GB2045767A - Epoxy resin-butadiene polymer compositions - Google Patents
Epoxy resin-butadiene polymer compositions Download PDFInfo
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- GB2045767A GB2045767A GB7943359A GB7943359A GB2045767A GB 2045767 A GB2045767 A GB 2045767A GB 7943359 A GB7943359 A GB 7943359A GB 7943359 A GB7943359 A GB 7943359A GB 2045767 A GB2045767 A GB 2045767A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/10—Fibres of continuous length
- B32B2305/18—Fabrics, textiles
- B32B2305/188—Woven fabrics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
Compositions comprise an epoxy resin and two tipped butadiene polymers. Preferably a dihydroxy compound, such as a diphenol, is also included. The compositions are gellable to an incompletely cross-linked, but tack-free state which enables the compositions to be used as adhesives. Substrates are coated with the compositions, gelled and substrates assembled. The cross- linking is completed to laminate the assembly. The adhesive compositions of the invention can be formulated to be substantially solvent-free and therefore there is not the problem, associated with many currently used adhesive compositions, of removing hazardous solvents in order to obtain adhesion.
Description
SPECIFICATION Rubberlresin compositions
This invention relates to novel compositions which may be used, for example, for coating purposes or as adhesives.
According to one aspect of the present invention, a composition comprises an epoxy resin and two liquid tipped, butadiene polymers selected from the following combinations:
(i) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with a vinyl-tipped butadiene/acrylonitrile copolymer or a vinyl-tipped butadiene homopolymer;
(ii) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolym
er; and
(iii) an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolymer
with a bromo-tipped butadiene/acrylonitrile copolymer or a bromo-tipped butadiene homopolymer.
According to a further aspect of the present invention, there is provided a method of coating by applying a composition which comprises a epoxy resin and two liquid, tipped, butadiene polymers selected from the following combinations:
(i) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with a vinyl-tipped butadiene/acrylonitrile copolymer or a vinyl-tipped butadiene homopolymer;
(ii) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolym
er; and
(iii) an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolymer
with a bromo-tipped butadiene/acrylonitrile copolymer or a bromo-tipped butadiene homopolymer, and then gelling the composition to a substantially tack-free state.
The compositions of the present invention have the property of being two-stage cross-linkable materials.
By a "two-stage cross-linkable" material is meant one that can be gelled to an incompletely cross-linked but substantially tack-free state and can subsequently be subjected to conditions such that cross-linking is completed. It is believed that the gelled, substantially tack-free state of the composition is due to the cross-linking of one of the butadiene polymers and that the final, completely cross-linked state is achieved by the cross-linking of the second butadiene polymer.
The gelling stage may occur automatically or may be caused or accelerated e.g. by the application of heat and/or radiation (such as U.V radiation). Usually, head and/or pressure and/or irradiation is required to complete the cross-linking. A composition of the present invention may be applied to a substrate, gelled by cross-linking to an incompletely cross-linked but substantiallytack4ree state, and subsequently assembled with at least one other identical or different substrate (which may also have been similarly coated) whereupon the assembly is subjected to conditions which cause cross-linking of the composition to be completed and the substrates to be bonded thereby.If desired this second stage, in which the cross-linking proceeds to completion, can be postponed for quite a long time and in tests it has been found that some compositions of the present invention at the gelled, tack-free stage will retain most of their ability to be used subsequently as adhesives after storage for six months or more.
The composition is preferably substantially solvent-free.
