GB2201677A - Process for producing a shaped, extruded product from a crosslinkable polymeric composition - Google Patents
Process for producing a shaped, extruded product from a crosslinkable polymeric composition Download PDFInfo
- Publication number
- GB2201677A GB2201677A GB08703469A GB8703469A GB2201677A GB 2201677 A GB2201677 A GB 2201677A GB 08703469 A GB08703469 A GB 08703469A GB 8703469 A GB8703469 A GB 8703469A GB 2201677 A GB2201677 A GB 2201677A
- Authority
- GB
- United Kingdom
- Prior art keywords
- copolymer
- extruder
- compacted
- mixer
- silanol condensation
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 235000012438 extruded product Nutrition 0.000 title claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000009833 condensation Methods 0.000 claims abstract description 45
- 230000005494 condensation Effects 0.000 claims abstract description 45
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 unsaturated silane compound Chemical class 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 11
- 239000004711 α-olefin Substances 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims description 42
- 238000004132 cross linking Methods 0.000 claims description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 description 21
- 150000004756 silanes Chemical class 0.000 description 16
- 229920000578 graft copolymer Polymers 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000002028 premature Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003707 silyl modified polymer Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004608 Heat Stabiliser Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001607 magnesium mineral Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-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
- PLYIPBIZXSTXCW-UHFFFAOYSA-N octanoic acid;tin Chemical compound [Sn].CCCCCCCC(O)=O PLYIPBIZXSTXCW-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-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
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/465—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers
- B29C48/467—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers using single rollers, e.g. provided with protrusions, closely surrounded by a housing with movement of the material in the axial direction
- B29C48/468—Cavity transfer mixing devices, i.e. a roller and surrounding barrel both provided with cavities; Barrels and rollers therefor
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The process comprises: (A) introducing into the feed zone of an extruder a copolymer of an alpha-olefin with a hydrolysable, unsaturated silane compound; (B) compacting and melting the copolymer in the extruder; (C) passing the compacted, molten copolymer through a distributive mixer positioned at the discharge end of the extruder; (D) injecting a silanol condensation catalyst into the compacted, molten copolymer after compacting and melting in the extruder; (E) blending the compacted, molten copolymer and the silanol condensation catalyst in the distributive mixer, and (F) extruding the resulting blend out of the distributive mixer through an extrusion die to form a shaped, crosslinkable, extruded product. The distributive mixer is preferably a cavity transfer mixer. The process which is particularity useful for coating wires and cables overcomes, or at least mitigates, the problem of procuring of the thermoformed copolymer.
Description
PROCESS FOR PRODUCING A SHAPED, EXTRUDED PRODUCT FROM A
CROSSLINKABLE POLYMERIC COMPOSITION
The present invention relates to a process for producing a shaped, extruded product from a crosslinkable composition comprising a copolymer of an alpha-olefin with a hydrolysable ethylenically unsaturated silane compound. In particular, the invention relates to a method for producing coated electric wire and cable from copolymers of ethylene.
It is well known that polymer compositions can be thermoformed by extrusion into a variety of useful articles such as pipe and coatings for electric wire and cable. For some applications the polymer compositions are not crosslinked, but for others, especially wire and cable insulation, the polymer compositions are crosslinked. Crosslinking the polymer composition improves the physical properties, particularly the high teuperature properties.
A number of methods for crosslinking a polyolefin are known.
For example, the polymer can be irradiated to cause crosslinking or an organic peroxide can be mixed with the polymer and then the mixture heated to decompose the peroxide. The irradiation technique requires special, expensive equipment and is not suitable for crosslinking thick sections of polymer. The use of organic peroxides can result in the generation of bubbles in the polymer due to decomposition gases.
Another method of crosslinking a polyolefin is to incorporate into the polymer hydrolysable silane groups which form crosslinks by hydrolysis and condensation in the presence of water.
