GB1584634A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1584634A – Vinyl silane copolymers
– Google Patents

GB1584634A – Vinyl silane copolymers
– Google Patents
Vinyl silane copolymers

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Publication number
GB1584634A

GB1584634A
GB15551/78A
GB1555178A
GB1584634A
GB 1584634 A
GB1584634 A
GB 1584634A
GB 15551/78 A
GB15551/78 A
GB 15551/78A
GB 1555178 A
GB1555178 A
GB 1555178A
GB 1584634 A
GB1584634 A
GB 1584634A
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GB
United Kingdom
Prior art keywords
copolymer
carbon atoms
units
radical
structural units
Prior art date
1976-06-03
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

Application number
GB15551/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Dynamit Nobel AG

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Dynamit Nobel AG
Priority date (The priority date 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 date listed.)
1976-06-03
Filing date
1977-06-02
Publication date
1981-02-18

1977-06-02
Application filed by Dynamit Nobel AG
filed
Critical
Dynamit Nobel AG

1981-02-18
Publication of GB1584634A
publication
Critical
patent/GB1584634A/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL

C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL

C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 – C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 – C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material

C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 – C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only

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

C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating

C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material

C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds

C—CHEMISTRY; METALLURGY

C03—GLASS; MINERAL OR SLAG WOOL

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

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials

C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres

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

C08K5/00—Use of organic ingredients

C08K5/54—Silicon-containing compounds

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2004/00—Particle morphology

C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Description

PATENT SPECIFICATION ( 11) 1 584 634
w ( 21) Application No15551/78 ( 22) Filed 2 Jun1977 ( 19) ( 52) Divided Out Of No 1584633 ( 31) Convention Application No 2624888 ( 32) Filed 3 Jun 1976 in ( 33) Fed Rep of Germany (DE) ( 44) Complete Specification Published 18 Feb 1981 ( 51) INT CL 3 C 08 F 8/14 8/12 230/08 (C 08 F 230/08 220/06 222/16) x N ( 52) Index at Acceptance C 3 J 400 402 AJ CJ C 3 W 209 C C 3 Y B 186 B 230 B 240 B 243 F 581 F 583 ( 54) VINYL SILANE COPOLYMERS ( 71) We, DYNAMIT NOBEL AKTIENGESELLSCHAFT, a German company, of 521 Troisdorf, Near Cologne, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:
This invention relates to vinyl silane copolymers 5 The invention provides copolymers comprising structural units having the general formula:
L t (I) 10 W and structural units having the general formula:
15 C-Ct(II) t Co/co} 20 modified in that from 50 to 100 % of the latter units are replaced by structural units having the general formula:
H CH CO (III)25 R OH wherein each radical R’ is a hydroxyl group, a phenyl group, a substituted phenyl group, an alkyl group having from 1 to 4 carbon atoms, or an alkoxy group having from 1 to 8 carbon atoms, optionally interrupted by an -O radical, with the proviso that at least one of the 30 radicals R is an akkoxy group having from 1 to 8 carbon atoms optionally interrupted by an -O radical, and radical R is a hydrocarbyl group containing from 1 to 20 carbon atoms, the sum of the number of units of formulae (II) and (III) being not greater than the number of units of formula (I).
The invention also provides a method of preparing such a copolymer, which comprises 35 reacting a copolymer comprising structural units having the formula:
4 CH 2-CH 40 L Si R 3 J 2 1 584 634 2 and structural units having the formula:
_-CH-CH + CO CO 5 wherein each radical R’ is as defined above, with an alcohol having the general formula ROH wherein radical R is as defined above 10 Preferred copolymers are those wherein R is a straight-chain or branchchain alkyl group containing from 1 to 20 carbon atoms, wherein R is an unsaturated hydrocarbyl group containing from 3 to 11 carbon atoms, and wherein R is a cycloaliphatic group containing 6, 7 or 8 carbon atoms.
These copolymers are valuable intermediate products for producing reactive silyl 15 copolymers which are used as adhesion promoters, coating compounds or as auxiliary materials for use in filtering These reactive silyl copolymers may also be used, together with known silanes, as adhesion promoters as described and claimed in Application No.
23519/77 (Serial No 1584633).
Copolymers of vinyl trialkoxysilanes and maleic anhydrides are known They are 20 produced by polymersation of vinyl trialkoxysilanes and maleic anhydride in the presence of organic peroxides at temperatures between 90 and 150 ‘C The alkoxy group of the vinyl trialkoxysilane may have 1 to 8 carbon atoms and possibly be interrupted by an -0radical such as in the case of vinyl tris-(p-methoxyethoxy)-silane, for example One of the alkoxy groups may be replaced by a hydroxy group, a C 1-4 alkyl group of a phenyl group 25 The production of these copolymers is described in, for example, U S Patent No.
3,560,589 According to this patent, these copolymers are suitable as adhesion promoters between epoxy resins and inorganic fillers.
We have now found that the half esters deriving from these copolymers have new, unexpected properties which the known copolymers do not have or only have to a hitherto 30 unknown small extent These half esters may further by hydrolysed into higherto unknown hydrolysates, which, among other things, may be used for the same applications as the half esters.
The new half esters of the vinyl alkoxysilane/maleic acid copolymers are characterised by the units already mentioned above The unit containing the silyl group is either bonded to a 35 maleic anhydride unit or to a maleic acid half ester unit The remaining bonds of the silyl group are either all bonded to an alkoxy group having 1 to 8 carbon atoms or at least one of the remaining bonds of the silyl group is bonded to such a group whilst the others are bonded to an alkyl group having 1 to 4 carbon atoms, to a hydroxyl group or to an optionally substituted phenyl group The free valencies of the silicon are thus bonded to the 40 same groups as in the vinyl alkoxysilane/maleic anhydride copolymer used as the starting material.
In the new half ester copolymers, the proportion of maleic acid half ester units is equal to or greater than that of the maleic anhydride units If the reaction is conducted appropriately, it is also possible for the maleic anhydride proportion to become virtually nil 45 The individual copolymer units alternate in irregular sequence along the copolymer chain The maximum sum of the maleic anhydride and maleic acid half ester units is just as great as the vinyl alkoxysilane units In general, the excess of vinyl alkoxysilane units is from 0 1 to 10 % It is also possible, however, for the excess to be greater if during the production of the vinyl akkoxysilane/maleic anhydride copolymer used as starting material, 50 a suitable excess of vinyl alkoxysilane is used.
The new vinyl alkoxysilane/maleic acid half ester copolymers are produced by esterification of the maleic anhydride component of vinyl alkoxysilane/maleic anhydride copolymers with an alcohol ROH wherein R is as defined above Esterification may take place at temperatures between 40 and 150 C, preferably between 60 and 110 C The longer 55 heating is conducted, the higher is the degree of esterification The degree of esterification may also be raised by raising the temperature and particularly by adding catalyst, e g.
sulphonic acids.
If the alcohol used in the esterified is liquid, esterification expediently takes place under reflux until reflux no longer occurs Heating can them be continued further, possibly at 60 raised temperatures and pressure.
Esterification takes place both with saturated and unsaturated or cycloaliphatic alcohols.
The carbon atom content of the alcohol is from 1 to 20 carbon atoms Examples of suitable alcohols are methyl alcohol, ethyl alcohol, octyl alcohol, 2-ethyl-1hexanol, cetyl alcohol, allyl alcohol, crotyl alcohol and cyclohexyl alcohol 65 1 584 634 1 584 634 The new vinyl alkoxysilane/maleic acid half ester copolymers can be used for conditioning effluent sludges by adding to the sludge fillers treated with the copolymers together with polyelectrolytes, e g polyacrylamides or polyethylene imine derivatives The sludge thus treated may be filtered more satisfactorily and its flocculation is more stable S than when an untreated filler or a filler treated with a known silane is used 5 The new half ester copolymers and their hydrolysis products may also be used, together with known silanes, as adhesion promoters This application of the hydrolysis products is described in more detail in Application No 23519/77 (Serial No 1584633) The wetting effect of a mixture of this type with regard to inorganic pigments is greater than that of the individual substances, i e a synergistic effect is obtained With a mixture of this type, even 10 chalk may be provided with an adhesion promoting layer, with the result that the further processing of this material, e g as a filler in organic polymers, is considerably improved.
This was not possible before with the hitherto known silanes.
The new vinyl alkoxysilane/maleic acid half ester copolymers are soluble in organic solvents such as alcohols or ketones (e g acetone) They react with water producing 15 hydrolysates, the alkoxy groups of the silyl units being dissocated to form hydroxyl groups.
Cross-linking, possibly with the formation of a-Si-O-Si bond, with a further silyl unit to form siloxanes may then take place During hydrolysis, the maleic acid half ester units and the maleic anhydride units react completely or partially, forming maleic acid units of the formula: 20 CH CH CO CO l l 25 OH OH These hydrolysates are soluble in dilute alkalis As soon as a solution has formed, the solutions may be diluted with water without a deposit being precipitated Dilution with weak acids is also possible after formation of the solution 30 The hydrolysates may be used for the same applications as the vinyl alkoxy/maleic acid half ester copolymers.
The invention will now be illustrated by the following Examples 2 to 10 The following Example 1 illustrates the preparation of a copolymer for use in Examples 2 to 8.
35 Example 1
In a three necked flask equipped with a stirrer, an inlet tube for nitrogen and a reflux cooler with a calcium chloride tube, 147 g of maleic acid anhydride ( 1 5 mol) were dissolved, while being stirred and while nitrogen was introduced, in 510 g of vinyl triethoxysilane ( 2 7 mol) at 70 ‘C When a solution had been formed, 3 9 g of dicumyl 40 peroxide were added and the temperature was raised to 130 C At this temperature the reaction began The heat evolved by polymerisation was removed by cooling At this point, the temperature was in the range of 130 to 150 c After the reaction had ceased, stirring was continued for a further 3 hours at 130 C, at which point the reaction had ended.
The excess vinyl triethoxysilane was first removed under a water jet vacuum at 60 C with 45 the temperature rising to 130 c The residual monomer was removed under an oil pump vacuum ( 0 1 mm Hg), and 480 g of a solid, slightly yellow tinted resin were obtained The theoretical yield with a strictly alternating copolymer would be 432 g The copolymer contains vinyl trialkoxy units with a number greater than 1 This is contingent on the use of an excess of vinyl triethoxysilane, which is necessary to achieve complete copolymerisation 50 of the maleic anhydride This is itself necessary as the residual monomer (i e maleic anhydride) is difficult to remove and can give rise to problems The copolymer had a softening point of 75 c.
Example 2 55
288 g of a vinyl triethoxysilane/maleic anhydride copolymer produced according to Example 1 were heated with 46 07 g of ethyl alcohol for 8 hours while being stirred The temperature was initially maintained at 80 C until the fluid component of the ethyl alcohol had completely reacted, i e until there was no longer any reflux The reaction mixture was 6 C then heated to 1000 C 60 The solidification point of the product obtained was determined, and an IR spectrum was taken The reaction of the extinctions of the CO ester group to the stretching vibration of the asymmetric CO anhydride group (EE/EA) was determined, this being an indication of the degree of esterification.
At 20 C, the half ester obtained was light yellow and very viscous Its solidification point 65 4 1 584 634 4 was -22 5 c The ration EE/EA was 1 10, and thus its mol percentage of anhydride groups was about 31, corresponding to 69 mol % of half ester Its elemental analysis was as follows:
theoretical: C:50 29 % H:7 78 % 0:33 53 % Si:8 38 % found: C:49 06 % H:7 69 % 0: Si:8 91 % 5 Example 3
288 g of a vinyl triethoxysilane/maleic anhydride copolymer produced according to Example 1 were stirred with 58 8 g of allyl alcohol for 8 hours at 60 C 10 At 20 C, the polymer obtained was a homogeneous, light yellow viscous melt whose solidification point was about -16 C Its EE/EA ratio was 0 88, and thus its mol percentage of anhydride groups was about 36 Its elemental analysis was as follows:
theoretical: C:52 02 % H:7 51 % 0:32 37 % Si:8 09 % 15 found: C:50 73 % H:7 45 % 0: Si:8 67 % Example 4
Example 3 was repeated except that the reaction temperature was held at 100 C At the 20 beginning of the reaction the allyl alcohol boiled with reflux The other reaction conditions were the same as in Example 3.
The polymer obtained had a solidification point of -45 C Its EE/EA ratio was about 1.11, i e its proportion of anhydride groups was about 31 mol % Its elemental analysis was as follows: 25 found: C:50 67 % H:7 78 % Si:8 51 % Example 5
Under the reaction conditions of Example 4, 288 g of vinyl triethoxysilane/maleic 30 anhydride copolymer (produced according to Example 1) were reacted with 242 g of cetyl alcohol.
The polymer obtained was a homogeneous, light yellow melt with a solidification point of + 15 4 C Its EE/EA ratio was 1 25, i e its mol percentage of anhydride groups was about 29 Its elemental analysis was as follows: 35 theoretical: C:63 4 % H:10 19 % 0:21 13 % Si:5 28 % found: C:63 88 % H:10 54 % 0: Si:5 67 % Example 6 40
Example 5 was repeated except that the reaction mixture was additionally heated to C with 0 46 g of toluenesulphonic acid for 24 hours The solidification point of the polymer obtained was about + 13 C Its EE/EA ratio was 3 45, i e its proportion of anhydride groups was about 13 mol %.
45 Example 7
In the same way as Example 5, 288 g of vinyl triethoxysilane/maleic anhydride copolymer were reacted with 130 2 g of 2-ethyl hexanol-1 at 100 C for 8 hours.
The product obtained had a solidification point of -41 C, and a proportion of anhydride groups of about 28 mol % (EE/EA = 1 31) Its elemental analysis was as follows: 50 theoretical: C:57 41 % H:9 09 % 0:26 79 % Si:6 70 % found: C:56 76 % H:9 32 % 0: Si:7 13 % Example 8 55
In the same way as Example 5, 288 g of vinyl triethoxysilane/maleic anhydride copolymer were heated with 72 g of butanol at 100 C for 8 hours.
The polymer obtained had a solidification point of -14 5 C, and a proportion of anhydride groups of about 27 mol % (EE/EA = 1 38) Its elemental analysis was as follows:
60 theoretical: C:53 05 % H:8 28 % 0:30 93 % Si:7 73 % found C:51 41 % H:8 47 % 0: Si:8 46 % Example 9
300 g of a vinyl triethoxysilane/maleic anhydride/maleic acid half ester copolymer, 65 1 584 634 1 584 634 5 produced according to Example 2, were dissolved in approximately 300 ml of ethanol The solution obtained was dripped into 3 litres of desalted water with vigorous stirring A fine, white deposit formed.
The deposit was easily isolated from the aqueous phase by filtering or centrifuging, and was subsequently washed It was then dried in a circulating air drying cabinet at 500 C A 5 white powder was obtained in a yield of 220 g.
The powder obtained was a copolymer containing maleic anhydride units, maleic acid units, and vinyl silanol units (or vinyl siloxane units resulting from cross-linking) The siloxane units may be easily broken by dilute alkalis (e g a 1 % aqueous ammonia solution) whereupon a solution is produced The hydrolysate of the vinyl alkoxysilane/maleic 10 acid/maleic acid half ester copolymers therefore contains in the dissolved state vinyl silanol units as well as maleic acid units When a film is formed, or when precipitation occurs during the hydrolysis, these vinyl silanol units are partially converted to vinyl siloxane units, depending upon the p H.
15 Example 10
Results similar to those obtained in Examples 2 to 9 were obtained by using, instead of the vinyl alkoxysilane/maleic anhydride copolymer according to Example 1, copolymers obtained from other vinyl alkoxysilanes, namely vinyl trimethoxysilane, vinyl tributoxysilane and vinyl methyl diethoxysilane The copolymers obtained were esterified and/or 20 hydrolysed in the same manner.

Claims (9)

WHAT WE CLAIM IS:-

1 A copolymer comprising structural units having the general formula:
f-CH 2-CH (I) 25 and structural units having the general formula: 30 F1 (II) -CH-CH-_ I C 35 modified in that from 50 to 100 % of the latter units are replaced by structural units having the general formula:
40 IC-C i (III) CH CO CO OR OH 45 wherein each radical R’ is a hydroxyl group, a phenyl group, a substituted phenyl group, an 50 alkyl group having from 1 to 4 carbon atoms, or an alkoxy group having from 1 to 8 carbon atoms, optionally interrupted by an -0 radical, with the proviso that at least one of the radicals R’ is an alkoxy group having from 1 to 8 carbon atoms, optionally interrupted by an -0 radical, and radical R is a hydrocarbyl group containing from 1 to 20 carbon atoms, the sum of the number of units of formulae (II) and (III) being not greater than the number 55 of units of formula (I).

2 A copolymer as claimed in claim 1, wherein R is a straight-chain or branched-chain alkyl group containing from 1 to 20 carbon atoms.

3 A copolymer as claimed in claim 1, wherein R is an unsaturated hydrocarbyl group containing from 3 to 11 carbon atoms 60

4 A copolymer as claimed in claim 1, wherein R is a cycloaliphatic group containing 6, 7 or 8 carbon atoms.

A copolymer as claimed in claim 1 or 2, wherein R contains from 1 to 10 carbon atoms.

6 A method of preparing a copolymer as claimed in claim 1, which comprises reacting a 65 1 584 634 6 1 584 634 6 copolymer comprising structural units having the formula:
-CH 2 CH 5 SIR’3 and structural units having the formula: 10 CH CH 1 I I 15 CO Co /U where each radical R’ is as defined in claim 1, with an alcohol having the general formula ROH wherein radical R is as defined in claim 1 20

7 A method according to claim 6, wherein the reaction is carried out in the presence of a catalyst.

8 A method of preparing a copolymer as claimed in claim 1, substantially as described in any one of the foregoing Examples 2 to 10.

9 A copolymer whenever prepared by the method claimed in claim 6, 7 or 8 25 A hydrolysate of a copolymer as claimed in any of claims 1 to 5 and 9.
HASELTINE LAKE & CO, Chartered Patent Agents, 28 Southampton Buildings, 30 Chancery Lane, London WC 2 A 1 AT -andTemple Gate House, Temple Gate, 35 Bristol B 51 6 PT Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1981.
Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

GB15551/78A
1976-06-03
1977-06-02
Vinyl silane copolymers

Expired

GB1584634A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

DE19762624888

DE2624888A1
(en)

1976-06-03
1976-06-03

AQUATIC SOLUTION OF MIXTURES OF ORGANIC SILICONE COMPOUNDS

Publications (1)

Publication Number
Publication Date

GB1584634A
true

GB1584634A
(en)

1981-02-18

Family
ID=5979697
Family Applications (2)

Application Number
Title
Priority Date
Filing Date

GB15551/78A
Expired

GB1584634A
(en)

1976-06-03
1977-06-02
Vinyl silane copolymers

GB23519/77A
Expired

GB1584633A
(en)

1976-06-03
1977-06-02
Aqueous solutions of organosilicon compounds useful as adhesion promoters and for forming coatings

Family Applications After (1)

Application Number
Title
Priority Date
Filing Date

GB23519/77A
Expired

GB1584633A
(en)

1976-06-03
1977-06-02
Aqueous solutions of organosilicon compounds useful as adhesion promoters and for forming coatings

Country Status (11)

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Link

US
(1)

US4247436A
(en)

JP
(1)

JPS52147654A
(en)

BE
(1)

BE855370A
(en)

CA
(1)

CA1100678A
(en)

DE
(1)

DE2624888A1
(en)

FR
(2)

FR2353594A1
(en)

GB
(2)

GB1584634A
(en)

IT
(1)

IT1115765B
(en)

NL
(1)

NL7706153A
(en)

NO
(2)

NO771940L
(en)

SE
(1)

SE7706446L
(en)

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Publication date
Assignee
Title

JPS5838766A
(en)

1981-09-01
1983-03-07
Dainippon Ink & Chem Inc
Cold-curing coating resin composition

DE3227552A1
(en)

1982-07-23
1984-01-26
Dynamit Nobel Ag, 5210 Troisdorf

COPOLYMERISATE WITH ETHYLENICALLY UNSATURATED BASIC BLOCKS AND SEVERAL FUNCTIONAL GROUPS

US4548733A
(en)

1984-10-05
1985-10-22
Dow Corning Corporation
Anionic siliconates of silylorganocarboxylates, sulfonates and phosphonates to reduce viscosities of particulate slurries

US4673354A
(en)

1985-10-01
1987-06-16
Minnesota Mining And Manufacturing Company
Stable silanol priming solution for use in dentistry

JPH0826280B2
(en)

1987-05-29
1996-03-13
東京応化工業株式会社

Silica-based film forming composition

DE10010669A1
(en)

2000-03-04
2001-09-06
Degussa

Process for producing an extrusion-coated metal object

AU1482702A
(en)

2000-11-17
2002-05-27
Peter Clifford Hodgson
Coupling of reinforcing fibres to resins in curable composites

FR2837818B1
(en)

2002-03-29
2005-02-11
Saint Gobain Vetrotex

REINFORCING GLASS THREADS AND CORROSIVE-RESISTANT COMPOSITES

US9093191B2
(en)

2002-04-23
2015-07-28
CTC Global Corp.
Fiber reinforced composite core for an aluminum conductor cable

NZ546772A
(en)

2003-10-22
2010-01-29
Ctc Cable Corp
A composite core for a reinforced aluminium cable

EP1957565B1
(en)

2005-10-17
2013-08-07
Advanced Composites International Pty Ltd
Reinforced composite material

US9132614B2
(en)

2008-02-29
2015-09-15
Mirteq Pty Limited
Reinforced composite materials for use in the manufacture moulds and the use of such moulds

JP6222404B2
(en)

2015-05-28
2017-11-01
Dic株式会社

Pigment printing agent and fabric using the same

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Assignee
Title

US2977334A
(en)

1956-10-04
1961-03-28
Monsanto Chemicals
Derivatives of ethylene/maleic anhydride copolymers

US3580893A
(en)

1966-10-25
1971-05-25
Gulf Research Development Co
Process for the preparation of cyclic acid anhydrides

US3560589A
(en)

1967-07-12
1971-02-02
Shinetsu Chemical Co
Epoxy resin containing a vinyl alkoxysilane-ethylenically unsaturated acid anhydride copolymer

US3692747A
(en)

1971-06-09
1972-09-19
Nalco Chemical Co
Chromium complexes of maleic anhydride copolymers

1976

1976-06-03
DE
DE19762624888
patent/DE2624888A1/en
not_active
Withdrawn

1977

1977-06-01
IT
IT49657/77A
patent/IT1115765B/en
active

1977-06-02
FR
FR7716915A
patent/FR2353594A1/en
not_active
Withdrawn

1977-06-02
GB
GB15551/78A
patent/GB1584634A/en
not_active
Expired

1977-06-02
NO
NO771940A
patent/NO771940L/en
unknown

1977-06-02
GB
GB23519/77A
patent/GB1584633A/en
not_active
Expired

1977-06-02
SE
SE7706446A
patent/SE7706446L/en
not_active
Application Discontinuation

1977-06-03
NL
NL7706153A
patent/NL7706153A/en
not_active
Application Discontinuation

1977-06-03
BE
BE178176A
patent/BE855370A/en
unknown

1977-06-03
JP
JP6564477A
patent/JPS52147654A/en
active
Pending

1977-06-03
CA
CA279,833A
patent/CA1100678A/en
not_active
Expired

1977-12-16
FR
FR7738129A
patent/FR2364227A1/en
active
Granted

1979

1979-08-27
US
US06/069,692
patent/US4247436A/en
not_active
Expired – Lifetime

1982

1982-06-14
NO
NO821974A
patent/NO821974L/en
unknown

Also Published As

Publication number
Publication date

FR2364227A1
(en)

1978-04-07

BE855370A
(en)

1977-10-03

FR2353594A1
(en)

1977-12-30

US4247436A
(en)

1981-01-27

JPS52147654A
(en)

1977-12-08

CA1100678A
(en)

1981-05-05

SE7706446L
(en)

1977-12-04

FR2364227B1
(en)

1984-05-18

NL7706153A
(en)

1977-12-06

IT1115765B
(en)

1986-02-03

DE2624888A1
(en)

1977-12-15

NO821974L
(en)

1977-12-06

GB1584633A
(en)

1981-02-18

NO771940L
(en)

1977-12-06

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