CA1054280A - Thermosetting resin compositions with low shrinkage on the base of unsaturated polyester resins suitable for the production of moulding compositions capable of freely flowing - Google Patents
Thermosetting resin compositions with low shrinkage on the base of unsaturated polyester resins suitable for the production of moulding compositions capable of freely flowingInfo
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- CA1054280A CA1054280A CA226,785A CA226785A CA1054280A CA 1054280 A CA1054280 A CA 1054280A CA 226785 A CA226785 A CA 226785A CA 1054280 A CA1054280 A CA 1054280A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Thermosetting resin compositions with low shrinkage on the base of unsaturated polyester resins suitable for the production of moulding compositions capable of freely flowing Abstract Polyester resin compositions curable with low shrinkage which are suitable for the production of free-flowing moulding compositions can be obtained from non-crystalline unsaturated polyesters, copolymerisable vinyl or vinylidene compounds and cellulose esters with elevated viscosity.
Description
The present application relates to thermosetting resin compositions of low shrinkage which are suitable for the pro-duction of free-flowing moulding compositions, said resin composltions being based on non-crystalline ~ ,~-ethyleni-cally unsaturated polyesters, copolymerisable vinyl or vinyli-d~ne compounds and certain cellulose esters as thermoplastic additives, as well as to the production and use of said thermosetting resin compositions.
For a long time it has been customary to produce poly-ester mouldings by curing suitable moulding compositions in metal apparatus at elevated temperatures with the application of pressureO The moulding compositions can be made, for example, by impregnating glass, natural fibres or man-made fibres, usually in the form of mats or bundles (rovings~,with a polyester resin, which generally contains hardening cata-lysts, fillers, viscosity-improving chemical thickeners, release agents and optionally pigments and/or auxiliaries.
Depending on the method of production, moulding compositions or foil-shaped resin mats with a more or less tacky surface are obtained. Since the resin mats tend to stick together, it has proved necessary to cover them on both sides with separation foils during ripening. These foils have to be removed prior to processing, a step one would like to have dispensed with a long time ago.
Conventional unsaturated polyester resins show con-siderable polymerisation shrinkage and this constitutes a severe disadvantage when producing mouldings which should exhibit flawless surfaces~ It is now known from numerous Le A 16 ~22 - 2 -~os4zsO
pu~l~ations (German OS 1,192,820, German AS 1,694,857, German OS 1,803,345, 1,~53,062, 2,051,663, 2,061,585, French patent 1,148,285) that polyester moulding compositions which were mixed prior to hardening with certain thermo-plasts, e.g. polyacrylates, polymethacrylates or cellulose esters, cure with low shrinkage.
It is known that the addition of fillers reduces poly-merisation shrinkage by a kind of dilution effect (cf, H.Hagen, Glasfaserverstarkte Kunststoffe, 2nd Edition, Springer, Berlin/Gottingen/Heidelberg 1961, page 170). Thus, by adding fillers to tacky resins which have been treated with chemi-cal thickeners, it is generally possible to obtain free-flow-ing compositions; however, such large quantities of filler have to be used that the resulting compositions no longer have any useful mechanical properties.
Free-flowing, low-shrinking thermosetting compositions on the basis of crystalline unsaturated polyesters, copoly-merisable monomers and cellulose esters of organic acids are known from German pS 2,234,3070 The crystalline polyesters render the composition free-flowing, the cellulose esters reduce polymerisation shrinkage and as a result the surface profile is improvedO These moulding compositions meet the requirements regarding reduction of polymerisation shrink-age and free-flowability, but are restricted to crystalline polyesters.
Low-shrinking thermosetting polyester resin mixtures on the base of non-crystalline polyesters and cellulose esters are known from German OS 2,302,842, which are charac-terized in that the polyesters have a styrene compatibility Le A 16 322 - 3 -between 45 and 90% by weight of unsaturated polyester or a styrene compatibility between 30 and 90% by weight of unsaturated polyester and a content of between 0.20 and 0.53 equivalents, that is mols, of radically polymerisable ~,B-ethylenically unsaturated dicarboxylic acid esters per 100g of unsaturated polyesterO Cellulose esters to be preferably used should have a viscosity corresponding to a time of outflow of 0.1 to 20, preferably 0.1 to 5 seconds.
Thermoplasts have been previously suggested as suit-able for reducing polymerisation shrinkage which are soluble in copolymerisable ~inyl or vinylidene compounds and/or polyester resin, that is in the solution of the poly-; ester in copolymerisable compounds, as well as those which although soluble in the copolymerisable compounds, are not compatible with the polyester. Polyvinyl acetate and cellu-lose ester belong for example to the first group and poly-styrene, polyacrylic, ester and polyme~hacrylic acid ester, for example, to the latter groupO Use of thermoplasts which do not dissol~e but merely swell up in polyester resin and in copolymerisable compounds,such as for example polyethy-lene, play no part in practice due to technical difficultiesO
When prccessing low-shrinking thermosetting polyester resins, difficulties will arise if the thQrmoplast exudes out of the moulding composition during storage of the mould-ing compositions or ripening of the resin mats.
Le A 16 322 - 4 -With thermoplasts o~ the last-mentioned group, this incom-patibility exists right from the startO With thermoplasts, which are compatible with the polyester J this phenomenon is produced due to the fact that the solubility properties are so changed by the chemical thickeners which are usually added that the thermoplast becomes incompatible with the polyester~ As a result the surfaces of the moulding compo-sitions are tacky. If such compositions are processed to form resin mats, it is extremely difficult to remove the separation foils. An even severer disadvantage is consti-tuted by the fact that such moulding compositions tend to form coatings on mouldings and on surfaces of the apparatus.
The moulded articles then exhibit dull and stained surfaces and the coating on the apparatus can build up to such an extent that force has to be applied to remove the noulded article~ this often entailing destruction of the moulded article.
Surprisingly, it has now been found that these diffi-culties can be avoided by the choice of highly viscous cellu-lose esters with a high OH number as shrinkage-reducing addi-tives in combination with certain polyester resins.
The subject matter of the invention relates to low-shrinking thermosetting resin compositions suitable for the production of free-flowing moulding compositions, said resin compositions consisting of Le A 16 322 - 5 -A) 10 to 50, preferably 25 to 45, parts by weight of non-crystalline ~ ethylenically unsaturated polyesters, B) 20 to 90, preferably 35 to 60, parts by weight of copolymerisable vinyl or vinylidene compounds and C) 10 to 50, preferably 20 to 40, parts by weight of cellulose esters of organic mono-carboxylic acids with
For a long time it has been customary to produce poly-ester mouldings by curing suitable moulding compositions in metal apparatus at elevated temperatures with the application of pressureO The moulding compositions can be made, for example, by impregnating glass, natural fibres or man-made fibres, usually in the form of mats or bundles (rovings~,with a polyester resin, which generally contains hardening cata-lysts, fillers, viscosity-improving chemical thickeners, release agents and optionally pigments and/or auxiliaries.
