Classifications

• • 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
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

Definitions

• This invention relates to resin compositions which cure as they are shaped / laminated, brushed, sprayed or otherwise more or less incrementally placed into the space where they are to form a product; such resins are broadly known as laminating resins, commonly have an unsaturated polyester resin base, are mixed with glass fiber reinforcement, and nearly always are employed in a solution of an organic monomer such as styrene.
• the organic monomer is intended to copolymerize with the resin but typically and notoriously may also tend to volatilize in significant amounts into the workplace environment.
• the present invention is drawn to compositions and methods which can be used in existing equipment, procedures, and workplaces, but which will emit far less monomer than the typical laminating resins and methods heretofore.
• Ethoxylated, difunctional, bisphenol-A has been used in the past as an ingredient in various types of resins, generally resins which include a significant diisocyanate component, as in Ford, Jr. et al U.S. Patent 3,876,726.
• European Patent Application 0 234 692 discloses a composition said to be useful as a molding resin, having the virtue of a low residual monomer concentration in the final product.
• the gist of the disclosure appears to be that dimethacrylates such as ethoxylated bisphenol-A dimethacrylate can be used as components of otherwise more or less conventional unsaturated polyester resins to reduce the amount of residual styrene monomer in contained molding processes such as cell molding, compression molding, and sheet molding. See also Reid and Rex U.S. Patent 5,202,366, which includes a low-profile additive in a similar composition.
• the new laminating resins comprises three components.
• the first is a more or less conventional base resin comprising glycols and unsaturated dicarboxylic acids; optionally the base resin may also contain a saturated dicarboxylic acid.
• they are typically maleic and phthalic acid residues, with optional isophthalic residues, interspersed with glycol residues.
• These glycols are commonly ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, usually as mixtures, but many other glycols can be utilized; dicyclopentadiene may be included as well, as is known in the art.
• the second component is a diacrylate or dimethacrylate of alkoxylated bisphenol-A of the formula
• Hydroxyethyl or hydroxypropyl groups can comprise about 19-71% of the weight of this ingredient. These two ingredients may be present in weight ratios of about
• composition also includes a third ingredient which may be (1) about 20-60% based on the total of the two above ingredients of a compound of the formula
• H on the ring is substituted by CH 3 , or (2) about 20-60%, based on the total of the two above ingredients of ethylene glycol dimethacrylate, or (3) about 10-60% based on the total of the two above ingredients, of styrene, divinyl benzene or mixtures thereof.
• compositions may also include from 1% to about 10% of N-vinyl pyrrolidone or 1% to about 20% cyclohexyl methacrylate or both, and/or 1% to about 30% of any combination of the following, provided the ingredient is not included above: ethylene glycol dimethacrylate, vinyl toluene, and divinyl benzene, all based on the overall composition. Since our objective is to design a composition which works very well as a laminating resin without significant emissions, the addition of styrene to the recipe is not required, but the composition will continue to be operable as an excellent laminating resin even though styrene is included either as the third ingredient, or as an additional component. The composition will also tolerate many other minor ingredients known to be useful in the unsaturated polyester and laminating art. Detailed Description of the Invention
• Viscosity that is similar to that of styrenated polyester resins - 100 to 400 cps.
• polyester compositions which may be used as a base. They are prepared by polycondensation of polycarboxylic acid derivatives, one of which must be an alpha, beta-ethylenically unsaturated polycarboxylic acid, and polyols.
• polycarboxylic acid derivatives we mean to include polycarboxylic acids, their esters of lower alcohols, their acid chlorides and their anhydrides.
• the ratio of polycarboxylic acid to polyol is usually a 1:1 molar ratio. However, in most esterification processes, a slight excess of polyol is utilized to compensate for polyol losses during esterification. Also, although dicarboxylic acids and diols are most frequently utilized and the 1:1 molar ratio is prevalent, the utilization of triols and the like requires the ratio of acid to polyol to be stated more precisely as one equivalent of acid per equivalent of polyol.
• the unsaturated polyesters useful in this invention may be prepared from an acid mixture wherein the unsaturated polycarboxylic acid comprises as little as 20 mole percent of the total acids present, although it is generally preferred that the unsaturated polycarboxylic acid comprises about 30% or more of the total acid content.
• Some of the unsaturated polycarboxylic acids useful in preparing unsaturated polyesters used in this invention include:
• saturated and aromatically unsaturated polycarboxylic acids optionally useful in preparing unsaturated polyesters used in this invention include:
• Adipic acid Sebacic acid and the like wherein the term “acid” includes the corresponding anhydrides where such anhydrides exist.
• Polyols useful in preparing polyesters for use in this invention are polyfunctional alcohols of the type conventionally utilized in polyester preparation.
• Such polyols include:
• diols are generally preferred in the preparation of unsaturated polyesters, the more functional polyols, i.e. polyols having a functionality of three to five, are sometimes used.
• dicyclopentadiene may be included and may be considered a normal part of the "base resin" as used herein.
• a base resin composition (hereafter designated "Resin A”) was prepared having the following ingredients:
• 1,6-hexanediol 0.001 high 241 7:54 3:34 ethylene glycol (EG) 0.001 low 275 2:48 3:37 ethylene glycol 0.005 low 274 2:52 3:50 diethylene glycol 0.001 medium >210 4:03 2:12 diethylene glycol 0.010 medium 252 5:40 3:13 triethylene glycol 0.001 medium 241 3:18 3:17 tetraethylene glycol 0.001 medium 229 2:52 3:46 neopentyl glycol 0.001 high 235 4:20 4:09 ethoxylated BPA 0.001 very high 171 8:50 7:30
• 'Mod is 25% hydroquinone in propylene glycol.
• Liquid resin properties measured in the experiments reported below were gel time, (reported in the tables herein in minutes and seconds, as 13:17, for example), room temperature interval time, which is the time between gelation and the exothermic peak, room temperature exothermic peak which is the highest temperature reached in a 100 g mass of resin during the curing process, Brookfield viscosity, and Barcol hardness by ASTM D2583.
• room temperature interval time which is the time between gelation and the exothermic peak
• room temperature exothermic peak which is the highest temperature reached in a 100 g mass of resin during the curing process
• Brookfield viscosity Brookfield viscosity
• Barcol hardness by ASTM D2583
• a brief outline of the test is as follows: An environment at 77°C and 50% relative humidity is maintained. If a controlled environment is not available, conditions should be reported for which measurements are made.
• a 200 gm pre-promoted resin is weighed out into a suitable dry and clean container. The container is covered and placed in a 25°C temperature bath. A balance is placed in a draft free enclosure. A gallon lid is cleaned with solvent and wiped dry. The diameter is measured to the nearest 0.1 cm. The gallon lid is placed on an inverted paper or plastic cup mounted on the balance pan. A bent paper clip is positioned in the center of the gallon lid.
• This weight (TARE WEIGHT) is recorded.
• the container is taken from the temperature bath and an appropriate volumetric or weight measure of catalyst is added. A timer is started at this point. The catalyst is mixed with the resin for one minute.
• the INITIAL WEIGHT is determined by pouring 100.0 + 0.5 gm of catalyzed resin into the can lid and recording the weight. Next, the paper clip is used to determine when the resin has hardened sufficiently to allow the resin or lid to be lifted. The time (gel time) is recorded at this point. The resin is then allowed to harden in the can lid and every 15 minutes it is reweighed until concurrent weights agree to within 0.05 gm. This is recorded as the FINAL WEIGHT. The entire procedure should be repeated until duplicate samples agree to the
• the volatile emissions per square meter are calculated as follows:
• Resin A is as described above in terms of weight; it is, in molar equivalents, a polyester resin composed of 1.0 mole maleic anhydride, 2.0 moles phthalic anhydride, 0.42 mole diethylene glycol and 2.71 moles propylene glycol.
• Resin B is similar to Resin A with a lower viscosity by an adjustment of the cook, as is known in the art.
• Sartomer CD480 is ethoxylated bisphenol-A dimethacrylate where m and n in the above formula total 10.
• Sartomer 348 is ethoxylated bisphenol-A dimethacrylate where m and n in the above formula are both 1.
• Mod L is 25% hydroquinone and 75% propylene glycol.
• formulations Z, S, and 0 have better than acceptable resin properties and clear casting properties, and have volatile emissions far less than the rate of the more or less classical commercial resin A2.
• Formulation Z is about one-fifth the rate of A2.
• Resin A 35.00 35.00 35.00 35.00 35.00 35.00
• Resin A 35.00 35.00 35.00 35.00 30.00
• Resin A 35.00 35.00 35.00 35.00 35.00 35.00 35.00 35.00
• Sartomer 480 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00
• Resin A 35.00 35.00 35.00 35.00 60.00 60.00
• our invention comprises compositions comprising (a) the base polyester polymer (resin) as described above and the alkoxylated bisphenol-A diacrylate or dimethacrylate in a ratio of 2:1 to 0.5:1 and (b) either (1) about 20-60%, based on the total of (a) and (b) of vinyl toluene or divinyl benzene or a combination thereof, (2) about 10% to about 60%, based on the total of (a) and (b), of either styrene or divinyl benzene or a combination thereof, or (3) about 20% to about 60%, based on the total of (a) and (b), of ethylene glycol dimethacrylate.
• the various "Sartomer" compositions i.e. the ethoxylated bisphenol-A dimethacrylates, have 1 and 5 ethoxy groups on each side of the bisphenol-A; however, we may employ a single compound or compounds having any variation of combinations of ethoxy or propoxy groups from two to about 20 groups, preferably a total of 2 to 8 alkoxy groups.

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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)

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• 1995
  • 1995-02-17 WO PCT/US1995/002101 patent/WO1995023828A1/en not_active Application Discontinuation
  • 1995-02-17 CA CA 2160884 patent/CA2160884A1/en not_active Abandoned
  • 1995-02-17 JP JP7522924A patent/JPH08510008A/ja not_active Ceased
  • 1995-02-17 EP EP95910305A patent/EP0698061A4/en not_active Withdrawn

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