CS253150B1 - Method of antiemission means preparation for undersaturated polyester resins - Google Patents

Abstract

Solution se concerns preparation resources against evaporation volatile components primarily styrene, from unsaturated polyester resins. His substance rests in that, that se submits each other reaction closer specified types alcohols or ether alcohols, polycarboxylic acids kyse # tench and epoxy compounds ve established ratios at temperature 40 to 240 ° C and possibly in presence accelerators to to decline numbers acidity reactionary product under 10 mg KOH / g taking on beginning, in progress or after at the end # it reaction can add still commonly used additives.

Description

BACKGROUND OF THE INVENTION The present invention relates to a process for preparing anti-emissive compositions for reducing the evaporation of volatile components, in particular styrene, from unsaturated polyester resins.

Various substances are used worldwide as anti-emissive agents such as paraffin, waxes, fatty acid esters of multifunctional alcohols (U.S. Pat. No. 2,554,930), cellulose acetobutyrate (Japanese Pat. S. 81 116 713), monoester maleate ( No. 2,065,663), aromatic hydrocarbon resins. compounds (European Pat. No. 27,666) or esters of higher fatty acids with epoxides (Pol. Nos. 216,027 and 221,931).

Paraffin alone has the highest anti-emissive effect, which, however, causes poor product surfaces and is unstable in the storage of unsaturated polyester resins. The other substances do not have these negative properties, but in turn have low antiemission activity.

These drawbacks are solved by the present invention, which relates to a process for the preparation of antiemissants for unsaturated polyester resins by the reaction of alcohols and / or ether alcohols, polycarboxylic acids and / or their anhydrides and epoxide compounds and the addition of waxy additives with a solubility parameter of 7.5 to 9 in mol. weight of 300 to 10,000 and softening temperature of 30 to 200 ° C, reactive and non-reactive solvents and diluents, antioxidants, polymerization inhibitors, corrosion inhibitors, flow agents, surfactants, accelerators, plasticizers, flexibleizers, extenders, dyes, pigments and fillers.

The essence of the invention is that 30 to 5,000 wt. parts by weight of alcohols and / or ether alcohols having 1 to 4 hydroxyl groups and with a mol. 30 to 5,000, 90 to 800 wt. % by weight of polycarboxylic acids having a carbon number of 4 to 400 and / or their anhydrides and 80 to 10,000 wt. parts of epoxy compounds of mol. 80 to 10,000 weight and an epoxy equivalent of 0.05 to 0.95 are subjected to a temperature of 40 to 240 ° C and optionally in the presence of up to 10 wt. parts of accelerators, especially quaternary ammonium base salts, react with each other until the acid value of the reaction product falls below 10 mg KOH / g.

At the beginning and / or during and / or after the reaction, 10 to 10,000 wt. parts of the above additives. Either all of the reactants may be subjected to this reaction simultaneously or first alcohols and / or ether alcohols may be reacted with polycarboxylic acids and / or their anhydrides at a temperature of 40 to 240 ° C until the acid number of the reaction mixture drops to 40 to 480 mg KOH. g and the partial ester thus obtained is then reacted with epoxy compounds at a temperature of 20 to 180 ° C until the acid number of the product falls below 10 mg KOH / g.

The anti-emissive compositions prepared according to the invention have very good anti-emissive activity, are well compatible with unsaturated polyester resins and do not affect the mechanical properties of the cured products. In addition, they inhibit the oxygen inhibitory effect during curing. Cured surfaces are hard, free of surface defects and mainly do not smell of styrene. Said production process is relatively simple and can therefore be carried out in conventional reactors with a heated jacket or a heating and cooling coil provided with an anchor stirrer and possibly an azeotropic extension. In systems where no reaction water is produced, the process is waste-free.

It may be conducted in one or more subsequent operations in the reactor until the final product is formed.

The main component of the antiemissant is a resin product resulting from the mutual reaction of the alcoholic, acidic and epoxy constituents. In particular, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanols, hexanols, heptanols, octanols, decanols, benzyl alcohol, tetrahydrofurfuryl alcohol, furyl alcohol, adducts of substituted alcohols or phenols with ethylene or propylene oxide, polyethers, polyetheres polyethylene oxides, polypropylene oxides, glycols and polyglycols, hydroxyl-terminated polybutadienes, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol etc.

Suitable acid components are various types of unsaturated or saturated acids, such as maleic, fumaric, tetrahydrophthalic, hexahydrophthalic, endomethylenetetrahydrophthalic, chlorotetrahydrophthalic, succinic, glutaric, adipic, sebacic, dimerized fatty acids, trimellitic acid, trimellitic acid, pyromellic acid, pyromalic acid, pyromellic acid, , sebacic and lemon, and their anhydrides.

Useful epoxy compounds can be, for example, condensation products of epichlorohydrin and its derivatives or dihalohydrins with substances containing at least one active hydrogen. These are in particular glycidyl ethers derived from phenols such as phenol, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylsulfone, tris- and tetrakis (hydroxyphenyl) alkanes, resorcinol, hydroquinone, phenol- and cresol-formaldehyde novolaks, further derived from aliphatic heterogeneous and cycloaliphatic alcohols such as butanol, tetrahydrofurfuryl alcohol, ethylene glycol, butylene glycol, cyclohexanol, ethylene-oxidized 4,4'-dihydroxydiphenylpropane, allyl glycidyl ether, further carboxylic acid-derived glycidyl esters such as phthalic acid, diphthalic acid and the like glycidylamines such as diglycidylaniline, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, epoxidized unsaturated compounds such as epoxidized unsaturated oils, cyclopentadiene pentoxide, divinylbenzene dioxide dioxide, bis (2,3-epoxycyclopentyl) ether, glycidyl esters of unsaturated acids such as glycidyl methacrylate, glycidyl acrylate, glycidyl thioethers and the like.

Examples of suitable non-polar waxy substances are ceresin, paraffin, beeswax, lanolin, stearic acid, palmitic acid, cerotic, ozokerite, carnauba wax, Japanese wax, Chinese wax, myristyl alcohol, cetyl alcohol, low molecular weight polymers of propylene, isobutylene, ethylene or vinyl chloride. resins, or others.

In particular, organic non-reactive solvents such as toluene, xylene, white spirit and diluents such as benzyl alcohol, reactive solvents such as styrene, acrylates and methacrylates, antioxidants and polymerization inhibitors such as hydroquinone or Ν, Ν'-dimethyldiaminodiphenylmethane are used as additives, flow agents, such as, for example, copolymers of butyl acrylate with methyl methacrylate of mol. surfactants such as phenol ethylene oxide adducts, corrosion inhibitors such as cyclized ammonium amide amides, accelerators such as zinc octoates, chromites and plasticizers such as dibutyl phthalate and dioctyl phthalate.

Anti-emission agents are used to reduce the evaporation of styrene from styrene-containing materials, mainly from unsaturated polyester resins used as paints, sealants; casting flooring, binders for preparation of laminates etc. They are added to the masses either directly at the producer of these masses or up to the consumer before their actual processing.

He did

517 wt. parts of fatty alcohols having a carbon number of 12 to 18, 245 wt. parts by weight of maleic anhydride, 1044 wt. 0.5 parts of dimethyllaurylbenzylammonium bromide (0.5 g) are successively weighed into a reaction vessel and heated at 100 ° C for 3 hours until the acid number drops to 0.1 mg KOH / g. It is then cooled to 80 ° C and 260 wt. parts by weight of paraffin having a softening point of 58-60 ° C and 2068 wt. parts of toluene. The system is stirred for 1 hour at 80 ° C, the resulting clear solution is allowed to cool to 60 ° C over 1 hour and then discharged into shipping containers. The mass, after cooling to 20 ° C, is in the form of a solidified jelly with a clarification temperature of 43 to 45 ° C.

Example 2 wt. parts of butanol and 98 wt. A portion of maleic anhydride was weighed into a reaction vessel and allowed to react at 100 ° C for 1 hour to a partial acid ester with an acid number of 350 mg KOH / g. 0.5 wt. parts of triethanolamine and 200 wt. parts of a phenolic novolak low molecular weight epoxy resin with an epoxy equivalent of 0.45 and reacted at

120 ° C for 5 h to an acid number below 1 mg KOH / g. The temperature is lowered to 90 ° C, 150 wt. parts of styrene. The resulting clear solution was allowed to cool to 60 ° C and discharged into shipping containers. The cold mass is semi-solid.

Example 3

000 wt. parts by weight of hydroxyl-terminated polybutadiene-based liquid rubber having a hydroxyl value of 320 mg KOH / g, 25 wt. parts of butanol, 150 wt. phthalic anhydride, 500 wt. parts by weight of a bisphenol A based epoxy resin having an epoxy equivalent of 0.3, 1,500 wt. parts of xylene and 50 wt. parts of benzyldimethylamine and reacted at 120 ° C for 8 h until the acid number fell below 1 mg KOH / g. 500 wt. After stirring for 2 h, cool to 60 ° C and discharge into transport containers. The composition is cold solid at a melting point of 55-60 ° C.

Example 4

000 wt. parts of polypropylene oxide having a hydroxyl value of 40 mg KOH / g are esterified in the melt at 220 ° C for 12 h with 800 wt. parts of dimerized fatty acids (with the addition of 3 parts by weight of chromium stearate) having an acid number of 180 mg KOH / g. After cooling to 150 ° C, 200 wt. parts of aniline-based epoxy resin having an epoxy equivalent of 0.7, heated for 5 h, and then at 2000C, 2000 wt. parts of ozokerite and condenses thoroughly. The resulting mass is solid at normal temperature, has a softening point of 80 ° C and is well soluble in styrene.

Example 5

108 wt. parts of benzyl alcohol, 450 wt. parts by weight of hexachlorenedomethylenetetrahydrophthalic anhydride, 200 wt. parts of epichlorohydrin, 8 wt. parts by weight of zinc octoate, 150 parts by weight of low molecular weight polypropylrene; parts of xylene and 50 wt. A portion of dibutyl phthalate was weighed into a reaction vessel and allowed to react at 100 ° C for 18 h until the acid number fell below 0.1 mg KOH / g. Upon completion of the reaction, the mass is discharged into shipping containers as a clear solution which, upon cooling, has the appearance of a slightly turbid viscous liquid.

Example 6

100 wt. parts of tetrahydrofurfuryl alcohol and 200 wt. parts of trimellitic anhydride were reacted at 140 ° C for 2 hours to give a partial acid ester with an acid number of 420 mg KOH / g. A 70% solution of epoxidized styrene-butadiene copolymers of mol. % by weight 8.10 in dibutyl maleate in an amount of 500 wt. parts, 800 wt. parts of lanolin and reacted at 160 ° C for 10 h until the acid number fell below 1 mg KOH / g. The clear product is bottled at 120 ° C in shipping containers in which it solidifies to a solid with a softening temperature of 60 to 70 ° C.

Example 7 wt. parts by weight of ethylene glycol and 146 wt. parts of carboxyl-terminated liquid polybutadiene are azeotropically esterified at 190 ° C until the acid number drops below 5 mg KOH / g. Then 10 wt. parts of maleic anhydride are added and the mixture is allowed to react at 120 ° C for 2 h. 20 parts by weight of epoxyester solution prepared by esterifying a bisphenol A-based medium-molecular epoxy resin with linseed fatty acids in a mixture of xylene and butanol and reacted at 120 DEG C. for 4 hours. % of butadiene methacrylate-styrene block copolymers containing 10 wt. % methacrylate and 20 wt. styrene and allowed to homogenize at 150 ° C for 2 h. The resulting melt is discharged onto sheets, where it cools to a mass with a softening point of 70-75 ° C.

Example 8

100 wt. parts of liquid polybutadiene of mol. weight 4,500 is heated for 2 h with 20 wt.

parts of maleic anhydride at 200 ° C. The reaction mixture was then cooled to 120 ° C and 20 wt. parts of butanol. To the resulting product having an acid number of about 80 mg KOH / g is added 1 wt. % magnesium octoate and 60 wt. parts of a low molecular weight epoxy resin having an epoxy equivalent of 0.48 and heated at 120 ° C for 2 h until the acid number fell below 5 mg KOH / g. 100 wt. parts by weight of a mixture of hydrocarbon resin and paraffin having a softening point of 64 to 66 ° C by weight 1: 1 ratio. Finally, 50 wt. parts of benzyl alcohol and the resulting melt is discharged into drums after stirring for 1 h. The final product is a jelly-like mass with a clarification temperature of 45 to 50 ° C.

Example 9

132 wt. parts of trimethylolpropane and 196 wt. A portion of maleic anhydride is weighed into a reaction flask and the mixture is allowed to react at 100 ° C for 2 h to give a partial ester with an acid number of 340 mg KOH / g. 0.7 wt. parts of chlorcholine chloride and 270 wt. parts of butyl glycidyl ether with an epoxide equivalent of 0.78 and reacted at 110 ° C for 6 h until the acid number fell below 0.1 mg KOH / g. 200 wt. parts of paraffin having a softening point of 52 DEG-56 DEG C. and stirred for 1 hour. The slightly colored solution is pumped hot to 80,000 wt. parts of a propylene glycol, phthalic anhydride and maleic anhydride polyester resin and mixed at 120 ° C for 2 h. The resulting resin is slightly opalescent and has a high antiemission efficiency (min. 90%) Example 10

The procedure of Example 1, except that 10,000 wt. parts of styrene containing hydroquinone as polymerization inhibitor. Upon cooling, a clear solution is formed which is easier to dispense into the unsaturated polyester resin under operating conditions.

Claims (3)

SUBJECT OF THE INVENTION A process for the preparation of antiemissant compositions for unsaturated polyester resins by reacting alcohols and / or ether alcohols, polycarboxylic acids and / or their anhydrides and epoxy compounds and adding additives from the group comprising waxy substances with a solubility parameter of 7.5 to 9, by mol. weight of 300 to 10,000 and softening temperature of 30 to 200 ° C, reactive and non-reactive solvents and diluents, antioxidants, polymerization inhibitors, corrosion inhibitors, flow agents, surfactants, accelerators, plasticizers, flexibleizers, extenders, dyes, pigments and fillers, characterized by in that 30 to 5 000 parts by weight of alcohols and / or ether alcohols having 1 to 4 hydroxyl groups and mol. 30 to 5000, 90 to 800 parts by weight of polycarboxylic acids having a number of carbon atoms of 4 to 400 and / or anhydrides thereof and 80 to 10,000 parts by weight of epoxy compounds having a mol. weighing 80 to 10,000 and an epoxy equivalent of 0.05 to 0.95 are subjected to a reaction at a temperature of 40 to 240 ° C and optionally in the presence of up to 10 parts by weight of accelerators, in particular quaternary ammonium salts, until the acid number of the reaction product falls below 10 mg KOH / g, optionally at 20 to 200 ° C at the beginning and / or during and / or after completion of the reaction. 10,000 parts by weight of the above additives. 2. A process according to claim 1, wherein all the components are subjected to the reaction simultaneously. Process according to claim 1, characterized in that the alcohols and / or ether alcohols are first reacted with polycarboxylic acids and / or their anhydrides at a temperature of 40 to 240 ° C until the acid number of the reaction mixture drops to 40 to 480 mg KOH. g and the partial ester thus obtained is then reacted with the epoxy compounds at a temperature of 20 to 180 ° C until the acid number of the product falls below 10 mg KOH / g.