The preferred molecular weight range of the liquid butadiene polymers is from 3,500 to 4,800. Where at least one topped butadiene/acrylonitrile copolymer is included in the composition the acrylonitrile content is preferably up to 50%. Generally, commercially available tipped butadiene/acrylonitrile copolymers have an acrylonitrile content up to 35%. Preferably a carboxyl-tipped butadiene/acrylonitrile copolymer and an amino-tipped butadiene/acrylonitrile copolymer are used and then the acrylonitrile content of each copolymer may be 5 to 30% and 5 to 20% respectively. Examples of suitable commercially available tipped copolymers are those available under the trade name Hycar e.g. the carboxyl-tipped CTBN and CTBNX ranges, the amino-tipped ATBN range, and the vinyl-tipped VTBN and VTBNX ranges.Also available under the trade name Hycar are tipped homopolymers e.g. the carboxyl-tipped CTB range and the vinyl-tipped VTB range. Preferably the average functionality (that is the average number of functional groups per polymer molecule) of both polymers is in the range 1.5 to 2.5. Where a copolymer has an average functionality of more than two the extra group(s) are usually situated at a position along the chain and one group is usually at each end. A further tipped butadiene polymer(s) may be included in the composition but this is not a requirement.
The ratio of the total weight of tipped butadiene polymers to the total weight of the composition is preferably up to 9:1. Preferably at least 5 parts by weight of each butadiene polymer are present in each 100 parts by weight of the combination of butadiene polymers.
The optimum relative proportions by weight of the two butadiene polymers and the optimum proportion of the total weight of butadiene polymers based on the entire composition usually vary according to the particular polymers selected. Generally where the functionality of the polymers is different, a lower proportion of the polymer having the higher functionality will be required. A person of ordinary skill in the art would be able to determine by minimal experimentation, implementing the teaching in this specification, the most suitable proportions for a particular combination of components.For example, where a carboxyltipped polymer and an amino-tipped polymer are used, preferably the polymers are present in amounts of at least 5 parts (more preferably at least 10 parts) and at least 10 parts (more preferably at least 20 parts) by weight respectively, based on 100 parts by weight of the polymer blend. Where an amino-tipped polymer and a vinyl-tipped polymer are used, preferably the polymers are present in amounts of from 50 to 90 parts and 50 to 10 parts respectively based on 100 parts by weight of the polymer blend. Where an amino-tipped polymer and a bromo-tipped homopolymer are used, preferably the polymers are present in amounts of from 50 to 90 parts and 50 to 10 parts respectively, based on 100 parts by weight of the polymer blend.
Where an amino-tipped polymer and a bromo-tipped copolymer are used, preferably the polymers are present in amounts of from 20 to 30 parts and 80 to 70 parts respectively, based on 100 parts by weight of the polymer blend. Where a carboxyl-tipped polymer and a vinyl tipped polymer are used, preferably the polymers are present in amounts of from 20 to 50 parts and 80 to 50 parts respectively, based on 100 parts by weight of the polymer blend.
Preferably the epoxy resin is in liquid form and has a bulk viscosity of from about 0.2 to 2,000 N.s/m2 measured by a Brookfield RVT viscometer at 25"C. Preferably the epoxy resin has an equivalent weight of 70 to 2000 and is acyclic. By "acylcic" is meant that the epoxy group is not part of a cycloaliphatic ring structure.
Examples include acylcic aliphatic resins of the glycidyl ether type such as are available under the trade name Epikote 815 and 828 from the Shell Chemical Company, The ratio of the weight of epoxy resin to the total weight of tipped butadiene polymers is preferably in the range 1:0.05 to 1:10 and more preferably 1:0.05to 1:5.
For some compositions, particularly where the weight ratio of epoxy resin to tipped butadiene polymers is less than 1 :5, it may be advisable to add a cross-linking agent to the composition to promote the reaction between the butadiene polymers and the epoxy resin, e.g. an amine-type cross-linking agent. Examples of amine-type cross-linking agents are given later.
Preferably a dihydroxy compound is included in the composition which may serve to increase the molecular weights and rubberiness of the cross-linked butadiene polymers. When used, the dihyroxy compound is preferably a diphenol and more preferably 2,2-di(4-hydroxy-phenyl) propane. This is available as bisphenol A from BDH Chemicals Limited. Other suitable diphenols include methylene bisphenol, bisphenol sulphide and bisphenol sulphone. The ratio of epoxy resin to dihydroxy compound is preferably in the range 100:3 to 100:30 by weight. Where the dihyroxy compound is a diphenol, a particularly preferred ratio of epoxy resin to diphenol is about 100:24 by weight.
