CA1062971A - Method of treating surfaces for bonding to polymers - Google Patents
Method of treating surfaces for bonding to polymersInfo
- Publication number
- CA1062971A CA1062971A CA238,717A CA238717A CA1062971A CA 1062971 A CA1062971 A CA 1062971A CA 238717 A CA238717 A CA 238717A CA 1062971 A CA1062971 A CA 1062971A
- Authority
- CA
- Canada
- Prior art keywords
- mercaptosilane
- carbon atoms
- oxidizing
- solution
- oxidizing agent
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
Abstract
ABSTRACT OF THE DISCLOSURE :
This invention relates to a method of treating metallic or oxidic surfaces which are suitable for bonding to polymers such as resol, furan, epoxide or polyurethane resin. This method comprises applying to the surface an aqueous solution comprising a mercaptosilane corresponding to the general formula in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R' represents a monovalent hydrocarbon radi-cal having from 1 to 4 carbon atoms, R" represents a divalent hydrocarbon radical having from 1 to 10 carbon atoms, Y is 0 or 1 and x is 0,1, 2 or 3, the radicals represented by R
being the same or different when x is greater than 1, oxidizing the mercaptosilane, and drying the surface to obtain the desired treated surface.
This invention relates to a method of treating metallic or oxidic surfaces which are suitable for bonding to polymers such as resol, furan, epoxide or polyurethane resin. This method comprises applying to the surface an aqueous solution comprising a mercaptosilane corresponding to the general formula in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R' represents a monovalent hydrocarbon radi-cal having from 1 to 4 carbon atoms, R" represents a divalent hydrocarbon radical having from 1 to 10 carbon atoms, Y is 0 or 1 and x is 0,1, 2 or 3, the radicals represented by R
being the same or different when x is greater than 1, oxidizing the mercaptosilane, and drying the surface to obtain the desired treated surface.
Description
~62~
This lnvention relates to a method of treating surfaces and, more especially to a method of treating surfaces which are suitable for bonding to polymers.
It is known that oxidic surfaces may be treated with silanes containing mercapto groups in order to improve bonding thereto of a sulphur-crosslinked rubber. Unfortunately, the use of silanes containing mercapto groups has a drawback, which is that -the oxidic surfaces pretreated with the silanes and mixed with the rubber, show undesirable and uncontrollable reactivity characterized by a premature vulcanisation. This premature ~ i vulcanisation occurs is a short time, which complicates control- ;~
led, uniform processing of the rubber compositions.
Attempts have already been made to obviate these disad-vantages by using silanes con-tainlng tetrasulphide groups, of the general formula (Ro)3Si-R'-S4-R'-Si(oR)3 wherein R is an alkyl radical and R' is an alkylene radical. Although this ~ -procedure has resulted in an improvement in the processing properties of the rubber compositions, it has the drawback that the sulphur bridges containing silanes are difficu1t to produce -in the pure form in which they have to be used. - -According to the present invention there is provided a method of treating a surface, which method comprises the steps of applying to the surface an aqueous solution comprising from O.Ol to 60% of a mercaptosilane of the general formula:
k 3-x ;~ ~i in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R' represents a monovalent hydrocarbon radical having from 1 to 4 carbon atoms, R" represents a divalent '':' .' ~ . ,.
C.`,, ' ~ ~
f',-,~,.'' ;297~
hydrocarbon radical having from 1 -to 10 carbon atoms, _ is . -0 or 1 and x is 0,1, 2 or 3, the radicals represented by Rbeing identical or different when x is grea-ter than l; oxidizing the mercaptosilane; and drying the surface to obtain the desired treated surface.
The radieal represented by R" may be linear or branched and preferably has from 2 to 4 earbon atoms. This radieal option-ally eontaining a hetero-atom.
Suitable solvents for the aqueous solution include water alone and aqueous alcohols. In the ease of alcohols, it is preferred to use those having from 1 to 4 carbon atoms.
Another water-immiscible or water-emulsifiable organic solvent which has a dissolving effect upon the mercapto silane, may also be used.
When alcohols or other organie solvents are used, it is important that they be mlxed with water so that silanol groups may form in the solution.
~ The eoncentration of the mercapto silane in the aqueous solution is governed by the speeific surface of the material to be treated. It may vary from 0.01% to 60~, the range from 0.1 to 10~ being preferred.
