CA1141642A - Laminated composite material of high molecular weight polyethylene and phenolic resin and the process for its manufacture - Google Patents
Laminated composite material of high molecular weight polyethylene and phenolic resin and the process for its manufactureInfo
- Publication number
- CA1141642A CA1141642A CA000308283A CA308283A CA1141642A CA 1141642 A CA1141642 A CA 1141642A CA 000308283 A CA000308283 A CA 000308283A CA 308283 A CA308283 A CA 308283A CA 1141642 A CA1141642 A CA 1141642A
- Authority
- CA
- Canada
- Prior art keywords
- composite material
- laminated composite
- bonding agent
- phenolic resin
- molecular weight
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/56—Damping, energy absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2361/00—Phenoplast, aminoplast
Abstract
ABSTRACT OF THE DISCLOSURE
A laminated composite material is disclosed which comprises a high molecular weight polyethylene with a viscosimetrically determined molecular weight above 500,000 and a phenolic resin. Also disclosed in a method of securing high molecular weight polyethylene to a phenolic resin composition by employing an ethylene copolymer thermoplastic bond-ing agent. The material possesses improved firmness, hardness and heat resistance and is useful in a variety of industrial fields, particularly where a combination of strength and heat resistance with impact and shock absorbing qualities is required. The material is particularly useful for the construction of apparatuses such as, by way of example only, weaving loom parts and brake linings in the motor industry. The material is also useful in railway track construction.
A laminated composite material is disclosed which comprises a high molecular weight polyethylene with a viscosimetrically determined molecular weight above 500,000 and a phenolic resin. Also disclosed in a method of securing high molecular weight polyethylene to a phenolic resin composition by employing an ethylene copolymer thermoplastic bond-ing agent. The material possesses improved firmness, hardness and heat resistance and is useful in a variety of industrial fields, particularly where a combination of strength and heat resistance with impact and shock absorbing qualities is required. The material is particularly useful for the construction of apparatuses such as, by way of example only, weaving loom parts and brake linings in the motor industry. The material is also useful in railway track construction.
Description
The present invention relates to a laminated composite material comprising high molecular weight polyethylene and phenolic resin.
Composite materials consisting of various plastics are well known and extensively applied in the most varied industrial fields. For example, composite constructions of glass fiber-reinforced plastics were polyvinyl chloride, polypropylene and polyethylene, as well as duroplasts, have found application in the construction of apparatus. (Cf. VDI-Taschenbuch "Konstruieren mit Kunststoffen" ("Constructing with Plastics") by Rainer Taprogge, VDI-Verlag, DUsseldorf 1971, p. 11). The merits of these com-posite materials generally lie with the combination of properties of their individual components. It is thus possible to manufacture materials suitable for special applications.
Composite materials can be manufactured according to various methods. According to a conventional method, all or individual components of the laminated material are plasticized and bonded together under pres-sure. Another frequently used method consists in combining components of the laminated material by means of a bonding agent. It is known that PVC
can be excellently bonded to glass fiber-reinforced plastics, if an adhes-ive polyester layer is first applied to the clean connecting surface.
Polyolefins cannot be directly bonded using epoxy or polyester resins.
A method employing a mechanical bonding agent is therefore chosen in the majority of cases. With this method glass fiber mats must first be pressed into the polyethylene or polypropylene after surface melting. In this way they are anchored inthe thermoplasts, forming a base for adhesive coating.
The object of this invention is to produce a composite material, that is tough, as well as impact and shock resistant, while at the same time possessing a hard, firm, thermally stable, resistant but not brittle ex-ternal layer.
The invention provides for a laminated composite material compris-ing a high molecular weight polyethylene with a viscosimetrically determined `'.`' ~"`'~.
` molecular weight aboYe 500,000 and a phenolic resin, wherein the polyethylene :.- and the phenolic resin are joined together by means of an ethylene copolymsr as bonding agent.
This invention also provides for a process for forming a laminated composite material comprising a layer of high molecular weight polyethylene with a viscosimetrically determined molecular weight above 500,000 and a layer of phenolic resin which comprises disposing between said polyethylene and said phenolic resin an ethylene copolymer as bonding agent and heating the result-ant material to a temperature sufficient to melt the bonding agent and to incorporate the bonding agent into the polyethylene and the phenolic resin.
; The new material possesses, in comparison with the individual com-; - la -ponents, considerably improved firmness, hardness and heat resistance. Fur-thermore, it is tough as well as being impact~ shock and wear resistant.
