Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-03-29
2002-12-03
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C528S275000, C528S283000, C528S300000, C528S301000, C528S302000, C528S306000, C528S307000, C528S308000, C528S308600, C525S437000, C525S444000, C524S040000, C524S041000, C524S042000, C524S043000
Reexamination Certificate
active
06489406
ABSTRACT:
The invention relates to unsaturated polyester resins and in particular to weather-resistant unsaturated polyester resin based products with excellent flexibility and to the use of the said resins in applications, such as concrete sealants and flooring resins. Additionally, the invention relates to a process for the manufacture of such unsaturated polyester resins.
Flexible unsaturated polyesters for coating, water-proofing and sealing applications have been traditionally processed from dicarboxylic acid and polypropylene oxides or polyethylene oxides. Part of the acid has to be unsaturated in order to have curing properties with normal peroxides or other radical initiators.
A method and a resinous product adapted for sealing pores in porous metal articles are disclosed in GB 792 854. More specifically, this patent describes a method for sealing pores in porous metal articles by impregnating the metal with a water-dispersible polymerizable impregnating composition comprising water-dispersible polyester and a polymerizable aryl monomer. The water-dispersible polyester comprises the product of esterifying a glycol with an ethylenically unsaturated dicarboxylic acid. The polymerizable aryl monomer is styrene or vinyl toluene and it is present in an amount from one-third to one time the total weight of the polyester.
An unsaturated polyester resin used as waterproof lining material of a roof floor and indoor floor and as filling material of a cable joint portion is described in KR 9411772. The unsaturated polyester resin is produced from diethylene glycol, propylene glycol, phthalic acid, maleic acid and benzoic acid with conventional additives.
Japanese patent application JP 04 253 717 discloses the use of polyglycols in a combination with aromatic dicarboxylic acids, such as isophthalic or terephthalic acid, and maleic acid. The resins are diluted with styrene to 40% and cured with methyl ethyl ketone peroxide and Co-naphtenoate to obtain a flexible unsaturated polyester resin for use as coating in engineering and construction.
Another Japanese patent application JP 05 186 572 A2 describes the preparation of waterproofing materials with good flexibility. The resin is composed of adipic acid, fumaric acid and Bisphenol A combined at the second stage with a maleic acid-DCPD derivative. The resin is diluted with styrene and cured as described in the preceding reference.
U.S. Pat. No. 5,696,225 describes a three step method of processing a flexible resin. At the first stage, an acid-terminated polyester is prepared, the chains are extended at the second stage with polypropylene oxides and, at the third stage, the compounded resin is diluted with styrene and cured with a peroxide/Co-naphtenoate system. This publication also refers to trials to improve flexibility, weather-resistance and duration of good performance. Typical improvements relate to variations of monomers and by copolymers, e.g. blending unsaturated polyester with vinyl esters and epoxy resins.
A major problem with prior art unsaturated polyester resin products is high water absorption, which affects the product by reducing flex strength and elongation at room temperature and at temperatures down to −20° C., which cause loss of flexibility and affect severely the stability of the product. Thus, there is a need for resins that would perform well, when cured, in demanding weather-conditions and retain flexibility and stability also at very low temperatures.
An object of this invention is to provide a linear unsaturated polyester with a high molecular weight and an unsaturated polyester resin for the manufacture of subzero flexible, weather-resistant unsaturated polyester based products. Another object of this invention is the use of the unsaturated polyester resin in applications wherein good chemical resistance, weather-resistance, subzero flexibility and water resistance are needed and high impact resistance is required, such as concrete sealants, flooring resins, coating resins, in gelcoats or as such combined with reinforcement to form flexible reinforced plastic parts. A further object of this invention is to provide a method for the manufacture of a linear unsaturated polyester with a high molecular weight and of an unsaturated polyester resin for the manufacture of a subzero flexible, weather-resistant unsaturated polyester based products.
The characteristic features of the linear unsaturated polyester, of the unsaturated polyester resin, the use thereof and the method for the manufacture thereof are set forth in the claims.
It has been surprisingly found that in processing of linear unsaturated polyesters and unsaturated polyester resins for the manufacture of a subzero flexible, weather-resistant, unstaurated polyester based products, the use and the combination of glycolic components play an important role in order to achieve a linear unsaturated polyester with a high molecular weight, and so do also extended processing periods in order to achieve very low acid values.
The linear unsaturated polyesters are prepared by allowing a combination of (A) ethylenically unsaturated dicarboxylic acid, such as maleic acid, maleic anhydride, fumaric acid or mixtures thereof, preferably maleic acid, maleic anhydride or fumaric acid, and of (B) another aliphatic or aromatic acid, such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1,2-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid or adipic acid, preferably phthalic acid, phthalic anhydride, isophthalic acid or terephthalic acid or mixtures thereof, to react with a slight excess of (C) two or more polyhydric alcohols. The choice of poly-hydric alcohols is crucial for obtaining a flexible, weather-resistant cured product. Thus, polyhydric alcohols, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, Bisphenol A, trimethylol ethane, trimethylol propane, polyethylene glycol or derivatives thereof, polypropylene glycol or derivatives thereof, polyethylene oxides, polypropylene oxides or tri-methylol propane polymers having an overall hydroxy functionality of 2-4 per molecule and a molecular weight of 300-12,000 are suitable. Preferred polyhydric alcohols are selected from a group consisting of triethylene glycol, dipropylene glycol, tripropylene glycol, Bisphenol A, trimethylol ethane, trimethylol propane, polyethylene oxides, polypropylene oxides and trimethylol propane polymers having an overall hydroxy functionality of 2 or 3 per molecule and a molecular weight of 400-1500, and mixtures thereof. At least two of the required polyhydric alcohols belong preferably to the group consisting of polyethylene glycol, polypropylene glycol, derivatives of polyethylene glycol and derivatives of polypropylene glycol, which include the polymerization products of oxirane and methyl oxirane with itself and/or with alcohols. Particularly preferably at least two of the polyhydric alcohols are selected from the group consisting of polypropylene glycol and derivatives thereof, such as trimethylol propane—polypropylene glycol derivatives and poly-propylen glycol. The ratio of difunctional compounds to trifunctional compounds plays also an important role, and a preferred ratio is 60-80 mol % of diols to 20-40 mol % of triols, but in certain cases only diols are used. Preferred conditions are achieved so that the component comprising triols is used in an amount of 50 mol % at the maximum calculated from the amount of all the polyhydric alcohols. Additionally, an inhibitor known in the art is needed for the prevention of solidification and geleation, the preferred inhibitor being hydroquinone, toluhydroquinone, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, di-tert-butyl hydroquinone, tri-tert-butyl hydroquinone and butyl toluhydroquinone. The weight-averag
Airola Karri
Mahbub Paul
Valtonen Eija
Acquah Samuel A.
Ashland Inc.
Birch & Stewart Kolasch & Birch, LLP
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