IE910466A1 - PROCESS FOR CONVERTING TPUs BY EXTRUSION USING MODIFYING¹AGENTS - Google Patents
PROCESS FOR CONVERTING TPUs BY EXTRUSION USING MODIFYING¹AGENTSInfo
- Publication number
- IE910466A1 IE910466A1 IE046691A IE46691A IE910466A1 IE 910466 A1 IE910466 A1 IE 910466A1 IE 046691 A IE046691 A IE 046691A IE 46691 A IE46691 A IE 46691A IE 910466 A1 IE910466 A1 IE 910466A1
- Authority
- IE
- Ireland
- Prior art keywords
- weight
- process according
- tpus
- modifying agent
- polyether
- Prior art date
Links
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 31
- 238000001125 extrusion Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229920002647 polyamide Polymers 0.000 claims abstract description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 23
- 229920000570 polyether Polymers 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 12
- 229920000299 Nylon 12 Polymers 0.000 claims description 8
- 229920002614 Polyether block amide Polymers 0.000 claims description 4
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000005259 measurement Methods 0.000 description 14
- 239000008187 granular material Substances 0.000 description 10
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 8
- -1 polyethylene adipate Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000009989 Posterior Leukoencephalopathy Syndrome Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- 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
Abstract
Conversion of TPUs by extrusion with the aid of modifying agents chosen from polyamide-based thermoplastic elastomers. The modifying agents improve especially the conversion parameters and the rheological behaviour of the TPUs during their processing.
Description
ATOCHEM, a French Body Corporate, of; 4 & 8 Cours Michelet, La Defense 10, 92800 Puteaux, France. -1IE 91466 The present invention relates to an improvement in the conversion of thermoplastic polyurethanes or TPUs in processing using extrusion with the aid of one or more modifying agents.
Among the properties of TPUs there may be mentioned hydrolysis resistance, low-temperature flexibility, heat resistance and abrasion resistance.
However, their processing or processability is not very reproducible from one operation to another and significant variations are observed in their rheological behaviour.
The present invention has been aimed especially at improving the rheological properties of TPUs and of making their conversion more reproducible.
Thermoplastic polyurethanes or TPUs are polyurethane-based copolymers which can be obtained by a combined reaction of a diol of high molecular mass or a polyol, which constitutes the crystallisable flexible block of the elastomer, with a diisocyanate and a diol of low molecular mass, which generate the rigid block, it being possible for the synthesis to take place in one or two stages.
Among the TPUs a distinction can be made between those in which the polyols are of polyester type (such as polyethylene adipate, polytetramethylene adipate and poly(e-caprolactone)) and those in which the polyols are of polyether type (such as polypropylene and IE 91466 polytetramethylene glycol).
The TPUs of polyether type generally have a better hydrolysis resistance and a glass transition temperature which is lower than that of the TPUs of polyester type, which have, in contrast, a better resistance to hydrocarbons and to oils.
The conversion or formation of objects such as filaments, sheets, plates, films, tubes and coating, for example for cables, is carried out according to extrusion techniques such as blow-extrusion, filament extrusion, sheath or cast extrusion, extrusion coating with acrylic resin, extrusion coating and coextrusion.
Processing TPUs by extrusion is generally done at temperatures of 150 to 240®C, which are controlled so as to increase progressively over the whole length of the screw and to decrease between the adaptor and the die.
Screw rotation speeds are generally from 12 to rev/min.
The process for converting the TPUs according to the invention consists in adding one or more modifying agents to the TPU-based plastic substance to be converted which it is desired to extrude. The modifying agents used are random or block, polyamide-based thermoplastic elastomers.
The random copolymers can be formed by the random chain sequencing of the various constituents (monomers and/or prepolymers), whereas the block copolymers, IE 91466 - 4 ~ which are preferred, can be formed from blocks exhibiting a certain chain length of their various constituents.
The polyamide-based copolymers used in the invention are either polyester amides or polyether amides.
The block polyether amides or polyether-blockamides can, in particular, result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends such as, among others: a) Polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends, b) Polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained by cyanoethylation and hydrogenation of aliphatic alpha,omega-dihydroxylated polyoxyalkylene blocks called polyether diols, c) Polyamide blocks with dicarboxylic chain ends with polyether diols, called polyetheresteramides, which are particularly preferred.
The composition and the manufacture of such polyetheresteramides have been described in FR-A- 74/18,913 and 77/26,678, to which reference should be made for further details.
