EP1200495A1 - Process for producing a cross-linked polymer product - Google Patents

Process for producing a cross-linked polymer product

Info

Publication number
EP1200495A1
EP1200495A1 EP00912707A EP00912707A EP1200495A1 EP 1200495 A1 EP1200495 A1 EP 1200495A1 EP 00912707 A EP00912707 A EP 00912707A EP 00912707 A EP00912707 A EP 00912707A EP 1200495 A1 EP1200495 A1 EP 1200495A1
Authority
EP
European Patent Office
Prior art keywords
cross
linked
silane
degree
product
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Withdrawn
Application number
EP00912707A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ali Harlin
Matti Hirvensalo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mindset Holding SA
Original Assignee
Nextrom Holding SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nextrom Holding SA filed Critical Nextrom Holding SA
Publication of EP1200495A1 publication Critical patent/EP1200495A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022Extrusion 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92609Dimensions
    • B29C2948/92657Volume or quantity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92714Degree of crosslinking, solidification, crystallinity or homogeneity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92828Raw material handling or dosing, e.g. active hopper or feeding device
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/06Rod-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2301/00Use of unspecified macromolecular compounds as reinforcement
    • B29K2301/10Thermosetting resins

Definitions

  • the invention relates to a process for producing a polymer product cross-linked by silane. It is known in the art that the properties of polymers, such as polyethylene and other polyolefins, can be modified by cross-linking. Polyethylene, for example, can be cross-linked using a peroxide initiator, a hydrolyzing silane compound and a condensation catalyst as described in US patents 3 646 155 and 4 117 195.
  • Said process can be carried out by injecting a polyethylene, a peroxide, for example dicumyl peroxide, a silane compound, for example vinyl trimethoxy silane or vinyl triethoxy silane and a condensation catalyst, for example dibutyltin dilaurate into an extruder and by extruding, whereby a grafted product is obtained which is then processed in condensation conditions in the presence of water or aqueous steam for providing a cross-linked product.
  • a peroxide for example dicumyl peroxide
  • a silane compound for example vinyl trimethoxy silane or vinyl triethoxy silane
  • a condensation catalyst for example dibutyltin dilaurate
  • What mainly affects the cross-linking degree is the amounts of components fed into the extruder, the specific cross-linking conditions, the pressures and temperatures, and also the size of the extruder.
  • the amounts of peroxide initiator, silane compound and condensation catalyst affect the cross-linking degree.
  • the insulation properties can be affected by varying said amounts.
  • the cross-linking degree has been manually determined in a laboratory by analyzing a sample taken from the cross-linked product obtained after the condensa- tion treatment. If the cross-linking degree has been unsatisfactory, the feed of the starting components has been readjusted in order to obtain the desired product.
  • the problem is that undesired changes may frequently occur in the reaction conditions of the continuous process that disadvanta- geously affect the properties of the final product. Since the manual analysis is slow, a lot of poor quality products may be formed that naturally cause economical losses. For example, when cables and conductors are insulated, and the production line is long, the amount of rejected items can be very high, if the feed of the components is adjusted on the basis of the manually obtained analyzing results of the final product.
  • the present invention relates to a process for producing a polymer product cross-linked by silane where a polymer, a silane, an initiator and a cross-linking catalyst and possible additives are fed into an extruder and extruded, whereafter the grafted material obtained is cross-linked using water and the catalyst for obtaining a cross-linked polymer product.
  • the process is characterized in that the grafting degree of the grafted material is determined using an on line method and based upon the result obtained the amounts of the components to be fed into the extruder are continuously adjusted in order to obtain the desired grafting degree.
  • the grafting degree is appropriately determined by measuring the contents of free and grafted silane in the grafted product.
  • the free silane content is determined by measuring the area of the absorption peak at 810 cm "1 in the IR spectrum of the silane, whereas the grafted silane content is similarly measured from absorption peak 1080 cm 1 .
  • grafted polyethylene silane mixtures are used, whose silane content as well as the silane content of a corresponding grafted material are defined by means of an NMR spectroscope, for example.
  • the amount of peroxide has to be appropriate, originally about 0.1 % by weight, in order that the silane, the amount of which is about 0.8 to 2 % by weight, is efficiently grafted so that no direct cross-linking disturbing the grafting takes place without silane. In a well-grafted material the amount of remaining peroxide is very low, hardly measurable.
  • the peroxide content can be controlled by measuring the area of the absorption peak at 1155 cm “1 by means of an IR spectroscope. The calibration is carried out in the same way as in the case of silane. As the grafting degree is determined using a continuous on line measuring method, the results are rapidly obtained, and the feed of starting components can also be rapidly affected if needed. On the basis of the measuring results the feed of starting components can automatically also be adjusted using a computer as described below.
  • the adjustment can, for example, be based on an algorithm that may be of a fuzzy logic type. Next the examples of the measurements and adjustments are shown when a silane/peroxide mixture is fed and when silane and peroxide are separately fed.
  • Example 1 Feeding a ready-mixed silane/peroxide mixture
  • Typical polymers to be cross-linked, whose grafting degree can be adjusted by the process of the invention, are polyolefins, preferably polyethylene and polypropylene.
  • the cross-linked product is preferably a cable or conductor insulation, a plastic pipe or profile.
  • the cross-linking catalyst is preferably a dibutyltin dilaurate.
  • a hydrolyzing silane compound, preferably vinyl trimethoxy silane, is used as the grafting agent and the initiator is typically a peroxide compound, preferably dicumyl peroxide.
  • Conventional additives include antioxidants and colourants.
  • the cross- linking degree can further be determined during the run, for example by utilizing a thermomechanical analyzer that measures the elastic properties of the material.
  • the thin measuring head is pressed by a constant load against the cross-linked material and the size of the elastic deflection depending on the cross-linking degree of the polymer, the temperature and the load put upon the measuring head is registered.
  • the registered deflection values are compared with a calibration curve measured with a corresponding material at the same temperature, thus providing the cross-linking degree corresponding to the deflection.
  • thermomechanical analyzer may be composed of two wheels placed at the opposite sides of a cable or another polymer product to be run and pressed against the same, one wheel being pressed by means of a known force, and the deflection caused by the wheel in the product is measured, and of a registration apparatus for registering deflections and also the temperature of the material.
  • the apparatus example shows only one way of measuring the elastic properties of the product on the line during the run, but the example is not intended to restrict the scope of the patent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processes Specially Adapted For Manufacturing Cables (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
EP00912707A 1999-03-18 2000-03-17 Process for producing a cross-linked polymer product Withdrawn EP1200495A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI990613A FI105198B (fi) 1999-03-18 1999-03-18 Menetelmä silloitetun polymeerituotteen valmistamiseksi
FI990613 1999-03-18
PCT/FI2000/000221 WO2000055225A1 (en) 1999-03-18 2000-03-17 Process for producing a cross-linked polymer product