Depending on the method of production, moulding compositions or foil-shaped resin mats with a more or less tacky surface are obtained. Since the resin mats tend to stick together, it has proved necessary to cover them on both sides with separation foils during ripening. These foils have to be removed prior to processing, a step one would like to have dispensed with a long time ago.
Conventional unsaturated polyester resins show con-siderable polymerisation shrinkage and this constitutes a severe disadvantage when producing mouldings which should exhibit flawless surfaces~ It is now known from numerous Le A 16 ~22 - 2 -~os4zsO
pu~l~ations (German OS 1,192,820, German AS 1,694,857, German OS 1,803,345, 1,~53,062, 2,051,663, 2,061,585, French patent 1,148,285) that polyester moulding compositions which were mixed prior to hardening with certain thermo-plasts, e.g. polyacrylates, polymethacrylates or cellulose esters, cure with low shrinkage.
It is known that the addition of fillers reduces poly-merisation shrinkage by a kind of dilution effect (cf, H.Hagen, Glasfaserverstarkte Kunststoffe, 2nd Edition, Springer, Berlin/Gottingen/Heidelberg 1961, page 170). Thus, by adding fillers to tacky resins which have been treated with chemi-cal thickeners, it is generally possible to obtain free-flow-ing compositions; however, such large quantities of filler have to be used that the resulting compositions no longer have any useful mechanical properties.
Free-flowing, low-shrinking thermosetting compositions on the basis of crystalline unsaturated polyesters, copoly-merisable monomers and cellulose esters of organic acids are known from German pS 2,234,3070 The crystalline polyesters render the composition free-flowing, the cellulose esters reduce polymerisation shrinkage and as a result the surface profile is improvedO These moulding compositions meet the requirements regarding reduction of polymerisation shrink-age and free-flowability, but are restricted to crystalline polyesters.
Low-shrinking thermosetting polyester resin mixtures on the base of non-crystalline polyesters and cellulose esters are known from German OS 2,302,842, which are charac-terized in that the polyesters have a styrene compatibility Le A 16 322 - 3 -between 45 and 90% by weight of unsaturated polyester or a styrene compatibility between 30 and 90% by weight of unsaturated polyester and a content of between 0.20 and 0.53 equivalents, that is mols, of radically polymerisable ~,B-ethylenically unsaturated dicarboxylic acid esters per 100g of unsaturated polyesterO Cellulose esters to be preferably used should have a viscosity corresponding to a time of outflow of 0.1 to 20, preferably 0.1 to 5 seconds.
Thermoplasts have been previously suggested as suit-able for reducing polymerisation shrinkage which are soluble in copolymerisable ~inyl or vinylidene compounds and/or polyester resin, that is in the solution of the poly-; ester in copolymerisable compounds, as well as those which although soluble in the copolymerisable compounds, are not compatible with the polyester. Polyvinyl acetate and cellu-lose ester belong for example to the first group and poly-styrene, polyacrylic, ester and polyme~hacrylic acid ester, for example, to the latter groupO Use of thermoplasts which do not dissol~e but merely swell up in polyester resin and in copolymerisable compounds,such as for example polyethy-lene, play no part in practice due to technical difficultiesO
When prccessing low-shrinking thermosetting polyester resins, difficulties will arise if the thQrmoplast exudes out of the moulding composition during storage of the mould-ing compositions or ripening of the resin mats.
Le A 16 322 - 4 -With thermoplasts o~ the last-mentioned group, this incom-patibility exists right from the startO With thermoplasts, which are compatible with the polyester J this phenomenon is produced due to the fact that the solubility properties are so changed by the chemical thickeners which are usually added that the thermoplast becomes incompatible with the polyester~ As a result the surfaces of the moulding compo-sitions are tacky. If such compositions are processed to form resin mats, it is extremely difficult to remove the separation foils. An even severer disadvantage is consti-tuted by the fact that such moulding compositions tend to form coatings on mouldings and on surfaces of the apparatus.
The moulded articles then exhibit dull and stained surfaces and the coating on the apparatus can build up to such an extent that force has to be applied to remove the noulded article~ this often entailing destruction of the moulded article.
Surprisingly, it has now been found that these diffi-culties can be avoided by the choice of highly viscous cellu-lose esters with a high OH number as shrinkage-reducing addi-tives in combination with certain polyester resins.
The subject matter of the invention relates to low-shrinking thermosetting resin compositions suitable for the production of free-flowing moulding compositions, said resin compositions consisting of Le A 16 322 - 5 -A) 10 to 50, preferably 25 to 45, parts by weight of non-crystalline ~ ethylenically unsaturated polyesters, B) 20 to 90, preferably 35 to 60, parts by weight of copolymerisable vinyl or vinylidene compounds and C) 10 to 50, preferably 20 to 40, parts by weight of cellulose esters of organic mono-carboxylic acids with
2 to 4 carbon atoms, characterized:in that a) the polyesters A have a B-compatibility of 45 to 90% by weight or a B-compatibility of 0.1 to 45% by weight and a content of 0.20 to 0.70 mol of radically polymerisable ,B-ethylenically unsaturated dicarboxylic acid radicals per 100 g of polyester A, and in that b) the cellulose esters C have a viscosity corresponding to a time of outflow of at least 10, prefer-ably 12 to 24 seconds, measured in accordance with ASTM D
871-56, formula B, and a hydroxyl number of between 40 and 100.
The invention further relates to the production of these resin compositions, characterized in that the com-ponents A to C are thoroughly mixed with one another in a manner known per se at temperatures between 60 and 80C
and allowed to solidify to a solid, gel-like composition by cooling to room temperature.
The invention further relates to the use of the herein described resin compositions to produce optionally fibre-reinforced moulding compositions.
Le A 16 322 - 6 -Whereas the known low-shrinking thermosetting poly-ester compo~itions have a two-phase structure after harden-ing, that is with thermoplast particles included in the polyester phase, no such phenomenon is detectable in the compositions according to the invention after they have hard-ened even when enlarged with the aid of an electronic microscope.
~,~-ethylenically unsaturated polyesters A within the scope of the invention are the usual polycondensation products of at least one ~,B-ethylenically unsaturated dicarboxylic acid generally with 4 to 5 carbon atoms or the ester-forming derivatives thereof, optionally in admixture with up to 90%
mol, based on the unsaturated acid components of at least one aliphatic saturated dicarboxylic acid with 4 to 10 carbon atoms, of a cyclo-aliphatic or aromatic dicarboxylic acid with 8 to 10 carbon atoms or the ester-forming derivatives thereof with at least one polyhydroxy compound, in particular dihydroxy compound, with 2 to 8 carbon atoms, that is poly-: ester as described by J. Bjorksten et al, in "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956.