The composition may contain additives e.g. an anti-oxidant or other stabiliser, a U.V. initiator, a reinforcing filler (such as carbon black, a metal carbonate or silicate, glass or textile fibres), a non-reinforcing filler (such as tale or titanium oxide), a colourant (such as metal oxide, a metal sulphide or an organic pigment) and a plasticizer (such as di-n-octyl azelate or di-iso-octyl azelate).
A cross-linking agent such as one of the amine or imidazole type may be incorporated in the composition to promote the reaction between the butadiene polymers and the epoxy resin. Suitable examples of the amine-type include tri-dimethyl amino methyi phenyl (available as DMP-30 from the Shell Chemical
Company), the hexanoic acid salt of tri-dimethyl amino methyl phenol (available as cure agent D (CAD) from the Shell Chemical Company), diethylene triamine (DTA), triethylene tetramine (TETA), amino ethyl piperazine (AEP), amino propyl piperazine (APP), piperidine and di-piperidine. An example of an imidazole cross-linking agent is 2-ethyl 4-methyl imidazole (2,4 EMI). Other suitable cross-linking agents include boron trifluoride/amine complexes, hexahydrophthalic anhydride and dicyandiamide.
The compositons of the present invention can be used in a variety of ways, including as mouldings or coatings which may subsequently be used as adhesives.
A specific example of a use of the compositions of the present invention is in the fabric-proofing area, e.g.
in the fabrication of flexible liquid containers, liferafts, fenders and dracones. One way offabric-proofing is by coating a textile material (e.g. of nylon, polyester or rayon) with a composition of the present invention which is then gelled to a substantially tack-free state, assembling the composite with at least one other similar composite and then subjecting the assembly to conditions which will complete the cross-linking of the composition and effect lamination. Usually heat and/or pressure are required.
Afurther application of the present invention is to cast the composition onto a releast paper or similar releasable material and then cause it to gel to a substantially tack-free state. The paper can then be removed and the gelled film used to bond a variety of substrates by assembling the substrates with at least one interlayer of the gelled film and completing the cross-linking of the film(s), usually under the action of heat and/or pressure.
Other substrates which can be coated with or bonded by the compositions of the present invention include vulcanized and vulcanizable rubbers (e.g. natural rubber, high cis-butadiene rubber or EPDM), thermoplastic
materials (e.g. a thermoplastic rubber, rigid (unplasticized) polyvinyl chloride, plasticized polyvinyl chloride, a styrene/ethylene/butene/styrene biock copolymer of a polyurethane), wood, concrete, asphalt, glass, steel, aluminium, brass and tin.
Other uses of the compositions are in diaphragms and gaskets. For end uses requiring oil-resistance the butadiene polymers used in the compositions may be selected with that in mind e.g. by selecting copolymers having a relatively high acrylonitrile content.
The invention is illustrated in the following Examples! to VI, Examples VII & Vlil being included for comparison only. The bond strengths were measured using an Instron tester on 1 inch strips at a cross-head speed of 5 inches per minute.
Example I
Six epoxy resin/bisphenol A/functional liquid elastomer compositions of various carboxy-tipped butadiene/acrylonitrile copolymer (CTBN): amino-tipped butadiene/acrylonitrile copolymer (CTBN) weight ratios were prepared according to the following formulations in which all the amounts are parts by weight:
A B C D E F
Epikote 815 and 100 100 100 100 100 100
Bisphenol A (in a ratio of 100:24 by weight)
CTBN (Hycar 120 140 180 200 200 0 1300 X 15)
ABTN (Hycar 80 60 20 0 0 200 1300 X16) DMP30 0 0 0 0 6 0
Compositions A, B, C, D, E and Fwere bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated fabric = 130 g/m2) and were dried at 1 300C for 30 minutes.
Compositions A, B and C gave coated fabrics of weights 415-450 g/m2 and samples of each of the coated fabrics were stored for 1,3 and 6 months after which time each coated fabric could still be laminated to a similar coated fabric by heating at 1500C for 1 hour at a pressure of 100 p.s.i. (689 kN/m2). Composition D failed to "gel" whist E and F had exceeded the "gel" point and could not subsequently be laminated.
Compositions E and F were applied to a plain woven nylon fabric (weight of uncoated fabric = 130 g/m2) to give coated fabrics of weights 415-450 g/m2 and each coated fabric was laminated to a similar coated fabric while still wet by heating at 150"C for 1 hour at a pressure of 100 p.s.i. (689.4 kN/m2). Satisfactory bonding was achieved but a considerable amount of adhesive exuded from the fabrics, in contrast to the bonding process using the pre-gelled A, B and C.
Interply adhesion of the laminates (in N/test-piece at 21"C) was assed by peel tests after various storage periods and the results obtained were as follows:
Initial Three
Formulation Adhesion One Month Months 6 Months
A Not 67 57 Not
measured measured
B Not 67 85 80
measured
C Not 103 124 Not
measured measured
D 0 Not Not Not
measured measured measured
E 47 Not Not Not
measured measured measured
F 75 Not Not Not
measured measured measured
Example Il Four epoxy resin/bisphenol A/functional liquid elastomer compositions were prepared according to the following formulations in which all the amounts are parts by weight:
A B C D
Epikote 815 and 100 100 100 100
Bisphenol A (in a ratio of 100::24 by weight)
Carboxyl-tipped 120 140 80 60 butadiene acrylonitrile copolymer (CTBNX-Hycar 1300X9)
Amino-tipped 80 60 120 140 butadienel acrylonitrile copolymer (CTBN-Hycar 1300 X 16)
Compositions A, B, C and D were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated fabric = 130 g/m2) and were dried at 130"C for 30 minutes. The coated fabrics of weights 415-450 g/m2 were each laminated to a similar coated fabric and heated at 1 500C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2), both immediately after drying at 130 C for 30 minutes and also after storing for three months.
Interply adhesion of the laminates was assessed by peel tests and the results obtained were as follows:
N/test piece at 21"C Formulation Initial Adhesion Three Months
A 70 71
B 50 74
C 39.8 30
D 50 39
Example IIl Two epoxy resin/bisphenol A/functional liquid elastomer compositions were prepared according to the following formulations in which all the amounts are parts by weight::
A B
Epikote 815 and 100 100
Bisphenol A (in a ratio of 100;24 by weight)
Carboxyl-tipped 40 100 butadienel acrylonitrile copolymer (CTBN-Hycar 1300x 15)
Vinyl-tipped butadiene/ 160 100 acrylonitrile copolymer (VTBN-Hycar 1300 x 22)
U.V. initiator - Quantacure
PDO (50% of 1 -phenyl-1,2- 8 5 propanediono-2-(0-ethoxy carbonyl)oxime in acetone) DMP30 4 10
Compositions A and B were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated fabric = 130 g/m2 and weight of coated fabric = 415-450 g/m2) and were exposed to a 5 kw UV source at a distance of 9 cm for 15 seconds. Each of the coated fabrics was laminated to a similar coated fabric by heating at 1 500C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2) soon after U.V. exposure.
Interply adhesion of the laminates was assessed by peel tests and the results obtained were as follows:
Formulation N/test piece at 21"C - Initial adhesion
A 19.6
B 14.7
Example IV
Two epoxy resin/bisphenol A/functional liquid elastomer compositions were prepared according to the following formulations in which the amounts are parts by weight:
A B
Epikote 815 and 100 100
Bisphenol A (in a ratio of 100:24 by weight)
ATBN (Hycar 1300 x 16) 160 180
Polysar RTV (Bromo-tipped 40 20 butadiene homopolymer, average functionality of 2)
Compositions A and B were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated and coated fabric = 130 g/m2 and 415-450 g/m2 respectively) and were dried at 1300C for 10 minutes.Each of the coated fabrics was laminated to a similar coated fabric by heating at 1300C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2)
Interply adhesion of the laminates was assessed by peel tests and the results obtained were as follows:
Formulation N/test piece at 21"C - Initial Adhesion
A 75
B 63.0
Example V
The epoxy resin/bisphenol A/functional liquid elastomer compositions were prepared according to the following formulations in which all the amounts are parts by weight:
A B
Epikote 815 and 100 100
Bisphenol A (in a ratio of 100::24 by weight)
ATBN (Hycar 1300x 16) 60 40
Bromo-tipped butadiene/ acrylonitrile copolymer 140 160
Compositions A and B were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated and coated fabric = 130g/m2 and 415-450 g/m2 respectively) and were dried at 130 Cfor45 minutes. Each of the coated fabrics was laminated to a similar coated fabric by heating at 130"C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2).
Interply adhesion of the laminates was assessed by peel tests and the results obtained were as follows:
Formulation N/test piece at 21"C - Initial Adhesion
A 68.7
B 65.0
Example W An enoxv resin/bisDhenol A/functional liquid elastomer composition was prepared according to the following formulation in which all the amounts are parts by weight:
Epikote 815 and 100
Bisphenol A (in a ratio of 100::24 by weight)
ATBN (Hycar 1300 x 16) 160
VTB (Hycar 2000 x 164) 40
Quantacure PDO (50% solution in 2 acetone)
The composition was bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated and coated fabric = 130 g/m2 and 415-450 g/m2 respectively) and samples were exposed to a 5 kw UV source at a distance of 9 cm for 10, 15 and 23 seconds, samples A, B and C respectively. Each of the coated fabrics was laminated to a similar coated fabric by heating at 150"C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2).
Interply adhesion of the laminates was assessed by peel tests and the results obtained were as follows:
Samples N/Test piece at 21"C - Initial adhesion
A 68.7
B 63.7
C 63.7
Example VII
Three epoxy resin/bisphenol A/functional liquid elastomer compositions of various bromo-tipped butadiene/acrylonitrile copolymer: vinyl-tipped butadiene/homopolymer (VTB) weight ratios were prepared according to the following formulations in which all the amounts are parts by weight:
A B C
Epikote 815 and 100 100 100
Bisphenol (in a ratio of 100:24 by weight)
Bromo-tipped butadiene/ 100 40 160 acrylonitrile copolymer VTB(Hycar2000x164) 100 160 40
Quantacure PDO 5 8 2
PEI-6 5 2 8 (Polyethylenimine- a mixed mono, di and tertiary aliphatic amine)
Compositions A, B and C were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated fabric = 130 g/m2) and were exposed to a 5 kw UV source at a distance of 9 cm for up to about 25 seconds. The coatings did not gel to a substantial Iy tack-free state.Each of the coated fabrics was assembled with a similarly coated fabric and heated at 1 500C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2). None of the assemblies bonded together to any significant extent.
Example Vlll Three epoxy resin/bisphenol A/functional liquid elastomer compositions of various bromo-tipped butadiene homopolymer: vinyl-tipped butadiene/acrylonitrile copolymer (VTBN) weight ratios were prepared according to the following formulations in which ail the amounts are parts by weight:
A B C
Epikote 815 and 100 100 100
Bisphenol A (in a ratio of 100:24 by weight)
Bromo-tipped butadiene/ 100 40 160 acrylonitrile copolymer VTB (Hycar 1300x 22) 100 160 40
Quantacure PDO 5 8 2
PEI-6 5 2 8 (Polyethylenimine - a mixed mono, di and tertiary aliphatic amine)
Compositions A, B and C were bar-coated onto a 0.25 mm thick plain woven nylon fabric (weight of uncoated fabric = 130 g/m2) and were exposed to a 5 kw UV source at a distance of 9 cm for up to about 25 seconds. The coatings did not gel to a substantially tack-free state. Each of the coated fabrics was assembled.
with a similarly coated fabric and heated at 150"C for one hour at a pressure of 100 p.s.i. (689.4 kN/m2). None of the assemblies bonded together to any significant extent.
Claims (38)
1. A composition which comprises an epoxy resin and two liquid, tipped, butadiene polymers selected from the following combinations:
(i) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with a vinyl-tipped butadiene/acrylonitrile copolymer or a vinyl-tipped butadiene homopolymer;
(ii) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolym
er; and
(iii) an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolymer
with a bromo-tipped butadiene/acrylonitrile copolymer or a bromo-tipped butadiene homopolymer.
2. A composition according to claim 1 which is substantially solvent-free.
3. A composition according to claim 1 or 2 which comprises an epoxy resin and two liquid, tipped, butadiene/acrylonitrile copolymers.
4. A composition according to claim 3 which comprises two liquid, tipped, butadiene/acrylonitrile copolymers having an acrylonitrile content of up to 50% by weight.
5. A composition according to claim 3 which comprises two liquid, tipped, butadiene/acrylonitrile copolymers having an acrylonitrile content of up to 35% by weight.
6. A composition according to any preceding claim in which the molecular weight of at least one butadiene polymer is in the range 3,500 to 4,800.
7. A composition according to claim 6 in which the molecular weight of each butadiene polymer is in the range 3500 to 4,800.
8. A composition according to any preceding claim in which the average functionality of the butadiene polymers is from 1.5 to 2.5.
9. A composition according to any preceding claim in which at least 5 parts by weight of each tipped butadiene polymer is present in each 100 parts by weight of the combination of butadiene polymers.
10. A composition according to any of claims 1 to 8 in which at least 10 parts by weight of each tipped butadiene polymer is present in each 100 parts by weight of the combination of butadiene polymers.
11. A composition according to any preceding claim in which the ratio of the total weight of tipped butadiene polymers to the total weight of the composition is up to 9:1.
12. A composition according to any preceding claim in which the epoxy resin is liquid.
13. A composition according to any preceding claim in which the epoxy resin has a bulk viscosity from 0.2 to 2000 N.s/m2 (measured by a Brookfield RTV viscometer at 25"C).
14. A composition according to any preceding claim in which the epoxy resin has an equivalent weight of 70 to 2000.
15. A composition according to any preceding claim in which the epoxy resin is acyclic.
16. A composition according to claim 15 in which the epoxy resin comprises an acyclic aliphatic resin of the glycidyl ether type.
17. A composition according to any preceding claim in which the ratio of the weight of epoxy resin to the total weight tipped butadiene polymers is in the range 1 :0.05 to 1:10.
IR. A comnosition according to any of claims 1 to 16 in which the ratio of the weight of epoxy resin to the total weight tipped butadiene polymers is in the range 1:0.05 to 1:5.
19. A composition according to any preceding claim in which the composition includes a cross-linking agent.
20. A composition according to claim 19, in which the cross-linking agent comprses an amino and/or an imidazole.
21. A composition according to any preceding claim which includes a dihydroxy compound.
22. A composition according to claim 21 in which the dihydroxy compound comprises a diphenol.
23. A composition according to claim 22 in which the diphenol comprises 2,2-di(4-hydroxyphenol)propane).
24. A composition according to claim 22 or 23 in which the ratio of epoxy resin to diphenol is about 100:24 by weight.
25. A composition according to any of claims 1 to 23 in which the ratio of epoxy resin to dihydroxy compound is in the range 100:3 to 100:30 by weight.
26. A composition according to any preceding claim which includes a U.V. initiator.
27. A composition according to claim 1 and substantially as described in any one of Examples I to VI.
28. A method of coating by applying a composition which comprises an epoxy resin and two liquid, tipped, butadiene polymers selected from the following combinations:
(i) a carboxyl-tipped butatiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with a vinyl-tipped butadiene/acrylonitrile copolymer or a vinyl-tipped butadiene homopolymer;
(ii) a carboxyl-tipped butadiene/acrylonitrile copolymer or a carboxyl-tipped butadiene homopolymer
with an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolym
er; and
(iii) an amino-tipped butadiene/acrylonitrile copolymer or an amino-tipped butadiene homopolymer
with a bromo-tipped butadiene/acrylonitrile copolymer or a bromo-tipped butadiene homopolymer, and then gelling the composition to a substantially tack-free state.
29. A method according to claim 28 in which the composition has the feature defined in any one of claims 1 to 27.
30. A method according to claim 28 or 29 in which gelling is caused or accelerated by heat and/or U.V.
radiation.
31. A method according to claim 28, 29 or 30 in which the composition is coated onto a textile material.
32. A method according to claim 28 and substantially as described in any one of Examples I to Vl.
33. A method according to claim 28 substantially as herein described.
34. A method according to claim 28,29 or 30 in which the composition is applied to a material from which it can be released after gelling.
35. A method according to claim 34 in which the material is a release paper.
36. A method according to claim 34 or 35 in which after the composition has been gelled to a substantially tack-free state, it is removed from the material.
37. A method of bonding a substrate to at least one other identical or different substrate which comprises:
(i) making a gelled film by the method according to claim 36;
(ii) assembling the substrates to be bonded with at least one interlayer of said gelled film; and
(iii) subjecting the assembly to conditions which will cause lamination of the assembly.
38. A method of bonding a substrate to at least one other identical or different substrate which comprises
(i) applying to at least one of the substrates a composition by the method according to any one of
claims 28 to 33;
(ii) assembling the substrates with the coating or coatings at the interface; and
(iii) subjecting the assembly to conditions which will cause lamination of the assembly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7943359A GB2045767B (en) | 1979-01-04 | 1979-12-17 | Epoxy resinbutadiene polymer compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7900271 | 1979-01-04 | ||
| GB7943359A GB2045767B (en) | 1979-01-04 | 1979-12-17 | Epoxy resinbutadiene polymer compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2045767A true GB2045767A (en) | 1980-11-05 |
| GB2045767B GB2045767B (en) | 1983-01-26 |
Family
ID=26270139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7943359A Expired GB2045767B (en) | 1979-01-04 | 1979-12-17 | Epoxy resinbutadiene polymer compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2045767B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482659A (en) * | 1983-10-21 | 1984-11-13 | Westinghouse Electric Corp. | Toughened thermosetting compositions for composites |
| EP0579284A2 (en) * | 1987-11-19 | 1994-01-19 | Mitsui Petrochemical Industries, Ltd. | Novel epoxy resins and electrostatographic toner containing the same as a binder |
| WO2007085291A2 (en) * | 2006-01-26 | 2007-08-02 | H.B. Fuller Licensing & Financing, Inc. | Use of polysulfide-containing two-component adhesives for the production of windows |
-
1979
- 1979-12-17 GB GB7943359A patent/GB2045767B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482659A (en) * | 1983-10-21 | 1984-11-13 | Westinghouse Electric Corp. | Toughened thermosetting compositions for composites |
| EP0579284A2 (en) * | 1987-11-19 | 1994-01-19 | Mitsui Petrochemical Industries, Ltd. | Novel epoxy resins and electrostatographic toner containing the same as a binder |
| EP0579284B1 (en) * | 1987-11-19 | 1999-03-24 | Mitsui Chemicals, Inc. | Novel epoxy resins and electrostatographic toner containing the same as a binder |
| WO2007085291A2 (en) * | 2006-01-26 | 2007-08-02 | H.B. Fuller Licensing & Financing, Inc. | Use of polysulfide-containing two-component adhesives for the production of windows |
| WO2007085291A3 (en) * | 2006-01-26 | 2008-01-03 | Fuller H B Licensing Financ | Use of polysulfide-containing two-component adhesives for the production of windows |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2045767B (en) | 1983-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |