DE19720345A1 - Adhesive polymers for e.g. lacquers, binders or sealants - Google Patents

Abstract

An adhesive contains a polymer comprising 0.1-100 wt.% monomers of formula (I). In (I): R1-R6 = H or 1-18C alkyl; Z = single bond or one of the groups of formulae (a)-(h); R7-R11 = H or 1-10C alkyl; X = 1-20C alkylene, 1-10C alkylene oxide or -O-(CH2)nm; m = 1-50; and n = 1-10. -C(O)-O-X- (a) -C(O)-NR11-X- (c) -O-C(O)-X- (d) -C(O)-NR11- (f) -O-X- (g) -O-CH2-X- (h) Also claimed are: (i) polymers comprising 0.1-100 wt.% (I), with the exception of compounds in which R3 is H and Z is a single bond; and (ii) the use of the polymers in coating materials, impregnating materials or adhesives.

Description

Furthermore, the invention relates to new polymers which 0.1 to 100 wt .-% consist of monomers of formula I, each but monomers of formula I with R³ = H and Z = single bond are closed.

US Pat. No. 3,954,863 discloses acrylamidines and their preparation knows. DE-A 26 45 128 relates to polymers which Contain acrylamidines and their use as additives for oils. Also a use for the production of molded parts, colors and Binder is mentioned.

Adhesives, in particular also pressure sensitive adhesives and laminating adhesives fabrics, in addition to good adhesion (liability to the adhesive substrates) also good cohesion (cohesion in the adhesive layer).

Generally, therefore, polymers are desired which are an improvement of adhesion, an improvement in cohesion or in particular improve adhesion and cohesion.

Accordingly, the adhesives defined at the outset were found. Ge polymers suitable for the adhesives were also found such as uses of these polymers.

The adhesives according to the invention contain a polymer, wel from 0.1 to 100% by weight, preferably from 0.5 to 100% by weight consists of the monomers of the formula I (hereinafter also Called monomers a)).

In general, a content of 0.1 to 10, in particular from 0.5 to 5% by weight of these monomers in the copolymer to significantly increase the adhesion or cohesion to achieve forces.

Preferred compounds of formula I are those in which R¹ to R⁶ independently of one another for an H atom or a C₁-C₄ alkyl group stand.

Z preferably represents a single bond or a given one if substituted phenylene group, where R⁷ to R¹⁰ independently stand for one another for an H atom or a C₁-C₄ alkyl group, where preferably at least 2 of the radicals R⁷ to R¹⁰ for an H atom stand.

Z particularly preferably represents a single bond or a Phenylene group (R⁷, R⁸, R⁹, R¹⁰ = H atom).  

Particularly suitable compounds of the formula I are those in which NEN R¹ and R² for an H atom, R³ for an H atom or a methyl group and R⁴ to R⁶ independently of one another for an H atom or represent a C₁-C₆ alkyl group and Z represents a single bond or an optionally substituted phenylene group (R⁷, R⁸, R⁹, R¹⁰ = H or C₁-C₁₀-, especially C₁-C₄-alkyl).

R⁶ particularly preferably represents an H atom.

Accordingly, preferred compounds are acrylamidines of the formula

Methacrylamidines of the formula

and styrylamidines of the formula

The compounds of the formula I can be free or protonated Form or as a complex with other compounds, e.g. B. carbon acids or sulfonic acids, phosphoric acids, phosphonic acids gene, preferably at least one of the radicals R⁵ and R⁶ for there is an H atom. The complexes can continue through later Wear addition of mono- or polyacids to the amidinium groups  the polymer can be produced, which in the case of polyacids can lead to crosslinking of the polymer.

The complexes have e.g. B. the following structure

where R stands for the carboxylic acid residue.

The preparation of the acrylamidines is known and z. B. in DE-A-26 45 128.