In this connection it must be taken into account that the phenolic resins are hard and can resist thermal influences in wide temperature ranges without changing shape. However, as they are not tough, they are brittle, sensitive to impact and shock and can fracture. High molecular weight poly-ethylene, on the other hand, is tough and possesses a high shock and impact abosrbing capacity whereas its hardness and heat resistance are unsatisfactory.
On bonding phenolic resins with high molecular weight polyethylene, a new material results, which surprisingly, in many cases, does not possess the undesired properties of the individual components, but does markedly ex-hibit behavior which is long desired in commercial applications.
In this invention the term high molecular weight polyethylene de-notes a polyethylene with a viscosimetrically determined molecular weight over 500,000. The new composite material possesses particularly favorable proper-ties, when the viscosimetrically determined molecular weight of the polyethy-lene components lies between 1 and 10 million. The manufacture of these high molecular weight polyethylenes is kno~m. A Process for their production using Ziegler catalysts is, for example, described in German OLS 23 61 508.
Phenolic resins (phenoplasts) are the condensation products of phenol and its homologs - cresols and xylenols - with formaldehyde. The conversion of the feedstocks occurs in the presence of either acidic or alkaline catalysts.
The first intermediary products resulting from the condensation are resols, which are still capable of being melted and hardened. After the addi-tion of hexamethylenetetramine they are converted into resitols, condensation products which are still capable of being hardened but are difficult to melt.
In the final stage the so-called resites are obtained, which are completely hardened and infusible.
Phenolic resins, with the same degree of condensation as the resitols and resites, are suitable components of the composite material according to the invention and can be used in pure form, i.e., without the addition of fillers.
One can, however, use phenolic resins containing fillers such as sawdust, as-bestos, mica powder and textile fibers. If used, the fillers are preferably present in an amount of 40 to 60%, based on the combined weight of phenolic resin and filler.
Within the scope of the present invention, fabric and paper webs impregnated with phenolic resins are important components of the composite material. The fabric can be made of natural or artificial fibers, e.g., linen, jute or polyester.
Laminated composites can be made, pursuant to the invention, in a wide variety of ways. For instance, a layer of high molecular weight poly-ethylene can be secured to a layer of phenolic resin. The phenolic resin can .; have any desired degree of hardening and can be present as such or in a carrier such as a fibrous mat. Alternatively, either or both of the polyethylene or phenolic resin can be present in a form such as a sheet, granules, powders, fibers, alone or with another material.
The union of high molecular weight polyethylene and phenolic resin, with or without filler, can be effected according to a preferred process of the invention by means of a bonding agent. By selecting a suitable adhesive, it can be ensured that the bond between plastics of differing chemical composi-tions is durable and can withstand high stress, without the separation of the components at their interface.
A lamination of the components without the application of a bonding agent, e.g., via melting of the surfaces of the individual layers and cooling under pressure, cannot usually be considered since the bond is readily loosened under stress. In this connection, it should be noted that high molecular eight polyethylene, in particular polyethylene with a viscosimetrically de-termined molecular weight over 500,000, no longer melts on heating, but in-stead transforms into a viscoelastic state. A loosening of the plastic layers, which can occur on heating under pressure, disappears again on cooling.
.
; .
z The permanent union of polyethylene and phenolic resin cannot be readily achieved with the usual bonding agents, as the majority of adhesives are unsuitable for the formation of a highly resistant ~ond between the plas-tics, due to the homopolar structure of the polyethylene.
A series of thermoplastic adhesives has been found to be particular-ly effective bonding agents. In particular, it has been found that copolymers of ethylene which are, for example, laid between the components in the form `~ of a film and melted under pressure, are especially effective as bonding agents which secure the high molecular weight polyethylene to the phenolic resin.
During the cooling, which can ensue under pressure, the melt adhesive partial-ly penetrates each of the individual layers and in this way bonds the compo-nents together. It is to be understood that a film of adhesive can be applied in any physical form~ e.g., as granules, powder, fiber, sphere etc. General-ly, the thermoplastic adhesive is applied in a thickness of 0.1 to 1 mm ~le thermoplastic adhesive preferably has a melt flow index ~ASTM D
1238-62, MFI 190/2) in the range of 2 to 50 g/10 min., preferably 2 to 10 g/10 min. It has a melting point (determined by differential thermal analysis) in the range of 90 to 110C. l~here a copolymer of ethylene is employed, ethylene units are preferably present in the copolymer in an amount between 80 and 95 weight percent, especially 90 to 95 weight percent.
Excellent results are obtained when ethylene copolymers containing acrylic acid and/or acrylic ester, e.g., Cl 4 alkyl ester and/or acrylamide and/or vinyl acetate, are used as bonding agents.
Methacrylic acid and/or methacrylic ester can be present in the above-named copolymers, instead of acrylic acid and/or acrylic ester. Ihe manufacture of the laminates can also occur with the aid of copolymers consist-ing of ethylene and acrylic acid or maleic anhydride, or mixtures of ethylene-vinyl acetate copolymer and maleic anhydride. Polyisobutylene can also be - used as adhesive, instead of ethylene copolymers, especially a polyisobutylene having a molecular weight between 50,000 and 200,000.
4'~
The temperatures employed for the manufacture of the composite ma-terial accGrding ~o the invention are dependent on the type of polymer used as bonding agent. Usually temperatures from 140 to 220C are applied and the bonding of the components is carried out at pressures from 20 to 250 bar.
Non-hardened phenolic resin hardens during this thermal treatment.
The thermoplastic adhesive is usually applied as a 0.1 to 1.0 mm thick layer between the surfaces to be bonded. The thickness of the adhesive layer can naturally vary depending on conditions, e.g.~ thickness and number of succes-sive layers of plastic.
It has already been stated that the union of the components of the new composite material preferably occurs on using adhesives. However, when employing textile fabrics impregnated with phenolic resins capable of being hardened, bonding agents can be dispensed with, if the composite material is not to be subjected to high mechanical s~ress.
The structure of the new composite material depends on the intended application. Depending on the intended use of the new material, layers of polyethylene and phenolic resin can be bonded together in varying numbers and thickness. In this way, the physical properties of the composite material, such as mechanical strength, thermal behavior, density, dimensional stability can be adapted according to the special areas of application. The most simple case is when the laminate consists of two layers according to the pattern A-B
~A = phenolic resin, B = polyethylene~. This type of composite material can be employed when the material is subjected on only one side to mechanical and/
or thermal stress. Sandwich structures of the type A-B-A find application in cases where the mechanical and/or thermal stresses affect both sides. The new composit material can, of course, consist of more than three layers, e.g., A-B-A-B-A, if demanded by the particular application. Similarly~ a sandwich structure can be provided of the type B-A-B or B-A-B-A-B. The thickness of the individual layers of the laminates is dependent on the intended use.
3Q The composite material according to the inven~ion can be applied in ` the most varied technical fields, particularly where a combination of strength and heat resistance with impact and shock absorbing qualities is required.
For example, it can be used for parts of weaving looms, which are under high strain, e.g., shuttles, or in the motor industry as brake linings and also in railway track construction.
In order to more fully illustrate the invention and the manner of practicing the same, the following Examples are presented. Examples 1 to 4 refer to composite materials containing adhesives. Example 5 refers to a com-posite material, which was manufactured without adhesives.
Example 1 Manufacture of laminàted composite material A 40 mm thick polyethylene block with a viscosimetrically determined molecular weight of approximately 4,000,000 was bonded on both sides with layers of fabric, impregnated with unhardened phenolic resin (resitol). A
0.5 mm thick copolymer layer consisting of 86.4% polyethylene, 4.1% acrylaide, 3.6% methacrylic acid, 5.9% acrylic ester was used as bonding agent. The bonding of the components occurred at a pressure of 100 bar. After heating for 20 minutes at 200C, the material was then slowly allowed to cool to room tem-perature, while maintaining the pressure. During this period the bonding of the components took place and the phenolic resin simultaneously hardened. The hardened phenolic resin layers were each 6 mm thick.
Testing the properties of the laminated composite material Testing of the adhesion between the components of the composite material was carried out on simple overlapping samples. The composite material was split in the center of the polyethylene layer, so that two parts resulted, each consisting of a polyethylene and a phenolic layer. Part of the phenolic layer from one side and part of the polyethylene from the other side were re-moved by milling. The resulting (overlapping) sample had the following dimen-sions: 60 x 40 x 3 mm3, with an overlap of 25 mm. The sample which was then placed in a vertical tension testing machine, was broken at a feed rate of 69~
` lO0 mm/minute at room temperature. The fracture of the sample occurred at a force of 2,700 N, not, however, in the adhesive surface, but in the polyethy-lene or the phenolic resin layer.
Examples 2 to 4 The manufacture of each laminated sample was carried out according .~:
to Example l, using copolymers of the following composition:
Example 2 3 4 Polyethylene 90% 92.1% 90%
: Acrylic acid 3.9%
Acrylic ester 6.1% 4.7%
Acrylamide 3.2%
Vinyl acetate 10%
Fracture took place in each case in the polyethylene layer at the following values:
Example 2 3 4 .... _ .. _ _ .
Force 2900 N 2950 N 2500 N
Example 5 The manufacture of a composite material is carried out as stated in Example 1, however without the application of a bonding agent.
~ Fracture resulted at a force of 40 N. Separation occurred at the interface of the two components.
Example 6 Polyethylene powder with a viscosimetrically determined molecular weight of approximately 4,000,000 was used in place of the polyethylene sheet in Examples 1 to 4.
Polyethylene powder, which is placed on the fabric layers, impreg-nated with phenolic resin and adhesive (composition as in Example 1), is pre-formed at a pressure of 50 bar. The upper surface of the powder is covered with the same bonding agent and layers of fabric, impregnated with unhardened phenolic resin.
This laminated sample is sintered and molded for four hours at ~00 C and 50 bar. It is subsequently allowed to cool to room temperature at a pressure of 50 bar.
` On testi.ng the laminated sample it was found that fracture resulted in the phenolic resin layer at a force of 2850 N.
Composite materials consisting of various plastics are well known and extensively applied in the most varied industrial fields. For example, composite constructions of glass fiber-reinforced plastics were polyvinyl chloride, polypropylene and polyethylene, as well as duroplasts, have found application in the construction of apparatus. (Cf. VDI-Taschenbuch "Konstruieren mit Kunststoffen" ("Constructing with Plastics") by Rainer Taprogge, VDI-Verlag, DUsseldorf 1971, p. 11). The merits of these com-posite materials generally lie with the combination of properties of their individual components. It is thus possible to manufacture materials suitable for special applications.
Composite materials can be manufactured according to various methods. According to a conventional method, all or individual components of the laminated material are plasticized and bonded together under pres-sure. Another frequently used method consists in combining components of the laminated material by means of a bonding agent. It is known that PVC
can be excellently bonded to glass fiber-reinforced plastics, if an adhes-ive polyester layer is first applied to the clean connecting surface.
Polyolefins cannot be directly bonded using epoxy or polyester resins.
A method employing a mechanical bonding agent is therefore chosen in the majority of cases. With this method glass fiber mats must first be pressed into the polyethylene or polypropylene after surface melting. In this way they are anchored inthe thermoplasts, forming a base for adhesive coating.
The object of this invention is to produce a composite material, that is tough, as well as impact and shock resistant, while at the same time possessing a hard, firm, thermally stable, resistant but not brittle ex-ternal layer.
The invention provides for a laminated composite material compris-ing a high molecular weight polyethylene with a viscosimetrically determined `'.`' ~"`'~.
` molecular weight aboYe 500,000 and a phenolic resin, wherein the polyethylene :.- and the phenolic resin are joined together by means of an ethylene copolymsr as bonding agent.
This invention also provides for a process for forming a laminated composite material comprising a layer of high molecular weight polyethylene with a viscosimetrically determined molecular weight above 500,000 and a layer of phenolic resin which comprises disposing between said polyethylene and said phenolic resin an ethylene copolymer as bonding agent and heating the result-ant material to a temperature sufficient to melt the bonding agent and to incorporate the bonding agent into the polyethylene and the phenolic resin.
; The new material possesses, in comparison with the individual com-; - la -ponents, considerably improved firmness, hardness and heat resistance. Fur-thermore, it is tough as well as being impact~ shock and wear resistant.
In this connection it must be taken into account that the phenolic resins are hard and can resist thermal influences in wide temperature ranges without changing shape. However, as they are not tough, they are brittle, sensitive to impact and shock and can fracture. High molecular weight poly-ethylene, on the other hand, is tough and possesses a high shock and impact abosrbing capacity whereas its hardness and heat resistance are unsatisfactory.
On bonding phenolic resins with high molecular weight polyethylene, a new material results, which surprisingly, in many cases, does not possess the undesired properties of the individual components, but does markedly ex-hibit behavior which is long desired in commercial applications.
In this invention the term high molecular weight polyethylene de-notes a polyethylene with a viscosimetrically determined molecular weight over 500,000. The new composite material possesses particularly favorable proper-ties, when the viscosimetrically determined molecular weight of the polyethy-lene components lies between 1 and 10 million. The manufacture of these high molecular weight polyethylenes is kno~m. A Process for their production using Ziegler catalysts is, for example, described in German OLS 23 61 508.
Phenolic resins (phenoplasts) are the condensation products of phenol and its homologs - cresols and xylenols - with formaldehyde. The conversion of the feedstocks occurs in the presence of either acidic or alkaline catalysts.
The first intermediary products resulting from the condensation are resols, which are still capable of being melted and hardened. After the addi-tion of hexamethylenetetramine they are converted into resitols, condensation products which are still capable of being hardened but are difficult to melt.
In the final stage the so-called resites are obtained, which are completely hardened and infusible.
Phenolic resins, with the same degree of condensation as the resitols and resites, are suitable components of the composite material according to the invention and can be used in pure form, i.e., without the addition of fillers.
One can, however, use phenolic resins containing fillers such as sawdust, as-bestos, mica powder and textile fibers. If used, the fillers are preferably present in an amount of 40 to 60%, based on the combined weight of phenolic resin and filler.
Within the scope of the present invention, fabric and paper webs impregnated with phenolic resins are important components of the composite material. The fabric can be made of natural or artificial fibers, e.g., linen, jute or polyester.
Laminated composites can be made, pursuant to the invention, in a wide variety of ways. For instance, a layer of high molecular weight poly-ethylene can be secured to a layer of phenolic resin. The phenolic resin can .; have any desired degree of hardening and can be present as such or in a carrier such as a fibrous mat. Alternatively, either or both of the polyethylene or phenolic resin can be present in a form such as a sheet, granules, powders, fibers, alone or with another material.
The union of high molecular weight polyethylene and phenolic resin, with or without filler, can be effected according to a preferred process of the invention by means of a bonding agent. By selecting a suitable adhesive, it can be ensured that the bond between plastics of differing chemical composi-tions is durable and can withstand high stress, without the separation of the components at their interface.
A lamination of the components without the application of a bonding agent, e.g., via melting of the surfaces of the individual layers and cooling under pressure, cannot usually be considered since the bond is readily loosened under stress. In this connection, it should be noted that high molecular eight polyethylene, in particular polyethylene with a viscosimetrically de-termined molecular weight over 500,000, no longer melts on heating, but in-stead transforms into a viscoelastic state. A loosening of the plastic layers, which can occur on heating under pressure, disappears again on cooling.
.
; .
z The permanent union of polyethylene and phenolic resin cannot be readily achieved with the usual bonding agents, as the majority of adhesives are unsuitable for the formation of a highly resistant ~ond between the plas-tics, due to the homopolar structure of the polyethylene.
A series of thermoplastic adhesives has been found to be particular-ly effective bonding agents. In particular, it has been found that copolymers of ethylene which are, for example, laid between the components in the form `~ of a film and melted under pressure, are especially effective as bonding agents which secure the high molecular weight polyethylene to the phenolic resin.
During the cooling, which can ensue under pressure, the melt adhesive partial-ly penetrates each of the individual layers and in this way bonds the compo-nents together. It is to be understood that a film of adhesive can be applied in any physical form~ e.g., as granules, powder, fiber, sphere etc. General-ly, the thermoplastic adhesive is applied in a thickness of 0.1 to 1 mm ~le thermoplastic adhesive preferably has a melt flow index ~ASTM D
1238-62, MFI 190/2) in the range of 2 to 50 g/10 min., preferably 2 to 10 g/10 min. It has a melting point (determined by differential thermal analysis) in the range of 90 to 110C. l~here a copolymer of ethylene is employed, ethylene units are preferably present in the copolymer in an amount between 80 and 95 weight percent, especially 90 to 95 weight percent.
Excellent results are obtained when ethylene copolymers containing acrylic acid and/or acrylic ester, e.g., Cl 4 alkyl ester and/or acrylamide and/or vinyl acetate, are used as bonding agents.
Methacrylic acid and/or methacrylic ester can be present in the above-named copolymers, instead of acrylic acid and/or acrylic ester. Ihe manufacture of the laminates can also occur with the aid of copolymers consist-ing of ethylene and acrylic acid or maleic anhydride, or mixtures of ethylene-vinyl acetate copolymer and maleic anhydride. Polyisobutylene can also be - used as adhesive, instead of ethylene copolymers, especially a polyisobutylene having a molecular weight between 50,000 and 200,000.
4'~
The temperatures employed for the manufacture of the composite ma-terial accGrding ~o the invention are dependent on the type of polymer used as bonding agent. Usually temperatures from 140 to 220C are applied and the bonding of the components is carried out at pressures from 20 to 250 bar.
Non-hardened phenolic resin hardens during this thermal treatment.
The thermoplastic adhesive is usually applied as a 0.1 to 1.0 mm thick layer between the surfaces to be bonded. The thickness of the adhesive layer can naturally vary depending on conditions, e.g.~ thickness and number of succes-sive layers of plastic.
It has already been stated that the union of the components of the new composite material preferably occurs on using adhesives. However, when employing textile fabrics impregnated with phenolic resins capable of being hardened, bonding agents can be dispensed with, if the composite material is not to be subjected to high mechanical s~ress.
The structure of the new composite material depends on the intended application. Depending on the intended use of the new material, layers of polyethylene and phenolic resin can be bonded together in varying numbers and thickness. In this way, the physical properties of the composite material, such as mechanical strength, thermal behavior, density, dimensional stability can be adapted according to the special areas of application. The most simple case is when the laminate consists of two layers according to the pattern A-B
~A = phenolic resin, B = polyethylene~. This type of composite material can be employed when the material is subjected on only one side to mechanical and/
or thermal stress. Sandwich structures of the type A-B-A find application in cases where the mechanical and/or thermal stresses affect both sides. The new composit material can, of course, consist of more than three layers, e.g., A-B-A-B-A, if demanded by the particular application. Similarly~ a sandwich structure can be provided of the type B-A-B or B-A-B-A-B. The thickness of the individual layers of the laminates is dependent on the intended use.
3Q The composite material according to the inven~ion can be applied in ` the most varied technical fields, particularly where a combination of strength and heat resistance with impact and shock absorbing qualities is required.
For example, it can be used for parts of weaving looms, which are under high strain, e.g., shuttles, or in the motor industry as brake linings and also in railway track construction.
In order to more fully illustrate the invention and the manner of practicing the same, the following Examples are presented. Examples 1 to 4 refer to composite materials containing adhesives. Example 5 refers to a com-posite material, which was manufactured without adhesives.
Example 1 Manufacture of laminàted composite material A 40 mm thick polyethylene block with a viscosimetrically determined molecular weight of approximately 4,000,000 was bonded on both sides with layers of fabric, impregnated with unhardened phenolic resin (resitol). A
0.5 mm thick copolymer layer consisting of 86.4% polyethylene, 4.1% acrylaide, 3.6% methacrylic acid, 5.9% acrylic ester was used as bonding agent. The bonding of the components occurred at a pressure of 100 bar. After heating for 20 minutes at 200C, the material was then slowly allowed to cool to room tem-perature, while maintaining the pressure. During this period the bonding of the components took place and the phenolic resin simultaneously hardened. The hardened phenolic resin layers were each 6 mm thick.
Testing the properties of the laminated composite material Testing of the adhesion between the components of the composite material was carried out on simple overlapping samples. The composite material was split in the center of the polyethylene layer, so that two parts resulted, each consisting of a polyethylene and a phenolic layer. Part of the phenolic layer from one side and part of the polyethylene from the other side were re-moved by milling. The resulting (overlapping) sample had the following dimen-sions: 60 x 40 x 3 mm3, with an overlap of 25 mm. The sample which was then placed in a vertical tension testing machine, was broken at a feed rate of 69~
` lO0 mm/minute at room temperature. The fracture of the sample occurred at a force of 2,700 N, not, however, in the adhesive surface, but in the polyethy-lene or the phenolic resin layer.
Examples 2 to 4 The manufacture of each laminated sample was carried out according .~:
to Example l, using copolymers of the following composition:
Example 2 3 4 Polyethylene 90% 92.1% 90%
: Acrylic acid 3.9%
Acrylic ester 6.1% 4.7%
Acrylamide 3.2%
Vinyl acetate 10%
Fracture took place in each case in the polyethylene layer at the following values:
Example 2 3 4 .... _ .. _ _ .
Force 2900 N 2950 N 2500 N
Example 5 The manufacture of a composite material is carried out as stated in Example 1, however without the application of a bonding agent.
~ Fracture resulted at a force of 40 N. Separation occurred at the interface of the two components.
Example 6 Polyethylene powder with a viscosimetrically determined molecular weight of approximately 4,000,000 was used in place of the polyethylene sheet in Examples 1 to 4.
Polyethylene powder, which is placed on the fabric layers, impreg-nated with phenolic resin and adhesive (composition as in Example 1), is pre-formed at a pressure of 50 bar. The upper surface of the powder is covered with the same bonding agent and layers of fabric, impregnated with unhardened phenolic resin.
This laminated sample is sintered and molded for four hours at ~00 C and 50 bar. It is subsequently allowed to cool to room temperature at a pressure of 50 bar.
` On testi.ng the laminated sample it was found that fracture resulted in the phenolic resin layer at a force of 2850 N.
Claims (25)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A laminated composite material comprising a high molecular weight polyethylene with a viscosimetrically determined molecular weight above 500,000 and a phenolic resin, wherein the polyethylene and the phenolic resin are joined together by means of an ethylene copolymer as bonding agent.
2. A laminated composite material according to claim 1 wherein the high molecular weight polyethylene has a viscosimetrically determined molecular weight between 1,000,000 and 10,000,000.
3. A laminated composite material according to claim 1 or 2 wherein the phenolic resin is present in a form of a resitol or resite.
4. A laminated composite material according to claim 1 wherein the phenolic resin is in admixture with a filler.
5. A laminated composite material according to claim 4 wherein the fil-ler is a filler of natural or artificial fibers.
6. A laminated composite material according to claim 1 wherein the ethylene copolymer has a melt flow index (190/2) between 2 and 50 g/10 min.
7. A laminated composite material according to claim 1, 2 or 6 wherein the ethylene copolymer has a melting point of between 90 and 110°C.
8. A laminated composite material according to claim 1, 2 or 6 wherein the copolymer is a copolymer of ethylene with a comonomer selected from acry-lic acid, acrylic acid ester, acrylamide and vinyl acetate.
9. A laminated composite material according to claim 1 wherein the bonding agent is a copolymer of ethylene with a comonomer selected from methacrylic acid, methacrylic acid ester and vinyl acetate.
10. A laminated composite material according to claim 1 wherein the bonding agent is a copolymer of ethylene and maleic anhydride.
11. A laminated composite material according to claim 1 wherein the bonding agent is a copolymer of ethylene with vinyl acetate and maleic anhy-dride.
12. A laminated composite material according to claim 1 wherein the bonding agent is polyisobutylene.
13. A laminated composite material according to claim 12 wherein the polyisobutylene has a viscosimetrically determined molecular weight of between 50,000 and 200,000.
14. A laminated composite material according to claim 4 or 5 wherein the filler is present in an amount of from 40 to 60 weight percent based upon the combined weight of phenolic resin and filler.
15. A laminated composite material according to claim 1 wherein the polyethylene is in the form of a sheet and the phenolic resin is in the form of a sheet.
16. A process for forming a laminated composite material comprising a layer of high molecular weight polyethylene with a viscosimetrically deter-mined molecular weight above 500,000 and a layer of phenolic resin which com-prises disposing between said polyethylene and said phenolic resin an ethylene copolymer as bonding agent and heating the resultant material to a temperature sufficient to melt the bonding agent and to incorporate the bonding agent into the polyethylene and the phenolic resin.
17. A process according to claim 16 wherein the process is performed under elevated pressure.
18. A process according to claim 16 wherein bonding is effected at a temperature of from 140 to 220°C and a presssure of from 20 to 250 bar.
19. A process according to claim 16 wherein the bonding agent is in the form of a film.
20. A process according to claim 19 wherein the film has a thickness of from 0.1 to 1 mm.
21. A process according to claim 16, 17 or 18 wherein the bonding agent is a copolymer of ethylene with acrylic acid, acrylic acid ester, acrylamide or vinyl acetate.
22. A process according to claim 16, 17 or 18 wherein the bonding agent is a copolymer of ethylene with methacrylic acid, methacrylic acid ester or vinyl acetate.
23. A process according to claim 16, 17 or 18 wherein the bonding agent is a copolymer of ethylene and maleic anhydride.
24. A process according to claim 16, 17 or 18 wherein the bonding agent is a copolymer of ethylene with vinyl acetate and maleic anhydride.
25. A process according to claim 16, 17 or 18 wherein the bonding agent is polyisobutylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2735147A DE2735147C3 (en) | 1977-08-04 | 1977-08-04 | Layered composite material made of high molecular weight polyethylene and phenolic resin and process for its production |
| DEP2735147.9 | 1977-08-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1141642A true CA1141642A (en) | 1983-02-22 |
Family
ID=6015618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000308283A Expired CA1141642A (en) | 1977-08-04 | 1978-07-27 | Laminated composite material of high molecular weight polyethylene and phenolic resin and the process for its manufacture |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS595429B2 (en) |
| AT (1) | AT374813B (en) |
| BE (1) | BE869416A (en) |
| CA (1) | CA1141642A (en) |
| CH (1) | CH632450A5 (en) |
| DE (1) | DE2735147C3 (en) |
| FR (1) | FR2401021A1 (en) |
| GB (1) | GB2003789B (en) |
| NL (1) | NL174440C (en) |
| YU (1) | YU39100B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58151215A (en) * | 1982-03-05 | 1983-09-08 | Asahi Organic Chem Ind Co Ltd | Fomation of formed body of polyolefin or polyolefin copolymer coated on surface with ultra-high-molecular- weight polyethylene formed member |
| JPS58155918A (en) * | 1982-03-11 | 1983-09-16 | Asahi Organic Chem Ind Co Ltd | Molding method of polymer molded object having surface covered with ultra-high-molecular-weight polyethylene molded object |
| JPS5931145A (en) * | 1982-08-12 | 1984-02-20 | 旭有機材工業株式会社 | Extra-high molecular weight polyethylene laminate |
| DE3309785C1 (en) * | 1983-03-18 | 1984-08-16 | Gebrüder Schmeing, 4280 Borken | Process for manufacturing a composite body |
| JPS60155428A (en) * | 1984-01-25 | 1985-08-15 | Nippon Petrochem Co Ltd | Manufacture of laminated sheet or laminated film |
| JP2749650B2 (en) * | 1989-08-01 | 1998-05-13 | 有限会社エステートルース | Automotive molded ceiling material and method of manufacturing the same |
| USH1542H (en) * | 1993-07-28 | 1996-06-04 | Shell Oil Company | Fiber-reinforced composites |
| DE9415840U1 (en) * | 1994-09-30 | 1994-12-08 | Schwartz G Gmbh & Co Kg | Molding compound |
| DE10029516B4 (en) * | 2000-06-15 | 2015-10-01 | Volkswagen Ag | Plastic molding and process for its preparation |
| TW200829741A (en) * | 2007-01-12 | 2008-07-16 | Far Eastern Textile Ltd | Modifying copolymer, sheath layer material modified with the same and core-sheath composite fiber |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543229A (en) * | 1948-04-27 | 1951-02-27 | Du Pont | Polythene layer bonded to another layer by ethylene-vinyl acetate interpolymer adhesive |
| FR1417656A (en) * | 1963-12-16 | 1965-11-12 | Grace W R & Co | Process for the production of laminated blanks and dies for the production of overmolding printing plates |
| GB1301023A (en) * | 1969-01-16 | 1972-12-29 | Ashland Oil Inc Formerly Ashla | Thermoformable laminates made from thermosetting resins |
| DE2236471A1 (en) * | 1971-08-06 | 1973-02-15 | Dow Chemical Co | TERPOLYMERES |
| JPS5043177A (en) * | 1973-08-22 | 1975-04-18 |
-
1977
- 1977-08-04 DE DE2735147A patent/DE2735147C3/en not_active Expired
- 1977-09-16 NL NLAANVRAGE7710215,A patent/NL174440C/en not_active IP Right Cessation
-
1978
- 1978-07-24 YU YU01761/78A patent/YU39100B/en unknown
- 1978-07-25 GB GB7831071A patent/GB2003789B/en not_active Expired
- 1978-07-27 CA CA000308283A patent/CA1141642A/en not_active Expired
- 1978-07-27 AT AT0545978A patent/AT374813B/en not_active IP Right Cessation
- 1978-07-28 FR FR7822476A patent/FR2401021A1/en active Granted
- 1978-07-28 JP JP53093086A patent/JPS595429B2/en not_active Expired
- 1978-07-28 CH CH816478A patent/CH632450A5/en not_active IP Right Cessation
- 1978-07-31 BE BE189625A patent/BE869416A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5428377A (en) | 1979-03-02 |
| GB2003789B (en) | 1982-02-10 |
| BE869416A (en) | 1979-01-31 |
| DE2735147B2 (en) | 1980-10-30 |
| FR2401021A1 (en) | 1979-03-23 |
| NL7710215A (en) | 1979-02-06 |
| YU39100B (en) | 1984-04-30 |
| ATA545978A (en) | 1983-10-15 |
| CH632450A5 (en) | 1982-10-15 |
| FR2401021B1 (en) | 1981-10-30 |
| AT374813B (en) | 1984-06-12 |
| YU176178A (en) | 1982-06-30 |
| DE2735147C3 (en) | 1982-02-04 |
| NL174440B (en) | 1984-01-16 |
| JPS595429B2 (en) | 1984-02-04 |
| DE2735147A1 (en) | 1979-02-08 |
| GB2003789A (en) | 1979-03-21 |
| NL174440C (en) | 1984-06-18 |
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