CA1058350A - Rapidly-hardenable resin and use thereof - Google Patents
Rapidly-hardenable resin and use thereofInfo
- Publication number
- CA1058350A CA1058350A CA220,479A CA220479A CA1058350A CA 1058350 A CA1058350 A CA 1058350A CA 220479 A CA220479 A CA 220479A CA 1058350 A CA1058350 A CA 1058350A
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- CA
- Canada
- Prior art keywords
- synthetic resin
- resin
- episulfide
- compounds
- hardening
- Prior art date
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Classifications
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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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)
- Epoxy Resins (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
INVENTION: RAPIDLY-HARDENABLE RESIN AND USE THEREOF ABSTRACT OF THE DISCLOSURE A rapid-hardening synthetic resin which also hardens at low temperatures without the application of heat and manifested by the features that the resin component contains an episulfide compound having on the average more than one group per molecule. The invention also concerns a method of using such synthetic resin in construction engineering, such as building constructions, container constructions, for producing coatings, coverings, as adhesive, mortar, injection agent or for impregnation.
Description
: `:
.05835Q
. .
BACKG~OUND OF THE INVENTION
: . .
The present invention ~elates to a rapid-hardening resin and the ; use thereof.
Cold hardenable mixtures of epoxide resins and amines and poly-amides containing amino groups have been used for considerable time in the construction industry as coating substances, coverings, mortar, adhesive, injection agent and for impregnation purposes.
The hardening time of such mixtures, in other words the time required for the mixtures to reach a condition where they can be used is dependent upon temperature. Generally, the hardening reaction at temperatures , beneath about 8C proceeds so slowly that such mixtures can no longer be employed.
;~ It has already been proposed to add to such hardenable mixtures :, ;~ compounds which accelerate the hardening reaction.
, '; What is disadvantageous with this proposal is that the accelera-tor, which is not consumed during the hardening reaction, unfavorably affects the use properties of the hardened mixture, for example, the surface hardness, the resistance against the affects of water and chemicals and the mechanical :. . . .
strength, and thus such accelerators can only be added in limited quantities.
Hence, the possibility of using the hardenable mixture containing the ~; accelerator is limited to temperatures above about 5C, and furthermore, ~;~ since most of the accelerators are toxic soluble compounds, it should be ` apparent that epoxide resins containing accelerators generally cannot be used ~' in the construction of swimming pools or drinking water installations. ~;
~;, .
,~ At temperatures between 5C and 10C there are employed so-;~ called highly reactive epoxide resins which, however, at temperatures exeed-ing 10C no longer can be used since their processing time is too short for , proper application.
., .
: OBJECTS OF THE INVENTION
It is therefore a primary object of the present invention to provide a rapidly hardening synthetic resin which is not associated with the aforementioned drawbacks and limitations.
~' ' ' ',:
.
: . . . .:~ . . .
,- , ~ . : ~ : : : , ~ .. :.
lOS8350 Another object of the invention is directed to a method of using such new and improved synthetic resin for different purposes, especially in construction engineering. -~
DETAILED DESCRIPTION OF THE INVENTION
., According to the present invention, there is provided a rapid-hardening synthetic resin which also hardens at low temperatures in the absence of heat, the improvement comprising the resin component containing -an episulfide compound having on the average more than one -CH - CH2 -group per molecule.
Preferably said resin contains an episulfide compound or a mixture of episulfied compounds having an episulfide value in the order of 0.2 to 0.9.
In another aspect, there is provided a method of forming a coating on a substrate which comprises applying the synthetic resin to the substrate.
In particular, it has been found that episulfide compounds containing on the average more than one -CH - CH2 - group per molecule with stochiometric quantities of amines preferably with aliphatic or cyclo-aliphatic amines, harden while forming products which can be rapidly loaded 20 and without the need to add heat to such mixture. -It has been further found that episulfide compounds markedly accelerate the hardening of epoxide resins by means of amine hardeners at low temperatures as a function of their dosage.
