WO2002038354A1 - Produit polymere presentant une durete progressive continue - Google Patents

Produit polymere presentant une durete progressive continue Download PDF

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Publication number
WO2002038354A1
WO2002038354A1 PCT/DK2001/000670 DK0100670W WO0238354A1 WO 2002038354 A1 WO2002038354 A1 WO 2002038354A1 DK 0100670 W DK0100670 W DK 0100670W WO 0238354 A1 WO0238354 A1 WO 0238354A1
Authority
WO
WIPO (PCT)
Prior art keywords
shore
substances
hardness
product
isocyanate
Prior art date
Application number
PCT/DK2001/000670
Other languages
English (en)
Inventor
Sten Nielsen
Henning Bitsch
Original Assignee
Pur Elastomer Aps
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 Pur Elastomer Aps filed Critical Pur Elastomer Aps
Priority to AU2002210382A priority Critical patent/AU2002210382A1/en
Publication of WO2002038354A1 publication Critical patent/WO2002038354A1/fr

Links

Classifications

    • 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
    • B29C31/00—Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/04—Feeding of the material to be moulded, e.g. into a mould cavity
    • B29C31/10—Feeding of the material to be moulded, e.g. into a mould cavity of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • B01F35/22—Control or regulation
    • B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
    • B01F35/2214—Speed during the operation
    • B01F35/22141—Speed of feeding of at least one component to be mixed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/80—Forming a predetermined ratio of the substances to be mixed
    • B01F35/81—Forming mixtures with changing ratios or gradients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/24—Feeding the material into the mould
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0091—Damping, energy absorption

Definitions

  • the present invention relates to a method for production of a polymer product according to the preamble of claim 1.
  • the invention further relates to an apparatus for production of a polymer product and to use of a polymer product.
  • German patent application DE 2 309 861 it is known to vary the density of a polymer foam in a product gradually by a temperature gradient throughout the product. This may be achieved by cooling the product from the outside during the hardening process.
  • US 4 974 852 discloses a solid golf ball with a three layer hardness variation.
  • a mixture of isocyanate, 1.4 butandiol, and a polyether polyol with certain relative amounts may produce a hardness of 60 Shore A. Varying the relative amounts of these substances may vary the hardness in the polymerised product between 60 and 115 Shore A. In order to vary the hardness continuously within the product, the relative amounts of substances in the mixture may be varied during the procedure, where the form for the polymer product is filled with the mixed substances. In principle, the filling of the form can be regarded as a stacking of polymer layers with layer thicknesses that are infinitely thin, where the single layers are not mixed in the form due to the viscosity of the mixture.
  • a catalyst substance may be added to the polymer, which results in a fast hardening of the polymer that has left the mix- ing unit and entered the casting form. This way, the polymer mixture may obtain a relatively high viscosity quickly further preventing mixing during the stacking of the polymer layers.
  • the a fibrous material may be added to the polymer mixture.
  • the isocyanate may gradually be substituted with a different type of isocyanate during the mixing process. This way, a large range of hardness variations between 45 Shore A and 60 Shore D or with even higher hardnesses can be achieved within one product.
  • 1,4-butanediol can be substituted by ethylene glycol to achieve a likewise effect.
  • the polyol may be substituted by a polyamine.
  • Another mixture for varying hardness within a solid product can be achieved by mixing a polyol with ethylene diamine and varying ratios of an isocyanate together with a further stream containing bisphenol A or F epoxy adduct. Also in this case, a variable hardness product would result. In this case, the ethylene diamine would react with isocyanate first, and then the amine terminated urea product would add onto the epoxy intermediate to give the final polymer.
  • FIG. 1 shows a diagram for continuously varying ratios in a blend of substances
  • FIG. 2 shows an apparatus according to the invention
  • FIG. 3 shows the apparatus according to the invention with computer control
  • FIG. 4 shows vibration dampers
  • FIG. 5 shows bend restrictors.
  • table 1 with relative weight amounts for specific substances used in a method according to the invention.
  • the substances used for illustration are products commercially available from the British company Hyperlast®.
  • the Prepolymer being a clear or slightly turbid liquid, contains isocyanate and polyols that have partly reacted.
  • the Hyperlast C 100/60 Curative also being a clear or slightly turbid liquid, is a mixture of a polyether polyol and a PTMEG polyol.
  • the Diprane C Curative which is a colourless clear liquid above the melting point of 20°C contains 1.4 butandiol.
  • Table 2 contains relative volume amounts for specific substances used in a method according to the invention with the corresponding hardness data for a product with this kind of mixture. As is apparent from table 2, an even broader variation of the hardness in the polymer product can be achieved, namely from Shore A hardness 60 to Shore A hardness 115.
  • the relative amount of Prepolymer 7855092 and Prepolymer 2875021 determines the hardness of the final product.
  • the change of the hardness from 60 Shore A to 115 Shore A implies a complete substitution of the Prepolymer 2875021 with the Prepolymer 7855092.
  • any hardness in the range 60 Shore A to 65 Shore D can be achieved by varying the relative amounts of the substances.
  • the scale for the hardness is from 60 Shore A to 95 Shore A, with a direct conversion to the Shore D range from 40 Shore D to 60 Shore D.
  • the curves with the shown hardness range can be extended to at least 85 Shore D by extending the curves in a linear fashion, where the curves have slopes as between hardness 60 Shore D to 65 Shore D.
  • the mentioned mixture has the further advantage that the polymerisation and hardening is roughly temperature independent in the range between 20°C and 140°C, where, however, a process temperature of between 60°C and 100°C is preferred.
  • FIG. 2 An apparatus for production of a product by a method according to the invention is shown in FIG. 2.
  • the apparatus comprises a number of tanks 201 with different sub- stances to be mixed in the mixing unit 202.
  • Each of the tanks 201 is connected to a feeder unit 203 with a frequency regulated pump unit 204 and a flow control unit 205 to assure that only the desired amount of substance is fed to the mixing unit 202 before the mixture is filled into the polymer casting form 309 as illustrated in FIG 3.
  • Each of the pump units 204 as shown in FIG. 2, is motor driven, where the motor 206 is frequency controlled to variable pumping speed.
  • the flow into the mixing unit 202 is regulated by a number of valve arrangements 206.
  • the apparatus according to the invention can be controlled by a computer 301, which is illustrated in FIG. 3.
  • a Programmable Logic Controller (PLC) 302 connected to the computer 301 via an interface 303.
  • the PLC 302 has a user interface 304 to indicate the state and functioning of the apparatus and to allow the operator to change parameters for the polymer casting process.
  • the pumping speed of the pump units 204 is controlled by frequency adjustment of the motors 206, as shown in FIG. 2.
  • the actual rotation frequency of the motor 206 is communicated to the computer 301 via an encoder 305, shown in FIG. 2 and in FIG. 3, a frequency converter 306, and the PLC 302.
  • the frequency converter 306 also translates the command for the frequency adjustment as received via a connection 307 from the PLC 302 to the motor 206.
  • the frequencies for the individual motors may be logically linked 308 by the frequency converters 306, 306', 306", 306'", which also may be functionally linked to a common communication network (not shown).
  • the flowing speed of the different substances to be mixed is calculated by the computer 301. For example, this can be achieved by interpolation between the data as shown in Table 2. From these data, a polynomial equation can be calculated which describes the continues variation of the flow speed for the different substances by regulation of the speed for each of the pump motors 206.
  • a first problem to be solved is in connection with shock or vibration dampers. Examples are shown in FIG. 4a for a translational damper 401 and in FIG. 4b for a rotational damper 401'. Those dampers 401, 401' are often constructed as a polymer block 401, 401' between two metal parts 402, 403 or 402', 403', respectively, to which the polymer block 401, 401 is vulcanised. A typical problem is damage of the dampers 401, 401' after relatively short term use due to cracks in the transition 404 between the polymer 401, 401' and the metal parts 402, 403.
  • the polymer 401, 401' breaks along this crack which evolves through the polymer block 401, 401 '.
  • the lifetime of such a vibration damper can be prolonged with a hard polymer.
  • a hard polymer does not damp sufficiently, so the chosen hardness is a compromise between the requirements for the damping properties and the requirements for reliability and lifetime of the damper.
  • an elastomer block 401, 401' produced with a continuous hardness variation according to the invention.
  • the polymer in the transition 404 near the metal part 402, 403 is chosen with a high hardness in order to omit evolving cracks in this part, while the middle part 405 of the elastomer block 401, 401' is of a much softer polymer in order to have optimum damping properties.
  • a second problem to be solved is in connection with pipe joints, as illustrated in FIG. 5a, where a pipe 501 with a flange 502 is fastened to an underlying coupling unit 503. Transversal forces on the pipe 501 may lead breakage of the pipe 501 from the flange
  • a stiffening polymer pipe sleeve 504 as a bend restrictor may be employed for stress and load absorption. Due to a certain stress exerted on the sleeve, cracks may occur in the interface region 505 between the sleeve 504 and the flange 502, which finally leads to breakage of the sleeve 504. Also this problem may be solved with a sleeve 504 that has a high hardness in the interface region 505 and a lower hardness in the outer re- gion 506.
  • the pipe 501 may be coupled to a coupling unit 503 which is surrounded by an elastic sleeve 504 as a bend stiffener and bend restrictor in order to damp motions and to absorb stress and load exerted on the pipe.
  • This elastic sleeve 504 may be subject to cracks in the interface 505 between the sleeve 504 and the coupling unit 503 or the sleeve 504 and the pipe 501 in the same manner as described above. Therefore, also in this case, a substantial improvement is achieved, if the sleeve 504 for such pipelines 501, where the sleeve 504 may weight several tons, has a continuous hardness variation. Due to the much better reliability and long term stability, a pipeline sleeve 504 according to the invention may be constructed much smaller than existing sleeves for this purpose, which results in a substantial reduction in labour and cost for this kind of elastomeric solutions.
  • a further application for the invention is production of vacuum hoses.
  • Such a hose must have two primary characteristics. It must be stiff enough to withstand the pres- sure from the outside against the low inner pressure and it must still be able to bend.
  • Such a hose can be produced according to the invention by continuously varying the hardness of the polymer in the direction along the hose, such that the hardness variation is a alternating function along the direction of the hose.
  • the hose will thus consist of hard rings which are connected by softer and flexible rings, where the hardness varies gradually between the hard and the soft rings.
  • a method for production and a product according to the invention is useful for toys, sports training equipment, vehicle equipment, helicopter equipment, aeroplane equipment, and other marine or oil field equipment.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Robotics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Procédé de production d'un produit polymère de dureté variable, qui comporte les étapes consistant à ajouter et à mélanger au moins deux matières dans des proportions prédéterminés, à remplir un moule de ces matières et à faire durcir celles-ci afin de former un produit élastique solide. Selon l'invention, les proportions desdites matières varient en continu pendant le remplissage du moule afin d'obtenir un produit présentant une dureté qui varie en continu. Le procédé est particulièrement utile pour former des produits absorbant les charges et amortissant les vibrations.
PCT/DK2001/000670 2000-11-09 2001-10-15 Produit polymere presentant une durete progressive continue WO2002038354A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002210382A AU2002210382A1 (en) 2000-11-09 2001-10-15 Polymer product with continuously graduated hardness

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200001667 2000-11-09
DKPA200001667 2000-11-09

Publications (1)

Publication Number Publication Date
WO2002038354A1 true WO2002038354A1 (fr) 2002-05-16

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AU (1) AU2002210382A1 (fr)
WO (1) WO2002038354A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1408063A1 (fr) * 2001-05-24 2004-04-14 Mitsui Takeda Chemicals, Inc. Procede et appareil de production de mousses de polyurethane flexibles
EP1410841A2 (fr) * 2002-10-18 2004-04-21 Ticona GmbH Procédé et appareil pour la production combinatoire de mélanges et leur utilisation
WO2006069849A1 (fr) * 2004-12-23 2006-07-06 Krauss-Maffei Kunststofftechnik Gmbh Tete de melange a manchon d'etancheite
CN108453971A (zh) * 2018-04-08 2018-08-28 大连理工大学 一种海洋柔性管缆防弯器及其制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE321343B (fr) * 1965-03-06 1970-03-02 Dunlop Rubber Co
GB2102331A (en) * 1981-07-09 1983-02-02 Permabond Adhesives Anisotropic resins
US4798694A (en) * 1985-08-09 1989-01-17 Canon Kabushiki Kaisha Method for producing composite materials
DE3938891A1 (de) * 1988-11-26 1990-05-31 Phoenix Ag Verfahren zum herstellen von formkoerpern, insbesondere pu-rim-artikeln, mit zonen unterschiedlicher eigenschaften
EP0771642A1 (fr) * 1995-11-06 1997-05-07 Metton America, Inc. Procédé pour la fabrication d'articles à gradients de concentrations de composants par moulage réaction-injection et articles ainsi préparés

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE321343B (fr) * 1965-03-06 1970-03-02 Dunlop Rubber Co
GB2102331A (en) * 1981-07-09 1983-02-02 Permabond Adhesives Anisotropic resins
US4798694A (en) * 1985-08-09 1989-01-17 Canon Kabushiki Kaisha Method for producing composite materials
DE3938891A1 (de) * 1988-11-26 1990-05-31 Phoenix Ag Verfahren zum herstellen von formkoerpern, insbesondere pu-rim-artikeln, mit zonen unterschiedlicher eigenschaften
EP0771642A1 (fr) * 1995-11-06 1997-05-07 Metton America, Inc. Procédé pour la fabrication d'articles à gradients de concentrations de composants par moulage réaction-injection et articles ainsi préparés

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1408063A1 (fr) * 2001-05-24 2004-04-14 Mitsui Takeda Chemicals, Inc. Procede et appareil de production de mousses de polyurethane flexibles
EP1408063A4 (fr) * 2001-05-24 2004-11-17 Mitsui Takeda Chemicals Inc Procede et appareil de production de mousses de polyurethane flexibles
EP1410841A2 (fr) * 2002-10-18 2004-04-21 Ticona GmbH Procédé et appareil pour la production combinatoire de mélanges et leur utilisation
EP1410841A3 (fr) * 2002-10-18 2004-06-02 Ticona GmbH Procédé et appareil pour la production combinatoire de mélanges et leur utilisation
WO2006069849A1 (fr) * 2004-12-23 2006-07-06 Krauss-Maffei Kunststofftechnik Gmbh Tete de melange a manchon d'etancheite
CN108453971A (zh) * 2018-04-08 2018-08-28 大连理工大学 一种海洋柔性管缆防弯器及其制造方法
CN108453971B (zh) * 2018-04-08 2020-06-02 大连理工大学 一种海洋柔性管缆防弯器及其制造方法

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