JP2014518310A - Vinyl alcohol polymer with silane side chain - Google Patents

Abstract

  The present invention relates to novel functionalized homopolymers and copolymers of vinyl alcohol containing one or more aminosilane and / or aminosilanol-containing side chains attached to the polymer backbone via reactive coupling groups, such copolymers To the use of such copolymers in methods, coatings, inks, sealants or adhesives.

Description

  The present invention relates to novel functionalized homopolymers and copolymers of vinyl alcohol comprising one or more aminosilane and / or aminosilanol-containing side chains attached to the polymer backbone via reactive coupling groups, such polymers And the use of such polymers in coatings, inks or adhesives.

  Poly (vinyl alcohol) is commonly used as the basis or ingredient for various forms of coatings. Hydrogen bonds between the alcohol groups present in such polymers result in a very regular structure with a high degree of crystallinity and a high melting point. This highly ordered structure with high crystallinity makes it difficult for small molecules to pass through films containing these polymers. However, protective films comprising poly (vinyl alcohol) and vinyl alcohol copolymers can suffer a loss of adhesion, especially when in contact with moisture or as a result of being immersed in water.

  Novel polymers that can be used in coatings, inks or adhesives and have improved adhesion compared to similar coatings, inks or adhesives prepared from unmodified poly (vinyl alcohol) and vinyl alcohol copolymers It is an object of the present invention to provide.

  JP 2003-171600 describes a gas barrier coating composition comprising an acetoacetyl modified polyvinyl alcohol; an amino or imino functionalized alkoxysilane; and water or a mixture of water and a lower alcohol. JP 2004-143197 describes a gas barrier coating composition comprising an acetoacetyl modified polyvinyl alcohol; an alkoxysilane; an acid catalyst and water or a mixture of water and a lower alcohol. The coatings described in JP 2003-171600 and JP 2004-143197 are stated to provide a high level of gas barrier performance and adhesion maintained under high humidity levels.

  JP 1997-291185 describes an adhesive composition comprising a predetermined amount of acetic acid and an alkali metal salt of acetic acid; and an acetoacetate functionalized poly (vinyl alcohol) resin containing a silane compound.

  Application of an aqueous solution containing an amino-functionalized alkoxysilane to a soft plastic film in the preparation of a gas barrier coating has been previously described in the literature (B. Singh et al., “Surface and Coatings Technology”, 2007, 201 (16-17). ), 7107-7114; and ibid., 2007, 202 (2), 208-216).

According to a first aspect of the present invention, the compound of formula (I)
P- (R) _n (I)
(Where
P represents a linear or branched polymer backbone that is a homopolymer of vinyl alcohol or a copolymer of vinyl alcohol and at least one other monomer, said homopolymer or copolymer comprising one or more reactive cups Including a ring group,
R represents an aminosilane and / or aminosilanol-containing side chain attached to the polymer backbone through the reactive coupling group (s);
n represents the number of side chains present in an amount of about 1 to about 25 mol% of the polymer backbone;
However, when P represents a homopolymer of vinyl alcohol, R is not a side chain derived from 3-aminopropyltriethoxysilane)
A functionalized homopolymer or copolymer of a vinyl alcohol is provided.

  The polymer backbone P is a linear or branched homopolymer of vinyl alcohol, or a copolymer of vinyl alcohol and at least one other monomer, and includes one or more reactive coupling groups. When the polymer backbone P is a copolymer of vinyl alcohol and at least one other monomer, the other monomer (s) are preferably copolymerized with a suitable precursor monomer such as vinyl alcohol or vinyl ester. Containing an alkene group (ie, a carbon-carbon double bond).

  In a preferred embodiment of the invention, P represents a copolymer of vinyl alcohol and an olefin such as ethylene or propylene, preferably ethylene. Preferably, the olefin is present in an amount from about 1 to about 50 mol%, more preferably from about 2 to about 40 mol%, and even more preferably from about 5 to about 20 mol% of the polymer backbone.

  In an alternative preferred embodiment of the invention, P represents a copolymer of vinyl alcohol and a non-hydrocarbon alkene-containing monomer, such as a vinyl-based (eg acrylic) or methacrylic monomer. Examples of suitable non-hydrocarbon alkene-containing monomers that may be used in the present invention include, but are not limited to, styrene, acrylonitrile, methacrylonitrile, crotononitrile, vinyl halide, vinylidene halide, (meth) acrylamide, N, N-dimethylacrylamide, vinyl polyethers or vinyl esters of ethylene or propylene oxide, such as vinyl formate, vinyl benzoate or vinyl ether (eg VeoVa ™ 10 available from Momentive ™), heterocyclic vinyl compounds Vinyl ethers, alkyl esters of monoolefinically unsaturated dicarboxylic acids, especially esters of acrylic acid and methacrylic acid; hydroxyl functional 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyls Vinyl monomers with pill (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyl stearyl methacrylate, N-methylol (meth) acrylamide; for crosslinking or adhesion promotion or post-functionalization of vinyl polymers Vinyl monomers having additional functional groups for example, diacetone acrylamide, acetoacetoxyethyl (meth) acrylate, glycidyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, beta carboxyethyl (meth) ) Acrylate, maleic anhydride, styrene sulfonic acid, sodium sulfopropyl methacrylate, itaconic acid; N, N-dimethylethylamino (meth) acrylate, N, N-die Ruethylamino (meth) acrylate, N, N-dimethylethylamino (meth) acrylate, N, N-dimethylpropylamino (meth) acrylate, N, N-diethylpropylamino (meth) acrylate, vinylpyridine, aminomethylstyrene, croton Examples include acids, esters of crotonic acid, crotononitrile, vinylimidazole; and basic amine monomers can be polymerized as free amines, protonated salts, or quaternized amine salts. Where a monomer is indicated with a prefix in parentheses (eg, meta), it should be understood that this may be used in the form with or without methyl substitution, or that an alternative alkyl group may be present. For example, in the case of acrylic acid, methacrylic acid or another derivative such as ethacrylic acid can be used.

  Preferably, the non-hydrocarbon alkene-containing monomer is acrylic acid, acrylonitrile, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacrylic acid, methyl methacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, methacrylic acid. Selected from the group consisting of ethyl and n-butyl methacrylate. In the case of copolymers of acrylic acid, methacrylic acid or crotonic acid, the resulting copolymer may exist as an adduct reacted in the form of a five-membered lactone ring.

  In a further alternative preferred embodiment of the invention, P represents a copolymer of vinyl alcohol and acetoacetoxyethyl methacrylate.

  In yet another alternative preferred embodiment of the invention, P represents a copolymer of diacetone acrylamide and vinyl alcohol.

  As used herein, the term “reactive coupling group” means any chemical group attached to a polymer backbone that can form a bond with an aminosilane and / or aminosilanol-containing side chain.

In a preferred embodiment of the invention, the reactive coupling group comprises a ketone or ketoester containing functional group, preferably a ketoester containing functional group. More preferably, the reactive coupling group comprises a ketoester-containing functional group that can be derived from an acetoacetylating agent such as diketene, diketeneacetone adduct and / or tert-butyl acetoacetate. Most preferably, the ketoester-containing functional group comprises the moiety —O (CO) CH—C (CH ₃ ) ═O.

  In a further preferred embodiment of the present invention, the ketone or keto ester-containing functional group is present in an amount of about 1 to about 25 mol%, such as about 2 to about 15 mol%, preferably about 3 to about 8 mol% of the polymer backbone.