The episulfide compounds or mixtures of episulfide compounds used according to the invention can be produced, for instance, according to the process which has been patented in DRP No. 636,708 (German Reichspatent 636,708) in 1934 and disco~ered by K. Dachlauer and L. Jackel, from epoxide compounds by reaction with thiocyanates, sodium thiosulfate, thio-urea or by reduction of chloropolysulfides with Al-amalgam (French patent 1,428,686).
~he episulfide groups of the inventive employed episulfide ~ .
r - 2 -. '. "
- : ~ : .
1(~58350 compounds can be possibly bound by heteroatoms, especially oxygen, or func~
tional groups, such as ester-, urea-, urethane-, or amide-groups of aliphatic-, cycloaliphatic-, possibly substituted aryl - or possibly sub-stituted aryl alkyl-residues.
The polyamines used for hardening the episulfide resins are preferably cycloaliphatic and aliphatic polyamines or mixtures of such amines with amines containing aryl- or substituted aryl alkyl-residues.
The increased reaction capabilities of episulfide compounds in contrast to the corresponding epoxide compounds is known to the art and has been discussed in detail for instance by P. Sigwalt in an article entitlcd "Ring- ~pening Polymerization", Marcel Dekker publishers, New York, 1969 page 191. The behavior of polyepisulfide compounds in :.
contrast to nucleophilic coreactants has been described, for instance, by P. Penczek et al in - 2a -,h ~
, .
, ,: . , ' :"i . ~ ' "Plaste und Kautschuk", 20 (3)! 176 (1973). These authors have found, among other things, that polyepisulfides with catalytic quantities of nucleophilic coreactants gell m~re rapidly at temperatures in the order of 24C and SOC
than the corresponding epoxide resins. The hardening of polyepisulfide com-pounds by means of nucleophilic coreactants in the presence or heat con-stitutes the subject matter of United States patent 3,378,522, granted in 1968 to R.W. Martin.
On the basis of these experimentations it can be assumed that the inventively employed episulfide compounds modify the course of the reaction between an epoxide resin and a polyamine. It has been found from kinetic tests that polyepisulfide compounds initially react with polyamines and that the reaction products formed by such reactions either react with other polyepisulfide molecules or with polyepoxide molecules, and such reaction proceeds quicker than the reaction between a polyepoxide compound and a polyamine. It could also be shown that the episulfide compound alone in the prescribed dosage does not essentially accelerate the hardening of an epoxide resin by an amine hardener.
It is therefore possible to previously admix any given amine hardener, for instance an aliphatic or a cycloaliphatic amine or mixture of such amines such that the stochiometric conditions are maintained, and to add the episulfide compound, prior to application of the system, in such a dosage that there is obtained a hardenable mixture which at a certain tempera-ture possesses the processing time and hardening time respectively, for the intended purpose of use. In this way it is possible to control the degree of the hardening acceleration by means of the dosing of the episulfide com-pound throughout a wide temperature range, for instance between -30C and +10 C .
The inventive episulfide resins are characterized by the features that they together with amines at a temperature of 20C gell and harden ~ -3Q within one minute.
The amines which are preferred for the hardening of such epi-sulfide compounds are aliphatic or cycloaliphatic amines, which can be ~058350 t employed alone or in mixture with another polyamine or polyaminoamide, for instance with aryl- or aryl alkyl-residues.
Since the inventively employed episulfide compounds are them-selves consumed during the hardening reaction, there is formed therefrom an amine hardener insoluble product, so that the rapid hardening resins or resin mixtures of the invention additionally fulfill the regulations concern-ing toxicity.
The inventive episulfide compounds or their mixtures with epoxide resin possess a low viscosity, thereby facilitating the admixing of the components at low temperatures.
The inventive episulfide compounds or their mixtures with epoxide resins can be employed without or with added substances or additives, such as fillers, pigments, plasticizers, extenders and auxiliary substances or adjuvants, such as surface-active agents, leveling agents, wetting agents, delustering or dulling agents, for instance as paint coats, coatings, cover-ings, adhesive, mortar or injection agent.
They are particularly suitable for processing with a so-called two-component or dual-component installation which separately conveys the resin components and the hardener components, for instance in injection pro-cesses, and reinforcing materials such as fabrics or fibers can be employed.
The invention will be further explained on the basis of the following examples. Testing of the chemical resistance was undertaken in accordance with the procedures of DIN 51958 (the symbol DIN representing German Industrial Standards) and the Brinell hardness according to DIN 50351).
Example 1 The following Table 1 shows the chemical resistances of an episulfide compound/TETA systems, the symbol TETA representing triethylene-tetramine. A stochiometric mixture of an episulfide compound with the epi-sulfide value 0.70 and TETA, which gelled at 18C within approximately 1 minute, was applied by means of a dual component spray gun in the form of a film having an average thickness of 200 ~. After hardening for 1 hour and 24 hours at 18C the film was loaded with the chemicals listed in Table 1 and .. , : : :
.. . , : : - .: ~ :
after 24 hours visually checked.
In Table 1 presented hereinafter the following symbols are intended to have the following meanings:
The symbol "A" means that the film is resistant to permanent contact, i.e., the film surface remained absolutely unchanged.
The symbol "B" means that the film is temporarily resistant to permanent contact, i.e., visual inspection thereof revealed slight discolora-tion of the surface.
The symbol "Z" means that the film is not resistant to permanent contact, i.e., the film was destroyed.
Table 1 Episulf de Resin Epoxy lesin 1 Hr 24 Hrs. 1 Hr. 24 Hrs.
.. .. -.
Concentrated Z Z Z Z
hydrochloric acid `
Hydrochloric acid 10% Z Z~ Z Z
Concentrated sulphuric acid Z Z Z Z
Sulphuric acid 10% Z Z Z Z
Nitric acid 10% Z Z Z Z
Acetic acid 5% B B Z Z
Caustic soda 50% A A Z Z
Sodium carbonate A A Z Z
solution 2% _ Acetone A A Z
. ;.
Diethyl ether A A Z_ Z
_ Ethyl acetate A A Z Z
Ethanol A A Z Z
Methanol A A Z Z
__ ~
Chloroform A A Z Z
Methylene chloride B A Z Z
Premium gasolene A A Z Z
Benzol A A Z Z
Heating oil CDIN 51507) ' . . , ,:, ' ~' ' ` -" ` lOS8350 Example 2 Table 2 illustrates the mechanical loading capacity of a coating formed on the basis of the episulfide compound of Table 1 and TETA as the hardener. The Brinell hardness was measured after hardening at -20C, +5C
and +20C.
Table 2 (Brinell Hardness kp/cm ) . ~ .
Episulfide Resin Epoxide Resin _ . . _ ~emPerature -20C +5C +20C -20C +5C +20C
30 Minutes _ ~ 930 _ _ ;~
45 Minutes 350 500 960 ~ ~ _ _0 Minutes 940 950 960 _ _ _ . __ , _ 90 Minutes 950 950 960 _ _ _ -~
. . ,-:
180 Minutes 980 1000 1050 _ _ _ ;
72 Hours1 loo1 lOo lloo 300 . ~ .
Example 3 The following Table 3 shows the accelerating influence of the inventive combination of episulfide compound and ethylene amine upon the hardening of an epoxide resin of bisphenol A-type by means of an amine hardener. The mixing ratio of resin:hardener is 4:1 parts by weight, the amine hardener contains 10% by weight triethylenetetramine (TETA~ and the resin component the quantities of episulfide compounds having an episulfide value of 0.78 and which quantities are set forth in Table 3 below. -Table 3 .
Inventive Without Mixture _ Episulfide Compounds Epoxy Resin 80 80 80 80 ~ 100 100100 100 (parts by wei~ht) _ . .
Amine Hardener 20 20 20 20 20 20 20 20 (parts by weight~
Episulfide compound 20 20 20 20 _ _ _ _ (parts by weight) _ Temperature CC)+10 +5 0 -5 +10 +5 0 -5 :
_ Processing Time 8 12 15 30 120 600 (minutes ) _ . . _ "
. . .
