CN1178228A - Rigid PVC stabilised with N, N-dimethyl-6-aminouracils - Google Patents
Rigid PVC stabilised with N, N-dimethyl-6-aminouracils Download PDFInfo
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- CN1178228A CN1178228A CN 97119584 CN97119584A CN1178228A CN 1178228 A CN1178228 A CN 1178228A CN 97119584 CN97119584 CN 97119584 CN 97119584 A CN97119584 A CN 97119584A CN 1178228 A CN1178228 A CN 1178228A
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Abstract
A composition is disclosed, comprising A) rigid or semi-rigid PVC having a plasticiser content of up to 20%, and B) at least one compound of formula 1, wherein X is O or S, and R is H or phenyl, with the proviso that compounds from the groups of the perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydro-pyridines, polydihydro-pyridines, polyhydric alcohols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali alumosilicates (zeolites), hydrotalcites, alkali alumocarbonates (dawsonites) are not present.
Description
The present invention relates to specific N, stable hard or the semi-rigid PVC of N-dimethyl-O-amino uracil (preferred heavy metal free) with following formula I definition.
DE1694873 discloses with specific uracil compound and has stablized PVC, makes its heat resistanceheat resistant and oxidation stress.Yet this disclosure has only been described the flexible PVC composition that contains these amino uracils.Also disclose other amino uracil and amino thiouracil compound as the stablizer of PVC (EP0065934, EP0354179, EP0041479).Have now found that these amino uracils and amino thiouracil compound are extremely limited to the suitability of flexible PVC, because their existence causes the painted of stabilising system or bubbles.Yet surprisingly, plasticizer loading is 20% PVC at the most, and promptly so-called hard or semi-rigid PVC can be stable well by the compound of following formula I.No longer including coloring problem exists.
Thus, the present invention relates to composition, it contains
A) plasticizer loading at the most 20% hard or semi-rigid PVC and
B) compound of at least a formula I
Wherein X is O or S, and R is H or phenyl,
Its restricted condition is not exist to be selected from the perchlorate compound, glycidyl compound, beta-diketon class, 'beta '-ketoester class, dihydropyridines, poly-dihydropyridines, polyvalent alcohol, disaccharides alcohols, steric hindrance amine (tetraalkyl piperidine compounds), alkali-metal aluminosilicate (zeolites), hydrogenant damourite class, the compound of alkali-metal aluminium carbonate (dawsonite class).
Preferred compositions is those wherein B) be the composition of the compound of formula I (wherein X=O), those B wherein particularly) be
Compound compositions.
The invention still further relates to the application of formula I compound in stablizing hard or semi-rigid PVC of above-mentioned restricted condition.
Formula I compound can be incorporated into the consumption of waiting to stablize among hard or the semi-rigid PVC and advantageously be the 0.01-10% weight based on whole compositions, preferred 0.05-5% weight and particularly 0.1-3% weight.
Composition of the present invention also can further comprise additive commonly used, as stablizer, and auxiliary agent and processing aid, typical alkali metal compound and alkaline earth metal compound, lubricant, softening agent, pigment, filler, phosphorous acid ester, thiophosphite and thiophosphatephosphorothioate, mercapto-carboxylic ester, epoxidized fatty acid ester, oxidation inhibitor, UV light absorber and photostabilizer, white dyes, impact modifying agent, jelling agent, static inhibitor, biocides, metal deactivator, fire retardant and whipping agent, and antifogging agent is (with reference to PVC batching handbook " Handbook of PVC-Formulating ", E.J.Wickson, John Wiley ﹠amp; Sons, New York 1993).The illustrative examples of these additives has: the I. filler: filler (PVC batching handbook (HANDBOOK OF PVCFORMULATING) E.J.Wickson John Wiley ﹠amp; Sons, Inc., 1993, pp.393-449) and toughener (TASCHENBUCH der KA ' e R.Gachter ﹠amp; H.M ü ller, Carl Hanser, 1990, pp.549-615).Lime carbonate is typically arranged, rhombspar, wollastonite, magnesium oxide, magnesium hydroxide, silicate, potter's clay, talcum, glass fibre, granulated glass sphere, wood powder, mica, metal oxide or metal hydroxides, carbon black, graphite, ore powder, barite, kaolin and chalk.Preferred chalk.Based on 100 weight part PVC, the consumption of filler is preferably at least 1 weight part, typically is 5 to 200 weight parts, is 10 to 150 weight parts easily, more preferably is 5 to 100 weight parts.II. metallic soap: metallic soap mainly is preferred long-chain carboxylic acid's a metal carboxylate.Standard example is stearate and lauroleate, and the salt of oleate and short-chain alkyl carboxylic acid.Metallic soap also should be understood that alkylbenzoic acid.The also normal so-called synergistic mixt (Synergistic blend) that uses, as barium/zinc, magnesium/zinc, calcium/zinc, or calcium/magnesium/zinc stabilizer.Metallic soap can be used alone or as a mixture.The summary of common metal soap will be in " the technical chemistry complete works of Ullmann ", and the 5th edition, A16 rolls up (1985), finds in the content below the 361st page.Use is selected from C
2-C
22Aliphatics saturated carboxylic acid salt series, C
3-C
22Aliphatics salt unsaturated carboxylic acid series, by at least one-C that OH replaces
2-C
22Aliphatic carboxylate's series contains the ring or the bicyclic carboxylic acid salt series of 5-22 carbon atom, unsubstituted or by at least one-OH and/or C
1-C
16The phenyl carboxylate series that alkyl replaces, unsubstituted or by at least one-OH and/or C
1-C
16The naphthyl carboxylate salt series that alkyl replaces, phenyl-C
1-C
16Alkyl carboxylate's series, naphthyl-C
1-C
16Alkyl carboxylate's series, or unsubstituted or C
1-C
12The phenates series that alkyl replaces, the organo-metallic soap of resinate is easily.
The exemplary of mentioning is monocarboxylic zinc, calcium, and magnesium or barium salt, acid is acetate for example, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, neodecanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, Palmiticacid, Unimac 5680, stearic acid, 12-oxystearic acid ， docosoic, phenylformic acid, right-p t butylbenzoic acid, N, N-dimethyl hydroxyl phenylformic acid, 3, the 5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, Whitfield's ointment, right-uncle's octyl group Whitfield's ointment and Sorbic Acid; The calcium of the monoesters of di-carboxylic acid, magnesium and zinc salt, acid is oxalic acid for example, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, the 7-dicarboxylic acid, octane-1,8-dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid and hydroxyl phthalic; Three or the calcium of two or three esters of quaternary carboxylic acid, magnesium and zinc salt, acid typically is hemimellitic acid, trimellitic acid, 1,2,4,5-pyromellitic acid, citric acid.
The preferred calcium carboxylates that uses the carboxylic acid that contains 7 to 18 carbon atoms, magnesium carboxylates and zinc carboxylate (more being metallic soap on the stricti jurise), typically be benzoate or alkanoate, preferred stearate, oleate, lauroleate, cetylate docosoic salt, hydroxyl stearate, dihydroxystearic acid salt or 2-ethylhexoate.Particularly preferably be stearate, oleate and the right-tertiary butyl-benzoate.Overbasic carboxylate salt such as high alkalinity zinc octoate also are preferred.
If suit, also can use the mixture of the carboxylate salt of different structure.
Preferred compositions is that as described those contain organic zinc compound or/and the organic calcium compound compositions.
Except that the compound that those are quoted, same suitable organo-aluminium compound in addition is preferably with above-mentioned similar compounds.Be suitable for using and the details of preferred aluminum compound can be found in US4060512 and US3243394.
Except that the compound of having mentioned so far, organic rare earth compounds is suitable too, compound particularly similar to the above.The term rare earth compound should be understood as that and particularly contain elemental cerium, praseodymium, and neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the compound of lanthanum and yttrium, particularly the mixture with cerium is preferred.Other preferred rare earth compound can be found in EP-A-0108023.
If suit, also can use the zinc of different structure, alkaline-earth metal, aluminium, the mixture of lanthanum or lanthanide compound.Also can be with organic zinc, aluminium, lanthanum or lanthanum prime element compound are coated on the aluminium salt compound; See DE-A-4031818 equally.
Based on 100 weight part PVC, the amount of spendable metallic soap or its mixture typically is 0.001 to 10 weight part, is 0.01 to 8 weight part easily, particularly preferably is 0.05 to 5 weight part.This is equally applicable to other metal(lic)stabilizer of other metal(lic)stabilizer: III.: mention organotin stabilizer here especially.These are preferably carboxylate salt, thiolate and sulfide.US4743640 discloses suitable example.IV. alkali metal compound and alkaline earth metal compound: these should be understood that, the carboxylate salt of above-mentioned acid particularly, but also have corresponding oxide compound or oxyhydroxide or carbonate.They and organic acid mixture are fit to too.Typical example is NaOH, KOH, CaO, Ca (OH)
2, MgO, Mg (OH)
2, CaCO
3And MgCO
3, and fatty acid sodium salt and lipid acid sylvite.Under the situation of using alkaline earth metal carboxylation and zinc carboxylate, also can use they and MO or M (OH)
2The adducts of (M=Ca, Mg, Sr or Zn), promptly so-called high alkaline compound.Except that new combination of stabilizers, preferably use alkali metal carboxylate, alkaline earth metal carboxylation and/or ALUMINUM CARBOXYLIC.V. lubricant: suitable lubricant for example is: ceresine, fatty acid ester, PE wax, amide waxe, clorafin, glyceryl ester or alkaling earth metal base.Spendable lubricant also is described in " plastics additive (Kunststoffadditive) ", R.Gachter/H.Muller, and Carl Hanser Verlag, the 3rd edition, in 1989, the 478-488 pages or leaves.Mention equally also have aliphatic ketone (for example being disclosed among the DE4204887) and based on the lubricant (for example being disclosed among the EP225261) of siloxanes, or their combination, as be disclosed among the EP259783.VI. softening agent: suitable organic softening agent is for example following group softening agent:
A) phthalate: the exemplary of these softening agent is dimethyl phthalates, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid two isotridecyl esters, dicyclohexyl phthalate, phthalic acid two (methyl cyclohexane ester), phthalic acid dimethyl diol ester, phthalic acid dibutyl diol ester, benzyl butyl phthalate and diphenyl phthalate, and phthalic ester, as mainly being the phthalic acid C of linear alcohols
7-C
9And C
9-C
11Alkyl ester, phthalic acid C
6-C
10Positive alkyl ester and phthalic acid C
8-C
10The mixture of positive alkyl ester.Wherein, preferred dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid two isotridecyl ester and benzyl butyl phthalates, and the mixture of the O-phthalic acid alkyl ester of quoting.Use di-2-ethylhexyl phthalate, diisononyl phthalate and Di Iso Decyl Phthalate are particularly preferred, these compounds are also by common abbreviation DOP (dioctyl phthalate (DOP), di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (Di Iso Decyl Phthalate) is known by people.
B) the ester class of aliphatic dicarboxylic acid, preferred hexanodioic acid, the ester of nonane diacid and sebacic acid: the exemplary of these softening agent is di-2-ethylhexyl adipates, di-isooctyladinpate (mixture), diisononyl adipate (mixture), diisodecyl adipate (mixture), hexanodioic acid benzyl butyl ester, benzyloctyl adipate, di(2-ethylhexyl)azelate, Diisooctyl Sebacate and DI(2ETHYLHEXYL)SEBACATE (mixture).Preferred di-2-ethylhexyl adipate and di-isooctyladinpate.
C) trimellitate class typically has tri trimellitate-2-ethylhexyl, triisodecyl trimellitate (mixture), tri trimellitate isotridecyl ester, triisooctyl trimellitate (mixture) and tri trimellitate (C
6-C
8Alkyl) ester, three (C
6-C
10Alkyl) ester, tri trimellitate (C
7-C
9Alkyl) ester and tri trimellitate (C
9-C
11Alkyl) ester.The trimellitate of back is to obtain with the esterification of corresponding chain triacontanol mixture by trimellitic acid.Preferred trimellitate is the trimellitate of tri trimellitate-2-ethylhexyl and the chain triacontanol mixture of quoting.Common abbreviation is TOTM (trioctyl trimellitate, a tri trimellitate-2-ethylhexyl), TIDTM (triisodecyl trimellitate) and TITDTM (tri trimellitate isotridecyl ester).
D) epoxide softening agent: these mainly comprise epoxidised unsaturated fatty acids, as epoxidized soybean oil.
E) polymeric plasticizer: the definition of these softening agent and example thereof can be at " plastics additive (Kunststoffadditive) ", R.Gachter/H.Muller, Carl Hanser Verlag, the 3rd edition, 1989, the 5,9,6 chapters find in the 412-415 page or leaf, and in " PVC technology ", W.V.Titow, the 4th edition, Elsevier Publ., can find in 1984, the 165-170 pages or leaves.The most frequently used initiator that is used to prepare polyester plasticizer is: di-carboxylic acid typically is hexanodioic acid, phthalic acid, nonane diacid and sebacic acid; Dibasic alcohol, as 1,2-propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol and glycol ether.
F) phosphoric acid ester: the definition of these esters is given in above-mentioned " plastics additive handbook (Taschenbuch der Kunststoffadditive) ", and the 5th, 9,5 chapters are in the 408-412 page or leaf.The illustrative examples of these phosphoric acid ester is a tributyl phosphate, tricresyl phosphate-2-ethyl butyl ester, tricresyl phosphate-2-ethylhexyl, Trichloroethyl Phosphate, phosphoric acid 2-ethylhexyl-diphenyl, phosphoric acid cresyl diphenyl, triphenylphosphate, tricresyl phosphate (cresyl) ester and tricresyl phosphate (xylyl) ester.Preferably phosphoric acid three-2-ethylhexyl and
Reofos 50 and 95 (Ciba-Geigy).
G) chlorinated hydrocarbon (paraffin)
H) hydrocarbon
I) monoesters typically is butyl oleate, oleic acid phenoxy ethyl, oleic acid tetrahydrofurfuryl ester and alkyl sulfonic ester.
J) binary alcohol esters, for example phenylformic acid glycol ether ester.
G) to J) the definition and the example of softening agent in the group can find in following handbook:
" Kunststoffadditive ", R.Gachter/H.Muller, Carl HanserVerlag, the 3rd edition, in the 5th, 9,14,2 chapters, the 422-425 page or leaf, (G group), and in the 5th, 9,14,1 chapters, the 422nd page, (H group).
" PVC technology ", W.V.Titow, the 4th edition, Elsevier Publishers, 1984, the 6,10,2 chapters, 171-173 page or leaf, (G group), the 6th, 10,5 chapters, the 174th page, (H group), the 6th, 10,3 chapters, the 173rd page, (I group), and the 6th, 10,4 chapters, 173-174 page or leaf, (J group).
Also can use the mixture of different softening agent.
Based on the PVC of 100 weight parts, plasticizer dosage typically is 5 to 20 parts, is 10 to 20 parts easily.Hard or semi-rigid PVC preferably contain at the most 10%, especially preferably contain 5% softening agent at the most, or plasticizer-containing not.VII. pigment: those skilled in the art know suitable material.The exemplary of mineral dye is TiO
2, BaSO
4, carbon black, Fe
2O
3, Sb
2O
3, (Ti, Ba, Sb) O
2, Cr
2O
3, spinels, as cobalt blue and cobalt green, Cd (S, Se), ultramarine blue.Pigment dyestuff is, azo class pigment for example, phthalocyanine pigment, quinacridone pigment ， perylene dye, diketopyrrolo-pyrrole pigment and anthraquinone pigment.The TiO of microparticle form
2Also be preferred.Its definition and describe in detail can be at " PVC prepare burden handbook ", EJ.Wickson, John Wiley ﹠amp; Sons finds among the New York 1993.VIII. phosphorous acid ester: exemplary is a triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl benzene) ester, trilauryl phosphite, tricresyl phosphite (octadecyl) ester, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite (2,4-two-tert.-butylbenzene) ester, diphosphorous acid diiso decyl pentaerythritol ester, diphosphorous acid two (2,4-two-tert-butyl-phenyl) pentaerythritol ester, two (2, the 6-two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol esters of diphosphorous acid, the two isodecyl oxygen base pentaerythritol esters of diphosphorous acid, diphosphorous acid two (2,4-two-tertiary butyl-6-aminomethyl phenyl) pentaerythritol ester, diphosphorous acid two (2,4,6-three-tert-butyl-phenyl) pentaerythritol ester, three tricresyl phosphite stearyl sorbitol esters, two (2, the 4-two-tertiary butyl-6-aminomethyl phenyl) methyl esters of phosphorous acid, two (2, the 4-two-tertiary butyl-6-aminomethyl phenyl) ethyl esters of phosphorous acid.Suitable especially is the tricresyl phosphite monooctyl ester, tridecyl phosphite, tricresyl phosphite (dodecyl) ester, tricresyl phosphite (tetradecyl) ester, the tricresyl phosphite stearyl, tricresyl phosphite oil base ester, triphenyl phosphite, tricresyl phosphite cresyl ester, tricresyl phosphite-, particularly preferably be aryl phosphite dialkyl and alkyldiaryl phosphite to nonyl phenyl ester or tricresyl phosphite cyclohexyl, as phenyl didecyl Dhosphite, phosphorous acid (2,4-two-tert-butyl-phenyl) two-(dodecyl) esters, phosphorous acid (2,6-two-tert-butyl-phenyl) two-(dodecyl) ester and diphosphorous acid dialkyl group and diaryl pentaerythritol ester, as diphosphorous acid distearyl pentaerythritol ester, and non-stoichiometric triaryl phosphites, for example composition (H
19C
9-C
6H
4O)
1.5P (OC
12,13H
25,27)
1.5Preferred organophosphite is a diphosphorous acid distearyl pentaerythritol ester, trisnonyl phenyl phosphite and phosphorous acid phenyl didecyl ester.Based on the PVC of 100 weight parts, the amount of spendable organophosphite typically is 0.01 to 10 weight part, is 0.05 to 5 weight part easily, is preferably 0.1 to 3 weight part.IX. thiophosphite and thiophosphatephosphorothioate: thiophosphite and thiophosphatephosphorothioate are general formula (RS)
3P, (RS)
3P=O or (RS)
3The compound of P=S, as at patent disclosure text DE2809492, described in EP090770 and the EP 573394.The exemplary of these compounds is: the own ester of tricresyl phosphite sulfo-, tricresyl phosphite sulfo-monooctyl ester, tricresyl phosphite sulfo-lauryl, tricresyl phosphite sulfo-benzyl ester, trithio phosphorous acid methyl three (carbon-different-octyloxy) ester, trithio phosphorous acid methyl three (carbon-trimethylammonium-cyclohexyloxy) ester, trithio phosphoric acid methyl-S, S, S-three (carbon-different-octyloxy) ester, trithio phosphoric acid methyl-S, S, S-three (carbon-2-ethyl hexyl oxy) ester, trithio phosphoric acid ethyl-S, S, S-three-1-(carbon hexyloxy) ester, trithio phosphoric acid ethyl-S, S, S-three-1-(carbon-2-ethyl hexyl oxy) ester, trithio phosphoric acid ethyl-S, S, S-three-2-(carbon-2-ethyl hexyl oxy) ester.X. mercapto-carboxylic ester: the exemplary of these compounds is: Thiovanic acid, thiomalic acid, the ester of thiohydracrylic acid; The ester of Thiosalicylic acid or thiolactic acid, as at FR2459816, EP90748, FR2552440, among the EP365483 disclosed like that.Described mercapto-carboxylic ester also comprises polyol ester or their partial ester.XI. epoxidized fatty acid ester: the new stabilizer molectron also can contain at least a epoxidised fatty acid ester.Especially, suitable ester is the ester (glycerin fatty acid ester) of the lipid acid of natural acquisition, as the ester of soya-bean oil or rape seed oil.Yet, also can use synthetic product, as epoxidised butyl oleate.XII. oxidation inhibitor: suitable oxidation inhibitor is:
1. alkylation monophenol class: 2,6 di tert butyl 4 methyl phenol for example, the 2-tertiary butyl-4, the 6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(phenol of 1 '-methyl undecane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl heptadecane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl tridecane-1 '-yl), octyl phenol, nonylphenol, dodecyl phenol and their mixture.
2. alkylthiomethyl phenol: for example 2,4-dioctyl sulphomethyl-6-tert.-butyl phenol, 2,4-dioctyl sulphomethyl-6-methylphenol, 2,4-dioctyl sulphomethyl-6-ethylphenol, 2,6-two-dodecyl sulphomethyl-4-nonylphenol.
3. alkylation quinhydrones: for example 2,6-di-t-butyl-4-methoxyphenol, 2, the 5-di-tert-butyl hydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2, the 6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyanisol, stearic acid 3,5-di-t-butyl-4-hydroxylphenyl ester, hexanodioic acid two (3,5-di-t-butyl-4-hydroxylphenyl ester.
4. hydroxylation sulfo-phenyl ether: for example 2,2 '-thiobis (6-tert-butyl-5-methyl phenol), 2,2 '-thiobis (4-octyl phenol), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (the 6-tertiary butyl-2-methylphenol), 4,4 '-thiobis (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulfide.
5. alkylidene bisphenols class: for example 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis (4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis (6-(α-Jia Jibianji)-4-nonylphenol), 2,2 '-methylene-bis (6-(α, α-Er Jiajibianji)-4-nonylphenol), 4,4 '-methylene-bis (2,6 di t butyl phenol), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl sulfydryl butane of 1-, two (3, two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric acid of 3-) glycol ester, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) dicyclopentadiene, two (2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-6-tertiary butyl-4-aminomethyl phenyl) esters of terephthalic acid, 1,1-two (3,5-dimethyl-2-hydroxy phenyl) butane, 2, two (3, the 5-di-tert-butyl-hydroxy phenyl) propane of 2-, 2, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-4-dodecyl sulfydryl butane of 2-, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
6. benzyl compounds, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-dihydroxyl dibenzyl ether, Thiovanic acid octadecyl-4-hydroxyl-3,5-dimethylbenzyl ester, Thiovanic acid three decyls-4-hydroxyl-3,5-di-t-butyl benzyl ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, two (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) esters of dithio terephthalic acid, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, Thiovanic acid iso-octyl-3,5-di-t-butyl-4-hydroxyl benzyl ester.
7. hydroxybenzyl malonic ester, propanedioic acid two-octadecyl-2 for example, 2-two (3,5-di-t-butyl-2-hydroxybenzyl) ester, propanedioic acid two-octadecyl-2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) ester, propanedioic acid two-dodecyl mercaptoethyl-2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) ester, propanedioic acid is two, and (4-(1,1,3, the 3-tetramethyl butyl) phenyl)-2, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) esters of 2-.
8. aromatic hydroxy benzyl compounds, for example 1,3,5-three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4, the 6-Three methyl Benzene, 1, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5 of 4-, the 6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.
9. triaizine compounds, for example 2, two (octyl group the sulfydryl)-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 4-, 3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3,5-di-t-butyl-4-hydroxybenzene amido)-and 1,3,5-triazines, 2-octyl group sulfydryl-4, two (3,5-di-t-butyl-4-the hydroxyphenoxy)-1,3,5-triazines of 6-, 2,4,6-three-(3,5-di-t-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-three-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2,4,6-three (3,5-di-t-butyl-4-leptodactyline)-1,3,5-triazines, 1,3,5-three (3,5-di-tert-butyl-hydroxy phenyl propionyl)-six hydrogen-1,3,5-triazine, 1,3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.
10. phosphonic acid ester and phosphinate, dimethyl-2 for example, 5-tertiary butyl-4-hydroxy benzylphosphonic acid ester, diethyl-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two (octadecyl)-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two (octadecyl)-5-tertiary butyl-4-hydroxies-3-methyl-benzylphosphonic acid ester, 3, the calcium salt of 5-di-t-butyl-4-hydroxyl-benzylphosphonic acid monoesters, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene bisphosphonates, 6-different octyloxy-2,4,8,10-tetra-tert-12H-dibenzo (d.g)-1,3,2-Er Evil phosphocin, 6-fluoro-2,4,8,10-four-tertiary butyl-12-methyl-dibenzo (d.g)-1,3,2-Er Evil phosphocin.
11. the amido phenol, 4-hydroxyl lauroyl aniline for example, 4-hydroxyl stearanilide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
12. the ester of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and monobasic or polyvalent alcohol, alcohol, methyl alcohol for example, ethanol, octanol, Stearyl alcohol, 1, the 6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, tris(2-hydroxy ethyl)isocyanurate, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring (2.2.2) octanes.
13. the ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monobasic or polyvalent alcohol, alcohol, for example methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, tris(2-hydroxy ethyl)isocyanurate, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring (2.2.2) octanes.
14. the ester of β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and monobasic or polyvalent alcohol, alcohol, methyl alcohol for example, ethanol, octanol, Stearyl alcohol, 1, the 6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, tris(2-hydroxy ethyl)isocyanurate, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring (2.2.2) octanes.
15.3, the ester of 5-di-tert-butyl-hydroxy phenyl acetate and monohydroxy-alcohol or polyvalent alcohol, alcohol, methyl alcohol for example, ethanol, octanol, Stearyl alcohol, 1, the 6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, tris(2-hydroxy ethyl)isocyanurate, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring (2.2.2) octanes.
16. β-(3, the 5-di-tert-butyl-hydroxy phenyl) acid amides of propionic acid, for example, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hexa-methylene diamide, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) trimethylene diamide, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazides.17. vitamins D (vitamin-E) and derivative thereof
Preferred oxidation inhibitor is group 1-5, those in 10 and 12, particularly 2, two (4-hydroxy phenyl) propane of 2-, 3,5-di-tert-butyl-hydroxy phenyl propionic acid and octanol, the ester of Stearyl alcohol or tetramethylolmethane, or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
As if suitable, also can use the mixture of the oxidation inhibitor of different structure.
Based on 100 weight part PVC, the consumption of oxidation inhibitor typically is 0.01 to 10 weight part, is 0.1 to 10 weight part easily, is preferably 0.1 to 5 weight part.XIII. UV light absorber and photostabilizer: their illustrative examples is:
(1.2-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-di-t-butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chloro-benzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-and hydroxy phenyl) benzotriazole, following mixture: 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl)-5-chloro-benzotriazole, 2-(3,-the tertiary butyl-5,-(2-(2-ethyl hexyl oxy)-carbonyl ethyl)-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-(2-(2-ethyl hexyl oxy) carbonyl ethyl)-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different carbonyl octyloxy ethyl of 2-) phenyl) benzotriazole, 2, (4-(1 for 2 '-methylene radical-two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base-phenol); The transesterification products of 2-(3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl)-2H-benzotriazole and Liquid Macrogol:
(RCH
2CH
2COO (CH
2)
3)
2, R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base-phenyl wherein.
2.2-hydroxy benzophenone, 4-hydroxyl for example, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivative.
3. replace and unsubstituted benzoic ether; Whitfield's ointment 4-tertiary butyl phenyl ester for example; salol; the Whitfield's ointment octyl octylphenyl; dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol; 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-t-butyl phenyl ester, 3; 5-di-t-butyl-4-hydroxy-benzoic acid cetyl ester; 3,5-di-tert-butyl-4-hydroxybenzoic acid stearyl, 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-t-butyl phenyl ester.
4. acrylate, alpha-cyano-β for example, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-carbo methoxy group methyl cinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamic acid methyl esters, alpha-cyano-β-p-methoxycinnamic acid butyl ester, α-carbo methoxy group-p-methoxycinnamic acid methyl esters and N-(β-carbo methoxy group-beta-cyano vinyl)-2-methyl indoline.
5. nickel compound containing, for example 2, (4-(1 for 2 '-sulfo--two, 1,3, the 3-tetramethyl butyl) nickel complex phenol), for example with or without other as n-Butyl Amine 99,1: 1 or 1: 2 complex compound of trolamine or N-cyclohexyl diethanolamine ligand, nickel dibutyl dithiocarbamate, 4-hydroxyl-3, the mono alkyl ester of 5-di-t-butyl benzylphosphonic acid is the nickel salt of methyl or ethyl ester for example, the nickel complex of ketoxime such as 2-hydroxy-4-methyl phenyl undecyl ketoxime, 1-phenyl-4-lauroyl-5-hydroxypyrazoles is with or without the nickel complex of other ligand.
6. oxamide, for example 4,4 '-two octyloxies-N, N '-oxalyl pentanoic, 2,2 '-diethoxy-N, N '-oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2,2 '-two (dodecyloxy)-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl-N, N '-oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl-N, N '-oxalyl pentanoic and it and 2-oxyethyl group-2 '-ethyl-5,4 '-di-t-butyl-N, the mixture of N '-oxalyl pentanoic is with adjacent-and right-methoxyl group-dibasic N, the mixture of N '-oxalyl pentanoic, with with adjacent-and right-oxyethyl group-dibasic N, the mixture of N '-oxalyl pentanoic.
(7.2-2-hydroxy phenyl)-1,3,5-triazines, for example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1,3 of 6-, the 5-triazine, 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1,3 of 6-, the 5-triazine, 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2 of 4-, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (the 4-aminomethyl phenyls)-1,3 of 6-, the 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-oxygen base in three last of the ten Heavenly stems phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3,5-triazine, 2-(2-hydroxyl-4-(2-hydroxyl-3-butoxy-propoxy-) phenyl)-4,6-two (2, the 4-dimethyl)-1,3,5-triazines, 2-(2-hydroxyl-4-(2-hydroxyl-3-octyloxy-propoxy-) phenyl)-4, two (2, the 4-dimethyl)-1,3 of 6-, the 5-triazine, 2-(4-(dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-2-hydroxyl-phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3, the 5-triazine.XIV. whipping agent: whipping agent is for for example, organic azo and hydrazo compound, tetrazolium ， oxazine, isatoic acid acid anhydride, and soda and sodium bicarbonate.Azodicarboamide and sodium bicarbonate, and their mixture is preferred.
Impact modifying agent, processing aid, jelling agent, static inhibitor, biocides, metal deactivator, white dyes, the definition and the example of fire retardant and antifogging agent are disclosed in " Kunststoffadditive ", R.G chter/H.M ü ller, Carl Hanser Verlag, the third edition, 1989 and " polyvinyl chloride batching handbook ", EJ.Wilson, J.Wiley ﹠amp; Sons, 1993.Impact modifying agent is also at " impact modifying agent of PVC ", J.T.Lutz/D.L.Dunkelberger, John Wiley ﹠amp; Sons describes in detail in 1992.
The exemplary of the hard PVC material that is stabilized is: the polymkeric substance of vinylchlorid, the unitary Vinylite of vinyl-chloride-containing in the structure, as vinylchlorid and aliphatic acid vinyl ester, the multipolymer of preferred vinyl acetate ester, vinylchlorid and acrylate, the multipolymer of methacrylic ester and vinyl cyanide, the multipolymer of vinylchlorid and diolefin compound and unsaturated dicarboxylic acid or their acid anhydrides, as vinylchlorid and ethyl maleate, the multipolymer of DEF or maleic anhydride, the polymkeric substance and the multipolymer of continuation chlorating vinylchlorid, vinylchlorid and vinylidene chloride and unsaturated aldehyde, ketone and other, as propenal, crotonaldehyde, ethenyl methyl ketone, vinyl methyl ether, the multipolymer of vinyl isobutyl ether and analogue; The multipolymer of the polymkeric substance of vinylidene chloride and it and vinylchlorid and other polymerisable compound; The polymkeric substance of vinyl chloroacetate and two chloroethene dialkylene ethers; The chlorinated polymer of vinyl acetate, the chlorinated polymer of the acrylate of vinylformic acid and alpha-substitution; The cinnamic polymkeric substance of chlorostyrene such as dichloro-; Chlorinated rubber; The chlorinated polymer of ethene; The polymkeric substance of chloroprene and continue chlorinated polymer, and they and vinylchlorid, the multipolymer of rubber hydrochloride and chlorination rubber hydrochloride; And the mixture of the polymkeric substance of quoting between mutually, or the mixture of the polymkeric substance of quoting and other polymerizable compound.
These materials also comprise PVC and EVA, the graftomer of ABS and MBS.Preferred matrix also has above-mentioned homopolymer and multipolymer, preferred ryuron, with other thermoplasticity or/and the mixture of elastomeric polymer, particularly with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, the blend of EPDM and polylactone.
The illustrative examples of this component A serve as reasons (i) 20-80 weight part ryuron (PVC) and the (ii) thermoplastic copolymer of at least a styrene-based of 80-20 weight part and vinyl cyanide are preferably ABS, NBR, NAR, the composition that SAN and EVA form.The abbreviation of multipolymer is familiar with those skilled in the art, and is expressed as: ABS: acrylonitrile/butadiene/styrene; SAN: styrene/acrylonitrile; NBR: acrylonitrile/butadiene; NAR: vinyl cyanide/acrylate; EVA: ethylene/vinyl acetate.Especially, the same suitable styrene/acrylonitrile copolymer that is based on acrylate (ASA).In this respect, component A is preferably the mixture of polymers of quoting of the PVC that contains 25-75% weight and 75-25% weight as component (i) and polymer composition (ii).The exemplary of this composition is: the multipolymer of the PVC of 25-50% weight and 75-50% weight, or the multipolymer of the 60-75% weight of the PVC of 40-75% weight.Preferred multipolymer is ABS, SAN and modified EVA, preferred ABS.NBR, NAR and EVA are suitable especially too.The multipolymer that in novel compositions, can exist one or more to quote.The component A of particularly important is for to contain (i) 100 weight part PVC (ii) 0-300 weight part ABS and/or the ABS of SAN modification and the multipolymer NBR of 0-80 weight part, NAR and/or EVA, the composition of preferred EVA.
Being used for other stable suitable batching within the scope of the present invention is, preferably, the regenerant of chlorine-containing polymer, they are polymkeric substance that foregoing detailed description is crossed, and in processing, are damaged in use or the storage.Preferred especially PVC regenerant.Can contain a spot of impurity in the regenerant, as the paper that is difficult to usually remove, pigment and tackiness agent.These impurity also can be derived from use or the course of processing in multiple material such as fuel resistates, coating component, the contacting of the metal of trace and initiator residues.
This novel stabilising acts on particularly advantageous in the PVC batching that is usually used in tubing.Static stabilization can carry out under the existence of no any heavy metal compound (Sn, Pb, Zn stablizer).This performance is favourable in some aspects, because may be except that Zn, heavy metal be because environment reason often is undesirable in the application of production and some PVC parts.
The invention still further relates to the method for a kind of stable hard or semi-rigid PVC, it is included in not have and is selected from perchlorate compound, glycidyl compound, the beta-diketon class, 'beta '-ketoester class, dihydropyridines, poly-dihydropyridines, polyvalent alcohol, disaccharides alcohols, steric hindrance amine (tetraalkyl piperidine compounds), alkali-metal aluminosilicate (zeolites), hydrogenant damourite class, the compound of alkali-metal aluminium carbonate (dawsonite class) exist down, in wherein adding the compound that at least a formula I represents.
Stablizer and with realizing easily by following method:
(a kind of adoptable form is a paste mixture with emulsion or dispersion form.Under this form that feeds intake, one of advantage of new combination is stability of slurry.)；
In the blend of additive component or polymeric blends with the form of dry mixture;
Directly it is added processing units (kneader is extruded agent and analogue for rolling press for example, mixing tank), or
Form with solution or melt.
By the stable PVC of the present invention, that is purpose of the present invention, known method is known in fact by using in fact, for example above-mentioned processing units will new stablizer in conjunction with mixing and prepare with PVC with body and other additive of choosing wantonly.Stablizer can be separately or is added with the form of mixture, and form that also can master batch adds.
To make required form by the stable PVC of the present invention with known method.These methods are, for example grind, and calendering is extruded, and blowing mould is also extruded in injection molding or spinning.Stable PVC also can be processed into foam.
The hard PVC stable by the present invention is particularly suitable for, hollow object (bottle) for example, packing film (thermoformable film), blown film, tubing, foam, large-scale framework (window frame), small-sized wall frame, building frame, wallboard, accessory, office film and device housings (computer, home appliances).
Preferred hard foamed shaped article of PVC and pvc pipe material for example are used for drinking-water or waste water, penstock, and flue, cable tube deferent and cable sheath pipe, industrial pipeline is with managing waste pipe, soil pipe and water shoot.Details can be at " plastics handbook (Kunststoffhandbnch) PVC " the 2/2nd volume, W.Becker/H.Braun, and the 2nd edition, 1985, Carl Hanser Verlag, the 1236-1277 page or leaf is found.
The compound of formula I is prepared by known method, as describing in detail in the following embodiments.Embodiment and the residue paragraph in, part and the percentage number average by weight, unless add explanation in addition.Embodiment 1:6-amino-1, the preparation of 3-dimethyl uracil
(embodiment 1)
Stirring heating 224.8g N under the nitrogen, N '-dimethyl uracil, 238.7g cyanoacetic acid and 310.9g diacetyl oxide to 80 ℃.This mixture stirred 2 hours down at 80 ℃, and be evacuated to 50 millibars so that acetate distill away.After this mixture is cooled to 35 ℃, add the 250g frozen water.Mixture was stirred 10 minutes, then with the sodium hydroxide solution that is added dropwise to 567g 15% in ice-cooled.The pH value does not surpass 7 when adding to 475ml.When the pH value surpassed 7, precipitation changed, and then mixture is heated to 50 ℃ by 23 ℃, and this moment, the pH value was 10.2.After adding 200g water, mixture was stirred 10 minutes and heating under refluxing.Reflux after 1 hour, mixture is cooled to 20 ℃ and carry out suction strainer.With 2 * 100g cold water washing filter cake, then with its in vacuum drying oven in 90 ℃ of dryings.
Productive rate: 334g (theoretical value 86.1%), fusing point: 282 ℃.Embodiment 2:6-phenylamino-1, the preparation of 3-dimethyl uracil
(embodiment 2)
In the three neck devices of a 100ml, stir 39.1g aniline and 24.5g 1, the mixture of 3-dimethyl barbital acyl chlorides refluxed 15 minutes down in 190 ℃.This mixture is cooled to room temperature and adds 300ml water.Stir the light blue precipitation of appearance down, then it is collected by drawing,, be dried to constant weight then with the ether washing.
Through methylene dichloride/activated carbon recrystallization, draw colourless product, be dried then.
Productive rate: 22.5g (theoretical value 69.5%), 190 ℃ of fusing points.Embodiment 3: quiet thermal test:
To in the mixing tank roller, roll 5 minutes by the dry mixture that the component that exemplifies in following preparation parameter is formed in 180 ℃ of rollings.Roll the test diaphragm of making 0.3mm the sheet from the rolling that so obtains.Make membrane sample under 180 ℃, in a baking oven, be subjected to the thermal stresses effect.Press the method for ASTM D-1925-70, measured yellowness index (YI) at interval in 5 or 10 minutes.The results are shown in the following table.Low yellowness index value explanation stabilization is good.
The compound-0.4 of mixture I mixtures II S-PVC (K value 64) 100 100 epoxidized soybean oils 22 embodiment 1
| The stress duration (minute) 0 10 20 30 40 50 60 |
| Yellowness index (mixture I) 24.9 86.9＞100 yellowness indexs (mixtures II) 3.1 9.4 18.0 27.4 44.0 73.5＞100 |
The epoxidised Tissuemat E 0.1 of mixtures III S-PVC (K value 64) 100 calcium stearate 0.35 zinc stearate, 0.15 epoxidized soybean oil 4 waxes 368 (ester type waxes), 0.6 parts is based on the compound 0.6 of processing aid 0.5 impact modifying agent 8 embodiment 1 of acrylate
| The stress time length (minute) 0 10 20 30 40 50 |
| Yellowness index (mixtures III) 9.3 11.0 17.9 26.0 37.1 59.8 |
The compound-0.6 of mixture IV mixture VS-PVC (K value 64) 100 100 epoxidized soybean oils 22 embodiment 2
| The stress time length (minute) 0 10 20 |
| Yellowness index (mixture IV) 13.1 73.6＞100 yellowness indexs (mixture V) 4.2 18.9 53.7 |
The epoxidised Tissuemat E 0.1 of mixture VIS-PVC (K value 64) 100 calcium stearate 0.35 zinc stearate, 0.15 epoxidized soybean oil 4 waxes 368 (ester type waxes), 0.6 parts is based on the compound 0.6 of processing aid 0.5 impact modifying agent 8 embodiment 2 of acrylate
| The stress time length (minute) 0 10 20 30 40 50 |
| Yellowness index (mixture VI) 7.3 11.9 22.1 62.4 87.0＞100 |
The compound 0.3 of mixture VIIS-PVC (K value 64) 100 epoxidized soybean oils 3 calcium stearates 0.35 Zinic stearas 0.15 embodiment 1
| The stress time length (minute) 0 10 20 30 40 50 |
| Yellowness index (mixture VII) 5.2 7.1 8.4 15.8 34.5 60.4 |
The compound-0.4 of mixture VIII mixture IXS-PVC (K value 64) 100 100 epoxidized soybean oils 22 embodiment 1
| The stress time length (minute) 0 10 20 30 40 50 60 |
| Yellowness index (mixture VIII) 48.6 115 173.9 yellowness indexs (mixture X I) 7.0 13.4 24.1 32.3 52.5 79.4＞100 |
Claims (11)
1. a composition contains
A) plasticizer loading at the most 20% hard or semi-rigid PVC and
B) compound of at least a formula I,
Wherein X is O or S, and R is H or phenyl, and its restricted condition is not exist to be selected from the perchlorate compound, glycidyl compound, beta-diketon class, 'beta '-ketoester class, dihydropyridines, poly-dihydropyridines, polyvalent alcohol, disaccharides alcohols, steric hindrance amine (tetraalkyl piperidine compounds), alkali-metal aluminosilicate (zeolites), hydrogenant damourite class, the compound of alkali-metal aluminium carbonate (dawsonite class).
2. the composition of claim 1, wherein A) be plasticizer loading 10% hard PVC at the most.
3. the composition of claim 1, wherein A) be plasticizer loading 5% hard PVC at the most.
4. the composition of claim 1, wherein A) be the hard PVC of no softening agent.
5. the composition of claim 1, wherein B) be the compound of the formula I of X=O.
6. the composition of claim 5, wherein B) be compound
7. the composition of claim 1, it is heavy metal free in fact.
8. the composition of claim 1, it also contains phosphorous acid ester.
9. the formula I compound of claim 1 is at most 20% hard or the application among the semi-rigid PVC at stabilizing plasticizer content, does not wherein exist to be selected from perchlorate compound, glycidyl compound, the beta-diketon class, the 'beta '-ketoester class, dihydropyridines, poly-dihydropyridines, polyvalent alcohol, the disaccharides alcohols, steric hindrance amine (tetraalkyl piperidine compounds), alkali-metal aluminosilicate (zeolites), hydrogenation damourite class, the compound of alkali-metal aluminium carbonate (dawsonite class).
10. the application of the composition of claim 1 in preparation tubing.
11. a stabilizing plasticizer content is at most 20% hard or the method for semi-rigid PVC, it is included among the PVC and with the compound of at least a formula I that defines as claim 1, wherein do not exist and be selected from the perchlorate compound, glycidyl compound, the beta-diketon class, the 'beta '-ketoester class, dihydropyridines, poly-dihydropyridines, polyvalent alcohol, disaccharides alcohols, steric hindrance amine (tetraalkyl piperidine compounds), alkali-metal aluminosilicate (zeolites), hydrogenation damourite class, the compound of alkali-metal aluminium carbonate (dawsonite class).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97119584 CN1178228A (en) | 1996-09-25 | 1997-09-24 | Rigid PVC stabilised with N, N-dimethyl-6-aminouracils |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2344/96 | 1996-09-25 | ||
| CN 97119584 CN1178228A (en) | 1996-09-25 | 1997-09-24 | Rigid PVC stabilised with N, N-dimethyl-6-aminouracils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1178228A true CN1178228A (en) | 1998-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97119584 Pending CN1178228A (en) | 1996-09-25 | 1997-09-24 | Rigid PVC stabilised with N, N-dimethyl-6-aminouracils |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1178228A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203556B (en) * | 2005-04-15 | 2012-06-27 | 圣艾斯凯克（Pte.）有限公司 | Stabiliser composition for chlorine-containing polymers |
| CN102617486A (en) * | 2012-03-01 | 2012-08-01 | 江西吉翔医药化工有限公司 | Process for preparing 6-chlorine-1,3-dimethyl uracil |
| CN102898741A (en) * | 2012-10-08 | 2013-01-30 | 太原市塑料研究所 | Polyvinyl chloride heat stabilizer and preparation method thereof |
| CN103193721A (en) * | 2012-01-09 | 2013-07-10 | 深圳市志海实业有限公司 | Heat stabilizer composition used for PVC, ketone compound and application of ketone compound |
| TWI408165B (en) * | 2006-04-12 | 2013-09-11 | Sun Ace Kakoh Pte Ltd | Stabiliser composition for halide-containing polymers |
| CN105802054A (en) * | 2014-12-29 | 2016-07-27 | 上海新光华塑胶有限公司 | Lead-free rigid polyvinyl chloride (PVC) composition for electrical engineering pipes and preparation method for lead-free rigid PVC composition |
| CN105802051A (en) * | 2014-12-29 | 2016-07-27 | 上海新光华塑胶有限公司 | Tin-free rigid polyvinyl chloride composition for drainpipe fitting and preparation method thereof |
| CN106189281A (en) * | 2016-08-09 | 2016-12-07 | 昌吉市新铭泰新型材料科技有限公司 | A kind of production technology of fine Ca-Zn composite heat stabilizer |
| CN107001697A (en) * | 2014-11-24 | 2017-08-01 | 路博润先进材料公司 | New coupling uracil compound for chloride polymer resin |
| CN110317418A (en) * | 2019-06-03 | 2019-10-11 | 盐城市朗创新材料有限公司 | A kind of Environment-friendlyheat heat stabilizer and preparation method thereof for PVC hard product |
| CN110922363A (en) * | 2019-12-28 | 2020-03-27 | 新华制药（寿光）有限公司 | Continuous production process of violuric acid |
| CN114369067A (en) * | 2021-12-29 | 2022-04-19 | 广东科力新材料有限公司 | Acylamino uracil and preparation method and application thereof |
-
1997
- 1997-09-24 CN CN 97119584 patent/CN1178228A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203556B (en) * | 2005-04-15 | 2012-06-27 | 圣艾斯凯克（Pte.）有限公司 | Stabiliser composition for chlorine-containing polymers |
| TWI408165B (en) * | 2006-04-12 | 2013-09-11 | Sun Ace Kakoh Pte Ltd | Stabiliser composition for halide-containing polymers |
| CN103193721A (en) * | 2012-01-09 | 2013-07-10 | 深圳市志海实业有限公司 | Heat stabilizer composition used for PVC, ketone compound and application of ketone compound |
| CN103193721B (en) * | 2012-01-09 | 2014-06-04 | 深圳市志海实业有限公司 | Heat stabilizer composition used for PVC, ketone compound and application of ketone compound |
| CN102617486A (en) * | 2012-03-01 | 2012-08-01 | 江西吉翔医药化工有限公司 | Process for preparing 6-chlorine-1,3-dimethyl uracil |
| CN102617486B (en) * | 2012-03-01 | 2014-04-16 | 江西吉翔医药化工有限公司 | Process for preparing 6-chlorine-1,3-dimethyl uracil |
| CN102898741A (en) * | 2012-10-08 | 2013-01-30 | 太原市塑料研究所 | Polyvinyl chloride heat stabilizer and preparation method thereof |
| CN102898741B (en) * | 2012-10-08 | 2015-03-25 | 太原市塑料研究所 | Polyvinyl chloride heat stabilizer and preparation method thereof |
| CN107001697B (en) * | 2014-11-24 | 2019-06-28 | 路博润先进材料公司 | Novel coupling uracil compound for chloride polymer resin |
| CN107001697A (en) * | 2014-11-24 | 2017-08-01 | 路博润先进材料公司 | New coupling uracil compound for chloride polymer resin |
| CN105802051A (en) * | 2014-12-29 | 2016-07-27 | 上海新光华塑胶有限公司 | Tin-free rigid polyvinyl chloride composition for drainpipe fitting and preparation method thereof |
| CN105802054A (en) * | 2014-12-29 | 2016-07-27 | 上海新光华塑胶有限公司 | Lead-free rigid polyvinyl chloride (PVC) composition for electrical engineering pipes and preparation method for lead-free rigid PVC composition |
| CN106189281A (en) * | 2016-08-09 | 2016-12-07 | 昌吉市新铭泰新型材料科技有限公司 | A kind of production technology of fine Ca-Zn composite heat stabilizer |
| CN110317418A (en) * | 2019-06-03 | 2019-10-11 | 盐城市朗创新材料有限公司 | A kind of Environment-friendlyheat heat stabilizer and preparation method thereof for PVC hard product |
| CN110922363A (en) * | 2019-12-28 | 2020-03-27 | 新华制药（寿光）有限公司 | Continuous production process of violuric acid |
| CN114369067A (en) * | 2021-12-29 | 2022-04-19 | 广东科力新材料有限公司 | Acylamino uracil and preparation method and application thereof |
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