In one embodiment of the invention the mereaptosilane is oxidized with oxygen in the presence of a catalyst, for example iron or copper. In a preferred embodiment the solution eomprises a mereaptosilane and an oxidizing agent eapable of ..' oxidizing the mereaptosilane to a disulphide. , -The eoneentration of the oxidizing agent is seleeted in aeeordanee with the concentration of -the mercapto silane.
The oxidizing agent is preferably present in an excess relative to the stoichiometrically necessary quantity. The stoichiome-trieally neeessary quantity is~the quantity theoretieally requir-ed for oxidizing mereaptans into disulphides. The preferred ~ -range for _ "
, ! . .
; ~ ~ 2 ~
: . , , . ,. , . .: ... " .. . ..
;,. .. . :. . ~
1C~62971 the excess of oxidizing agent is compri~ed between 10 and 50%
of the stoichiometrically necessary quantity.
In addit~on to atmospheric oxygen acting in conjunction with a catalyst (for example Fe or Cu), suitable oxidizing agents are hydrogen peroxide or o~idiæing agents of the type described in Houben-Weyl "Methoden der Organishen Chemie", 4th Edition (1955), Vol. 9, pages 59 to 65. When applying the solutions to the sur~aces to be treated, it is possible to work in the acid or alkaline condition, depending upon the oxidizing agent used or the mercapto sila~e used.
~ he surface which may be treated by the method according to the invention may be oxidic or metallic. The~e include both natural mineral oxidic surfaces and also surfaces of synthetically produced products. ~hey also include surfaces of silica and carbonate-containing minerals. Examples of materials which may be subjected to surface pretreatment by the process according to ,~ `~
the invention include quartz, mica, asbestos, aluminium silicates, kaollns, silica~, iron oxide, titanium o~ide, chalk, glass fibres, iron~copper, zinc, aluminium and also alloy~ such as brass and bronze~
.: . . .. . .
When treated by the method according to the invention ;~
the surfaces may be bonded to a polymer. Polymers, whose adhesion ~;
to the above-mentioned surfaces i~ improved by the pretreatment according to the invention, include natural and synthetic rubbers, polymerisation product~, such as PVC, and polycondensation and polyaddition products, such as resol resins, furan resins, epoxide resins or polyurethane resin~.
~ he treatment of the above-mentioned surface~ with the solution according to the invention i9 preferably carried out at a temperature below 30C in order to a~oid undesirable further oxidation of the di~ulphlde bond. It is also advisable to use freshly prepared solutio~s of mercapto silane and oxidizing age~t.
,'' ."''. ' .,,'' ':
, ', , , . " ,' ' ' ' ' ' , ' ' ' " ' ' . " ' ' ' . ,, : ' ', . . . ' ' ., :, ' ' ". ', ' . i ' " ' ' ', , , . " " ', ', ' ,' ' , ., ~' , ' ' ' ' ' ' . ' , , ::, . ' ' ~ ' , , .. ,.,' , . ' . " . '' ' . ' . ' . ,: ' ~062~71 :
~he ~olution may be applied to the surfaces by any of the standard coating technique~, for example dip-coating, spray-coating or spread-coating. After the ~olution has been applied, the material silanized in this way is ~ubjected to a dr~ing process.
~XAMPIæ ~ ' ~ .
Water-sized glass filaments were immersed for 1 minute in a 0.5% aqueou3 alcoholic solution of -mercapto propyl triethoxy silane containing 0.2% of hydrogen peroxide and having a pH-value of about 8. ~he filaments were removed and le~t to drain a~d then dried for 15 minutes at 130GC. ~he solution was examined for mercaptan immediately before coating, the result being negative. ~he sized gla~s filaments were then dipped into an epoxide resin and processed into round glass fibre rein~orced ,: , , bars. ~he bars obtained were hardened for 17 hours at 130C.
~he flexural strength of the hardened bars was determined in accordance with DIN 53432 after 72 hours storage in boiling water.
~he results are set out in the following ~able:
,; . . .
Flexural ~trength of glass-fibre-rei~forced epo~ide resin roundbars (kp/cm2) Adhesion promoter without ¦ with 3torage in water . _ _ ..
a) none 9,500 4,500 b) -aminoprop~l triethoxy sila~e 9,600 7,600 c) oxidation produot of HS-(CH2)3-Si(OC2H5)3 10,400 8,300 i : , . , ~ .