, . .. .. : , .. .
.
```~ 1058350 Example 4 Table 4 given hereinafter illustrates the influence of the dosing of the episulfide compound of Table 3 upon the hardening speed of the resin-hardener-mixture also employed in Table 3. The amine hardener contains 10% , by weight TETA.
Table 4 Episulfide Resin 30 20 15 10 ~parts by weight) ~
Temperature (C) 0 0 0 0 -Processing Time 8 15 18 30 (minutes ) Example 5 The following Table 5 illustrates the influence of the dosing of the ethylene amine (DETA) upon the hardening speed of the epoxide resin-amine hardener mixture used in Table 3, wherein the epoxide resin component contains 10% by weight episulfide compound with an "episulfide value" of 0.60 and the hardener component contains the quantities of DETA given in Table 5.
Table 5 Delta 5 8 10 12 Temperature (C) 5 5 5 5 Processing Time (minutes) 28 20 15 12 Example 6 The following Table 6 illustrates the development of the Brinell hardness at a temperature of 10C and -5C for a non-accelerated and an accelerated resin-hardener-mixture. There was produced a respective 100 g mixture of an aliphatic epoxy resin and an amine hardener in a ratio of 3:1, wherein the accelerated resin component contained 25% by weight of the episulfide compound of Table 3 and the accelerated resin component 15% by weight TETA.
. . . ~ , ~`` 1058350 :`
Table 6 . . .
Te erature ~Cl 10 -5 mp Brinell Hardness lO 50 lO0 lO 50 lO0 ~kp/cm ) after hour Accelerated 3601180 1250 230 780 1050 Non-Accelerated 20 93 220 + o + 0 + o Example 7 `~
Table 7 given hereinafter illustrates the influence of the epi-sulfide compound of Table 3 upon the viscosity of an epoxide resin and the possibility through the addition of an inventive episulfide compound to an epoxy resin of stepwise lowering its viscosity. The viscosities were measured at 20C + 1C by means of a reometer. The epoxide resin is bisphenol A-type.
Table 7 ~Episulf de percent by w g ~ ~ ~ 1000 ~ 700 ~ 450 ~ 100 It will be understood that while the invention has been des-lOcribed specifically with reference to certain embodiments thereof, various changes and modifications may be made, all within the full and intended scope of the claims which follow.
.05835Q
. .
BACKG~OUND OF THE INVENTION
: . .
The present invention ~elates to a rapid-hardening resin and the ; use thereof.
Cold hardenable mixtures of epoxide resins and amines and poly-amides containing amino groups have been used for considerable time in the construction industry as coating substances, coverings, mortar, adhesive, injection agent and for impregnation purposes.
The hardening time of such mixtures, in other words the time required for the mixtures to reach a condition where they can be used is dependent upon temperature. Generally, the hardening reaction at temperatures , beneath about 8C proceeds so slowly that such mixtures can no longer be employed.
;~ It has already been proposed to add to such hardenable mixtures :, ;~ compounds which accelerate the hardening reaction.
, '; What is disadvantageous with this proposal is that the accelera-tor, which is not consumed during the hardening reaction, unfavorably affects the use properties of the hardened mixture, for example, the surface hardness, the resistance against the affects of water and chemicals and the mechanical :. . . .
strength, and thus such accelerators can only be added in limited quantities.
Hence, the possibility of using the hardenable mixture containing the ~; accelerator is limited to temperatures above about 5C, and furthermore, ~;~ since most of the accelerators are toxic soluble compounds, it should be ` apparent that epoxide resins containing accelerators generally cannot be used ~' in the construction of swimming pools or drinking water installations. ~;
~;, .
,~ At temperatures between 5C and 10C there are employed so-;~ called highly reactive epoxide resins which, however, at temperatures exeed-ing 10C no longer can be used since their processing time is too short for , proper application.
., .
: OBJECTS OF THE INVENTION
It is therefore a primary object of the present invention to provide a rapidly hardening synthetic resin which is not associated with the aforementioned drawbacks and limitations.