The number-average molecular mass of these polyamide blocks is generally from 500 to 10,000, and more particularly from 600 to 5,000. The polyamide blocks of the IE 91466 - 5 polyetheresteramides are preferably made of polyamide 6, 66, 612, 11, 12 or 1212 and/or of amorphous polyamide or of copolyamide resulting from the polycondensation of their monomers.
The number-average molecular mass of the polyethers is generally from 200 to 6,000, and more particularly from 600 to 3,000.
The polyether blocks preferably consist essentially of polytetramethylene glycol (PTMG). In addition to PTMG, they may, for example, contain polyethylene glycol (PEG) and/or polypropylene glycol (PPG).
The inherent viscosity of the polyetheresteramides is advantageously from 0.8 to 2.05, measured in metacresol at 20°C with an initial concentration of 0.5 g of polymer per 100 g of meta-cresol.
The polyetheresteramides are typically made up of 5 to 85 % by weight of polyether, and of 95 to 15 % by weight of polyamides, and preferably of 30 to 85 % by weight of polyether and of 70 to 15 % by weight of polyamide.
The polyetheresteramides which are preferred are those in which the polyether blocks are essentially made up of PTMG and/or PEG and more particularly those in which the polyamide blocks are derived from polyamide 11, 12 and/or 1212.
The quantity of modifying agents needed for the conversion of the TPUs is generally from 5 to 45 %, advantageously from 10 to 30 %, and preferably 10 to 20 %, IE 91466 - 6 by weight of TPU.
The modifying agent(s) is (are) incorporated in the TPUs before their conversion, by any mixing process such as dry blending or compounding, which is particularly preferred.
In the case of dry blending, the constituents are generally in the form of granules with a mean diameter of 2 to 5 mm.
In the case of compounding, the constituents 10 are mixed in the molten state, generally in a mixer at a temperature of 190 to 240°C.
Once the mixing of the constituents has been carried out, generally in the form of granules with a mean diameter of 2 to 5 mm and before the actual conversion stage, it is preferable to stove the mixture under vacuum, for example for 2 hours at 110°C, and then to package it in a leakproof packaging in order to avoid moisture regain.
In the case of the conversion of TPUs by extrusion, it is observed that the presence of modifying agent(s) makes it possible to improve significantly one or more of the following conversion parameters: - the maximum throughput of the machine, more particularly in the case of the TPU/modifying agent mixtures prepared by compounding - the pressure, which is generally reduced, whatever the throughput of the machine - the torque, and hence the energy consumed by Έ91466 — 7 the machine, is reduced the rheological behaviour of the TPUs and especially: - the melt strength at the tool exit, - the melt viscosity within the machine is reduced - the extrudability of the melt, that is to say shape formation which is made easier and more particularly when manufacturing tubes based on TPU of polyether type as well as the mechanical characteristics of 10 the finished products: - the cold flexibility when compared with the TPUs extruded in the absence of any modifying agent.
In the case of Examples 1 to 4 which follow and which further illustrate the present invention, the extrusion is carried out with the aid of a Haake rheometer with a 2-zone screw 30 mm in diameter and with L/D = 27.
The screw barrel comprises an air-cooled feed zone and five control zones; the die has its own control zone.
The compression ratio of the screw is equal to 2.
A temperature sensor and a pressure sensor are placed at the entry of the die, which is a vertical rod die, 3 mm in diameter and with L/D = 6.
Depending on the tests, the screw speed varies between 10 and 42 rev/min.
The characteristics of the TPUs processed are IE 91466 shown in Table 1 and those of the modifying agents employed are shown in Table 2.
EXAMPLE 1 A-A compound is extruded consisting of 5 90 parts by weight of TA and 10 parts by weight of Alf prepared beforehand in a Buss kneader.
The extrusion temperature is between 190 and 220°C. At the die entry the melt temperature is between 195 and 198°C. Rod is obtained at the die exit.
The pressure, the absorbed torque and the screw speed are measured continuously, together with the throughput at various screw speeds.
The maximum throughput of the machine is also measured.
The rheological behaviour of the product at the die exit is also evaluated by measuring the time taken by the rod to flow over a certain height H^, measured starting at the die exit under gravity.
The heights noted are 0.1(^), 0.2(H2), 0.3(H3), 0.5(H5) and 1(1^0)111.
The viscosity is measured with the aid of an Instron capillary viscometer..
The change in the stiffness of the product is followed by measuring its flexural modulus at different temperatures T according to ASTM standard D 790 and calculating the ratio IE 91466 - 9 flexural modulus at TeC Rrp " ' — ' —.. ' —. flexural modulus at 23 °C B-A mixture of granules or dry blend 5 consisting of 90 parts by weight of TA and 10 parts of Ais extruded under the same conditions as under A.
