CA1198539A - Heat stable, polymer-forming composition - Google Patents
Heat stable, polymer-forming compositionInfo
- Publication number
- CA1198539A CA1198539A CA000361662A CA361662A CA1198539A CA 1198539 A CA1198539 A CA 1198539A CA 000361662 A CA000361662 A CA 000361662A CA 361662 A CA361662 A CA 361662A CA 1198539 A CA1198539 A CA 1198539A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- polymer
- antioxidant
- transition metal
- methoxyphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/36—Embedding or analogous mounting of samples
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S522/901—Dark storage stabilizer
Abstract
Abstract of the Disclosure A heat-stable, liquid, polymer-forming adhesive composition comprising: (a) a polymerizable material selec-ted from a vinyl monomer containing at least one reactive double bond, an unsaturated polymer containing ethylenic carbon-carbon double bonds or a mixture thereof; (b) a transition metal compound; (c) a polymer chain terminating antioxidant; and (d) a preventive antioxidant for decom-posing hydroperoxides; wherein the resulting composition is a stable, storable, pourable liquid, which is curable to a solid polymer on initiation of a curing step is dis-closed as well as particular uses of such composition.
Description
5~39 .
Background of the Invention This invention relates generally to the s-tabili-zation of a polymerizable composition and the use of such composition, inter alia, as a trans~er medium ~or diagnos-tic purposes.
In U.S. Patent 4,120,262, commonly assiyned, there is described an apparatus for -transferring biological sub-stances supported on the surface of a substrate to the re-ceiving surface of a backing element, wherein the transfer medium is pressed between the surfaces of the subs-trate and backing element so as to encapsula-te the substance within the transfer medium, and removing the substrate to expose the encapsulated substance which is supported on the backing element.
In one embodi.ment of this invention, the adhesive compositions disclosed and claimed herein are effective transfer media in the above-identified ~pparatus.
Generally, this invention relates to heat-stable, polymer-forming compositions, ei-ther heat- or ligh-t-cu.rable, ~0 which are characterized by rapid cure when exposed to light, if photo initiated, or to heat, if thermally initiated, and by extreme stability under storaye conditions. In the described embo~iment, curing of the composition does not affect the morphological or stained characteristics of the encapsulated biological specimen and the refractive index of cured composition closely matches the refractive index of the encapsulated biological specimen and glass.
Also, the composition is virtually odor free; has low toxicity, has a moderate viscosity before cure, i.e. 100-mab/ ~
L~ 3~
200 cps/25~C; adheres to glass and other surfaces after cure;
and is stable for at least 6 months at 45C. Further, the cured films with encapsulated biological specimens can be - stored indefinitely.
In sum, the compositions of this invention find many uses and can be applied broadly in the diaynostic area where biological specimens are to be placed in a protec-ted state for extended periods, without affecting their morpho-logical or stained characteristics~ In addition, such com-:L0 positions can be used as polymeric coatings, per se, and also as adhesive layers in laminated structures.
Summary of the Invention In accordance with a composition aspect of this invention, there is provided a heat-stable, liquid, polymer-forming adhesive composition comprising: (a) a polymer-izable material selected from a vinyl monomer containing at least one reactive double bond, an unsaturated polymer containing ethylenic carbon-carbon double ~onds or a mix-ture thereof; (b) a transition metal compound; (c) a po]ymer chain terminating antioxidant; and (d) a preventive anti-oxidant for decomposing hydroperoxides; wherei~n the result-ing composition is a stable, storable, pourable liquid, which is curable to a solid polymer on initi`ati`on of a curing step.
In addition, the composition ~ay opti~onally con-tain other materials such as glass-adhesi~on promoters~
photo-initiators, thermal-ini~tiators~ water scavengers and acid catalysts. Further, a suitable solvent is one that dissolves the components but does not react with them.
30 ~ In accordance with a method aspect of this inven-mab/ ~
tion, there is provided a method of transferring a substance adhering to t~e sur~ace of a substrate to a receiving sur-~ace which comprises contacting the substance with an ad-hesive composition as defined above contained on the re~
ceiving surface and thereby encapsulating the substance in the adhesive composition to the receiving surface.
The substrate may be in the form of a tape of mylar~, cellulose acetate~ polyethylene or polypropyleneO
Detailed Description of the Invention The novel compositions of this invention find broad application in ~any diverse areas beside the pre-viously mentioned diagnostic ~ield including: adhesives and coatings for glass, plastic, wood, silicone rubber, natural rubber and metal~
The compositions disclosed herein are comprised of four basic components namely:
(a) a polymerizable material selected from vinyl, acrylate or methacrylate monomers or an un-saturated polymer containing ethylenic car-bon-carbon double bonds;
(b) a transition metal compound selected from transition metal salts or chelates;
(C2 a polymer chain terminating antioxidant; and (d) a preventive antioxidant for decomposing hydroperoxides, wherein the resulting composi-tion is a stable, storable, pourable liquid, which is curable to a solid polymer on initiation of a curing step.