~' ' ' ',:
.
: . . . .:~ . . .
,- , ~ . : ~ : : : , ~ .. :.
lOS8350 Another object of the invention is directed to a method of using such new and improved synthetic resin for different purposes, especially in construction engineering. -~
DETAILED DESCRIPTION OF THE INVENTION
., According to the present invention, there is provided a rapid-hardening synthetic resin which also hardens at low temperatures in the absence of heat, the improvement comprising the resin component containing -an episulfide compound having on the average more than one -CH - CH2 -group per molecule.
Preferably said resin contains an episulfide compound or a mixture of episulfied compounds having an episulfide value in the order of 0.2 to 0.9.
In another aspect, there is provided a method of forming a coating on a substrate which comprises applying the synthetic resin to the substrate.
In particular, it has been found that episulfide compounds containing on the average more than one -CH - CH2 - group per molecule with stochiometric quantities of amines preferably with aliphatic or cyclo-aliphatic amines, harden while forming products which can be rapidly loaded 20 and without the need to add heat to such mixture. -It has been further found that episulfide compounds markedly accelerate the hardening of epoxide resins by means of amine hardeners at low temperatures as a function of their dosage.
The episulfide compounds or mixtures of episulfide compounds used according to the invention can be produced, for instance, according to the process which has been patented in DRP No. 636,708 (German Reichspatent 636,708) in 1934 and disco~ered by K. Dachlauer and L. Jackel, from epoxide compounds by reaction with thiocyanates, sodium thiosulfate, thio-urea or by reduction of chloropolysulfides with Al-amalgam (French patent 1,428,686).
~he episulfide groups of the inventive employed episulfide ~ .
r - 2 -. '. "
- : ~ : .
1(~58350 compounds can be possibly bound by heteroatoms, especially oxygen, or func~
tional groups, such as ester-, urea-, urethane-, or amide-groups of aliphatic-, cycloaliphatic-, possibly substituted aryl - or possibly sub-stituted aryl alkyl-residues.
The polyamines used for hardening the episulfide resins are preferably cycloaliphatic and aliphatic polyamines or mixtures of such amines with amines containing aryl- or substituted aryl alkyl-residues.
The increased reaction capabilities of episulfide compounds in contrast to the corresponding epoxide compounds is known to the art and has been discussed in detail for instance by P. Sigwalt in an article entitlcd "Ring- ~pening Polymerization", Marcel Dekker publishers, New York, 1969 page 191. The behavior of polyepisulfide compounds in :.
contrast to nucleophilic coreactants has been described, for instance, by P. Penczek et al in - 2a -,h ~
, .
, ,: . , ' :"i . ~ ' "Plaste und Kautschuk", 20 (3)! 176 (1973). These authors have found, among other things, that polyepisulfides with catalytic quantities of nucleophilic coreactants gell m~re rapidly at temperatures in the order of 24C and SOC
than the corresponding epoxide resins. The hardening of polyepisulfide com-pounds by means of nucleophilic coreactants in the presence or heat con-stitutes the subject matter of United States patent 3,378,522, granted in 1968 to R.W. Martin.
On the basis of these experimentations it can be assumed that the inventively employed episulfide compounds modify the course of the reaction between an epoxide resin and a polyamine. It has been found from kinetic tests that polyepisulfide compounds initially react with polyamines and that the reaction products formed by such reactions either react with other polyepisulfide molecules or with polyepoxide molecules, and such reaction proceeds quicker than the reaction between a polyepoxide compound and a polyamine. It could also be shown that the episulfide compound alone in the prescribed dosage does not essentially accelerate the hardening of an epoxide resin by an amine hardener.
It is therefore possible to previously admix any given amine hardener, for instance an aliphatic or a cycloaliphatic amine or mixture of such amines such that the stochiometric conditions are maintained, and to add the episulfide compound, prior to application of the system, in such a dosage that there is obtained a hardenable mixture which at a certain tempera-ture possesses the processing time and hardening time respectively, for the intended purpose of use. In this way it is possible to control the degree of the hardening acceleration by means of the dosing of the episulfide com-pound throughout a wide temperature range, for instance between -30C and +10 C .