The same measurements are carried out as under A.
C - A dry blend consisting of 80 parts by weight of T^ and 20 parts by weight of A^ is extruded under the same conditions as under A, and the same measurements are carried out as under A.
D - By way of comparison, the same measurements are carried out as those described under A in the case of T^ by itself.
The results of A to D are combined in Table 3.
EXAMPLE 2 A-A compound consisting of 90 parts by weight of T2 and 10 parts by weight of A2, prepared beforehand in a Buss kneader (co-kneader) is extruded under the same conditions as Example l.A, anl the same measurements are carried out as in l.A.
B-A mixture of granules (dry blend) consisting of 90 parts by weight of T2 and 10 parts by weight of A2 is extruded under the same conditions as Example l.A, and the same measurements are carried out as in IE 91466 - 10 l.A.
C - A mixture of granules (dry blend) consisting of 90 parts by weight of T2 and 10 parts by weight of Αχ is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
D - A mixture of granules (dry blend) consisting of 90 parts by weight of T2 and 10 parts by weight of A4 is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
E - By way of comparison, the product T2 is extruded under the same conditions as in Example l.A, and the same measurements are carried out as in l.A.
The results of A to E are combined in Table 3.
EXAMPLE 3 A-A mixture of granules (dry blend) consisting of 90 parts by weight of T3 and 10 parts by weight of Αχ is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
B - A mixture of granules (dry blend) consisting of 80 parts by weight of T3 and 20 parts by weight of Αχ is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
C - By way of comparison, the product T3 is - 11 extruded under the same conditions as in Example l.A, and the same measurements are carried out as in l.A.
The results of A to C are combined in Table 3.
EXAMPLE 4 A-A mixture of granules (dry blend) consisting of 90 parts by weight of T4 and 10 parts by weight of Aj is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
B - A mixture of granules (dry blend) consisting of 90 parts by weight of T4 and 10 parts by weight of A2 is extruded under the same conditions as Example l.A, and the same measurements are carried out as in l.A.
C - By way of comparison, the product T4 is extruded under the same conditions as in Example l.A.
The same measurements are carried out as in l.A.
The results of A to C are combined in Table 3. - 12 IE 91466 TABLE 1 TPU No. TYPE DENSITY SHORE A/D HARDNESS (± 2/± 2) Tl polyester 1.19 87/34 T2 polyester 1.21 92/41 T3 polyether 1.12 87/36 T4 polyether 1.14 96/47 - 13 TABLE 2 MODIFYING AGENT No. TYPE CHARACTERISTICS Al polyether ester amide polyether blocks = PTMG polyamide blocks = PA-12 50 % by weight of PTMG Mn = 2000 50 % by weight of PA-12 Mn = 2000 a2 33 % by weight of PTMG Mn = 1000 67 % by weight of PA-12 Mn = 2000 a4 polyether ester amide polyether blocks = PEG polyamide blocks = PA-12 50 % by weight of PEG Mn - 1500 50 % by weight of PA-12 Mn = 1500 TABLE 3 IE 91466 EX 3BR0U0B- BBSS- TORQUE MAXIMUM KELT VXBCOSXT? R R No. BUT (kg/h) SURE (bar·) (B/·) TBROUOB- BUT STRSROTB* () (Boo) at 210 C -20 -40 (kg/h) for «crow apeod 23 rov/oln 7-10^ 7-10° l.A. 4.4 53 68 12 B10/7 530 215 l.B 5.4 93 102 8.5 B10/6.5 440 190 l.C 5.4 92 100 9.7 B10/7 1.0 5.2 102 140 6.7 B10/5.6 180 120 2.A 4.9 78 60 11 B2/2.9 B5/5.2 515 255 2.1 6.7 2.B 4.2 65 80 12 B2/3.3 B5/4.5 550 255 1.5 6.3 2.C 5.1 125 125 6.5 B2/2.5 H5/S.6 1600 400 3.5 7.5 2.0 5.1 125 125 10 B2/1.9 B5/4.4 670 225 2.E 5.2 130 150 5.2 B2/1.8 B5/4.4 1950 500 3.3 13.4 S.A 5.8 77 85 13 810/3.7 3.B 4.9 65 66 13.5 B10/S 3.C 5.85 73 68 11.6 B10/3 485 235 4.A 5.23 95 no 6 B2/1.9 B3/2.9 B5/4 535 255 IE 91466 BX Ho. THROUGH- PUT <Κβ/Μ PRES- SURE (bar·) TORQUE (H/a) MAXIMUM THROUGH- PUT (ki/h) MELT STRBHOTH» (») VZ6COS (Paa) at 210 CTT ’c B -20 B -40 for acrau 23 rev/ad ipMd - a • 2 -rio4 7«10® 4.B 4.C 5.15 5.65 96 95 110 135 6 6.6 B2/2 B3/3 BS/4.4 B2/1.6 B3/2.5 B5/3.7 590 530 270 265 - * for the Examples 1. A to l.C the throughput is 6.2 kg/h 2. A to 2.E the throughput is 5.2 kg/h 3. A to 3.C the throughput is 5.8 kg/h 4. A to 4.C the throughput is 5.6 kg/h
Claims (13)
1. Process for converting a thermoplastic polyurethane (TPU) based composition by extrusion, which comprises adding thereto one or more random or block, polyamide-based thermoplastic elastomers, as modifying agents.