The polymer side chain R comprises at least one primary amine group capable of reacting with the reactive coupling group (s) present in the polymer main chain, and at least one silanol group (Si-OH) or silanol Derived from amino silanes containing a precursor group for e.g. alkoxysilanes or aryloxysilanes. In a preferred embodiment of the present invention, the side chain R has the general formula (II)
(Where
R ₁ , R ₂ and R ₃ independently represent H, C _1-9 alkyl, aryl, C _1-9 alkoxy or aryloxy, provided that at least one of R ₁ , R ₂ or R _{3 Represents a} C _1-9 alkoxy or aryloxy group,
x is in the range of 0-9, preferably 0-2,
y is in the range of 1-9, preferably 2-6)
Derived from the compound

In a preferred embodiment of the invention, x is 0, 1 or 2 and y is 3. In a further preferred embodiment of the invention, at least two of R ₁ , R ₂ and R ₃ independently represent C _1-9 alkoxy, preferably selected from the group consisting of methoxy, ethoxy, propoxy and butoxy Is done.

  In a more preferred embodiment of the present invention, the side chain R has the following compounds: aminoethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltripropoxysilane, 2- Aminoethyltributoxysilane, 1-aminoethyltrimethoxysilane, 1-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyl Tributoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyl-3-aminopropyldiethylethoxysilane ethyldiethoxysilane, 3-aminopropylmethyldipropo Sisilane, 3-aminopropylethyldipropoxysilane, 3-aminopropylpropyldipropoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropyldimethylpropoxy Silane, 3-aminopropyldiethylpropoxysilane, 3-aminopropyldipropylpropoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminopropyltributoxysilane 1-aminopropyltrimethoxysilane, 1-aminopropyltriethoxysilane, 1-aminopropyltripropoxysilane, 1-aminopropyltributoxysila N-aminomethylaminomethyltrimethoxysilane, N-aminomethylaminomethyltripropoxysilane, N-aminomethyl-2-aminoethyltrimethoxysilane, N-aminomethyl-2-aminoethyltriethoxysilane, N-amino Methyl-2-aminoethyltripropoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane, N-aminomethyl-3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltripropoxysilane, N -Aminomethyl-2-aminopropyltrimethoxysilane, N-aminomethyl-2-aminopropyltriethoxysilane, N-aminomethyl-2-aminopropyltripropoxysilane, N-aminopropyltrimethoxysilane, N-aminopropyl Trier Toxisilane, N- (2-aminoethyl) -2-aminoethyltrimethoxysilane, N- (2-aminoethyl) -2-aminoethyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltri Propoxysilane, N- (2-aminoethyl) -aminoethyltrimethoxysilane, N- (2-aminoethyl) -1-aminoethyltriethoxysilane, N- (2-aminoethyl) -1-aminoethyltripropoxy Silane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltripropoxysilane, N- (3-aminopropyl) -2-aminoethyltri Methoxysilane, N- (3-aminopropyl) -2-aminoethyltriethoxysilane, N- (3-aminopropyl ) -2-Aminoethyltripropoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, 3-diethylene 3-diethylenetriaminepropyltriethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) ) Propyl] triethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] tripropoxysilane and / or trimethoxysilylpropyldiethylenetriamine.

Even more preferably, the side chain R is the following compound (a) 3-aminopropyltrimethoxysilane (APMES)

(B) 3-Aminopropyltriethoxysilane (APTES)

(C) N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane (ETAPMS)

(D) N- (2-aminoethyl) -3-aminopropyl-triethoxysilane (ETAPES)

(E) 3- [2- (2-Aminoethylamino) ethylamino] propyltrimethoxysilane (DETAPMS)

(F) 3- [2- (2-Aminoethylamino) ethylamino] propyltriethoxysilane (DETAPES)

And (g) 3-aminopropylmethyldimethoxysilane (APMS)
Derived from one or more of the following:

  Most preferably, the side chain R is 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, or 3- [2- (2-aminoethylamino) ethylamino]. Derived from propyl-triethoxysilane.

  Those skilled in the art will appreciate that suitable hydrazine or hydrazide functionalized aminosilanes may also be used in accordance with the present invention.

  In a preferred embodiment of the present invention, the side chain R is present in an amount of about 2 to about 15 mol%, more preferably about 3 to about 8 mol% of the polymer backbone. Alternatively, excess aminosilane and / or aminosilanol may be used during polymer synthesis in conjunction with the reactive coupling groups present (eg, ketones). In such cases, some of the aminosilane and / or aminosilanol may exist in a non-reactive form and therefore may not be bound to the polymer backbone.

  In an alternative preferred embodiment of the present invention, the side chain R is in an amount of about 25 to about 200 mol%, such as an amount of about 50 to about 150 mol%, based on the amount of reactive coupling groups present in the polymer backbone. , Preferably in an amount of about 75 to about 125 mol%.

  Surprisingly, by carefully adjusting the ratio of reactive coupling groups (eg ketoester groups) to polymer backbone and / or aminosilane side chains to reactive coupling groups, the corresponding unmodified polymer ( That is, it has been found that superior adhesion of the resulting polymer to the substrate can be obtained when compared to polymers that do not contain aminosilane functionalization. This advantageously corresponds to the fact that films comprising the polymer of the invention cast on a substrate can be immersed in water and retain their adhesion and rapidly lose under such conditions. In contrast to unmodified polymers.

  In a preferred embodiment, the polymers of the present invention are substantially free of acetic acid and alkali metal salts thereof such as sodium acetate. Preferably, neither acetic acid nor its metal salt is added to aid crosslinking.

According to a further aspect of the present invention, there is provided a process for preparing a functionalized vinyl alcohol homopolymer or copolymer of the type described above,
a. Preparing a linear or branched homopolymer of vinyl acetate or a copolymer of vinyl acetate and at least one other monomer;
b. Hydrolyzing the vinyl acetate homopolymer or copolymer of step (a) to obtain a homopolymer or copolymer of vinyl alcohol;
c. Reacting the vinyl alcohol homopolymer or copolymer of step (b) with a suitable reactive coupling agent to obtain a vinyl alcohol homopolymer or copolymer comprising one or more reactive coupling groups;
d. Reacting the resulting vinyl alcohol homopolymer or copolymer containing one or more reactive coupling groups of step (c) with a suitable aminosilane and / or aminosilanol;
e. Optionally, isolating the copolymer thus formed.

  The polymer obtained at the completion of each reaction detailed in steps (a) to (d) of the above method may be isolated prior to the start of the following steps or reacted in situ.

  According to one embodiment of step (a) of the above method, vinyl acetate is reacted with at least one other monomer to obtain a linear or branched vinyl acetate copolymer. Thereafter, according to step (b), the copolymer of vinyl acetate is hydrolyzed to obtain a copolymer of vinyl alcohol. As an example, ethylene may be copolymerized with vinyl acetate to obtain an ethylene-vinyl acetate copolymer, as described below, which is then hydrolyzed to form an ethylene-vinyl alcohol copolymer (EVOH). May be.

  Alternatively, according to a further embodiment of step (a) of the above method, vinyl acetate is polymerized to obtain a linear or branched vinyl acetate homopolymer, ie poly (vinyl acetate). Thereafter, according to step (b), the homopolymer of vinyl acetate is hydrolyzed to poly (vinyl alcohol) as described below.

  It will be appreciated that PVOH may also be prepared by hydrolysis of other poly (vinyl esters) such as poly (vinyl formate), poly (vinyl benzoate) or poly (vinyl ether). Similarly, copolymers of vinyl alcohol, such as EVOH, can also be prepared by copolymerizing related monomers and vinyl esters other than vinyl alcohol, for example, by hydrolyzing the resulting polymer. Such polymers are also within the scope of the present invention.

  It can be seen that in step (b) of the process, the numerous vinyl acetate groups present may remain unhydrolyzed in the resulting polymer. In a preferred embodiment of the present invention, step (b) comprises partial hydrolysis of a vinyl acetate homopolymer or copolymer, such as during about 25 to about 100% hydrolysis, more preferably from about 50 to about 100. % Hydrolysis, even more preferably between about 70 and about 100% hydrolysis, most preferably between about 80 and about 100% hydrolysis.

  Poly (vinyl alcohol) s suitable for use in the method of the invention are commercially available (thus eliminating steps (a) and (b) of the method) or prepared by conventional synthetic methods. May be.

Thus, in one preferred embodiment, the method of the present invention comprises:
c. Reacting a vinyl alcohol homopolymer or copolymer with a suitable reactive coupling agent to obtain a vinyl alcohol homopolymer or copolymer comprising one or more reactive coupling groups;
d. Reacting the resulting vinyl alcohol homopolymer or copolymer containing one or more reactive coupling groups of step (c) with a suitable aminosilane and / or aminosilanol;
e. Optionally isolating the copolymer thus formed.

  For example, poly (vinyl alcohol) is commercially available from Nippon Gohsei under the trade name Gohsenol (TM) or from Kuraray under the trade name Poval (TM). Suitable copolymers of vinyl alcohol (eg, EVOH) for use in the methods of the invention are commercially available or may be prepared by conventional synthetic methods. For example, copolymers of ethylene and vinyl alcohol are commercially available from Kuraray under the trade name Exceval ™ and from Gohsei under the trade name Soarnol ™.

  According to step (c) of the method, a homopolymer or copolymer of vinyl alcohol is reacted with a suitable reactive coupling agent to obtain a copolymer of vinyl alcohol containing one or more reactive coupling groups. Step (c) is typically inert to both the appropriate solvent (ie, both the homopolymer or copolymer of vinyl alcohol and the reactive coupling agent). Solvent) such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or dimethylacetamide (DMAc) at an elevated temperature in the range of about 90-190 ° C, for example about 135 ° C.

  As an alternative to carrying out the reaction of step (c) with the reactant dissolved in the solvent, this step of the method can be carried out in the concentrated phase or by using essentially solvent-free methods. By way of example, US Pat. No. 5,719,231 describes the reaction of an acetoacetate forming composition with a vinyl alcohol-based polymer in the solid phase by spraying the acetoacetate forming composition onto a solid polymer at an elevated temperature. Similar methods can be used in the present invention.

  Alternatively, a polymer paste or dispersion in a solvent such as water or a dipolar aprotic solvent, or a non-solvent such as an organic acid may be made. As an example, acetic acid may be adsorbed, sprayed or mixed with a polymer of vinyl alcohol prior to reacting with diketene (in a manner similar to that described in JP-A-9291185). Alternatively, a paste of vinyl alcohol polymer in water may be made by mixing the polymer and water, optionally mixed at an elevated temperature, and stirring at high strength, or an existing solution of the polymer under vacuum, for example. May be made by concentrating. Functionalization can be performed using a polymer dispersed or suspended in a liquid medium that is a good solvent for the acetoacetylating agent. By way of example, the polymer can be dispersed in a hydrocarbon solvent, such as hexane, or an organic acid, such as acetic acid and diketene, added to the mixture. After the reaction of the acetoacetylating agent with the polymer, the liquid can be separated by filtration and, optionally, can be reused in methods that take advantage of the higher efficiency provided thereby. Solvent / dispersion media such as unreacted acetoacetylating agent or acid may be removed by evaporation or may be removed by washing it from the material with a suitable solvent.

  It can be seen that in the process of reacting the polymer as a solid, the particle size and shape of the granulated or powdered polymer is important. The smaller particle size advantageously results in a larger surface area that allows a more efficient reaction with the acetoacetylating agent. As a result, a product with a more uniform degree of ketoester functionality or, if desired, a greater degree of functionality may be obtained. It will be appreciated that the reaction process may be performed using any number of devices that can provide sufficient mixing. These may include reactors or other vessels, in which case the agitation is carried out by means of an overhead stirrer, magnetic stirrer, most preferably the mixing is carried out with a suitable extruder, z-blade mixer, batch mixer, U Trough mixer, RT mixer, blender, internal mixer, Banbury mixer, 2-roll mill, Brabender mixer, wide blade mixer (or hydrofoil blade mixer), horizontal (delta or spiral) blade mixer, kneader This is accomplished using a reactor, or a related variation of one of these mixers, such as a double z-blade mixer or a twin screw extruder. The heat introduced into the system may be supplied by conventional means or from microwave radiation.

  Preferably, the reactive coupling group comprises a ketone or keto ester containing functional group, more preferably a keto ester containing functional group. Suitable reagents capable of generating ketoester (or acetoacetate) groups are commercially available and are collectively referred to as acetoacetylating agents. In a preferred embodiment of the invention, the reactive coupling group comprises a ketoester-containing functional group derived from an acetoacetylating agent. Preferred commercially available acetoacetylating agents include diketene (DK), diketene acetone adduct (DKAA), and alkyl acetoacetates such as tert-butyl acetoacetate (t-BAA):

  DK and DKAA are important acetoacetylating agents that find wide utility and are suitable for use in the present invention.

  Both DK and DKAA have some problems with their long-term stability that can make transport more difficult, especially in the case of DK. Degradation of the active ketoester functionalization means that many acetoacetylating agents are somewhat below 100%, such as 95%, 90% or lower grades and are probably supplied in a fading manner.

  A particularly preferred acetoacetylating agent is t-BAA. Other alkyl acetoacetates may also be used in the present invention; examples include methyl acetoacetate, ethyl, n-propyl, iso-propyl, or n-butyl, t-pentyl. When alkyl acetoacetate is used as the acetoacetylating agent, it is an optional aspect of the present invention that the reactor is designed to vent the alcohol discharged from the system.

  Prior to use, the acetoacetylating agent may optionally be purified to facilitate a more efficient reaction and / or to obtain a purer end product. Suitable purification methods are known in the art. As an example, DKAA may be purified by dissolving DKAA in acetone, followed by the addition of a hydrocarbon solvent such as hexane and precipitating some or all of the impurities as a solid, separating pure DKAA, It can be concentrated. Alternatively, the acetoacetylating agent may be purified by distillation.

  In general, it is considered in the art that the reaction between DKAA and alcohol proceeds via an acetylketene intermediate while eliminating acetone (for example, “Acetic Acid and its Derivatives”, Victor H Edited by Agreda and Joseph R. Zoeller, see Marcel Dekker Inc., New York, USA). The resulting acetylketene exists in equilibrium with DKAA, so that we have a stabilizing effect on DKAA in which the presence of excess acetone slows the rate of acetylketene formation and acetoacetylation. Predicted to get. The inventors have found that good results are generally obtained when acetone is removed from the reactor system used to acetoacetylate the polymer. When DKAA is used as the acetoacetylating agent, it is a preferred embodiment of the present invention that the reactor is configured to exhaust any produced acetone.

  t-BAA is an example of a particularly preferred acetoacetic acid alkyl acetoacetylating agent. Many alkyl acetoacetates can be used as simple acetoacetylating agents, and as a result can give potential in the functionalization of polymers with ketoester groups. These involve the formation of ketoester groups by a transacetoacetylation process and the formation of alcohols that can establish equilibrium with the reactants. In the case of t-BAA, the process thus results in the removal of tert-butanol. As an alternative to t-BAA, any other alkyl acetoacetate such as methyl acetoacetate, ethyl, n-propyl, iso-propyl, or n-butyl, t-pentyl may be used. Sterically hindered esters such as t-butyl or t-pentyl groups (synonymously t-amyl groups) react significantly faster than less sterically hindered esters such as methyl acetoacetate or ethyl, but the identity of the alcohol Depending on the production of alcohol by-products with higher boiling points. When alkyl acetoacetate is used as the acetoacetylating agent, it is an optional aspect of the present invention that the reactor is designed to vent alcohol that has been excluded from the system.

In a preferred embodiment of the present invention, the ketoester-containing functional group comprises the moiety —O (CO) CH—C (CH ₃ ) ═O. As an example, ketoester functionalized poly (vinyl alcohol) (PVOH-KE) can be prepared according to the method of the present invention as follows.

  Alternatively, a ketoester functionalized ethylene-vinyl alcohol copolymer (EVOH-KE) can be prepared according to the method of the present invention as follows.

  Ketoester functionalized homopolymers and copolymers of vinyl alcohol of the type prepared in step (c) can also be prepared using alternative known methods. In one embodiment, a monomer comprising a suitable alkene having an acetoacetic acid group may be grafted to the vinyl alcohol copolymer by a radical mechanism. For example, acetoacetoxyethyl methacrylate (AAEM), commercially available from Eastman Company, may be combined with a vinyl alcohol polymer and a suitable radical initiator such as an azo or peroxide compound in solution or dispersion. Alternatively, a monomer containing a suitable alkene with an acetoacetate base may be copolymerized with vinyl acetate or another vinyl ester, and the resulting polymer may be selectively hydrolyzed. Such a method constitutes an alternative embodiment of the method of the present invention.

  According to step (d) of the process, a homopolymer or copolymer of vinyl alcohol containing one or more reactive coupling groups obtained in step (c), for example EVOH-KE or PVOH-KE, is converted to a suitable aminosilane. And / or reacting with aminosilanol. The amino group of the aminosilane reacts with a reactive coupling group (eg, a ketoester group) on the polymer backbone to form a secondary amine, for example as follows.

The aminosilane may be used in non-hydrolyzed form or may be hydrolyzed in water before being added to the polymer. Preferably, the solvent used in step (d) is a polymer backbone, and the resulting aminosilane functionalized polymer has good solubility in, for example, water or a dipolar aprotic solvent such as DMF or DMSO It is. In a preferred embodiment of the invention, the reaction is of one or more such solvents and another miscible solvent such as an alcohol (eg methanol, ethanol, n-propanol or iso-propanol, preferably n-propanol). Performed in the mixture. In one embodiment of the present invention there is provided a composition comprising the functionalized poly (vinyl alcohol) or vinyl alcohol copolymer of the present invention and water or a mixture of water and C _1-4 alcohol. Such compositions are preferably free of acid catalyst and may be used to prepare coatings comprising functionalized homopolymers and copolymers of the vinyl alcohol of the present invention.

  The aminosilanes and aminosilanols used in the present invention are commercially available and / or can be prepared by conventional synthetic methods.

  3-aminopropyltrimethoxysilane is commercially available from Sigma-Aldrich, commercially available from Power Chemical Corporation under the trade name PC1110 ™, and commercially available from Onichem under the trade name A301 ™.

  3-aminopropyltriethoxysilane is commercially available from Sigma-Aldrich, commercially available from Wacker Chemie under the trade name Geniosil GF 93 ™, and from Gelest under the trade name SIA0610.0 ™. .

  N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is commercially available from Evonik under the trade name Dynasylan DAMO ™ and from Dow Corning under the name Z-6094 Silane ™. .

  3- [2- (2-Aminoethylamino) ethylamino] propyltrimethoxysilane is commercially available from UCT under the trade name T2910 (TM) and from Evonik under the trade name Dynasylan TRIAMO (TM). .

  3- [2- (2-Aminoethylamino) ethylamino] propyltriethoxysilane is commercially available from Tianjin Zhongxin.

  3-Aminopropylmethyldimethoxysilane is commercially available from Power Chemical Corporation under the trade name SiSiB PC1130 ™.

  It is often observed that the addition of aminosilane to the polymer (backbone) solution results in an increase in viscosity that can lead to undesirable gelling of this system. Typically, the gel strength has been found to increase with increasing amounts of ketoester and aminosilane. Without being bound by theory, it is believed that this gelation is the result of complex formation of the polymer backbone, aminosilane and / or the reaction product of both, or some intermediate species.

  Surprisingly, it has been found that the maximum viscosity encountered in the method, ie the degree of gelation in the method, can be very controlled by adjusting some process variables. Thus, in a preferred embodiment, step (d) of the method comprises either a solution of a homopolymer or copolymer of vinyl alcohol containing one or more reactive coupling groups, or more preferably a polymer in solid form, This is done by adding to the appropriate aminosilane and / or aminosilanol solution. In a further preferred embodiment, the reaction mixture obtained after step (d) of the process is in the range of about 0 to about 100 ° C, preferably in the range of about 40 to about 95 ° C, more preferably about 60 to about 90 ° C. Heat to a temperature in the range. In a still further preferred embodiment, the reaction mixture obtained after step (d) is treated with an acid, for example a mineral acid such as HCl or an organic acid such as acetic acid. In an even more preferred embodiment, the reaction mixture obtained after step (d) is treated with carbon dioxide. Optionally, step (d) may be performed under an inert gas such as nitrogen.

  The functionalized vinyl alcohol polymer of the present invention may optionally be isolated from the solution by conventional means such as evaporation or spray drying.

  In an alternative embodiment of the present invention, aminosilane and / or aminosilanol can be combined with the functionalized polymer backbone in the absence of a solvent such as water. As an example, a ketoester functionalized homopolymer or copolymer of vinyl alcohol may be mixed with an aminosilane in the absence of a solvent at an elevated temperature at which the polymer may be a melt. One skilled in the art will recognize that this method may be performed using any number of devices capable of providing sufficient mixing. These may include reactors or other vessels, in which case the agitation is carried out by means of an overhead stirrer, magnetic stirrer, most preferably the mixing is carried out with a suitable extruder, z-blade mixer, batch mixer, U Trough mixer, RT mixer, blender, internal mixer, Banbury mixer, 2-roll mill, Brabender mixer, wide blade mixer (or hydrofoil blade mixer), horizontal (delta or spiral) blade mixer, kneader This is accomplished using a reactor, or a related variation of one of these mixers, such as a double z-blade mixer or a twin screw extruder. As an alternative to conducting the reaction with the polymer, the polymer may be dispersed in a medium that does not dissolve the polymer. Any heat introduced into the system may be supplied by conventional means or from microwave radiation.

  According to a further aspect of the present invention there is provided a functionalized homopolymer or copolymer of vinyl alcohol obtainable or obtained by the method described above.

The vinyl alcohol functionalized homopolymers and copolymers of the present invention contain one or more silanol (Si-OH) groups. The silanol group of aminosilanol has the following general formula:
_{2T-Si (T 2) -OH} → T-Si (T 2) -O-Si (T 2) -T + H 2 O
Where T is any suitable functional group such as alkyl, H, OH or alkoxy.
Are known to be cross-linked to form a Si-O-Si network.

  This type of cross-linking can be useful in the preparation of protective (barrier) coatings, since the resulting polymer typically provides increased resistance to abrasion, particularly in the presence of a solvent in which the polymer is soluble. . However, it has previously been suggested that the addition of an acid catalyst under heating is required to achieve substantial crosslinking. The use of such catalysts negatively affects the resulting coatings in terms of their performance (any free acid can lead to reduced barrier performance) or aesthetic appearance from a visual or odor perspective. There is a possibility of effect.

This time, surprisingly, the general formula (III)
(Where
R ₁ , R ₂ and R ₃ are as defined above for formula (II);
x is in the range of 2-9, preferably x is 2,
y is in the range of 3-9, preferably y is 3.
It has been found that homopolymers and copolymers of vinyl alcohol when functionalized with certain aminosilanes are easily cross-linked by heating to form a resistant coating without the addition of an acid catalyst. .

Accordingly, in a further aspect of the invention, a method for preparing a crosslinked polymer coating comprising two or more aminosilanes and / or aminosilanol side chains of formula (III) in the absence of an acid catalyst A method is provided comprising the step of heating the polymer. Preferably, the polymer is of the formula P- (R) _n , where P is as defined above and R is derived from an aminosilane or aminosilanol of formula (III) as described above. Preferably, the polymer is heated to a temperature of about 80 to about 120 ° C, more preferably about 100 ° C. Preferably, the polymer comprising two or more amino side chains of formula (III) is a homopolymer or copolymer of a linear or branched vinyl alcohol of the type defined in formula (I) herein. It has a main chain P. The present invention also provides a cross-linked polymer coating obtainable from such a method.

  The vinyl alcohol functionalized homopolymers and copolymers of the present invention can be used in a wide range of commercial applications where they can form films or layers or which are components of films or layers. These include various coating applications, including inks and adhesives, such as architectural, decorative, industrial, automotive, aviation, marine operational protection and functional coatings; newspaper and magazine printing Inks for home use, printing solutions for household and commercial use; adhesives or sealants for consumer and industrial use. There are many forms and methods for delivering such coatings, e.g., architectural coatings for home and industrial use may be applied in the form of paint, or the surface may be cleaned. It is understood that it may be distributed from a multifunctional composition designed to apply a coating. The coating may be applied to the human or other animal body (eg, cosmetics or pharmaceuticals). The adhesive may also take the form of a coating between two surfaces that functions as a sealant in machine assembly, for example. The polymer may act as a binder in formulations of the type described herein. In a preferred embodiment of the present invention, the use of a functionalized homopolymer or copolymer of vinyl alcohol of the present invention as a coating in a composite film structure is provided. Also provided is a coating comprising a functionalized homopolymer or copolymer of vinyl alcohol according to the present invention. It will be appreciated that coating compositions comprising the vinyl alcohol functionalized homopolymers and copolymers of the present invention may optionally include a number of other ingredients suitable for use in the composition. These components include, as non-limiting examples, dyes, preservatives, wetting agents, surfactants, dispersants, open time extenders, and the like.

Figure 2 shows the bond strength of oriented polyamide (OPA) and polyethylene (PE) laminates using a variety of different polymers.

  The following non-limiting examples illustrate the invention.

PVOH-KE series materials Mowiol (TM) 4-98 (M4-98 (TM)) and Exceval (TM) AQ-4104 (AQ-4104 (TM)) were obtained from Kuraray and used as supplied . Gohsenol ™ GH-17R (GH-17R ™) was supplied by Nippon Gohsei and used as supplied. PVOH grade viscosity is typically expressed in MPas and is measured using a Brookfield viscometer by recording the relevant value of a 4% solution maintained at 20 ° C. M4-98 ™ is a poly (vinyl alcohol) having a viscosity of 4.0 to 5.0 MPas and a degree of hydrolysis of 98.0 to 98.8%. AQ-4104 (trademark) has a viscosity of 3.8 to 4.5 MPas and a hydrolysis degree of 98.0 to 99.0%, vinyl alcohol (85 to 90 mol%) and ethylene (10 to 15 mol%). ). GH-17R (TM) is a poly (vinyl alcohol) having a viscosity of 27-33 MPas and a degree of hydrolysis of 86.5-89.0%.

  3-Aminopropyltrimethoxysilane (APMES) and 3-aminopropyltriethoxysilane (APTES) were obtained from Sigma-Aldrich and used as supplied. N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane (ETAPMS) was obtained from Evonik under the trade name Dynasylan ™ DAMO. 3- [2- (2-Aminoethylamino) ethylamino] propyl-trimethoxysilane (DETAPMS) was obtained as T2910 from UCT and used as received. 3- [2- (2-Aminoethylamino) ethylamino] propyl-triethoxysilane (DETAPES) was obtained from Tianjin Zhongxin and used as received.

  Anhydrous dimethyl sulfoxide (DMSO) and acetic acid were used as supplied by Sigma Aldrich. Acetone was standard laboratory grade and was used without further preparation. 2,2,6-trimethyl-4H-1,3-dioxin-4-one (diketenacetone adduct, DKAA) from Sigma Aldrich, Lonza quality (> 93.0%) or Aldrich (> 95.0%) And purified by the methods outlined below before use. Diketene (DK) and tert-butyl acetoacetate (t-BAA) were obtained from Sigma Aldrich and used as received.

Purification method of DKAA DKAA is supplied by Sigma Aldrich as a dark brown liquid. Prior to use in the ketoester grafting process, impurities were removed from DKAA by selective precipitation to prevent contamination of the polymer with brown impurities.

  Hexane (2 L) was charged into a large beaker. DKAA (100 g, 0.703 mol) was added to the beaker with stirring from an overhead stirrer equipped with a PTFE anchor type stirring shaft. DKAA is not miscible with hexane.

  Acetone was added dropwise until the solution turned yellow and a small amount of brown tar precipitated at the bottom of the beaker. The solution was gently transferred to a clean beaker leaving an oil behind, and then the oil was discarded. Subsequently, the solution was passed through a Buchner filter and transferred to a pear-shaped Buchi flask. Hexane and acetone were removed from the solution by rotary evaporation at 40 ° C. to give a yellow / orange liquid.

  This liquid was added to a portion (2 L) of fresh hexane and the above process was repeated. After removal of hexane and acetone, the temperature of the rotary evaporator water bath was raised to 50 ° C. and maintained for 1 hour (pressure <50 mbar) to ensure evaporation of all solvents.

Synthesis Method of Ketoester Functionalized Polymer Main Chain PVOH-KE1
M4-98 ™ (60.0 g) and DMSO (540.0 g) were charged to a 1 L flange flask. The flask was equipped with an overhead stirrer equipped with a PTFE anchor stirrer shaft and placed under a nitrogen blanket. Using an oil bath, the flask was heated to an external temperature of 135-145 ° C. to completely dissolve M4-98 ™. Next, the internal temperature of the flask was adjusted to 120 ° C.

  Purified DKAA (14.5 g, 0.102 mol) was added dropwise over 1 hour. One end of the flange flask was opened, and the acetone produced during the acetoacetylation process was released. The flask temperature was maintained at 120 ° C. for an additional hour before the flask was cooled to ambient temperature.

  The polymer was precipitated in acetone (2 × 50 mL DMSO solution to 1 L acetone) and dried under vacuum (<50 mbar) at 50 ° C. for 24 hours. This polymer was redissolved in water to obtain a 10 w / w% solution. Again, the polymer was precipitated in acetone (2 × 50 mL aqueous solution to 1 L acetone) and dried under vacuum (<50 mbar) at 50 ° C. for 48 hours.

PVOH-KE2
The polymer was prepared in exactly the same way as described for PVOH-KE1. However, the filling level of DKAA was set to 30.0 g and 0.211 mol rather than 14.5 g and 0.102 mol.

PVOH-KE3
The polymer was prepared in exactly the same way as described for PVOH-KE1. However, the filling level of DKAA was 41.6 g and 0.293 mol rather than 14.5 g and 0.102 mol.

PVOH-KE4
M1-98 (50.0 g) and DMSO (450.0 g) were charged to a 1 L flange flask. An overhead stirrer equipped with a PTFE anchor stirrer shaft was attached to the flask, and nitrogen was constantly flowed. Using an oil bath, the flask was heated to an external temperature of 135-145 ° C. to completely dissolve M4-98. Next, the internal temperature of the flask was adjusted to 120 ° C.

  Purified DKAA (64.5 g, 0.454 mol) was added dropwise over 1 hour. One end of the flange flask was opened, and the acetone produced during the acetoacetylation process was released. The flask temperature was maintained at 120 ° C. for an additional hour before the flask was cooled to ambient temperature.

  The polymer was precipitated in toluene (600 mL DMSO solution to 2.5 L toluene) and dried at 50 ° C. overnight under vacuum (<50 mbar). The polymer was redissolved in methanol (250 mL), precipitated into acetonitrile (80 mL of methanol solution per 800 mL of acetonitrile) and dried under vacuum (<50 mbar) for 24 hours.

PVOH-KE5
AQ-4104 (55.0 g) and DMSO (495.0 g) were charged to a 1 L flange flask. An overhead stirrer equipped with a PTFE anchor stirrer shaft was attached to the flask, and nitrogen was constantly flowed. Using an oil bath, the flask was heated to an external temperature of 135-145 ° C. to completely dissolve AQ-4104. Next, the internal temperature of the flask was adjusted to 120 ° C.

  Purified DKAA (3.55 g, 0.025 mol) was added dropwise over 1 hour. One end of the flange flask was opened, and the acetone produced during the acetoacetylation process was released. The flask temperature was maintained at 120 ° C. for an additional hour before the flask was cooled to ambient temperature.

  The polymer was precipitated in acetone (2 × 50 mL DMSO solution to 1 L acetone) and dried under vacuum (<50 mbar) at 50 ° C. for 24 hours. This polymer was redissolved in water to obtain a 10 w / w% solution. Again, the polymer was precipitated in acetone (2 × 50 mL aqueous solution to 1 L acetone) and dried under vacuum (<50 mbar) at 50 ° C. for 48 hours.

PVOH-KE6
The polymer was prepared in exactly the same way as described for PVOH-KE5. However, the filling level of AQ-4104 is 60.0 g rather than 55.0 g, the filling level of DMSO is 540.0 g rather than 495.0 g, and the filling level of DKAA is 3.55 g, 0.025 mol. Rather, it was set to 16.5 g and 0.116 mol.

PVOH-KE7
The polymer was prepared in exactly the same way as described for PVOH-KE6. However, the filling level of DKAA was 8.30 g, 0.058 mol rather than 16.5 g, 0.116 mol.

PVOH-KE8
The polymer was prepared in exactly the same way as described for PVOH-KE6. However, the filling level of DKAA was 26.40 g and 0.186 mol rather than 16.5 g and 0.116 mol.

  Diketene is used to graft the ketoester functional group onto the PVOH backbone. The initial goal is to functionalize 25% of the alcohol groups.

Preparation of PVOH-KE sample using DK M4-98 ™ (5.0 g, 0.1134 mol) was dissolved in DMSO (45.0 g) at 100 ° C. with stirring. The flask was then cooled to an internal temperature of 60 ° C. DK (2.39 g, 0.0284 mol) was added dropwise over 1 hour. The reaction was left for 45 minutes before cooling to ambient temperature.

  The red / brown solution was precipitated into acetone (300 mL) and a pale yellow solid was collected by filtration. The polymer was then collected by filtration and cut into small pieces and stirred in acetone (300 mL) to extract impurities before drying at 50 ° C. under vacuum overnight. Finally, the polymer was subsequently redissolved in distilled water at 100 ° C. prior to reprecipitation in acetone (300 mL) and drying at 50 ° C. under vacuum overnight.

Preparation of PVOH-KE sample using t-BAA GH-17R ™ (50 g) was weighed and added to a flanged reactor flask to which DMSO (105 g) was added followed by t-BAA (20 g). Added. Finally, acetic acid (2.5 g) was added. The flask was equipped with an overhead stirrer and condenser and the contents were placed under a nitrogen blanket. The reaction mixture was then stirred and heated using an oil bath maintained at 130 ° C. for 3 hours. After this time, the reaction mixture was allowed to cool to ambient temperature. This is subsequently precipitated in acetone by adding two equal sized aliquots to acetone (1 L), and the precipitate formed from the first aliquot liquid is filtered by vacuum filtration prior to addition, The second aliquot was then filtered. The resulting white fibrous product was dried at 50 ° C. under vacuum overnight.

Functionalization with Aminosilane A stock solution of APTES was made by simply adding aminosilane to water with stirring and allowing the mixture to stand for a minimum of 24 hours. This solution was then used in the following exemplary formulation.
% W / w
1. Deionized water 56.59
2. 25% w / w APTES (aqueous solution) 8.55
3. PVOH-KE6 7.86
4). Ethanol 27.00
100.0

  Subsequently, aminosilane and PVOH-KE6 were mixed together in one of the two different methods outlined below.

Method A-No pH modification:
Add 1 and 2 to the mixing vessel and stir to make a uniform solution with pH 11. Add 3 with good agitation to prevent clump formation.
After 2-5 minutes, the mixture starts to gel, at which point the stirrer is turned off.
-Turn on the heat source, set the internal temperature to about 90 ° C, and leave it to heat. After a period of approximately 15-30 minutes, a liquid is observed as the gel begins to disintegrate.
• Restart the stirrer at this point (slowly initially) and, if feasible, with stirring (achieved on a laboratory scale, such as with a spatula) to help accelerate the final disintegration of the gel Disintegrate the gel.
Maintain agitation and heating until the gel is completely disintegrated.
• When completely dissolved, reduce internal temperature to about 70 ° C.
• Then slowly add 4 with stirring.
Allow to stir for 10 minutes and then cool to ambient temperature.

Method B-Method using carbon dioxide:
The basic blending method is modified to include carbon dioxide gas. In order to prevent or regulate the gelation process, CO ₂ gas was added to generate carbonic acid in situ. It remains essentially the same as in Basic Method A, except that carbon dioxide has been added to adjust the process viscosity.
Add 1 and 2 to the mixing vessel and stir to make a homogeneous solution. Next, CO ₂ was bubbled through the solution at 1 L / min through the sintered glass, resulting in a pH reduction from pH 11 to pH 7. The passage of gas was continued during the preparation of the formulation with the aim of maintaining a pH of 7.
Next, acetoacetylated polymer (3) is added to the formulation with sufficient agitation to prevent aggregation. Stirring is continued to dissolve the polymer, but it is necessary to raise the temperature to completely dissolve the polymer. During the heating process, the loss of carbon dioxide from the solution appears to cause at least some degree of gelation. It is our view that if the resulting mass can be kept moving at high temperature, it is possible to stir the mixture until the viscosity decreases. Next, ethanol (4) is added in a manner similar to that described for A.

  Various aminosilane functionalized homopolymers and copolymers according to the present invention by changing the ratio to aminosilane or by replacing APTES with eg APMS, ETAPMS, DETAPMS or DETAPES, or by using an alternative ketoester functionalized PVOH Can be prepared.

Experimental Results A series of vinyl alcohol ketoester functionalized homopolymers and copolymers were prepared by reaction of DKAA with various vinyl alcohol homopolymers and copolymers as follows.

  Mowiol ™ 4-98 (M4-98 ™) is PVOH sold by Nippon Gohsei, and AQ-4104 ™ is EVOH sold by Kuraray.

  In addition, a series of compositions are prepared by reaction of certain aminosilanes with commercially supplied ketoester functionalized polymers, or homopolymers of vinyl alcohol that are subsequently functionalized with an acetoacetylating agent as follows: Prepared from polymers and copolymers.

  Ketoester mol%: Ratio of repeating unit having ketoester (KE) functional group. At the 10% level, one tenth of the PVOH units in the polymer is KE functionalized.

  Crosslinker mol%: ratio of KE functional group to be reacted with aminosilane. At the 50% level, this means that half of the KE groups should react with the crosslinker.

  Z-200 ™ and OKS-3551 ™ (O3551) poly (vinyl alcohol) (PVA) functionalized with KE groups were obtained from Nippon Gohsei. All other polymer backbones include diketeneacetone adducts in DMSO solution with Mowiol 4-98 ™ (M4-98 ™, Kuraray) or Exceval ™ AQ-4104 (AQ-4104 ™ ), Kuraray). M4-98 ™ is a PVA with a viscosity of 4.0-5.0 MPas and a degree of hydrolysis of 98.0-98.8%. AQ4104 ™ is a PVA that contains about 14% ethylene, has a viscosity of 3.8-4.5 MPas, and a degree of hydrolysis of 98.0-99.0%. Sample AS 1G was prepared as a control without KE functionalized PVA.

  An estimate of the actual grafted KE functional group is obtained using FT-IR. The quoted values for AQ4104 ™ are equivalent to 100% vinyl alcohol material.

  In order to evaluate the adhesion of the vinyl alcohol functionalized homopolymers and copolymers of the present invention, films of these solutions were cast on a substrate representative of the packaging material and allowed to air dry. The packaging material contained oriented polyamide (OPA) and polyolefins such as polyethylene (PE) and polypropylene (PP) in a film format suitable for use in packaging laminates. The adhesive typically used in the construction of such laminates was then applied to the top of the aminosilane modified polymer layer and to an additional layer of film placed on top of it, and air bubbles were rubbed off from the laminate. . After the isocyanate adhesive was cured for a week, the resulting film was cut into strips for subsequent testing. Subsequently, the adhesion of the barrier layer was determined by examining the bond strength between the two laminates using a conventional T-peel test. This test involved measuring the force (Newton: N) required to separate the polymer film from the substrate by pulling two mechanically separated. Next, the force required to break apart a laminate constructed with the functionalized polymer of the present invention was compared to a similar laminate made with an unmodified ketoester functionalized polymer backbone. . The results obtained are summarized in FIG.

  As is apparent from FIG. 1, the addition of layers of unmodified poly (vinyl alcohol) polymer backbone M4-98 ™ and ketoester modified poly (vinyl alcohol) polymer backbone Z-200 ™ It was observed that the bond strength was not weakened. In contrast, polymers modified with aminosilanes maintained a similar and possibly greater degree of adhesion between laminate layers.

  A formulation was prepared in which the unmodified polymer backbone was mixed with the resulting adhesive of a laminate containing aminosilane (AS 1G) and the measured polymer. For amino groups, there is no group that attaches itself to the main chain, both exist as a mixture in solution, and the resulting laminate-to-sheet adhesion is very weak as expected. there were. In this example, the excellent adhesion of aminosilane functionalized homopolymers and copolymers of vinyl alcohol makes them usable in examples where no other barrier layer can be used.

  In general, unmodified homopolymer and copolymer vinyl alcohol films are susceptible to attack from or immersion in water. It has been unexpectedly found that reasonable levels of ketoester and aminosilane functionalization in the polymer backbone promote a significant increase in the adhesion of oriented polypropylene (PP) and polyethylene (PE) film laminates.

  Several different aminosilanes were mixed with ketoester poly (vinyl alcohol) samples obtained from Nippon Gohsei (OKS 3551 ™) and the films were cast on glass slides cured or dried at 100 ° C. The adhesion of the resulting coating was determined using ASTM test method number ASTM D5402-06, Method A using “Standard Practicing for Assessing the Solvent Resistance of Organic Coatings Using Solvent Rubs” with methyl ethyl ketone as water. Tested by exposure to solvent. According to this test method, the water-moistened cloth was rubbed back and forth along the polymer film by a human hand with an almost constant amount of force of 1-2 Kg. The number of rubs before and after needed to destroy the film was recorded. The results are summarized in the following table.

  Unmodified poly (vinyl alcohol) begins to dissolve essentially immediately upon contact with a damp cloth. In contrast, APTMS, APTES and ETAPMS modified PVOH were found to survive a little longer due to their more hydrophobic composition and increased adhesion. However, after several rubs under these harsh conditions, they also began to peel due to little or no crosslinking. The DETAPMS film cross-linked to a significant or substantial degree upon curing and, as a result, was able to withstand the test period (200 rubs). In some cases, therefore, the increased adhesion of the present invention can also benefit from cross-linking with aminosilanes having multiple repeating ethyleneamine units to obtain excellent mechanical adhesion.

  Various changes and modifications to the described embodiments of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. is there. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims.

Claims (37)

Formula (I)
P- (R) _n (I)
(Where
P represents a linear or branched polymer backbone that is a homopolymer of vinyl alcohol or a copolymer of vinyl alcohol and at least one other monomer, said homopolymer or copolymer comprising one or more reactive cups Including a ring group,
R represents an aminosilane and / or aminosilanol-containing side chain attached to the polymer via the reactive coupling group (s);
n represents the number of side chains present in an amount of about 1 to about 25 mol% of the polymer backbone;
However, when P represents a homopolymer of vinyl alcohol, R is not a side chain derived from 3-aminopropyltriethoxysilane)
A functionalized homopolymer or copolymer of vinyl alcohol.   The polymer of claim 1, wherein P represents poly (vinyl alcohol).   2. A polymer according to claim 1, wherein P represents a copolymer of vinyl alcohol and an olefin, such as ethylene or propylene, preferably ethylene.   4. The polymer of claim 3, wherein the olefin is present in an amount of from about 1 to about 50 mol%, such as from about 2 to about 40 mol%, preferably from about 5 to about 20 mol% of the copolymer backbone.   2. A polymer according to claim 1, wherein P represents a copolymer of vinyl alcohol and an alkene-containing monomer, preferably an acrylic or methacrylic monomer.   6. The polymer of claim 5, wherein the acrylic monomer is selected from the group consisting of acrylic acid, acrylonitrile and acrylamide.   6. The polymer of claim 5, wherein the methacrylic monomer is selected from the group consisting of methacrylic acid, methyl methacrylate, 2-hydroxyethyl acrylate, hydroxyl methacrylate, ethyl methacrylate and n-butyl methacrylate.   The copolymer of claim 1, wherein P represents a copolymer of vinyl alcohol and acetoacetoxyethyl methacrylate.   2. Copolymer according to claim 1, wherein the reactive coupling group comprises a ketone or ketoester containing functional group, preferably a ketoester containing functional group.   The copolymer of claim 9, wherein the reactive coupling group comprises a ketoester-containing functional group derived from an acetoacetylating agent.   11. Copolymer according to claim 10, wherein the acetoacetylating agent is diketene, diketene acetone adduct or alkyl acetoacetate, such as methyl acetoacetate, ethyl, tert-butyl or tert-pentyl. Ketoester containing functional group comprises a moiety -O (CO) CH-C ( CH 3) = O, The copolymer of claim 10 or 11.   13. The ketone or ketoester-containing functional group is present in an amount of about 1 to about 50 mol%, such as about 2 to about 15 mol%, preferably about 3 to about 8 mol% of the polymer backbone. The copolymer according to item. The side chain R is represented by the general formula (II)
(Where
R ₁ , R ₂ and R ₃ independently represent H, C _1-9 alkyl, aryl, C _1-9 alkoxy or aryloxy, provided that at least one of R ₁ , R ₂ or R _{3 Represents a} C _1-9 alkoxy or aryloxy group,
x is in the range of 0-9, preferably 0-2,
y is in the range of 1-9, preferably 2-6)
14. A copolymer according to any of claims 1 to 13 derived from the compound of   The copolymer of claim 14, wherein x is 0, 1 or 2, and y is 3. R _1, R ₂ and of R ₃ at least two, independently, represent C _1-9 alkoxy, preferably methoxy, ethoxy, propoxy, and butoxy, according to claim 14 or 15 Copolymer.   The side chain R is the following compound: aminoethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltripropoxysilane, 2-aminoethyltributoxysilane, 1-amino Ethyltrimethoxysilane, 1-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, 3-aminopropylmethyl Dimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyl-3-aminopropyldiethylethoxysilane ethyldiethoxysilane, 3-aminopropylmethyldipropoxysilane, 3-aminopropylethyldi Lopoxysilane, 3-aminopropylpropyldipropoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropyldimethylpropoxysilane, 3-aminopropyldiethylpropoxysilane 3-aminopropyldipropylpropoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminopropyltributoxysilane, 1-aminopropyltrimethoxysilane, 1-aminopropyltriethoxysilane, 1-aminopropyltripropoxysilane, 1-aminopropyltributoxysilane, N-aminomethylaminomethyltrimethyl Xysilane, N-aminomethylaminomethyltripropoxysilane, N-aminomethyl-2-aminoethyltrimethoxysilane, N-aminomethyl-2-aminoethyltriethoxysilane, N-aminomethyl-2-aminoethyltripropoxysilane N-aminomethyl-3-aminopropyltrimethoxysilane, N-aminomethyl-3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltripropoxysilane, N-aminomethyl-2-aminopropyltri Methoxysilane, N-aminomethyl-2-aminopropyltriethoxysilane, N-aminomethyl-2-aminopropyltripropoxysilane, N-aminopropyltrimethoxysilane, N-aminopropyltriethoxysilane, N- (2- Aminoethyl) 2-aminoethyltrimethoxysilane, N- (2-aminoethyl) -2-aminoethyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltripropoxysilane, N- (2-aminoethyl) ) -Aminoethyltrimethoxysilane, N- (2-aminoethyl) -1-aminoethyltriethoxysilane, N- (2-aminoethyl) -1-aminoethyltripropoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltripropoxysilane, N- (3-aminopropyl) -2-aminoethyltrimethoxysilane, N- (3-aminopropyl) ) -2-Aminoethyltriethoxysilane, N- (3-aminopropyl) -2-aminoethyltripropoxy N-methyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- Diethylene 3-diethylenetriaminepropyltriethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] triethoxysilane, 3 15. Copolymer according to claim 14, derived from one or more of [2- (2-aminoethylaminoethylamino) propyl] tripropoxysilane and / or trimethoxysilylpropyldiethylenetriamine.   The side chain R is the following compound: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltriethoxysilane and 3 18. Copolymer according to claim 17, derived from one or more of aminopropylmethyldimethoxysilane.   Side chain R. From about 5 to about 200 mol%, such as from about 50 to about 150 mol%, preferably from about 75 to about 125 mol%, relative to the amount of reactive coupling groups present in the polymer backbone. 19. A copolymer according to any one of 18.   20. The copolymer according to any one of claims 1 to 19, wherein the side chain R is present in an amount of about 2 to about 15 mol%, more preferably about 3 to about 8 mol% of the polymer backbone. A process for preparing the functionalized vinyl alcohol homopolymer or copolymer of claim 1 comprising:
a. Preparing a linear or branched homopolymer of vinyl acetate or a copolymer of vinyl acetate and at least one other monomer;
b. Hydrolyzing the vinyl acetate homopolymer or copolymer of step (a) to obtain a homopolymer or copolymer of vinyl alcohol;
c. Reacting the vinyl alcohol homopolymer or copolymer of step (b) with a suitable reactive coupling agent to obtain a vinyl alcohol homopolymer or copolymer comprising one or more reactive coupling groups;
d. Reacting the resulting vinyl alcohol homopolymer or copolymer containing one or more reactive coupling groups of step (c) with a suitable aminosilane and / or aminosilanol;
e. Optionally isolating the copolymer thus formed.   The method of claim 21, wherein step (b) comprises partial hydrolysis of the vinyl acetate copolymer.   The process according to claim 21 or 22, wherein the reaction mixture obtained after step (d) is heated to a temperature in the range of about 0 ° C to about 100 ° C, preferably in the range of about 60 ° C to about 90 ° C.   24. Any of claims 21 to 23, wherein step (d) is performed by adding a homopolymer or copolymer of vinyl alcohol containing one or more reactive coupling groups to a suitable aminosilane and / or aminosilanol solution. The method according to claim 1.   25. A process according to any one of claims 21 to 24, wherein the reaction mixture obtained after step (d) is treated with an acid.   26. A process according to any one of claims 21 to 25, wherein the reaction mixture obtained after step (d) is treated with carbon dioxide.   27. A method according to any one of claims 21 to 26, wherein the copolymer is isolated by evaporation.   28. A functionalized homopolymer or copolymer of vinyl alcohol obtainable or obtained by the method according to any one of claims 21 to 27. A method for preparing a crosslinked polymer coating comprising:
Formula (III)
(Where
R ₁ , R ₂ and R ₃ are as described in claim 14;
x is in the range of 2-9, preferably x is 2,
y is in the range of 3-9, preferably y is 3.
Heating the polymer comprising two or more aminosilanes and / or aminosilanol side chains derived from the compound of claim 1, wherein the method is performed in the absence of an acid catalyst.   30. The method of claim 29, wherein the polymer is heated to a temperature of about 80 to about 120C, more preferably to about 100C. _21. A composition comprising the functionalized vinyl alcohol copolymer according to any one of claims 1 to 20 and water or a mixture of water and _C1-4 alcohol.   21. Use of a functionalized vinyl alcohol copolymer according to any one of claims 1 to 20 as a coating agent.   21. An ink, coating, sealant or adhesive comprising a vinyl alcohol functionalized homopolymer or copolymer according to any one of claims 1-20.   34. Ink, coating, adhesive or sealant according to claim 33, wherein a functionalized homopolymer or copolymer of vinyl alcohol is used as a binder.   21. Use of a functionalized homopolymer or copolymer of vinyl alcohol according to any one of claims 1 to 20 as a binder in inks, coatings, sealants or adhesives.   A cross-linked polymer coating obtainable or obtained by the method according to claim 29 or 30.   Functionalized homopolymers or copolymers, methods, cross-linked polymers, compositions, inks, coatings, sealants or adhesives, or uses substantially as described herein with reference to the accompanying examples .