US Patent 3 075 948 discloses the production of graft copolymers of polyolefins, such as polyethylene, and hydrolysable ethylenically unsatured silanes in the presence of a solvent, such as xylene and catalysed using a peroxide or hydroperoxide.
US Patent 3 646 155 discloses the production of shaped crosslinked polymer product from a graft copolymer of polyethylene and a hydrolysable ethylenically unsaturated silane. The polyethylene and hydrolysable ethylenically unsaturated silane are first reacted together in an extruder in the presence of a peroxide catalyst. The graft copolymer is extruded and granulated and then mixed by tumbling with a masterbatch blend of polyethylene and a silanol condensation catalyst made in a second extrusion step. The resulting blend is finally extruded in a third extrusion step to produce the shaped article. It is possible to carry out this technique using only two, instead of three, extrusions but even then it still involves a relatively large amount of handling and an excessive use of extruder time.
Other patents which disclose processes for the production of graft copolymers of polyolefin and hydrolysable ethylenically unsaturated silane which require two or more extrusion steps include
US 3 802 913, US 4 117063, US 4136 132 and US 4 228 255. A commercial example of the multi-extrusion process for producing the graft copolymers is the SIOPLAS (Registered Trade Mark) process.
It is difficult, if not impossible, or impractical to produce a graft copolymer by simply mixing together in a conventional extruder a polyolefin, a hydrolysable ethylenically unsaturated silane, a peroxide catalyst and a silanol condensation catalyst. A conventional extruder does not provide adequate mixing and localised premature crosslinking tends to cause gels in the product. However a process for producing a graft copolymer using a single extrusion process is known and is disclosed in US 4 117 195 and US 4 351 790. This process requires the use of a specially designed, complex and expensive extruder which is substantially longer than a conventional extruder. A special extruder screw is required as described in British Patent 964 428. Also the temperatures at various points along the length of the extruder need to be carefully controlled.The one extrusion process therefore requires the installation of new, specially designed extruders or difficult and expensive adaptations to an existing, conventional extruder. The one-extrusion process is operated commercially as the
MONOSIL (Registered Trade Mark) process.
Published European Patent Application No.O 163 865 discloses a method and apparatus for producing shaped crosslinked product from a graft copolymer by extruding compacted molten polymer, e.g.
polyethylene, into a mixer formed on or fitted to the discharge end of an extruder, injecting proportionate amounts of a compounding mixture comprising olefinically unsaturated hydrolysable silane, free-radical generator and, preferably, a silanol condensation catalyst into the compacted, molten polymer. The polymer and compounding mixture are blended in the mixer until the silane is grafted to the polymer and the resulting graft copolymer mixed with the silanol condensation catalyst is extruded through a die to form the shaped product. The process disclosed in EP 0 163 865 is therefore an alternative one-extrusion process for grafting hydrolysable ethylenically unsaturated silane onto a polyolefin.
The processes for producing crosslinked products by graft copolymerising a polyolefin with a hydrolysable ethylenically unsaturated silane have certain advantages over techniques involving crosslinking by the use of.free-radical generators. However, the surface characteristics of products produced from the graft copolymers are generally not very good. The surface defects are generally most noticeable following a change in the speed of the extrusion line; such as, for example, when the speed of a line for coating a cable is increased again following a decrease in line speed to enable lengths of conductor to be joined. The surface characteristics can be important in a number of possible applications of the graft copolymer but the application for which it is most critical is coating wire and cable. A smooth surface is required for good insulation properties.The graft copolymers produced according to the known processes are generally crosslinked by storing them in a steam filled chamber (a "sauna") at 800C for a relatively long period of time, typically 8 to 16 hours. British
Patents GB2 028 831B and GB 2 039 513B disclose the preparation and use of a crosslinkable polyethylene resin composition comprising (a) a copolymer of ethylene and ethylenically unsaturated silane and (b) a silanol condensation catalyst. The copolymer of ethylene and unsaturated silane is prepared at a temperature of from 150 to 4000C under a pressure of from 1000 to 4000 kg/cm2in the presence of a radical polymerisation initiator.