2. Process according to Claim 1, in which from 5 to 45 % by weight of modifying agent is added to the TPU.
3. Process according to Claim 2 in which from 10 to 30% by weight of modifying agent is added.
4. Process according to Claim 3 in which from 10 to 20% by weight of modifying agent is added.
5. Process according to any one of the preceding claims in which the modifying agent is a block copolymer.
6. Process according to Claim 5, in which the modifying agent is a polyether-block-amide.
7. Process according to Claim 5 or 6, in which the polyether blocks are based on PTMG and/or PEG.
8. Process according to any one of Claims 5 to 7, in which the polyamide blocks are based on PA-11, PA-12 and/or PA-1212.
9. Process according to any one of Claims 1 to 8, in which the TPU and modifying agent are premixed dry.
10. Process according to any one of Claims 1 to 8, in which the TPU and the modifying agent(s) are precompounded. IE 91466 - 17
11. Process according to Claim 1 substantially as described in any one of the Examples.
12. A TPU-based composition whenever converted by a process as claimed in any one of the preceding claims.
13. A composition according to Claim 12 in the form of a filament, film, sheet, plate, tube or coating. Dated this the 12th day of February, 1991
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9001691 | 1990-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IE910466A1 true IE910466A1 (en) | 1991-08-14 |
Family
ID=9393662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE046691A IE910466A1 (en) | 1990-02-13 | 1991-02-12 | PROCESS FOR CONVERTING TPUs BY EXTRUSION USING MODIFYING¹AGENTS |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0442786B1 (en) |
| JP (1) | JP2574541B2 (en) |
| KR (1) | KR950000218B1 (en) |
| CN (1) | CN1041427C (en) |
| AT (1) | ATE127503T1 (en) |
| AU (1) | AU650245B2 (en) |
| BR (1) | BR9100527A (en) |
| CA (1) | CA2036157C (en) |
| DE (1) | DE69112661T2 (en) |
| DK (1) | DK0442786T3 (en) |
| ES (1) | ES2075941T3 (en) |
| FI (1) | FI910672A (en) |
| IE (1) | IE910466A1 (en) |
| NO (1) | NO178733C (en) |
| PT (1) | PT96742A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0819631B2 (en) * | 1990-11-30 | 1996-02-28 | 新王子製紙株式会社 | Bleaching method for lignocellulosic material |
| DE59202134D1 (en) * | 1991-08-06 | 1995-06-14 | Atochem Elf Deutschland | Use of polyurethane foils for gluing. |
| 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 |
| DE19652037A1 (en) * | 1996-12-13 | 1998-06-18 | Wolff Walsrode Ag | Elastic films with improved biodegradability and processes for their production |
| WO2003024570A1 (en) * | 2001-09-11 | 2003-03-27 | S. T. Chemical Co., Ltd. | Dehumidifying agent of coating film delaminating type |
| FR2831175B1 (en) * | 2001-10-22 | 2004-02-13 | Salomon Sa | POLYURETHANE COMPATIBILIZING AGENT, THERMOPLASTIC MATERIAL CONTAINING SUCH AN AGENT AND USE OF SUCH MATERIAL FOR MAKING SPORTS ARTICLES |
| CN1321155C (en) * | 2004-03-03 | 2007-06-13 | 中国纺织科学研究院 | Polyurethane composition for film and its use |
| EP2412508A1 (en) | 2010-07-29 | 2012-02-01 | Innovent e.V. | Method for coating surfaces with a thermoplastic elastomer on a polyurethane basis and the manufactured article |
| CN111040420A (en) * | 2019-09-04 | 2020-04-21 | 晋江兴迅新材料科技有限公司 | Method for preparing TPV (thermoplastic vulcanizate) foam material from PEBAX (polyethylene-ethylene-butylene-styrene copolymer) and TPV foam material |
| CN111040429B (en) * | 2019-12-30 | 2021-12-24 | 脉通医疗科技(嘉兴)有限公司 | Medical tube and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2854409A1 (en) * | 1978-12-16 | 1980-06-26 | Bayer Ag | METHOD FOR PRODUCING THERMOPLASTIC CHEMICAL MATERIALS |
| CH665648A5 (en) * | 1984-12-21 | 1988-05-31 | Inventa Ag | THERMOPLASTICALLY PROCESSABLE MASSES MADE OF POLYAMIDE, THERMOPLASTIC POLYURETHANE AND ACTIVATED POLYOLEFIN. |
| JPS61179257A (en) * | 1985-02-05 | 1986-08-11 | Toray Ind Inc | Resin composition |
| FR2579612A1 (en) * | 1985-03-29 | 1986-10-03 | Atochem | METHOD OF ASSEMBLING SURFACES BY APPLYING A POLYURETHANE OR POLYETHERAMIDE JOINT, SUPERFICIAL FUSION OF THE SEAL AND COOLING |
| DE3810078A1 (en) * | 1988-03-25 | 1989-10-05 | Bayer Ag | THERMOPLASTIC POLYMER BLEND AND METHOD FOR THE PRODUCTION THEREOF |
| KR0147066B1 (en) * | 1988-09-07 | 1998-08-17 | 아사구라 다쓰오 | Thermoplastic resin composition |
-
1991
- 1991-02-07 DE DE69112661T patent/DE69112661T2/en not_active Expired - Fee Related
- 1991-02-07 BR BR919100527A patent/BR9100527A/en not_active Application Discontinuation
- 1991-02-07 AT AT91400298T patent/ATE127503T1/en not_active IP Right Cessation
- 1991-02-07 JP JP3016624A patent/JP2574541B2/en not_active Expired - Fee Related
- 1991-02-07 EP EP91400298A patent/EP0442786B1/en not_active Expired - Lifetime
- 1991-02-07 DK DK91400298.5T patent/DK0442786T3/en active
- 1991-02-07 ES ES91400298T patent/ES2075941T3/en not_active Expired - Lifetime
- 1991-02-11 PT PT96742A patent/PT96742A/en unknown
- 1991-02-12 AU AU70996/91A patent/AU650245B2/en not_active Ceased
- 1991-02-12 IE IE046691A patent/IE910466A1/en unknown
- 1991-02-12 FI FI910672A patent/FI910672A/en not_active Application Discontinuation
- 1991-02-12 CA CA002036157A patent/CA2036157C/en not_active Expired - Fee Related
- 1991-02-12 KR KR1019910002353A patent/KR950000218B1/en not_active IP Right Cessation
- 1991-02-12 NO NO910558A patent/NO178733C/en not_active IP Right Cessation
- 1991-02-13 CN CN91100913A patent/CN1041427C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2574541B2 (en) | 1997-01-22 |
| AU650245B2 (en) | 1994-06-16 |
| PT96742A (en) | 1991-10-31 |
| ATE127503T1 (en) | 1995-09-15 |
| EP0442786B1 (en) | 1995-09-06 |
| AU7099691A (en) | 1991-08-15 |
| BR9100527A (en) | 1991-10-29 |
| JPH051154A (en) | 1993-01-08 |
| NO178733C (en) | 1996-05-22 |
| DE69112661D1 (en) | 1995-10-12 |
| NO178733B (en) | 1996-02-12 |
| FI910672A (en) | 1991-08-14 |
| DK0442786T3 (en) | 1996-01-02 |
| CN1054087A (en) | 1991-08-28 |
| FI910672A0 (en) | 1991-02-12 |
| CA2036157C (en) | 1997-12-30 |
| DE69112661T2 (en) | 1996-04-18 |
| KR910015655A (en) | 1991-09-30 |
| KR950000218B1 (en) | 1995-01-12 |
| CN1041427C (en) | 1998-12-30 |
| NO910558L (en) | 1991-08-14 |
| EP0442786A1 (en) | 1991-08-21 |
| NO910558D0 (en) | 1991-02-12 |
| CA2036157A1 (en) | 1991-08-14 |
| ES2075941T3 (en) | 1995-10-16 |
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