The inclusion of the transition metal compound, mab/`,~
5;3~
the chain terminating antioxidant and the preventive an-ti-oxidant, which serve as stabllizers, provides a composition, when properly stored, with a stability in excess of 6 months at ~5C. In the absence of the transition metal compound, the composition undergoes gelation which is complete with-in 24 hr. at 25C. In the absence of the chain terminating and preventive antioxidant, the composition is stable for one month at 45C. This appears to indicate a catalytic role for the transition metal cation, i.e., the cation is regenerated. The transition metal cation appears to act as a free-radical decomposer during "dark" storage. These stabilizers protect the monomer system against free radical induced polymerization during "dark" storage, but do not interfere with the rapid curing of the composition during use as a bonding agent.
Without the transition metal compound, the re-sulting composition would have a se-verely curtailed useful life, i.e. it would have to be used within ~ hours after formulation. Otherw;se, the composition becomes increas-ingly more viscous and is then polymerized to a soft gel.
Preferably, the polymerizable composition should have flow characteristics between 100-500 cps at 25C to find wide-spread application.
The polymerizable material component (a~ can be any vinyl monomer which includes vinyl compounds, acrylates and methacrylates, for example, vinyl chloride, styrene and methyl me~acrylate. It can also be any polyvinyl compound, for example, butadiene, ethoxylated bisphenol-A dimethacry-late, etc. Such polyvinyl compounds are capable of forming --4 ~
mab/~
3~
cross-links in the cured ma-trix which results in enhanced mechanical strength. In addition, the polymerizable mater-ial can be any unsaturated polymer containing double bonds free to react with free radicals, for example, unsaturated polyesters. These substances include the copolymers of glycols, such as ethylene or propylene ~lycol, and unsatur ated acid derivatives, such as maleic or fumaric anhydride.
Such unsaturated polyesters can also be copoly-meri~ed with a vinyl monomer, e.g. vinyl acetate, styrene, methyl methacrylate, acrylamide, methacrylic acid, butadiene, divinyl benzene or ethoxylated bisphenol-A dimethacrylate.
These copolymers are within the scope of polymerizable materials disclosed herein.
Component (b) is any soluble transition metal (for the purposes of this application a transition metal or element is defined as being one which has an incomplete d shell, in its elemental form) compound in which the anion is inorganic or organic! for example, FeC13 or Fe(CH3CO2)3 respectively. Other illustrative transition metal cations i2~- C 3t Ru3+ Mn2~t, Co2+, Ti , Eu and Pr These metal cations can also be employed in their chelated form, for example, as the acetylacetonate chelate, such as chromium acetylacetorlate and titanium acetylaceto-nate.
Component (c) is a polymer chain terminating anti-oxidant. The function of such component is to reduce peroxy radicals, so as to yield hydroperoxides~ Par-ticularly useful are the p-alkoxyphenols having the formula:
mab/S)~
I
OH
Rl ~ R2 X
wherein Rl and R2 are each selected from H, phenyl or t-butyl, and X is alkyl or alkyloxy, said alkyl group con~
taining from 1 to 4 carbon atoms. Suitable examples in-clude p-methoY~yphenol, 2,6-di-tert-butyl-4-methoxyphenol and 2,6-diphenyl-4-methoxyphenol.
Component (d) is a preven~ive antioxidant which appears to regenerate the chain breaking antioxidant and to decompose hydroperoxides. ~Il example of such preventive antioxidant are ~-activated thioethers having the following formula:
( 2 2 ~
wherein Y can be: ~ - z in which Z is El or NO2 or Y can be -~-OR whexe R is an alkyl group containing from 4-18 carbons.
mab/~ J
s~
Besides tile above three components, other materials can be op-tionally inc]uded as herein discussed to provide useful properties in the composi-tion~ both before and after curing.
For example, a glass aclhesion promotor can be included, as when a microscope slide is used as the backing material. Suitable glass adhesion promoters include trialkoxysilanes and, preferably, one having a -terminal vinyl group such as gamma-(methacryloxy)-propyltrimethoxy-silane. Other employable silanes include those ha~ing the formula:
E O
CH2=C--~C-)m (CH2-~ Si--~OR')3 wherein R' is alkyl or alkyloxy, said alky] containing from 1 to 4 carbons; E is hydrogen or lower alkyl (1-4 carbons); n = l-10i and m = 0, or 1.
Also, a photo-initiator such as 2,2-dime~oxy-
Background of the Invention This invention relates generally to the s-tabili-zation of a polymerizable composition and the use of such composition, inter alia, as a trans~er medium ~or diagnos-tic purposes.
In U.S. Patent 4,120,262, commonly assiyned, there is described an apparatus for -transferring biological sub-stances supported on the surface of a substrate to the re-ceiving surface of a backing element, wherein the transfer medium is pressed between the surfaces of the subs-trate and backing element so as to encapsula-te the substance within the transfer medium, and removing the substrate to expose the encapsulated substance which is supported on the backing element.
In one embodi.ment of this invention, the adhesive compositions disclosed and claimed herein are effective transfer media in the above-identified ~pparatus.
Generally, this invention relates to heat-stable, polymer-forming compositions, ei-ther heat- or ligh-t-cu.rable, ~0 which are characterized by rapid cure when exposed to light, if photo initiated, or to heat, if thermally initiated, and by extreme stability under storaye conditions. In the described embo~iment, curing of the composition does not affect the morphological or stained characteristics of the encapsulated biological specimen and the refractive index of cured composition closely matches the refractive index of the encapsulated biological specimen and glass.
Also, the composition is virtually odor free; has low toxicity, has a moderate viscosity before cure, i.e. 100-mab/ ~
L~ 3~
200 cps/25~C; adheres to glass and other surfaces after cure;
and is stable for at least 6 months at 45C. Further, the cured films with encapsulated biological specimens can be - stored indefinitely.
In sum, the compositions of this invention find many uses and can be applied broadly in the diaynostic area where biological specimens are to be placed in a protec-ted state for extended periods, without affecting their morpho-logical or stained characteristics~ In addition, such com-:L0 positions can be used as polymeric coatings, per se, and also as adhesive layers in laminated structures.
Summary of the Invention In accordance with a composition aspect of this invention, there is provided a heat-stable, liquid, polymer-forming adhesive composition comprising: (a) a polymer-izable material selected from a vinyl monomer containing at least one reactive double bond, an unsaturated polymer containing ethylenic carbon-carbon double ~onds or a mix-ture thereof; (b) a transition metal compound; (c) a po]ymer chain terminating antioxidant; and (d) a preventive anti-oxidant for decomposing hydroperoxides; wherei~n the result-ing composition is a stable, storable, pourable liquid, which is curable to a solid polymer on initi`ati`on of a curing step.
In addition, the composition ~ay opti~onally con-tain other materials such as glass-adhesi~on promoters~
photo-initiators, thermal-ini~tiators~ water scavengers and acid catalysts. Further, a suitable solvent is one that dissolves the components but does not react with them.
30 ~ In accordance with a method aspect of this inven-mab/ ~
tion, there is provided a method of transferring a substance adhering to t~e sur~ace of a substrate to a receiving sur-~ace which comprises contacting the substance with an ad-hesive composition as defined above contained on the re~
ceiving surface and thereby encapsulating the substance in the adhesive composition to the receiving surface.
The substrate may be in the form of a tape of mylar~, cellulose acetate~ polyethylene or polypropyleneO
Detailed Description of the Invention The novel compositions of this invention find broad application in ~any diverse areas beside the pre-viously mentioned diagnostic ~ield including: adhesives and coatings for glass, plastic, wood, silicone rubber, natural rubber and metal~
The compositions disclosed herein are comprised of four basic components namely:
(a) a polymerizable material selected from vinyl, acrylate or methacrylate monomers or an un-saturated polymer containing ethylenic car-bon-carbon double bonds;
(b) a transition metal compound selected from transition metal salts or chelates;
(C2 a polymer chain terminating antioxidant; and (d) a preventive antioxidant for decomposing hydroperoxides, wherein the resulting composi-tion is a stable, storable, pourable liquid, which is curable to a solid polymer on initiation of a curing step.
The inclusion of the transition metal compound, mab/`,~
5;3~
the chain terminating antioxidant and the preventive an-ti-oxidant, which serve as stabllizers, provides a composition, when properly stored, with a stability in excess of 6 months at ~5C. In the absence of the transition metal compound, the composition undergoes gelation which is complete with-in 24 hr. at 25C. In the absence of the chain terminating and preventive antioxidant, the composition is stable for one month at 45C. This appears to indicate a catalytic role for the transition metal cation, i.e., the cation is regenerated. The transition metal cation appears to act as a free-radical decomposer during "dark" storage. These stabilizers protect the monomer system against free radical induced polymerization during "dark" storage, but do not interfere with the rapid curing of the composition during use as a bonding agent.
Without the transition metal compound, the re-sulting composition would have a se-verely curtailed useful life, i.e. it would have to be used within ~ hours after formulation. Otherw;se, the composition becomes increas-ingly more viscous and is then polymerized to a soft gel.
Preferably, the polymerizable composition should have flow characteristics between 100-500 cps at 25C to find wide-spread application.
The polymerizable material component (a~ can be any vinyl monomer which includes vinyl compounds, acrylates and methacrylates, for example, vinyl chloride, styrene and methyl me~acrylate. It can also be any polyvinyl compound, for example, butadiene, ethoxylated bisphenol-A dimethacry-late, etc. Such polyvinyl compounds are capable of forming --4 ~
mab/~
3~
cross-links in the cured ma-trix which results in enhanced mechanical strength. In addition, the polymerizable mater-ial can be any unsaturated polymer containing double bonds free to react with free radicals, for example, unsaturated polyesters. These substances include the copolymers of glycols, such as ethylene or propylene ~lycol, and unsatur ated acid derivatives, such as maleic or fumaric anhydride.
Such unsaturated polyesters can also be copoly-meri~ed with a vinyl monomer, e.g. vinyl acetate, styrene, methyl methacrylate, acrylamide, methacrylic acid, butadiene, divinyl benzene or ethoxylated bisphenol-A dimethacrylate.
These copolymers are within the scope of polymerizable materials disclosed herein.
Component (b) is any soluble transition metal (for the purposes of this application a transition metal or element is defined as being one which has an incomplete d shell, in its elemental form) compound in which the anion is inorganic or organic! for example, FeC13 or Fe(CH3CO2)3 respectively. Other illustrative transition metal cations i2~- C 3t Ru3+ Mn2~t, Co2+, Ti , Eu and Pr These metal cations can also be employed in their chelated form, for example, as the acetylacetonate chelate, such as chromium acetylacetorlate and titanium acetylaceto-nate.
Component (c) is a polymer chain terminating anti-oxidant. The function of such component is to reduce peroxy radicals, so as to yield hydroperoxides~ Par-ticularly useful are the p-alkoxyphenols having the formula:
mab/S)~
I
OH
Rl ~ R2 X
wherein Rl and R2 are each selected from H, phenyl or t-butyl, and X is alkyl or alkyloxy, said alkyl group con~
taining from 1 to 4 carbon atoms. Suitable examples in-clude p-methoY~yphenol, 2,6-di-tert-butyl-4-methoxyphenol and 2,6-diphenyl-4-methoxyphenol.
Component (d) is a preven~ive antioxidant which appears to regenerate the chain breaking antioxidant and to decompose hydroperoxides. ~Il example of such preventive antioxidant are ~-activated thioethers having the following formula:
( 2 2 ~
wherein Y can be: ~ - z in which Z is El or NO2 or Y can be -~-OR whexe R is an alkyl group containing from 4-18 carbons.
mab/~ J
s~
Besides tile above three components, other materials can be op-tionally inc]uded as herein discussed to provide useful properties in the composi-tion~ both before and after curing.
For example, a glass aclhesion promotor can be included, as when a microscope slide is used as the backing material. Suitable glass adhesion promoters include trialkoxysilanes and, preferably, one having a -terminal vinyl group such as gamma-(methacryloxy)-propyltrimethoxy-silane. Other employable silanes include those ha~ing the formula:
E O
CH2=C--~C-)m (CH2-~ Si--~OR')3 wherein R' is alkyl or alkyloxy, said alky] containing from 1 to 4 carbons; E is hydrogen or lower alkyl (1-4 carbons); n = l-10i and m = 0, or 1.
Also, a photo-initiator such as 2,2-dime~oxy-
2-phenylacetophenone, 2,2-diethoxyacetophenone or 1-phenyl-1,2-propanedione-2-0-benzoyloxime may be included if curing is to be effected op-tically.
Alternatively, a thermal initiator, such as benzoyl peroxide, acetylperoxide or azoisobutyronitrile may be lncluded, if curin~ is to be effected thermally When cured in tilis rnanner, it is preferable -to add the initia-tor just prior to curing. The thermal treatment is effectively achieved by heating a-t a temperature from about 40C to about 200C.
rnab/ ~ ¦
35~3~
Optionally, a water scavenger, such as tri-methoxyorthoformate or -trie~hylorthoformate may be aaded to protect the alkoxysilane against attack by ~ater.
To allow efficient operation of the water scavenger, an acid ca-talyst such as p-toluenesulfonic acid, benzenesulfonic acid or methanesulfonic acid may be added.
It is also within the contemplation of this invention to include an inert solvent for the composi-tions disclosed herein. A suitable solvent is any solvent which dissolves the components but does not react with them.
Suitable solvents include methanol, CC14 and mixtures oE benzene and chloroform. The solvent aLso serYes to control the viscosity of the resulting composition.
The compositions of this invention can effectively be used to bond opaque materials such as wood, metal, plastics and rubber by thermally curing In the case where the ma-terial to be polymerized is exposable to light, photo or radiation curing is the method o~
2Q choice.
In the preferred embodiment of this invention, the ingredients are used in the following proportionate ranges:
(a) polymerizable substance 80-95%
tb) transition metal compound 1 x 10 - 1 x 10 M
(c) chain breaking antioxidant 0.03 0.3 (d) preventive antioxidant 0.03 - 0.3 - B --~ mab/~
5~3~
EXAMPLE I
An adhesive composition is prepared by mixing the following ingredients:
Ingredient Amount (a) ethoxylated bisphenol A
dimethacrylate 82.0 g (b) FeC13 in Methanol 1 x 10 M solution 1.0 ml (c) p-methoxyphenol 0.3 g (d) 2,2-dimethoxy-2-phenyl-ac~tophenone 2.0 g (e) t:rimethylorthoformate 2.0 g (f~ p-toluenesulfonic acid 1 mg (g) gamma-(methacxyloxy) propyltrimethoxysilane 13.0 g The resulting composition cures rapidly under UV light to provide a useful coverslip for a bloo~l smear or a glass slide.
_ 9 _ mab/ '~
5'3~
EXAMPLE II
The composition of Example I is prepared in a solvent medium in which the followiny solvents or mixtures thereof are employed:
carbon tetrachloxide ch]oroform benzene methanol The resulting compositions exhibit comparable curing properties and pro~ide equivalent utility.
EXAMPLE III
The composition of Example I is duplicated except that the following thermal initiators, in stoichio-metric equivalent amounts, are employed insteaa of the photoinitiator, component ~e). The resulting composi-tions utilize -the solvents indicated:
ben~oyl peroxide benzene azoisobutyronitrile methanol The thermal:initiators are incorpora-ted just prior to thermal treatment which is effected at a temperature of abou-t 100C. The resulting cured com-positions provide effective adhesive compositions mab/ ~
S~3~
EX~MPLE IV
The following adhesive composition was prepared with the foll.owing ingredients:
Composition A
Inyredient Amount (a) ethoxylated bisphenol A
dime-thacrylate 82.0 g tb) FeC13 in MeOH
1 x 10 M soln. 1.0 ml (c) p-methoxyphenol 0,3 g (d) dilaurylthiodipropionate 0.3 g (e) 2,2-dimethoxy-2~phenyl-acetophenone 2.0 g (f) trimethylorthoformate 2.0 g (g) p-toluenesulfonic acid 1 mg (h) gamma-(methacryloxy)-propyltrime-thoxysilane 13.0 g In its performance in -the a:Eoresaid system, the adhesive composition rapidly cured under UV light to provide a useful coversl.ip for a blood smear on a glass slide. The cured adhesive film exhibi-ted a refractive inclex compatible with the encapsulated blood ~;' - 1]. -mab/ ' cells and was extremely s~able , i.e., storable for an indefinite perio~ of time. The adhesive composition itself had a shelf life of 6 mo/45~C and virtuall~ no odor or toxici-ty. It has a viscosity of 100-~00 cps~25~C
and adhered very well to glass.
EXAMPLE V
A composition as described in Example IV
is prepared except that -the following vinyl monomer is used in place of component (a) wi-th comparable results:
CH2=C-C~--CH2CH2--CH2-CE~2--0{O r CH3 ~ ~ ,, O C~3 -OCH2CH~OCH2CH2O ICl 2 EXAMPLE VI
A composition as described in Example IV is prepared excep-t that the following transition metal com-pounds are used in place of FeC13 with comparable results-CrC13 MnCl~
FeBr3 CoCl~
NiC12 RuCl, ~j~
mab/
E u ( fod)3i fod = tris~6,6~7,7,8,8-hepta-E]uoro-2,2-dimethyL-3,5-octanedionate~
chromium acetylacetonate titani.um acetylacetonate ferric acetate cobalt oleate Pr(fod)3 EXAMPLE VII
A composition as described in Example IV is prepared except that 2,6-di-t-butyl-4-methylphenol is used as the polymer chain terminator to give comparable results.
EXAMPLE VIII
A composition as described in Example IV
is prepared except the following preventive antioxiaants are used in place of component (d) with comparable results:
S--~CH2CH2 C )2 where R = C8H17' 18 37 mab/ ~ ?
53~
It should be understood by those skilled in the art that Various modi~ications may be made in the present invention without departing from the spirit and scope thereof as described in the speciEication ~nd defined in the appended claims.
~r nl~}~/ ~'`1'-''
Alternatively, a thermal initiator, such as benzoyl peroxide, acetylperoxide or azoisobutyronitrile may be lncluded, if curin~ is to be effected thermally When cured in tilis rnanner, it is preferable -to add the initia-tor just prior to curing. The thermal treatment is effectively achieved by heating a-t a temperature from about 40C to about 200C.
rnab/ ~ ¦
35~3~
Optionally, a water scavenger, such as tri-methoxyorthoformate or -trie~hylorthoformate may be aaded to protect the alkoxysilane against attack by ~ater.
To allow efficient operation of the water scavenger, an acid ca-talyst such as p-toluenesulfonic acid, benzenesulfonic acid or methanesulfonic acid may be added.
It is also within the contemplation of this invention to include an inert solvent for the composi-tions disclosed herein. A suitable solvent is any solvent which dissolves the components but does not react with them.
Suitable solvents include methanol, CC14 and mixtures oE benzene and chloroform. The solvent aLso serYes to control the viscosity of the resulting composition.
The compositions of this invention can effectively be used to bond opaque materials such as wood, metal, plastics and rubber by thermally curing In the case where the ma-terial to be polymerized is exposable to light, photo or radiation curing is the method o~
2Q choice.
In the preferred embodiment of this invention, the ingredients are used in the following proportionate ranges:
(a) polymerizable substance 80-95%
tb) transition metal compound 1 x 10 - 1 x 10 M
(c) chain breaking antioxidant 0.03 0.3 (d) preventive antioxidant 0.03 - 0.3 - B --~ mab/~
5~3~
EXAMPLE I
An adhesive composition is prepared by mixing the following ingredients:
Ingredient Amount (a) ethoxylated bisphenol A
dimethacrylate 82.0 g (b) FeC13 in Methanol 1 x 10 M solution 1.0 ml (c) p-methoxyphenol 0.3 g (d) 2,2-dimethoxy-2-phenyl-ac~tophenone 2.0 g (e) t:rimethylorthoformate 2.0 g (f~ p-toluenesulfonic acid 1 mg (g) gamma-(methacxyloxy) propyltrimethoxysilane 13.0 g The resulting composition cures rapidly under UV light to provide a useful coverslip for a bloo~l smear or a glass slide.
_ 9 _ mab/ '~
5'3~
EXAMPLE II
The composition of Example I is prepared in a solvent medium in which the followiny solvents or mixtures thereof are employed:
carbon tetrachloxide ch]oroform benzene methanol The resulting compositions exhibit comparable curing properties and pro~ide equivalent utility.
EXAMPLE III
The composition of Example I is duplicated except that the following thermal initiators, in stoichio-metric equivalent amounts, are employed insteaa of the photoinitiator, component ~e). The resulting composi-tions utilize -the solvents indicated:
ben~oyl peroxide benzene azoisobutyronitrile methanol The thermal:initiators are incorpora-ted just prior to thermal treatment which is effected at a temperature of abou-t 100C. The resulting cured com-positions provide effective adhesive compositions mab/ ~
S~3~
EX~MPLE IV
The following adhesive composition was prepared with the foll.owing ingredients:
Composition A
Inyredient Amount (a) ethoxylated bisphenol A
dime-thacrylate 82.0 g tb) FeC13 in MeOH
1 x 10 M soln. 1.0 ml (c) p-methoxyphenol 0,3 g (d) dilaurylthiodipropionate 0.3 g (e) 2,2-dimethoxy-2~phenyl-acetophenone 2.0 g (f) trimethylorthoformate 2.0 g (g) p-toluenesulfonic acid 1 mg (h) gamma-(methacryloxy)-propyltrime-thoxysilane 13.0 g In its performance in -the a:Eoresaid system, the adhesive composition rapidly cured under UV light to provide a useful coversl.ip for a blood smear on a glass slide. The cured adhesive film exhibi-ted a refractive inclex compatible with the encapsulated blood ~;' - 1]. -mab/ ' cells and was extremely s~able , i.e., storable for an indefinite perio~ of time. The adhesive composition itself had a shelf life of 6 mo/45~C and virtuall~ no odor or toxici-ty. It has a viscosity of 100-~00 cps~25~C
and adhered very well to glass.
EXAMPLE V
A composition as described in Example IV
is prepared except that -the following vinyl monomer is used in place of component (a) wi-th comparable results:
CH2=C-C~--CH2CH2--CH2-CE~2--0{O r CH3 ~ ~ ,, O C~3 -OCH2CH~OCH2CH2O ICl 2 EXAMPLE VI
A composition as described in Example IV is prepared excep-t that the following transition metal com-pounds are used in place of FeC13 with comparable results-CrC13 MnCl~
FeBr3 CoCl~
NiC12 RuCl, ~j~
mab/
E u ( fod)3i fod = tris~6,6~7,7,8,8-hepta-E]uoro-2,2-dimethyL-3,5-octanedionate~
chromium acetylacetonate titani.um acetylacetonate ferric acetate cobalt oleate Pr(fod)3 EXAMPLE VII
A composition as described in Example IV is prepared except that 2,6-di-t-butyl-4-methylphenol is used as the polymer chain terminator to give comparable results.
EXAMPLE VIII
A composition as described in Example IV
is prepared except the following preventive antioxiaants are used in place of component (d) with comparable results:
S--~CH2CH2 C )2 where R = C8H17' 18 37 mab/ ~ ?
53~
It should be understood by those skilled in the art that Various modi~ications may be made in the present invention without departing from the spirit and scope thereof as described in the speciEication ~nd defined in the appended claims.
~r nl~}~/ ~'`1'-''
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A heat-stable, liquid, polymer-forming adhesive composition comprising:
(a) a polymerizable material selected from a vinyl monomer containing at least one reactive double bond, an unsaturated polymer containing ethylenic carbon-carbon double bonds or a mixture thereof;
(b) a soluble transition metal compound;
(c) a polymer chain terminating antioxidant; and (d) a preventive antioxidant for decomposing hydroperoxides; wherein the resulting composition is a stable, storable, pourable liquid, which is curable to a solid polymer on initiation of a curing step.
(a) a polymerizable material selected from a vinyl monomer containing at least one reactive double bond, an unsaturated polymer containing ethylenic carbon-carbon double bonds or a mixture thereof;
(b) a soluble transition metal compound;
(c) a polymer chain terminating antioxidant; and (d) a preventive antioxidant for decomposing hydroperoxides; wherein the resulting composition is a stable, storable, pourable liquid, which is curable to a solid polymer on initiation of a curing step.
2. A composition as claimed in claim 1, wherein said vinyl monomer is ethoxylated bisphenol-A dimethacrylate.
3. A composition as claimed in claim 1, wherein said unsaturated polymer is an unsaturated polyester derived from the condensation of a glycol with an anhydride, and said vinyl monomer copolymerized therewith is selected from vinyl acetate, styrene, methylmethacrylate, butadiene, divinyl benzene and ethoxylated bisphenol-A dimethacrylate.
4. A composition as claimed in claim 1, wherein said transition metal compound is selected from chromium, manganese, nickel, iron and cobalt metal salts.
5. A composition as claimed in claim 4, wherein said transition metal compound is a ferric metal salt.
6. A composition as claimed in claim 5, wherein said ferric metal salt is ferric chloride.
7. A composition as claimed in claim l, wherein said polymer chain terminating antioxidant is of the for-mula:
wherein R1 and R2 are each selected from H, phenyl and t-butyl, and X is alkyl or alkyloxy, said alkyl group contain-ing from 1 to 4 carbon atoms.
wherein R1 and R2 are each selected from H, phenyl and t-butyl, and X is alkyl or alkyloxy, said alkyl group contain-ing from 1 to 4 carbon atoms.
8. A composition as claimed in claim 7, wherein said antioxidant is selected from p-methoxyphenol, 2,6-di-t-butyl-4-methoxyphenol and 2,6-diphenyl-4-methoxyphenol.
9. A composition as claimed in claim 1, wherein said preventive antioxidant is a compound of the formula:
wherein Y is selected from wherein Z is H or N02, and R is alkyl containing from 4-18 carbons.
wherein Y is selected from wherein Z is H or N02, and R is alkyl containing from 4-18 carbons.
10. A composition as claimed in claim 9, wherein said preventive antioxidant is dilaurylthiodipropionate.
11. A composition as claimed in claim l, which is essentially free of an inert solvent.
12. A composition as claimed in claim 1, wherein a photo initiator is included.
13. A composition as claimed in claim 1, wherein thermal initiator is included.
14. A composition as claimed in claim 1, which comprises:
(a) ethoxylated bisphenol-A dimethacrylate;
(b) ferric chloride;
(c) p-methoxyphenol; and (d) dilaurylthiodipropionate.
(a) ethoxylated bisphenol-A dimethacrylate;
(b) ferric chloride;
(c) p-methoxyphenol; and (d) dilaurylthiodipropionate.
15. A composition as claimed in claim 1, wherein said resulting composition contains about 1% volume/weight of inert solvent.
16. A method of transferring a substance ad-hering to the surface of a substrate to a receiving sur-face which comprises contacting said substance with an adhesive composition as claimed in claim 1 contained on said receiving surface and thereby encapsulating said sub-stance in said adhesive composition to said receiving sur-face .
17. The method as claimed in claim 16, wherein said substance is a biological substance.
18. The method as claimed in claim 16, wherein said substrate is in the form of a tape selected from mylar ?, cellulose acetate , polyethylene and polypropylene.
19. The method as claimed in claim 16, wherein said receiving surface is a microscope slide.
20. The method as claimed in claim 16, further incorporating a photopolymerization step wherein said adhesive composition is cured by exposure to light of an appropriate wavelength.
21. The method as claimed in claim 20, wherein said curing is effected by exposure to UV radiation.
22. The method as claimed in claim 16, further incorporating a thermal step wherein said adhesive com-position is cured by heat treatment.
23. The method as claimed in claim 22, wherein said heat treatment comprises heating at a temperature from about 40°C to about 200°C.
24. A composition according to claim 3, where-in the glycol is selected from ethylene and propylene glycol, and the anhydride is selected from fumaric and maleic anhydride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/113,480 | 1980-01-21 | ||
| US06/113,480 US4376839A (en) | 1980-01-21 | 1980-01-21 | Heat stable, polymer-forming composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198539A true CA1198539A (en) | 1985-12-24 |
Family
ID=22349688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000361662A Expired CA1198539A (en) | 1980-01-21 | 1980-10-07 | Heat stable, polymer-forming composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4376839A (en) |
| JP (1) | JPS56104956A (en) |
| CA (1) | CA1198539A (en) |
| DE (1) | DE3043164A1 (en) |
| FR (1) | FR2474047A1 (en) |
| GB (1) | GB2067577B (en) |
| IT (1) | IT1134548B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4463117A (en) * | 1980-01-21 | 1984-07-31 | Technicon Instruments Corporation | Heat stable, polymer-forming composition |
| EP0058514A1 (en) * | 1981-02-17 | 1982-08-25 | Dentsply International, Inc. | Radiation curable silaneous adhesives |
| US4552682A (en) * | 1982-09-30 | 1985-11-12 | Ppg Industries, Inc. | Peroxide composition containing phenolic antioxidant |
| JPS5984908A (en) * | 1982-11-04 | 1984-05-16 | Cosmo Co Ltd | Production of p-vinylphenol polymer |
| US4533446A (en) * | 1983-07-20 | 1985-08-06 | Loctite (Ireland) Ltd. | Radiation-activatable anaerobic adhesive composition |
| US5626863A (en) * | 1992-02-28 | 1997-05-06 | Board Of Regents, The University Of Texas System | Photopolymerizable biodegradable hydrogels as tissue contacting materials and controlled-release carriers |
| US5462990A (en) * | 1990-10-15 | 1995-10-31 | Board Of Regents, The University Of Texas System | Multifunctional organic polymers |
| US5410016A (en) * | 1990-10-15 | 1995-04-25 | Board Of Regents, The University Of Texas System | Photopolymerizable biodegradable hydrogels as tissue contacting materials and controlled-release carriers |
| DK0627911T3 (en) * | 1992-02-28 | 2000-11-20 | Univ Texas | Photopolymerizable biodegradable hydrogels as tissue contact materials and controlled release carriers |
| US5573934A (en) * | 1992-04-20 | 1996-11-12 | Board Of Regents, The University Of Texas System | Gels for encapsulation of biological materials |
| JP3040032B2 (en) * | 1992-03-27 | 2000-05-08 | 日東電工株式会社 | Pressure-sensitive adhesives having excellent heat resistance, their adhesive sheets, and their production methods |
| JP3052972B2 (en) * | 1992-03-27 | 2000-06-19 | 日東電工株式会社 | Pressure sensitive adhesives and their adhesive sheets |
| DE19509933C1 (en) * | 1995-03-18 | 1996-05-23 | Univ Dresden Tech | Milling cutter for timber, plastics, etc. |
| JP3765346B2 (en) * | 1996-05-28 | 2006-04-12 | ジャパンコンポジット株式会社 | Thermosetting resin composition, molding material containing the same, and artificial marble |
| DE19651307A1 (en) * | 1996-12-10 | 1998-06-18 | Basf Ag | Mixtures of compounds containing vinyl group-containing compounds and stabilizers |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2616875A (en) * | 1951-09-06 | 1952-11-04 | Us Rubber Co | Shortstopping of butadiene-1,3 emulsion polymerization |
| US2919259A (en) * | 1956-08-22 | 1959-12-29 | Ralph A Naylor | Light stabilized polyvinyl chloride compositions |
| US3275715A (en) * | 1962-12-04 | 1966-09-27 | Container Corp | Process for incorporating additives into polyolefins |
| JPS4842467B1 (en) * | 1970-12-04 | 1973-12-12 | ||
| JPS4889234A (en) * | 1972-02-29 | 1973-11-21 | ||
| JPS5226253B2 (en) * | 1973-05-08 | 1977-07-13 | ||
| US4077902A (en) * | 1974-11-18 | 1978-03-07 | Ciba-Geigy Corporation | Nickel stabilizers for synthetic polymers |
| JPS5936671B2 (en) * | 1975-10-01 | 1984-09-05 | 株式会社クラレ | glue |
| CA1093248A (en) * | 1976-05-20 | 1981-01-06 | Kenneth E. Russell | Phenolic antioxidants with polymer tails |
| JPS5311932A (en) * | 1976-07-19 | 1978-02-02 | Kyoritsu Kagaku Sangyo | Adhesive composition |
| JPS6010552B2 (en) * | 1976-08-09 | 1985-03-18 | 関西ペイント株式会社 | photosensitive adhesive composition |
-
1980
- 1980-01-21 US US06/113,480 patent/US4376839A/en not_active Expired - Lifetime
- 1980-10-07 CA CA000361662A patent/CA1198539A/en not_active Expired
- 1980-10-10 GB GB8032798A patent/GB2067577B/en not_active Expired
- 1980-11-15 DE DE19803043164 patent/DE3043164A1/en active Granted
- 1980-11-25 FR FR8024957A patent/FR2474047A1/en active Granted
- 1980-12-02 IT IT26366/80A patent/IT1134548B/en active
-
1981
- 1981-01-20 JP JP604081A patent/JPS56104956A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH028632B2 (en) | 1990-02-26 |
| GB2067577B (en) | 1984-02-29 |
| FR2474047A1 (en) | 1981-07-24 |
| IT8026366A0 (en) | 1980-12-02 |
| DE3043164A1 (en) | 1981-08-06 |
| GB2067577A (en) | 1981-07-30 |
| IT1134548B (en) | 1986-08-13 |
| DE3043164C2 (en) | 1991-08-14 |
| FR2474047B1 (en) | 1985-03-08 |
| JPS56104956A (en) | 1981-08-21 |
| US4376839A (en) | 1983-03-15 |
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