Styrylamidines can e.g. B. starting from the acid chloride of the formula

can be produced by the following process steps:

• a) reaction with a primary amine according The acid chloride is thus converted into an acid amide.
  The reaction is preferably carried out at room temperature in the presence of a base, e.g. B. also an excess of the primary amine in a solvent, e.g. B. absolute dichloromethane.
• b) reaction of the acid amide from a) with an oxonium salt or a dialkyl sulfate according to where X⊖ for a non-nucleophilic anion, e.g. B. BF₄⊖ or SO₄²⊖ in, to a substituted imido ester.
• c) implementation of the substituted imido ester with an ammonium compound (z. B. alkylamine hydrochloride) to the styrylamidine according to

Process step b) is preferably at 10 to 40 ° C in one anhydrous solvents, e.g. B. absolute dichloromethane leads.

Process step c) is preferably at 10 to 40 ° C in one performed anhydrous solvents.

The methacrylamidines can be prepared analogously to the preparation of the styrylamidines take place, starting from methacrylamides can be carried out and process steps b) and c) analogously can be.

The preferred temperature in process step c) is -5 to + 10 ° C.  

The polymer can, in addition to the above monomers a), so-called called main monomers b) and other monomers c) contain.

Main monomers b) are selected from C₁-C₂₀ alkyl (meth) acrylates, Vinyl esters of carboxylic acids containing up to 20 carbon atoms, Vinyl aromatics with up to 20 carbon atoms, ethylenically unsaturated Nitriles, vinyl halides, vinyl ethers or allyl ethers of 1 alcohols containing up to 10 carbon atoms, aliphatic coal water substances with 2 to 8 carbon atoms and 1 or 2 double bonds or Mixtures of these monomers.

To mention are z. B. (meth) acrylic acid alkyl ester with a C₁-C₁₀ alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate and iso-butyl methacrylate.

In particular, mixtures of the (meth) acrylic acid alkyl esters suitable.

Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are e.g. B. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.

As vinyl aromatic compounds come vinyl toluene α and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are Acrylonitrile and methacrylonitrile.

The vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.

Examples of vinyl ethers include B. vinyl methyl ether or vinyl isobutyl ether. Vinyl ether of 1 to 4 carbon atoms is preferred keeping alcohols.

As hydrocarbons with 2 to 8 carbon atoms and two olefinic Double bonds are butadiene, isoprene and chloroprene and with a double bond z. B. called ethylene.

Other monomers c) are, for. B. containing hydroxyl groups Monomers, in particular C₁-C₁ Hydrox hydroxyalkyl (meth) acrylates, (Meth) acrylamide, ethylenically unsaturated acids, in particular Carboxylic acids, sulfonic acids such as (meth) acrylic acid or itaconic acid, Dicarboxylic acids and their anhydrides or half esters, e.g. B. Malein acid, fumaric acid and maleic anhydride, acrylamidopropane sulfonic acid, vinyl sulfonic acid, sulfoethyl or sulfopro  pyl (meth) acrylate or its salts, especially ammonium or Alkali salts.

Phenyloxyethyl glycol are also further monomers c) mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, Amino (meth) acrylates such as 2-aminoethyl (meth) acrylate called.

Monomers c) which, in addition to the double bond, have further functions wear small groups, e.g. B. isocyanate, amino, hydroxy, amide, Ureido, Gycidyl or carboxyl groups, z. B. liability further improve on substrates.

The polymer can be structured as follows, in particular for use as an adhesive:
0.1 to 100 a), 0 to 99.9 b) and 0 to 30% by weight of monomers c); prefers
0.1 to 10 a), 70 to 99.9 b) and 0 to 20% by weight of monomers c); particularly preferred
0.5 to 5 a), 75 to 99.5 b) and 0 to 20% by weight of monomers c).

The monomers can preferably be free radical or as far as possible can also be polymerized anionically or cationically. Both the radical as well as anionic polymerization are as usual Liche polymerization methods known to those skilled in the art.

The radical polymerization can e.g. B. in solution, e.g. B. one organic solvent (solution polymerization) in aqueous Dispersion (emulsion polymerization, suspension polymerization) or in bulk, d. H. essentially in the absence of water or organic solvents (bulk polymerization) be performed.

The emulsion polymerization can e.g. B. discontinuously, with or without the use of seed latices, with presentation of all or individually ner components of the reaction mixture, or semi-continuously preferably with partial submission and replenishment of the or individual components of the reaction mixture, or after Dosing procedures can be carried out without a template. Likewise, the Polymerization are carried out gradually, the Different composition of the individual stages and monomers a) z. B. in one stage, d. H. can be enriched in a phase nen.  

The monomers can be used as usual in emulsion polymerization in the presence of a water-soluble initiator and one Emulsifier are polymerized at preferably 10 to 95 ° C.

Suitable initiators are e.g. B. sodium, potassium and ammonium persulfate, tert-butyl hydroperoxides, water-soluble azo compounds or redox initiators such as H₂O₂ / ascorbic acid.

As emulsifiers z. B. Alkaline salts of longer chain fat acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated biphenyl ether sulfonates. Furthermore come as Emulsifiers Reaction products of alkylene oxides, in particular Ethylene or propylene oxide with fatty alcohols, acids or Phenol, or alkylphenols and their sulfated derivatives in Be dress.

In the case of aqueous secondary dispersions, the copolymer first by solution polymerization in an organic Solvent produced and then with the addition of salt formers, e.g. B. from ammonia to carboxylic acid groups Copolymers, in water without the use of an emulsifier or Dispersing aid dispersed. The organic solvent can be distilled off. The production of aqueous secondary dispersions is known to the skilled worker and z. B. in the DE-A 37 20 860.

To adjust the molecular weight in the Polymerisa tion controller can be used. Are suitable for. B. -SH containing Compounds such as mercaptoethanol, mercaptopropanol, thiophenol, Thioglycerin, thioglycolic acid ethyl ester, thioglycolic acid methyl ester and tert-dodecyl mercaptan.

The solids content of the polymer dispersions obtained is preferably 40 to 80% by weight, particularly preferably 45 to 75% by weight. High polymer solids can e.g. B. by procedure ren, which in German patent application P 4 307 683.1 or EP 37 923 are set.

Solution polymerization can be continuous, discontinuous as a batch process or preferably semi-continuously in Inlet procedures are carried out. In the latter case, a Part of the monomers submitted to the polymerization temperature heated and the rest of the monomers fed continuously.

As a solvent for radical solution polymerization, see above as for any subsequent implementations in Solution z. B. alcohols such as i-butanol, i-propanol, aromatics  such as toluene or xylene, ethers such as dioxane or tetrahydrofuran, Ketones such as acetone, cyclohexanone or esters such as ethyl acetate or n-Butyl acetate can be used.

Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-amyl-2-ethyl hexyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, Cumene hydroperoxide, dilauroyl peroxide, didecanoyl peroxide, methyl ethyl ketone peroxide, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile) and 2,2'-azobisisobutyro to call nitrile.

In bulk polymerization, part of the Submitted polymerization approach to the polymerization temperature heated, after which the rest is continuous is fed.

The polymer is used depending on the selected poly merization method in the form of an aqueous dispersion of the polymer risats, a solution in an organic solvent or in obtained essentially free of water and solvents.

The glass transition temperature of the polymer is for Use in adhesives and coating compositions preferably -50 to + 100 ° C, particularly preferably -40 to + 50 ° C.

The glass transition temperature of the polymer can be done according to the usual methods such as differential thermal analysis or differential Scanning calorimetry (see, for example, ASTM 3418/82, so-called "midpoint temperature ").

The polymer is preferably by emulsion polymerization produced.

The adhesives according to the invention preferably contain the poly merisat and furthermore, if appropriate, customary additives for Adhesives such as B. Takifier, especially rosins, Thickener or rheology aid.

The adhesives according to the invention are particularly suitable as Ka sheer adhesives, d. H. for bonding large-area substrates.

The adhesives according to the invention can differ Lichlich substrates z. B. on textile fabrics, papers, plastic made of polyvinyl chloride, polyester, polyethylene or poly propylene, cellulose acetate, on metals, especially metal foils be applied and then with another of the above  upright substrates laminated, d. H. be glued where can be obtained by film composites.

The polymer according to the invention (ie a polymer which contains the monomers of the formula I, but monomers of the form mel I with R³ = H and Z = single bond are excluded) preferably a polymer, the methacrylamidines of formula III or contains styrylamidines of formula IV) can be in coating mass z. B. in paints and varnishes, impregnation compounds or adhesives are used. Basically they are all Suitable uses where there is good adhesion to substrates and if necessary, good cohesion is also desired.

Good cohesion (= internal strength) of the polymer layers or films leads to good mechanical end properties of the coating produced by the polymers according to the invention materials, paints and varnishes.

In addition, coatings are based on the polymers according to the invention by good resistance ge compared to organic solvents and chemicals.

If the polymers according to the invention are used as Binder or additive in paints and varnishes can be a good adhesion to substrates such as wood, paper, mineral, leather, me tall or plastic (specially corona treated material) right sult.

Particularly noteworthy is the good adhesion of such types paints and varnishes based on oil paints or alkyd resin Old coatings or primers even under critical conditions conditions such as high humidity and low temperature (= Wet grip).

The polymer according to the invention can therefore be used alone or in com combination with other polymers z. B. as a binder in Lac ken, paints, adhesives, sealants, nonwoven bandage medium or paper coating materials are used. The The polymer according to the invention is also suitable as flocculation medium, retention aid for the paper industry, as ion ex exchanger material, adsorbent or thickening polymer.  

Examples I. Monomer Syntheses a) Synthesis of N'N'-diethyl-4-vinylbenzamidine

Raw materials
4-vinylbenzoyl chloride (T. Ishizone et al .: Macromolecules 1989, 22, 2895), triethyloxonium tetrafluoroborate (H Meerwein; Org. Synth., Collect, Vol. 5, 1080)

i) N-ethyl-4-vinylbenzamide

To a solution of 27.5 g (0.61 mol) of ethylamine in 150 ml of abs. Dichloromethane is added dropwise at -20 ° C a solution of 50 g (0.30 mol) of 4-vinylbenzoyl chloride in 50 ml abs. Dichloromethane, he warmed to room temperature and stirred for a further 15 h. It sucks off ethylamine hydrochloride, washed with dichloromethane, the solvent is removed and recrystallized from ethyl acetate.
Yield: 51.5 g (0.29 mol) = 98% of theory

ii) Ethyl N-ethyl-4-vinylbenzocarboximate

To a solution of 58.5 g (0.308 mol) of triethyloxoni umtetrafluoroborate in 150 ml abs. Dichloromethane there 40.0 g (0.228 mol) of N- Ethyl 4-vinylbenzamide. The mixture is stirred at room temperature for 2 hours tur, adds 0.2 g phenothiazine, stirs more 36 h and then removes the solvent in Va vacuum.

The remaining syrup is mixed with 80 ml of an ice-cold 3M sodium hydroxide solution and immediately shaken out with 250 ml of ice-cold diethyl ether. The aqueous phase is extracted four more times with ether, and the combined organic phases are dried over sodium sulfate. After removal of the solvent, fractionation is carried out in a diffusion pump vacuum or crystallized from a little absolute ethanol at -25 ° C.
Sp: 55 ° C, 10 ^-3 mbar
Yield: 46.2 g (0.227 mol) = 100% of theory

iii) N, N'-diethyl-4-vinylbenzamidine

To a solution of 25 g (0.113 mol) of N-ethyl-4-vinyl ethyl benzocarboximidate in 50 ml abs. Ethanol 12 g (0.147 mol) are added in the inert gas countercurrent Ethylamine hydrochloride.

The mixture is stirred at 15 ° C. for 5 h, 0.2 g of 4-tert-butyl catechol is added, the mixture is stirred at room temperature for a further 5 days and then the solvent is removed in vacuo. The residue is mixed with 100 ml of an ice-cooled 6M sodium hydroxide solution and shaken immediately with an ice-cooled mixture of ethyl acetate / diethyl ether (1: 1). The aqueous phase is extracted a further four times, the combined organic phases are dried over sodium sulfate. The solvent is removed in vacuo, the remaining solid sublimes at 0.01 mbar and 100 ° C bath temperature.
Yield: 21.6 g (0; 107 mol) = 87% of theory
M.p .: 76 ° C

b) Synthesis of 4-vinylbenzamidine

Starting materials:
4-vinylbenzonitrile (R. Broos, M. Anteunis; Synth. Commun. 1976, 6, 53)

i) 4-Vinylbenzocarboximidsäureethylester hydrochloride

In a mixture of 56.13 g (0.435 mol) of 4-vinylbenzonitrile, 20.11 g (0.436 mol) of abs. Ethanol, 1 spatula of 4-tert.-butylpyrocatechol and 520 ml abs. Toluene is introduced at -10 to -15 ° C with gentle stirring for 6 h of hydrogen chloride, which with conc. Sulfuric acid is dried. The mixture is stirred for a further hour and then the reaction mixture is left to stand at 3 ° C. for 90 hours with occasional shaking. The toluene is largely removed at 50 mbar, the solid which precipitates is filtered off with suction and washed with a little cold toluene.
Yield: 72.85 g (0.372 mol) = 86% of theory
M.p .: 98 ° C

ii) 4-vinylbenzamidinium chloride

To a solution of 42.33 g (0.216 mol) of ethyl 4-vinylbenzo carboximate hydrochloride and a spatula tip of 4-tert-butyl catechol in 50 ml abs. Ethanol is given a solution of 5.86 g (0.344 mol) ammonia in abs at 0 ° C. Ethanol. After 100 h at 3 ° C with occasional shaking, the ammonium chloride is suctioned off and the solvent is removed in vacuo. The remaining brown oil is brought to crystallization by treatment with diethyl ether and recrystallized from 10 ^-2 M hydrochloric acid.
Yield: 21.70 g (0.135 mol) = 63% of theory

iii) 4-vinylbenzamidine

2.00 g (0.011 mol) of 4-vinylbenzamidinium chloride are dissolved in 10 ml of water, mixed with 20 ml of cold saturated potassium carbonate solution and extracted with ethyl acetate, which is removed in vacuo. Pale yellow acicular crystals are obtained which can be sublimed at 0.01 mbar and a bath temperature of 90 ° C.
Yield: 1.58 g (0.011 mol) = 99%
M.p .: 120 ° C

II. Preparation of solution polymers 1. Homopolymerization of N, N'-diethyl-4-vinylbenzamidine

The homopolymerization of N, N'-diethyl-4-vinylbenzamidine takes place as solution polymerization in ethanol (abs.) 60 ° C. Here, 2 g (0.00988 mol) of monomer in 19.57 g Dissolved ethanol (0.4 mol / l). 0.0162 g serves as the starter AIBN, which is a concentration of 1 mol% based on that Corresponds to monomer.

The homopolymer is precipitated using cyclohexane. After drying in a vacuum, it is available as a white powder.
Polymerization time: 72 hours
Yield: 1.79 g = 90% of theory. Th.
Molar mass (M _w ) using membrane osmometry in ethanol:
19500 g / mol

2. Copolymerization of N, N'-diethyl-4-vinylbenzamidine with Styrene

The copolymerization of N, N'-diethyl-4-vinylbenzamidine with styrene takes place as solution polymerization in tetra hydrofuran (abs.) at 60 ° C, the amount (g) of THF equal to the amount (g) of monomer mixture. As The starting substance is AIBN with the concentration of 1 mol%, based on the monomer mixture used. As Precipitation reagent for the copolymer serves cyclohexane. After drying in vacuo a white powdery one Get polymer. From this copolymer system the Copolymerization parameters to r₁ = 0.5 (amidine) and r₂ = 0.5 (styrene) determined. For the series of measurements, the Monomer concentration (mole percent) of the amidine as follows changed: 16%, 33%, 50%, 67%, 84%. The investigation the parameter is carried out by means of elemental analysis and H¹-NMR according to the usual evaluation methods of Fineman and Horse. The polymerizations are abge after 5% conversion broken.

example 33 mol% of N, N′-diethyl-4-vinylbenzamidine, 67 mol% styrene

N, N′-diethyl-4-vinylbenzamidine: 4.0000 g (0.01977 mol)
Styrene: 4.1810 g (0.0401 mol)
AIBN (azoisobutyronitrile): 0.0984 g
Tetrahydrofuran (abs.): 8.2 g
Polymerization time: 90 min
Yield: 0.4896 g = 6% of theory. Th.
Molar mass (M _w by means of membrane osmometry in ethanol (abs.): 10500 g / mol

3. Copolymerization of N, N'-diethyl-4-vinylbenzamidinium propionate with styrene

The copolymerization of N, N'-diethyl-4-vinylbenzamidini Umpropionate with styrene takes place as solution polymerization in tetrahydrofuran (abs.) at 60 ° C, the amount (g) THF is equal to the amount (g) of monomer mixture. AIBN is the starting substance with the concentration of 1 mol%, based on the monomer mixture used. As Precipitant for the copolymer is petroleum ether (40-60 ° C). A sticky polymer falls after the precipitation risat, which after drying in vacuum as a white Powder is present. From this copolymerization system who the copolymerization parameters to r₁ = 0.4 (amidine) and r₂ = 0.2 (styrene) determined. The selection of the series of measurements and the evaluation is carried out analogously to point 2.

example 16 mol% of N, N'-diethyl-4-vinylbenzamidiniumpro pionate, 84 mol% styrene

N, N′-diethyl-4-vinylbenzamidine: 2.0000 g (0.00988 mol)
Propionic acid: 0.7324 g (0.0098 mol)
Styrene: 5.4057 g (0.0519 mol)
Tetrahydrofuran (abs.) 8.1 g
AIBN: 0.1015 g
Polymerization time: 60 min
Yield: 0.3165 g = 3.9% of theory. Th.
Molar mass (M _w by means of membrane osmometry in ethanol (abs.): 13400 g / mol

4. Copolymerization of N, N'-diethyl-4-vinylbenzamidine with MMA (methyl methacrylate)

The copolymerization of N, N'-diethyl-4-vinylbenzamidine with MMA takes place as solution polymerization in tetrahydro furan (abs.) at 60 ° C, the amount (g) of THF being equal to the Amount (g) of monomer mixture corresponds. As a starting substance becomes AIBN with the concentration of 1 mol%, based on used the monomer mixture. As a precipitation reagent for  the copolymer serves cyclohexane. After drying in A white powdery polymer is obtained under vacuum. From this copolymer system become the copolymerization para meters determined to r₁ = 0.3 (amidine) and r₂ = MMA. The The selection of the series of measurements and the evaluation is carried out analogously Point 2.

example 84 mol% of N, N′-diethyl-4-vinylbenzamidine, 16 mol% MMA

N, N′-diethyl-4-vinylbenzamidine: 6.0000 g (0.0296 mol)
MMA: 0.5656 g (0.0056 mol)
Tetrahydrofuran (abs.): 7 g
AIBN: 0.0579 g
Polymerization time: 90 min
Yield: 0.1476 g = 2.2% of theory. Th.
Molar mass (M _w by means of membrane osmometry in ethanol (abs.): 9600 g / mol

5. Copolymerization of N, N'-diethyl-4-vinylbenzamidinium propionate with MMA

The copolymerization of N, N'-diethyl-4-vinylbenzamidini Umpropionate with MMA takes place as solution polymerization in Ethanol (abs.) At 60 ° C, the amount (g) of ethanol corresponds to twice the amount (g) of monomer mixture. As The starting substance is AIBN with the concentration of 1 mol%, based on the monomer mixture, used. As Precipitant for the copolymer serves n-pentane. After the precipitation results in a sticky polymer, which however, it is present as a white powder after drying. From this copolymer system become the copolymerization para meters determined to r₁ = 0.3 (amidine) and r₂ = 0.4 (MMA). The selection of the series of measurements and the evaluation is carried out analogous to point 2.

example 84 mol% of N, N'-diethyl-4-vinylbenzamidiniumpro pionate, 16 mol% MMA

N, N′-diethyl-4-vinylbenzamidine: 6.0000 g (0.0296 mol)
Propionic acid: 2.1971 g (0.0296 mol)
MMA: 0.5656 g (0.0056 mol)
AIBN: 0.0579 g
Ethanol (abs.): 14 g
Polymerization time: 90 min
Yield: 0.4221 g = 4.8% of theory. Th.
Molar mass (M _w by means of membrane osmometry in ethanol (abs.): 19700 g / mol

6. Copolymerization of N, N'-diethyl-4-vinylbenzamidine with Butyl acrylate

The copolymerization of N, N'-diethyl-4-vinylbenzamidine with butyl acrylate as solution polymerization. mol% N, N'-diethyl-4-vinylbenzamidine (2 g = 0.00988 mol) with 80 mol% butyl acrylate (5.0685 = 0.0395 mol) in 7 g tetrahydrofuran (abs.) Ver puts. The polymerization is carried out with AIBN (0.0812 g). After a polymerization time of 72 hours, the Solvent removed.

When adding a solution of the copolymer in acetone with an equimolar amount of adipic acid in acetone occurs Gel from, which by adding a little water back in Solution goes.

By evaporating the solution at 60 ° C in a drying cabinet a clear film was obtained which was insensitive to Is water.

III. Production of polymer dispersions Basic recipe

400 g of demineralized water, 150 g of feed 1 (see below), 25 g of a 20% strength by weight aqueous solution of a fatty alcohol etherified with 18 ethylene oxide units (in a reaction vessel with stirrer, reflux condenser and two feed vessels (feed 1 and feed 2)) C₁₆ / C₁₈), 5 g of a 20 wt .-% aqueous solution of the disodium salt of p-dodecyldiphenyl ether disulfonate and 50 g of feed 2 and heated to 85 ° C. After 15 minutes, feed 1 was uniformly added to the reaction vessel at the same time, starting within 2 h, and feed 2 was evenly added over the course of 2.25 h. After the complete addition of initiator (feed 2), the dispersion was stirred at 85 ° C. for a further 2 h. The mixture was then cooled to room temperature and, if appropriate, the dispersion was adjusted to pH = 7.5 using 10% strength by weight aqueous sodium hydroxide solution.
Inlet 1:
(is stirred during the polymerization)
320 g of demineralized water
50 g 20% by weight aqueous solution of a fatty alcohol etherified with 18 ethylene oxide units (C₁₆ / C₁₈) (emulsifier)
75 g 20% by weight aqueous solution of the disodium salt of dodecdyldiphenyl ether disulfonate (emulsifier)
xg active monomer
30 g 50% by weight aqueous solution of acrylamide
300 g methyl methacrylate
700 g of n-butyl acrylate
Inlet 2:
195 g of demineralized water
5 g sodium peroxodisulfate

Table 1

III. Application tests Determination of the source values Q

The dispersions were 4 days at 23 ° C and 50% air moisture in silicon pans to approx. 500 µm thick Filmed polymer films. 4 cm² film pieces were over a period of 24 h at room temperature in 100 ml Swollen tetrahydrofuran. The source value Q is the THF  Recording of the specimen, based on the mass of the off corridor, in% (determined gravimetrically). The bigger Q, the lower the internal strength.

Determination of tensile strength K [N / mm²] and elongation at break D [%]

The tests were carried out according to DIN 53504, at one Take-off speed of 200 mm / min, one test tempe rature of 23 ° C and using sample form S2. The larger K and the smaller D, the more pronounced it is internal strength (cohesion).

Table 2

By incorporating the amidine monomers (polymers 2 and 3) it comes to the non-functionalized Ver I am looking for an increase in film cohesion, which is reflected in an increase in K and a decrease in D and Q expresses.

In contrast, this effect with the same mass fraction not for the basic standard monomer DMAEMA in V2 takes care.

The effects of the amidine monomers are comparable to the influence of an equal weight proportion in the Capable of self-condensation and thus known to be coherent sion-increasing AAEM (V 3).

Laminating aluminum foils with paper Test specification

Substrate: aluminum foil; Thickness 0.015 mm on one side matt
Buxine paper 80 g / m²
Applicator: 0.05 mm or 0.07 mm wire doctor blade with holder for the magnetic holder of the spreading table
Glue application: directly on the film
Application weight 2-3 g / m² (dry)
Drying: 3 minutes with a hot air gun
Test strip size: 200 mm × 30 mm

Procedure

On the matt side of the aluminum foil with the Wire squeegee of adhesive applied. In the wet Adhesive bed is the paper with a rubber roller on ge rolls and then dried. After at the earliest The liability test is carried out by peeling off for 24 hours the two slides by hand.

Assessment of liability by marks 1 to 5:

1 = full paper tear (very good adhesion)
2 = partial tear out of paper (good adhesion)
3 = good adhesion with broken adhesive film or paper (AF, AP)
4 = weak adhesion with AF or PA
5 = no liability

Results are shown in Table 3.

Table 3

The incorporation of the amidine monomers (polymers 1-3) leads to a Improvement of the adhesion of an alumi glued with polymer nium / paper composite.

In contrast, this effect with the same mass fraction for the basic standard monomers DMAEMA not observed in V2.

Claims (9)

1. Adhesives containing a polymer which contains 0.1 to 100% by weight of monomers of the formula consists,
wherein R¹ to R⁶ independently of one another represent an H atom or a C₁-C₁₈ alkyl group and Z can be a single bond (Z is therefore absent) or can have one of the following meanings: R⁷ to R¹¹ independently of one another represent an H atom or a C₁-C₁₀ alkyl group and X represents a C₁-C₂₀ alkylene group, a C₁-C₁₀ alkylene oxide group or [-O- (CH₂-) _n ] _m , where n can be a number from 1 to 10 and m can be a number from 1 to 50. The adhesive of claim 1, wherein R¹ to R⁶ are independent stand for an H atom or a C₁-C₄ alkyl group and Z for a single bond or a phenylene group (R⁷ to R¹⁰ = H atom). 3. Adhesives according to claim 2, wherein R¹ and R² represent an H atom stand, R³ represents an H atom or a methyl group, R⁴ bis R⁵ represents an H atom or a C₁-C₆ alkyl group, R⁶ represents an H atom and Z stands for a single bond or a Phenylene group. 4. Adhesives according to claim 1, wherein the polymer to 0.1 to 10 wt .-% consists of monomers of formula I. 5. Polymers which 0.1 to 100 wt .-% of monomers of Formula I exist, but with monomers of formula I with R³ = H and Z = single bond are excluded. 6. Polymers according to claim 5, which 0.1 to 10 wt .-% consist of monomers of the formula I. 7. Polymers according to claim 5 or 6, wherein Z for an bond, R¹ and R² stand for an H atom, R³ for represents a methyl group and R⁴ and R⁵ represent an H atom or a C₁-C₆ alkyl group and R⁶ represents an H atom. 8. Polymers according to claim 5 or 6, wherein Z is for a Phenyl group, R¹, R² and R³ represent an H atom and R⁴ and R⁵ represents an H atom or a C₁-C₆ alkyl group and R⁶ stands for an H atom. 9. Use of the polymers according to one of claims 5 to 8 than in coating compositions, impregnation compositions or adhesive fabrics.