Examples of unsaturated dicarboxylic acids or their derivatives to be preferably used are maleic acid or maleic anhydride and fumaric acid. However, it is also possible to employ mesaconic acid, citraconic acid, itaconic acid or chloro maleic acid. Examples of aliphatic saturated, cyclo-aliphatic and aromatic dicarboxylic acids or their deri-vatives to be used are phthalic acid or phthalic anhydride, Le A 16 322 - 7 -isophthalic acid, terephthalic acid, hexa or tetrahydrophthalic acid or their anhydrides, endomethylene tetrahydrophthalic acid or their anhydPide, succinic acid or succinic anhydride and succinic acid ester and succinic acid chlorides, adipic acid, sebacic acid. To produce almost non-inflammable resins, hexachloro-endomethylene tetrahydrophthalic acid, tetrachlorophthalic acid or tetrabromophthalic acid can be used. The polyesters to be preferably used con-tain maleic acid of which up to 25 mol % can be replaced by phthalic acid or by isophthalic acid. As bivalent alcohols there may be used ethylene glycol, propanediol-1,2, propane-diol-1,3, diethylene glycol, dipropylene glycol, butane diol-1,3, butane diol-1,4, neopentyl glycol, hexane diol-1,6~2,2-bis-(4-hydroxycyclohexyl)-propane, bis-oxalkylated bisphenol A, perhydrobisphenol and others. Ethylene glycol, propane diol-1,2, diethylene glycol and dipropylene glycol are preferably used.
Further modifications are possible by incorporating up to 10 mol %, based on the alcohol or acid component, of monohydric alcohols with 1 to 6 carbon atoms, such as methanol, ethanol, butanol, allyl alcohol, benzyl alcohol, cyclohexanol and tetrahydrofurfuryl alcohol, trimethylol propane, glycerine and pent~rythrite as well as of mono-allyl ethers, dially ethers and triallyl ethers and benzyl ethers of trihydric and polyhydric alcohols with 3 to 6 carbon atoms in accordance with German AS 1,024,654, as well as by incor-porating monobasic acids such as benzoic acid or long-chain unsaturated fatty acids such as oleic acid, fatty acid of linseed oil and ricinoleic acid.
Le A 16 322 - 8 -The acid numbers of polyester A should be between 5 and 30, preferably between 10 and 20, the OH numbers between 20 and 70, preferably between 30 and 50, and the molecular weights Mn.between about 500 and 5000, preferably between about 1000 and 2500 ~easured by vapour pressure osmosis in dioxane and acetone; where the values `differ the lower value is taken as being the more accurate one)O
Basically the content of ~ ethylenically unsaturated dicarboxylic acid residues which are condensed into the polyesters A can vary within a wide range. However, the articles manufactured from the moulding compositions accord-ing to the invention are removed from the mould a~ter application of pressure whilst still hot and should there-fore exhibit satisfactory resistance to thermal distortion.
It follows that high contents of ~,~-ethylenically unsatu-rated dicarboxylic acid residues of 0.70 to O.20 mols / 100 g of unsaturated polyester are preferred~
Preferred polyesters A are those having a B-compati-bility of 001 to 30~ by weight and a content of 0.20 to 0.70 mol of radically polymerisable ~,~-ethylenically un-saturated dicarboxylic acid radicals per 100 g of polyester A, or a B-compatibility of 30 to 45% by weight and a con-tent of 0.53 to 0.70 mol of radically polymerisable ~,B-ethylenically unsaturated dicarboxylic acid radicals per 100 g of polyester Ao The B-compatibility or B-solubility of unsaturated polyesters is a term analogous with the term styrene com-patibility known in the chemistry and technology of unsatu-rated polyester resins (cf. Johannes Scheiber, "Chemie uO
Technologie der k~nstlichen Harze," vol. 1, "Die Polymerisat-Le A 16 322 - 9 -.. , ....... . , .. ., ., .. ,~,.. ~ .. . . .
~054Z80 harze", Wissenschaftliche Verlagsgesellschaft MBH, Stutt-gart, 1961, 2nd Edition, pages 563 et seq., in particular pages 751/572).
The B-compatibility of the unsaturated polyesters, given in % by weight (unsaturated polyester), based on the total amount of unsaturated polyester and component B, is de~ined and determined as follows.
Unsaturated polyester is dissolved in component B
at about 80 to 100C in an amount just sufficient to yield a clear solution of known concentration after immediate cooling to room temperature. This solution is treated with additional amounts of component B at room temperature, whilst stirring, until the solution becomes turbid. The concentration, based on the total amount of component B
and unsaturated polyester, of the unsaturated polyester in percent by weight at turbidity point is defined as B-compatibilityO
The following example is given by way of explanation.
E (g) = total weight in grams of the clear polyester solution dissolved in component B with P ~ of unsaturated polyester, e.g~ 20 gO
P % = percent by weight of unsaturated polyesters dissol-ved to give a clear solution in component B, e.g.
60 %
S (g3 = component B, added up to the point of turbidity, is given in grams, e.g. 10 g B-compatibility = E(~ P (%3 e.g~ ~ ~ =
E(g) + S(g) 20g + 10g Le A 16 322 - 10 -.... . . ..
1054Z~30 It is known from experience that the B-compatibility of an unsaturated polyester is affected by the polyester components involved in its synthesis, that is by the acid and alcohol components used to synthesize the polyester.
Esterification components which give rise to B-incom-patibility are for example: maleic acid, maleic anhydride, fu-maric acid, ethylene glycol, diethylene glycol, hexane diol-1,6.
Esterification components which give rise to B-com-patibility are for example: phthalic acid, isophthalic acid, tetrachlorophthalic acid, hexachloro-endo-methylene tetPa-hydrophthalic acid or its anhydrides, propylene glycol-1,2, dipropylene glycol, butylene glycol-1,3, neopentyl glycol, trimethylol propane allyl ethers, perhydro bisphenol, bis-oxalkyl bisphenol etc.
Suitable copolymerisable vinyl and vinylidene compounds B within the scope of the invention are unsaturated compounds usually employed in polyester tecbnology, which preferably have ~-substituted vinyl groups or ~-substituted allyl groups, preferably styrene; but also, for example, nuclear-chlorinated and nuclear alkylated or alkenylated styrenes, the alkyl groups containing 1 to 4 carbon atoms, such as, for example vinyl toluene, divinyl benzene, ~-methyl styrene, tert.-butyl styrene, chloro styrenes; vinyl esters of carboxylic acids with 2 *o 6 carbon atoms, preferably vinyl acetate;
vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and/or the esters thereof (prefer-ably viny~ allyl and methallyl ester~ with Le A 16 322 - 11 -.. . ~ .. . .
1 to 4 carbon atoms in the alcohol component, the amides and nitriles thereof, maleic anhydride, semi-esters and disesters with 1 to 4 carbon atoms in the alcohol compo-nent, semi-amides and diamides or cyclic imides such as N-methyl maleimide or N-cyclohexyl maleimide; allyl com-pounds such as allyl benzene and allyl este~ such as allyl acetate, phthalic acid diallylester, isophthalic acid diallyl ester, fumaric acid diallylester, allyl carbonates, diallyl carbonates, triallylphosphate and triallyl cyanurate.
The cellulose esters G to be used for the mixture according to the invention are obtained by conventional pro-cesses by esterification of cellulose with aliphatic mono-carboxylic anhydrides, preferably acetic anhydride and butyric anhydride, or acetic anhydride and propi-onic anhy-dride. The hydrolysis to be carried out in the crude solu-tion is controlled by a slight excess of water so that the desired hydroxyl content (40 to 100) is obtained. Bleaching by oxidation of the cellulose ester isolated from the solu-tion must be carried out so that oxidizing agent is no longer detectable in the end product. If necessary, after-treatment can be carried out with reducing agents.
To determine the OH number, the free hydroxyl groups of the cellulose ester are esterified with acetic anhydride in pyridine, the excess of anhydride reacted with water and retitrated (receipe: C~Jo Mahn, L.B. Genung and R.F. Williams, Analysis of Cellulose Derivatives, Industrial and Engineering Chemistry, Vol. 14, No. 12, 935 - 940 (1942).
Le A 16 322 - 12 -~054280 The cellulose esters C to be preferably used have an acetic acid content of 17 to 23% by weight and a butyric acid content of 45 to 50% by weight in the case of acetobuty-rates, a propionic acid content of 61 to 69% by weight and an acetic acid content of 2 to 7% by weight in the ~ase of acetopropionates. The OH numbers lie between 40 and 100.
Inorganic fillers, chemical thickeners, reinforcing agents, hardening catalysts, polymerisation inhibitors and optionally thixotroping agents,plgments, dyestuffs, release agents, ultra-violet absorbers etc. are usually added to the resin compositions in accordance with the invention, in order to produce free-flowing moulding compositions.
As inorganic fillers which are usually employed in amounts of 50 to 350 % by weight, based on the sum of the components A to C, there may be mentioned chalk, talcum, silica flour and slate flour, kaolin, calcite, dolomite, mica, barite, kieselguhr and aluminas.
- As chemical thickeners there may be mentioned the known oxides and hydroxides of the metals of the second main group of the periodic system, preferably of magnesium and calcium, in amounts of 0.1 to 10, preferably 1.0 to
871-56, formula B, and a hydroxyl number of between 40 and 100.
The invention further relates to the production of these resin compositions, characterized in that the com-ponents A to C are thoroughly mixed with one another in a manner known per se at temperatures between 60 and 80C
and allowed to solidify to a solid, gel-like composition by cooling to room temperature.
The invention further relates to the use of the herein described resin compositions to produce optionally fibre-reinforced moulding compositions.
Le A 16 322 - 6 -Whereas the known low-shrinking thermosetting poly-ester compo~itions have a two-phase structure after harden-ing, that is with thermoplast particles included in the polyester phase, no such phenomenon is detectable in the compositions according to the invention after they have hard-ened even when enlarged with the aid of an electronic microscope.
~,~-ethylenically unsaturated polyesters A within the scope of the invention are the usual polycondensation products of at least one ~,B-ethylenically unsaturated dicarboxylic acid generally with 4 to 5 carbon atoms or the ester-forming derivatives thereof, optionally in admixture with up to 90%
mol, based on the unsaturated acid components of at least one aliphatic saturated dicarboxylic acid with 4 to 10 carbon atoms, of a cyclo-aliphatic or aromatic dicarboxylic acid with 8 to 10 carbon atoms or the ester-forming derivatives thereof with at least one polyhydroxy compound, in particular dihydroxy compound, with 2 to 8 carbon atoms, that is poly-: ester as described by J. Bjorksten et al, in "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956.
Examples of unsaturated dicarboxylic acids or their derivatives to be preferably used are maleic acid or maleic anhydride and fumaric acid. However, it is also possible to employ mesaconic acid, citraconic acid, itaconic acid or chloro maleic acid. Examples of aliphatic saturated, cyclo-aliphatic and aromatic dicarboxylic acids or their deri-vatives to be used are phthalic acid or phthalic anhydride, Le A 16 322 - 7 -isophthalic acid, terephthalic acid, hexa or tetrahydrophthalic acid or their anhydrides, endomethylene tetrahydrophthalic acid or their anhydPide, succinic acid or succinic anhydride and succinic acid ester and succinic acid chlorides, adipic acid, sebacic acid. To produce almost non-inflammable resins, hexachloro-endomethylene tetrahydrophthalic acid, tetrachlorophthalic acid or tetrabromophthalic acid can be used. The polyesters to be preferably used con-tain maleic acid of which up to 25 mol % can be replaced by phthalic acid or by isophthalic acid. As bivalent alcohols there may be used ethylene glycol, propanediol-1,2, propane-diol-1,3, diethylene glycol, dipropylene glycol, butane diol-1,3, butane diol-1,4, neopentyl glycol, hexane diol-1,6~2,2-bis-(4-hydroxycyclohexyl)-propane, bis-oxalkylated bisphenol A, perhydrobisphenol and others. Ethylene glycol, propane diol-1,2, diethylene glycol and dipropylene glycol are preferably used.
Further modifications are possible by incorporating up to 10 mol %, based on the alcohol or acid component, of monohydric alcohols with 1 to 6 carbon atoms, such as methanol, ethanol, butanol, allyl alcohol, benzyl alcohol, cyclohexanol and tetrahydrofurfuryl alcohol, trimethylol propane, glycerine and pent~rythrite as well as of mono-allyl ethers, dially ethers and triallyl ethers and benzyl ethers of trihydric and polyhydric alcohols with 3 to 6 carbon atoms in accordance with German AS 1,024,654, as well as by incor-porating monobasic acids such as benzoic acid or long-chain unsaturated fatty acids such as oleic acid, fatty acid of linseed oil and ricinoleic acid.
Le A 16 322 - 8 -The acid numbers of polyester A should be between 5 and 30, preferably between 10 and 20, the OH numbers between 20 and 70, preferably between 30 and 50, and the molecular weights Mn.between about 500 and 5000, preferably between about 1000 and 2500 ~easured by vapour pressure osmosis in dioxane and acetone; where the values `differ the lower value is taken as being the more accurate one)O
Basically the content of ~ ethylenically unsaturated dicarboxylic acid residues which are condensed into the polyesters A can vary within a wide range. However, the articles manufactured from the moulding compositions accord-ing to the invention are removed from the mould a~ter application of pressure whilst still hot and should there-fore exhibit satisfactory resistance to thermal distortion.
It follows that high contents of ~,~-ethylenically unsatu-rated dicarboxylic acid residues of 0.70 to O.20 mols / 100 g of unsaturated polyester are preferred~
Preferred polyesters A are those having a B-compati-bility of 001 to 30~ by weight and a content of 0.20 to 0.70 mol of radically polymerisable ~,~-ethylenically un-saturated dicarboxylic acid radicals per 100 g of polyester A, or a B-compatibility of 30 to 45% by weight and a con-tent of 0.53 to 0.70 mol of radically polymerisable ~,B-ethylenically unsaturated dicarboxylic acid radicals per 100 g of polyester Ao The B-compatibility or B-solubility of unsaturated polyesters is a term analogous with the term styrene com-patibility known in the chemistry and technology of unsatu-rated polyester resins (cf. Johannes Scheiber, "Chemie uO
Technologie der k~nstlichen Harze," vol. 1, "Die Polymerisat-Le A 16 322 - 9 -.. , ....... . , .. ., ., .. ,~,.. ~ .. . . .
~054Z80 harze", Wissenschaftliche Verlagsgesellschaft MBH, Stutt-gart, 1961, 2nd Edition, pages 563 et seq., in particular pages 751/572).
The B-compatibility of the unsaturated polyesters, given in % by weight (unsaturated polyester), based on the total amount of unsaturated polyester and component B, is de~ined and determined as follows.
Unsaturated polyester is dissolved in component B
at about 80 to 100C in an amount just sufficient to yield a clear solution of known concentration after immediate cooling to room temperature. This solution is treated with additional amounts of component B at room temperature, whilst stirring, until the solution becomes turbid. The concentration, based on the total amount of component B
and unsaturated polyester, of the unsaturated polyester in percent by weight at turbidity point is defined as B-compatibilityO
The following example is given by way of explanation.
E (g) = total weight in grams of the clear polyester solution dissolved in component B with P ~ of unsaturated polyester, e.g~ 20 gO
P % = percent by weight of unsaturated polyesters dissol-ved to give a clear solution in component B, e.g.
60 %
S (g3 = component B, added up to the point of turbidity, is given in grams, e.g. 10 g B-compatibility = E(~ P (%3 e.g~ ~ ~ =
E(g) + S(g) 20g + 10g Le A 16 322 - 10 -.... . . ..
1054Z~30 It is known from experience that the B-compatibility of an unsaturated polyester is affected by the polyester components involved in its synthesis, that is by the acid and alcohol components used to synthesize the polyester.
Esterification components which give rise to B-incom-patibility are for example: maleic acid, maleic anhydride, fu-maric acid, ethylene glycol, diethylene glycol, hexane diol-1,6.
Esterification components which give rise to B-com-patibility are for example: phthalic acid, isophthalic acid, tetrachlorophthalic acid, hexachloro-endo-methylene tetPa-hydrophthalic acid or its anhydrides, propylene glycol-1,2, dipropylene glycol, butylene glycol-1,3, neopentyl glycol, trimethylol propane allyl ethers, perhydro bisphenol, bis-oxalkyl bisphenol etc.
Suitable copolymerisable vinyl and vinylidene compounds B within the scope of the invention are unsaturated compounds usually employed in polyester tecbnology, which preferably have ~-substituted vinyl groups or ~-substituted allyl groups, preferably styrene; but also, for example, nuclear-chlorinated and nuclear alkylated or alkenylated styrenes, the alkyl groups containing 1 to 4 carbon atoms, such as, for example vinyl toluene, divinyl benzene, ~-methyl styrene, tert.-butyl styrene, chloro styrenes; vinyl esters of carboxylic acids with 2 *o 6 carbon atoms, preferably vinyl acetate;
vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and/or the esters thereof (prefer-ably viny~ allyl and methallyl ester~ with Le A 16 322 - 11 -.. . ~ .. . .
1 to 4 carbon atoms in the alcohol component, the amides and nitriles thereof, maleic anhydride, semi-esters and disesters with 1 to 4 carbon atoms in the alcohol compo-nent, semi-amides and diamides or cyclic imides such as N-methyl maleimide or N-cyclohexyl maleimide; allyl com-pounds such as allyl benzene and allyl este~ such as allyl acetate, phthalic acid diallylester, isophthalic acid diallyl ester, fumaric acid diallylester, allyl carbonates, diallyl carbonates, triallylphosphate and triallyl cyanurate.
The cellulose esters G to be used for the mixture according to the invention are obtained by conventional pro-cesses by esterification of cellulose with aliphatic mono-carboxylic anhydrides, preferably acetic anhydride and butyric anhydride, or acetic anhydride and propi-onic anhy-dride. The hydrolysis to be carried out in the crude solu-tion is controlled by a slight excess of water so that the desired hydroxyl content (40 to 100) is obtained. Bleaching by oxidation of the cellulose ester isolated from the solu-tion must be carried out so that oxidizing agent is no longer detectable in the end product. If necessary, after-treatment can be carried out with reducing agents.
To determine the OH number, the free hydroxyl groups of the cellulose ester are esterified with acetic anhydride in pyridine, the excess of anhydride reacted with water and retitrated (receipe: C~Jo Mahn, L.B. Genung and R.F. Williams, Analysis of Cellulose Derivatives, Industrial and Engineering Chemistry, Vol. 14, No. 12, 935 - 940 (1942).
Le A 16 322 - 12 -~054280 The cellulose esters C to be preferably used have an acetic acid content of 17 to 23% by weight and a butyric acid content of 45 to 50% by weight in the case of acetobuty-rates, a propionic acid content of 61 to 69% by weight and an acetic acid content of 2 to 7% by weight in the ~ase of acetopropionates. The OH numbers lie between 40 and 100.
Inorganic fillers, chemical thickeners, reinforcing agents, hardening catalysts, polymerisation inhibitors and optionally thixotroping agents,plgments, dyestuffs, release agents, ultra-violet absorbers etc. are usually added to the resin compositions in accordance with the invention, in order to produce free-flowing moulding compositions.
As inorganic fillers which are usually employed in amounts of 50 to 350 % by weight, based on the sum of the components A to C, there may be mentioned chalk, talcum, silica flour and slate flour, kaolin, calcite, dolomite, mica, barite, kieselguhr and aluminas.
- As chemical thickeners there may be mentioned the known oxides and hydroxides of the metals of the second main group of the periodic system, preferably of magnesium and calcium, in amounts of 0.1 to 10, preferably 1.0 to
3.0~ by weight, based on the sum of the components A to C;
further, effective amounts of additives which accelerate or regulate chemical thickening, such as 0.1 to 0.5% by weight of water, based on the sum of the components A to C, or the additives in accordance with German OS 1,544,8~1, e.g.
aliphatic carboxylic acid or partial phosphoric acid esters.
Le A 16 322 - 13 --As fibre-forming reinforcing materials there may be used the customary inorganic fibres such as metal fibres, asbestos fibres, carbon fibres, in particular glass fibres, and organic fibres, for example cotton fibres, polyamide fibres, polyester fibres, polyacrylonitrile fibres, or polycarbonate fibres in amounts of 5 to 100 % by weight, ; based on the sum of the components A to C.
Polymerisation initiators in normal amounts, prefer-ably 0.5 to 5% by weight, based on the sum of the components A to C, are added at any time prior to hardening of the moulding compositions produced from the resin compositions of the invention. Suitable polymerisation initiators are for example: diacyl peroxides, such as diacetyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, tert.-butyl peroxide; peroxyester such as tert.- butyl peroxy-acetate, tert.-butyl peroxy-benzoate, tert.-butyl peroctoate;
dicyclohexyl peroxydicarbonate or 2,5-dimethyl hexane-2,5-diperoctoate; alkyl peroxides such as bis-(tert.-butyl peroxybutane), dicumyl peroxide, tert.-butyl cumyl peroxide;
hydroperoxides such as cumol hydroperoxide, tert.-butyl hydroperoxide, cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide; perketals; ketone peroxides such as acetyl acetone peroxide, or azoisobutyrodinitrile.
In order to protect the resin compositions of the invention from unwanted, premature polymerisation, it is advisable to treat them during production with 00001 to 0.1 by weight, based on the sum of the components A to C~of polymerisation inhibitors or antioxidantsO
Le A 16 322 - 14 -Suitable auxiliaries of thls kind are, ~or example, phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with 1 to 6 carbon atoms, in both o-positions to the phenolic hydroxy group, amines, preferably secondary aryl amines and their derivatives, quinones, copper salts of organic acids, addi-tion compounds of copper-(I) halides to phosphites, such as for example 4,4'-bis-(2,6-di-tert.-butyl phenol), 1,3,5-trimethyl-2~4,6-tris-(3~5-di-tert.-butyl-4-hydroxy-benzyl)-benzene, 4,4'-butylidene-bis-(6-tert.-butyl-m-cresol), 3,5-di-tert.-butyl-4-hydroxy-benzyl-phosphonic acid diethyl ester, N,N'-bis-(B-naphthyl-p-phenylene diamine, N,N'-bis-(1-methyl heptyl)-p-phenylene diamine, phenyl-B-naphthyl-amine, 4,4'-bis~ -dimethyl-benzyl)-diphenyl am~n~,1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxy-hydrocinnamoyl)-hexane-hydro-s-triazine, hydroquinone, p-benzoquinone, toluhydro-quinone, p-tert.-butyl pyrocatechol, chloro-aniline, naphthoquinone, copper naphthenate, copper oct~a$e, copper(I) chloride/triphenyl phosphite, copper (I) chloride/trimethyl phosphite, copper (I) chloride/trischloroethyl-phosphite, copper (I) chloride/tripropyl phosphite, p-nitroso-dimethyl aniline. Other suitable stabilizers are described in "Methoden der organischen Chemie" (Houben-Weyl), 4th Edition, Vol. XIV/1, pages 433-452, Georg Thieme publishing company, Stuttgart, 1961. P-benzoquinone in a concentration of 0.01 to 0.05 % by weight, based on the sum of the components A ~ C, is, for example~excellently suitable.
Le A 16 322 - 15 -~OS4Z80 Furthermore, it is possible, if desired, to add effective amounts of the usual thixotroping agents, for example inorganic agents, such as aerosil or organic agents such as polyisocyanates, polyester amides, polyamides, polyure-thanes or cyclohexyl amides of higher fatty acids (German AS
1,182,816, 1,217,611, Belgian patent specifications 693,580 and 727,952).
Mixing of the different components of the moulding compositions to be prepared ~rom the resin compositions of the invention is preferably carried out in kneaders, dissol-vers, on roller mills, and possibly in mortars for manually performed tests. The production of a free-flowing granulate can be carried out for example in such a manner that a glass-fibre skein is impregnated with the molten moulding composi-tion of the invention, and after cooling to room temperature chopped into granul~s~
The moulding compositions of the invention can be cured at about 120 - 160C employing a pressure of approximately 20 to 140 kp/cm2. The time required will be about 0.5 to 5 minutes depending on the size and shape of the mouldings.
It will be seen that the resulting mouldings undergo a minimum amount of shrinkage.
The degree of shrinkage depends essentially on the processing conditions (cf. Schulz-Walz and 0. Walter, Kunststoff-Rundschau 1972, NQ . 1 1, page 592:
Le A 16 322 - 16 -10 Mouldings, in which the glass fibres are arranged in the direction of pressure, undergo considerably less shrinkage than those in which the glass-fibres are arranged transversely to the direction of pressureO
2~ Shrinkage increases with rising pressureO
30 Surface gloss and smoothness increase as the mould temperature rises; however, if a certain tempera-ture is exceeded, then dull spots will appear.
further, effective amounts of additives which accelerate or regulate chemical thickening, such as 0.1 to 0.5% by weight of water, based on the sum of the components A to C, or the additives in accordance with German OS 1,544,8~1, e.g.
aliphatic carboxylic acid or partial phosphoric acid esters.
Le A 16 322 - 13 --As fibre-forming reinforcing materials there may be used the customary inorganic fibres such as metal fibres, asbestos fibres, carbon fibres, in particular glass fibres, and organic fibres, for example cotton fibres, polyamide fibres, polyester fibres, polyacrylonitrile fibres, or polycarbonate fibres in amounts of 5 to 100 % by weight, ; based on the sum of the components A to C.
Polymerisation initiators in normal amounts, prefer-ably 0.5 to 5% by weight, based on the sum of the components A to C, are added at any time prior to hardening of the moulding compositions produced from the resin compositions of the invention. Suitable polymerisation initiators are for example: diacyl peroxides, such as diacetyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, tert.-butyl peroxide; peroxyester such as tert.- butyl peroxy-acetate, tert.-butyl peroxy-benzoate, tert.-butyl peroctoate;
dicyclohexyl peroxydicarbonate or 2,5-dimethyl hexane-2,5-diperoctoate; alkyl peroxides such as bis-(tert.-butyl peroxybutane), dicumyl peroxide, tert.-butyl cumyl peroxide;
hydroperoxides such as cumol hydroperoxide, tert.-butyl hydroperoxide, cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide; perketals; ketone peroxides such as acetyl acetone peroxide, or azoisobutyrodinitrile.
In order to protect the resin compositions of the invention from unwanted, premature polymerisation, it is advisable to treat them during production with 00001 to 0.1 by weight, based on the sum of the components A to C~of polymerisation inhibitors or antioxidantsO
Le A 16 322 - 14 -Suitable auxiliaries of thls kind are, ~or example, phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with 1 to 6 carbon atoms, in both o-positions to the phenolic hydroxy group, amines, preferably secondary aryl amines and their derivatives, quinones, copper salts of organic acids, addi-tion compounds of copper-(I) halides to phosphites, such as for example 4,4'-bis-(2,6-di-tert.-butyl phenol), 1,3,5-trimethyl-2~4,6-tris-(3~5-di-tert.-butyl-4-hydroxy-benzyl)-benzene, 4,4'-butylidene-bis-(6-tert.-butyl-m-cresol), 3,5-di-tert.-butyl-4-hydroxy-benzyl-phosphonic acid diethyl ester, N,N'-bis-(B-naphthyl-p-phenylene diamine, N,N'-bis-(1-methyl heptyl)-p-phenylene diamine, phenyl-B-naphthyl-amine, 4,4'-bis~ -dimethyl-benzyl)-diphenyl am~n~,1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxy-hydrocinnamoyl)-hexane-hydro-s-triazine, hydroquinone, p-benzoquinone, toluhydro-quinone, p-tert.-butyl pyrocatechol, chloro-aniline, naphthoquinone, copper naphthenate, copper oct~a$e, copper(I) chloride/triphenyl phosphite, copper (I) chloride/trimethyl phosphite, copper (I) chloride/trischloroethyl-phosphite, copper (I) chloride/tripropyl phosphite, p-nitroso-dimethyl aniline. Other suitable stabilizers are described in "Methoden der organischen Chemie" (Houben-Weyl), 4th Edition, Vol. XIV/1, pages 433-452, Georg Thieme publishing company, Stuttgart, 1961. P-benzoquinone in a concentration of 0.01 to 0.05 % by weight, based on the sum of the components A ~ C, is, for example~excellently suitable.
Le A 16 322 - 15 -~OS4Z80 Furthermore, it is possible, if desired, to add effective amounts of the usual thixotroping agents, for example inorganic agents, such as aerosil or organic agents such as polyisocyanates, polyester amides, polyamides, polyure-thanes or cyclohexyl amides of higher fatty acids (German AS
1,182,816, 1,217,611, Belgian patent specifications 693,580 and 727,952).
Mixing of the different components of the moulding compositions to be prepared ~rom the resin compositions of the invention is preferably carried out in kneaders, dissol-vers, on roller mills, and possibly in mortars for manually performed tests. The production of a free-flowing granulate can be carried out for example in such a manner that a glass-fibre skein is impregnated with the molten moulding composi-tion of the invention, and after cooling to room temperature chopped into granul~s~
The moulding compositions of the invention can be cured at about 120 - 160C employing a pressure of approximately 20 to 140 kp/cm2. The time required will be about 0.5 to 5 minutes depending on the size and shape of the mouldings.
It will be seen that the resulting mouldings undergo a minimum amount of shrinkage.
The degree of shrinkage depends essentially on the processing conditions (cf. Schulz-Walz and 0. Walter, Kunststoff-Rundschau 1972, NQ . 1 1, page 592:
Le A 16 322 - 16 -10 Mouldings, in which the glass fibres are arranged in the direction of pressure, undergo considerably less shrinkage than those in which the glass-fibres are arranged transversely to the direction of pressureO
2~ Shrinkage increases with rising pressureO
30 Surface gloss and smoothness increase as the mould temperature rises; however, if a certain tempera-ture is exceeded, then dull spots will appear.
4. By applying pressure for a longer period of time the surface gloss can be considerably improved.
5. The tendency to form spots is reduced the slower the catalyst system reacts, that is the higher the tempera-ture at which the catalyst becomes effective.
In summary it may be said that the shrinkage occurring in the reaction of a low-shrinking, thermosetting polyester resin depends on the pressure applied. This not only means that shrinkage will vary depending on the pressure applied, but that the shrinkage will vary wi-thin the moulding de-pending on the location, direction, glass-fibre arrange-ment or thickness of material.
The resin compositions of the invention can be widely used in large-scale production. From these compositions granulatable, free-flowing moulding compositions can be prepared, which can be injection-moulded in conventional injection-moulding apparatus, such as have been used up to now to process thermoplasts, and mouldings obtained without Le A 16 322 - 17 -1054Z~30 more filler having to be added to these mixtures than to - conventional resin mats or moulding compositions which do not possess free-flowing properties. Accordingly, the mouldings prepared from the mixtures of the invention are distinguished by excellent mechanical strength, and since curing proceeds without any shrinkage worth mentioning, the mouldings have none of the negative features usually accom-panying shrinkage. They have a very smooth, glossy surface and excellent dimensional accuracy. The mouldings can be easily removed from the mould and are free from any un-wanted coatings. No signs of internal crac~ing are detect-able even in the thicker partsO They can be advantageously used where mouldings are required with great accuracy to size and flawless surfaces, e.g. in the furniture industry or in the car industryO
The following Examples serve to illustrate the inven-tionO The percentages indicated in the ~ollowing are ~ by weight O
The polyester A, used in the following Examples, was prepared in the following manner:
1.05 mol of propylene glycol, 0.85 mol of maleic an-hydride and 0.15 mol of phthalic anhydride were slowly hea~ed to 190C in a protective gas atmosphere and kept at this temperature until an acid number of 15 had been reached.
The OH number of the resulting polyester A was 40; the vis-cosity was 1500 centipoises (65% in styrene30 Le A 16 322 - 18 -.. . . . ......
~054Z80 Two cellulose aceto-butyrates with the ~ollowing characteristics were used as cellulose ester C:
C I C II
(comparison) Acetic acid content 22 % 22 %
Butyric acid content 45 % 45 %
Viscosity (sec.)measured according to ASTM D 871-56, formula B O.l 16 OH number 45 56 Le A 16 322 - 19 -Example i (Com~arison) 30 parts by weight of C I were admixed with 35 parts by weight of styrene at 80C. 35 parts by weight of the hot melts of the unsaturated polyester A were then made to flow into the hot solution. The mixture was thoroughly stirred and allowed to cool. A clear solution was formed at room temperature which did not solidifyO
Example 2 The following components were mixed analogously to Example 1:
30 parts by weight of C II
35 parts by weight of styrene 35 parts by weight of polyester A.
This mixture solidified to a gel on cooling which had a dry, tacky-free surface, Exam~le 3 A mixture of 100 parts by weight of a polyester solu-tion according to Example 2, 100 parts by weight of filler ; (calcium carbonate,Durcal 5, commercial product of the firm of Omya), 4 parts by weight of zinc stearate, 0.75 parts by weight of tert.-butyl perbenzoate, 50 parts by weight of glass-fibre (2.5 cm long) were mixed in a Co-kneader or extruder at a temperature of 60Co The skein emerging from the nozzle of the kneader was cooled and granulated.
The resultant granulate had a dry, non-adhesive surface and showed no tendency to become tacky even if stored for months.
Le A 16 322 - 20 -~o~4~BO
Moulded pieces could be easily produced ~rom the granu-late both in moulds in steel apparatus and in fully auto-matic injection-moulding machines. The resulting mouldings exhibited high mechanical strength (corresponding to the moulding compositions in accordance with DIN 16 911). In addition, they had a high-surface finish and perfect dimen-sional accuracy.
Le A 16 322 - 21 -
In summary it may be said that the shrinkage occurring in the reaction of a low-shrinking, thermosetting polyester resin depends on the pressure applied. This not only means that shrinkage will vary depending on the pressure applied, but that the shrinkage will vary wi-thin the moulding de-pending on the location, direction, glass-fibre arrange-ment or thickness of material.
The resin compositions of the invention can be widely used in large-scale production. From these compositions granulatable, free-flowing moulding compositions can be prepared, which can be injection-moulded in conventional injection-moulding apparatus, such as have been used up to now to process thermoplasts, and mouldings obtained without Le A 16 322 - 17 -1054Z~30 more filler having to be added to these mixtures than to - conventional resin mats or moulding compositions which do not possess free-flowing properties. Accordingly, the mouldings prepared from the mixtures of the invention are distinguished by excellent mechanical strength, and since curing proceeds without any shrinkage worth mentioning, the mouldings have none of the negative features usually accom-panying shrinkage. They have a very smooth, glossy surface and excellent dimensional accuracy. The mouldings can be easily removed from the mould and are free from any un-wanted coatings. No signs of internal crac~ing are detect-able even in the thicker partsO They can be advantageously used where mouldings are required with great accuracy to size and flawless surfaces, e.g. in the furniture industry or in the car industryO
The following Examples serve to illustrate the inven-tionO The percentages indicated in the ~ollowing are ~ by weight O
The polyester A, used in the following Examples, was prepared in the following manner:
1.05 mol of propylene glycol, 0.85 mol of maleic an-hydride and 0.15 mol of phthalic anhydride were slowly hea~ed to 190C in a protective gas atmosphere and kept at this temperature until an acid number of 15 had been reached.
The OH number of the resulting polyester A was 40; the vis-cosity was 1500 centipoises (65% in styrene30 Le A 16 322 - 18 -.. . . . ......
~054Z80 Two cellulose aceto-butyrates with the ~ollowing characteristics were used as cellulose ester C:
C I C II
(comparison) Acetic acid content 22 % 22 %
Butyric acid content 45 % 45 %
Viscosity (sec.)measured according to ASTM D 871-56, formula B O.l 16 OH number 45 56 Le A 16 322 - 19 -Example i (Com~arison) 30 parts by weight of C I were admixed with 35 parts by weight of styrene at 80C. 35 parts by weight of the hot melts of the unsaturated polyester A were then made to flow into the hot solution. The mixture was thoroughly stirred and allowed to cool. A clear solution was formed at room temperature which did not solidifyO
Example 2 The following components were mixed analogously to Example 1:
30 parts by weight of C II
35 parts by weight of styrene 35 parts by weight of polyester A.
This mixture solidified to a gel on cooling which had a dry, tacky-free surface, Exam~le 3 A mixture of 100 parts by weight of a polyester solu-tion according to Example 2, 100 parts by weight of filler ; (calcium carbonate,Durcal 5, commercial product of the firm of Omya), 4 parts by weight of zinc stearate, 0.75 parts by weight of tert.-butyl perbenzoate, 50 parts by weight of glass-fibre (2.5 cm long) were mixed in a Co-kneader or extruder at a temperature of 60Co The skein emerging from the nozzle of the kneader was cooled and granulated.
The resultant granulate had a dry, non-adhesive surface and showed no tendency to become tacky even if stored for months.
Le A 16 322 - 20 -~o~4~BO
Moulded pieces could be easily produced ~rom the granu-late both in moulds in steel apparatus and in fully auto-matic injection-moulding machines. The resulting mouldings exhibited high mechanical strength (corresponding to the moulding compositions in accordance with DIN 16 911). In addition, they had a high-surface finish and perfect dimen-sional accuracy.
Le A 16 322 - 21 -
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Thermosetting low-shrinking resin compositions suitable for the production of free-flowing moulding compositions, said resin compositions consisting of A) 10 to 50 parts by weight of non-crystalline .alpha.,.beta.-ethylenically unsaturated polyesters B) 20 to 90 parts by weight of copolymerisable vinyl or vinylidene compounds and C) 10 to 50 parts by weight of cellulose ester of organic monocarboxylic acids with 2 to 4 carbon atoms, characterized in that a) the polyesters A have a B-compatibility of 45 to 90% by weight or a B-compatibility of 0.1 to 45% by weight and a content of 0.20 to 0.70 mol of radically polymerisable .alpha.,.beta.-ethylenically unsaturated dicarboxylic acid radicals per 100 g of polyester A, and b) the cellulose esters C have a viscosity corresponding to a time of outflow of at least 10 seconds and a hydroxyl number of between 40 and 100.
2. A process for the production of resin compositions according to Claim 1, characterized in that the components A to C are thoroughly mixed with one another at temperatures between 60 and 80°C and allowed to solidify by cooling to room temperature to form a solid, gel-like composition.
3. A method of forming a moulded article comprising adding a resin composition according to Claim 1 to a mould and applying heat thereto.
4. The method according to Claim 3, characterized in that the resin composition is glass-fibre toughened.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752513252 DE2513252A1 (en) | 1975-03-26 | 1975-03-26 | FOR THE PRODUCTION OF RIBBON MOLDING COMPOUNDS, LOW-SCREENING RESIN COMPOUNDS BASED ON UNSATURATED POLYESTER RESINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1054280A true CA1054280A (en) | 1979-05-08 |
Family
ID=5942387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA226,785A Expired CA1054280A (en) | 1975-03-26 | 1975-05-13 | Thermosetting resin compositions with low shrinkage on the base of unsaturated polyester resins suitable for the production of moulding compositions capable of freely flowing |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS51111285A (en) |
| AT (1) | AT348767B (en) |
| BE (1) | BE828947A (en) |
| CA (1) | CA1054280A (en) |
| CH (1) | CH611322A5 (en) |
| DE (1) | DE2513252A1 (en) |
| ES (1) | ES437543A1 (en) |
| FR (1) | FR2305464A1 (en) |
| GB (1) | GB1476591A (en) |
| IT (1) | IT1035694B (en) |
| NL (1) | NL7505674A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE435520B (en) * | 1980-05-07 | 1984-10-01 | Mo Och Domsjoe Ab | CELLULOSAMASSA FOR USE IN CEMENT PLASTS AND SETS FOR ITS MANUFACTURING |
| DE3048697A1 (en) | 1980-12-23 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS FROM COPROPPER POLYMERISAT |
| DE3048696A1 (en) * | 1980-12-23 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS FROM COPROPROPY POLYMERISATES OF CELLULOSE ESTERS |
| JPS61276836A (en) * | 1985-05-31 | 1986-12-06 | Daihachi Kagaku Kogyosho:Kk | Cellulose derivative resin composition |
-
1975
- 1975-03-26 DE DE19752513252 patent/DE2513252A1/en not_active Withdrawn
- 1975-05-05 AT AT342175A patent/AT348767B/en not_active IP Right Cessation
- 1975-05-06 GB GB1896675A patent/GB1476591A/en not_active Expired
- 1975-05-07 CH CH589875A patent/CH611322A5/en not_active IP Right Cessation
- 1975-05-09 ES ES437543A patent/ES437543A1/en not_active Expired
- 1975-05-12 BE BE156244A patent/BE828947A/en unknown
- 1975-05-12 IT IT4954575A patent/IT1035694B/en active
- 1975-05-13 CA CA226,785A patent/CA1054280A/en not_active Expired
- 1975-05-14 NL NL7505674A patent/NL7505674A/en not_active Application Discontinuation
- 1975-05-15 FR FR7515261A patent/FR2305464A1/en active Granted
- 1975-05-16 JP JP5753575A patent/JPS51111285A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ES437543A1 (en) | 1977-01-16 |
| DE2513252A1 (en) | 1976-10-07 |
| JPS51111285A (en) | 1976-10-01 |
| IT1035694B (en) | 1979-10-20 |
| GB1476591A (en) | 1977-06-16 |
| AT348767B (en) | 1979-03-12 |
| CH611322A5 (en) | 1979-05-31 |
| NL7505674A (en) | 1976-09-28 |
| FR2305464B1 (en) | 1978-10-27 |
| ATA342175A (en) | 1978-07-15 |
| BE828947A (en) | 1975-11-12 |
| FR2305464A1 (en) | 1976-10-22 |
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