CA1111042A - Silicon-modified imidyl-phthalic acid derivatives - Google Patents
Silicon-modified imidyl-phthalic acid derivativesInfo
- Publication number
- CA1111042A CA1111042A CA310,794A CA310794A CA1111042A CA 1111042 A CA1111042 A CA 1111042A CA 310794 A CA310794 A CA 310794A CA 1111042 A CA1111042 A CA 1111042A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- compound
- radical
- cyclised
- phthalic acid
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Abstract
Abstract of the Disclosure The compounds according to the invention are Si-modified imidyl-phthalic acid derivatives of the formula (I) and the corresponding cyclised imide derivatives; in the formula, A is a radical which completes to a substituted or unsubstituted imidyl group, R is a divalent organic radical, R1 and R2 are each hydrogen or a monovalent organic radical and Q, Q1 and Q2 are each a monovalent organic radical. A typical example is 3-dimethyl-maleimidyl-phthalic acid N-(di-n-propoxymethylsilyl)-propylimide, which is obtained by reacting 3-dimethyl-maleimidyl-phthalic acid N-allylmide and di-n-propoxy-methylsilane in solution, followed by cyclisation.
The products are used as adhesion promoters, for example between inorganic solids and organic resins.
The products are used as adhesion promoters, for example between inorganic solids and organic resins.
Description
m e present invention rèlates to novel silicon-modified imidyl-phthalic acid derivatives, processes for their preparation, and their use as adhesion promoters, for example between inorganic solids and organic resins.
- German Offenlegungsschrift 2,020,842 has already disclosed unsaturated, imido-substituted organosilane compounds in which the imido group is bonded to the Si atom via a divalent hydrocarbon radical which may or may not be halogen-substituted. These products may be used for modifying the surface of cellulose substrates and for ; the preparation of aliphatically unsatura-ted, imido-substituted organopolysiloxanes.
The literature further discloses that various silanes, for example vinyltrichlorosilane, vinyl-tris-(2-methoxyethoxy)-silane and ~-aminopropyltriethoxysilane, may be used as adhesion promoters for various applications, for example for the production of glass-fibre reinforced plastics, for sealants, for lacquers and for adhesives rcompare, for example, Defazet, 28, 207-211 (1974) and Kunststoffe, 55, 909-912 (1965)].
However, the properties of the products obtained using these known adhesion promoters in part leave some-thing to be desired, especially in respect of water absorption, resistance to -thermal oxidation and/or dielectric properties.
It is the object of the present invention to provide novel adhesion promoters by means of which the i~
.
. .... . . . . . .
above disadvantages may be avoided.
The novel silicon-modified imidyl-ph-thalic acid derivatives correspond to the formula I
. Ql CONH-R-S -Q (I) - 0~ 0 A Rl R2 in which A is a radical of the formula -C = C -, - CH
-C ~ CH2-' ~ ~ ~ ~ or ~
Rl and R2 independently of one another are hydrogen or methyl, Q is methyl, phenyl or -Q3, Ql' Q2 and Q3 ; independently of one another are alkyl with 1-6 C atoms or phenyl, R is -~CH2-~-X or ~ CH2 ~ and, if A is - a radical other than -C = C- or ~
may also be ~ O-(CH2 ~ and x is an integer from
- German Offenlegungsschrift 2,020,842 has already disclosed unsaturated, imido-substituted organosilane compounds in which the imido group is bonded to the Si atom via a divalent hydrocarbon radical which may or may not be halogen-substituted. These products may be used for modifying the surface of cellulose substrates and for ; the preparation of aliphatically unsatura-ted, imido-substituted organopolysiloxanes.
The literature further discloses that various silanes, for example vinyltrichlorosilane, vinyl-tris-(2-methoxyethoxy)-silane and ~-aminopropyltriethoxysilane, may be used as adhesion promoters for various applications, for example for the production of glass-fibre reinforced plastics, for sealants, for lacquers and for adhesives rcompare, for example, Defazet, 28, 207-211 (1974) and Kunststoffe, 55, 909-912 (1965)].
However, the properties of the products obtained using these known adhesion promoters in part leave some-thing to be desired, especially in respect of water absorption, resistance to -thermal oxidation and/or dielectric properties.
It is the object of the present invention to provide novel adhesion promoters by means of which the i~
.
. .... . . . . . .
above disadvantages may be avoided.
The novel silicon-modified imidyl-ph-thalic acid derivatives correspond to the formula I
. Ql CONH-R-S -Q (I) - 0~ 0 A Rl R2 in which A is a radical of the formula -C = C -, - CH
-C ~ CH2-' ~ ~ ~ ~ or ~
Rl and R2 independently of one another are hydrogen or methyl, Q is methyl, phenyl or -Q3, Ql' Q2 and Q3 ; independently of one another are alkyl with 1-6 C atoms or phenyl, R is -~CH2-~-X or ~ CH2 ~ and, if A is - a radical other than -C = C- or ~
may also be ~ O-(CH2 ~ and x is an integer from
2 to 4.
The invention also relates to the derivatives which have been cyclised to give the corresponding imides.
The compounds of the formula I and the corres-ponding cyclised derivatives may be prepared by a method wherein a compound of the formula II
CO~ (II) . ,.N
C~A~C
in which A is as defined undeF formula I, is reacted with .
.- , , ~.
.. . . .
.
1 ~.L~
an aminosilane of the formula III
Ql ` H2N-R-Si-Q (III) in which R, Q~ Ql and Q2 are as defined under formula I, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide.
According to a modif:ied process, compounds of the formula I which have been cyclised to the imide can also : be prepared by a method wherein a compound of the formula IV
N-R~-CH-CH2 ~N~ (IV) 0~ ~CO
A
is reacted with a compound of the formula V
Ql H-Si-Q (V) in which A, Q~ Ql and Q2 are as defined under formula II
and R' is -CH2-, ~ CH- O-CH2-.
me starting materials of the formula IV, in which A is -CH=CH-, -C-CH2-, or ~ are novel, Alkyl groups Ql' Q2 and Q3 may be straight-chain or branched, but the former is preferred. As examples of alkyl groups according to the definition there may be mentioned the methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl and n-hexyl group.
, .
.
_ L~ _ The imidyl groups A~ N- are preferably bonded to the benzene ring in the ortho-posi-tion to the -COOH or -CONH group. A is advantageously -CH=CH-, or -C = C- .
' CH CH
Preferred meanings of R are -~CH2~-3, ~ C~
and, if A is a radical other than -C = C- or als ~ -O-~CH2~-3 .
Preferred compounds of the formula I and prefer-red corresponding cyclised imide derivatives are those in which A is a radical -C = C- , Q is methyl or alkoxy with 1-4 C atoms, Ql and Q2 are each alkyl with 1-4 C atoms and R is -~CH2~-3, or in which A is a radical and especially -CH=CH-, Q is methyl or alkoxy with 1-4 C atoms, Ql and Q2 are each alkyl with 1-4 C atoms and R is -~CH2~-3 and especially ~ -~CH2~-3 -Particularly preferred compounds of the formula I,and corresponding cyclised imide derivatives, are those in which A and R have the abovementioned preferred meanings and Q is methyl, ethoxy or n-propoxy and Ql and Q2 are n-propyl or ethyl.
The starting materials of the formula II are described in German Offenlegungsschrift 2,459,673. The aminosilanes of the formula III and the silanes of -the ~ormula V are also known. The compounds of the , . ~ .
.
formula IV which may be used in the modified process of preparation, and which in some cases are novel compounds, may be prepared by reacting compounds of the formula II, in which A is -CH=CH-, -C-CH2--, ~ ~ ~
or ~ with allylamine, or H2N ~ CH2CH~CH2or OCH C~l=C~I
H2N ~ 2 2 in the melt at temperatures of up to about 250C or in an aqueous-organic, or organic, medium at temperatures between about -15C and +150C.
. Examples of inert organic solvents suitable for the reaction in an aqueous-organic or organic medium are aromatic hydrocarbons, for example benzene, toluene and xylenes, cyclic ethers, for example tetrahydrofuran, tetrahydropyran and dioxane, N,N-dialkylamides of aliphatic monocarboxylic acids with 1-3 Catoms in the acid part, for example N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide, cyclic amides 9 for example N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl--caprolactam, dialkyl ethers in which each alkyl part has 1-~ C atoms, for example diethyl ether and di-n-butyl ether, and dialkyl-sulphoxides, for example dimethyl-sulphoxide and diethyl-sulphoxide.
The reaction of the phthalic anhydrides of the formula II with the aminosilanes of the formula III is advantageously carried out in an anhydrous organic solvent at temperatures between about -20C and +50C, especially between about -15C and +25C.
Suitable organic solvents are cyclic ethers, N,N-dialkylamides of aliphatic monocarboxylic acids, cyclic amides, dialkyl ethers and dialkyl-sulphoxides of the abovementioned type, as well as aliphatic and cyclo-aliphatic ketones, for example acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone, hexamethylphos-, - 6 _ phorotriamide (hexame-tapol), N,N,N',N'-tetramethylurea and tetrahydrothiophene dioxide (sulfolane).
m e reaction can also be carried out in mixtures of such solvents. On the other hand, it is also possible to dilute these preferred solvent systems with other organic solvents, for example aroma-tic, cyclo-aliphatic or aliphatic, chlorinated or non-chlorinated, hydrocarbons, for instance benzene, toluene, xylenes, cyclohexane, n-pentane, n-hexane, petroleum ether and methylene chloride.
m e compounds of the formulae II and III are employed in approximately the stoichiome~ric amount.
Advantageously, a slight excess of the aminosilane of the formula III, for example approximately 5-20% molar excess, is used. Aminosllanes of the formula III, in which R is ~ CH2 ~ and especially ~ 0-(CH2 ~
are particularly suitable for the reaction with anhydrides of the formula II.
The optional cyclisation of the amidocarboxylic acids, obtained from the above reaction, to give the corresponding imides may be carried out chemically or thermally, by methods known per se. Chemical cycli-sation is advantageously effected by treatment with a dehydrating agent, used by itself or as a mixture with a tertiary amine. Examples of suitable dehydrating agents are acetic anhydride, propionic anhydride and dicyclohexylcarbodiimide, or mixtures of acetic anhydride and triethylamine.
The thermal cyclisation is effected by heating to temperatures of about 50-250C, preferably about 100-150C, with or without addition of an inert organic solvent and/or of an azeotropic entraining agent, for example xylenes or toluene. However, in some cases cyclisation of the amidocarboxylic acids obtained is :
superfluous, if these acids can be applied in the form of solutions as obtained from the reaction.
The reaction of compounds of the formula IV with silanes of the formula V by the modified process directly leads to imides and is advantageously also carried out in an inert organic solvent and in the presence of a catalyst.
Examples of catalysts which may be used are organic peroxides, for instance tert.-butyl hydroperoxide, di-tert.-butyl peroxide) benzoyl peroxide, diacyl perox-ides and cumene hydroperoxide, and platinum and palladium catalysts, for instance platinum/charcoal catalysts or PtC16H2 catalysts.
Examples of suitable inert organic solvents are aromatic hydrocarbons, for instance benzene, toluene and xylenes, cyclic ethers, for instance tetrahydrofuran, tetrahydropyran and dioxane, and ethylene glycol mono-alkyl ethers and dialkyl ethers each with 1-4 C atoms in the alkyl portions, for instance ethylene glycol mono-methyl ether, monoethyl ether, diethyl ether and di-n-butyl ether. Aromatic hydrocarbons are preferred.
m e reaction is advantageously carried out under a pro-tective gas, for example nitrogen or argon.
The reaction temperatures are in general approxi-mately between 80 and 150C; reaction temperatures between about 90 and 120C are preferred.
me compounds of the formula I are valuable adhesion promoters, especially between inorganic solids and organic resins, and may be used for a large number of applications in the adhesives industry and in the lacquer-using and plastics-processing industries.
e following are examples of some fields of use:
improving the adhesion of special sealants, for example polysulphides, polyurethanes and polyacrylates, to various substrates, for example glass, aluminium and ceramics; encapsulating mineral fillers so as to improve the mechanical properties of the products prepared .
- ~, , .: ..
therewith, for example in the case of sand-filled masks and cores used in the foundry indus-try, mineral-filled cable mixtures or other mineral-filled plastics, for example filled thermosetting resins, for instance quartz-filled epoxide resins and filled unsaturated polyesters, filled thermoplastics, for instance polyamide-6,6 and polyethylene terephthalate, and filled elastomers, for instance natural rubber and synthetic rubber; and incor-poration in adhesives, adhesive compositions and lacquers, for example adhesive compositions containing epoxide resins, and lacquers based on epoxides,polyacrylates, polyurethanes and vinyl chloride copolymers. However, the compounds mentioned are especially suitable for the manufacture of reinforced plastics, especially glass fibre-reinforced plastics, in particular composite materials, for instance laminates, in order to improve the adhesion between the substrate or matrix and the plastic applied thereto. The substrate per se may be in any desired form, for example in the form of fibres, ~abrics or nonwovens, and preferably consistsof glass or of mineral materials, for example quartz, mineral wool, asbestos, mica or metal fibres and foils. Examples of suitable plastics for the manufacture of such laminates are acrylates and polyester, epoxide, silicon, melamine, phenolic and furan resins, and also polyamides, polyamido-acids and polyimides, but especially polymers crosslink-able via C=C double bonds, for instance unsaturated poly-esters, homopolymers and copolymers containing maleimidyl and nadicimidyl groups, their precursors or their mixtures with other polymers.