~est~ a) and b) are comparison tests. ~he ~xample shows that the oxidation of the mercapto silane i~ solution gives products which show an improved adhesion-promoting effect, u r : .
clthough ro mcroapto groups are preoc~t.
,",,, ;",, ";,,",", ,,; s "; ," ,, , ,, -,,,-~ "" " , ~"; ,", ,, ,,"" " " " . , ~ , " ",
This lnvention relates to a method of treating surfaces and, more especially to a method of treating surfaces which are suitable for bonding to polymers.
It is known that oxidic surfaces may be treated with silanes containing mercapto groups in order to improve bonding thereto of a sulphur-crosslinked rubber. Unfortunately, the use of silanes containing mercapto groups has a drawback, which is that -the oxidic surfaces pretreated with the silanes and mixed with the rubber, show undesirable and uncontrollable reactivity characterized by a premature vulcanisation. This premature ~ i vulcanisation occurs is a short time, which complicates control- ;~
led, uniform processing of the rubber compositions.
Attempts have already been made to obviate these disad-vantages by using silanes con-tainlng tetrasulphide groups, of the general formula (Ro)3Si-R'-S4-R'-Si(oR)3 wherein R is an alkyl radical and R' is an alkylene radical. Although this ~ -procedure has resulted in an improvement in the processing properties of the rubber compositions, it has the drawback that the sulphur bridges containing silanes are difficu1t to produce -in the pure form in which they have to be used. - -According to the present invention there is provided a method of treating a surface, which method comprises the steps of applying to the surface an aqueous solution comprising from O.Ol to 60% of a mercaptosilane of the general formula:
k 3-x ;~ ~i in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R' represents a monovalent hydrocarbon radical having from 1 to 4 carbon atoms, R" represents a divalent '':' .' ~ . ,.
C.`,, ' ~ ~
f',-,~,.'' ;297~
hydrocarbon radical having from 1 -to 10 carbon atoms, _ is . -0 or 1 and x is 0,1, 2 or 3, the radicals represented by Rbeing identical or different when x is grea-ter than l; oxidizing the mercaptosilane; and drying the surface to obtain the desired treated surface.
The radieal represented by R" may be linear or branched and preferably has from 2 to 4 earbon atoms. This radieal option-ally eontaining a hetero-atom.
Suitable solvents for the aqueous solution include water alone and aqueous alcohols. In the ease of alcohols, it is preferred to use those having from 1 to 4 carbon atoms.
Another water-immiscible or water-emulsifiable organic solvent which has a dissolving effect upon the mercapto silane, may also be used.
When alcohols or other organie solvents are used, it is important that they be mlxed with water so that silanol groups may form in the solution.
~ The eoncentration of the mercapto silane in the aqueous solution is governed by the speeific surface of the material to be treated. It may vary from 0.01% to 60~, the range from 0.1 to 10~ being preferred.
In one embodiment of the invention the mereaptosilane is oxidized with oxygen in the presence of a catalyst, for example iron or copper. In a preferred embodiment the solution eomprises a mereaptosilane and an oxidizing agent eapable of ..' oxidizing the mereaptosilane to a disulphide. , -The eoneentration of the oxidizing agent is seleeted in aeeordanee with the concentration of -the mercapto silane.
The oxidizing agent is preferably present in an excess relative to the stoichiometrically necessary quantity. The stoichiome-trieally neeessary quantity is~the quantity theoretieally requir-ed for oxidizing mereaptans into disulphides. The preferred ~ -range for _ "
, ! . .
; ~ ~ 2 ~
: . , , . ,. , . .: ... " .. . ..
;,. .. . :. . ~
1C~62971 the excess of oxidizing agent is compri~ed between 10 and 50%
of the stoichiometrically necessary quantity.
In addit~on to atmospheric oxygen acting in conjunction with a catalyst (for example Fe or Cu), suitable oxidizing agents are hydrogen peroxide or o~idiæing agents of the type described in Houben-Weyl "Methoden der Organishen Chemie", 4th Edition (1955), Vol. 9, pages 59 to 65. When applying the solutions to the sur~aces to be treated, it is possible to work in the acid or alkaline condition, depending upon the oxidizing agent used or the mercapto sila~e used.
~ he surface which may be treated by the method according to the invention may be oxidic or metallic. The~e include both natural mineral oxidic surfaces and also surfaces of synthetically produced products. ~hey also include surfaces of silica and carbonate-containing minerals. Examples of materials which may be subjected to surface pretreatment by the process according to ,~ `~
the invention include quartz, mica, asbestos, aluminium silicates, kaollns, silica~, iron oxide, titanium o~ide, chalk, glass fibres, iron~copper, zinc, aluminium and also alloy~ such as brass and bronze~
.: . . .. . .
When treated by the method according to the invention ;~
the surfaces may be bonded to a polymer. Polymers, whose adhesion ~;
to the above-mentioned surfaces i~ improved by the pretreatment according to the invention, include natural and synthetic rubbers, polymerisation product~, such as PVC, and polycondensation and polyaddition products, such as resol resins, furan resins, epoxide resins or polyurethane resin~.
~ he treatment of the above-mentioned surface~ with the solution according to the invention i9 preferably carried out at a temperature below 30C in order to a~oid undesirable further oxidation of the di~ulphlde bond. It is also advisable to use freshly prepared solutio~s of mercapto silane and oxidizing age~t.
,'' ."''. ' .,,'' ':
, ', , , . " ,' ' ' ' ' ' , ' ' ' " ' ' . " ' ' ' . ,, : ' ', . . . ' ' ., :, ' ' ". ', ' . i ' " ' ' ', , , . " " ', ', ' ,' ' , ., ~' , ' ' ' ' ' ' . ' , , ::, . ' ' ~ ' , , .. ,.,' , . ' . " . '' ' . ' . ' . ,: ' ~062~71 :
~he ~olution may be applied to the surfaces by any of the standard coating technique~, for example dip-coating, spray-coating or spread-coating. After the ~olution has been applied, the material silanized in this way is ~ubjected to a dr~ing process.
~XAMPIæ ~ ' ~ .
Water-sized glass filaments were immersed for 1 minute in a 0.5% aqueou3 alcoholic solution of -mercapto propyl triethoxy silane containing 0.2% of hydrogen peroxide and having a pH-value of about 8. ~he filaments were removed and le~t to drain a~d then dried for 15 minutes at 130GC. ~he solution was examined for mercaptan immediately before coating, the result being negative. ~he sized gla~s filaments were then dipped into an epoxide resin and processed into round glass fibre rein~orced ,: , , bars. ~he bars obtained were hardened for 17 hours at 130C.
~he flexural strength of the hardened bars was determined in accordance with DIN 53432 after 72 hours storage in boiling water.
~he results are set out in the following ~able:
,; . . .
Flexural ~trength of glass-fibre-rei~forced epo~ide resin roundbars (kp/cm2) Adhesion promoter without ¦ with 3torage in water . _ _ ..
a) none 9,500 4,500 b) -aminoprop~l triethoxy sila~e 9,600 7,600 c) oxidation produot of HS-(CH2)3-Si(OC2H5)3 10,400 8,300 i : , . , ~ .
~est~ a) and b) are comparison tests. ~he ~xample shows that the oxidation of the mercapto silane i~ solution gives products which show an improved adhesion-promoting effect, u r : .
clthough ro mcroapto groups are preoc~t.
,",,, ;",, ";,,",", ,,; s "; ," ,, , ,, -,,,-~ "" " , ~"; ,", ,, ,,"" " " " . , ~ , " ",
Claims (28)
1. A method of treating a surface, which method comprises the steps of:
applying to the surface an aqueous solution comprising from 0.01 to 60% of a mercaptosilane of the general formula in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R1 represents a monovalent hydrocarbon radical having from 1 to 4 carbon atoms, R" represents a diva-lent hydrocarbon radical having from 1 to 10 carbon atoms, Y is 0 or 1 and x is 0,1, 2 or 3, the radicals represented by R being the same or different when x is greater than l;
oxidizing the mercaptosilane; and drying the surface to obtain the desired treated surface.
applying to the surface an aqueous solution comprising from 0.01 to 60% of a mercaptosilane of the general formula in which R represents an alkyl or alkoxyalkyl radical having from 1 to 8 carbon atoms, R1 represents a monovalent hydrocarbon radical having from 1 to 4 carbon atoms, R" represents a diva-lent hydrocarbon radical having from 1 to 10 carbon atoms, Y is 0 or 1 and x is 0,1, 2 or 3, the radicals represented by R being the same or different when x is greater than l;
oxidizing the mercaptosilane; and drying the surface to obtain the desired treated surface.
2. A method according to claim 1 wherein the mercaptosilane is oxidized with oxygen in the presence of a catalyst.
3. A method according to claim 2 wherein the catalyst comprises iron or copper.
4. A method according to claim 1 wherein the solution comprises a mercaptosilane and an oxidizing agent capable of oxidizing said mercaptosilane to a disulphide.
5. A method according to claim 1 wherein R" has from 2 to 4 carbon atoms.
6. A method according to claim 5 wherein the mercaptosilane is mercaptopropyltriethoxysilane.
7. A method according to claim 1 wherein the solution comprises water alone.
8. A method according to claim 1 wherein the solution comprises an aqueous alcohol as solvent.
9. A method according to claim 8 wherein the alcohol has from 1 to 4 carbon atoms.
10. A method according to claim 1 wherein the mercap-tosilane is present in the solution in a concentration of from 0.1 to 10%.
11. A method according to claim 4 wherein the oxidizing agent is present in an excess, based on the amount stoichiometrically required to oxidize the mercaptosilane to the disulphide.
12. A method according to claim 11 wherein the oxidi-zing agent is an excess of from 10 to 50%.
13. A method according to claim 4 wherein the oxidizing agent comprises hydrogen peroxide.
14. A method according to claim 1 wherein the treatment is carried out at a temperature below 30°C.
15. A method according to claim 1 wherein the surface is metallic.
16. A method according to claim 15 wherein the metal comprises iron, copper, zinc or aluminium.
17. A method according to claim 15 wherein the metal comprises brass or bronze.
18. A method according to claim 1 wherein the surface is oxidic.
19. A method according to claim 18 wherein the surface comprises glass fibers.
20. A method according to claim 18 wherein the surface comprises iron oxide or titanium oxide.
21. A method according to claim 18 wherein the surface comprises a silica containing mineral.
22. A method according to claim 21 wherein the mineral comprises quartz, mica, asbestos, aluminium silicate, or kaolin.
23. A method according to claim 18 wherein the surface comprises a carbonate containing mineral.
24. A method according to claim 23 wherein the mineral comprises chalk.
25. A metallic or inorganic oxidic surface treated by the method according to claim 1 and coated with a polymer selected in the group consisting of natural or synthetic rubber, polymerisation products and polycondensation products.
26. A surface according to claim 25 wherein the polymer comprises a natural or synthetic rubber.
27. A surface according to claim 25 wherein the polymer comprises polyvinyl chloride.
28. A surface according to claim 25 wherein the polymer comprises a resole furan, epoxide or polyurethane resin.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742451706 DE2451706C2 (en) | 1974-10-31 | 1974-10-31 | Surface pretreatment of metallic or inorganic oxide surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062971A true CA1062971A (en) | 1979-09-25 |
Family
ID=5929668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,717A Expired CA1062971A (en) | 1974-10-31 | 1975-10-28 | Method of treating surfaces for bonding to polymers |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE834893A (en) |
| CA (1) | CA1062971A (en) |
| DE (1) | DE2451706C2 (en) |
| ES (1) | ES442229A1 (en) |
| FR (1) | FR2289558A1 (en) |
| GB (1) | GB1522976A (en) |
| IT (1) | IT1048040B (en) |
| NL (1) | NL7512800A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4644077A (en) * | 1984-07-11 | 1987-02-17 | The Sherwin-Williams Company | Process for producing organophilic silica |
-
1974
- 1974-10-31 DE DE19742451706 patent/DE2451706C2/en not_active Expired
-
1975
- 1975-10-21 GB GB4322575A patent/GB1522976A/en not_active Expired
- 1975-10-27 BE BE161270A patent/BE834893A/en unknown
- 1975-10-28 CA CA238,717A patent/CA1062971A/en not_active Expired
- 1975-10-29 FR FR7533013A patent/FR2289558A1/en active Granted
- 1975-10-30 IT IT5200575A patent/IT1048040B/en active
- 1975-10-30 ES ES442229A patent/ES442229A1/en not_active Expired
- 1975-10-31 NL NL7512800A patent/NL7512800A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2451706A1 (en) | 1976-05-06 |
| FR2289558A1 (en) | 1976-05-28 |
| BE834893A (en) | 1976-02-16 |
| NL7512800A (en) | 1976-05-04 |
| ES442229A1 (en) | 1977-08-16 |
| GB1522976A (en) | 1978-08-31 |
| DE2451706C2 (en) | 1982-11-04 |
| IT1048040B (en) | 1980-11-20 |
| FR2289558B1 (en) | 1980-05-30 |
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