Publications (1)

Publication Number Publication Date
EP1200495A1 true EP1200495A1 (en) 2002-05-02

Family

ID=8554235

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00912707A Withdrawn EP1200495A1 (en) 1999-03-18 2000-03-17 Process for producing a cross-linked polymer product

Country Status (7)

Country Link
EP (1) EP1200495A1 (zh)
JP (1) JP2002539304A (zh)
KR (1) KR20010114221A (zh)
CN (1) CN1137166C (zh)
AU (1) AU3436700A (zh)
FI (1) FI105198B (zh)
WO (1) WO2000055225A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0019074D0 (en) * 2000-08-03 2000-09-27 Ranier Ltd Precision polyurethane manufacture
EP1541601A1 (en) * 2003-12-09 2005-06-15 SOLVAY (Société Anonyme) Improved process for producing silane crosslinked polyethylene
FI20055673L (fi) * 2005-12-14 2007-06-15 Conenor Oy Menetelmä komposiittituotteen tekemiseksi ja komposiittituote
DE102007026751A1 (de) * 2007-06-09 2008-12-11 Inoex Gmbh Verfahren zur Herstellung von peroxidvernetzten Polyethylen-Rohren in einer Extrusionslinie
CN105440215A (zh) * 2014-08-25 2016-03-30 蒋小华 一种硅烷交联聚乙烯电缆料的制备工艺
EP3339366A1 (en) 2016-12-22 2018-06-27 Borealis AG A crosslinkable polyolefin composition
EP3409701A1 (en) 2017-05-31 2018-12-05 Borealis AG A crosslinkable propylene polymer composition
WO2019160883A1 (en) 2018-02-13 2019-08-22 Cool Vapor Solutions Methods and compositions for humidification and cooling of gas streams

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1526398A (en) * 1974-12-06 1978-09-27 Maillefer Sa Manufacture of extruded products
DE3021105A1 (de) * 1980-06-04 1982-01-21 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von polarmodifiziertem polypropylen und seine verwendung
US4448736A (en) * 1982-05-24 1984-05-15 Standard Oil Company (Indiana) Continuous in-line melt flow rate control system
GB8704673D0 (en) * 1987-02-27 1987-04-01 Bicc Plc Control of grafting processes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0055225A1 *

Also Published As

Publication number Publication date
KR20010114221A (ko) 2001-12-31
FI990613A0 (fi) 1999-03-18
CN1137166C (zh) 2004-02-04
FI105198B (fi) 2000-06-30
CN1344284A (zh) 2002-04-10
JP2002539304A (ja) 2002-11-19
AU3436700A (en) 2000-10-04
WO2000055225A1 (en) 2000-09-21

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