Copolymers of alpha-olelfins with hydrolysable olefinically unsaturated silane compounds (hereinafter referred to, for convenience, as "silane copolymers") such as those disclosed in
GB 2 028 831 and GB 2 039 513 can be used in the fabrication of a large variety of useful products. The blends of silane copolymers and silanol condensation catalysts can be handled and processed using apparatus and techniques conventionally used for plastics fabrication. For example, blends of the silane copolymers and silanol condensation catalysts can be subjected to conventional extrusion, injection moulding, blow-moulding and film-blowing processes. Generally, the crosslinking of a silane copolymer is effected subsequent to the shaping process because the crosslinked polymer cannot be satisfactorily thermoformed.
A problem encountered with silane copolymers is that during thermoforming operations, the polymer can undergo premature crosslinking. In addition, extrusion of blends of silane copolymer and silanol condensation e4tdalyst can result in scorching" of the extruded product. "Scorching" is a term used in the art to describe the formation of surface imperfections due to polymer which has crosslinked in the extruder being deposited on the surface of the extrudate. Premature crosslinking, including "scorching" can lead to difficulties in the fabrication of products or the production of articles having unsatisfactory physical and mechanical properties.
One method of reducing premature crosslinking proposed in
British Patent GB-A-1357549 is to mould or extrude articles from silyl modified polymers in the absence of the silanol condensation catalyst and then to contact the produced article with an
4 aqueous dispersion or solution of a tin carboxylate to cause the crosslinking. However, in many applications it is preferred to include the silanol condensation catalyst as a component of the polymer composition because this generally results in higher crosslinking rates and to more complete crosslinking, particularly in articles having a relatively thick cross section.
It is known to use mixers formed or attached at the discharge ends of extruders. US Patents 4 169 679 and 4 302 409 disclose mixer heads capable of being attached to the discharge end of an existing extruder forwarding screw. The mixer head is disposed in the extruder barrel between the screw and the die and turns with the screw to mix the compacted molten polymer delivered to it by the forwarding screw. A fluid additive, such as a blowing agent, can be introduced through the barrel wall to the compacted, molten polymer at the upstream end of the mixer head. Neither of these patents teaches or suggests the addition of a silanol condensation catalyst to a silane copolymer in order to produce a crosslinkable composition.
US Patents 2 540 146 and 3 035 303 disclose the use of mixing heads constructed at the downstream end of an extruder screw upstream from the extrusion die. These patents do not disclose the provision of a separate mixer head adapted to be attached to an existing extruder or the production of a crosslinkable polymer composition comprising a silane copolymer and a silanol condensation catalyst.
Mixer units adapted to be fitted onto existing extruders are known. For example, a cavity-transfer type extruder mixer is disclosed in British Patent 930 339 which comprises a hollow cylindrical stator member and a cylindrical rotor member which is rotable within the stator. The facing surfaces on the rotor and stator carry respective pluralities of rows of elongate longitudinally extending grooves. The rows of grooves on each member extend circumferentially around the member and are spaced apart axially, the rows of one member being axially offset from the rows on the other member such that there is axial overlap of the grooves in adjacent rows on the stator and rotor.European Patent O 048 590 discloses an improved cavity-transfer mixer in which the facing surfaces of the stator and rotor are each provided with circumferentially extending rows of cavities, the cavities in adjacent rows on the stator being circumferentially offset; the cavities in adjacent rows on the rotor being circumferentially offset; and the rows of cavities on the stator and rotor being axially offset. British patent 1 475 216 discloses a mixer head which can be adapted to be fitted onto existing extruders in which the mixer head has grooves and lands on the facing surfaces of the rotor and stator. None of these patents teaches or suggests the production of a crosslinkable composition comprising a blend of a silane copolymer and a silanol condensation catalyst.
An object of the present invention is to provide an improved process for producing shaped, extruded product from a crosslinkable silane copolymer. In particular, it is an object of the present invention to provide a process for producing shaped, extruded product from a crosslinkable silane copolymer which process overcomes or at least mitigates the problems of precuring, including scorching often experienced with the known processes.
A further object of the present invention, at least in its preferred embodiments, is to provide a process for producing shaped, extruded product from a silane copolymer which can be crosslinked in a relatively short period of time at moderate temperatures.
According to the present invention a process for producing a shaped, extruded product from a crosslinkable copolymer of an alpha-olefin with a hydrolysable, ethylenically unsaturated silane compound comprises: (A) introducing the copolymer into the feed zone of an extruder; (B) compacting and melting the copolymer in the extruder; (C) passing the compacted, molten copolymer through a distributive
mixer positioned at the discharge end of the extruder; (D) injecting a silanol condensation catalyst into the compacted,
molten copoylmer after compacting and melting in the extruder; (E) blending the compacted, molten copolymer and the silanol
condensation catalyst in the distributive mixer and (F) extruding the resulting blend out of the distributive mixer
through an extrusion die to form a shaped, crosslinkable,
extruded product.
The shaped, extruded product is crosslinked by exposure to H20
The crosslinking can be effected by simply storing the product, storing in a humid atmosphere or by treating the product with water or steam. For example, the shaped, extruded product can be passed through a water bath, sprayed with water or stored in a steam filled cabinet.
Shaped, extruded products formed from blends comprising (A) silyl-modified polymers i.e. silane copolymers (as hereinbefore defined) or polyolefins grafted with hydrolysable ethylenically unsaturated silane and (B) silanol condensation catalysts are commonly crosslinked by placing the product in a steam-filled chamber (a "sauna") maintained at an elevated temperature, typically 800C, for a period of time which is typically from 8 to 16 hours.
It is a feature of the present invention that shaped products can be formed from blends of silane copolymer and silanol condensation catalyst which can be crosslinked in a relatively short period of ttlne at moderate temperature e.g. 24 hours at 200C. The improved rate of crosslinking which is obtainable by using the process according to the present invention offers the possibility of "in-line curing" i.e. manufacturing and curing the product on a single processing line such that the product at the end of the line is adequately crosslinked and requires no further treatment. The possibility of "in-line curing" would be especially advantageous in the manufacture of wire and cable coated with crosslinked silane copolymers.
The silane copolymer can be prepared using known techniques and equipment and is preferably a copolymer of ethylene with a hydrolysable ethylenically unsaturated silane compound.
The unsaturated silane compound copolymerised with the alpha-olefin is preferably a compound having the general formula, R1siR2my3-m wherein R1 represents an ethylenically unsaturated hydrocarbyl or hydrocarbyloxy group; R2 represents an aliphatic saturated hydrocarbyl group; Y represents a hydrolysable organic group and m is O, 1 or 2. If the compound has more than one Y, they need not be the same. More specific examples of suitable hydrolysable ethylenically unsaturated silane compounds having the above general formula are those in which R1 is vinyl, allyl isopropenyl, butenyl, cyclohexenyl or methacryloxypropyl; Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, alkylamino or arylamino; and R2 is methyl, ethyl, propyl, decyl or phenyl.
Particularly suitable unsaturated silane compounds suitable for use in the present invention are those having the general formula CH2-CHSi(OZ)3 wherein Z is a hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Most preferably, the unsaturated silane is selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane and vinyl triacetoxy silane.
The silane copoylmer preferably contains from 0.1 to 105 by weight, more preferably 0.5 to 5 by weight of copolymerised units of the silane compound.
In addition to the alpha-olefin and hydrolysable ethylenically unsaturated silane, the silane copolymer can optionally contain one or more further comonomers. The further comonomers can be selected from various monomers which are copolymerisable with the alpha-olefin and hydrolysable ethylenically unsaturated silane compound and which are, in#ddition, compatible with the unsaturated silane and the crosslinking reaction. Suitable further comonomers include vinyl esters, aklkyl (meth) acrylates, unsaturated ethers, unsaturated carboxylic acids and derivatives of (meth) acrylic acid. Generally, the silane copolymer will contain less than 40, preferably less than 30 per cent by weight of the further comonomer. Most preferably, the further comonomer, if present, is used in an amount of from 1 to 20 per cent by weight of the total weight of the silane copolymer.
Silanol condensation catalysts suitable for use in crosslinking copolymers containing hydrolysable silane are known and include metal carboxylates, organic bases, inorganic acids and organic acids. Specific examples of suitable silanol condensation catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethylamines, dibutylamine, hexylamines, pyridine, sulphuric acid, hydrochloric acid, toluenesulphonic acid, acetic acid, stearic acid and maleic acid.
The preferred silanol condensation catalysts are the tin carboxylates, particularly dibutyl tin dilaurate. The amount of silanol condensation catalyst introduced into the compacted, molten copolymer will depend on the selected catalyst and the copolymer to be crosslinked The optimum quantity can readily be determined by a person skilled in the art using simple experiments. In general, the amount of silanol condensation catalyst used will be from 0.01 to 10 per cent by weight of the silane copolymer, preferably from 0.05 to 3 per cent by weight.
The amount of silanol condensation catalyst used in the known commercial processes is typically about 0.05% by weight of the silane copolymer whereas the amount used in the process according to the present invention is preferably at least 0.3Z by weight of the silane copolymer.
Other additives can be included in the compositions prepared according to the process of the present invention such as antioxidants and heat stabilisers commonly used in the processing of polyolefins. The composit###s s can also include fillers for example, minerals for improving flame retardancy or providing water for the crosslinking reaction e.g. metal hydroxides such as aluminium hydroxide and magnesium hydroxide or minerals such as electrically conductive carbon black, chalk, talc, mica and silica.The additives and fillers can be included with the silane copolymer fed into the extruder, can be introduced at the upstream end of the distributive mixer, either separately from or together with the silanol condensation catalyst, or can be mixed using a further mixing unit, with the blend of silane copolymer and silanol condensatLon catalyst leaving the distributive mixer before the composition is extruded to form a shaped product. Preferably, the additives are introduced into the distributive mixer with the silanol condensation catalyst.
The compositions prepared according to the process of the present invention can also contain other polymers, thermoplastics or elastomers.
Known equipment can be used to carry out the method according to the present invention. The extruder can be any conventional extruder comprising a hollow barrel and a forwarding screw rotatably mounted in the barrel. Generally the ratio of the length to diameter of the extruder screw is about 15:1 to 25:1.
The distributive mixer is preferably of the cavity-transfer type disclosed in British patents 930 339 and 1 475 216 and European patent 0 048 590. Such mixers provide rapid mixing of the silanol condensation catalyst with the silane copolymer and are readily fitted onto conventional extruders.
The method according to the present invention is suitable for producing various products by extrusion, such as, for example, coatings for wire and cable, foam, film, sheets, rods and pipes. It is to be noted that the term extrusion as used in this specification includes blow moulding and injection moulding processes.
The present invention is particularly useful for the coating of wires and cables and includes a process for producing wire and cable coated with a crosslinked copolymer of an alpha-olefin preferably ethylene, and a hydrolysable, ethylenically unsaturated silane compound which process comprises::
(A) introducing the copolymer into the feed zone of an
extruder;
(B) compacting and melting the copolymer in the extruder;
(C) passing the compacted, molten copolymer through a
distributive mixer positioned at the discharge end of the
extruder;
(D) injecting a silanol condensation catalyst into the
compacted, molten copolymer after compacting and melting
in the extruder;
(E) blending the compacted, molten copolymer and the silanol
condensation catalyst in the distributive mixer;
(F) extruding the resulting blend out of the distributive
mixer through an extrudion die to form a coating about an
electrical conductor, wire or cable and
(G) cross linking the coated electrical conductor by exposure
to H20.
