CN101184816B - An embedment casting composition - Google Patents
An embedment casting composition Download PDFInfo
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- CN101184816B CN101184816B CN2006800185783A CN200680018578A CN101184816B CN 101184816 B CN101184816 B CN 101184816B CN 2006800185783 A CN2006800185783 A CN 2006800185783A CN 200680018578 A CN200680018578 A CN 200680018578A CN 101184816 B CN101184816 B CN 101184816B
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Abstract
An embedment casting composition and a process of embedding a specimen in an acrylic polymer matrix is described. The composition comprises an acrylic copolymer and a suitable solvent. The acrylic copolymer is derived from 80-99.9 % w/w methyl methacrylate, 0.1-10 % w/w of a C3-C10 olefinically unsaturated acid co-monomer selected from carboxylic, phophonic, sulphonic or phosphinic acids and 0-10 % w/w other suitable monomers and/or additives. A process of embedding a specimen in an acrylic polymer matrix, a cast of an embedded metal specimen, the use of an embedment composition for coating a specimen prior to an embedment coating process and use of an embedment composition as the copolymer resin component of an embedment slurry are also described.
Description
The present invention relates to a kind of embedment casting, especially but authority is not in, embedment casting composition with a kind of sample is embedded in the method in the acrylic acid polymer matrix.
Gather (TEB 3K) (PMMA) the pearl resin be generally used for the embedment casting occasion.Method of use is with the PMMA pearl resin and TEB 3K (MMA) monomer of part mix about equally.MMA begins to dissolve PMMA, forms high mucilage material.This is inclined in mold, thereby it continues sclerosis, and finally can support the weight of embedding sample.The embedding part places the top of the first layer PMMA/MMA mixture, is full of another layer PMMA/MMA slurries in the mold.Then, usually mold is placed autoclave, slurries carry out polymerization under the situation of being heated with pressurized there.After the polymerization,, foundry goods is further processed usually the cooling of the content in the autoclave.Usually, this further processing comprises mechanical workout, sandblast and polishing foundry goods, forms cleaning, crystalline decorative cover.
Various samples can be embedded among the PMMA through aforesaid method.But metal and hard mineral goods have produced specific problem.It is found that these goods come unstuck usually from the polymkeric substance of parcel, cause the appearance of final casting through " silver color " outward appearance (wherein metal and PMMA come unstuck) that makes the goods of embedding have.Be not entangled in any particular theory, cause this reason of coming unstuck to be that the thermal expansivity between sample and the PMMA is different.When polymerization postcooling solidified mold spare, metal products possibly take place to shrink greatly than PMMA.This causes interfacial stress to be assembled, and makes the final and polymkeric substance of metal come unstuck.Past the someone propose to prevent the method for " patina ", such as, in the monomer/solvent systems of embedment casting composition, add softening agent or methylacrylic acid (MAA), but these modes are not successes fully, and may produce other problems.For example, softening agent may reduce the surface hardness of solidifying foundry goods, uses monomer acids, like MAA, may cause some metal variable color.
Surprisingly, have now found that, the unsaturated acid monomer copolymerization of relatively small amount is incorporated into prevents final curing foundry goods " patina " in the polymeric beads resin effectively.Avoid using additive method, in the time of like the viewed defective of above-mentioned those methods, also can realize this advantage.
According to a first aspect of the invention; A kind of embedment casting composition is provided; It comprises acrylic copolymer and appropriate solvent, and wherein said acrylic copolymer is derived from the TEB 3K (MMA) of 80-99.9 weight %, the C that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight %
3-C
10Other suitable monomers and/or the additive of ethylenic unsaturated acid comonomer and 0-10 weight %.
According to a second aspect of the invention; Provide a kind of sample is embedded in the method in the acrylic acid polymer matrix; It may further comprise the steps: the sample of embedding is contacted with the embedment casting composition that comprises acrylic copolymer and appropriate solvent; Wherein said acrylic copolymer is derived from the TEB 3K (MMA) of 80-99.9 weight %, the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight % and other suitable monomers and/or the additive of 0-10 weight %; And preferred, solidify said acrylic acid polymer matrix, more preferably it is cured to complete polymerization.
Preferably, said acid is that olefinic is undersaturated, and is preferred, α, beta-unsaturated acid.Preferably, said acid has and is lower than 40 atoms, more preferably less than 30 atoms.Said acid can be single, two or polyprotonic acid.Usually, said acid is carboxylic acid.
Typical acid comprises vinylformic acid, methylacrylic acid, Sorbic Acid, Ba Dousuan, iso-crotonic acid; Toxilic acid, ethyl toxilic acid, dimethyl maleic acid, methylene radical pentanedioic acid, fumaric acid; The ethyl fumaric acid, dimethyl fumarate, methylene-succinic acid, itaconic anhydride, dimethyl-methylene-succinic acid; γ-methyl methylene-succinic acid, Alpha-Methyl methylene-succinic acid, γ-propyl group methylene-succinic acid, γ-n-hexyl methylene-succinic acid, equisetic acid; Citraconic acid, dimethyl-citraconic acid, paraconic acid, anti-ethyl paraconic acid, dimethyl-paraconic acid; The monochloro toxilic acid, dichloromaleic acid, hydromuconic acid (hydromuconic acid), propene dicarboxylic acid, β-propyl group propene dicarboxylic acid; Alpha-Methyl propene dicarboxylic acid (genial anti-), Beta-methyl propene dicarboxylic acid (genial anti-), hexene-(2)-dicarboxylicacid, hexene-(3)-dicarboxylicacid; β-propyloic acrylic ester, the SULPHOSUCCINIC ACID ESTER of methylacrylic acid 2-sulfoethyl ester and various methylacrylic acids, for example from Sipomer PAM-100 and the PAM-200 phosphate functional specific monomer of Rhodia, styracin, vinyl furancarboxylic acid, alpha-chloro Sorbic Acid, to vinyl benzoic acid and atropic acid.Preferred especially α, β-ethylenically unsaturated carboxylic acids comprises the carboxylic acid with 3-8 carbon atom, more preferred vinylformic acid and methylacrylic acid.
Preferably, the solvent that is used for said acrylic copolymer in the casting composition slurries comprises the MMA monomer of 80-100%w/w.Preferably; Said solvent comprises and is lower than total monomer 0.5%w/w, more preferably, is lower than 0.2%w/w; Most preferably, be lower than 0.05%w/w for first and/or second aspect and corresponding paragraph thereof described in the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid.Usually, the polymkeric substance the acrylic copolymer that compsn of the present invention defines in the present invention for this acid mono or by its deutero-does not have the selectivity source, wherein; For fear of wakeing suspicion, " not having the selectivity source " is appreciated that this acid mono is lower than 0.5%w/w in order to mean in the compsn except helping acrylic copolymer; More preferably; Be lower than 0.2%w/w, most preferably, be lower than 0.05%w/w.
Preferably, said solvent and multipolymer at first mix in this casting composition slurries, so that form the embedment casting slurries.In addition or perhaps, said solvent and multipolymer can mix so that form the sample coating composition.
Preferably, acrylic copolymer in the embedment casting composition slurries: the mass ratio of solvent is 1: 5-5: in 1 scope, more preferably, 1: 3-3: 1, most preferably, 1: 2-2: 1.
Preferably, acrylic copolymer in the embedment casting sample coating composition: the mass ratio of solvent is 0.5: 99.5-70: in 30 scopes, more preferably, 2: 98-60: 40, most preferably, 5: 95-50: 50.
Preferably, the method for second aspect present invention comprises the step that compsn is thickened to be enough to the degree that supports sample, contacts with sample more afterwards, and said contact is usually included in and makes before the complete polymerization of slurries, with sample place said thickening the surface of slurries on.
Preferably, said method comprises that the other a part of casting composition of other usefulness covers sample, thereby makes sample be embedded in the step in the acrylic acid or the like casting composition before the polymerization fully.Preferably, thereby final foundry goods comprises part at least, and is preferred, fully the sample of embedding embedding wherein.Aforesaid method also comprise through or place identical layer to go up, or cover preceding sample and repeat the possibility of a plurality of samples of mode embedding of embedding process several samples with fresh slurries.
The present invention also extends to the foundry goods of the sample of embedding, and wherein said sample comprises the metal that contacts with the polymeric matrix that surrounds foundry goods, and the polymeric matrix of said foundry goods stems from the compsn according to first aspect present invention.
Said acrylic copolymer solvent can be selected from one or more such as C
1-C
20Alkyl (C
0-C
6Alkyl) monomer of propenoate is like vinylformic acid and methacrylic acid metal salt, the ester of vinylformic acid, methylacrylic acid and Lv Daibingxisuan and pure and mild phenol; Acrylic amide and USAF RH-1; Vinyl cyanide and methacrylonitrile; Alkoxyalkyl acrylic amide and USAF RH-1; For example butoxymethyl acrylic amide and methoxymethyl USAF RH-1, hydroxyalkyl acrylic amide and USAF RH-1, for example, N hydroxymethyl acrylamide and USAF RH-1; Vinyl aromatic compounds, for example vinylbenzene and its substituted verivate are like its halo derivatives and Vinyl toluene; Vinyl ester, for example vinyl acetate, and vinyl pyrrolidone; Maleic anhydride, methylene-succinic acid, N-alkyl (aryl) maleimide, vinyl pyridine, N, N-dialkyl methyl acrylic amide.
The instance of suitable simple function group (methyl) acrylate monomer solvent comprises that (methyl) acrylic acid low alkyl group is C
1-C
20Alkyl ester, (methyl) methyl acrylate for example, (methyl) ethyl propenoate; (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate; (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate; (methyl) Octyl acrylate, or (methyl) dodecylacrylate.In addition, can use the naphthenic base monomeric substance, like (methyl) vinylformic acid cyclohexyl ester, (methyl) isobornyl acrylate and (methyl) vinylformic acid dicyclopentenyl ester.Further, the vinylformic acid aryl ester is like (methyl) vinylformic acid benzyl ester and (methyl) phenyl acrylate.Functionalized monomer such as methylacrylic acid and vinylformic acid; (methyl) acrylic acid hydroxyl or haloalkyl ester are like (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid chloro-ethyl ester, (methyl) vinylformic acid hydroxypropyl ester and (methyl) hydroxybutyl acrylate, (methyl) vinylformic acid glycidyl esters, and (methyl) propenoic acid dialkyl aminoalkyl ester is like (methyl) vinylformic acid dimethylaminoethyl ester, (methyl) vinylformic acid diethyl aminoethyl ester, (methyl) vinylformic acid dimethyl aminopropyl ester, (methyl) vinylformic acid diethyl amino propyl diester and (methyl) vinylformic acid tertiary butyl aminoethyl ester.(methyl) propenoate meaning is to use methacrylic ester or similar propenoate.
Polyfunctional monomer also can be as solvent monomer or as the part of solvent monomer.This monomer per molecule has two polymerisable double bonds at least.The instance of suitable difunctional monomer comprises: ethylene glycol bisthioglycolate (methyl) propenoate, pinakon two (methyl) propenoate, tripropylene glycol two (methyl) propenoate, butyleneglycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, glycol ether two (methyl) propenoate, triglycol two (methyl) propenoate, dipropylene glycol two (methyl) propenoate, (methyl) vinylformic acid allyl ester, Vinylstyrene and its substituted homologue.The instance of trifunctional comprises: tripropylene glycol three (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate.Also can use the monomer of four-functional group, like the monomer of tetramethylolmethane four (methyl) propenoate and six functional groups, Dipentaerythritol six (methyl) propenoate for example.Optional, polyfunctional monomer can comprise the mixture more than a kind of polyfunctional compound.
Final cast poymerization thing also can use per molecule to have reactive oligomers or the reactive polymer or the prepolymer formation of at least two polymerisable double bonds in solvent monomer.The typical reaction oligomers includes but are not limited to, epoxy-(methyl) propenoate, polyethers-(methyl) propenoate, polyester-(methyl) propenoate and urethane-(methyl) propenoate.Typical reaction property polymkeric substance comprises addition or condensation polymer, as comprises polymerisable (methyl) acrylate group that dangles or the vinylbenzene or the acrylic copolymer of unsaturated polyester.
The amount of the polyfunctional monomer solvent that exists can be up to the 50wt% of total initial monomer concentration.Preferably, when polyfunctional monomer is a simple monomer when promptly not being reactive oligomers or polymkeric substance, when existing, the amount of polyfunctional monomer is based on the 0.3-25wt% of total initial monomer concentration, for example 0.5-10wt%.When using reactive polymer or oligopolymer, said concentration can change to up to about 50%w/w of total initial monomer or bigger, like 1-60%w/w.
Vinyl monomer is preferred solvent monomer like polystyrene, propenoate and methacrylic ester, (methyl) acrylic amide and vinyl cyanide.
Can use mixture more than a kind of above-mentioned solvent.
Usually, solvent monomer comprises the TEB 3K that accounts for total monomer 80-100%w/w and one or more monomers that are selected from above-mentioned tabulation of 0-20%w/w.This second monomeric more typical scope is to account for the 0.1-20%w/w of total monomer, the most normally 0-5-5%w/w.Usually, at the total monomer that joins the acrylic copolymer that is used for preparing the present composition, solvent monomer provides more than 95%, more generally is more than 99%w/w, the most normally 100%w/w.Preferably, in the polymkeric substance in final curing compsn, acrylic copolymer and solvent monomer provide more than 95%w/w, more generally are more than 99%w/w, the most normally the resistates of 100%w/w.
Said solvent, especially casting composition solvent coated also can be selected from aliphatic ester, aliphatic ether, and aliphatic ketone and fatty alcohol, it can be selected from methyl alcohol, ethanol, butanols; Virahol, n-propyl alcohol, acetone, methyl ethyl ketone, MIBK, diethyl ketone, 2-heptanone; N-Methyl pyrrolidone, diethyl carbonate, methyl acetate, ETHYLE ACETATE, n-butyl acetate, isobutyl acetate, the own ester of acetate 2-; The lactic acid n-butyl, ethyl lactate, methyl propionate, THF, N, N-N,N-DIMETHYLACETAMIDE, ethylene dichloride; Methylene dichloride, chloroform, ether, isopropyl ether, toluene, ketopentamethylene, hexanaphthene; Pimelinketone, phenylethane, 1-decanol, 1-methoxyl group-2-butanols, 1-sec.-propyl-glyoxal ethyline, acetate methylcellulose gum ester, methylene dichloride; Nitromethane 99Min., methyl-formiate, gamma-butyrolactone, propylene carbonate, 1,2-glycol dimethyl ether (glyme), 3-ethoxyl ethyl propionate (EEP); YLENE, benzene, diisobutyl carbinol(DIBC), methyl amyl ketone, hexyl and heptyl acetic ester, and glycol ethers and diol ester are like the arbitrary proportion mixture of glycol ether, Ucar 35 monoethyl ether acetic ester, diethylene glycol butyl ether acetic ester, isobutyl isobutyrate and above-mentioned solvent.
More particularly, said solvent coated is selected from TEB 3K, acetone, methyl ethyl ketone, ETHYLE ACETATE, n-butyl acetate, lactic acid n-butyl and THF.
Said coating composition also can comprise polymerisable material usually, like the monomer that is used for slurries as stated, functionalized oligopolymer and multipolymer.
Other additives and/or the acrylic copolymer that is used for said compsn comprises the compound such as linking agent, polymkeric substance, vulcanizing agent, curing catalyst and accelerator, dyestuff, solvent, dispersing auxiliary, lubricant, processing aid, weighting agent, carrier fluid and toughner, softening agent, soft agent, stablizer, perfume compound, initiator and other components of depending on the circumstances.This additive amount in said final curing compsn usually is lower than 20 weight %, more generally is to be lower than 10 weight %, more preferably less than 5 weight %.
Suitable radical initiator comprises organo-peroxide, hydroperoxide, persulphate, peroxyester and azo cpd.The instance of this initiator is a butanone peroxide, Lucidol, isopropyl benzene hydroperoxide, Potassium Persulphate, Diisopropyl azodicarboxylate (AIBN), azo two (2-methylbutyronitrile); Azo two (2, the 4-methyl pentane nitrile), azo two (4-cyanovaleric acid), peroxo-neodecanoic acid tertiary butyl ester, dibenzoyl peroxide, dicumyl peroxide; Caproic acid t-butyl peroxy 2-ethyl ester, t-butyl peroxy diethylacetic acid ester and phenylformic acid t-butyl peroxy ester, lauroyl peroxide, 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane; Diethyl peroxide, peroxo-dipropyl, peroxo-dilauryl, peroxo-two oleyls, peroxo-distearyl, two (tertiary butyl) superoxide; Two (tert-pentyl) superoxide, tert-butyl hydroperoxide, t-amyl hydroperoxide, acetylperoxide, peroxo-propionyl, stearoyl; The peroxo-malonyl-, succinyl peroxide, peroxo-phthalyl, acetylbenzoyl peroxide, propionyl group Lucidol, ascaridol(e); Ammonium persulphate, Sodium Persulfate, Potassium Persulphate, SPC-D, antihypo; Sodium peroxoborate, potassium per(oxy)borate, peroxophosphoric acid sodium, potassium super phosphate, naphthane hydroperoxide; Tertiary butyl diperoxy phthalic ester, tert butyl peroxy benzoate, 2,4-dichlorobenzoyl peroxide, urea peroxide; Sim peroxides, right-the chlorobenzene formacyl superoxide, 2, two (tertiary butyl peroxide) butane of 2-, hydroxyl heptyl superoxide.But when having enough residual initiators in the acrylic copolymer, the adding of initiator is unessential.
Suitable dispersing auxiliary comprises chain polymer dispersion agent component.The instance of this dispersing auxiliary comprises propenoate and methylacrylic acid ester homopolymer and multipolymer, PS, epoxy resin, polyester and its verivate.
The suitable dyestuff that can join in the polymerizable matrix comprises pigment, like titanium oxide, and carbon black, zinc oxide, indanthrone, quinacridone, phthalocyanine, red stone, titanium oxide and ultramarine.Suitably, said pigment can be particle form, and it can directly join in the polymerisable matrix, like informal voucher sand, and common brick ash and grey ashes.Perhaps or in addition, granular pigments can mix with carrier fluid, join then in the polymerisable matrix.Perhaps, pigment can be soluble dye, for example, dissolves in the dyestuff among the MMA.
The cross-linked material that is suitable for joining in the said compsn comprises crosslinkable monomer, as in molecule, having the monomer of two polymerisable vinyl groups at least.But the cross-linking monomer of suitable copolymerization comprises (alkyl) propenoate of dual functional (alkyl) propenoate and/or trifunctional.The instance of this crosslinkable monomers comprises ethylene glycol bisthioglycolate (methyl) propenoate, 1,3 butylene glycol two (methyl) propenoate; 1,4-butyleneglycol two (methyl) propenoate, polyethyleneglycol diacrylate and dimethacrylate; Ucar 35 dimethacrylate and diacrylate, SY-Monomer G, Vinylstyrene; Triethylene glycol dimethacrylate or trimethylolpropane tris (methyl) propenoate, and allylic cpd are like allyl methacrylate(AMA); Triallyl cyanurate, and allyl diglycol carbonate.
Suitably, weighting agent can be the natural inorganic filler particle that is selected from aluminum oxide, silicate, metal aluminate, metal phosphate, metal sulfate, metal carbonate, metallic sulfide, metallic carbide, MOX and combination thereof.Suitable natural inorganic filler particulate instance comprises nesosilicate (single tetrahedron); Twin islet shape silicate (ditetrahedron); Chain silicate (single and double-stranded); Cyclosilicate (ring); Phyllosilicate (thin slice) and tectosilicate (skeleton).Other suitable inorganic silicates are tectosilicate subclasses, comprise feldspar family, feldspathoides family, quartzy family and zeolite family.The instance of quartzy family tectosilicate subclass weighting agent comprises coesite, cristobalite, quartz and tridymite.Perhaps, can use suitable synthetic weighting agent.This suitable synthetic weighting agent comprises glass powder, pottery, chinaware, cinder, slag and finely divided silicon-dioxide.
Suitable curing catalyst and accelerator comprise amine.The instance of suitable amine comprises for example N of tertiary amine, N-dimethylamino-para-totuidine, N, N-diethylamino-para-totuidine or N, N-dihydroxy ethyl-para-totuidine.
The suitable processing aid that is used for said compsn comprises the polymerized unit of being made up of one or more ethylenically unsaturated monomers, for example positive alkyl ester monomer of vinylformic acid and the positive alkyl ester monomer of methylacrylic acid.
The suitable flexible softening agent that is used for joining said compsn comprises polyoxyethylene glycol, W 166, polyoxyethylene glycol/propylene glycol copolymers, dimethyl phthalate; Witcizer 300, DOP, Dinonylphthalate; The phthalic acid dodecyl ester, butyl benzyl phthalate, phthalic acid iso-octyl benzyl ester; Citrate such as ethanoyl three normal-butyl citrates, adipic acid ester such as hexanodioic acid dialkyl, for example Octyl adipate; Sebate such as Uniflex DBS, azelate is like two (2-ethylhexyl) azelate, and SULPHOSUCCINIC ACID ESTER such as Tritolyl Phosphate.
The stablizer that is suitable for said compsn comprises UV stabilizer.Suitable UV stabilizer comprises hindered amine as light stabilizer, 2-dihydroxy benaophenonel, 2-hydroxy phenyl benzotriazole, and transition metal complex such as Ni (II) oxime inner complex.
Preferably; The amount of unsaturated acid comonomer does in the acrylic acid series co-polymer, 0.2 weight %-10 weight %, more preferably 0.4-5 weight % of the amount before acrylic copolymer joins in the solvent; 0.6-3 weight % most preferably, particularly about 0.8-3 weight %.
Usually, said acrylic copolymer is the suspension polymerization preparation through the PMMA pearl resin that is used for the embedment casting field that is used for preparation standard, and it is known for a person skilled in the art.
On the other hand; The present invention also relates to the purposes that embedding composition is used for coating sample before the embedment casting process; Said embedding composition comprises the solvent of acrylic copolymer and acrylic copolymer, and wherein said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, other suitable monomers and the additive like defined unsaturated acid comonomer of first aspect present invention and 0-10 weight % of 0.1-10 weight %.
The present invention also relates to the purposes of embedding composition as the copolymer resin component of embedding slurries in the embedment casting process; Said embedding composition comprises acrylic copolymer, its stem from 80-99.9 weight % TEB 3K (MMA), 0.1-10 weight % as defined unsaturated acid comonomer of first aspect present invention and 0-10 weight % other suitable monomers and additive.
Preferably, said resin is the solid particulate form of suitable 1-800 micron, like pearl, and powder, or the like.The normally solid or hollow piece of sample that is used for embedding.But liquid also can generally be the ampoule form by embedding.When the embedding sample is metal or hard mineral goods, can demonstrate advantage of the present invention usually.Usually, said sample is a metal or metal alloy, as can be as those of sample, for example, aluminium, copper, brass, bronze, gold, silver, mercury, platinum, steel, iron, nickel, zinc, or the galvanized metal of above-mentioned metal.
Preferably, the weight-average molecular weight of acrylic copolymer resin (Mw) is 50,000-4, and in 000,000 dalton's scope, more preferably 100,000-2, between 000,000 dalton, most preferably 200,000-1 is between 000,000 dalton.
The suitable technology that is used to measure the weight-average molecular weight that as above defines is to use the gel permeation chromatography of PMMA molecular weight standard.
Preferably, in the time of in being poured into mold, the viscosity of said casting composition is at 0.1-10, in the 000 pool scope, more preferably at 1-5, between 000 pool, most preferably at 3-3, between 000 pool.
The typical condition that is used to carry out the embedment casting process is well known to those skilled in the art.
Preferably, the polymerization temperature of casting composition is 30-120 ℃, more preferably 30-110 ℃, and most preferably 35-100 ℃.
Preferably being used for cast polymerized pressure is the 1-50 crust, more preferably 2-30 crust, most preferably 3-15 crust.
The coating drying can be carried out under environment or higher a little temperature, under 10-60 ℃, carries out more preferably 15-50 ℃.
Preferably, the coat-thickness on the sample is 5 microns-500 microns, more preferably 30 microns-300 microns, and most preferably 50 microns-200 microns.
To specify indefiniteness embodiment of the present invention in an embodiment now.
Embodiment: the preparation of acrylic copolymer
Be used to make and be used to cast the general method that gathers (methacrylic ester) bead polymer (weight-average molecular weight (Mw) 200,000-1,000,000 dalton) of experiment:
Gathering (methacrylic ester) bead polymer prepares through following illustrational standard suspension polymerization method:
With the deionized water solution that gathers (methylacrylic acid) of 22.4kg deionized water, 176g 3% and 133g Di-Sodium Phosphate join be equipped with can speed change 4 propeller agitators have a stainless steel autoclave that retaining is pulled, and in nitrogen purging, be heated to 60 ℃.Add 10kg monomer and the 47g dibenzoyl peroxide initiator of dissolved 75 weight % in advance, then mixture is being stirred and is being heated under the 450rpm under 90 ℃ the polymerization temperature.Polymerization takes place in monomer droplet when heating.After mixture has carried out so-called Tromsdorff heat release, think that polymerization accomplishes, at this moment, the quick self-heating of the content of autoclave is to about 95-100 ℃.Then said content is cooled to below 40 ℃, filters, use deionized water wash, and in 60 ℃ air circulation oven drying several days.Raw material monomer comprises MMA, unsaturated acid comonomer such as MAA or AA and lubricant such as VLTN 6 or Triple Pressed Stearic Acid, or softening agent such as Witcizer 300 or ethanoyl three normal-butyl citrates.
Be used for measuring the acid functionality's who gathers (methacrylic ester) bead polymer general method:
Carboxylic acid in the bead polymer and other acid functionalities can use following titration method to measure:
The 1g copolymer resin at room temperature is dissolved in the 45ml THF, spends the night.Add 45ml Denatured alcohol and 1-2ml phenolphthalein indicator (ethanolic soln of 1 weight %) then, with this solution of aqueous sodium hydroxide solution titration of 0.1N up to reaching terminal point (solution appearance is from the colourless pink that becomes).Calculate the weight percentage that is incorporated into the unsaturated acid in the copolymer skeleton then, perhaps use acid number (mgKOH/g resin) expression, perhaps represent with weight % unsaturated acid comonomer.
Be used for general method at PMMA embedding metal identification:
At room temperature, 60g PMMA pearl (being total to)-polymkeric substance and 40g MMA monomer are mixed the formation slurries in plastic beaker.(PMMA pearl (being total to) polymkeric substance has 80 microns median size usually, and molecular weight is 500k, comprises remaining peroxide initiator).When mixture has thickened to high must be enough to prevent the settled degree of PMMA (being total to) polymeric beads the time; Slurries are poured in the plastic mold; And make its viscosity continue to increase, up to mixture can support the endless metal that 2mm is thick, diameter is 25mm (as, brass or aluminium) weight of sign.Metal identification (before through in acetone, flooding, be immersed in then among the MMA, make its at room temperature drying and degreasing afterwards) is placed in the top of PMMA (being total to) polymkeric substance/MMA mixture.Then, through being mixed with the 40gMMA monomer, 60g PMMA pearl (being total to) polymkeric substance prepares another part slurries.When viscosity is enough, slurries are poured into above the metal identification and fill the plastic covering mould, it was hardened about 1 hour.Then mold is dropped in the autoclave, cling to, heated 5 hours down, heated 1 hour down at 90 ℃ then, make it arrive room temperature afterwards at 16 hours internal cooling at 50 ℃ with oxygen-free nitrogen pressure to 8.Discharge the pressure of autoclave, and with the foundry goods demoulding.Check the variable color and the patina vestige of the metal identification of embedding then.The patina degree is by the classification that is described below:
Grade:
0=does not have patina (about 100% melts combine is on acrylic acid series matrix)
The slight patina of 1=(melts combine of 75-100% is on acrylic acid series matrix)
The serious patina of 2=(＜75% melts combine is on acrylic acid series matrix)
Comparative example 1-3 through add at the MMA monomer that is used for casting composition the monomer contain carboxylic acid or through with the softening agent embedding before the said metal identification of coating preventing patina.
The methylacrylic acid (MAA) of 0.5-2 weight part (total monomer) or the MMA monomer of vinylformic acid (AA) and 99.5-98 weight part are mixed, and as the monomer segment in the casting experiment of using standard cast level PMMA bead polymer.
Table 1 illustrates to join with MAA or from the concentration at 2 weight % and prevents patina the monomer component, and sign becomes green but it but causes brass.More a spot of MAA (0.5 weight %) can not prevent patina, and still causes the brass sign to become green.
In independent experiment (comparative example 4), said being identified at used softening agent before the embedding, like ethanoyl three normal-butyl citrate coatings.But this method does not prevent patina fully.
Table 1:
Show embodiments of the invention:
The described monomer mixture of table 2 then, is used as the bead polymer component of embedding experiment with it with the raw material monomer that acts on the different bead polymer of a series of carboxylic functionality of preparation.Check the variable color and the patina vestige of the metal identification of embedding then.Show the embodiment of being 6-8 of the present invention and 10-15.Embodiment 5 and 9 can be considered to the comparative example.
Abbreviation:
The MMA=TEB 3K
The MAA=methylacrylic acid
The StOH=VLTN 6
The DOA=Octyl adipate
The DBP=Witcizer 300
Table 2:
As in the monomer/polymer slurries casting process of above-mentioned standard, using acidiferous pearl, have been found that another kind is used to prevent the mode of patina, that is, will contain acid polymer and be dissolved in MMA monomer or the solvent, and with gained solution coatings sample.Make its drying, then with normal mode with the PMMA/MMA slurries of standard or with PMMA/ acid copolymer/MMA slurries embedding sample.
Be noted that relevant with the application, with this specification sheets simultaneously or before the All Files submitted to, to the disclosed All Files of the public, and the content in said these files all is hereby incorporated by with this specification sheets.
The institute of disclosed all characteristics and/or disclosed any method or technology can combine with any combination in steps in this specification sheets (comprising any claim, summary and accompanying drawing subsequently), only if having at least some this characteristic and/or step mutually exclusive in the combination.
Disclosed each characteristic can be applied identical, the character displacement selected of equal value or similar purpose in this specification sheets (comprising any claim, summary and accompanying drawing subsequently), only if clearly explanation is in addition arranged.Therefore, only if clearly demonstrate in addition, disclosed each characteristic all is an instance of universal serial Equivalent or similar characteristics.
The present invention is not limited to the detailed content of above-mentioned embodiment.The present invention extends to the combination of any novelty of disclosed any one novel characteristics of this specification sheets (comprising any claim, summary and accompanying drawing subsequently) or characteristic, perhaps extends to the combination of any novelty of any one novel step or the step of disclosed any method or technology.
Claims (36)
1. be embedded with the foundry goods of sample; Wherein said sample comprises the metal that contacts with on every side cast poymerization thing matrix; Said cast poymerization thing matrix stems from following compsn: said composition comprises acrylic copolymer and appropriate solvent, and wherein said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight % and other suitable monomers and/or the additive of 0-10 weight %.
2. sample is embedded in the method in the acrylic acid polymer matrix; It may further comprise the steps: the sample of treating embedding is contacted with embedment casting composition; Said embedment casting composition comprises acrylic copolymer and appropriate solvent, and wherein said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight % and other suitable monomers and/or the additive of 0-10 weight %.
3. according to the method for claim 2, wherein this method comprises, is enough to support the step of said sample making sample compsn thickened to before contacting with compsn.
4. embedding composition is used for the purposes of coated sample before the embedment casting process; Wherein said embedding composition comprises acrylic copolymer and acrylic copolymer solvent, and said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight % and other suitable monomers and/or the additive of 0-10 weight %.
5. according to the method for claim 2; It may further comprise the steps: with the step of the compsn coated sample that comprises acrylic copolymer and acrylic copolymer solvent, said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, unsaturated acid comonomer that 0.1-10 weight % is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid and other suitable monomers and/or the additive of 0-10 weight % before the embedding sample.
6. according to the foundry goods of claim 1, wherein said acid is ethylenic unsaturated acid.
7. comprise the purposes of the compsn of acrylic copolymer and appropriate solvent as the copolymer resin component of embedding slurries in the embedment casting process, wherein said acrylic copolymer stems from the TEB 3K (MMA) of 80-99.9 weight %, the unsaturated acid comonomer that is selected from carboxylic acid, phosphonic acids, sulfonic acid or phospho acid of 0.1-10 weight % and other suitable monomers and/or the additive of 0-10 weight %.
8. according to the foundry goods of claim 1 or 6, wherein, acrylic copolymer described in the compsn: the mass ratio of solvent is 0.5: 99.5-70: in 30 scopes.
9. according to claim 1,6 or 8 foundry goods, wherein acrylic copolymer described in the compsn: the mass ratio of solvent is 1: 5-5: in 1 scope.
10. according to claim 1,6 or each the foundry goods of 8-9; Wherein said appropriate solvent is selected from one or more monomers and this solvent monomer comprises the TEB 3K that accounts for total monomer 80-100 weight %, accounts for one or more other the monomeric monomer of being selected from of total monomer 0-20 weight %.
11. according to claim 1,6 or each the foundry goods of 8-10; Wherein the amount of the said unsaturated acid comonomer in the acrylic acid series co-polymer does, 0.2 weight %-10 weight % of the total monomer composite of the acrylic copolymer before it joins in the solvent.
12. according to claim 1,6 or each the foundry goods of 8-11, wherein the weight-average molecular weight of acrylic copolymer resin (Mw) is 50,000-4 is in 000,000 dalton's scope.
13. according to claim 1,6 or each the foundry goods of 8-12, in the time of wherein in being poured into mold, the viscosity of casting composition is at 0.1-10, in the 000 pool scope.
14. according to claim 1,6 or each the foundry goods of 8-13, wherein the polymerization temperature of casting composition is in 30-120 ℃ scope.
15. according to claim 1,6 or each the foundry goods of 8-14, wherein being used for cast polymerized suitable pressure is the 1-50 crust.
16. according to claim 1,6 or each the foundry goods of 8-15, wherein said unsaturated acid comonomer is selected from vinylformic acid, methylacrylic acid, Sorbic Acid, Ba Dousuan, iso-crotonic acid; Toxilic acid, ethyl toxilic acid, dimethyl maleic acid, methylene radical pentanedioic acid, fumaric acid, ethyl fumaric acid; Dimethyl fumarate, methylene-succinic acid, itaconic anhydride, dimethyl-methylene-succinic acid, γ-methyl methylene-succinic acid, Alpha-Methyl methylene-succinic acid; γ-propyl group methylene-succinic acid, γ-n-hexyl methylene-succinic acid, equisetic acid, citraconic acid, dimethyl-citraconic acid, methylfumaric acid; Anti-ethyl methylfumaric acid, dimethyl-methylfumaric acid, monochloro toxilic acid, dichloromaleic acid, hydromuconic acid, propene dicarboxylic acid; β-propyl group propene dicarboxylic acid, genial anti-Alpha-Methyl propene dicarboxylic acid, genial anti-Beta-methyl propene dicarboxylic acid, hexene-(2)-dicarboxylicacid, hexene-(3)-dicarboxylicacid, β-propyloic acrylic ester; The SULPHOSUCCINIC ACID ESTER of methylacrylic acid 2-sulfoethyl ester and methylacrylic acid, styracin, vinyl furancarboxylic acid, alpha-chloro Sorbic Acid, right-vinyl benzoic acid and atropic acid.
17. according to claim 2,3 or 5 method, wherein said acid is ethylenic unsaturated acid.
18. according to claim 2,3,5 or 17 method, wherein acrylic copolymer described in the compsn: the mass ratio of solvent is 0.5: 99.5-70: in 30 scopes.
19. according to claim 2,3,5,17 or 18 each method, wherein acrylic copolymer described in the compsn: the mass ratio of solvent is 1: 5-5: in 1 scope.
20. according to claim 2,3,5 or each the method for 17-19; Wherein said appropriate solvent is selected from one or more monomers and this solvent monomer comprises the TEB 3K that accounts for total monomer 80-100 weight %, accounts for one or more other the monomeric monomer of being selected from of total monomer 0-20 weight %.
21. according to claim 2,3,5 or each the method for 17-20; Wherein the amount of the said unsaturated acid comonomer in the acrylic acid series co-polymer does, 0.2 weight %-10 weight % of the total monomer composite of the acrylic copolymer before it joins in the solvent.
22. according to claim 2,3,5 or each the method for 17-21, wherein the weight-average molecular weight of acrylic copolymer resin (Mw) is 50,000-4 is in 000,000 dalton's scope.
23. according to claim 2,3,5 or each the method for 17-22, in the time of wherein in being poured into mold, the viscosity of casting composition is at 0.1-10, in the 000 pool scope.
24. according to claim 2,3,5 or each the method for 17-23, wherein the polymerization temperature of casting composition is in 30-120 ℃ scope.
25. according to claim 2,3,5 or each the method for 17-24, wherein being used for cast polymerized suitable pressure is the 1-50 crust.
26. according to claim 2,3,5 or each the method for 17-25, wherein said unsaturated acid comonomer is selected from vinylformic acid, methylacrylic acid, Sorbic Acid, Ba Dousuan, iso-crotonic acid; Toxilic acid, ethyl toxilic acid, dimethyl maleic acid, methylene radical pentanedioic acid, fumaric acid, ethyl fumaric acid; Dimethyl fumarate, methylene-succinic acid, itaconic anhydride, dimethyl-methylene-succinic acid, γ-methyl methylene-succinic acid, Alpha-Methyl methylene-succinic acid; γ-propyl group methylene-succinic acid, γ-n-hexyl methylene-succinic acid, equisetic acid, citraconic acid, dimethyl-citraconic acid, methylfumaric acid; Anti-ethyl methylfumaric acid, dimethyl-methylfumaric acid, monochloro toxilic acid, dichloromaleic acid, hydromuconic acid, propene dicarboxylic acid; β-propyl group propene dicarboxylic acid, genial anti-Alpha-Methyl propene dicarboxylic acid, genial anti-Beta-methyl propene dicarboxylic acid, hexene-(2)-dicarboxylicacid, hexene-(3)-dicarboxylicacid, β-propyloic acrylic ester; The SULPHOSUCCINIC ACID ESTER of methylacrylic acid 2-sulfoethyl ester and methylacrylic acid, styracin, vinyl furancarboxylic acid, alpha-chloro Sorbic Acid, right-vinyl benzoic acid and atropic acid.
27. according to the purposes of claim 4 or 7, wherein said acid is ethylenic unsaturated acid.
28. according to claim 4,7 or 27 purposes, wherein acrylic copolymer described in the compsn: the mass ratio of solvent is 0.5: 99.5-70: in 30 scopes.
29. according to claim 4,7 or each the purposes of 27-28, wherein acrylic copolymer described in the compsn: the mass ratio of solvent is 1: 5-5: in 1 scope.
30. according to claim 4,7 or each the purposes of 27-29; Wherein said appropriate solvent is selected from one or more monomers and this solvent monomer comprises the TEB 3K that accounts for total monomer 80-100 weight %, accounts for one or more other the monomeric monomer of being selected from of total monomer 0-20 weight %.
31. according to claim 4,7 or each the purposes of 27-30; Wherein the amount of the said unsaturated acid comonomer in the acrylic acid series co-polymer does, 0.2 weight %-10 weight % of the total monomer composite of the acrylic copolymer before it joins in the solvent.
32. according to claim 4,7 or each the purposes of 27-31, wherein the weight-average molecular weight of acrylic copolymer resin (Mw) is 50,000-4 is in 000,000 dalton's scope.
33. according to claim 4,7 or each the purposes of 27-32, in the time of wherein in being poured into mold, the viscosity of casting composition is at 0.1-10, in the 000 pool scope.
34. according to claim 4,7 or each the purposes of 27-33, wherein the polymerization temperature of casting composition is in 30-120 ℃ scope.
35. according to claim 4,7 or each the purposes of 27-34, wherein being used for cast polymerized suitable pressure is the 1-50 crust.
36. according to claim 4,7 or each the purposes of 27-35, wherein said unsaturated acid comonomer is selected from vinylformic acid, methylacrylic acid, Sorbic Acid, Ba Dousuan, iso-crotonic acid; Toxilic acid, ethyl toxilic acid, dimethyl maleic acid, methylene radical pentanedioic acid, fumaric acid, ethyl fumaric acid; Dimethyl fumarate, methylene-succinic acid, itaconic anhydride, dimethyl-methylene-succinic acid, γ-methyl methylene-succinic acid, Alpha-Methyl methylene-succinic acid; γ-propyl group methylene-succinic acid, γ-n-hexyl methylene-succinic acid, equisetic acid, citraconic acid, dimethyl-citraconic acid, methylfumaric acid; Anti-ethyl methylfumaric acid, dimethyl-methylfumaric acid, monochloro toxilic acid, dichloromaleic acid, hydromuconic acid, propene dicarboxylic acid; β-propyl group propene dicarboxylic acid, genial anti-Alpha-Methyl propene dicarboxylic acid, genial anti-Beta-methyl propene dicarboxylic acid, hexene-(2)-dicarboxylicacid, hexene-(3)-dicarboxylicacid, β-propyloic acrylic ester; The SULPHOSUCCINIC ACID ESTER of methylacrylic acid 2-sulfoethyl ester and methylacrylic acid, styracin, vinyl furancarboxylic acid, alpha-chloro Sorbic Acid, right-vinyl benzoic acid and atropic acid.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0510865A GB0510865D0 (en) | 2005-05-27 | 2005-05-27 | An embedment casting composition |
| GB0510865.9 | 2005-05-27 | ||
| GB0526248.0 | 2005-12-23 | ||
| GB0526248A GB0526248D0 (en) | 2005-12-23 | 2005-12-23 | An embedment casting composition |
| PCT/GB2006/001894 WO2006125976A1 (en) | 2005-05-27 | 2006-05-24 | An embedment casting composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101184816A CN101184816A (en) | 2008-05-21 |
| CN101184816B true CN101184816B (en) | 2012-05-30 |
Family
ID=34834759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800185783A Expired - Fee Related CN101184816B (en) | 2005-05-27 | 2006-05-24 | An embedment casting composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101184816B (en) |
| GB (1) | GB0510865D0 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232423B (en) * | 2022-07-12 | 2023-11-03 | 浙江华帅特新材料科技有限公司 | Manufacturing method of metal embedded PMMA composite board and metal embedded PMMA composite board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2934510A (en) * | 1956-02-02 | 1960-04-26 | Du Pont | Coating compositions containing polymer of methyl methacrylate |
| CN1283205A (en) * | 1997-12-24 | 2001-02-07 | 国际壳牌研究有限公司 | Copolymers of ethylenically unsaturated monomers to be used in powder coatings |
-
2005
- 2005-05-27 GB GB0510865A patent/GB0510865D0/en not_active Ceased
-
2006
- 2006-05-24 CN CN2006800185783A patent/CN101184816B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2934510A (en) * | 1956-02-02 | 1960-04-26 | Du Pont | Coating compositions containing polymer of methyl methacrylate |
| CN1283205A (en) * | 1997-12-24 | 2001-02-07 | 国际壳牌研究有限公司 | Copolymers of ethylenically unsaturated monomers to be used in powder coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0510865D0 (en) | 2005-07-06 |
| CN101184816A (en) | 2008-05-21 |
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