The inventive episulfide resins are characterized by the features that they together with amines at a temperature of 20C gell and harden ~ -3Q within one minute.
The amines which are preferred for the hardening of such epi-sulfide compounds are aliphatic or cycloaliphatic amines, which can be ~058350 t employed alone or in mixture with another polyamine or polyaminoamide, for instance with aryl- or aryl alkyl-residues.
Since the inventively employed episulfide compounds are them-selves consumed during the hardening reaction, there is formed therefrom an amine hardener insoluble product, so that the rapid hardening resins or resin mixtures of the invention additionally fulfill the regulations concern-ing toxicity.
The inventive episulfide compounds or their mixtures with epoxide resin possess a low viscosity, thereby facilitating the admixing of the components at low temperatures.
The inventive episulfide compounds or their mixtures with epoxide resins can be employed without or with added substances or additives, such as fillers, pigments, plasticizers, extenders and auxiliary substances or adjuvants, such as surface-active agents, leveling agents, wetting agents, delustering or dulling agents, for instance as paint coats, coatings, cover-ings, adhesive, mortar or injection agent.
They are particularly suitable for processing with a so-called two-component or dual-component installation which separately conveys the resin components and the hardener components, for instance in injection pro-cesses, and reinforcing materials such as fabrics or fibers can be employed.
The invention will be further explained on the basis of the following examples. Testing of the chemical resistance was undertaken in accordance with the procedures of DIN 51958 (the symbol DIN representing German Industrial Standards) and the Brinell hardness according to DIN 50351).
Example 1 The following Table 1 shows the chemical resistances of an episulfide compound/TETA systems, the symbol TETA representing triethylene-tetramine. A stochiometric mixture of an episulfide compound with the epi-sulfide value 0.70 and TETA, which gelled at 18C within approximately 1 minute, was applied by means of a dual component spray gun in the form of a film having an average thickness of 200 ~. After hardening for 1 hour and 24 hours at 18C the film was loaded with the chemicals listed in Table 1 and .. , : : :
.. . , : : - .: ~ :
after 24 hours visually checked.
In Table 1 presented hereinafter the following symbols are intended to have the following meanings:
The symbol "A" means that the film is resistant to permanent contact, i.e., the film surface remained absolutely unchanged.
The symbol "B" means that the film is temporarily resistant to permanent contact, i.e., visual inspection thereof revealed slight discolora-tion of the surface.
The symbol "Z" means that the film is not resistant to permanent contact, i.e., the film was destroyed.
Table 1 Episulf de Resin Epoxy lesin 1 Hr 24 Hrs. 1 Hr. 24 Hrs.
.. .. -.
Concentrated Z Z Z Z
hydrochloric acid `
Hydrochloric acid 10% Z Z~ Z Z
Concentrated sulphuric acid Z Z Z Z
Sulphuric acid 10% Z Z Z Z
Nitric acid 10% Z Z Z Z
Acetic acid 5% B B Z Z
Caustic soda 50% A A Z Z
Sodium carbonate A A Z Z
solution 2% _ Acetone A A Z
. ;.
Diethyl ether A A Z_ Z
_ Ethyl acetate A A Z Z
Ethanol A A Z Z
Methanol A A Z Z
__ ~
Chloroform A A Z Z
Methylene chloride B A Z Z
Premium gasolene A A Z Z
Benzol A A Z Z
Heating oil CDIN 51507) ' . . , ,:, ' ~' ' ` -" ` lOS8350 Example 2 Table 2 illustrates the mechanical loading capacity of a coating formed on the basis of the episulfide compound of Table 1 and TETA as the hardener. The Brinell hardness was measured after hardening at -20C, +5C
and +20C.
Table 2 (Brinell Hardness kp/cm ) . ~ .
Episulfide Resin Epoxide Resin _ . . _ ~emPerature -20C +5C +20C -20C +5C +20C
30 Minutes _ ~ 930 _ _ ;~
45 Minutes 350 500 960 ~ ~ _ _0 Minutes 940 950 960 _ _ _ . __ , _ 90 Minutes 950 950 960 _ _ _ -~
. . ,-:
180 Minutes 980 1000 1050 _ _ _ ;
72 Hours1 loo1 lOo lloo 300 . ~ .
Example 3 The following Table 3 shows the accelerating influence of the inventive combination of episulfide compound and ethylene amine upon the hardening of an epoxide resin of bisphenol A-type by means of an amine hardener. The mixing ratio of resin:hardener is 4:1 parts by weight, the amine hardener contains 10% by weight triethylenetetramine (TETA~ and the resin component the quantities of episulfide compounds having an episulfide value of 0.78 and which quantities are set forth in Table 3 below. -Table 3 .
Inventive Without Mixture _ Episulfide Compounds Epoxy Resin 80 80 80 80 ~ 100 100100 100 (parts by wei~ht) _ . .
Amine Hardener 20 20 20 20 20 20 20 20 (parts by weight~
Episulfide compound 20 20 20 20 _ _ _ _ (parts by weight) _ Temperature CC)+10 +5 0 -5 +10 +5 0 -5 :
_ Processing Time 8 12 15 30 120 600 (minutes ) _ . . _ "
. . .
, . .. .. : , .. .
.
```~ 1058350 Example 4 Table 4 given hereinafter illustrates the influence of the dosing of the episulfide compound of Table 3 upon the hardening speed of the resin-hardener-mixture also employed in Table 3. The amine hardener contains 10% , by weight TETA.
Table 4 Episulfide Resin 30 20 15 10 ~parts by weight) ~
Temperature (C) 0 0 0 0 -Processing Time 8 15 18 30 (minutes ) Example 5 The following Table 5 illustrates the influence of the dosing of the ethylene amine (DETA) upon the hardening speed of the epoxide resin-amine hardener mixture used in Table 3, wherein the epoxide resin component contains 10% by weight episulfide compound with an "episulfide value" of 0.60 and the hardener component contains the quantities of DETA given in Table 5.
Table 5 Delta 5 8 10 12 Temperature (C) 5 5 5 5 Processing Time (minutes) 28 20 15 12 Example 6 The following Table 6 illustrates the development of the Brinell hardness at a temperature of 10C and -5C for a non-accelerated and an accelerated resin-hardener-mixture. There was produced a respective 100 g mixture of an aliphatic epoxy resin and an amine hardener in a ratio of 3:1, wherein the accelerated resin component contained 25% by weight of the episulfide compound of Table 3 and the accelerated resin component 15% by weight TETA.
. . . ~ , ~`` 1058350 :`
Table 6 . . .
Te erature ~Cl 10 -5 mp Brinell Hardness lO 50 lO0 lO 50 lO0 ~kp/cm ) after hour Accelerated 3601180 1250 230 780 1050 Non-Accelerated 20 93 220 + o + 0 + o Example 7 `~
Table 7 given hereinafter illustrates the influence of the epi-sulfide compound of Table 3 upon the viscosity of an epoxide resin and the possibility through the addition of an inventive episulfide compound to an epoxy resin of stepwise lowering its viscosity. The viscosities were measured at 20C + 1C by means of a reometer. The epoxide resin is bisphenol A-type.
Table 7 ~Episulf de percent by w g ~ ~ ~ 1000 ~ 700 ~ 450 ~ 100 It will be understood that while the invention has been des-lOcribed specifically with reference to certain embodiments thereof, various changes and modifications may be made, all within the full and intended scope of the claims which follow.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A rapid-hardening synthetic resin which also hardens at low temperatures in the absence of heat, the improvement comprising the resin component containing an episulfide compound having on the average more than one group per molecule.
2. The synthetic resin as defined in claim 1, wherein said resin contains an episulfide compound or a mixture of episulfide compounds having an episulfide value in the order of 0.2 to 0.9.
3. The synthetic resin as defined in claim 1, wherein the episulfide value is in the order of 0.5 and 0.9.
4. The synthetic resin as defined in claim 1, wherein said resin contains a quantity of an aliphatic or cycloaliphatic amine and which quantity is at least equivalent to the contained quantity of the episulfide compound.
5. The synthetic resin as defined in claim 4, wherein said aliphatic or cycloaliphatic amine is a compound selected from the group consisting of diethylenetriamine, triethylenetetramine or tetraethylenepentamine, or mixtures of the aforesaid compounds.
6. The synthetic resin as defined in claim 1, wherein the resin contains an episulfide compound or a mixture of episulfide compounds, the groups of which are bonded by a member selected from the group consisting essentially of bivalent aliphatic, bivalent cycloaliphatic, substituted aryl residues or substituted aryl alkylene residues.
7. The synthetic resin as defined in claim 6, wherein said member is interrupted by heteroatoms.
8. The synthetic resin as defined in claim 6, wherein said member is interrupted by functional groups.
9. A method of forming a coating on a substrate which comprises applying the synthetic resin as defined in claim 1 to said substrate.
10. A method of attaching one member to a second member which comprises applying the synthetic resin as defined in claim 1 to at least one of said members and then bringing said members into contact with each other, wherein said synthetic resin is an adhesive or mortar.
11. The synthetic resin as defined in claim 9, wherein the components of the resin are applied by means of a two-component installation in an injection process, said two-component installation separately conveying the resin component and the hardener component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH245374A CH598297A5 (en) | 1974-02-21 | 1974-02-21 | Polyepisulphides, opt. with polyepoxides, hardening rapidly |
| CH245474A CH594713A5 (en) | 1974-02-21 | 1974-02-21 | Polyepisulphides, opt. with polyepoxides, hardening rapidly |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1058350A true CA1058350A (en) | 1979-07-10 |
Family
ID=25690484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,479A Expired CA1058350A (en) | 1974-02-21 | 1975-02-20 | Rapidly-hardenable resin and use thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS50124952A (en) |
| CA (1) | CA1058350A (en) |
| DE (1) | DE2505368A1 (en) |
| FR (1) | FR2262067B1 (en) |
| GB (1) | GB1503213A (en) |
| IT (1) | IT1031779B (en) |
| NO (1) | NO750575L (en) |
| SE (1) | SE7501875L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69921991T2 (en) * | 1999-02-08 | 2005-11-03 | The Yokohama Rubber Co., Ltd. | RESIN COMPOSITIONS |
| US20050288458A1 (en) | 2002-07-29 | 2005-12-29 | Klemarczyk Philip T | Reworkable thermosetting resin composition |
| US7012120B2 (en) | 2000-03-31 | 2006-03-14 | Henkel Corporation | Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3378522A (en) * | 1961-11-29 | 1968-04-16 | Shell Oil Co | Epithio compounds, their preparation and polymers |
-
1975
- 1975-02-08 DE DE19752505368 patent/DE2505368A1/en active Granted
- 1975-02-17 IT IT20322/75A patent/IT1031779B/en active
- 1975-02-19 SE SE7501875A patent/SE7501875L/xx unknown
- 1975-02-20 CA CA220,479A patent/CA1058350A/en not_active Expired
- 1975-02-20 FR FR7505290A patent/FR2262067B1/fr not_active Expired
- 1975-02-20 NO NO750575A patent/NO750575L/no unknown
- 1975-02-21 GB GB7269/75A patent/GB1503213A/en not_active Expired
- 1975-02-21 JP JP50021821A patent/JPS50124952A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50124952A (en) | 1975-10-01 |
| DE2505368A1 (en) | 1975-09-04 |
| FR2262067B1 (en) | 1979-03-09 |
| GB1503213A (en) | 1978-03-08 |
| IT1031779B (en) | 1979-05-10 |
| NO750575L (en) | 1975-08-22 |
| DE2505368C2 (en) | 1989-06-08 |
| FR2262067A1 (en) | 1975-09-19 |
| SE7501875L (en) | 1975-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |
Effective date: 19960710 |