If the process is to use win-line curing", the silane copolymer can be crosslinked, for example, by drawing the coated electrical conductor, wire or cable through a trough filled with hot water, the trough being of sufficient length that the silane copolymer is adequately crosslinked by the time the coated product is drawn from the downstream end of the trough.
The invention will now be described with reference to the accompanying drawings Figures 1 to 4.
Figure 1 is a diagramatic representation of a longitudinal section of a conventional extruder fitted with a cavity-transfer mixer and provided with means for injecting a silanol condensation catalyst.
Figure 2 is an enlarged transverse section through the rotor of the cavity transfer mixer taken along the line 21 - 21 in Figure 1.
Figure 3 is an enlarged transverse section through the stator of the cavity transfer mixer taken along the line 20 - 20 in Figure 1.
Figure 4 is a developed view of part of the rotor and stator of the cavity transfer mixer illustrating the offset of the rows of cavities on the facing surfaces of the rotor and stator.
The extruder (1) shown in Figure 1 is a conventional extruder comprising a feed hopper (2), a barrel (3) and a forwarding screw (4). The extruder has the usual three processing zones; the feed zone (5); the compression-melting zone (6); and the metering zone (7). Cooling means (8) are provided at the upstream end of the extruder and along the barrel of the extruder (9).
Attached at the downstream end of the extruder is a distributive mixer (10) of the cavity-transfer type as described in
European patent EP048 590. The disclosure of which is incorporated herein by reference. The mixer (10) comprises a stator (11) bolted to the barrel (3) of the extruder (1) and a rotor (12) attached to the forwarding screw (4). The rotor (12) can be attached to the forwarding screw (4) by any convenient means, such as by screw threads (not shown) so that it rotates with the screw.
A crosshead (13) is attached to the downstream end of the mixer (10) by any suitable means e.g. a clamp or bolts (14).
Heating units(15) can be provided around the stator (11) and crosshead (13).
Means (16) are provided for injecting the silanol condensation catalyst into the upstream part of the mixer (10). Any suitable means (16) for injecting the silanol condensation catalyst into the compacted, molten silane copolymer entering the mixer can be used.
Generally the injection means (16) will comprise a reservoir (17) a pump (18) and a non-return valve (19).
The facing surfaces of the stator(ll) and rotor (12) of the mixer (10) have pluralities of rows of or biradial cavities (22,23). These cavities are shown in more detail in Figures 2, 3 and 4. The cavities (23) on the rotor (12) and the cavities (22) on the stator (11) are arranged in circumferential rows.
The invention is illustrated by the following example.
Example
The appartus used inothe example comprised a single screw extruder, a distributive mixer fitted at the discharge end of the extruder, means for introducing liquid components, including a silanol condensation catalyst, into the upstream portion of the mixer and a die capable of coating an electrical conductor.
The extruder used was manufactured by Nokia Cable Machinery and sold under the trade designation MP80-24D fitted with a low compression metering screw.
The distributive mixer used was a cavity-transfer mixer of the type disclosed in European patent 0 048 590. but having the shape and distribution of cavities illustrated in Figures 2 to 4.
The silane copolymer used was prepared by copolymerising ethylene and vinyl trimethoxysilane in a tubular reactor to produce a copoylmer having a silane content of about 1.5X by weight of the total weight of the silane coppolymer. The silane copolymer had a density of 0.925g/cm3(IS0/1872/l-1986) and a melt index of 0.Sdg/min (ISO/1133 1981 (E) Condition 4).
The silane copolymer was loaded into the hopper of the extruder together with an antioxidant masterbatch. The antioxidant masterbatch comprised 95 parts by weight of high pressure, low density polyethylene and 5 parts by weight of a commercial antioxidant which is polymerised 2, 2, 4-trimethyl-1, 2-dihydroquinolene. The amount of the antioxidant masterbatch used was about 5 parts by weight per hundred parts by weight of the silane copolymer.
The silanol condensation catalyst used was dibutyl tin dilaurate.
The mixture of silane copolymer and antioxidant masterbatch was compacted and melted in the extruder. The compacted molten polymer composition was passed through the cavity transfer mixer into which the silanol condensation catalyst was injected. The quantity of silanol condensation catalyst injected into the upstream portion of the mixer was about 0.4t by weight of the silane copolymer. The polymer mixture and silanol condensation catalyst were blended together in the mixer and extruded through the die to form a substantially cylindrical coating about a 2.14mm diameter copper wire. The coating was about 1.7mm thick. Typically, the insulation layer for a low voltage wire of 2.14mm diameter is about 0.8mm and so the coating used in this experiment was substantially thicker than would normally have been used on such a wire.
The coated wire was then drawn through a conventional cooling trough filled with water.
The coating was stripped from the wire and samples were crosslinked by (A) immersing in water at about 200C for 24 hours; (B) immersing in water at about 200C for 96 hours; and (C) storing at room temperature and humidity for 168 hours.
The crosslinked samples were then subjected to the test method disclosed in 1EC540 (20N/cm2, 15 mins, 2000C) in order to determine their heat elongation. The IEC 540 specification requires that the coating composition should have a heat elongation of less than 175%. All of the samples satisfied this requirement. The samples subjected to curing conditions A had a heat elongation of about 125%, the samples subjected to curing conditions B had a heat elongation of about 55Z and the samples subjected to curing conditions C had a heat elongation of 100X. These results are considered to be particularly good in view of the fact that the coating was substantially thicker than would normally have been used on a 2.14mm diameter wire.
Claims (13)
1. A process for producing a shaped, extruded product from a crosslinkable copolymer of an alpha-olefin with a hydrolysable ethylenically unsaturated silane compound which process comprises: (A) introducing the copolymer into the feed zone of an extruder; (B) compacting and melting the copolymer in the extruder; (C) passing the compacted, molten copolymer through a distributive
mixer positioned at the discharge end of the extruder; (D) injecting a silanol condensation catalyst into the compacted,
molten copolymer after compacting and melting in the extruder; (E) blending the compacted, molten copolymer and the silanol
condensation catalyst in the distributive mixer and (F) extruding the resulting blend out of the distributive mixer
through an extrusionvate to form a shaped, crosslinkable,
extruded product.
2. A process as claimed in claim 1 in which the shaped, crosslinkable, extruded product is crosslinked by exposure to 820
3. A process as claimed in either claim 1 or claim 2 in which the copolymer of an alpha-olefin with a hydrolysable ethylenically unsaturated silane compound comprises ethylene as the alpha-olefin.
4. -A process as claimed in any one of claims 1 to 3 in which the copolymer comprises vinyltrimethoxysilane, vinyltriethoxysilane or vinyl triacetoxysilane as the hydrolysable ethylenically unsaturated silane compound.
5. A process as claimed in any one of claims 1 to 4 in which the copolymer comprises 0.5 to 5 weight per cent of silane.
6. A process as claimed in any one of claims 1 to 5 in which the silanol condensation catalyst is dibutyltin dilaurate.
7. A process as claimed in any one of claims 1 to 5 in which the distributive mixer comprises a hollow stator, a rotor journalled for rotation within the stator, the facing surfaces of the rotor and stator having respective mixing elements such that the compacted, molten copolymer is subjected to rapid distributive mixing action as it passes through the mixer and the silanol condensation catalyst is dispersed in the compacted, molten copolymer to produce a substantially homogeneous blend.
