the case that the copolyolefin proportion of, e.g., propene and octene, predominates. In addition to the a-olefin, the copolyolefin can contain additionally an amount suitable for further grafting of a non-conjugated diene such as, say, 1,4-hexadiene or diethylidene-norbornene.
The technology of the grafting of these copolyolefins is state of the art and is widely described. DE-A2722720 and JP-A-7801291, for example, relate to grafting with the use of organic peroxide, and US-A4026967 and EP-A-0109342 to peroxide-free grafting which requires high temperatures, and copolyolefins which are prepared together with a diolefin with non-conjugated double bonds.
The activated copolyolefins can have properties varying over a wide range, e.g. in which their crystalline proportion is 1-35% and their so-called MFI (melt flow index according to ASTM D 1238) is 0.1-50 gl 10 minutes.
The thermoplastically processable compositions of the invention can- of course be further modified, according to the state of the art, in which they contain, e.g., further additives such as fillers such as glass and/or minerals, plasticizers, in lower amounts other thermoplasts, processing aids such as internal and external lubricants, mould release agents, stabilisers (heat, light, oxidation), carbon black, dyes, pigments, flame retardant agents etc. as well as combinations of these additives, as required.
The invention will now be described in more detail with reference to examples.
Examples 1-9
Comparative experiments are marked in Table 1 with an asterisk (*), and the proportions of the individual components are parts by weight. The materials used are more closely characterised in the addendum to Table 1.
For the purpose of the experimental procedure, the dry components (water content lower than 0.05% by weight) of polyamide, TPUR and, according to the experiment, activated- polyolefin, were mixed, and then the additives, in premixed form introduced and further mixed, until the added materials were distributed uniformly in a thin layer on the granulate particles. This mixture was then introduced in to the feed hopper of a double screw extruder of the type ZSK-30 from Werner und Pfleiderer, Stuttgart, and the temperature in the six heat zones in the range of 180-230"C so regulated, at a screw speed of 150 rpm, that a strand as homogeneous as possible and easily granulable was obtained using a 4 mm nozzle.
The throughput in this case was about 8 kg/hour. A typical initial temperature profile of the six heat zones is, for example, 180/190/220/230/220 (each "C). The extrusion strand was passed through a water bath, and granulated, and the granules were dried to a water content of less than 0.05% by weight.
The measured melt temperatures in the nozzle are given in Table 1.
Examination of the melt strands from the nozzle gave an initial interesting result:
In all cases, the addition of the activated polyolefin gave a homogeneous strand with a smooth surface, while this is often knotted and rough and leaves the nozzle in a pulsing manner, as described in the invention, if the inventive blend component c), the activated polyolefin, is absent.
So the addition of an activated polyolefin to the mixture of polyamide and TPUR gives already a clearly favourable behaviour even at the preparation stage of the polymer alloy.
The preparation of test pieces (small DIN bars, DIN 53453, tensile test bars, DIN 53455/3) was conducted on an injection moulding machine available from Netstal, Niederurnen, Switzerland, of the Neomat N 110/565-type, which includes an efficient melt extruder.
The processing parameters such as temperature profile of the screw, troughput etc. were adapted in each case, as satisfactorily as possible to the particular blend formulation.
As the observations on the injection-moulding procedure in Table 1 show, problems appeared in all cases in the comparative tests. By contrast, the formulations according to the invention allowed processing to homogeneous test pieces with a smooth surface. Only in the case of blends with TPUR proportions above 50%, does the moulding time have to be extended somewhat.
In addition to the improved processability, the blends according to the invention also possess a clearly improved toughness according to DIN 53453. In Table 1, oB indicates: the test bodies do not break on testing.
The tensile strength at yield according to DIN 53455 gives also a favourable result. While, e.g. polyamide 12 blends with a high polyurethane content, cannot be prepared and processed (comparative test 7), without the addition of an activated polyolefin, the stress/strain curve of the corresponding blends according to the invention exhibits high tensile strength and elongation at break without any yield point being visible.
If the stress/strain curve gives no defined yield point, no values for yield strength and elongation at yield are given in Table 1.
TABLE 1
Test No. 1 2 3 4 5 6 7 8 9
*Comparative Test * * * *
Composition: -PA 12, Type 1 80 70 80 70 25 25 25
- PA 12, Type 2 80 70 - TPUR, Type 1 20 20 20 20
- TPUR ,Type 2 20 20 80 65 55
-Activated 10 10 10 10 20
Polyolefin - Additives 1 1 1 1 1 1 1 1 Extrusion:
- Melt temperature 216 223 231 222 216 225 - 191 184 ( C) Processing:
- Observed prob- 1) 1) 1) 5) 4) 4)
lems (s.) 3)
Mechanical proper
ties::
- Notched impact
strength, DIN
53'453 23OC(kJ/m2) 11 oB 27 oB 16 oB - oB oB -20 C (kJ/m2) 5 8 7 8 5 9 - oB oB -40 C (kJ/m2) 5 5 5 5 5 6 - oB oB
Tensile test,
DIN 53'455/3, 23"C - Tensile strength 34.8 27.7 - - 23.4 -
at yield (N/mm2)
- Tensile strength 27.2 38.8 27.0 30 25.0 17.8 16.3
at break (N/mm2)
- Elongation at 7.7 15.8 - - 18.5 -
yield (%)
- Elongation at 34.7 198.2 3.2 66.5 31.5 250 225
break (%)
Flexural moduius,
DIN 53452: 23 C (N/mm2) 1215 791 1045 823 1302 677 - 78.1 67.4 0 C (N/mm2) 1630 980 -20 C (N/mm2) 1887 1122 -40 C (N/mm2) 2104 1192 1550 1182
Flexural strength at
yield, DIN 53452:: 23"C (N/mm2) 57.4 39.8 47 39.4 58 32.6 - 5.1 4.5 0 C (N/mm2) 86 55 -20 C (N/mm2) 104 65 -40 C (N/mm2) 121 71 94 70
Addendum to Table 1:
Abbreviations have the following meanings:
- PA 12, type 1:
Medium viscosity, injection-moulding-type, chain-length regulated so that it has the following terminal groups (each expressed as me-glkg polymer): -COOH = 49,-NH2 = 27
- PA 12, type 2:
Medium viscosity, injection-moulding-type, chain-length regulated so that it has the following terminal groups: -COOH = 20,-NH2 = 57
- TPUR, type 1:
Pellethane 2102-80a, Polyester-type
- TPUR, type 2
Pellethane 2103-80AE, Polyether-type from Upjohn Europe SA, St.Galleon, Switzerland
- Additives:
Mixture of processing aids and stabilisers which is formulated from (in % by weight): 20% Tinuvin P, 20% Irganox 1076, 20% Irganox 1098 (stabilisers from Ciba-Geigy AG, Basel, Switzerland), 20% lubricant
PAT-712/11 from Wurtz GmbH, Bingen-Sponsheim, West Germany, and also 10% of each of zinc stearate and magnesium stearate from 0. Baerlocher, 8000 Munich, 50, West Germany
- Activated Polyolefin: APO,AP712 T from Mitsubishi Chemical, Tokyo
- In the injection-moulding procedure, the observations have the following meanings:
1) Non-homogeneous blend, skin separation from surface of strand
2) Tensile test bars DIN 53455/3 cannot be moulded
3) Apparent decomposition of the melt on injection; test bodies have blistered surfaces.Tensile test bars (DIN 53455/3) cannot be prepared 4)Test pieces having good, smooth surfaces; minor adhesion in the mould
5) Even the preparation of the blends in the double-screw extruder was impossible because of incompatibility of the components and indications of decomposition
Examples 10-14 and Comparative Examples 15-19
After having shown in Examples 1-9, that by the addition of an activated polyolefin, the ease of preparation, the processability and several mechanical properties are improved, only blends containing activated polyolefin are described in the examples which follow, and they are comared with the pure polyamide and polyurethane types.
The preparation and processing of the blends were conducted according to the parameters described above, but instead a single-screw extruder with an efficient mixing zone was used in the blend preparation. The exact processing-parameter for each formulation was thus optimised to the best possible extent.
The comparative materials according to tests 15-19 were processed in accordance with the conventional parameters for these thermoplasts. For most of the tests, polyamide 12 injection-moulding grade,
GRILAMID L 20 G, from EMS-CHEMIE AG, Domat/Ems, Switzerland 7013, was used, which already contains lubricants and stabilisers, so that for the blend-preparation no additives besides the base polymeres, are used.
The composition of the blends and their mechanical properties are summarized in Table 2.
TABLE 2
TEST Examples Comparative Examples 10 11 12 13 14 15 16 17 18 19
Composition (% by weight)
Polyamide 12, 20 20 35 60 100
GRILAMID L 20 G
Polyamide elastomer, 35 100
GRILAMID ELY-60
Polyamide 6, 20 15
GRILON A-28
TPUR: - Adipate-type, 70 30 100
Pellethane 2355-90A - Lactone-type, 70 35 100
Elastollan E 590 FNAT -Polyether-type, 30 100
Elastollan E 190 FNAT - Activated polyolefin, 10 10 15 15 10
APO AP 712 T TABLE 2 (Continued)
Test Examples Comparative Examples 10 11 12 13 14 15 16 17 18 19
Mechanical properties
Test: Norm:Unit:
ASTM D
Tensile strenght 638 kg/cm 200 410 270 280 350 610 350 440 450 450 at break
Elongation at 638 % 450 585 390 570 450 310 300 550 500 550 break
Hardness, Shore A 2240 - 92 87 96 92 90 - - 90 90 90
E-Modulus 790 kg/cm 1000 1000 2800 3200 11000 2750 - -
Resilience 2632 % 57 58 60 44 50 75 60 45 50 45
Density 792 g/cm 1.10 1.11 1.01 1.02 1.03 1.01 1.01 1.20 1.18 1.22
Notched impact kg/cm/ strenght (oB = 256 cm oB oB oB oB oB 8 8 oB oB oB no break) Addendum to Table2:
The raw materials are commercial products from the following companies::
- The polyamide types used from EMS-CHEMIE AG, 7013 Domat/Ems, Switzerland
- Pellethane 2355-90/A from Upjohn, La Porte, USA
- Elastollan E 590 FNAT and E 190 FNAT from Elastogran- Chemie, GmbH, 2844 Lemförde, West Germany
- APO, AP 712 T from Mitsubishi Chemical, Tokyo
To make evident the new combinations of properties of the blends according to the invention, a range of special comparative tests was conducted. The results of these tests are summarized in Table 3.
Instead of numerical values, the overall properties are represented by symbols, with the aim of good clarity.
The symbols are on a decreasing scale of values: + 0 8 -, i.e. in which + = very favourable properties and - = comparatively poor properties.
TABLE 3
Test No. Test Examples Comparative Examples
1 Flexibility at low + + + + + - 0 - - +
temperatures (-20 to -40 C) 2 Flexural fatigue + + + + + - + 0 0 +
resistance
3 Adhesive strength of + + 0 0 0 - 6 + + +
bonds performed with
a polyurethane
adhesive-system
4 Kink resistance + + 0 0 0 - - + + +
5 Tack on tool during + + + + + + + 6 (3 8 injection moulding
6 Hydrolysis-resistance + + + + + + + - - 0
Test Nos. 1-6 in Table 3 will now be briefly described:
- No. 1: The E-moduli of formulations according to the invention are in Tables 1 and 2. For a favourable flexibility-performance at low temperatures, the value of the E-modulus at -40 C should increase as little as possible from the value at 23"C. This is clearly better achieved by the blends according to the invention in comparison with the pure polyamide-TPUR blends.
- No. 2:
Test pieces according to Table 2 were provided with a 2 mm deep notch and subjected to an extended blending test of 105 cycles: formulations according to the invention and also Comparative Examples 16 and 19 = no determinable chance
Comparative Example 18 and also polyamide 6, injection-moulding material = break after 800 cycles
Comparative Example 17 or 18 = break after 117,000 respectively 20,000 cycles
- No. 3:
In order to examine the adhesive strength of urethane adhesive systems, a peel strength test was conducted. In this, test bodies according to Table 2, in the form of strips, were bonded to synthetic leather using a polyurethane adhesive, Bostic 4120 H and an isocyanate hardener, mixed in a ratio of 100:5, were used as the adhesive. The peeling speed was 200 mm/min.
Tearing-apart of the test body occurred as follows: Example 10 and 11 and also pure polyurethane in the leather or in the test bodies, but not at the adhesive join Example 12, 13, 14, to 70% in the leather or test bodies and onyl to 30% as the result of peeling off the adhesive joint, in which the peeling strength was 13 mg/25 mm In Comparative Example 15, using polyamide 12, the peeling strength was only 5 kg/25 mm (the same applies for polyamide 6); it was 12 kg/25 mm in Comparative Example 16
It is apparent from these results that, if blends according to the invention are used as the material for shoe soles, it is no longer necessary that the shoe upper material is sewn on to it, as the adhesion with the given adhesive provides sufficient strength.By contrast, shoe soles of pure nylon must be sewn on to the shoe upper material.
- No. 4:
In order to test the kink resistance, tubes of 18 mm outer and 17 mm inner diameter were prepared and subjected to a prolonged kink test.
For Example 10 and 11, no kinks could be detected even after prolonged testing For Example 12, 13 and 14, the first kinks appeared only after 50 cycles . For Comparative Examples 15 and 16, kinks were already immediately apparent after the beginning of the test . From Comparative Example 17, 18 and 19, and also pure polyurethane, no tubes of the given dimensions could be prepared on account of their poor processability (adhesion in the nozzle). It is however known from the tests on flat bars that polyurethanes have a good kink resistance
- No. 5:
Tendency to adhesion in the mould.It is apparent from preparation of test pieces corresponding to Table 2 and also preparation of tubes that test pieces or tubes without a tendency to adhesion in the mould or nozzle can only be prepared using blends according to the invention or pure polyamides. It was also quite impossible to prepare thin-walled tubes for the kink test for example, using the pure TPUR-types (as in comparative tests 17-19).
- No. 6:
Hydrolysis-resistance
For this test, tubes having an outer dimension of 6 mm and an inner diameter of 4 mm were prepared and subjected to a burst pressure test of 15 kg/cm2, which all passed. They were then filled with water, sealed and stored for 20 days at about 60"C. They were then subjected to a burst-pressure test of 15 kg/ cm2 at room temperature.
The tubes corresponding to Example 10-14 and according to Comparative Example 15 and 16 (pure nylon tubes) remained undestroyed The TPUR-tubes corresponding to Comparative Example 17-19 all burst.
This shows that the formulations according to the invention have a clearly improved hydrolysis-resistance.
Claims (18)
1. A thermoplastically processable composition which comprises a mixture consisting of 5 to 90% by weight of a thermoplastic polyamide, 5 to 90% by weight of a thermoplastic polyurethane, and 5 to 50% by weight of a thermoplastic, activated polyolefin.
2. A composition according to claim 1, wherein the mixture comprises 0.2 to 5 parts by weight of the polyamide per part by weight of the polyurethane, and at least 10% by weight of the polyolefin.
3. A composition according to claim 1 or claim 2, wherein the polyamide is a homopolyamide, a copolyamide, a segmented polyamide (elastomer polyamide) or a mixture or alloy of different polyamides, and the polyamide has a softening point below 235 C.
4. A composition according to claim 3, wherein the polyamide is polyamide 12 or polyamide 11.
5. A composition according to claim 3, wherein the polyamide is polyamide 6.
6. A composition according to claim 3, wherein the polyamide is the condensation product of diaminohexane and a dicarboxylic acid having at least 9 carbon atoms.
7. A composition according to claim 3, wherein the polyamide is a polyamide elastomer or a polyamide blend which contains a- polyamide elastomer.
8. A composition according to any preceding claim, wherein the polyurethane is of the polyester-type.
9. A composition according to any of claims 1 to 7, wherein the polyurethane is of the polyether-type.
10. A composition according to any preceding claim, wherein the polyolefin comprises an olefin copolymer on to which is grafted 0.1 to 2% by weight of an unsaturated carboxylic acid or a derivative of such a carboxylic acid.
11. A composition according to claim 10, wherein the olefin copolymer is derived from ethylene and at least one higher a-olefin, and the grafting is achieved radically by the use of a peroxide.
12. A composition according to claim 10, wherein the olefin copolymer is derived from ethylene, at least one higher a-olefin, and a non-conjugated diene, and the grafting is achieved without peroxide, at high temperature.
13. A composition according to claim 10, wherein the olefin copolymer is derived from ethylene, at least one higher o-olefin, and a non-conjugated diene, and the grafting is achieved by the use of a peroxide.
14. A composition according to any of claims 10 to 13, wherein the acid or acid derivative is a dicarboxylic acid or a derivative thereof.
15. A composition according to claim 14, wherein the dicarboxylic acid or derivative isfumaric acid, maleic acid anhydride, bicyclo[2.2.2]-2,3: 5,6-dibenzooctadiene-2,5-dicarboxylic acid-7,8-anhydride or a mixture thereof.
16. A composition according to any preceding claim, wherein the polyolefin has a glass transition temperature below -20 C, a degree of crystallisation of 1 to 35%, and a melt index of 0.2 to 50 g/10 minutes at 190 C and 2.16 kp load.
17. A composition according to any preceding claim, wherein the polyolefin is a mixture of graft copolyolefin as defined in any of claims 10 to 15 and non-grafted copolyolefin, and in which the proportion of the graft copolyolefin in the mixture is at least 30% by weight.
18. A composition according to claim 1, substantially as described in any of Examples 2, 4, 6 and 8 to 14.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH6112/84A CH665648A5 (en) | 1984-12-21 | 1984-12-21 | THERMOPLASTICALLY PROCESSABLE MASSES MADE OF POLYAMIDE, THERMOPLASTIC POLYURETHANE AND ACTIVATED POLYOLEFIN. |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8530606D0 GB8530606D0 (en) | 1986-01-22 |
GB2170502A true GB2170502A (en) | 1986-08-06 |
GB2170502B GB2170502B (en) | 1988-05-25 |
Family
ID=4304450
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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GB08530606A Expired GB2170502B (en) | 1984-12-21 | 1985-12-12 | Thermoplastic polymer blends |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS61215655A (en) |
CH (1) | CH665648A5 (en) |
DE (1) | DE3545033A1 (en) |
FR (1) | FR2575167B1 (en) |
GB (1) | GB2170502B (en) |
IT (1) | IT1182093B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU650245B2 (en) * | 1990-02-13 | 1994-06-16 | Atochem | Process for the conversion of TPUs by extrusion modifying agents employed according to this process |
US5605961A (en) * | 1993-09-08 | 1997-02-25 | Bayer Corporation | Thermoplastic composition containing polyurethane and polypropylene |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0147066B1 (en) * | 1988-09-07 | 1998-08-17 | 아사구라 다쓰오 | Thermoplastic resin composition |
WO1995019403A2 (en) * | 1994-01-13 | 1995-07-20 | Bemis Associates | High-performance adhesive film |
DE19502206A1 (en) * | 1995-01-25 | 1996-08-01 | Buna Sow Leuna Olefinverb Gmbh | Functionalized polymers, processes for their production and their use in thermoplastic molding compositions |
FR2752579B1 (en) * | 1996-08-23 | 1998-10-30 | Atochem Elf Sa | FILM AND OBJECT OBTAINED FROM A MATERIAL COMPRISING A POLYURETHANE AND A POLYAMIDE AND POLYETHER BLOCK POLYMER, THE USE THEREOF FOR THE MANUFACTURE OF SAID FILM AND OBJECT |
US5973013A (en) * | 1997-08-26 | 1999-10-26 | E. I. Du Pont De Nemours And Company | Polyamide/polyurethane micro-blend and process |
DE19820661C2 (en) * | 1998-05-08 | 2002-10-24 | Inventa Ag | Unplasticized polyamide and molding compound and their use |
JP5465459B2 (en) * | 2008-05-15 | 2014-04-09 | 大日精化工業株式会社 | Thermoplastic polyurethane resin composition |
CN109096593B (en) * | 2018-09-01 | 2021-04-02 | 广东恒骏工贸发展有限公司 | EVA rubber-plastic composite foaming material used as sole and preparation method thereof |
CN117603492B (en) * | 2023-10-24 | 2024-06-11 | 安徽开捷汽车部件有限公司 | Polyurethane gasket for automobile damping and buffering and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0085115A1 (en) * | 1981-08-13 | 1983-08-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2207955A1 (en) * | 1972-11-24 | 1974-06-21 | Aquitaine Total Organico | Polyurethane polyamide compsn. - for injection moulding ski boots or brake pipes |
JPS5651107B2 (en) * | 1973-07-06 | 1981-12-03 | ||
JPS55165952A (en) * | 1979-06-14 | 1980-12-24 | Unitika Ltd | Polyamide composition |
DE2931689A1 (en) * | 1979-08-04 | 1981-02-26 | Bayer Ag | POLYAMIDE MOLDS WITH IMPROVED TOUGHNESS |
DE3101771A1 (en) * | 1981-01-21 | 1982-09-02 | Rudi H. Ing.(grad.) 8000 München Keuerleber | Process for the preparation of polyamides which have high impact strength in the dry state and at low temperatures from chemically reactive mixtures |
US4384083A (en) * | 1981-07-22 | 1983-05-17 | Applied Polymer Technology, Incorporated | Thermoplastic adhesive |
FR2532653B1 (en) * | 1982-09-06 | 1986-06-13 | Rhone Poulenc Spec Chim | COMPOSITIONS FOR MOLDING BASED ON SEMI-RIGID COPOLYAMIDES DERIVED FROM FATTY ACID DIMERS, ELASTOMERS AND POSSIBLY CONVENTIONAL POLYAMIDES |
-
1984
- 1984-12-21 CH CH6112/84A patent/CH665648A5/en not_active IP Right Cessation
-
1985
- 1985-12-12 GB GB08530606A patent/GB2170502B/en not_active Expired
- 1985-12-17 IT IT48942/85A patent/IT1182093B/en active
- 1985-12-19 DE DE19853545033 patent/DE3545033A1/en active Granted
- 1985-12-20 FR FR858519007A patent/FR2575167B1/en not_active Expired
- 1985-12-21 JP JP60287667A patent/JPS61215655A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0085115A1 (en) * | 1981-08-13 | 1983-08-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU650245B2 (en) * | 1990-02-13 | 1994-06-16 | Atochem | Process for the conversion of TPUs by extrusion modifying agents employed according to this process |
US5605961A (en) * | 1993-09-08 | 1997-02-25 | Bayer Corporation | Thermoplastic composition containing polyurethane and polypropylene |
Also Published As
Publication number | Publication date |
---|---|
FR2575167A1 (en) | 1986-06-27 |
JPS61215655A (en) | 1986-09-25 |
IT8548942A0 (en) | 1985-12-17 |
DE3545033A1 (en) | 1986-07-03 |
GB8530606D0 (en) | 1986-01-22 |
GB2170502B (en) | 1988-05-25 |
DE3545033C2 (en) | 1989-04-06 |
IT1182093B (en) | 1987-09-30 |
FR2575167B1 (en) | 1989-12-01 |
CH665648A5 (en) | 1988-05-31 |
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