Relative to comparable composite materials which have been manufactured using known silicon-containing adhesion promoters, especially those of the type men-tioned at the outset, glass fibre-reinforced composite materials manufactured using the adhesion promoters accordlng to the invention, of the formula I, are ' ' , ' ' . .' ' distinguished especially by improved resistance to thermal oxidation, improved dielectric properties after exposure to moisture, and/or lower water absorption.
The compounds of the formula I are also distinguished by good wetting of the substrates.
The adhesion promoters according to the invention are advantageously applied in the form of solutions in suitable organic solvents, for example N,N-dimethylforma-mide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, tetrahydrofuran and dioxane, or in the form of dispersions or emulsions, in accordance with conventional techniques.
Preparation Examples Exam~le 1 C0\ 0-n.Propyl 4CH2 ~ Si-CH3 ~ C0 0-n.Propyl OC CO
C~=<CH3 43.5 g (0.14 mol) of 3-dimethylmaleimidyl-phthalic acid N-allylimide and 0.5 ml (1 x 10 5 mol) of a solution of H2PtC16. 6 H20 in propanol are heated, in 200 ml of anhydrous toluene, to 105C in a sulphonation flask,under a nitrogen atmosphere. A solution of 23 g (0.142 mol) of freshly distilled di-n-propoxymethylsilane in 100 ml of anhydrous toluene is added dropwise over a period of one hour, with stirring. The reaction mixture is then stirred for a further 3 hours at 105C. After removing the solvent, the crude product obtained is distilled.
50 g (76% of theory) of 3-dimethylmaleimidyl-phthalic acid N-(di-n-propoxymethylsilyl)-propylimide are ob-tained in the form of a yellowish, very viscous oil; boiling ., - - --- 10 _ point 225-235C/10 3 mm Hg.
Analysis for C24H32N206Si (molecular weight 472):
Calculated: C 60.99% H 6.82% N 5.93% Si 5~94%
Found: C 61.0 % H 6.9 % N 6!1 % Si 6.1 %
The 3-dimethylmaleimidyl-phthalic acid N-allyl-imide used in the above example may be prepared as follows:
54 g (0.2 mol) of 3-dimethylmaleimidyl-phthalic anhydride are dissolved in 200 ml of xylene at 50C. A
solution of 15 ml (0.2 mol) o:E allylamine is added drop-wise The reaction mixture is then heated under reflux for 5 hours, using a water separator. The solvent is removed in vacuo and the crude product is twice recrystal-lised from ethanol. 43 2 g (70% of theory) of 3-dimethylmaleimidyl-phthalic acid N-allylimide are obtained as white crystals of melting point 97-100C.
Analysis for C17H14N204 (molecular weight 310):
calculated: C 65.8% H 4.55% N 9.03%
found: C 65.~% H 4.6 % N 9.1 %
Example 2 9.48 g (0 035 mol) of a 1:1 mixture of 3-dimethyl-and 4-dimethyl-maleimidyl-phthalic anhydride are dissolved in 140 ml of anhydrous N,N-dimethylacetamide in a sulpho-nation flask under nitrogen, and the solution is cooled to 0C. A solution of 7.68 g (0.035 mol) of Y-amino-propyl-di-n-propoxy-methylsilane in 20 ml of N,N-dimethyl-acetamide is added dropwise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20-25C. A mixture of 3- and 4-dimethylmaleimidyl-phthalic acid mono-(di-n-propoxy-methylsilyl)-propylamide, dissolved in N,N-dimethylacetamide, is obtained. This solution can be used for finishing glass fibres intended for the manufacture of glass fibre-reinforced composite materials.
The starting material 3-dimethylmaleimidyl-phthalic anhydride or the mixture of 3- and 4-dimethyl-maleimidyl-phthalic anhydride can be prepared by the pro-~ . .
b~ ~
cess described in German Offenlegungsschrift 2,459,673.Example 3 7.29 g (0.03 mol) of 4-maleimidyl-phthalic anhydride are dissolved in 125 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a N2 atmosphere and the solution is cooled to 0C. A solution o~ 8.86 g (0.03 mol) of 4-[r-di-n-propoxymethyl-silyl]-propylaniline in 29 ml of N,NI-dimethylacetamide is added dropwise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20 to 25C. The solu-tion of the amidoacid formed can be used for finishing glass fibres intended for the manufac-ture of glass fibre-reinforced composite materials.
~0 + H?N ~ (CH2)3 Si - CH3 N \ 1l OC3H7 o=c~ &=
HC- CH
Example 4 9.27 g (0.03 mol) of 3-nadic-imidyl-phthalic anhydride are dissolved in 125 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a nitro-gen atmosphereand the solution is cooled to 0C. A
solution of 6.63 g (0.03 mol) of ~-aminopropyl-triethoxy-silane in 26 ml of N,N'-dimethylacetamide is added drop-wise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20 to 25C, me solu-tion of the amidoacid formed can be used for finishing glass fibres intended for the manufacture of glass fibre-reinforced composite materials.
O
C ~ + ~ H ~ - (C~2)3 Sl- oczH5 N ~ C2H5 O=C~ C--O
w ~ C2H5 C - OH2 3 f OC~H5 ~ b solvent DMA' O--C C=O
- "\~/, .
Example 5 12.86 g (0.05 mol) of 3-itaconimidyl-phthalic anhydride are dissolved in 100 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a nitro-gen atmosphere and the solution is cooled to 0C. A
solution of 14 77 g (0.05 mol) of 4-(r-di-n-propoxymethyl-silyl)-propyl-aniline in 15 ml of N,N'-dimethylacetamide is added dropwise, with stirring, and the reaction mix-ture is then stirred for a further 2 hours at 20 to 25C.
m ereafter, the amidoacid is thermally cyclised by heating to 120-130C, with addition of toluene as an azeotropic entraining agent; the corresponding 3-itacon-imidyl-phthalic acid 4-(di-n-propoxymethyl-silyl)-propyl-: phenylimide is formed.- After dilution with 140 ml of N,N'-dimethylacetamide, this solution can be used for finishing g:Lass fibres intended for the manufacture of glass fibre--reinforced composite materials.
~ ' .
: ' . . : . -- ' . ' ~
'' . -,' .
11 . 1OC3H7 O +H2N ~ ~ (CH2)3 1 3 I ~ ~ OC3~7 `, O--C~ ~C=O
~ .
::~ C~ O
2 C OC3~7 ~ C ~ ~ (C~2)3 li- CH3 [-H20] ¦ o OC3H7 removal ~N ~
=~ - &--o ., .
Use Example a) Impregnation of a glass fibre fabric A glass fibre fabric made from so-called E-glass, having a satin weave and weighing 280 g/m2, is first thermally desized to about 0.1 % by weight residual size content and is then impregnated with 2% solutions or emulsions of the adhesion promoters listed below. The adhesion promoter solutions are applied by immersion, with an impregnation speed of O.5 m/minute, and the impreg-nated material is then dried for 20 minutes at 180C in a circulating air oven.
me prepregs obtained contain from 0.09 to 0 11 yO by weight, based on glass, of adhesion promoter.
The following are used as adhesion promoters (finishes):
1) No adhesion promoter ...... ,, ..... ,~ .. , ;~$~
-- lL~ -2) Vinyltri-(2-methoxyethoxy)-silane ("Silan ~ 172" from Messrs. Union Carbide), 2% solution in N,N-dimethyl-formamide (DMF)
The invention also relates to the derivatives which have been cyclised to give the corresponding imides.
The compounds of the formula I and the corres-ponding cyclised derivatives may be prepared by a method wherein a compound of the formula II
CO~ (II) . ,.N
C~A~C
in which A is as defined undeF formula I, is reacted with .
.- , , ~.
.. . . .
.
1 ~.L~
an aminosilane of the formula III
Ql ` H2N-R-Si-Q (III) in which R, Q~ Ql and Q2 are as defined under formula I, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide.
According to a modif:ied process, compounds of the formula I which have been cyclised to the imide can also : be prepared by a method wherein a compound of the formula IV
N-R~-CH-CH2 ~N~ (IV) 0~ ~CO
A
is reacted with a compound of the formula V
Ql H-Si-Q (V) in which A, Q~ Ql and Q2 are as defined under formula II
and R' is -CH2-, ~ CH- O-CH2-.
me starting materials of the formula IV, in which A is -CH=CH-, -C-CH2-, or ~ are novel, Alkyl groups Ql' Q2 and Q3 may be straight-chain or branched, but the former is preferred. As examples of alkyl groups according to the definition there may be mentioned the methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl and n-hexyl group.
, .
.
_ L~ _ The imidyl groups A~ N- are preferably bonded to the benzene ring in the ortho-posi-tion to the -COOH or -CONH group. A is advantageously -CH=CH-, or -C = C- .
' CH CH
Preferred meanings of R are -~CH2~-3, ~ C~
and, if A is a radical other than -C = C- or als ~ -O-~CH2~-3 .
Preferred compounds of the formula I and prefer-red corresponding cyclised imide derivatives are those in which A is a radical -C = C- , Q is methyl or alkoxy with 1-4 C atoms, Ql and Q2 are each alkyl with 1-4 C atoms and R is -~CH2~-3, or in which A is a radical and especially -CH=CH-, Q is methyl or alkoxy with 1-4 C atoms, Ql and Q2 are each alkyl with 1-4 C atoms and R is -~CH2~-3 and especially ~ -~CH2~-3 -Particularly preferred compounds of the formula I,and corresponding cyclised imide derivatives, are those in which A and R have the abovementioned preferred meanings and Q is methyl, ethoxy or n-propoxy and Ql and Q2 are n-propyl or ethyl.
The starting materials of the formula II are described in German Offenlegungsschrift 2,459,673. The aminosilanes of the formula III and the silanes of -the ~ormula V are also known. The compounds of the , . ~ .
.
formula IV which may be used in the modified process of preparation, and which in some cases are novel compounds, may be prepared by reacting compounds of the formula II, in which A is -CH=CH-, -C-CH2--, ~ ~ ~
or ~ with allylamine, or H2N ~ CH2CH~CH2or OCH C~l=C~I
H2N ~ 2 2 in the melt at temperatures of up to about 250C or in an aqueous-organic, or organic, medium at temperatures between about -15C and +150C.
. Examples of inert organic solvents suitable for the reaction in an aqueous-organic or organic medium are aromatic hydrocarbons, for example benzene, toluene and xylenes, cyclic ethers, for example tetrahydrofuran, tetrahydropyran and dioxane, N,N-dialkylamides of aliphatic monocarboxylic acids with 1-3 Catoms in the acid part, for example N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide, cyclic amides 9 for example N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl--caprolactam, dialkyl ethers in which each alkyl part has 1-~ C atoms, for example diethyl ether and di-n-butyl ether, and dialkyl-sulphoxides, for example dimethyl-sulphoxide and diethyl-sulphoxide.
The reaction of the phthalic anhydrides of the formula II with the aminosilanes of the formula III is advantageously carried out in an anhydrous organic solvent at temperatures between about -20C and +50C, especially between about -15C and +25C.
Suitable organic solvents are cyclic ethers, N,N-dialkylamides of aliphatic monocarboxylic acids, cyclic amides, dialkyl ethers and dialkyl-sulphoxides of the abovementioned type, as well as aliphatic and cyclo-aliphatic ketones, for example acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone, hexamethylphos-, - 6 _ phorotriamide (hexame-tapol), N,N,N',N'-tetramethylurea and tetrahydrothiophene dioxide (sulfolane).
m e reaction can also be carried out in mixtures of such solvents. On the other hand, it is also possible to dilute these preferred solvent systems with other organic solvents, for example aroma-tic, cyclo-aliphatic or aliphatic, chlorinated or non-chlorinated, hydrocarbons, for instance benzene, toluene, xylenes, cyclohexane, n-pentane, n-hexane, petroleum ether and methylene chloride.
m e compounds of the formulae II and III are employed in approximately the stoichiome~ric amount.
Advantageously, a slight excess of the aminosilane of the formula III, for example approximately 5-20% molar excess, is used. Aminosllanes of the formula III, in which R is ~ CH2 ~ and especially ~ 0-(CH2 ~
are particularly suitable for the reaction with anhydrides of the formula II.
The optional cyclisation of the amidocarboxylic acids, obtained from the above reaction, to give the corresponding imides may be carried out chemically or thermally, by methods known per se. Chemical cycli-sation is advantageously effected by treatment with a dehydrating agent, used by itself or as a mixture with a tertiary amine. Examples of suitable dehydrating agents are acetic anhydride, propionic anhydride and dicyclohexylcarbodiimide, or mixtures of acetic anhydride and triethylamine.
The thermal cyclisation is effected by heating to temperatures of about 50-250C, preferably about 100-150C, with or without addition of an inert organic solvent and/or of an azeotropic entraining agent, for example xylenes or toluene. However, in some cases cyclisation of the amidocarboxylic acids obtained is :
superfluous, if these acids can be applied in the form of solutions as obtained from the reaction.
The reaction of compounds of the formula IV with silanes of the formula V by the modified process directly leads to imides and is advantageously also carried out in an inert organic solvent and in the presence of a catalyst.
Examples of catalysts which may be used are organic peroxides, for instance tert.-butyl hydroperoxide, di-tert.-butyl peroxide) benzoyl peroxide, diacyl perox-ides and cumene hydroperoxide, and platinum and palladium catalysts, for instance platinum/charcoal catalysts or PtC16H2 catalysts.
Examples of suitable inert organic solvents are aromatic hydrocarbons, for instance benzene, toluene and xylenes, cyclic ethers, for instance tetrahydrofuran, tetrahydropyran and dioxane, and ethylene glycol mono-alkyl ethers and dialkyl ethers each with 1-4 C atoms in the alkyl portions, for instance ethylene glycol mono-methyl ether, monoethyl ether, diethyl ether and di-n-butyl ether. Aromatic hydrocarbons are preferred.
m e reaction is advantageously carried out under a pro-tective gas, for example nitrogen or argon.
The reaction temperatures are in general approxi-mately between 80 and 150C; reaction temperatures between about 90 and 120C are preferred.
me compounds of the formula I are valuable adhesion promoters, especially between inorganic solids and organic resins, and may be used for a large number of applications in the adhesives industry and in the lacquer-using and plastics-processing industries.
e following are examples of some fields of use:
improving the adhesion of special sealants, for example polysulphides, polyurethanes and polyacrylates, to various substrates, for example glass, aluminium and ceramics; encapsulating mineral fillers so as to improve the mechanical properties of the products prepared .
- ~, , .: ..
therewith, for example in the case of sand-filled masks and cores used in the foundry indus-try, mineral-filled cable mixtures or other mineral-filled plastics, for example filled thermosetting resins, for instance quartz-filled epoxide resins and filled unsaturated polyesters, filled thermoplastics, for instance polyamide-6,6 and polyethylene terephthalate, and filled elastomers, for instance natural rubber and synthetic rubber; and incor-poration in adhesives, adhesive compositions and lacquers, for example adhesive compositions containing epoxide resins, and lacquers based on epoxides,polyacrylates, polyurethanes and vinyl chloride copolymers. However, the compounds mentioned are especially suitable for the manufacture of reinforced plastics, especially glass fibre-reinforced plastics, in particular composite materials, for instance laminates, in order to improve the adhesion between the substrate or matrix and the plastic applied thereto. The substrate per se may be in any desired form, for example in the form of fibres, ~abrics or nonwovens, and preferably consistsof glass or of mineral materials, for example quartz, mineral wool, asbestos, mica or metal fibres and foils. Examples of suitable plastics for the manufacture of such laminates are acrylates and polyester, epoxide, silicon, melamine, phenolic and furan resins, and also polyamides, polyamido-acids and polyimides, but especially polymers crosslink-able via C=C double bonds, for instance unsaturated poly-esters, homopolymers and copolymers containing maleimidyl and nadicimidyl groups, their precursors or their mixtures with other polymers.
Relative to comparable composite materials which have been manufactured using known silicon-containing adhesion promoters, especially those of the type men-tioned at the outset, glass fibre-reinforced composite materials manufactured using the adhesion promoters accordlng to the invention, of the formula I, are ' ' , ' ' . .' ' distinguished especially by improved resistance to thermal oxidation, improved dielectric properties after exposure to moisture, and/or lower water absorption.
The compounds of the formula I are also distinguished by good wetting of the substrates.
The adhesion promoters according to the invention are advantageously applied in the form of solutions in suitable organic solvents, for example N,N-dimethylforma-mide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, tetrahydrofuran and dioxane, or in the form of dispersions or emulsions, in accordance with conventional techniques.
Preparation Examples Exam~le 1 C0\ 0-n.Propyl 4CH2 ~ Si-CH3 ~ C0 0-n.Propyl OC CO
C~=<CH3 43.5 g (0.14 mol) of 3-dimethylmaleimidyl-phthalic acid N-allylimide and 0.5 ml (1 x 10 5 mol) of a solution of H2PtC16. 6 H20 in propanol are heated, in 200 ml of anhydrous toluene, to 105C in a sulphonation flask,under a nitrogen atmosphere. A solution of 23 g (0.142 mol) of freshly distilled di-n-propoxymethylsilane in 100 ml of anhydrous toluene is added dropwise over a period of one hour, with stirring. The reaction mixture is then stirred for a further 3 hours at 105C. After removing the solvent, the crude product obtained is distilled.
50 g (76% of theory) of 3-dimethylmaleimidyl-phthalic acid N-(di-n-propoxymethylsilyl)-propylimide are ob-tained in the form of a yellowish, very viscous oil; boiling ., - - --- 10 _ point 225-235C/10 3 mm Hg.
Analysis for C24H32N206Si (molecular weight 472):
Calculated: C 60.99% H 6.82% N 5.93% Si 5~94%
Found: C 61.0 % H 6.9 % N 6!1 % Si 6.1 %
The 3-dimethylmaleimidyl-phthalic acid N-allyl-imide used in the above example may be prepared as follows:
54 g (0.2 mol) of 3-dimethylmaleimidyl-phthalic anhydride are dissolved in 200 ml of xylene at 50C. A
solution of 15 ml (0.2 mol) o:E allylamine is added drop-wise The reaction mixture is then heated under reflux for 5 hours, using a water separator. The solvent is removed in vacuo and the crude product is twice recrystal-lised from ethanol. 43 2 g (70% of theory) of 3-dimethylmaleimidyl-phthalic acid N-allylimide are obtained as white crystals of melting point 97-100C.
Analysis for C17H14N204 (molecular weight 310):
calculated: C 65.8% H 4.55% N 9.03%
found: C 65.~% H 4.6 % N 9.1 %
Example 2 9.48 g (0 035 mol) of a 1:1 mixture of 3-dimethyl-and 4-dimethyl-maleimidyl-phthalic anhydride are dissolved in 140 ml of anhydrous N,N-dimethylacetamide in a sulpho-nation flask under nitrogen, and the solution is cooled to 0C. A solution of 7.68 g (0.035 mol) of Y-amino-propyl-di-n-propoxy-methylsilane in 20 ml of N,N-dimethyl-acetamide is added dropwise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20-25C. A mixture of 3- and 4-dimethylmaleimidyl-phthalic acid mono-(di-n-propoxy-methylsilyl)-propylamide, dissolved in N,N-dimethylacetamide, is obtained. This solution can be used for finishing glass fibres intended for the manufacture of glass fibre-reinforced composite materials.
The starting material 3-dimethylmaleimidyl-phthalic anhydride or the mixture of 3- and 4-dimethyl-maleimidyl-phthalic anhydride can be prepared by the pro-~ . .
b~ ~
cess described in German Offenlegungsschrift 2,459,673.Example 3 7.29 g (0.03 mol) of 4-maleimidyl-phthalic anhydride are dissolved in 125 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a N2 atmosphere and the solution is cooled to 0C. A solution o~ 8.86 g (0.03 mol) of 4-[r-di-n-propoxymethyl-silyl]-propylaniline in 29 ml of N,NI-dimethylacetamide is added dropwise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20 to 25C. The solu-tion of the amidoacid formed can be used for finishing glass fibres intended for the manufac-ture of glass fibre-reinforced composite materials.
~0 + H?N ~ (CH2)3 Si - CH3 N \ 1l OC3H7 o=c~ &=
HC- CH
Example 4 9.27 g (0.03 mol) of 3-nadic-imidyl-phthalic anhydride are dissolved in 125 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a nitro-gen atmosphereand the solution is cooled to 0C. A
solution of 6.63 g (0.03 mol) of ~-aminopropyl-triethoxy-silane in 26 ml of N,N'-dimethylacetamide is added drop-wise, with stirring, and the reaction mixture is then stirred for a further 2 hours at 20 to 25C, me solu-tion of the amidoacid formed can be used for finishing glass fibres intended for the manufacture of glass fibre-reinforced composite materials.
O
C ~ + ~ H ~ - (C~2)3 Sl- oczH5 N ~ C2H5 O=C~ C--O
w ~ C2H5 C - OH2 3 f OC~H5 ~ b solvent DMA' O--C C=O
- "\~/, .
Example 5 12.86 g (0.05 mol) of 3-itaconimidyl-phthalic anhydride are dissolved in 100 ml of anhydrous N,N'-dimethylacetamide in a sulphonation flask under a nitro-gen atmosphere and the solution is cooled to 0C. A
solution of 14 77 g (0.05 mol) of 4-(r-di-n-propoxymethyl-silyl)-propyl-aniline in 15 ml of N,N'-dimethylacetamide is added dropwise, with stirring, and the reaction mix-ture is then stirred for a further 2 hours at 20 to 25C.
m ereafter, the amidoacid is thermally cyclised by heating to 120-130C, with addition of toluene as an azeotropic entraining agent; the corresponding 3-itacon-imidyl-phthalic acid 4-(di-n-propoxymethyl-silyl)-propyl-: phenylimide is formed.- After dilution with 140 ml of N,N'-dimethylacetamide, this solution can be used for finishing g:Lass fibres intended for the manufacture of glass fibre--reinforced composite materials.
~ ' .
: ' . . : . -- ' . ' ~
'' . -,' .
11 . 1OC3H7 O +H2N ~ ~ (CH2)3 1 3 I ~ ~ OC3~7 `, O--C~ ~C=O
~ .
::~ C~ O
2 C OC3~7 ~ C ~ ~ (C~2)3 li- CH3 [-H20] ¦ o OC3H7 removal ~N ~
=~ - &--o ., .
Use Example a) Impregnation of a glass fibre fabric A glass fibre fabric made from so-called E-glass, having a satin weave and weighing 280 g/m2, is first thermally desized to about 0.1 % by weight residual size content and is then impregnated with 2% solutions or emulsions of the adhesion promoters listed below. The adhesion promoter solutions are applied by immersion, with an impregnation speed of O.5 m/minute, and the impreg-nated material is then dried for 20 minutes at 180C in a circulating air oven.
me prepregs obtained contain from 0.09 to 0 11 yO by weight, based on glass, of adhesion promoter.
The following are used as adhesion promoters (finishes):
1) No adhesion promoter ...... ,, ..... ,~ .. , ;~$~
-- lL~ -2) Vinyltri-(2-methoxyethoxy)-silane ("Silan ~ 172" from Messrs. Union Carbide), 2% solution in N,N-dimethyl-formamide (DMF)
3) ~-Aminopropyl-triethoxysilane ("Silan A 1100" from Messrs. Union Carbide), 256 solution in DMF
4) Adhesion promoter according to Preparation,Example 1, 2% emulsion in DMF
5) Adhesion promoter solution according to Preparation ; Example 2, diluted with DMF to 2% by weight
6) Adhesion promoter according to Preparation Example 3, 2% solution in DMF
7) Adhesion promoter according to Preparation Example 4, 2% solution in DMF
8) Adhesion promoter according to Prepar,ation Example 5, 2% solution in DMF
b) Production of copper-covered laminate sheets 1.0 mol of N,N'-4,4'-diphenylmethane-bis-malei- ' ' mide is dissolved in 500 g of furfuryl alcohol at 100C
and the solution is cooled to 25C. 0.4 mol of 4,4'-diaminodiphenylmethane is dissolved in 200 g of methyl glycol at 25C. The two solutions are combined and mixed thoroughly. The glass fibre fabrics finished in accordance with section a) are impregnated with this mixed solution by the immersion process at 25C and are then dried in a circulating air oven for 18 minutes at ' 180C; the resulting prepregs contain 29 % by weight of-resin. 10 layers of the impregnated fabric are then pressed hot between two 35 microns thick copper foils which have been pretreated by electrolytic surface coat-ing with brass. The press is first kept under light -contact pressure for 2 to 3 minutes; the pressure is then raised to 40 kp/cm2 and the assembly is pressed for one hour at 180C. The test specimens are then taken out of the press and post-cured for a further 6 hours in an oven at 240 C; the resulting laminate sheets contain 35 % by weight of resin.
'3' ~
' ~ .
.. . ..
Properties of the copPer-covered laminate sheets obtained ._ Flexural stren~th in N/mm' according to ISO/R 178 a) Initial value b) after 10 days' aging a-t 270C
Water absorption in % by weight, after 24 hours at 23C. The measure-ments are carried out on flexural test specimersaccording to VSM Standard Specification 77,103, Dielectric_loss factor tg ~/50 c/s according to DIN
53,483 a) Initial value measured at 23C
b) after 6 hours' storage in boiling water Dielectric constant r/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) after 6 hours~ storage in boiling water.
ISO/R = Intemational Standards Organisation/Recommendations VSM = Verein Schweizerischer Maschinenindustrieller DIN = _eutsche Industrie-Norm me results are summarised in Table I which follows. m e numbering of the experimental productsis the same as under a).
....... . . . ... ~.. ~
C~ _ _ ~ ~- O~ _ ~D. , ~ ~o l o ~ .~ U~
_ ~ ~ ~r~ _~
~ ~ l ~ ~ o ~
,, ' . ~ ~ ~0D O ~ u~ ~
~ ~ oo ~ CU ~ ~ ~
~ ~ o o o L~ ~
~ . _ ._. . _ ~ o ~ ~ ~
., ~ Z Ll~ ~ r- ~ ~ ~ ~ oo . ~ ~ ~ ~D O O O ~ L~
., tq ~o _ u~ ,t~
~ h ~\I ~ ~
O ~ ~ ~D ~ C~l C~l. ~ ~ 0~
O O ~ U~ U~
~: _ _ 'CJ h C~ ~1 t~l . ~ ~ ~ 1~ a) tu 1~ (\t rl Lf~
c~ 5 00 ~D O (\i ~ L~ 1~
U~Pl -- ~\ r-l _ g C~l 0 ~0 ~ 0 ~ 0 ~l ~ 0 o ~ c~i Lr~ L~
~ ~ --cl ~ 0 r-r-~ ~ Lr~ O Lr~ ~ cr~
C~i ~ O ~ ~D Lr~ ~D
. ~--l ~ 0 - - -~
~h ~D ~ A ~
O h a~ O ~l ~) ~ D~ O :~ ~ ta ~o oo ID ~aD h ~ ~ ~ ~ t~
a) ~ ~ ~ ~ t~ ~ h +' h 1~1 o ~ ~ O ~ ~ O
~0 ta ~ ~ ~ ~ ~tq ~-,1 ~0 - O ~ U~
~ ~ -~1 ~ U~ rl ~ ' t~ O.) F~ v~ ~ O t' rq h o ~ ~a h u~ h ~ ~,. P~ h ~ 1h a~ O ~1 h a a~ t~ ~ ~h O ~: ~ ~ ~ ~
E~ ~q ~1 ~O +~ c) ~10 ~ c~ ~` O ~a ~ $i~~Q ~1 ~
~1 rl O V ~ t~h ~ h~
H ~a , i O t~ ~ u~ 0 ~ o ~D
h ~` O+' c~ ~ ~ c) ~:
a~ ~I h t~h ~ a~ ~h rl a) O h r ~ X ~ $ ~ $ .bDoV ~ $ ~ ~ $ ~
FJ ~ tH ~ F~ a~ ~ ,~ ~ O ~1 h q I O
E I _ ~ ~ ~ ,n ~ ,n
b) Production of copper-covered laminate sheets 1.0 mol of N,N'-4,4'-diphenylmethane-bis-malei- ' ' mide is dissolved in 500 g of furfuryl alcohol at 100C
and the solution is cooled to 25C. 0.4 mol of 4,4'-diaminodiphenylmethane is dissolved in 200 g of methyl glycol at 25C. The two solutions are combined and mixed thoroughly. The glass fibre fabrics finished in accordance with section a) are impregnated with this mixed solution by the immersion process at 25C and are then dried in a circulating air oven for 18 minutes at ' 180C; the resulting prepregs contain 29 % by weight of-resin. 10 layers of the impregnated fabric are then pressed hot between two 35 microns thick copper foils which have been pretreated by electrolytic surface coat-ing with brass. The press is first kept under light -contact pressure for 2 to 3 minutes; the pressure is then raised to 40 kp/cm2 and the assembly is pressed for one hour at 180C. The test specimens are then taken out of the press and post-cured for a further 6 hours in an oven at 240 C; the resulting laminate sheets contain 35 % by weight of resin.
'3' ~
' ~ .
.. . ..
Properties of the copPer-covered laminate sheets obtained ._ Flexural stren~th in N/mm' according to ISO/R 178 a) Initial value b) after 10 days' aging a-t 270C
Water absorption in % by weight, after 24 hours at 23C. The measure-ments are carried out on flexural test specimersaccording to VSM Standard Specification 77,103, Dielectric_loss factor tg ~/50 c/s according to DIN
53,483 a) Initial value measured at 23C
b) after 6 hours' storage in boiling water Dielectric constant r/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) after 6 hours~ storage in boiling water.
ISO/R = Intemational Standards Organisation/Recommendations VSM = Verein Schweizerischer Maschinenindustrieller DIN = _eutsche Industrie-Norm me results are summarised in Table I which follows. m e numbering of the experimental productsis the same as under a).
....... . . . ... ~.. ~
C~ _ _ ~ ~- O~ _ ~D. , ~ ~o l o ~ .~ U~
_ ~ ~ ~r~ _~
~ ~ l ~ ~ o ~
,, ' . ~ ~ ~0D O ~ u~ ~
~ ~ oo ~ CU ~ ~ ~
~ ~ o o o L~ ~
~ . _ ._. . _ ~ o ~ ~ ~
., ~ Z Ll~ ~ r- ~ ~ ~ ~ oo . ~ ~ ~ ~D O O O ~ L~
., tq ~o _ u~ ,t~
~ h ~\I ~ ~
O ~ ~ ~D ~ C~l C~l. ~ ~ 0~
O O ~ U~ U~
~: _ _ 'CJ h C~ ~1 t~l . ~ ~ ~ 1~ a) tu 1~ (\t rl Lf~
c~ 5 00 ~D O (\i ~ L~ 1~
U~Pl -- ~\ r-l _ g C~l 0 ~0 ~ 0 ~ 0 ~l ~ 0 o ~ c~i Lr~ L~
~ ~ --cl ~ 0 r-r-~ ~ Lr~ O Lr~ ~ cr~
C~i ~ O ~ ~D Lr~ ~D
. ~--l ~ 0 - - -~
~h ~D ~ A ~
O h a~ O ~l ~) ~ D~ O :~ ~ ta ~o oo ID ~aD h ~ ~ ~ ~ t~
a) ~ ~ ~ ~ t~ ~ h +' h 1~1 o ~ ~ O ~ ~ O
~0 ta ~ ~ ~ ~ ~tq ~-,1 ~0 - O ~ U~
~ ~ -~1 ~ U~ rl ~ ' t~ O.) F~ v~ ~ O t' rq h o ~ ~a h u~ h ~ ~,. P~ h ~ 1h a~ O ~1 h a a~ t~ ~ ~h O ~: ~ ~ ~ ~
E~ ~q ~1 ~O +~ c) ~10 ~ c~ ~` O ~a ~ $i~~Q ~1 ~
~1 rl O V ~ t~h ~ h~
H ~a , i O t~ ~ u~ 0 ~ o ~D
h ~` O+' c~ ~ ~ c) ~:
a~ ~I h t~h ~ a~ ~h rl a) O h r ~ X ~ $ ~ $ .bDoV ~ $ ~ ~ $ ~
FJ ~ tH ~ F~ a~ ~ ,~ ~ O ~1 h q I O
E I _ ~ ~ ~ ,n ~ ,n
Claims (7)
1. A compound of the formula I
(I) and its corresponding cyclised imide derivative, in which A is a radical of the formula , , , , , or , R1 and R2 independently of one another are hydrogen or methyl, Q is methyl, phenyl or -OQ3, Q1, Q2 and Q3 independently of one another are alkyl with 1-6 C atoms or phenyl, R is or and, if A is a radical other than or , may also be and x is an integer from 2 to 4.
(I) and its corresponding cyclised imide derivative, in which A is a radical of the formula , , , , , or , R1 and R2 independently of one another are hydrogen or methyl, Q is methyl, phenyl or -OQ3, Q1, Q2 and Q3 independently of one another are alkyl with 1-6 C atoms or phenyl, R is or and, if A is a radical other than or , may also be and x is an integer from 2 to 4.
2. A compound of the formula I according to claim 1 and its corresponding cyclised imide derivative, in which A is a radical, Q is methyl or alkoxy with 1-4 C atoms, Q1 and Q2 are each alkyl with 1-4 C atoms and R is .
3. A compound of the formula I according to claim 1 and its corresponding cyclised imide derivative, in which A is a radical or -CH=CH-, Q is methyl or alkoxy with 1-4 C atoms, Q1 and Q2 are each alkyl with 1-4 C atoms and R is or ,
4. A compound of the formula I according to claim 1 and its corresponding cyclised imide derivative, in which A is the radical and R is or or A is a radical or -CH=CH- and R is or Q is methyl, ethoxy or n-propoxy and Q1 and Q2 are n-propyl or ethyl.
5. A process for the preparation of a compound of the formula I according to claim 1 and of its corres-ponding cyclised imide derivatives, which comprises A. reacting a compound of the formula II
(II) in which A is as defined in claim 1, with an aminosilane of the formula III
(III) in which R, Q, Q1 and Q2 are as defined in claim 1, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide, or B. reacting a compound of the formula IV
(IV) with a compound of the formula V
(V) in which A, Q, Q1 and Q2 are as defined in claim 1 and R' is -CH2-, or .
(II) in which A is as defined in claim 1, with an aminosilane of the formula III
(III) in which R, Q, Q1 and Q2 are as defined in claim 1, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide, or B. reacting a compound of the formula IV
(IV) with a compound of the formula V
(V) in which A, Q, Q1 and Q2 are as defined in claim 1 and R' is -CH2-, or .
6. A process for the preparation of a compound of the formula I accor-ding to claim 5 and of its corresponding cyclised imide derivatives, which comprises reacting a compound of the formula II
(II) in which A is as defined in claim 1, with an aminosilane of the formula III
(III) in which R, Q, Q1 and Q2 are as defined in claim 1, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide.
(II) in which A is as defined in claim 1, with an aminosilane of the formula III
(III) in which R, Q, Q1 and Q2 are as defined in claim 1, after which the resulting amidocarboxylic acid may or may not be cyclised to the corresponding imide.
7. A process for the preparation of a compound of the formula I accor-ding to claim 5, which comprises reacting a compound of the formula IV
(IV) with a compound of the formula V
(V) in which A, Q, Q1 and Q2 are as defined in claim 1 and R' is -CH2-, or .
(IV) with a compound of the formula V
(V) in which A, Q, Q1 and Q2 are as defined in claim 1 and R' is -CH2-, or .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH11068/77 | 1977-09-09 | ||
| CH1106877A CH630089A5 (en) | 1977-09-09 | 1977-09-09 | METHOD FOR THE PRODUCTION OF SILICON-MODIFIED IMIDYL-PHTHALIC ACID DERIVATIVES. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111042A true CA1111042A (en) | 1981-10-20 |
Family
ID=4369710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA310,794A Expired CA1111042A (en) | 1977-09-09 | 1978-09-07 | Silicon-modified imidyl-phthalic acid derivatives |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4210588A (en) |
| JP (1) | JPS5448755A (en) |
| CA (1) | CA1111042A (en) |
| CH (2) | CH630089A5 (en) |
| DE (2) | DE2838844A1 (en) |
| FR (1) | FR2402661A1 (en) |
| GB (1) | GB2004290B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH630089A5 (en) | 1977-09-09 | 1982-05-28 | Ciba Geigy Ag | METHOD FOR THE PRODUCTION OF SILICON-MODIFIED IMIDYL-PHTHALIC ACID DERIVATIVES. |
| US4342832A (en) * | 1979-07-05 | 1982-08-03 | Genentech, Inc. | Method of constructing a replicable cloning vehicle having quasi-synthetic genes |
| JPH0637609B2 (en) * | 1986-01-24 | 1994-05-18 | マサチユ−セツツ インスチチユ−ト オブ テクノロジ− | Adhesion promoter |
| JP2627632B2 (en) * | 1987-12-28 | 1997-07-09 | 旭化成工業株式会社 | Coating composition |
| US4871788A (en) * | 1988-06-03 | 1989-10-03 | Dow Corning Corporation | Inomeric coupling agents based on amic acid-functional silanes |
| DE3935638A1 (en) * | 1989-10-26 | 1991-05-02 | Consortium Elektrochem Ind | ORGANOSILYL ALKYL FLAVORS |
| AU4085797A (en) * | 1996-08-23 | 1998-03-06 | First Chemical Corporation | Polymerization processes using aliphatic maleimides |
| US20040235976A1 (en) * | 1996-08-23 | 2004-11-25 | Hoyle Charles E. | Polymerization processes using alphatic maleimides |
| JP4882146B2 (en) * | 2000-11-09 | 2012-02-22 | Ｊｎｃ株式会社 | Imide compound, resin composition containing the same, liquid crystal alignment film, liquid crystal composition, and liquid crystal display element |
| US20090071584A1 (en) * | 2007-09-19 | 2009-03-19 | Ping Zhang | Tire having tread with an internal closed cellular rubber transition layer |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414584A (en) * | 1961-07-17 | 1968-12-03 | Monsanto Co | Silicon- and nitrogen-containing fourmembered ring compounds and process for preparing |
| US3478074A (en) * | 1964-12-29 | 1969-11-11 | Union Carbide Corp | Preparation of organosilicon compounds from hydrosilicon compounds |
| US3576031A (en) * | 1969-05-05 | 1971-04-20 | Gen Electric | Amide acid and imido-substituted organosilanes |
| CH587272A5 (en) * | 1973-12-20 | 1977-04-29 | Ciba Geigy Ag | |
| FR2259833B1 (en) * | 1974-02-05 | 1978-03-10 | Rhone Poulenc Ind | |
| US3901913A (en) * | 1974-06-07 | 1975-08-26 | Dow Corning | Imidoorganosilicon compounds |
| US4098796A (en) * | 1975-06-13 | 1978-07-04 | Novvo Industri A/S | P-trimethylsilyloxyphenyl glycyloxyphthalimide |
| US4107174A (en) * | 1975-06-18 | 1978-08-15 | Ciba-Geigy Corporation | Imidyl compounds |
| CH630089A5 (en) * | 1977-09-09 | 1982-05-28 | Ciba Geigy Ag | METHOD FOR THE PRODUCTION OF SILICON-MODIFIED IMIDYL-PHTHALIC ACID DERIVATIVES. |
-
1977
- 1977-09-09 CH CH1106877A patent/CH630089A5/en not_active IP Right Cessation
-
1978
- 1978-08-30 US US05/938,169 patent/US4210588A/en not_active Expired - Lifetime
- 1978-09-06 DE DE19782838844 patent/DE2838844A1/en active Granted
- 1978-09-06 DE DE2858710A patent/DE2858710C2/de not_active Expired
- 1978-09-07 GB GB7835967A patent/GB2004290B/en not_active Expired
- 1978-09-07 CA CA310,794A patent/CA1111042A/en not_active Expired
- 1978-09-08 FR FR7825827A patent/FR2402661A1/en active Granted
- 1978-09-09 JP JP11123878A patent/JPS5448755A/en active Granted
-
1981
- 1981-10-12 CH CH650681A patent/CH632273A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB2004290A (en) | 1979-03-28 |
| CH632273A5 (en) | 1982-09-30 |
| US4210588A (en) | 1980-07-01 |
| DE2858710C2 (en) | 1988-04-14 |
| JPS5448755A (en) | 1979-04-17 |
| FR2402661B1 (en) | 1984-07-20 |
| JPS6154033B2 (en) | 1986-11-20 |
| CH630089A5 (en) | 1982-05-28 |
| DE2838844A1 (en) | 1979-03-15 |
| DE2838844C2 (en) | 1987-10-08 |
| GB2004290B (en) | 1982-08-11 |
| FR2402661A1 (en) | 1979-04-06 |
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