8. A process as claimed in claim 7 in which the mixing elements are hemispherical or biradial cavities.
9. A process for producing electrical conductors, wire or cable coated with a crosslinked copolymer of an alpha-olefin and a hydrolysable ethylenically unsaturated silane compound comprising:
(A) introducing the copolymer into the feed zone of an
extruder;
(B) compacting and melting the copolymer in the extruder;
(C) passing the compacted, molten copolymer through a
distributive mixer positioned at the discharge end of the
extruder;
(D) injecting a silanol condensation catslyst into the
compacted, molten copolymer after compacting and melting
in the extruder; ;
(E) blending the compacted, molten copolymer and the silanol
condensation catalyst in the distributive mixer and
(F) extruding the resulting blend out of the distributive
mixer through an extrusion die to form a coating about an
electrical conductor, wire or cable and
(G) crosslinking the coated electrical conductor by exposure
to H20
10. A shaped extruded product produced according to the process as claimed in claim 1.
11. A wire or cable produced according to the process as claimed in claim 9.
12. A process substantially as described with reference to the
Example.
13. A process substantially as described with reference to the accompanying drawings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08703469A GB2201677A (en) | 1987-02-14 | 1987-02-14 | Process for producing a shaped, extruded product from a crosslinkable polymeric composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08703469A GB2201677A (en) | 1987-02-14 | 1987-02-14 | Process for producing a shaped, extruded product from a crosslinkable polymeric composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8703469D0 GB8703469D0 (en) | 1987-03-18 |
| GB2201677A true GB2201677A (en) | 1988-09-07 |
Family
ID=10612339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08703469A Withdrawn GB2201677A (en) | 1987-02-14 | 1987-02-14 | Process for producing a shaped, extruded product from a crosslinkable polymeric composition |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2201677A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2644099A1 (en) * | 1989-03-10 | 1990-09-14 | Fairex | Method of manufacturing extruded elements made of crosslinked polymer, especially crosslinked polyolefin |
| EP0547277A1 (en) * | 1991-12-16 | 1993-06-23 | BP Chemicals Limited | Process for producing stabilized silane copolymers |
| WO2000047687A1 (en) * | 1999-02-11 | 2000-08-17 | Jowat Lobers Und Frank Gmbh & Co. Kg | Multicomponent coating and adhesive material |
| EP1923404A1 (en) * | 2006-11-16 | 2008-05-21 | Borealis Technology Oy | Method for preparing an ethylene-silane copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2028831A (en) * | 1978-07-05 | 1980-03-12 | Mitsubishi Petrochemical Co | Moisture-curable polymer composition |
| GB2039513A (en) * | 1978-11-13 | 1980-08-13 | Mitsubishi Petrochemical Co | Process for producing electric conductors coated with crosslinked polyethylene resin |
| EP0163865A1 (en) * | 1984-04-13 | 1985-12-11 | Union Carbide Corporation | One-extrusion method for making a shaped crosslinked polymeric product |
-
1987
- 1987-02-14 GB GB08703469A patent/GB2201677A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2028831A (en) * | 1978-07-05 | 1980-03-12 | Mitsubishi Petrochemical Co | Moisture-curable polymer composition |
| GB2039513A (en) * | 1978-11-13 | 1980-08-13 | Mitsubishi Petrochemical Co | Process for producing electric conductors coated with crosslinked polyethylene resin |
| EP0163865A1 (en) * | 1984-04-13 | 1985-12-11 | Union Carbide Corporation | One-extrusion method for making a shaped crosslinked polymeric product |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2644099A1 (en) * | 1989-03-10 | 1990-09-14 | Fairex | Method of manufacturing extruded elements made of crosslinked polymer, especially crosslinked polyolefin |
| EP0547277A1 (en) * | 1991-12-16 | 1993-06-23 | BP Chemicals Limited | Process for producing stabilized silane copolymers |
| WO2000047687A1 (en) * | 1999-02-11 | 2000-08-17 | Jowat Lobers Und Frank Gmbh & Co. Kg | Multicomponent coating and adhesive material |
| US7005476B1 (en) | 1999-02-11 | 2006-02-28 | Jowat Lobers Und Frank Gmbh & Co. Kg | Multicomponent coating and adhesive material |
| EP1923404A1 (en) * | 2006-11-16 | 2008-05-21 | Borealis Technology Oy | Method for preparing an ethylene-silane copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8703469D0 (en) | 1987-03-18 |
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