USRE27093E - Thick, cured polymethyl methacrylate article and process for its preparation - Google Patents

Thick, cured polymethyl methacrylate article and process for its preparation Download PDF

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USRE27093E
USRE27093E US1123970A USRE27093E US RE27093 E USRE27093 E US RE27093E US 1123970 A US1123970 A US 1123970A US RE27093 E USRE27093 E US RE27093E
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methyl methacrylate
thick
hemi
weight
perester
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Donald H Slocum
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

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  • This invention relates to the polymerization and curing of methyl methacrylate-containing sirups. More particularly, it relates to the production of relatively thick articles of polymeric methyl methacrylate, e.g., methyl methacrylate homopolymer and copolymers of methyl methacrylate with m-fi-ethylenically unsaturated compounds (vinyl acetate, styrene, alkyl acrylates, other alkyl methacrylates, etc.).
  • m-fi-ethylenically unsaturated compounds vinyl acetate, styrene, alkyl acrylates, other alkyl methacrylates, etc.
  • the objects are accomplished by mixing a sirup containing -35% by weight of methyl methacrylate polymer having an inherent viscosity of 025-10 dissolved in monomeric methyl methacrylate, at least 40%, preferably 4085% by Weight of inert additives (preferably particles or fibers selected from the group consisting of calcium carbonate, calcium sulfate and clay), with 0.2 6% (preferably 0.75-2%) based on the total weight of the mixture of a herni-perester of maleic acid having the formula:
  • R is a saturated tertiary alkyl radical, preferably where R is tertiary butyl as in monotertiary butyl peroxymaleate sometimes referred to as t-butyl permaleic acid;
  • the process described will generally produce a commercially acceptable article that is substantially smooth and void-free in not more than about 2.5 hours, usually less than one hour.
  • the specific time period will depend upon the geometry of the casting, the amount of inert additives used, the amount of the hemi-perester catalyst used, etc.
  • the time Will also depend upon the sequence of adding the various ingredients.
  • the preferred sequence involves mixing the sirup and the hemi-perester catalyst before adding the inert additives or filler. However, if a shorter process time is desired, then the catalyst may be added immediately after the filler. It should also be understood that the process provides considerable latitude in the incorporation of pigments into the mixture. These may be added at anytime before the mixture has hardened to provide a variety of color effects diifering in hue and pattern.
  • the starting sirup or polymer-in-monomer solution may be prepared by any of the methods described in British Patent No. 870,191, or US. Patent No. 3,154,600. Specifically, the sirup may be made by heating a small amount of a polymerization initiator in solution in the methacrylic ester and in the presence of a chain transfer agent at a suitable pressure and temperature. Heating is continued until the solution reaches a predetermined viscosity. Thereafter, the hot solution is quenched by the addition of cold monomer containing a polymerization inhibitor. More specifically, a sirup having a viscosity of 0.5-50 poises at 25 C.
  • methyl methacrylate can be produced from methyl methacrylate by heating the monomeric methyl methacrylate in a jacketed kettle at a temperature of 5 0-1 5 0 C. under refluxing conditions. Atmospheric pressure is used and the refluxing material is stirred. Heating is conducted in the presence of a very small amount of initiator and from 0.05-l.0 mole percent of a chain transfer agent such as the alkyl mercaptans and the mercaptans described in US. Pat. No. 3,154,600.
  • a chain transfer agent such as the alkyl mercaptans and the mercaptans described in US. Pat. No. 3,154,600.
  • the polymerization is stopped bycooling in any suitable manner.
  • One method of cooling involves adding l-10% by weight of cold methyl methacrylate containing sufiicient hydroquinone or other polymerization inhibitor to inhibit further polymerization of the methyl methacrylate.
  • the final solution contains 10-35% by weight of the methyl methacrylate polymer dissolved in the methyl methacrylate monomer.
  • the polymer has an inherent viscosity of 025-10 determined at 20 C.
  • the polymer may also be a copolymer involving a major portion of the methyl methacrylate monomer with such monomers as vinyl acetate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, etc.
  • the sirup may also contain a cross-linking agent, added to the sirup in an amount up to 20% by weight upon completion of quenching.
  • a cross-linking agent e.g., ethylene dimethacrylate, propylene dimethacrylate, polyethylene glycol dimethacrylate, divinyl benzene, triallyl cyanurate, and diallyl phthalate.
  • a portion, i.e., up to about 2% of the cross-linking agent may be added to the sirup prior to quenching.
  • the preferred hemi-perestcr is monotertiary butyl peroxymaleate.
  • other useful hemi-peresters include those where the saturated tertiary alkyl of the hemi-perester is t-amyl, l-methylcyclohexyl and the p-methyl.
  • the hemi peresters may be prepared by processes well known in the art.
  • monotertiary butyl peroxymaleate may be prepared by the following reaction:
  • the hemi-perester of the difunctional acid should be present in an amount greater than 0.2% by weight in order to obtain the advantages of the present invention.
  • the upper limit of 6% is merely to indicate that no additional advantage seems to be obtained by adding more than that percentage of the hemi-perester.
  • other initiators may be used with the critical hemi-perester.
  • curing acids may be used. These include the chlorides of antimony and soluble copper salts as disclosed in US. Patent No. 3,084,068, the chlorides of tin, etc.
  • the critical finding in the present invention is that by using at least 40% of a filler, relatively thick articles can be produced in a commercially acceptable fashion, both from the standpoint of the process and the appearance of the final article.
  • the fillers used may be any of those that do not interfere with the polymerization of the acrylic resin, e.g., calcium carbonate, calcium sulfate, clay, silica, glass, calcium silicate, alumina, carbon black, titania, powdered metals, etc.
  • the preferred fillers are particles or fibers of calcium carbonate, calcium sulfate and clay.
  • the clacium carbonate may be obtained by precipitation or by grinding marble or limestone.
  • the process of the present invention provides an additional commercial advantage.
  • Example 1 A sirup of 10% methyl methacrylate homopolymer in methyl methacrylate monomer is prepared by partial polymerization in situ, as described in Example 2 of US.
  • the resulting mixture is poured into an aluminum pan to form a layer /4 inch deep.
  • the layer is then permitted to cure autogenically. After 2.5 hours it is removed from the pan as a hard, void-free sheet, /1 inch thick.
  • Control A is prepared without any calcium carbonate filler.
  • the sirup of 10% methyl methacrylate homopolymer in methyl methacrylate monomer containing 1% tbutyl peroxymaleic acid is poured into the aluminum pan r to a depth of 4 inch. No cure is realized after 16 hours.
  • Controls B, C and D the example is repeated using 1% benzoyl peroxide (2.25 grams), 0.75% t-butyl peroxypivalate (1.68 grams) and 2% methyl ethyl ketone peroxide (4.5 grams), respectively.
  • the inch thick layers of Controls B, C and D do not harden nor show any signs of curing after 5 hours.
  • Example 2 The 55% filled siru of Example 1 containing 1% of t-butyl peroxymaleic acid is poured into two open containers. In the container of Example 2, a 1-inch layer is obtained; in that of Example 3, a 2-inch layer. The casting of Example 2 is cured hard without boiling to counter top quality in about 2.5 hours. The casting of Example 3 is similarly cured hard in less than 1.5 hours.
  • a /s-inch layer from the identical mixture is only partially cured after 2.5 hours.
  • Example 4 A sirup containing 25% methyl methacrylate homopolymer (inherent viscosity between 0.25-1.0) in methyl methacrylate monomer is filled with calcium carbonate. t-Butyl peroxymaleic acid to the extent of 1% is added and the mixture is cured in a 2-inch thick section open to the air in a period of less than 2 hours.
  • a sirup composed of 800 grams of a 25 solution of methyl methacrylate homopolymer in methyl methacrylate monomer may be used with 1200 grams of calcium carbonate tiller, 8 grams of lauryl mercaptan and 6.4 grams of a 5% stannous chloride solution in alcohol.
  • Example 5 2 grams of t-butyl peroxymaleic acid is added; the blend is degassed under a vacuum of 20 inches of mercury; and the degassed blend is cast onto an aluminum tray to form a 1-inch thick section.
  • 1 gram of t-butyl peroxymaleic acid is added along with 2 grams of lauroyl peroxide prior to degassing and casting the 1- inch thick section.
  • the section of Example 5 cured in 30 minutes and the section of Example 6 cured in 60 minutes.
  • a process for preparing articles which comprises mixing (a) a sirup containing 1035% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,;3-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.251.0, in monomeric methyl methacrylate,
  • inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, and
  • a process [as in claim 1] for preparing articles which comprises mixing (a) a sirup containing -35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with aJS-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.25].0, in monomeric methyl methacrylate,
  • inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, and
  • a mixture for preparing articles at least A inch thick which comprises (a) a sirup containing 10-35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,p-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.251.0, in monomeric methyl methacrylate,
  • inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, and
  • a mixture [as in claim 7] for preparing articles at least 4 inch thick which comprises (a) a sirup containing 10-35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,,8-ethyleuically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.25-1.17, in monomeric methyl methacrylate,
  • inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, and
  • a mixture as in claim 7 wherein said hemi-perester of maleic acid is monotertiary butyl peroxymaleate.
  • An article comprising a methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,fl-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate and 4-085% by weight of inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, said article being at least inch thick, said inert additive being distributed substantially uniformly throughout said polymer.
  • An article as in claim 12 that is -%-2 inches thick.
  • An article [as in claim 12] comprising a methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,,8-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate and 4085% by weight of inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, said article being at least 4 inch thick, said inert additive being distributed substantially uniformly throughout said polymer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

THE USE OF AT LEAST 40% OF AN INERT FILLER, E.G., CALCIUM CABONATE, CALCIUM SULFATE, CLAY, SILICA, CALCIUM SILICATE, ETC. ALONG WITH A HEMI-PERESTER OF MALEIC ACID CATALYST IN THE POLYMERIZATION AND CURING OF METHYL METHACRYLATECONTAINING SIRUPS PROVIDES A PROCESS FOR FORMING THICK (1/4" TO 2" OR MORE) ARTICLES OF POLYMERIC METHYL METHACRYLATE WITHIN REASONABLE PERIODS AND AT MODERATE TEMPERATURES.

Description

United States Patent ABSTRACT OF THE DISCLOSURE The use of at least 40% of an inert filler, e.g., calcium carbonate, calcium sulfate, clay, silica, calcium silicate, etc. along with a hemi-perester of maleic acid catalyst in the polymerization and curing of methyl methacrylatecontaining sirups provides a process for forming thick 0 4" to 2 or more) articles of polymeric methyl methacrylate within reasonable periods and at moderate temperatures.
BACKGROUND OF INVENTION This invention relates to the polymerization and curing of methyl methacrylate-containing sirups. More particularly, it relates to the production of relatively thick articles of polymeric methyl methacrylate, e.g., methyl methacrylate homopolymer and copolymers of methyl methacrylate with m-fi-ethylenically unsaturated compounds (vinyl acetate, styrene, alkyl acrylates, other alkyl methacrylates, etc.).
The desirability and commercial utility of thick (from about A to 2 or more inches) articles of polymeric methyl methacrylate is well acknowledged. Such articles would be extremely useful as counter tops, dresser tops, vanity tops, shelving, wainscoting, etc. However, the processes heretofore suggested for producing such sections of methyl methacrylate polymer either require too much time or they cannot be operated at moderate temperatures; and, in most cases, such processes yield a product containing unsightly voids and/or surface blemishes. In short, the processes of the prior art will not produce a methyl methacrylate polymeric product that can compete against wood, laminates or other synthetic materials in todays market place.
It is an object of this invention to provide a commercially acceptable section, sheet or article of polymeric methyl methacrylate having a thickness of at least inch and preferably a thickness of %2 inches or more. It is a further object to provide a commercially feasible process for producing such articles. Other objects will appear hereinafter.
SUMMARY OF THE INVENTION The objects are accomplished by mixing a sirup containing -35% by weight of methyl methacrylate polymer having an inherent viscosity of 025-10 dissolved in monomeric methyl methacrylate, at least 40%, preferably 4085% by Weight of inert additives (preferably particles or fibers selected from the group consisting of calcium carbonate, calcium sulfate and clay), with 0.2 6% (preferably 0.75-2%) based on the total weight of the mixture of a herni-perester of maleic acid having the formula:
wherein R is a saturated tertiary alkyl radical, preferably where R is tertiary butyl as in monotertiary butyl peroxymaleate sometimes referred to as t-butyl permaleic acid;
pouring the mixture into a container to form a layer that is at least A inch (preferably 4-2 inches) thick; and permitting the layer to cure autogenically in air at a temperature of 15-40 C.
The process described will generally produce a commercially acceptable article that is substantially smooth and void-free in not more than about 2.5 hours, usually less than one hour. The specific time period will depend upon the geometry of the casting, the amount of inert additives used, the amount of the hemi-perester catalyst used, etc. The time Will also depend upon the sequence of adding the various ingredients. The preferred sequence involves mixing the sirup and the hemi-perester catalyst before adding the inert additives or filler. However, if a shorter process time is desired, then the catalyst may be added immediately after the filler. It should also be understood that the process provides considerable latitude in the incorporation of pigments into the mixture. These may be added at anytime before the mixture has hardened to provide a variety of color effects diifering in hue and pattern.
The starting sirup or polymer-in-monomer solution may be prepared by any of the methods described in British Patent No. 870,191, or US. Patent No. 3,154,600. Specifically, the sirup may be made by heating a small amount of a polymerization initiator in solution in the methacrylic ester and in the presence of a chain transfer agent at a suitable pressure and temperature. Heating is continued until the solution reaches a predetermined viscosity. Thereafter, the hot solution is quenched by the addition of cold monomer containing a polymerization inhibitor. More specifically, a sirup having a viscosity of 0.5-50 poises at 25 C. can be produced from methyl methacrylate by heating the monomeric methyl methacrylate in a jacketed kettle at a temperature of 5 0-1 5 0 C. under refluxing conditions. Atmospheric pressure is used and the refluxing material is stirred. Heating is conducted in the presence of a very small amount of initiator and from 0.05-l.0 mole percent of a chain transfer agent such as the alkyl mercaptans and the mercaptans described in US. Pat. No. 3,154,600. When a bulk viscosity in the range of 0.5 to 50 poises, which corresponds to an inherent viscosity of 0.25-1.0, is attained and the initiator content has been reduced substantially to zero, i.e., below 20 parts per million, the polymerization is stopped bycooling in any suitable manner. One method of cooling involves adding l-10% by weight of cold methyl methacrylate containing sufiicient hydroquinone or other polymerization inhibitor to inhibit further polymerization of the methyl methacrylate. For the purpose of the present invention, the final solution contains 10-35% by weight of the methyl methacrylate polymer dissolved in the methyl methacrylate monomer. The polymer has an inherent viscosity of 025-10 determined at 20 C. using a solution of 0.50 gram of the polymer per 100 milliliters of chloroform in accordance with the method described in F. W. Billmeyer, Textbook of Polymer Chemistry, Interscience Publishing Inc. (1957), p. 128. As mentioned previously, the polymer may also be a copolymer involving a major portion of the methyl methacrylate monomer with such monomers as vinyl acetate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, etc.
The sirup may also contain a cross-linking agent, added to the sirup in an amount up to 20% by weight upon completion of quenching. Any suitable poly-unsaturated cross-linking agent may be used, e.g., ethylene dimethacrylate, propylene dimethacrylate, polyethylene glycol dimethacrylate, divinyl benzene, triallyl cyanurate, and diallyl phthalate. If desired, a portion, i.e., up to about 2% of the cross-linking agent may be added to the sirup prior to quenching.
The preferred hemi-perestcr, as stated previously, is monotertiary butyl peroxymaleate. However, other useful hemi-peresters include those where the saturated tertiary alkyl of the hemi-perester is t-amyl, l-methylcyclohexyl and the p-methyl. The hemi peresters may be prepared by processes well known in the art. For example, monotertiary butyl peroxymaleate may be prepared by the following reaction:
CH3 As mentioned previously, the hemi-perester of the difunctional acid should be present in an amount greater than 0.2% by weight in order to obtain the advantages of the present invention. The upper limit of 6% is merely to indicate that no additional advantage seems to be obtained by adding more than that percentage of the hemi-perester. If desired, other initiators may be used with the critical hemi-perester. In addition, curing acids may be used. These include the chlorides of antimony and soluble copper salts as disclosed in US. Patent No. 3,084,068, the chlorides of tin, etc.
The critical finding in the present invention is that by using at least 40% of a filler, relatively thick articles can be produced in a commercially acceptable fashion, both from the standpoint of the process and the appearance of the final article. The fillers used may be any of those that do not interfere with the polymerization of the acrylic resin, e.g., calcium carbonate, calcium sulfate, clay, silica, glass, calcium silicate, alumina, carbon black, titania, powdered metals, etc. However, the preferred fillers are particles or fibers of calcium carbonate, calcium sulfate and clay. The clacium carbonate may be obtained by precipitation or by grinding marble or limestone. It has been found that at least 40% of the filler is necessary for a satisfactory process and product where the product is A inch thick. However, where the final product is two inches thick, it has been found that as much as 80% filler may be used for obtaining optimum results. Because of the relative inexpensiveness of the filler compared to the resin, the process of the present invention provides an additional commercial advantage.
The invention will be more clearly understood by referring to the examples which follow. The examples, which illustrate specific embodiments of the present invention, should not be construed to limit the invention in any way.
Example 1 A sirup of 10% methyl methacrylate homopolymer in methyl methacrylate monomer is prepared by partial polymerization in situ, as described in Example 2 of US.
4 Pat. No. 3,154,600. To 225 grams of the sirup is added 275 grams of Non Fer A1, a precipitated particulate calcium carbonate having an average particle size of 7 microns. To the mixture, which contains 55% of the inert additive, is then added 1% (2.25 grams) of t-butyl peroxymaleic acid.
The resulting mixture is poured into an aluminum pan to form a layer /4 inch deep. The layer is then permitted to cure autogenically. After 2.5 hours it is removed from the pan as a hard, void-free sheet, /1 inch thick.
Control A is prepared without any calcium carbonate filler. The sirup of 10% methyl methacrylate homopolymer in methyl methacrylate monomer containing 1% tbutyl peroxymaleic acid is poured into the aluminum pan r to a depth of 4 inch. No cure is realized after 16 hours.
In Controls B, C and D, the example is repeated using 1% benzoyl peroxide (2.25 grams), 0.75% t-butyl peroxypivalate (1.68 grams) and 2% methyl ethyl ketone peroxide (4.5 grams), respectively. The inch thick layers of Controls B, C and D do not harden nor show any signs of curing after 5 hours.
Examples 2 and 3 The 55% filled siru of Example 1 containing 1% of t-butyl peroxymaleic acid is poured into two open containers. In the container of Example 2, a 1-inch layer is obtained; in that of Example 3, a 2-inch layer. The casting of Example 2 is cured hard without boiling to counter top quality in about 2.5 hours. The casting of Example 3 is similarly cured hard in less than 1.5 hours.
In a control, a /s-inch layer from the identical mixture is only partially cured after 2.5 hours.
Example 4 A sirup containing 25% methyl methacrylate homopolymer (inherent viscosity between 0.25-1.0) in methyl methacrylate monomer is filled with calcium carbonate. t-Butyl peroxymaleic acid to the extent of 1% is added and the mixture is cured in a 2-inch thick section open to the air in a period of less than 2 hours.
In a control only 30% calcium carbonate is used. In all other respects the procedure is the same as Example 4. The time to effect a cure is over 3 hours.
Examples 5 and 6 The process will operate in the presence of other peroxide initiators provided that the t-butyl peroxymaleic acid is also present.
Thus, a sirup composed of 800 grams of a 25 solution of methyl methacrylate homopolymer in methyl methacrylate monomer may be used with 1200 grams of calcium carbonate tiller, 8 grams of lauryl mercaptan and 6.4 grams of a 5% stannous chloride solution in alcohol. In Example 5, 2 grams of t-butyl peroxymaleic acid is added; the blend is degassed under a vacuum of 20 inches of mercury; and the degassed blend is cast onto an aluminum tray to form a 1-inch thick section. In Example 6, 1 gram of t-butyl peroxymaleic acid is added along with 2 grams of lauroyl peroxide prior to degassing and casting the 1- inch thick section. The section of Example 5 cured in 30 minutes and the section of Example 6 cured in 60 minutes.
What is claimed is:
1. A process for preparing articles which comprises mixing (a) a sirup containing 1035% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,;3-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.251.0, in monomeric methyl methacrylate,
(b) 40-85% by weight of inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, and
(c) O.26% by weight of a hemi-perester of maleic acid having the formula wherein R is a saturated tertiary alkyl radical; pouring the mixture into a container to form a layer, said layer being at least 4 inch thick; and permitting said layer to cure autogenically in air at a temperature of 15-40 C. to form an article that is at least t inch thick.
2. A process as in claim 1 wherein said methyl methacrylate polymer is methyl methacrylate homopolymer.
3. A process [as in claim 1] for preparing articles which comprises mixing (a) a sirup containing -35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with aJS-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.25].0, in monomeric methyl methacrylate,
(b) 40-85% by weight of inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, and
(c) 0.26% by weight of a hemi-perester of maleic acid having the formula it wherein R is a saturated tertiary alkyl radical; pouring the mixture into a container to form a layer, said layer being at least inch thick; and permitting said layer to cure autogenically in air at a temperature of -40% C. to form an article that is at least A inch thick.
4. A process as in claim 1 wherein said inert additive is calcium carbonate.
5. A process as in claim 1 wherein said hemi-perester of maleic acid is monoteritary butyl peroxymaleate.
6. A process as in claim 1 wherein said layer and said article are %2 inches thick.
7. A mixture for preparing articles at least A inch thick which comprises (a) a sirup containing 10-35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,p-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.251.0, in monomeric methyl methacrylate,
(b) 40-85% by weight of inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, and
(c) 0.26% by weight of a hemi-perester of maleic acid having the formula wherein R is a saturated tertiary alkyl radical.
8. A mixture as in claim '7 wherein said methyl methacrylate polymer is methyl methacrylate homopolymer.
9. A mixture [as in claim 7] for preparing articles at least 4 inch thick which comprises (a) a sirup containing 10-35% by weight of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,,8-ethyleuically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate, said polymer having an inherent viscosity of 0.25-1.17, in monomeric methyl methacrylate,
(b) 40-85% by weight of inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, and
(c) 0.245% by weight of a hemi-perester of maleic acid having the formula wherein R is a saturated tertiary alkyl radical.
10. A mixture as in claim 7 wherein said inert additive is calcium carbonate.
11. A mixture as in claim 7 wherein said hemi-perester of maleic acid is monotertiary butyl peroxymaleate.
12. An article comprising a methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,fl-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate and 4-085% by weight of inert additive selected from the group consisting of calcium carbonate, calcium sulfate, [clay] alumina, silica and calcium silicate, said article being at least inch thick, said inert additive being distributed substantially uniformly throughout said polymer.
13. An article as in claim 12 that is -%-2 inches thick.
14. An article [as in claim 12] comprising a methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymer and copolymers of methyl methacrylate with a,,8-ethylenically unsaturated compounds, said copolymers containing more than 50% methyl methacrylate and 4085% by weight of inert additive comprising [wherein said inert additive is selected from the group consisting of calcium carbonate, calcium sulfate and] clay, said article being at least 4 inch thick, said inert additive being distributed substantially uniformly throughout said polymer.
15. An article as in claim 12 wherein said inert additive is calcium carbonate.
16. A process as in claim 1 wherein said sirup and said hemi-perester of maleic acid are mixed prior to the addition of said inert additive.
References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
P9495) UNITED STATES PATENT OFFICE 6g CERTIFICATE OF CORRECTION Patent No. 1 1EL27 OQ3 Dated Mgrch 23, 1,911
Inventofls) Donald H. Slocum It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
[- Column 5, line 25 of Claim 3, "15-uo% c. should read Signed and sealed this 2nd day of November 1971.
(SEAL) Attest:
EDNARD M.FLETCHER, JR. Attesting Officer ROBERT GOTTSCHALK Acting Commissioner of Patents
US1123970 1965-02-23 1970-02-02 Thick, cured polymethyl methacrylate article and process for its preparation Expired USRE27093E (en)

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US1123970 Expired USRE27093E (en) 1965-02-23 1970-02-02 Thick, cured polymethyl methacrylate article and process for its preparation

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DE (1) DE1694726C3 (en)
FR (1) FR1469795A (en)
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DE2627081A1 (en) * 1975-06-18 1977-01-20 Du Pont GRANITIMITATION AND METHOD OF MANUFACTURING THE SAME
US4184030A (en) 1975-09-22 1980-01-15 E. I. Du Pont De Nemours And Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4188315A (en) 1975-09-22 1980-02-12 E. I. Du Pont De Nemours & Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4189451A (en) 1975-09-22 1980-02-19 E. I. Du Pont De Nemours And Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4197215A (en) 1975-09-22 1980-04-08 E. I. Du Pont De Nemours And Company Composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4230613A (en) 1979-03-07 1980-10-28 Pratt & Lambert, Inc. Peroxy-free methacrylate lacquer and adhesive method employing same
US4323400A (en) 1979-05-03 1982-04-06 Henning William J Articles having an insulative coating containing kaolin and staple fibers
US6743327B2 (en) 2001-07-25 2004-06-01 Schober, Inc. Solid surface products
US20040247801A1 (en) * 2001-07-25 2004-12-09 Dennis Schober Solid surface products
US20060147655A1 (en) * 2001-07-25 2006-07-06 Lumicor Solid surface products
EP1987933A1 (en) 2007-05-01 2008-11-05 The Diller Corporation Thick solid surface laminate product and method of making same
US20080274343A1 (en) * 2007-05-01 2008-11-06 The Diller Corporation Thick solid surface laminate product and method of making same
US20090286902A1 (en) * 2004-12-16 2009-11-19 Grasso Jr Louis P Cast Solid Surface Materials Manufactured From Polymers and Post-Consumer Waste Glass

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US4695251A (en) * 1980-04-07 1987-09-22 Minnesota Mining And Manufacturing Company Orthodontic bracket adhesive and abrasive for removal thereof
US4458051A (en) * 1980-07-15 1984-07-03 Ciba-Geigy Corporation Pourable solid mixture
US4435160A (en) 1980-07-25 1984-03-06 Minnesota Mining And Manufacturing Company Method and manufacture for applying and removal of orthodontic bracket
DE3576703D1 (en) * 1984-07-27 1990-04-26 Inax Corp OBJECT FROM IMITATION OF MARBLE.
JPS6191054A (en) * 1984-10-09 1986-05-09 フクビ化学工業株式会社 Manufacture of artificial marble
US4717504A (en) * 1984-12-04 1988-01-05 Miles Inc. Reflectance standard
DE3617702C2 (en) * 1985-04-18 1997-04-10 Hilti Ag Use of curable acrylate derivatives as fixing mortar
US5407627A (en) * 1992-08-03 1995-04-18 Polycryl Enterprises Inc. Process and apparatus for forming stress-free thermosetting resin products
US5457152A (en) * 1993-02-19 1995-10-10 Ralph Wilson Plastics Company Varicolored articles with crystalline thermoplastic chips
DE4413903A1 (en) * 1994-04-21 1995-10-26 Andreas Zellmann Feed distribution device for cleansing or disinfectants etc.
GB9825066D0 (en) * 1998-11-17 1999-01-13 Ici Plc Moulded article and moulding composition
US6271281B1 (en) * 1999-08-26 2001-08-07 Medennium, Inc. Homopolymers containing stable elasticity inducing crosslinkers and ocular implants made therefrom
US6764977B2 (en) * 2000-03-21 2004-07-20 Atofina Chemicals, Inc. Safe, free-flowing solid peroxide compositions
MXPA06010229A (en) * 2006-09-08 2008-03-07 Plastiglas De Mexico S A De C Composition and process for producing acrylic composite materials with mineral charges having superior mechanical, thermal and processing properties.
US20080119595A1 (en) * 2006-11-17 2008-05-22 Waters Steve W Flame retardant synthetic solid surface material
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DK98917C (en) * 1958-11-13 1964-06-01 Du Pont Polymer-in-monomer syrup for use in the manufacture of plastic products and process for its manufacture.
US3073795A (en) * 1959-09-25 1963-01-15 Joseph E Veverka Dental liner comprising polymethyl methacrylate, talc and methyl methacrylate
US3085080A (en) * 1960-01-12 1963-04-09 Minerals & Chemicals Phillipp Kaolin clay coated with salt of polymerizable acid and polyester resins containing the same
US3234194A (en) * 1963-06-12 1966-02-08 Du Pont Methyl methacrylate polymer-in-monomer polymerization in the presence of a peroxymaleate and an amine

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2627081A1 (en) * 1975-06-18 1977-01-20 Du Pont GRANITIMITATION AND METHOD OF MANUFACTURING THE SAME
US4184030A (en) 1975-09-22 1980-01-15 E. I. Du Pont De Nemours And Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4188315A (en) 1975-09-22 1980-02-12 E. I. Du Pont De Nemours & Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4189451A (en) 1975-09-22 1980-02-19 E. I. Du Pont De Nemours And Company Process and composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4197215A (en) 1975-09-22 1980-04-08 E. I. Du Pont De Nemours And Company Composition for polymerizing and curing methyl methacrylate monomer-polymer syrups in the presence of metal salts of hemi-peresters of maleic acid
US4230613A (en) 1979-03-07 1980-10-28 Pratt & Lambert, Inc. Peroxy-free methacrylate lacquer and adhesive method employing same
US4323400A (en) 1979-05-03 1982-04-06 Henning William J Articles having an insulative coating containing kaolin and staple fibers
US6743327B2 (en) 2001-07-25 2004-06-01 Schober, Inc. Solid surface products
US20040247801A1 (en) * 2001-07-25 2004-12-09 Dennis Schober Solid surface products
US20060147655A1 (en) * 2001-07-25 2006-07-06 Lumicor Solid surface products
US20090286902A1 (en) * 2004-12-16 2009-11-19 Grasso Jr Louis P Cast Solid Surface Materials Manufactured From Polymers and Post-Consumer Waste Glass
EP1987933A1 (en) 2007-05-01 2008-11-05 The Diller Corporation Thick solid surface laminate product and method of making same
US20080274343A1 (en) * 2007-05-01 2008-11-06 The Diller Corporation Thick solid surface laminate product and method of making same

Also Published As

Publication number Publication date
DE1694726A1 (en) 1971-10-28
DE1694726C3 (en) 1973-09-20
DE1694726B2 (en) 1973-02-01
GB1132439A (en) 1968-10-30
FR1469795A (en) 1967-02-17
US3405088A (en) 1968-10-08
SE333462B (en) 1971-03-15

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