GB2292152A - Improvements relating to resin curing systems - Google Patents
Improvements relating to resin curing systems Download PDFInfo
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- GB2292152A GB2292152A GB9513974A GB9513974A GB2292152A GB 2292152 A GB2292152 A GB 2292152A GB 9513974 A GB9513974 A GB 9513974A GB 9513974 A GB9513974 A GB 9513974A GB 2292152 A GB2292152 A GB 2292152A
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- United Kingdom
- Prior art keywords
- resin
- resin system
- cure
- heat
- acid
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 84
- 239000011347 resin Substances 0.000 title claims abstract description 84
- 239000005011 phenolic resin Substances 0.000 claims abstract description 23
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003377 acid catalyst Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 239000001166 ammonium sulphate Substances 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 1
- IPJBGMUIXVHVPD-UHFFFAOYSA-O azanium azane nitric acid nitrate Chemical compound N.[NH4+].O[N+]([O-])=O.[O-][N+]([O-])=O IPJBGMUIXVHVPD-UHFFFAOYSA-O 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- ZJQKISPTWPQBSR-UHFFFAOYSA-N methanamine;toluene Chemical compound NC.CC1=CC=CC=C1 ZJQKISPTWPQBSR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LSQBSJGVGHPYAZ-UHFFFAOYSA-N triazanium;hydrogen sulfate;sulfate Chemical compound [NH4+].[NH4+].[NH4+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O LSQBSJGVGHPYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
To control when a phenolic resin system will cure, the acid catalyst is chemically blocked so that at ambient conditions, although the catalyst is mixed in the resin matrix, it will not cure. Cure can be initiated by the application of heat which "unblocks" the catalyst to enable it to commence the cure. The invention has particular application to the placement of tubular liners impregnated with the resin in pipes or passageways where the liner is inflated into the pipe or passageway before curing of the resin and then curing can be effected at the installers convenience, which is of considerable advantage.
Description
Improvements Relating to Resin Curing Systems
This invention relates to resin curing systems, and in particular concerns a resin formulation designed so that the resin can be cured i.e. changed from a fluent mass to a rigid mass at the selection of the user.
There are many applications where a fluent or at least pliable resin mass is required to be cured to a solid mass to produce for example a shaped article. Some synthetic resins which are referred to as thermoplastic in nature will soften when heated and can be shaped or moulded when soft, and then cooled to form a rigid article. Other forms of synthetic resin referred to as thermosetting resins initially are fluent in nature, and remains so until mixed with a curing agent or catalyst when they change structure and become rigid. This is a one time process hence the expression thermosetting insofar as after the material has rigidified, it cannot be reconstituted into the fluent form.The present invention is concerned with thermosetting resins comprising the combination of a basic resin matrix, and a curing agent, which may be and usually is a catalyst, but the mix may also include what is referred to as an accelerator or promoter which enhances the curing reaction. Some thermosetting resins are what is referred to as ambient cure resins which means that when the curing agent and resin matrix are mixed, it is only a matter of time before the resin cures without the application of any external influence such as heat, although the presence of heat always accelerates the cure.
Other resins need the application of heat before curing will take place within a reasonable time, although even these resins will eventually cure after mixing of the resin matrix and catalyst, and without the application of external influence, but the curing time is much greater. An example of an ambient cure resin is an epoxy resin, whilst polyester resin represents a material which normally requires the application of heat to achieve cure within a reasonable time.
Epoxy resin and polyester resin mixes are used extensively in the application in which we are particularly interested, namely the formation of lining pipes formed on passageways and pipelines, in particular underground sewers or the rehabilitation of same. These processes, which are explained for example in US Patents Nos 4009163 and 4064211 involve the use of a flexible lining tube which is impregnated with the resin mix. The lining tube is then inserted into the sewer for which it is tailored, and then is inflated onto the sewer surface and held inflated whilst curing takes place. In the case of a lining tube impregnated with epoxy resin, it is simply a matter of keeping the tube in inflated condition, but if a polyester resin is used, it is usual to supply hot water to the inside of the inflated tube in order to initiate and effect the cure.In each case, when curing has been completed, the inflating pressure can be removed leaving a rigid lining pipe on the sewer surface. This process has been extremely successful throughout the world, and has been practised for many years. The main resin which is used in this process is polyester resin requiring the use of heat for the cure of same.
The process of sewer lining as indicated above can be enhanced if the resin used can be quiescent or latent in nature which means that the resin is of a type which will remain in the fluent state for a long time after mixing so that the lining tubes can be pre-impregnated with or formed by the resin mixture long before they are to be used. Indeed if this can be achieved, then lining tubes can be prepared in advance and can be stored in stock ready for subsequent orders. Additionally, the tubes can be transported all over the world upon request. Obviously, it is undesirable to provide a stock of such tubes if the resin will in the course of time cure, but if a quiescent or latent resin system can be developed, then considerable advantages can be achieved.
Another requirement is that when the lining tube is eventually placed in position of the sewer, it is desirable that curing should be effected in the shortest time possible so that the contractor can spend the minimum of time on site and therefore can complete the contract at the minimum cost to the customer. The requirement is therefore for a resin system which has a long shelf life, and a fast cure time after the cure is initiated.
Many attempts have been made to achieve this arrangement, and one particular method has been to provide a resin system which is curable by ultraviolet or other high intensity light. This system has not found commercial favour however, because of the problems concerned with taking high intensity lights into underground passageways such as sewers in which there may exist a wet and hostile environment.
The present invention is concerned with providing a latent or quiescent resin system which, after mixture of the resin ingredients, the resin will remain in the uncured state until the application of heat, and the present invention has particular application in connection with the utilisation of high reactivity ambient cure resin systems, such as those based upon the phenolic resins of which the curing agents are acids, and in accordance with the present invention, the resin system comprises a resin matrix of which the curing agent is an acid which is chemically blocked; preferably the chemical blocking is achieved in that mixed with the resin is either (i) a neutral substance which can be caused to become acidic, or (ii) an acid and an inhibiting substance of which the inhibiting effect of the inhibiting substance can be released to allow the acid to cure the resin matrix; upon the application of heat.
It can be seen therefore that an extremely simple system can result insofar as in the one case a substance such as a salt for example ammonium chloride can be mixed with a phenolic resin matrix. The mixture of these two ingredients does not cause the curing of the phenolic resin matrix, because no free curing agent acid is present, but when heat is applied, the ammonium chloride changes to ammonia and hydrochloric acid, and the hydrochloric acid then commences curing of the phenolic resin. In an alternative case, an acid and a volatile inhibiting substance for example methylamine, dimethylamine or isopropylamine is used in conjunction with the acid to inhibit the acidic effect, but the inhibiting substance is volatilized under the application of heat, leaving the acid to commence cure of the phenolic resin.
In the case of the utilisation of a compound such as a salt, that salt may have a relatively neutral pH value in the order of 6 or 7, but when the salt is heated and for example in the case of ammonium chloride, the ammonia is driven off leaving hydrochloric acid which has a pH in the order of 1, and the phenolic resin would normally commence cure when mixed with an acid of pH of 3 or less. It can be considered therefore that the salt in the change from the salt formulation to a gas and acid, moves to an activated pH level which causes curing of the phenolic resin.
Similarly, in the case of a mixture of curing acid and neutralising compound, that mixture may have a pH in the order of 13 or 14 and be relatively neutral, but when the neutralising substance which can be considered as a buffer is driven off, the pH value falls into the acidic range which results in curing of the phenolic resin.
These resin mixtures can of course be used in connection with the lining of underground sewers as described above, and the lining tubes can be pre-impregnated or resin mixtures and will remain in the resin uncured state for a long time enabling the tubes to be stored and used at will, providing the advantages described.
The lining tubes disclosed in the aforementioned US patents involve the use of fibrous felt which acts as a carrier for the resinous material. Instead of the lining tube being constructed in this way, it could be in the form of a prepreg material which comprises basically a resin matrix with fibrous reinforcement. The fibrous reinforcement can be loose fibres or a fibrous mat, as opposed to a dense felt.
Indeed, the lining tube may be constructed from a flat sheet comprising the resinous mass either impregnating material such as felt, or being in the form of a pre mixed mass, and to use the flat sheet, it is wrapped in tubular form before being placed in the pipeline or passageway. Some means may be necessary to join the overlap edges to produce a tubular form, but in other cases the edges may simply be overlapped, and will remain so as the tubular form is applied to the pipeline or passageway surface. The application of the invention to the lining of pipelines and passageways is important, but the structure of the lining as long as it embodies the resinous mass which is latent in nature by virtue of the invention, can vary within wide constructions.
When the lining tube is inserted, it may be inflated using water heated to the appropriate temperature, which typically will be in the order of 800C, which gives rise to the increase in acidity as referred to above.
In a typical mixture using a neutral salt, a 100 g of the resin may be mixed with a 10 g of the salt, and when such a mixture is subjected to heat of a temperature over 500C and preferably in the order of 800C, curing is effected in a period in the order of ten minutes, which is extremely effective. In the case of the utilisation of the phenolic resin and acid and neutraliser, 100 g of phenolic resin typically may be mixed with 10 g of the curing acid, and 5 g of the volatile neutralising substance (which may have a boiling point of the order of 35/50 C). The curing temperature again is typically in the order of 800C.
Some more specific examples are given below.
(1) A first example involves using any of the amine(s) indicated below of high pH (e.g. pH 14) to neutralise the acid catalyst "phencat 10" as sold by BP which is a toluene sulphonic/phosphoric acid which has pH 1 to pH 7, generating a stable resin system at ambient temperature with good shelflife properties. Upon heating the resin system, the low boiling point amine(s) will volatilise off quickly, leaving the active acid catalyst in the resin. Since the amine has been removed, the pH of the acid catalyst has returned to its original value of 1 and has regained its active curing properties. Examples of amines used in this chemical neutralisation technique are as follows; isopropylamine, methylamine, dimethylamine.
Properties of the Amine(s)
pH Boiling point
Isopropylamine 14 SOoC (40% aqueous) Methylamine 14 450C (40% aqueous)
Dimethylamine 14 sooC (40% aqueous)
Experiment
It has been found that when 2gms (by wt) methyl amine solution is mixed with 10gms "phencat 10" acid catalyst, this generates a chemically stable (or neutral) catalyst in 100gms of phenolic resin at ambient temperature. When the phenolic system is heated in an oven at 800C, the amine volatilises off and a full cure is obtained within 15 minutes. At higher temperatures, the cure process is much quicker. See
Table 2.
Amine % concentration Oven Temperature Cure Time
(solution) (Oc) (mins) Methylamine 2 approx 800C 15 mins
(40% aqueous) " " 500C 20 mins
H n 1000C 7 mins
1100C 4 mins
The respective reactions are as follow
CH3NH2 + Acid
[CH3NH3 Acid ] stable (pH-14) (pH-l) amino acid complex
250C
Methylamine Toluene Sulphonic pH 6-7
/phosphoric acid
(Phencat 10)
An initial mixing and ambient temperature the stable amino acid complex of pH 6-7 is formed. When heat at over 500C is applied the reaction reverces and the complex breaks down to methylamine and the original acid enabling cure of the resin to take place.
(2) In a second example a catalytic powder is mixed with the resin at ambient temperature but shows no reactivity and does not initiate curing of the resin. Examples of such catalytic powders are as follows; Ammonium Chloride,
Ammonium Sulphate, Ammonium Nitrate. These powders or crystalline salts as they are more commonly referred to, are slightly acidic (e.g. pH 5-6) but very stable in phenolic resins. However, when a phenolic resin/ammonium chloride mixture is placed in an oven at 800C, the ammonium chloride undergoes chemical change, giving hydrogen chloride and ammonia. The hydrogen chloride is a strong acid catalyst (pH 1) and curing agent, hence a phenolic cure is obtained quickly.
Chemical Dissociation of Crystalline Salt NH + Cl NH3 + HC1 Ammonium chloride Ammonia Hydrogen chloride (NH4+)2SO42- 2NH3 + H2SO4 Ammonium Sulphate Ammonia Sulphuric Acid NH + NO3 NH3 + HNO3
Ammonium Nitrate Ammonia Nitric Acid
Experimental 10g of Ammonium Chloride is mixed with 100g of Phenolic resin. This at ambient temperature is a stable resin/catalyst system with good shelf-life. Upon heating the mixture at 800C for 10 minutes, a cure is obtained.
Higher temperatures will generate a cure more quickly since the formation of Hydrogen chloride will take place more quickly.
There is prior art in the field of the use of phenolic resins as binders for example for felt manufacture, phenolic resins with acid catalysts and extending liquids, and resins for producing baking enamels, as well as prior art in the field of applying tubular linings to passageways but none of the prior patent specifications, discussed below, discloses the present invention.
Japanese Patent Application No 87-318677
This discloses a phenolic resin used as a binder for felt manufacture. The resin includes an amonium salt the purpose of which is to lower the heat treatment temperature. The advantage is reduced energy cost and improved productivity.
Japanese Patent Application No 900320047
A phenolic resin is used as a binder for fibre, wood meal, ceramic, casting sand etc which can be cured at a low temperature by using a catalyst which is a salt of an acid with a notrogen containing base. This appears similar to
Japanese Patent Application 87-318677 discussed above.
Japanese Patent Application No 92-190059
This specification relates to a pre-preg of which the resin includes expandable particles. The resin is a phenol or melamine resin and the catalyst may be salt or a particular acid of amonium. The resin is for impregnating chopped strand, mat or non-woven fabrics etc. The material is used for a laminate for automobiles. There is no discussion of any chemical blocking.
European Patent Application No 0390535
This specification discloses that a rigid structure may be made by bringing together lengths of tubing or sections of tubing and impregnating same with a composition which comprises a thermosetting resin, an extending liquid for the thermosetting resin and a catalyst. The resin in one example is described as a phenolic resin and the extending liquid suitably a C1-C4 alcohol. The acid is described as suitable acidic catalyst. It is specified that the composition may include other components such as an inhibitor.
More detail is given as to the reasons for using this composition. For example at page 5 line 29 it is specified that it is desirable that the pre-catalysed thermosetting composition has an extended pot life, for example in the order of 14-25 days. The specification specifically talks about the use of resins from BP such as Cellobond J2027L and others, which may be catalysed with a catalyst such as
Phencat 10.
When describing that the resin may be epoxy resin, it is specified that suitably epoxy resins include epoxy resins with blocked amine functions.
The resin systems are referred to as latent catalyst systems which in some cases can trigger polymerisation at a temperature of around 800C or upwards.
Specifically at pages 7 and 8, lines 54 to 59 page 7 and 1 to 5 page 8, an actual example of the preferred liquid composition is given.
US Patent 3474054
This patent concerns the chemistry of coating compositions which are referred to as "baking enamels". The known baking enamels have to be cured to a hard finish at a high temperature in the order of 4000F. This patent is concerned with making a composition which can be cured at a much lower temperature e.g. 1000F, but the composition will be storage stable i.e. it will have a reasonable pot life. This is done by adding an acid catalyst of a specific type to a specific resin composition. The resin composition is either an amino resin or an unmodified alkyd resin and the catalyst is an amine salt of an aromatic sulphonic acid.
French Patent Specification 2584018
This appears to relate to the provision of a tubular structure which initially is flexible, but is impregnated with a polymerisable material, and a number of examples are given, one of which is phenolic resin. The invention is concerned with the method of making the tube, and not the specific chemical composition of the resin.
European Patent Application 0620104A2
This specification discloses a pipe lining operation. The specification also discloses what is claimed to be a novel form of tube. The tube is made up by everting one impregnated tube into another. The outer impregnated tube is impregnated with a resin of a first and low viscosity with small diameter particle filler, whilst the inner tube is impregnated with a resin of high viscosity and large diameter particle filler. When the composite tube is eventually turned inside out to line the pipe, the layer with the high viscosity large diameter filler lies to the outside, and this is alleged to form a much better water barrier for the lining tube.
US Patent 4366012
This relates to vacuum impregnation of lining tubes. The patent also shows that the tube is everted into and along the passageway to line same.
Claims (23)
1. A resin system comprising a resin matrix including an acid curing agent which is chemically blocked so that the system remains latent at ambient conditions and the curing agent can be released by the application of heat.
2. A resin system according to Claim 1, wherein the resin matrix is a high reactivity ambient cure resin matrix.
3. A resin system according to Claim 2, wherein the resin matrix is a phenolic resin matrix.
4. A resin system according to Claim 3, wherein the chemical blocking is achieved by a neutral substance which can be caused to become acidic by the application of heat.
5. A resin system according to Claim 4, wherein the neutral substance is a salt.
6. A resin system according to Claim 5, wherein the salt is ammonium chloride, ammonium sulphate or ammonium nitrate.
7. A resin system according to Claim 5 or 6, wherein the resin matrix and salt are contained in the system in the proportions by weight of 10:1.
8. A resin system according to Claim 3, wherein the chemical blocking is achieved by an acid catalyst and inhibiting substance of which the inhibiting effect is removed by the application of heat.
9. A resin system according to Claim 8, wherein said acid catalyst is the substance "Phencat 10" (sold by B.P.Plc).
10. A resin system according to Claim 9, wherein the inhibiting substance is an amine which can be driven off by heat.
11. A resin system according to Claim 10, wherein the amine is methylamine, dimethylamine or isopropylamine.
12. A resin system according to Claim 10 or 11, wherein the acid catalyst is mixed with the amine by combining 2 parts by wt of a 40% aqueous of the amine with 10 parts by wt of the acid catalyst to produce the blocked catalyst arrangement, which is mixed with 100 parts by wt of the resin matrix.
13. A flexible hardenable sheet member comprising within its wall thickness a resin system according to any preceding claim.
14. A member according to Claim 13, wherein said resin system includes fibrous reinforcing material.
15. A member according to Claim 14, wherein said fibrous reinforcing material comprises one or more layers of a fibrous fabric.
16. A member according to Claim 15, wherein said layer or each of said layers is of fibrous felt.
17. A member according to Claim 15, wherein said member is flat.
18. A member according to any of Claims 13 to 16, wherein said member is tubular.
19. A member according to Claim 18 wherein said member is inflatable by eversion and has on its outer surface a film or skin providing the means whereby the member can be inflated by eversion.
20. A member according to Claim 18 or 19, wherein the said member has an inner skin or film by which it can be inflated.
21. A method of providing a pipe comprising inflating a member according to any of claims 18 to 20 accompanied by the application of heat to unblock the curing agent to cause the resin in the member to cure causing the member to form a rigid pipe.
22. The method of claim 21 wherein the member is inflated against the inner surface of a host pipe or passageway so as to form a rigid pipe within a pipe.
23. The method of claim 22 wherein the host pipe or passageway is located underground.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9414180A GB9414180D0 (en) | 1994-07-13 | 1994-07-13 | Improvements relating to resin curing systems |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9513974D0 GB9513974D0 (en) | 1995-09-06 |
| GB2292152A true GB2292152A (en) | 1996-02-14 |
Family
ID=10758298
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9414180A Pending GB9414180D0 (en) | 1994-07-13 | 1994-07-13 | Improvements relating to resin curing systems |
| GB9513974A Withdrawn GB2292152A (en) | 1994-07-13 | 1995-07-08 | Improvements relating to resin curing systems |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9414180A Pending GB9414180D0 (en) | 1994-07-13 | 1994-07-13 | Improvements relating to resin curing systems |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9414180D0 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051960A1 (en) * | 1997-05-15 | 1998-11-19 | Sound Pipe Ltd. | Improvements relating to curing of synthetic resin systems, for example, in the lining of pipelines and passageways |
| WO2023076565A1 (en) * | 2021-11-01 | 2023-05-04 | Tex Tech Industries, Inc. | Pipe and tube rehabilition liner with homogeneous reinforcing fiber blend |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1067043A (en) * | 1964-04-06 | 1967-04-26 | Mo Och Domsjoe Ab | Improvements in or relating to the forming of composite wood products |
| GB1238255A (en) * | 1969-02-13 | 1971-07-07 | ||
| US4064211A (en) * | 1972-12-08 | 1977-12-20 | Insituform (Pipes & Structures) Ltd. | Lining of passageways |
| US4689376A (en) * | 1984-12-22 | 1987-08-25 | Bayer Aktiengesellschaft | Heat-hardenable epoxide resin mixtures |
| JPS62227945A (en) * | 1986-03-28 | 1987-10-06 | Aisin Chem Co Ltd | Phenolic resin composition for felt |
| EP0240459A1 (en) * | 1986-03-26 | 1987-10-07 | Ciba-Geigy Ag | Curable compositions |
| US4725612A (en) * | 1986-08-06 | 1988-02-16 | Drew Chemical Corporation | Synergistic microbiocidal compositions containing a mixture of a bicyclic polyoxymethylene oxazolidine and a 1,2-benzisothiazolin-3-one |
| US4728676A (en) * | 1986-01-14 | 1988-03-01 | Bayer Aktiengesellschaft | Thermosetting reactive resin mixtures and a process for the production of moldings using these mixtures |
| EP0257640A2 (en) * | 1986-08-29 | 1988-03-02 | Nippon Zeon Co., Ltd. | Vulcanizable elastomer composition |
| JPH04128013A (en) * | 1990-09-19 | 1992-04-28 | Dainippon Ink & Chem Inc | Prepreg and manufacture of prepreg |
| US5319024A (en) * | 1990-04-19 | 1994-06-07 | Nippon Oil And Fats Company, Limited | Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof |
-
1994
- 1994-07-13 GB GB9414180A patent/GB9414180D0/en active Pending
-
1995
- 1995-07-08 GB GB9513974A patent/GB2292152A/en not_active Withdrawn
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1067043A (en) * | 1964-04-06 | 1967-04-26 | Mo Och Domsjoe Ab | Improvements in or relating to the forming of composite wood products |
| GB1238255A (en) * | 1969-02-13 | 1971-07-07 | ||
| US4064211A (en) * | 1972-12-08 | 1977-12-20 | Insituform (Pipes & Structures) Ltd. | Lining of passageways |
| US4689376A (en) * | 1984-12-22 | 1987-08-25 | Bayer Aktiengesellschaft | Heat-hardenable epoxide resin mixtures |
| US4728676A (en) * | 1986-01-14 | 1988-03-01 | Bayer Aktiengesellschaft | Thermosetting reactive resin mixtures and a process for the production of moldings using these mixtures |
| EP0240459A1 (en) * | 1986-03-26 | 1987-10-07 | Ciba-Geigy Ag | Curable compositions |
| JPS62227945A (en) * | 1986-03-28 | 1987-10-06 | Aisin Chem Co Ltd | Phenolic resin composition for felt |
| US4725612A (en) * | 1986-08-06 | 1988-02-16 | Drew Chemical Corporation | Synergistic microbiocidal compositions containing a mixture of a bicyclic polyoxymethylene oxazolidine and a 1,2-benzisothiazolin-3-one |
| EP0257640A2 (en) * | 1986-08-29 | 1988-03-02 | Nippon Zeon Co., Ltd. | Vulcanizable elastomer composition |
| US5319024A (en) * | 1990-04-19 | 1994-06-07 | Nippon Oil And Fats Company, Limited | Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof |
| JPH04128013A (en) * | 1990-09-19 | 1992-04-28 | Dainippon Ink & Chem Inc | Prepreg and manufacture of prepreg |
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| Title |
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| Patent Abstracts of Japan Vol.12, No.96 (C-484)[2943] March 28,1988 page 61 & JP 62 227 945 A * |
| WPI ACC.NO. 92-190060/23 & JP 04 128 013 A * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051960A1 (en) * | 1997-05-15 | 1998-11-19 | Sound Pipe Ltd. | Improvements relating to curing of synthetic resin systems, for example, in the lining of pipelines and passageways |
| WO2023076565A1 (en) * | 2021-11-01 | 2023-05-04 | Tex Tech Industries, Inc. | Pipe and tube rehabilition liner with homogeneous reinforcing fiber blend |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9414180D0 (en) | 1994-08-31 |
| GB9513974D0 (en) | 1995-09-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |