CA2014780A1 - Non-aqueous synthetic resin compositions - Google Patents
Non-aqueous synthetic resin compositionsInfo
- Publication number
- CA2014780A1 CA2014780A1 CA002014780A CA2014780A CA2014780A1 CA 2014780 A1 CA2014780 A1 CA 2014780A1 CA 002014780 A CA002014780 A CA 002014780A CA 2014780 A CA2014780 A CA 2014780A CA 2014780 A1 CA2014780 A1 CA 2014780A1
- Authority
- CA
- Canada
- Prior art keywords
- synthetic resin
- compositions
- aqueous synthetic
- monomer
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
BAFS Aktiengesellschaft O.Z. 0050/40756 Abstract of the disclosure.
A non-aqueous synthetic resin composition essentially comprising A) from 20 to 95% w/w of at least one synthetic resin composed of a) from 90 to 99.95% w/w of at least one acrylate and/or methacrylate of an alkanol containing from 1 to 12 carbon atoms, b) from 0.05 to 10% w/w of at least one monomer of the general formula I
I, in which the variables have the following meanings:
hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen, and c) from 0 to 10% w/w of one or more ethylenically unsaturated monomers capable of undergoing radical copolymerization, and B) from 5 to 80% w/w of at least one inorganic filler.
Such non-aqueous synthetic resin compositions are suitable for use as adhesive compositions, sealing compounds and coating compositions.
A non-aqueous synthetic resin composition essentially comprising A) from 20 to 95% w/w of at least one synthetic resin composed of a) from 90 to 99.95% w/w of at least one acrylate and/or methacrylate of an alkanol containing from 1 to 12 carbon atoms, b) from 0.05 to 10% w/w of at least one monomer of the general formula I
I, in which the variables have the following meanings:
hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen, and c) from 0 to 10% w/w of one or more ethylenically unsaturated monomers capable of undergoing radical copolymerization, and B) from 5 to 80% w/w of at least one inorganic filler.
Such non-aqueous synthetic resin compositions are suitable for use as adhesive compositions, sealing compounds and coating compositions.
Description
r~
BASF Aktiengesellschafk O. ~, 0050/40756 NON-AOUEOUS SY~rH~TIC RESIN COMPOStTIONS
s The present invention relates to non-aqueous synthetic resin composi-tions essentially comprising A) from 20 to 95% w/w of at least one synthetic resin composed of a) from 90 to 99.95% w/w of at least one acrylate and/or methacrylate of an alkanol containing from 1 to 12 carbon atoms, b) from 0.05 to 10% w/w of at least one monomer of the general formula I
CH2=CI-C-O-R2-N=C=O I, Rl in which the variables have the following meanings:
Rl hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen, and c) from 0 to 10% w/w of one or more ethylenically unsatu-~o rated monomers capable of undergolng radical copoly-merization, and B) from 5 to 80% w/w of at least one inorganic filler.
3s The invention also relates to the use of these preparations as adhesive compositions, sealing compounds and coating compositions.
DE-C 2, 915, 864 discloses non-aqueous synthetic resin compositions which ~o contain, as synthetic resins, the reaction products of low molecular weight acrylic copolymers with organic diisocyanates. Such synthetic resin preparations are recommended for use as single-component elastic I~SF Alcti~nKo~011~ch,3e~ ,. UtJSO/4U/51;
sealing compounds which cure on ~xposure to molsture but are stable on storage under dry conditions.
However, these sealing compounds suffer from the drawback that the sur-s face of the cured compound shows increased tack and the preparation of the synthetic resins contained therein demands a comp.licated manufac-turing process. It is thus an object of the present invention to provide non-aqueous synthetic resin preparations which contain, as synthetic resins, polymers predominantly based on acrylates and/or methacrylates o and containing isocyanate groups and which are obtainable by simple methods and are stable on storage under dry conditions and are particu-larly suitable for use as single-component elastic sealing compounds which cure on exposure to moisture and show no surface tack in the cured conditionO Accordingly, we have found the synthetic resin compositions defined above.
The monomers a) contained in the synthetic resins A) as polymerizedunits are advantageously acrylates or methacrylates of alkanols contain-ing from 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol, n-20 butanol, isobutanol, n-pentanol, n-hexanol and 2-ethyl hexanol, acry-lates being preferred. Particularly preferred acrylates a) are ethyl acrylate, n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate.
Compounds of the general formula I are known in the axt and are de-~s scribed, for example, in DE-A 3,523,6~2. The proportion thereof in A ls preferably from 0.2 to 8% and more preferably from 1 to 6%, by weight.
It is particularly advantageous for A to contain polymeri~ed units oE a monomer b) of the general formula I whLch comprise ~-isocyanato-ethyl acrylate or 5-isocyanato-3-oxapentyl methacrylate units.
Whilst the Lnclusion of copolymerized units of the monomers a) and b) in A is obligatory, the monomer c) is merely an auxiliary monomer which will usually be included when it is desired to impart a specific degree of hardness to the polymer. Examples of possible monomers c) are 35 acrylonitrile, methacrylonitrile, vinyl ethers of Cl-C8-alkanols such as vinyl C2-Cl~-n-alkanoates, e.g. vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride, aromatic vinyl compounds such as styrene, vinyl toluenes, chl.orostyrenes or t-butyl styrenes, and lower unsaturated hydrocarbons such as ~-olefines or conjugated hydrocarbons 40 such as butadiene, the preferred monomers being acrylonitrile, mPth~
3--~
BASF ~kti~ 03~119ch~ft 3 ;;~ O.~.~J050/bl)75B
acrylonitrile and styrene. Advantageously, the proportions of a) and c), by weight, are adjusted with reference to the Fox equation such that a polymer containing polymerized units of these two monomers only would have a glass temperature of from -70 to +20 , preferably from -50 to s +20- and more preferably from -30 to -10C. ~ccording to Fox (T.G.Fox, Bull. Am. Phys. Soc. [Ser. II~, l, 123 [1956]), the following equation applies to the glass temperatures of copolymers, to a good degree of approximation:
-- = ~ + i~ ~ ''''' T~n where Xl, X2, ~ Xn are the mass fractions of monomers 1, 2, --- n and T8l, Tg2, --- Tgn are the glass temperatures, in C, of polymers consist-15 ing of polymerized units of one (respective) monomer only. ~he glasstemperatures of said homopolymers of the monomers a) and c) are ~nown and are listed, for example, in J. Brandrup, E.H. Immergut, Polymer Handbook lse Edition, J. Wiley, New York, 1966 and 2n~ Edition, J. Wiley, New York, 1975.
The synthetic resins A are preferably prepared by radical polymeriza-tion, preferably in solution.
Such solution polymerization may be carried out batchwise or continu-25 ously. The latter method is preferred, the procedure being to start witha portion of the polymerization mixture and heat it up to tha polymer-ization temperature and then to feed in the remaining mixture continu-ously.
30 The solvent used i9 usually an ether such as tetrahydroEuran or dioxane, an ester such as othyl or n-butyl acetate, a ketone such as acetone or cyclohexanone, an N,N-d~alkyl carboxamide such as N,N-dimethyl for-mamide, N,N-dimethyl acetamide or N-methyl-2-pyrrolidone, an aromatic compound such as ~oluene or xylene, an aliphatic hydrocarbon such as 35 iso-octane, a chlorinated hydrocarbon such as t-butyl chloride, or a plasticizer such as di-n-butyl phthalate.
The weight-mean molecular weight ~ of the synthetic resins A is gener-.0 ally from 3,000 to 150,000, pre-ferably from 10,000 to 100,000.
Accordingly, the synthetic resins A usually have a K-value in tetra-hydrofuran (THF) of from 15 to 90 and preferably from 25 to 60 ~ASF A~ctiong~ Ll~cbaft ~ .Z,,OOSO/I~U/SG
The K-value is a relative viscosity index which is determined in a rnan-ner similar to that specified in DIN 53,726 at 25 C. It denotes the ratio of the velocity o~ flow of a O.Ol:l w/w resin A/THF mixture to that of s pure THF and is a measure of the average degree of polymerization of resin A, as can be controlled by varying the polymerization conditions in known manner. A particularly suitable radical starter is an organic azo compound or organic peroxide such as azo-diisobutyronitrile, dibenzoyl peroxide or t-butyl perben~oate. This is advantageously used ~o in a concentration of from 0.05 to 5.0% and preferably from 0.3 to 1%, by weight of the total monomers. The polymerization temperature is usually 50 to 150 C and preferably 80 to 130 C. Other auxiliaries which may be added are for example chain-transfer agents such as aliphatic, aromatic or alicyclic mercaptans, e.g. n-butyl mercaptan or n-lauryl mercaptan, or alkyl thioglycolates such as ethyl thioglycolate, a suitable concentration being from 0 to 3% by weight of the total monomers.
It is advantageous to work in an "anhydrous" polymerization medium, i.e.
20 a medium containing less than lO0 ppm of water. The solution polymeriza-tion of the reactants, which are in themselves anhydrous, is advanta-geously carried out in the presence of a small amount of a desiccant such as a tetraalkoxy silane, e.g. tetramethoxy silane, or a trialkyl o-formate, e.g. triethyl o-formate, optionally with the addition of a 25 Lewis acid. The solvent can be removed from the resulting solution of the synthetic resins A either partially or completely, as requirecl, Eor example by distillation in vacuo.
The component B to be added to the synthetic resin preparations of the30 invention is advantageously an aluminum siltcate, quartz, precipitated or pyrogen-containing silicic acid (which may be hydrophobized), ].ight or heavy spar, talcum, dolomite, calcium carbonate, lamp black or color-ing pigments. Preferred whitening pigments are titanium white, lead white, zinc white, lithopone and antimony white and preferred blackening 35 pigments are iron oxide black, manganese black, cobalt black and anti-mony black. Preferred colored pigments are, for example, chromium yel-low, red lead, zinc yellow, zinc green, pink salt, cadmium red, cobalt blue, Prussian blue, ultramarine, manganese violet, cadmium yellow, molybdate orange and strontium yellow. The filler is generally added in ~o the form of fine particles. The average particle size, taken as the E~ASF Alctione~ chaLt 5 ~ 3 O.Z.OOS0/40-/5~
arithmetic mean of the greatest diameters, is preferably from 0.01 to 200 ~m and more preferably from 0.01 to 10 ~m.
The compositions of the invention may additionally contain up to 15% w/w s of a low ~olecular weight organic substance suitable to serve as exter-nal plasticizer C, preferred compositions containing fro~ 2 to 15% w/w thereof. Examples of suitable external plasticizers are phthalates such as diethyl phthalate, di-n-butyl phthalate, diisoheptyl phthalate or di(2-ethylhexyl) phthalate, adipates such as di(2-ethylhexyl) adipate or 10 diisooctyl adipate, sebacates such as di(2-ethylhexyl) sebacate, phos-phates such as tri-n-butyl phosphate, triisobutyl phosphate or tri(~-chloroethyl) phosphate, and chlorinated hydrocarbons.
The compositions of the invention may be used free from solvent, but to improve their working properties and in particular to lower their vis-cosity they can contain up to 40%, preferably from 2 to 40%, of their weight, of an organic solvent. The solvent used is preferably one which is also suitable for use in the solution polymerization carried out to manufacture the synthetic resin A.
~0 The synthetic resin compositions of the invention may also contain minor amounts of not more than 5% w/w of other auxiliaries, such as agents for improving ageing resistance, e.g. fungicides, dyes, thickeners and agents for accelerating curing under the action of molsture ~e.g. tetra-25 n-butyl titanate, di-n-butyl-tin di-n-dodecanate, di-n-butyl-tin diacetate or tertiary amines such as 1,4-diazo-bicyclo(2,2.2)octane arld triethylamine).
The compositions oE the invention may by prepared in the form of single-,o component systems by mixing together all ingredients and storing the mixture in a sealed container ready for use. To this end, the ingredi-ents B and, if used, C and any other auxiliaries to be used are prefer-ably stirred into a solution of the synthetic resin A containing the or-ganic solvent D or into a melt of synthetic resin A.
~s Alternatively, the compositions of the invention may be used in the for~
13ASF Altti~n~os~llschnft ;~ 7~ o ~ o~ro/4u~sii of a two-component system, the ingredients B and, if used, C and D and any other auxiliarie5 bein~ mixed toget~er to ~orm one component, which will be stirred, prior to use, into a r~elt or solution of the synthetic resin A forming the second component. The use of a single-component systcm necessitates meticulous exclusion of water to avoid prernature curing of the composition. In the case of a two-component system, the presence of small traces of water in the separate components is less critical, which facilitates processing of the components and storage of the system.
The preparations of the invention cure in a short time when exposed toatmospheric moisture. When cured, they show improved elasticity and have improved stretching properties, but their surface is not tacky. In addi-tion, the cured compositions show improved adhesion on substrates such 15 as aluminum, wood, glass, ceramics, concrete, building bricks and most plastics. They also exhibit improved weathering resistance and can be coated with domestic paints.
They are particularly well-suited ~or use as adhesive compositions, 20 sealing compounds and coating compositions, their use as moisture-curing sealing compounds being especially preferred, Due to their improved elasticity in the cured condition, they are preferably used when it is desired to cover cracks in the surface of the substrate or to fill in expansion gaps. For external applications, it is preferred to use a syn-~s thetic resin composition of the invention which contains a syntheticresin A having a glass temperature of from -30 to -10 C.
Examples 30 _x~
Manufacture of various solutions Al to A12 of synthetic resins A
General procedure A solution of 2 g o~ triethyl o-formate in 300 g of toluene was heatedto the polymerization temperature of lOO'C and held at this temperature while 600 g of a mixture of monomers a to c optionally containing a small amount of a chain-transfer agent were added over a period of 4 hours and a low-concentration solution of azo-diisobutyronLtrile in lOOg 7--~
~ASF Aktl~ne~s~llsch~ft 7 - ~.Z.0050/~l01~0 of toluene was added simultaneously through a separate feedline over a period of 5 hours. The resulting mixture was then further polymeri~ed for 2 hours at llO C. The solids contents of the resulting synthetic resin solutions, the K-value of the associated synthetic resins in THF, s the composition of the monomer mixtures used and the amoune of radical starter used and of chain-transfer agent, if any, are listed in Table 1 below. With the exception of the nondimensional K-value, the data are expressed as percentages by weight based on the mixture of ~onomers ex-cept for the solids content, which is based on the synthetic resin solu-tion.
Table 1 A1 A2 A3 A~ AS A6 A7 A8 A9 A10 A11A12 ethyl acrylate el.7 90 98 92 97 65 38 80 70 80 n-butyl acrylate 83 33 60 60 10 ~ethyl ~ethacrylate 18.2 5-isocyanato-3-oxapentyl methacrylate 1.6 2 2 2 1 3 2 1.8 2.5 2.520 ~-isocyanatoethyl acrylate 2 2 acrylonitrile 16.7 1~ 8 7 38 1017.5 styrene 7-5 azo-diisobutyronitrile 0.3 0.3 0.7 Q.7 0.3 0.2 0.5 0.4 0.5 0.6 0.3 O.g ethyl thioglycolate 0.3 0.4 0.5 ~5 K-value 39.5 ~2 36.6 26.1 43.4 37.3 35.1 24.1 32 25.1 33.4 42.
solids content 58.858.2 58.9 59.1 58 58.559.1 59.6 57.9 58.8 57.2 58 Examp].e 2 Various synthetic resi.n compositlons To prepare various synthetic resin composltions of the invention, the solutions A7 to A12 were distilled to remove the solvent, and various 35 additives were then addedt in each case, to 300 g of the resulting pure synthetic resin. A sample was taken from each of the compositions thus obtained and applied to a plate of glass to form a 2 mm layer thereon and then left to cure for 3 weeks at room temperature and a relative humidity of 60%.
.0 Table 2 below gives the ultimate tensile strength (N/mm2) and the elongati.on at break (7O) (both determined as specified in DIN 53,50~ at a chart speed of 100 mm/min using a test specimen type S3A) of the resulting elastic films and their surface tack. Table 2 also lists the 45 quantities of additives used. Table 2 further contains data on a 8--~ .
DASi' A~tl~n8~1lollochllft ~ 0.1',.0050/bO15 comparative test using a synthetic resin composit.Lon :Lncorporating a synthetic resin V obtained as speciiied in ~xample 1 of D~-C-2,915,864 by reacting 300 g of n-butyl acrylate, 10.2 g oE 2-hydroxyethyl acrylate, 6.6 g of mercaptoethanol and 30 g of a mixture of 2,4- and 2,6-diisocyanatotoluene.
Table 2 Additives [g] A7 A8 A9 A10 All A12 V
hydrophobized pyrogen-containing silicic acid 60 50 30 20 60 calciun carbonate 200 100 titaniuo white 20 30 diethyl phthalate 30 lO
di-n-butyl-tin-di-n-dodecanate2.5 3 3 3 3 3 1,4-diazo-bicyclol2.2.2]octane 2 Ulti~ate tensile strength 0.25 0.20.3 0.25 0.2 0.7 ,0 Elongation at break 312 290 310277 338 410 Surface tack no no no no no no yes Example 3 ,s Weathering resistance oE cured synthetic resin compositions of the invention as prepared in Example 2.
The weathering resistance was determined using the short-period weathering tester X~NOTEST*1200 (Heraeus GmbH, Hanau, GFR) set to give a 30 cycle oE
"rainfall" 3 mLnutes dry lnterva:L .L7 minutes.
The blackboard temperature measured ln the interior oE tha tester was 48 C.
~5 Test rssult: no changes were observed after a testing period of 2,000 hours.
* trade mark A 9-~
BASF Aktiengesellschafk O. ~, 0050/40756 NON-AOUEOUS SY~rH~TIC RESIN COMPOStTIONS
s The present invention relates to non-aqueous synthetic resin composi-tions essentially comprising A) from 20 to 95% w/w of at least one synthetic resin composed of a) from 90 to 99.95% w/w of at least one acrylate and/or methacrylate of an alkanol containing from 1 to 12 carbon atoms, b) from 0.05 to 10% w/w of at least one monomer of the general formula I
CH2=CI-C-O-R2-N=C=O I, Rl in which the variables have the following meanings:
Rl hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen, and c) from 0 to 10% w/w of one or more ethylenically unsatu-~o rated monomers capable of undergolng radical copoly-merization, and B) from 5 to 80% w/w of at least one inorganic filler.
3s The invention also relates to the use of these preparations as adhesive compositions, sealing compounds and coating compositions.
DE-C 2, 915, 864 discloses non-aqueous synthetic resin compositions which ~o contain, as synthetic resins, the reaction products of low molecular weight acrylic copolymers with organic diisocyanates. Such synthetic resin preparations are recommended for use as single-component elastic I~SF Alcti~nKo~011~ch,3e~ ,. UtJSO/4U/51;
sealing compounds which cure on ~xposure to molsture but are stable on storage under dry conditions.
However, these sealing compounds suffer from the drawback that the sur-s face of the cured compound shows increased tack and the preparation of the synthetic resins contained therein demands a comp.licated manufac-turing process. It is thus an object of the present invention to provide non-aqueous synthetic resin preparations which contain, as synthetic resins, polymers predominantly based on acrylates and/or methacrylates o and containing isocyanate groups and which are obtainable by simple methods and are stable on storage under dry conditions and are particu-larly suitable for use as single-component elastic sealing compounds which cure on exposure to moisture and show no surface tack in the cured conditionO Accordingly, we have found the synthetic resin compositions defined above.
The monomers a) contained in the synthetic resins A) as polymerizedunits are advantageously acrylates or methacrylates of alkanols contain-ing from 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol, n-20 butanol, isobutanol, n-pentanol, n-hexanol and 2-ethyl hexanol, acry-lates being preferred. Particularly preferred acrylates a) are ethyl acrylate, n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate.
Compounds of the general formula I are known in the axt and are de-~s scribed, for example, in DE-A 3,523,6~2. The proportion thereof in A ls preferably from 0.2 to 8% and more preferably from 1 to 6%, by weight.
It is particularly advantageous for A to contain polymeri~ed units oE a monomer b) of the general formula I whLch comprise ~-isocyanato-ethyl acrylate or 5-isocyanato-3-oxapentyl methacrylate units.
Whilst the Lnclusion of copolymerized units of the monomers a) and b) in A is obligatory, the monomer c) is merely an auxiliary monomer which will usually be included when it is desired to impart a specific degree of hardness to the polymer. Examples of possible monomers c) are 35 acrylonitrile, methacrylonitrile, vinyl ethers of Cl-C8-alkanols such as vinyl C2-Cl~-n-alkanoates, e.g. vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride, aromatic vinyl compounds such as styrene, vinyl toluenes, chl.orostyrenes or t-butyl styrenes, and lower unsaturated hydrocarbons such as ~-olefines or conjugated hydrocarbons 40 such as butadiene, the preferred monomers being acrylonitrile, mPth~
3--~
BASF ~kti~ 03~119ch~ft 3 ;;~ O.~.~J050/bl)75B
acrylonitrile and styrene. Advantageously, the proportions of a) and c), by weight, are adjusted with reference to the Fox equation such that a polymer containing polymerized units of these two monomers only would have a glass temperature of from -70 to +20 , preferably from -50 to s +20- and more preferably from -30 to -10C. ~ccording to Fox (T.G.Fox, Bull. Am. Phys. Soc. [Ser. II~, l, 123 [1956]), the following equation applies to the glass temperatures of copolymers, to a good degree of approximation:
-- = ~ + i~ ~ ''''' T~n where Xl, X2, ~ Xn are the mass fractions of monomers 1, 2, --- n and T8l, Tg2, --- Tgn are the glass temperatures, in C, of polymers consist-15 ing of polymerized units of one (respective) monomer only. ~he glasstemperatures of said homopolymers of the monomers a) and c) are ~nown and are listed, for example, in J. Brandrup, E.H. Immergut, Polymer Handbook lse Edition, J. Wiley, New York, 1966 and 2n~ Edition, J. Wiley, New York, 1975.
The synthetic resins A are preferably prepared by radical polymeriza-tion, preferably in solution.
Such solution polymerization may be carried out batchwise or continu-25 ously. The latter method is preferred, the procedure being to start witha portion of the polymerization mixture and heat it up to tha polymer-ization temperature and then to feed in the remaining mixture continu-ously.
30 The solvent used i9 usually an ether such as tetrahydroEuran or dioxane, an ester such as othyl or n-butyl acetate, a ketone such as acetone or cyclohexanone, an N,N-d~alkyl carboxamide such as N,N-dimethyl for-mamide, N,N-dimethyl acetamide or N-methyl-2-pyrrolidone, an aromatic compound such as ~oluene or xylene, an aliphatic hydrocarbon such as 35 iso-octane, a chlorinated hydrocarbon such as t-butyl chloride, or a plasticizer such as di-n-butyl phthalate.
The weight-mean molecular weight ~ of the synthetic resins A is gener-.0 ally from 3,000 to 150,000, pre-ferably from 10,000 to 100,000.
Accordingly, the synthetic resins A usually have a K-value in tetra-hydrofuran (THF) of from 15 to 90 and preferably from 25 to 60 ~ASF A~ctiong~ Ll~cbaft ~ .Z,,OOSO/I~U/SG
The K-value is a relative viscosity index which is determined in a rnan-ner similar to that specified in DIN 53,726 at 25 C. It denotes the ratio of the velocity o~ flow of a O.Ol:l w/w resin A/THF mixture to that of s pure THF and is a measure of the average degree of polymerization of resin A, as can be controlled by varying the polymerization conditions in known manner. A particularly suitable radical starter is an organic azo compound or organic peroxide such as azo-diisobutyronitrile, dibenzoyl peroxide or t-butyl perben~oate. This is advantageously used ~o in a concentration of from 0.05 to 5.0% and preferably from 0.3 to 1%, by weight of the total monomers. The polymerization temperature is usually 50 to 150 C and preferably 80 to 130 C. Other auxiliaries which may be added are for example chain-transfer agents such as aliphatic, aromatic or alicyclic mercaptans, e.g. n-butyl mercaptan or n-lauryl mercaptan, or alkyl thioglycolates such as ethyl thioglycolate, a suitable concentration being from 0 to 3% by weight of the total monomers.
It is advantageous to work in an "anhydrous" polymerization medium, i.e.
20 a medium containing less than lO0 ppm of water. The solution polymeriza-tion of the reactants, which are in themselves anhydrous, is advanta-geously carried out in the presence of a small amount of a desiccant such as a tetraalkoxy silane, e.g. tetramethoxy silane, or a trialkyl o-formate, e.g. triethyl o-formate, optionally with the addition of a 25 Lewis acid. The solvent can be removed from the resulting solution of the synthetic resins A either partially or completely, as requirecl, Eor example by distillation in vacuo.
The component B to be added to the synthetic resin preparations of the30 invention is advantageously an aluminum siltcate, quartz, precipitated or pyrogen-containing silicic acid (which may be hydrophobized), ].ight or heavy spar, talcum, dolomite, calcium carbonate, lamp black or color-ing pigments. Preferred whitening pigments are titanium white, lead white, zinc white, lithopone and antimony white and preferred blackening 35 pigments are iron oxide black, manganese black, cobalt black and anti-mony black. Preferred colored pigments are, for example, chromium yel-low, red lead, zinc yellow, zinc green, pink salt, cadmium red, cobalt blue, Prussian blue, ultramarine, manganese violet, cadmium yellow, molybdate orange and strontium yellow. The filler is generally added in ~o the form of fine particles. The average particle size, taken as the E~ASF Alctione~ chaLt 5 ~ 3 O.Z.OOS0/40-/5~
arithmetic mean of the greatest diameters, is preferably from 0.01 to 200 ~m and more preferably from 0.01 to 10 ~m.
The compositions of the invention may additionally contain up to 15% w/w s of a low ~olecular weight organic substance suitable to serve as exter-nal plasticizer C, preferred compositions containing fro~ 2 to 15% w/w thereof. Examples of suitable external plasticizers are phthalates such as diethyl phthalate, di-n-butyl phthalate, diisoheptyl phthalate or di(2-ethylhexyl) phthalate, adipates such as di(2-ethylhexyl) adipate or 10 diisooctyl adipate, sebacates such as di(2-ethylhexyl) sebacate, phos-phates such as tri-n-butyl phosphate, triisobutyl phosphate or tri(~-chloroethyl) phosphate, and chlorinated hydrocarbons.
The compositions of the invention may be used free from solvent, but to improve their working properties and in particular to lower their vis-cosity they can contain up to 40%, preferably from 2 to 40%, of their weight, of an organic solvent. The solvent used is preferably one which is also suitable for use in the solution polymerization carried out to manufacture the synthetic resin A.
~0 The synthetic resin compositions of the invention may also contain minor amounts of not more than 5% w/w of other auxiliaries, such as agents for improving ageing resistance, e.g. fungicides, dyes, thickeners and agents for accelerating curing under the action of molsture ~e.g. tetra-25 n-butyl titanate, di-n-butyl-tin di-n-dodecanate, di-n-butyl-tin diacetate or tertiary amines such as 1,4-diazo-bicyclo(2,2.2)octane arld triethylamine).
The compositions oE the invention may by prepared in the form of single-,o component systems by mixing together all ingredients and storing the mixture in a sealed container ready for use. To this end, the ingredi-ents B and, if used, C and any other auxiliaries to be used are prefer-ably stirred into a solution of the synthetic resin A containing the or-ganic solvent D or into a melt of synthetic resin A.
~s Alternatively, the compositions of the invention may be used in the for~
13ASF Altti~n~os~llschnft ;~ 7~ o ~ o~ro/4u~sii of a two-component system, the ingredients B and, if used, C and D and any other auxiliarie5 bein~ mixed toget~er to ~orm one component, which will be stirred, prior to use, into a r~elt or solution of the synthetic resin A forming the second component. The use of a single-component systcm necessitates meticulous exclusion of water to avoid prernature curing of the composition. In the case of a two-component system, the presence of small traces of water in the separate components is less critical, which facilitates processing of the components and storage of the system.
The preparations of the invention cure in a short time when exposed toatmospheric moisture. When cured, they show improved elasticity and have improved stretching properties, but their surface is not tacky. In addi-tion, the cured compositions show improved adhesion on substrates such 15 as aluminum, wood, glass, ceramics, concrete, building bricks and most plastics. They also exhibit improved weathering resistance and can be coated with domestic paints.
They are particularly well-suited ~or use as adhesive compositions, 20 sealing compounds and coating compositions, their use as moisture-curing sealing compounds being especially preferred, Due to their improved elasticity in the cured condition, they are preferably used when it is desired to cover cracks in the surface of the substrate or to fill in expansion gaps. For external applications, it is preferred to use a syn-~s thetic resin composition of the invention which contains a syntheticresin A having a glass temperature of from -30 to -10 C.
Examples 30 _x~
Manufacture of various solutions Al to A12 of synthetic resins A
General procedure A solution of 2 g o~ triethyl o-formate in 300 g of toluene was heatedto the polymerization temperature of lOO'C and held at this temperature while 600 g of a mixture of monomers a to c optionally containing a small amount of a chain-transfer agent were added over a period of 4 hours and a low-concentration solution of azo-diisobutyronLtrile in lOOg 7--~
~ASF Aktl~ne~s~llsch~ft 7 - ~.Z.0050/~l01~0 of toluene was added simultaneously through a separate feedline over a period of 5 hours. The resulting mixture was then further polymeri~ed for 2 hours at llO C. The solids contents of the resulting synthetic resin solutions, the K-value of the associated synthetic resins in THF, s the composition of the monomer mixtures used and the amoune of radical starter used and of chain-transfer agent, if any, are listed in Table 1 below. With the exception of the nondimensional K-value, the data are expressed as percentages by weight based on the mixture of ~onomers ex-cept for the solids content, which is based on the synthetic resin solu-tion.
Table 1 A1 A2 A3 A~ AS A6 A7 A8 A9 A10 A11A12 ethyl acrylate el.7 90 98 92 97 65 38 80 70 80 n-butyl acrylate 83 33 60 60 10 ~ethyl ~ethacrylate 18.2 5-isocyanato-3-oxapentyl methacrylate 1.6 2 2 2 1 3 2 1.8 2.5 2.520 ~-isocyanatoethyl acrylate 2 2 acrylonitrile 16.7 1~ 8 7 38 1017.5 styrene 7-5 azo-diisobutyronitrile 0.3 0.3 0.7 Q.7 0.3 0.2 0.5 0.4 0.5 0.6 0.3 O.g ethyl thioglycolate 0.3 0.4 0.5 ~5 K-value 39.5 ~2 36.6 26.1 43.4 37.3 35.1 24.1 32 25.1 33.4 42.
solids content 58.858.2 58.9 59.1 58 58.559.1 59.6 57.9 58.8 57.2 58 Examp].e 2 Various synthetic resi.n compositlons To prepare various synthetic resin composltions of the invention, the solutions A7 to A12 were distilled to remove the solvent, and various 35 additives were then addedt in each case, to 300 g of the resulting pure synthetic resin. A sample was taken from each of the compositions thus obtained and applied to a plate of glass to form a 2 mm layer thereon and then left to cure for 3 weeks at room temperature and a relative humidity of 60%.
.0 Table 2 below gives the ultimate tensile strength (N/mm2) and the elongati.on at break (7O) (both determined as specified in DIN 53,50~ at a chart speed of 100 mm/min using a test specimen type S3A) of the resulting elastic films and their surface tack. Table 2 also lists the 45 quantities of additives used. Table 2 further contains data on a 8--~ .
DASi' A~tl~n8~1lollochllft ~ 0.1',.0050/bO15 comparative test using a synthetic resin composit.Lon :Lncorporating a synthetic resin V obtained as speciiied in ~xample 1 of D~-C-2,915,864 by reacting 300 g of n-butyl acrylate, 10.2 g oE 2-hydroxyethyl acrylate, 6.6 g of mercaptoethanol and 30 g of a mixture of 2,4- and 2,6-diisocyanatotoluene.
Table 2 Additives [g] A7 A8 A9 A10 All A12 V
hydrophobized pyrogen-containing silicic acid 60 50 30 20 60 calciun carbonate 200 100 titaniuo white 20 30 diethyl phthalate 30 lO
di-n-butyl-tin-di-n-dodecanate2.5 3 3 3 3 3 1,4-diazo-bicyclol2.2.2]octane 2 Ulti~ate tensile strength 0.25 0.20.3 0.25 0.2 0.7 ,0 Elongation at break 312 290 310277 338 410 Surface tack no no no no no no yes Example 3 ,s Weathering resistance oE cured synthetic resin compositions of the invention as prepared in Example 2.
The weathering resistance was determined using the short-period weathering tester X~NOTEST*1200 (Heraeus GmbH, Hanau, GFR) set to give a 30 cycle oE
"rainfall" 3 mLnutes dry lnterva:L .L7 minutes.
The blackboard temperature measured ln the interior oE tha tester was 48 C.
~5 Test rssult: no changes were observed after a testing period of 2,000 hours.
* trade mark A 9-~
Claims (2)
1. A non-aqueous synthetic resin composition essentially comprising A) from 20 to 95% w/w of at least one synthetic resin composed of a) from 90 to 95% w/w of at least one monomer selected from the group consisting of acrylates and methacrylates of an alkanol containing from 1 to 12 carbon atoms, b) from 0.05 to 10% w/w of at least one monomer of the general formula I
I, in which the variables have the following meanings:
hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen and c) from 0 to 10% w/w of one or more ethylenically unsaturated monomers capable of undergoing radical copolymerization, and B) from 5 to 80% w/w of at least one inorganic filler.
I, in which the variables have the following meanings:
hydrogen or methyl a hydrocarbon chain having up to 12 C-atoms, which may be interrupted at one or more points by oxygen and c) from 0 to 10% w/w of one or more ethylenically unsaturated monomers capable of undergoing radical copolymerization, and B) from 5 to 80% w/w of at least one inorganic filler.
2. Use of the synthetic resin composition claimed in claim 1, as an adhesive composition, a sealing compound or a coating composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3913168A DE3913168A1 (en) | 1989-04-21 | 1989-04-21 | Non-aqueous synthetic resin preparations |
| DEP3913168.8 | 1989-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2014780A1 true CA2014780A1 (en) | 1990-10-24 |
Family
ID=6379169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002014780A Abandoned CA2014780A1 (en) | 1989-04-21 | 1990-04-18 | Non-aqueous synthetic resin compositions |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0393666A2 (en) |
| CA (1) | CA2014780A1 (en) |
| DE (1) | DE3913168A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532329A (en) * | 1990-12-06 | 1996-07-02 | Basf Aktiengesellschaft | Copolymers and mixtures which are self-curable with atmospheric humidity |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5596036A (en) * | 1991-06-14 | 1997-01-21 | Sandoz Ltd. | Hardenable acrylic monomer compositions |
| US5712337A (en) * | 1992-06-11 | 1998-01-27 | Mbt Holding Ag | Hardenable acrylic monomer compositions |
| DE4315880A1 (en) * | 1993-05-12 | 1994-11-17 | Basf Ag | By the action of humidity self-curing copolymers and mixtures |
-
1989
- 1989-04-21 DE DE3913168A patent/DE3913168A1/en not_active Withdrawn
-
1990
- 1990-04-18 CA CA002014780A patent/CA2014780A1/en not_active Abandoned
- 1990-04-19 EP EP90107434A patent/EP0393666A2/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532329A (en) * | 1990-12-06 | 1996-07-02 | Basf Aktiengesellschaft | Copolymers and mixtures which are self-curable with atmospheric humidity |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3913168A1 (en) | 1990-10-25 |
| EP0393666A2 (en) | 1990-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0736050B1 (en) | Moisture-curable modified acrylic polymer sealant composition | |
| US4368297A (en) | Paint containing a silyl group containing vinyl resin, and a method of manufacturing the same with ethyl silicate and curing catalyst | |
| EP1048676B2 (en) | Polymer compositions | |
| EP0184705B1 (en) | Curable composition | |
| WO2015130729A1 (en) | Gradient polymer compositions for elastomeric wall and roof coatings | |
| KR20160025584A (en) | Use of a 2-octyl acrylate polymer as a binding agent in a coating composition | |
| CN106893381B (en) | A kind of methacrylate modified reactive resin | |
| CA2014780A1 (en) | Non-aqueous synthetic resin compositions | |
| BRPI0821560B1 (en) | MOISTURE-CURED ALPHA SILAN MODIFIED ACRYLIC COATINGS | |
| JPS5978220A (en) | Room temperature-curable elastic composition | |
| EP0387587B1 (en) | Polymers of esters of acrylic or methacrylic acid containig silicium | |
| JPS62187749A (en) | Crosslinkable resin composition | |
| JP5667854B2 (en) | 1 component composition | |
| JP3765343B2 (en) | Non-aqueous dispersion type resin composition and curable coating | |
| JPS5871966A (en) | Coating composition | |
| JPH0269507A (en) | Dispersing unit composition for ambient temperature curing type coating | |
| US5322714A (en) | Coated article with metallic finish | |
| JP3874834B2 (en) | Coating composition | |
| AU671907B2 (en) | Copolymers and blends which are self-curable under the action of atomospheric humidity | |
| JP2764995B2 (en) | Low temperature curable resin composition | |
| JP3920369B2 (en) | Sealer composition for inorganic molded board | |
| KR100357450B1 (en) | Process for producing thermoplastic acryl resin and anticorrosive paint containing the same | |
| JP2875810B2 (en) | Stabilized coating composition | |
| JPS6059267B2 (en) | Film-forming composition | |
| GB2130227A (en) | Acrylic polymers useful in sealing compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |