GB2102440A - Anisotropic polymers - Google Patents
Anisotropic polymers Download PDFInfo
- Publication number
- GB2102440A GB2102440A GB08219966A GB8219966A GB2102440A GB 2102440 A GB2102440 A GB 2102440A GB 08219966 A GB08219966 A GB 08219966A GB 8219966 A GB8219966 A GB 8219966A GB 2102440 A GB2102440 A GB 2102440A
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- United Kingdom
- Prior art keywords
- monomers
- different
- proportions
- monomer mix
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 72
- 239000000203 mixture Substances 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 17
- 229920001225 polyester resin Polymers 0.000 claims description 10
- 239000004645 polyester resin Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- -1 acrylate ester Chemical class 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 2
- 230000008859 change Effects 0.000 description 7
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- 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
- B29C31/06—Feeding of the material to be moulded, e.g. into a mould cavity in measured doses, e.g. by weighting
-
- 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
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
- B29C70/0035—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties comprising two or more matrix materials
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0407—Processes of polymerisation
-
- 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
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/127—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by spraying
-
- 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
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
-
- 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
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- 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
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/06—Unsaturated polyesters
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Mathematical Physics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Robotics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Polymeric structures having anisotropic properties en masse are produced by the addition polymerisation of a mixture of monomers, in which the proportions of the monomers in different regions of the structure are varied. The invention is particularly applicable to acrylic monomers and unsaturated polyester resins.
Description
SPECIFICATION
Anisotropic polymers
This invention relates to anisotropic polymers.
Polymers are known which have anisotropic properties at least at the molecular level, for example, elastomeric block polymers of the ABA and other similar types. However, the anisotropy does not extend to the polymer en masse.
The present invention, on the other hand, contemplates polymers and polymeric structures having anisotropic properties en masse. In accordance with this invention these are produced by in situ polymerisation of a monomer mix to produce a polymerised structure, wherein, in different regions of the structure, the composition and/or proportions of the monomers in the mix are varied thereby to give rise to a polymeric structure having anisotropic properties en masse. Preferably, there will be a gradual change of composition and/or proportions of the monomers in the mix from one region of the structure to the next, thereby to provide a gradual, rather than an abrupt charge in the physical or other properties of the structure.This will be of advantage in eliminating internal stress and strain characteristics within the polymeric structure resulting from discontinuities in the polymer composition. In this connection, it will be understood that the term 'anisotropy' is being used in a broad sense to include any change of properties, whether physical or chemical, from one region of the polymer to the other.
The concept of the invention can theoretically be applied to any moulding process, continuous or otherwise, involving the in situ polymerisation of a monomer mix, wherein it is possible during the process or in different regions of the mould, to vary the composition and/or proportions of the monomers. For example, in an extrusion moulding process involving the extrusion of a monomer mix through a nozzle with concomitant or subsequent polymerisation of the monomer mix in the extrudate, the proportion or composition of the monomers fed to the nozzle can be varied as the extrusion proceeds so that the properties of the extrudate vary along its length.In another example, in a typical process of laying up a glass reinforced polyester (GRP) structure, the composition and/or proportions of the resin can be varied to give a GRP structure with differing property characteristics, e.g. hardness or flexibility in different regions.
Most generally in accordance with this invention it is envisaged that there will be a change in the monomer composition, for example, a change in the proportion of a cross-linking monomer so as to give a polymeric structure which is more highly cross-linked in some areas than in others, or a change in proportion of monomers giving rise to a rigid polymer relative to elastomeric monomers in a mixture of the two, thereby to give a polymeric structure having en masse, regions of high rigidity merging into elastomeric regions.Thus in general the invention
comprises a method of producing a polymeric
structure which comprises polymerising a
monomer mix in situ to form said structure, said
mix comprising two or more monomers capable
of providing different polymeric characteristics,
wherein the proportions of said two or more
monomers are varied in different regions of the
structure, thereby to produce said anisotropic
properties in the polymeric structure en masse.
The concept of the invention is applicable to a
wide range of polymeric types, e.g. vinyl resins, polyester resins, acrylic resins and others. The
invention is believed to have particular utility in the field of polyester and acrylic resins. For
example, there are specifically envisaged in accordance with this invention polymerised acrylic structures having regions of high strength and rigidity and high load bearing characteristics
merging gradually with regions of increased resilience and flexibility, and produced, for example, by in situ polymerisation of an acrylic monomer mix comprising, in the high load bearing areas, a high proportion of polyfunctional acrylate monomers such as trimethylolpropane trimethacrylate, and in the more resilient flexible areas a monomer mix comprising a monoacrylate such as tetrahydrofurfuryl methacrylate and an elastomeric monomeric material, e.g. a low molecular weight vinyl- or acrylate-terminated polybutadiene or poly(butadieneacrylonitrile) rubber, such as the Hycar VTBN and VTBNX polymers, or a chlorosulfonated polyethylene. A gradual transition of properties between the rigid and flexible regions of the structure can be provided by a gradual replacement of the trimethylolpropane trimethacrylate in the monomer mix by the tetrahydrofurfuryl methacrylate.
In the case of polyester resins several possibilities exist for the variation of the monomer mix to give different physical or different physical properties in different regions of the polymeric structure. For example, either the polyester component can be varied, for example by using unsaturated polyesters derived from polyfunctional carboxylic acids and polyhydroxy compounds'of different chain lengths, or the cross-linking monomer can be varied. In particular it is envisaged, in accordance with this invention, that the properties en masse of the final crosslinked polyester product can be varied from one region to the next by varying additions of toughening agents such as VTBN and VTBNX to the polyester resin composition in different regions of the structure.In a more simple case the anisotropic properties of the cured resin can be obtained simply by varying the proportions of resin to cross-linking monomer from one region to the next.
In certain cases it may be desirable to incorporate thickeners or thixotropic agents in the monomer mix in order to prevent undue spreading of monomer components from one region of the structure to the next.
Another type of structure envisaged by the present invention comprises, for example, a polymeric structure having a substantially rigid core surrounded by shell of polymeric material of progressively increasing flexibility in a radial direction.
As well as variations within the monomer mix itself to give the desired anisotropic properties to the polymeric structure, the anisotropic characteristics can be increased or modified by incorporating reinforcing materials such as glass or carbon fibre into the structure.
It is envisaged that anisotropic polymeric structures in accordance with the invention can be utilised in a wide variety of ways where anisotropic properties are required. For example, it is envisaged that car body panels can be fabricated having areas of high rigidity and other areas of high flexibility; dinghy masts can be constructed having a rigid foot but with closely controlled bending and torsional characteristics along its length; helicopter rotor blades can be fabricated having the desired flexibility, but yet providing a rigid load bearing end for connection to the rotor hub; vehicle transmission shafts can be constructed having rigid load bearing ends for connection to the drive and separated by a central, flexible section; and so on.
Two methods of carrying out the present invention are further described with reference to and illustrated by the accompanying drawings, in which
Fig. 1 is a diagrammatic lay out of a mould and injection nozzle system for use in accordance with this invention; and
Fig. 2 is a diagrammatic view of a technique for winding a flexible drive shaft in accordance with this invention.
Referring to Fig. 1, a mould 1 defines a shallow
longitudinally extending mould cavity 2 of a desired shape. Mounted above the mould is a mixing nozzle 3 which is movable, by means not shown, along the length of the mould in the direction of the arrow A and back again. A plurality of feed lines X, Y and Z are connected to the nozzle for individually feeding thereto three different monomers, for example tetrahydrofurfuryl
methacrylate in line X, trimethylolpropane trimethacrylate in line Y and vinyl-terminated low molecular weight polybutadiene (VTBN) in line Z, the flow of each monomer being controlled by suitable control means, not shown. At the beginning of the casting operation, a reinforcement material 4, e.g. glass or carbon fibre, is laid in the mould cavity.The mould cavity is then filled with the monomer mix by moving the nozzle along the length of the mould and discharging the monomers X, Y and Z, which in accordance with the principles of this invention will vary in proportion along the length of the
mould to produce a structure having anisotropic properties en masse. In a particular structure envisaged in accordance with this invention, at one or both ends the monomer mix will contain a high proportion of the trimethylolpropane trimethacrylate monomer to produce a highly cross-linked, rigid structure at one or both ends, suitable for the subsequent mounting or attachment of those ends to a supporting structure, whilst the central region contains higher proportion of the tetrahydrofurfuryl methacrylate and/or the VTBN monomer, thereby to produce a central region of greater flexibility and/or toughness.Instead of varying the monomer mix at the end or ends of the structure, in an alternative embodiment, a layered structure can be built up by several passes of the nozzle, optionally with the addition of further reinforcement prior to each pass and varying the monomer composition in one or more passes thereby to provide for example a structure having a flexible or toughened central core or layer and a rigid or hard surface layer or layers.
As already indicated, a gradual transition is desirable in the composition of the monomer mix from one region to the next, rather than an abrupt change, and with highly fluid monomers it may be necessary to incorporate thickness of thixotropic agents to reduce flow of monomer from one region to the next.
Following the charging of the mould, polymerisation can be initiated to complete the polymerisation process.
Referring to Fig. 2, this diagrammatically represents the winding of a web 10, e.g. of carbon or glass fiber, on to a rotating mandrel 1 1, to form a helically wound shaft 12 of resin impregnated reinforcement. As the web is wound onto the shaft it is impregnated with a monomer mix applied through a mixing nozzle 13 and supplied through lines P, 0 and R. In the case of a polyester, for example, the monomer mix might comprise the unsaturated resin fed through line P, cross-linking monomer, e.g. styrene, fed through line Q a vinyl-terminated low molecular weight polybutadiene fed through line R, the proportions being varied depending on the part of the shaft being wound, for example, the ends or the middle section, or alternatively the inner or the outer layers.
As will be appreciated many variations may be made to the above techniques without departing from the scope of the invention as claimed. For example, an anisotropic structure may be built up in accordance with the principles of this invention by superimposing two or more layers of reinforcement material pre-impregnated with a polyester resin or with an acrylic monomer or monomer mixture, and varying the polyester resin or acrylic monomer composition in at least one of those layers, for example the bottom-most or the top-most layer, to provide an anisotropic laminate composed of two or more layers whose physical and/or chemical properites differ one from the other.
In yet another variation according to the invention, the monomer or polyester composition can be sprayed onto a substrate, or into a reinforcement material, with controlled variation of the sprayed composition in different regions of the structure.
In a still further refinement in accordance with the present invention it is proposed to use two monomers which are differently coloured, so that the process operator can see by the merging or mixing of the colours that the desired gradation in the change of monomer composition from one region to the next has been achieved.
Although the invention has been described with reference to certain particular monomers, both acrylic and polyester, it will be apparent that the invention is not restricted to the use of any particular monomer or combination of monomers.
Thus other acrylate or methacrylate esters which can be used to modify the properties of the polymeric structure include a wide range of short chain acrylates or methacrylates such as methyl, ethyl propyl acrylates and methacrylates etc.
medium chain acrylates and methacrylates, and longer chain acrylates and methacrylates such as lauryl methacrylate and other esters of long chain alkanols. Also highly cross-linked structures can be obtained using multifunctionai acrylates and methacrylates other than the trimethylol propane trimethacrylate previously mentioned which is but one example. Moreover, it is to be understood that the term 'monomer' as used herein covers any molecule or macro-molecule containing ethylenic unsaturation capable of undergoing polymerisation by an addition mechanism, thus the term includes unsaturated polymers and prepolymers such as the VTBN and VTBNX polymers previously mentioned and other internally plasticised long chain addition polymerisable compounds as well as individual monomers such as alkyl acrylate and methacrylate esters, acrylic acid, acrylamide etc., or in the case of polyesters, individual cross
linking monomers such as styrene and vinyl toluene.
Claims (10)
1. A method of producing a polymeric structure
having anisotropic properties en masse which comprises the addition polymerisation of a
monomer mix in situ to form said structure, wherein said monomer mix comprises two or
more monomers each capable of undergoing
addition polymerisation to provide polymer of
differing characteristics, and wherein the
proportions of said two or more monomers are varied in different regions of the structure.
2. A method according to claim 1, wherein the proportion of said two monomers is gradually varied from one region of the structure to the next.
3. A method according to claim 1 or 2, wherein the monomers is or are acrylic monomers.
4. A method according to claim 1 or 2, wherein the monomer mix comprises an unsaturated polyester resin and a cross-linking agent, and wherein the anisotropic properties are produced by using a different polyester resin, or a different cross-linking agent, or different proportions of two different polyester resins or of two different cross-linking agents, or of different proportions of the polyester resin and the cross-linking agent in different regions of the structure.
5. A method according to claim 4, wherein the anisotropic properties of the cured polyester are obtained by using different proportions of a vinylterminated low molecular weight polybutadiene or polybutadiene/acrylonitrile rubber in different regions of the structure.
6. A method according to claim 3, wherein the monomer mix comprises a mixture of polyfunctional and monofunctional acrylate monomers and the anisotropic properties en masse are obtained varying the proportions of those two types of monomer.
7. A method according to claim 3, wherein the monomer mix comprises a mono- or polyfunctional acrylate ester and a vinyl- or acrylate-terminated low molecular weight polybutadiene or polybutadiene/acrylonitrile rubber, and the anisotropic properties are obtained by varying the proportions of said acrylate ester or said vinyl- or acrylate terminated low molecular weight rubber.
8. An addition polymerised polymeric structure having anisotropic properties en masse resulting from the use of different monomers, or different proportions of monomers, in different regions of the structure.
9. A structure according to claim 8, which is comprised of polymerised acrylic monomers.
10. A structure according to claim 8, which is comprised of polyester resin.
1 1. A structure according to any one of claims 8-10, which is elongated in form and which comprises, in a central section, a polymerised monomer mix providing flexibility to said central section, and, at one or both ends, a polymerised monomer mix providing rigidity to said end or ends.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08219966A GB2102440B (en) | 1981-07-09 | 1982-07-09 | Anisotropic polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8121249 | 1981-07-09 | ||
| GB08219966A GB2102440B (en) | 1981-07-09 | 1982-07-09 | Anisotropic polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2102440A true GB2102440A (en) | 1983-02-02 |
| GB2102440B GB2102440B (en) | 1985-02-13 |
Family
ID=26280077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08219966A Expired GB2102440B (en) | 1981-07-09 | 1982-07-09 | Anisotropic polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2102440B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340395A2 (en) * | 1988-05-04 | 1989-11-08 | Technoform Caprano + Brunnhofer Kg | Method and apparatus for producing a composite plastics structure |
| EP0548991A1 (en) * | 1991-12-26 | 1993-06-30 | Nippon Petrochemicals Co., Ltd. | Method for preparing uniform polymer rod |
-
1982
- 1982-07-09 GB GB08219966A patent/GB2102440B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340395A2 (en) * | 1988-05-04 | 1989-11-08 | Technoform Caprano + Brunnhofer Kg | Method and apparatus for producing a composite plastics structure |
| EP0340395A3 (en) * | 1988-05-04 | 1991-10-30 | Technoform Caprano + Brunnhofer Kg | Method and apparatus for producing a composite plastics structure |
| EP0548991A1 (en) * | 1991-12-26 | 1993-06-30 | Nippon Petrochemicals Co., Ltd. | Method for preparing uniform polymer rod |
| US5378776A (en) * | 1991-12-26 | 1995-01-03 | Nippon Petrochemicals Company, Limited | Method for preparing optical polymer with radial transition in refractive index |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2102440B (en) | 1985-02-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |