CN1302067C - Vinylidene chloride-based resin composition and its production - Google Patents
Vinylidene chloride-based resin composition and its production Download PDFInfo
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- CN1302067C CN1302067C CNB2004100120508A CN200410012050A CN1302067C CN 1302067 C CN1302067 C CN 1302067C CN B2004100120508 A CNB2004100120508 A CN B2004100120508A CN 200410012050 A CN200410012050 A CN 200410012050A CN 1302067 C CN1302067 C CN 1302067C
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Abstract
The present invention relates to a vinylidene chloride-based resin composition having more improved thermal stability and photostability than those achieved by conventional techniques, and to a method for producing the same. A vinylidene chloride-based resin composition comprises 100 pts.wt. of a vinylidene chloride copolymer having a reduced viscosity of 0.038-0.065 L/g and 0.0005-1 pt.wt. of an antioxidant containing 2,4-demethyl-6-(1- methylpentadecyl)phenol and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
Description
The application be No. 99107650.8, application for a patent for invention of the same name divide an application April 30 1999 original application day.
The invention relates to good heat stability, vinylidene chloride resin composition and manufacture method thereof that heat-age discoloration is few.
Use the heating and melting extrusion molding, the vinyl resins of chloride elements such as vinylidene chloride resin can be processed into film, bottle, silk etc.When shaping, this resin is easy to suffer because the portion of hot that causes of heat is aging and because the deterioration by oxidation that oxygen causes, so molding is easy to change, and the situation that the obvious damage goods are worth is many.In addition, variable color is arranged also when those goods are exposed to light, damaged the value of goods.For the variable color that prevents to cause, generally use thermo-stabilizer owing to this light and heat.Wherein suggestion the epoxies stablizer as suppressing vinylidene chloride resin owing to thermal ageing and the thermo-stabilizer of variable color, and the necessary composition of the vinylidene chloride resin composition of extruding as heating and melting and being extensive use of.In addition, except that the epoxy type thermal stabilizing agent, various antioxidants and other stabilization aid have been proposed.For example, octadecyl-3 is proposed, 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate, four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate] methane (the clear 57-10894 of Japanese patent laid-open publication gazette), vitamin-E and propane thioic acid alkyl ester and with inorganic phosphate and with (the clear 61-26813 of Japanese patent laid-open publication gazette), vitamin-E and edetate are also used (the flat 1-990 of Japanese patent laid-open publication gazette), triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and trisodium phosphate are also used (the flat 6-18963 of Japanese patent laid-open publication gazette), 2,4-dimethylated-6-sec-alkylphenol (Japanese Patent discloses flat 3-50247), 2, stratified mixture (Japanese Patent discloses flat 9-227862) four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane that 4-dimethylated-6-sec-alkylphenol and sterically hindered phenol constitute and citric acid or alkali metal citrates and usefulness (Japanese Patent discloses flat 8-165394) etc.
Yet the extrusion molding condition of vinylidene chloride resin is owing to will boost productivity etc. former thereby become more and more harsher in recent years; Wish more and more strongly that on the other hand the molding variable color is few,, and wish the further improved vinylidene chloride resin composition of thermostability and light stability so completed thermostability and light stability are enough in the not talkative prior art.
The present inventor is in view of this present situation, once proposed in vinylidene chloride resin, cooperating and to be the vinylidene chloride resin composition and the manufacture method (Japanese Patent discloses flat 9-137023) thereof of the improvement thermostability of feature, and proposed with cooperation in vinylidene chloride resin and be the vinylidene chloride resin composition and the manufacture method (the flat 9-208174 of Japanese patent application) thereof of the improvement thermostability of feature with ethylene dinitrilotetra-acetic acid salt and organic monoacid salt with edetate class and inorganic phosphate.But this composition is not very good sometimes aspect thermostability.
The objective of the invention is to, provide than the thermostability of finishing with prior art and more improved vinylidene chloride resin composition of light stability and manufacture method thereof.
For thermostability and light stability to the vinylidene chloride resin finished with prior art are further improved, the present inventor furthers investigate antioxidant, found that, with the metachloroethylene copolymer of specific reduced viscosity with contain 2, the antioxidant combination of 4-dimethyl-6-(1-methyl pentadecyl) phenol just can realize above-mentioned purpose of the present invention, has finished the present invention based on these discoveries.
Promptly, the invention provides by 100 weight part reduced viscositys is that 0.038-0.065 liter/gram metachloroethylene copolymer and 0.0005-1 weight part contain 2, the vinylidene chloride resin composition that vinylidene chloride resin composition that the antioxidant of 4-dimethyl-6-(1-methyl pentadecyl) phenol is formed and foregoing comprise the weak acid salt.The pvdf resin composition that comprises octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester antioxidant in foregoing also is provided.In addition, the present invention also provides in foregoing the vinylidene chloride monomer in the metachloroethylene copolymer and can be the vinylidene chloride resin composition of 60/40-98/2 with the monomeric weight ratio of its copolymerization and can be the vinylidene chloride resin composition of vinylchlorid or methyl acrylate with the monomer of vinylidene chloride monomer copolymerization.The invention provides at the weak acid salt described in the above-mentioned composition is the organic monoacid salt that is selected from nonnitrogenous atom, at least a permalon composition in the inorganic phosphate salt, and described weak acid salt comprises the vinylidene chloride resin composition of edetate class.The present invention also provides antioxidant to comprise at least a vinylidene chloride resin composition that is selected from thioether kind antioxidant and phosphoric acid ester oxidation inhibitor.
The present invention also provides the manufacture method of vinylidene chloride resin composition, it is characterized in that, make comprise vinylidene chloride monomer, can with the vinylidene chloride interpolymer of the monomer of vinylidene chloride monomer copolymerization and antioxidant in, add at least a organic monoacid salt of edetate class, nonnitrogenous atom and the weak acid salt of inorganic phosphate salt of being selected from, the preoperative aqueous pH values of reaction system de-watering of slurries after polyreaction ends is in the 2.5-10 scope.
Below describe the present invention in detail.
Metachloroethylene copolymer described in the present invention, its vinylidene chloride monomer composition with can be 60/40-98/2 with the weight ratio of the monomer composition of its copolymerization, preferred 70/30-96/4.
The reduced viscosity of metachloroethylene copolymer is 0.038-0.065 liter/gram, is preferably 0.040-0.062 liter/gram.If than degree viscosity less than 0.038 liter/gram, the stretch process reduction; If reduced viscosity surpasses 0.065 liter/gram on the contrary, it is big that the resin frictional heating during melt-shaping becomes, and is easy to thermolysis, so the tendency that has variable color to increase.Metachloroethylene copolymer of the present invention can be and reduced viscosity and the mixture of forming different metachloroethylene copolymers.For example, if metachloroethylene copolymer be and the mixture of the lower metachloroethylene copolymer of reduced viscosity, the flowability of this resin combination improves, the frictional heating of resin in the time of suppressing melt-shaping is so can prevent variable color.
As in the present invention can with other monomer of vinylidene chloride copolymerization, for example can enumerate: alkyl acrylates (the alkyl carbon atoms number is 1-18) such as vinylchlorid, vinylformic acid formic acid, butyl acrylate, ethyl acrylate, dodecylacrylate, vinylformic acid stearyl; Alkyl methacrylates (the alkyl carbon atoms number is 1-18) such as methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, methacrylic acid stearyl; Vinyl cyanide such as vinyl cyanide, methacrylonitrile; Aromatic ethenyl compounds such as vinylbenzene; Carbonatomss such as vinyl acetate are the aliphatic carboxylic acid vinyl acetate of 1-18; Carbonatoms is the alkyl vinyl ester of 1-18; Vinyl polymerized unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid; The alkyl ester (also comprise the part ester, the carbonatoms of alkyl is 1-18) of vinyl polymerized unsaturated carboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid; Glycidyl acrylate, glycidyl methacrylate etc. contain the vinyl polymerized monomer of epoxy group(ing); Chlorination diolefins such as diolefin such as divinyl, isoprene or chloroprene; Has the multi-functional monomer of the two keys of copolymerization more than at least two etc. in Vinylstyrene, two (methyl) the vinylformic acid glycol ester equimolecular.Wherein preferably use vinylchlorid, methyl acrylate.In metachloroethylene copolymer, if these other copolymerizable monomer compositions surpass the quality 40% of co-polymer, the vapour lock reduction of gained multipolymer is if but less than 2 quality %, the melt processable of gained multipolymer probably can reduce.
The manufacture method of vinylidene chloride resin composition of the present invention is, at the vinylidene chloride class monomer and the monomer of copolymerization with it, as required in the presence of the ethylene dinitrilotetra-acetic acid salt, suitably regulate at least a addition that is selected from the weak acid salt of inorganic phosphate salt and organic monoacid salt, carry out polyreaction, the pH value of polymerization system, the pH value of the water before the dehydration operation after polymerization stops must be in the 2.5-10 scope especially.
When using the situation of inorganic phosphate salt, polymerization finishes the preferred 2.5-8 of pH value of the water before the dehydration operation of back, more preferably 2.5-5; When using the situation of organic monoacid salt, polymerization finishes the preferred 3-10 of water pH, the more preferably 3-8 before the dehydration operation of back.
Above-mentioned antioxidant and aforementioned at least a weak acid salt can be in the middle of polymerization begin preceding, polymerization, polymerization finishes the back or add in these any periods by stages.
Using the stainless steel polymeric kettle to carry out polymerization is preferred scheme.Metachloroethylene copolymer of the present invention, can be by other polymkeric substance of the mixed below 30 weight parts or multipolymer and the hybrid resin that obtains to the aforementioned metachloroethylene copolymer of 100 weight parts, at this moment, the vinylidene chloride component content is 50-98 weight % in this hybrid resin.
As blendable other polymkeric substance or multipolymer in metachloroethylene copolymer of the present invention, for example can enumerate: ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethene and vinylformic acid, methacrylic acid, (methyl) alkyl acrylate (C
1-18Alkyl) or the multipolymer of (methyl) glycidyl acrylate, vinyl iolon, (methyl) acrylic polymers, MBS, nylon, polyester etc.The blending ratio of these other polymkeric substance or multipolymer, with respect to 100 weight part metachloroethylene copolymers, if greater than 30 weight parts, the vapour lock of gained hybrid resin probably has reduction; If the vinylidene chloride composition in this hybrid resin less than 50 weight %, the vapour lock reduction of gained hybrid resin, if on the other hand greater than 98 weight %, melt processable probably can reduce.
In permalon composition of the present invention, can mix as 2 of necessary composition, the phenol antioxidant of 4-dimethyl-6-(1-methyl pentadecyl) phenol.Its use level is with respect to 100 weight part metachloroethylene copolymers, cooperates separately or cooperates the weight part for 0.0005-1, more preferably 0.005-0.5 weight part altogether with other antioxidant.If this use level is less than 0.0005 weight part, the effect of the thermostability that just can not be improved; On the other hand, if greater than 1 weight part, even, consider it also is undesirable from economic aspect how with also can not get and adding proportional thermal stability result.
Spendable in the present invention above-mentioned antioxidant can also be used with more than one known antioxidants less than 50 weight %.As known antioxidant, for example can enumerate: 2,6-di-t-butyl-4-methyl-phenol (BHT), butyl-hydroxyl-methyl-phenoxide, 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester (Irganox1076), triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (Irganox245), α, β, γ, various vitamin-Es of δ and composition thereof, four-[methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane (Irganox1010), the 2-tertiary butyl-6-(uncle 3--2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate (ス ミ ラ イ ザ-GM) etc.Can enumerate preferred use octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester especially.
2, the blending ratio (weight ratio) of 4-dimethyl-6-(1-methyl pentadecyl) phenol and octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester preferred 100/0-50/50, more preferably 90/10-70/30.
In the present invention, except that above-mentioned phenol antioxidant, also can be also with at least a thioether class antioxidant and the phosphate-based antioxidants of being selected from.At this moment, because the thermostability improvement effect that can obtain working in coordination with, so be preferred operational version.Its cooperation ratio is the 0-1 weight part with respect to 100 weight part metachloroethylene copolymers, preferred 0.001-0.1 weight part.This cooperation ratio during less than 0.0005 weight part the further improvement effect of thermostability few, on the other hand, though surpass 0.2 weight part many with also rare to the improvement effect of the proportional thermostability of addition, and consider it is undesirable from economic aspect.
As spendable thioether class antioxidant in the present invention, for example can enumerate: thio-2 acid; Propane thioic acid alkyl esters such as Tyox B, the two tetradecyl esters of thio-2 acid, the two stearyl of thio-2 acid; The propane thioic acid alkyl ester of tetramethylolmethane-four-Pentaerythritols such as (3-lauryl-thiopropionates) etc.The thioether class antioxidant of Shi Yonging can be a mixture more than two kinds in the present invention.
As the phosphate-based antioxidants that can use in the present invention, for example can enumerate: three nonyl phenyl phosphate ester, (one and/or dinonyl phenyl) phosphoric acid ester, 4,4 '-isopropylidene biphenol alkyl phosphate, two octadecyl pentaerythritol diphosphate (PEP-8) etc.The phosphate-based antioxidants of Shi Yonging can be a mixture more than two kinds in the present invention.
In addition, vinylidene chloride resin composition of the present invention can comprise the weak acid salt.So-called in the present invention weak acid salt is meant at least a weak acid salt that is selected from inorganic phosphate salt and organic monoacid salt.In the present invention, the weak acid salt shows collaborative thermostability improvement effect for independent antioxidant series, so be preferred user mode.This cooperation ratio is to 100 weight part vinylidene chloride resins, preferred 0.00001-1 weight part, more preferably .0.0005-0.1 weight part.This cooperation ratio is during less than 0.00001 weight part, and the further improvement effect of thermostability is little; On the other hand, when greater than 1 weight part,, consider it also is unfavorable from economic aspect even many with also seldom arriving and the proportional thermostability improvement effect of addition.
The inorganic phosphate salt of Shi Yonging is an alkali metal salt of phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid etc. in the present invention.Can enumerate SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, Sodium hexametaphosphate 99, hexa metaphosphoric acid potassium, Sodium Acid Pyrophosphate, tetra-sodium dihydro dipotassium, trisodium phosphate, potassium pyrophosphate etc. as an example, especially since the paralled system of the paralled system of trisodium phosphate and Sodium Acid Pyrophosphate or trisodium phosphate and SODIUM PHOSPHATE, MONOBASIC than the pH value that is easier to adjust polymerization system, so be preferred.
Employed in the present invention organic monoacid salt is that the pKa value of the dissociation constant Ka (25 ℃) in the aqueous solution has at least 1 to be more than 2.5, preferred organic monoacid and an alkali metal salt thereof more than 3.As this organic monoacid salt, can enumerate the organic monoacid salt of nonnitrogenous atom, for example, saturated aliphatic mono and an alkali metal salts thereof such as formic acid, acetate, propionic acid; Radical of saturated aliphatic dicarboxylic acid and an alkali metal salts thereof such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid; Hydroxyl such as oxyacetic acid, lactic acid saturated aliphatic mono and an alkali metal salt thereof; Hydroxyl such as tartronic acid, hydroxy-butanedioic acid radical of saturated aliphatic dicarboxylic acid and an alkali metal salt thereof; Dihydroxyl saturated aliphatic mono and an alkali metal salts thereof such as R-Glyceric acid; Dihydroxyl radical of saturated aliphatic dicarboxylic acid and an alkali metal salts thereof such as tartrate; Hydroxyl such as citric acid, isocitric acid radical of saturated aliphatic tricarboxylic acid and an alkali metal salt thereof; Aromatic monocarboxylate or dicarboxylic acid and an alkali metal salts thereof etc. such as phenylformic acid, phthalic acid, m-phthalic acid.Wherein can preferably enumerate citric acid, propanedioic acid, tartrate and an alkali metal salt thereof.
As the example of other organic monoacid salt, can enumerate the edetate class.In the present invention, can be edetate class and aforementioned antioxidant and at least a weak acid salt (following also claim " at least a weak acid salt ") and the usefulness that are selected from the organic monoacid salt of inorganic phosphate salt and nonnitrogenous atom.At this moment just can further obtain the excellent heat stability improvement effect.This cooperation ratio with respect to 100 weight part vinylidene fluoride copolymers, is preferably used the 0.00001-0.2 weight part, more preferably 0.0005-0.1 weight part edetate class.This cooperation ratio is during less than 0.00001 weight part, and it is little further to improve thermal stability result, during on the other hand greater than 0.2 weight part, even use also rare to and the proportional thermostability improvement effect of addition, consider it also is undesirable from economic aspect.
The edetate class of Shi Yonging is ethylenediamine tetraacetic acid (EDTA) and an alkali metal salt thereof in the present invention.For example can enumerate as an example: ethylenediamine tetraacetic acid (EDTA), sodium ethylene diamine tetracetate, ethylenediamine tetraacetic acid (EDTA) potassium etc.In the middle of these edetate classes, can enumerate disodium edta as preferred example.In the present invention, with at least a being matched with in the metachloroethylene copolymer that is selected from these edetates.This edetate class improves the reason of the thermostability of metachloroethylene copolymer, consideration is because in the polyreaction system of vinylidene chloride analog copolymer, iron ion combines with chlorion and can promote vinylidene chloride and metachloroethylene copolymer desalination acid-respons, and can suppress the promoter action of desalination acid-respons by interpolation edetate class.The effect particular significant effect when using the situation of stainless steel polymeric kettle that causes by the interpolation of edetate class.
The vinylidene chloride resin that uses among the present invention can be made by arbitrary polymerization process of suspension polymerization, emulsion polymerization, solution polymerization process etc., is preferably made by suspension polymerization especially.
In the present invention, in the middle of metachloroethylene copolymer, contain edetate class and at least a weak acid salt in order to make, can in vinylidene chloride class monomer, add mixing at the polymerization stage of making this multipolymer, perhaps also can under the slurry form behind the polymerization vinylidene chloride monomer, mix with other reagent and additive in polymerization.In addition, also can under the pulverulence before the processing of vinylidene chloride resin, add mixing with other processing aid.
Can all once add simultaneously or divide and add edetate class and at least a weak acid salt several times.Generally speaking, making these edetate classes and at least a weak acid salt state ratio in the past is included in the middle of the metachloroethylene copolymer just passable.When these additives are joined vinylidene chloride class co-polymer, can in solvent or water, dissolve the back and add, or with Powdered direct interpolation.In the middle of these addition meanss, in the vinylidene chloride class monomer polymerization stage, edetate class and at least a weak acid salt and aforementioned as required antioxidant are present in when carrying out polymeric in the prepolymerization system, suitably regulate the kind and the addition of edetate class and at least a weak acid salt, regulate the pH value in the polymerization system, telo merization finishes the pH value of afterreaction system slurry (before the preferred dehydration operation) water especially, just can make to have the more vinylidene chloride resin composition of excellent heat stability.When using inorganic phosphate salt situation, the pH that regulates water (before the preferred dehydration operation) is at 2.5-8, in the preferred 2.5-5 scope; When using organic monoacid salt situation, regulate the pH3-10 of water (before preferably dehydrating), in the preferred 3-8 scope, just can obtain having the vinylidene chloride resin composition of excellent heat stability.
In the present invention, suitably use edetate class and at least a weak acid salt, just can adjust the pH value of this polymerization system.Be not only salt, add form strong acid such as the weak base of the ethylenediamine tetraacetic acid (EDTA) of salt or alkali metal hydroxides such as at least a weak acid salt and sodium hydroxide or hydrochloric acid by interpolation, also the pH value of polymerization system can be adjusted in the above-mentioned scope.Importantly, as long as edetate class and at least a weak acid salt are present in the polymerization system, and the pH value of polymerization system can be adjusted in the above-mentioned scope, the acid of these additives that add in polymerization system, alkali form are indifferent, also can add highly basic or strong acid.
In the present invention, also can used antioxidant separately wherein add on a small quantity in the prepolymerization system.Though the detailed mechanism of action of this situation it be unclear that, the situation comparison with the antioxidant that adds full dose after polymerization can obtain better thermostability.Add the addition in the prepolymerization system to, in order more effectively to bring into play its effect, with respect to 100 weight part vinylidene chloride monomers, preferred 0.0002-0.02 weight part.If this addition is less than 0.0002 weight part, the thermostability improvement effect is few; If on the other hand greater than 0.02 weight part, thermostability not only worsens but also hinders the infringement polyreaction on the contrary, so be undesirable.
The manufacture method of above-mentioned vinylidene chloride resin composition in the present invention also is applicable to emulsion polymerization or suspension polymerization, but considers from the manufacturing aspect, preferably is applicable to suspension polymerization.The manufacture method of above-mentioned vinylidene chloride resin when the situation of using stainless steel polymeric kettle to implement, can significantly be brought into play the improvement effect of thermostability, so be ideal especially in the present invention.
Vinylidene chloride resin composition of the present invention as mentioned above, is characterized in that, in the vinylidene chloride analog copolymer, must comprise phenol antioxidant 2,4-dimethyl-6-(1-methyl pentadecyl) phenol comprises weak acid salt, edetate class as required; Also comprise other general various additives that use, for example softening agent, stablizer, UV light absorber, lubricant, tensio-active agent, pigment, weighting agents etc. in addition.
Object lesson as these additives, for example can enumerate: softening agent such as dioctyl phthalate (DOP), tributyl acetylcitrate, Uniflex DBS, dioctyl sebacate, acetylated monoglyceride, perhaps the polyester softening agent of radical of saturated aliphatic dicarboxylic acid and polyvalent alcohol formation; Epoxidised soybean oil, epoxidised linseed oil, epoxidation octyl stearate, epoxies stablizers such as epoxy-containing yl resin; Inorganic base stablizers such as magnesium hydroxide, magnesium oxide, secondary calcium phosphate; Waxes such as oxidized polyethlene wax, paraffin, polyethylene wax, 20 caprylate waxes; Fatty acid esters such as monoglyceride, lubricants such as one and diamide of lipid acid; Nonionic class tensio-active agents such as sorbitan-fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid ester; 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-UV light absorber such as 5-chlorobenzotriazole etc.In the middle of these additives, the addition separately of softening agent and stablizer is with respect to the preferred 1-10 weight part of 100 weight part vinylidene chloride resins, more preferably 2-6 weight part.In the present invention, these additives mix in vinylidene chloride resin during Powdered before processing usually, but also can when the slurry form after vinylidene chloride class monomer polymerization finishes, mix, perhaps also can join and carry out the polymerization mixing in the preceding vinylidene chloride class monomer of prepolymerization.
The thermostability of vinylidene chloride resin composition of the present invention increases substantially, thereby improves the forming speed that forms the shaping thing by this resin combination and become possibility, and can effectively obtain the shaping thing of the little excellent color tone of xanthochromia degree.Therefore, can enlarge the purposes of wrapping material greatly, for example as the wrapping material of field of food such as single or multiple lift film, sheet material, pipe, container.Heat-age discoloration is little in addition, uses so can stand recirculation, can supply with the goods of looking after environment and use.
Embodiment
Below specify the present invention with embodiment, but the present invention is not so limited.
[heat stability test]
The mensuration of b value: the resin combination that in embodiment, comparative example, obtains with pressing machine do not pressurize, preheating 2 minutes under 175 ℃ of conditions, pressurizeed then 15MPa5 minute, cooled off 2 minutes under the 5MPa load with the cooling pressure machine then, make the thick compacting sheet stock of 3mm.This compacting sheet stock as test piece, is used colour-difference meter (ミ ノ Le Co., Ltd. system: CR-200) measure the b value.Just representing because thermal ageing change xanchromatic degree is just big more of this b value on the occasion of big more.
[mensuration of reduced viscosity]
With methyl alcohol as solvent, after the polymkeric substance that will dehydrate with apparatus,Soxhlet's extracts and handles, the exsiccant polymkeric substance as test portion, with Ubbelodhe (Ubbelodhe) viscometer, be made into the polymers soln that concentration is 4 grams per liters with cyclohexanone solvent, measuring the reduced viscosity that records permalon under 30 ℃ of conditions of temperature.The unit of reduced viscosity is a liter/gram.
In the embodiment of the invention and comparative example, use following antioxidant and weak acid salt,
Begin preceding monomer with respect to 100 weight part polymerizations and add 0.003 part of antioxidant A.When stopping, polymerization adds 0.023 part of antioxidant A and 0.017 part of Tyox B (DLTDP).Wherein said antioxidant A is by octadecyl-3-(3 of 20%, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 80% 2, the composite antioxidant that 4-dimethyl-6-(1-methyl pentadecyl) phenol is formed (trade(brand)name: CGXAO-141, チ バ ガ イ ギ-Co., Ltd. makes).
Begin preceding monomer with respect to 100 weight part polymerizations and add 0.003 part of antioxidant B.When stopping, polymerization adds 0.023 part of antioxidant B and 0.017 part of Tyox B.Wherein said antioxidant B is triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (goods name Irganox245, チ バ ガ イ ギ-Co., Ltd. makes).
Slightly acidic salt: use tetrasodium pyrophosphate decahydrate, tetrasodium pyrophosphate, Sodium Acid Pyrophosphate, disodium ethylene diamine tetraacetate and citric acid.
(embodiment 1)
In 10 liters of autoclaves of the stainless steel with paddle stirrer, add and dissolved 2.975g methoxyl group Mierocrystalline cellulose, 2.625g tetrasodium pyrophosphate decahydrate, the deionized water 4505g of 2.625g Sodium Acid Pyrophosphate.
Behind the air in the nitrogen replacement system, inject the mixture that the diisopropyl peroxydicarbonate of necessary amount and epoxidised soybean oil and 0.0875g antioxidant A is dissolved in the mix monomer of 2870g vinylidene chloride monomer and 630g vinyl chloride monomer.
Stirring under the raw mix situation of these inputs, temperature in the kettle is risen to the temperature of regulation, initiated polymerization carries out polyreaction.Behind certain hour in order to stop polyreaction, in still, be pressed into the material that has dissolved 0.70g antioxidant A and 0.525g dilauryl thiodipropionate (DLTDP) in the 50g vinylidene chloride monomer, be pressed into the back and continue to stir after 1 hour, discharge the still internal pressure, in still, take out polymer paste.After making the gained de-watering of slurries,, obtain copolymer powder with dry 20 hours of 50 ℃ of hot air dryers.The pH value that polymerization finishes disposed slurry is 5.7, and the polymerization yield is that benchmark is 87.8% to drop into amount of monomer, and the reduced viscosity of gained resin is 0.045.For the thermostability of gained vinylidene chloride resin composition is tested, heat resin combination down at 170 ℃, with the thick test piece of 3mm that pressurization obtains, measure the tone (b value) of test piece.The heat stability test of resin combination the results are shown in the table 1.
(comparative example 1)
Replace the antioxidant A except when feeding intake, replacing antioxidant A and when polymerization stops, adding 0.70g antioxidant B, with the embodiment 1 identical polyreaction of carrying out with 0.0875g antioxidant B.The pH value that polymerization finishes disposed slurry is 5.6, and the polymerization yield is that benchmark is 88.5% to drop into amount of monomer, and reduced viscosity is 0.045.The heat stability test of gained resin combination the results are shown in the table 1.
(embodiment 2)
Except when feeding intake, adding 2.975g methoxyl group Mierocrystalline cellulose, 2.625g tetrasodium pyrophosphate decahydrate, 2.625g Sodium Acid Pyrophosphate, use 4505g to dissolve beyond the deionized water of 2.10g edta disodium dihydrate, with the embodiment 1 identical polyreaction of carrying out.The pH value that polymerization finishes disposed slurry is 5.0, and the polymerization yield is that benchmark is 87.1% to drop into amount of monomer, and reduced viscosity is 0.045.The heat stability test of gained resin combination the results are shown in the table 1.
(comparative example 2)
Except when feeding intake, replacing antioxidant A and when polymerization stops, the adding 0.70g antioxidant B replacement antioxidant A, carrying out same polyreaction with embodiment 2 with 0.0875g antioxidant B.The pH value that polymerization finishes disposed slurry is 5.0, and the polymerization yield is that benchmark is 86.6% to drop into amount of monomer, and reduced viscosity is 0.045.The heat stability test of gained resin combination the results are shown in the table 1.
(embodiment 3)
Except when feeding intake with 4505g deionized water dissolving 2.975g methoxyl group Mierocrystalline cellulose, 2.275g citric acid and 2.1g disodium ethylene diamine tetraacetate, adjust beyond this pH value of water solution to 5.2 with aqueous sodium hydroxide solution, carry out same polyreaction with embodiment 1.The pH value that polymerization finishes disposed slurry is 4.4, and the polymerization yield is 87.1%.Reduced viscosity is 0.045.The heat stability test of gained resin combination the results are shown in the table 1.
(comparative example 3)
Except when feeding intake, replacing antioxidant A and when polymerization stops, the adding 0.70g antioxidant B replacement antioxidant A, carrying out same polyreaction with embodiment 3 with 0.0875g antioxidant B.The pH value that polymerization finishes disposed slurry is 4.4, and the polymerization yield is 86.6%, and reduced viscosity is 0.045.The heat stability test of gained resin combination the results are shown in the table 1.
Table 1
| Antioxidant (* 1) | Weak acid salt (* 2) | Slurry pH | Reduced viscosity | Thermostability b value | |
| Embodiment 1 | A | TEPY1/TEPY2 0.01/0.016 | 5.7 | 0.045 | 13.4 |
| Comparative example 1 | B | 0.01/0.016 | 5.6 | 0.045 | 15.1 |
| Embodiment 2 | A | TEPY1/TEPY2/EDTA 0.01/0.016/0.012 | 5.0 | 0.045 | 11.9 |
| Comparative example 2 | B | 0.01/0.016/0.012 | 5.0 | 0.045 | 13.5 |
| Embodiment 3 | A | Citric acid/EDTA 0.015/0.012 | 5.2 | 0.045 | 11.1 |
| Comparative example 3 | B | 0.015/0.012 | 4.4 | 0.045 | 12 |
The amount (weight part) of (* 1) per 100 weight part metachloroethylene copolymers
Antioxidant A:
Octadecyl-3-by 20% (3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 80% 2, the composite antioxidant that 4-dimethyl-6-(1-methyl pentadecyl) phenol is formed.
Before polymerization, add in the monomer: 0.003 part
When finishing, polymerization adds: 0.023 part
Tyox B
When finishing, polymerization adds: 0.017 part
Antioxidant B: triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester
Before polymerization, add in the monomer: 0.003 part
When finishing, polymerization adds: 0.023 part
Tyox B
When finishing, polymerization adds: 0.017 part
The amount (weight part) of (* 2) per 100 weight part metachloroethylene copolymers
TEPY1: tetrasodium pyrophosphate scaled value
TEPY2: Sodium Acid Pyrophosphate scaled value
EDTA: disodium ethylene diamine tetraacetate scaled value
Citric acid: citric acid scaled value
As seen from Table 1, according to the present invention by containing octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) antioxidant of propionic ester and this antioxidant and 2, the composite antioxidant of 4-dimethyl-6-(1-methyl pentadecyl) phenol combination and inorganic phosphate and usefulness such as tetra-sodium as the weak acid salt just can significantly improve the thermostability of this resin combination.
In addition, in known inorganic phosphate and edetate class paralled system or organic monoacid salt and edetate class paralled system with thermostability improvement effect, if also use above-mentioned antioxidant, just significantly improve the thermostability of resin combination.
Claims (11)
1. vinylidene chloride resin composition, it is characterized in that, what said composition comprised metachloroethylene copolymer that 100 weight part reduced viscositys are 0.038-0.065 liter/gram and 0.0005-1 weight part contains 2, the antioxidant of 4-dimethyl-6-(1-methyl pentadecyl) phenol, and being selected from the organic monoacid salt of nonnitrogenous atom, at least a weak acid salt in the inorganic phosphate salt, described organic monoacid salt is that 25 ℃ the pKa value of dissociation constant Ka has at least 1 to be organic monoacid and an alkali metal salt thereof more than 2.5 in the aqueous solution.
2. according to the vinylidene chloride resin composition described in the claim 1, wherein said antioxidant comprises 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and octadecyl-3-(3, the 5-tert-butyl-hydroxy phenyl) propionic ester.
3. according to claim 1 or 2 described vinylidene chloride resin compositions, wherein, in metachloroethylene copolymer the vinylidene chloride monomer composition and with it the part by weight of the monomer composition of copolymerization be 60/40-98/2.
4. according to the vinylidene chloride resin composition described in the claim 3, wherein, can with the monomer of vinylidene chloride monomer copolymerization vinylchlorid or methyl acrylate.
5. according to the described vinylidene chloride resin composition of claim 1, wherein also comprise the edetate class.
6. according to claim 1, each described vinylidene chloride resin composition in 2,5, wherein, antioxidant comprises 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and be selected from antioxidant at least a in thioether class antioxidant and the phosphate-based antioxidants.
7. according to the described vinylidene chloride resin composition of claim 3, wherein, antioxidant comprises 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and be selected from antioxidant at least a in thioether class antioxidant and the phosphate-based antioxidants.
8. according to the described vinylidene chloride resin composition of claim 4, wherein, antioxidant comprises 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and be selected from antioxidant at least a in thioether class antioxidant and the phosphate-based antioxidants.
9. according to the described vinylidene chloride resin composition of claim 5, wherein, antioxidant comprises 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and be selected from antioxidant at least a in thioether class antioxidant and the phosphate-based antioxidants.
10. the manufacture method of each described vinylidene chloride resin composition of claim 1～9, it is characterized in that, from vinylidene chloride class monomer with it when the monomer of copolymerization obtains the vinylidene chloride analog copolymer, add and be selected from the organic monoacid salt of nonnitrogenous atom and at least a weak acid salt in the inorganic phosphate salt, edetate class and antioxidant, the controlled polymerization reaction finishes the pH value of disposed slurry water in the 2.5-10 scope.
11. according to the manufacture method of vinylidene chloride resin composition described in the claim 10, wherein, using internal surface is the polymeric kettle of stainless steel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP137731/1998 | 1998-05-01 | ||
| JP13773198A JPH11315179A (en) | 1998-05-01 | 1998-05-01 | Vinylidene chloride-based resin composition and its production |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99107650 Division CN1203125C (en) | 1998-05-01 | 1999-04-30 | Vinylidene chloride resin composition and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1616540A CN1616540A (en) | 2005-05-18 |
| CN1302067C true CN1302067C (en) | 2007-02-28 |
Family
ID=15205525
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99107650 Expired - Lifetime CN1203125C (en) | 1998-05-01 | 1999-04-30 | Vinylidene chloride resin composition and method for preparing the same |
| CNB2004100120508A Expired - Lifetime CN1302067C (en) | 1998-05-01 | 1999-04-30 | Vinylidene chloride-based resin composition and its production |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99107650 Expired - Lifetime CN1203125C (en) | 1998-05-01 | 1999-04-30 | Vinylidene chloride resin composition and method for preparing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH11315179A (en) |
| CN (2) | CN1203125C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4861223B2 (en) * | 2001-05-09 | 2012-01-25 | 株式会社クレハ | Polyvinylidene chloride resin composition Coloring resin composition |
| CN100467517C (en) | 2003-11-03 | 2009-03-11 | 西巴特殊化学品控股有限公司 | Stabilizer compositions for halogen containing polymers |
| JP5804738B2 (en) * | 2011-03-23 | 2015-11-04 | 旭化成ケミカルズ株式会社 | Paints for ceramic siding materials and ceramic siding materials |
| JP6013489B2 (en) * | 2011-09-26 | 2016-10-25 | ダウ グローバル テクノロジーズ エルエルシー | Process of incorporating additives into vinylidene chloride polymer without using a mixer |
| GB201320919D0 (en) * | 2013-11-27 | 2014-01-08 | Addivant Switzerland Gmbh | Composition |
| CN111704689B (en) * | 2020-06-29 | 2022-04-26 | 天津城建大学 | High-adhesion water-based vinylidene chloride copolymer emulsion for metal surface and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09137023A (en) * | 1995-11-10 | 1997-05-27 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin composition and production thereof |
| GB2309697A (en) * | 1996-01-31 | 1997-08-06 | Ciba Geigy Ag | Stabilisation of polymers using a mixture of phenols |
-
1998
- 1998-05-01 JP JP13773198A patent/JPH11315179A/en active Pending
-
1999
- 1999-04-30 CN CN 99107650 patent/CN1203125C/en not_active Expired - Lifetime
- 1999-04-30 CN CNB2004100120508A patent/CN1302067C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09137023A (en) * | 1995-11-10 | 1997-05-27 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin composition and production thereof |
| GB2309697A (en) * | 1996-01-31 | 1997-08-06 | Ciba Geigy Ag | Stabilisation of polymers using a mixture of phenols |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1203125C (en) | 2005-05-25 |
| JPH11315179A (en) | 1999-11-16 |
| CN1241592A (en) | 2000-01-19 |
| CN1616540A (en) | 2005-05-18 |
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