CN105602153A - PVC compound stabilizer and preparation method - Google Patents
PVC compound stabilizer and preparation method Download PDFInfo
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- CN105602153A CN105602153A CN201610089048.3A CN201610089048A CN105602153A CN 105602153 A CN105602153 A CN 105602153A CN 201610089048 A CN201610089048 A CN 201610089048A CN 105602153 A CN105602153 A CN 105602153A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a PVC compound stabilizer. The PVC compound stabilizer is characterized by being composed of, by mass, 85-90% of a main stabilizing agent and 5-15% of a subsidiary stabilizing agent; the main stabilizing agent is composed of polyvinylpyrrolidone, bis(5-oxo-L-prolinato-N1,O2) zinc, calcium disodium ethylenediamine tetraacetate and titanium tetraisopropanolate, and the subsidiary stabilizing agent is composed of N,N-ethylene bis-stearamide, pentaerythrityl tetrastearate, epoxidized linseed oil and mannitol. The invention further discloses a preparation method of the PVC compound stabilizer. The PVC compound stabilizer has the advantages of being free of toxin, environmentally friendly, good in lubricity and the like, is high in thermal stability, high in transparency, high in impact resistance and high in profile welded corner strength, can reduce damage to PVC molecules caused by ultraviolet light, improve outdoor aging performance of a product and further has good internal and external lubricating properties, and processing can be conducted stably.
Description
Technical field
The present invention relates to a kind of PVC compound stabilizer and preparation method thereof, belong to composite preparing technical field.
Background technology
Polyvinyl chloride (PVC) is one of most widely used synthetic resin in the world, and its goods are numerous excellent because havingDifferent performance and be widely used in the every field of productive life. But, PVC be in strand, contain manyThe high molecular polymer of chlorine atom, due to the obvious inhomogeneities of Cloud Distribution in chlorine atom and whole strand,Make strand occur serious defect. This has caused PVC will take off HCl more than 110 DEG C, and heat occursDegradation reaction, due to only more than 140 DEG C, PVC just has mobility, therefore, for ensureing that PVC is smoothComplete processing, just must add heat stabilizer. Conventional lead salts and organic tin heat stabilizer all exists at presentCertain toxicity, and contaminated environment, along with the raising of people to environmental requirement, nontoxic and heavy metal free pollutionHeat stabilizer has caused that researcher more and more payes attention to.
At present, the stabilization of improving PVC to add rare earth becomes the focus of concern, and research is also mainly with rare earthOrganic monoacid salt stabilizing agent is main, has that good long-term thermal stability, tolerance, toxicity are low, greasy propertyThe feature such as good. Aspect PVC heat endurance, showing good effect although add the organic monoacid salt such as rare earth,But the problems such as while using rare-earth stabilizer separately, the stability of material is not good enough, tinctorial property is low.
Chinese patent 201010159481.2 discloses the preparation method of a kind of PVC composite thermal stabilizer ZWS, comprisesSome steps: 1, get the raw materials ready: the preparation of in-lubricant; The preparation of composite antioxidant; The preparation of intermediate; OutwardThe preparation of lubricant; The preparation of rare-earth stabilizer; The preparation of lead salt stabilizer; 2, proportioning. The prior artTechnological process is simple and direct, and combination property is superior, contribute to improve PVC section bar fillet weld strength, surface smoothness andImprove low-temperature impact resistance, but contain lead acetate in the formula of this technology, can cause potential harm to environment.
Chinese patent 201410085374.8 discloses the preparation method of the rare earth thermal stabilizer of a kind of PVC tin dope,It is characterized in that: taking rare earths salt and pink salt as raw material, be made into mixed solution, then add dispersant to dissolve;Precipitating reagent is added drop-wise in the mixed solution of above-mentioned preparation, stirs, until react complete; Above-mentioned reaction is madeSediment after washing separates, dry obtain precursor powder, then precursor powder arrived through gradient increased temperature1100 DEG C are incubated 2 hours, obtain the rare earth oxide of tin dope; By organic monoacid heating and melting, add catalysisAgent is stirred, then adds the rare earth oxide of tin dope, and reaction obtains the rare earth thermal stabilizer of tin dope. This is existingTechnology preparation method is simple, workable, and environment-protecting asepsis is with low cost, is easy to realize industrialization and produces;But be difficult to overcome the problems such as preparation PVC material settling out performance is not good enough, tinctorial property is low.
Summary of the invention
For overcome the stability of the leaded murder by poisoning environment of the PVC stabilizing agent existing in prior art, material not good enough,The problems such as tinctorial property is low, the invention provides a kind of PVC compound stabilizer, also disclose this PVC simultaneouslyThe preparation method of compound stabilizer.
Technical scheme of the present invention is: a kind of PVC compound stabilizer, is characterized in that: described compound stabilizerThe main stabilizer that is 85-95% by mass fraction and mass fraction are that 5-15% auxiliary stabilizer forms, and described master is steadyDetermine agent by polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na), ethylenediamine tetremAcid disodium calcium (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) composition, described auxiliary stabilizerBy vinyl bis-stearamides (C38H76N2O2), pentaerythritol stearate (C77H148O8), epoxy linseed oil,Mannitol (C6H14O6) composition.
Further, described polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na),Calcium disodium chelate (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) account for stable compositionAgent mass fraction is respectively: 15-22%, 25-34%, 32-45%, 8-15%; Described vinyl bis-stearamides(C38H76N2O2), pentaerythritol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6)Accounting for compound stabilizer mass fraction is respectively: 1-3%, 1-6%, 1-4%, 1-5%.
Further, described PVC compound stabilizer is added with rare-earth stabilizer outward, and described rare-earth stabilizer is stearic acidA kind of in lanthanum, yttrium stearate, maleamic acid lanthanum, maleamic acid yttrium, isooctyl acid lanthanum, isooctyl acid yttrium orMultiple, described additional rare-earth stabilizer accounts for the 3-6% of described PVC compound stabilizer quality.
Further, as one of the present invention preferred embodiment, described PVC compound stabilizer China and foreign countries are added with modifierIndium acetate, described modifier indium acetate accounts for the 1.2-3.6% of described PVC compound stabilizer quality.
Further, as one of the present invention preferred embodiment, described PVC compound stabilizer China and foreign countries are added with poly-Mould assembly surface modifier FC4432, described surface modifier FC4432 accounts for the mass fraction of PVC compound stabilizerFor 0.6-1.8%.
The calcium-zinc composite stabilizing agent that a kind of PVC uses by the above-mentioned PVC compound stabilizer of mass fraction 70-90%,The fatty acid calcium of mass fraction 4-15% or fatty acid zinc or both mixtures, mass fraction 4-10%'s is auxiliaryThe lubricant composition of agent, mass fraction 2-8%. In described PVC compound stabilizer, containing mass fraction is: 85-95%Main stabilizer and 5-15% auxiliary stabilizer, and the additional rare earth that accounts for PVC compound stabilizer gross mass 3-6% is steadyDetermine the indium acetate of agent, 1.2-3.6%, the surface modifier FC4432 of 0.6-1.8%. Described fatty acid calcium is for containingCarbon atom number is the calcium salt that 6 to 20 straight chain fatty acid root and calcium ion form, and described fatty acid zinc is for containingCarbon atom number is the zinc salt that 6 to 20 straight chain fatty acid root and zinc ion form; Below described lubricant isCompound: paraffin, Tissuemat E, Fischer-Tropsch synthetic wax, aliphatic acid, fatty acid ester, fatty acid alcohol and fatAt least one in acid acid amides; Described adjuvant be pentaerythritol resin, phosphite antioxidant, beta-diketon,Sai Ke, uracil and uracil zinc salt, hydrotalcite, zeolite, basic calcium aluminium phosphite and calcium hydroxide thisAt least one in a little compounds; Described beta-diketon is dibenzoyl methane, stearoyl benzoyl methane, twoBenzoyl methane calcium, dibenzoyl methane zinc, stearoyl benzoyl methane magnesium, stearoyl benzoyl methane zinc,At least one in these compounds of calcium acetylacetonate and zinc acetylacetonate.
A preparation method for PVC compound stabilizer, is characterized in that: comprise the following steps:
1) preparation of main stabilizer: in mass ratio example take respectively polyvinylpyrrolidone ((C6H9NO) n), pyrrolesAlkane keto carboxylic acid zinc (PCA-Na), calcium disodium chelate (C10H12CaN2Na2O8), tetra isopropyl metatitanic acidEster (C12H28O4Ti), mix and blend at the temperature of 50 DEG C;
2) preparation of auxiliary stabilizer: example takes respectively vinyl bis-stearamides (C in mass ratio38H76N2O2), seasonPenta tetrol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6), mixing and stirring,Make auxiliary stabilizer;
3) successively rare-earth stabilizer and indium acetate are joined in the mixed solution of ethylenediamine and water composition, at 90 DEG CAt temperature, heating water bath 2 hours, is then added into surface modifier FC4432, and disperses at ultrasonic wave30 minutes, make additive agent mixture;
4) above-mentioned stabilizer blend and additive agent mixture are put into planetary ball mill tank, by batch mixing: nothingWater-ethanol mixes for the ratio of 1:2 by volume, moves 20 minutes with the rotating speed of 200-300r/min,Take out mixture and be placed in cold wind suction filtration container, suction filtration is dry, makes PVC compound stabilizer.
In above-mentioned steps, described main stabilizer accounts for the 85-95% of compound stabilizer gross weight, described auxiliary stableAgent accounts for the 5-15% of main stabilizer weight, described polyvinylpyrrolidone ((C6H9NO) n), 2-pyrrolidone-5-carboxylic acidZinc (PCA-Na), calcium disodium chelate (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti)Accounting for compound stabilizer mass fraction is respectively: 15-22%, 25-34%, 32-45%, 8-15%; Described vinylBis-stearamides (C38H76N2O2), pentaerythritol stearate (C77H148O8), epoxy linseed oil, mannoseAlcohol (C6H14O6) account for compound stabilizer mass fraction and be respectively: 1-3%, 1-6%, 1-4%, 1-5%.
Described step 3) in, the volume of the mixed solution of described rare-earth stabilizer and indium acetate and ethylenediamine and water compositionRatio be 1:5, described rare-earth stabilizer is Lanthanum Stearate, yttrium stearate, maleamic acid lanthanum, maleic amideOne or more in acid yttrium, isooctyl acid lanthanum, isooctyl acid yttrium; It is compound steady that described rare-earth stabilizer accounts for described PVCDetermine the 3-6% of agent quality; Described indium acetate accounts for the 1.2-3.6% of described PVC compound stabilizer quality; Described tableThe mass fraction that face modifier FC4432 accounts for PVC compound stabilizer is 0.6-1.8%.
Further, the preparation method of described PVC compound stabilizer also comprises step 5): the PVC making is multipleClose stabilizing agent and carry out slaking, the condition of described slaking is 60 DEG C of-90 DEG C of temperature 2 hours.
Compared with prior art, the invention has the beneficial effects as follows:
(1) PVC compound stabilizer of the present invention has the features such as nontoxic, environmental protection, lubricity be good. Stabilizing agentIn contain zinc pyrrolidone carboxylate (PCA-Na), calcium disodium chelate (C10H12CaN2Na2O8) chemical combinationThing, makes the PVC compound stabilizer of preparation can make PVC have higher heat endurance and thermo oxidative stability,While being used in conjunction with the rare-earth stabilizer in formula of the present invention, there is higher cooperative effect.
(2) PVC compound stabilizer of the present invention contains terres rares heat stabilizer, have the melting, coupling of promotion,Internal plasticization, toughness reinforcing, increase the functions such as gorgeous, can make PVC compound plasticizing evenly, be easy to processing; Can also overcome and containThe PVC compound stabilizer of calcium zinc compound " zinc burning " problem in use, and can improve PVCThe impact strength of goods and section bar fillet weld strength; Can reduce the destruction of ultraviolet light to PVC molecule, improve goodsOutdoor aging performance.
(3) PVC compound stabilizer of the present invention contains modifier indium acetate, can overcome containing the PVC of rare earth multipleClose the poor problem of the anti-initial coloring of stabilizing agent, and can obviously improve the heat endurance of PVC, can improveThe shock resistance of PVC goods, the PVC goods of preparation have good inside and outside lubricity, and processing can be protectedHold stably and carry out.
(4) PVC compound stabilizer of the present invention, by adding surface modifier FC4432, has changed PVCThe surface property of compound stabilizer, has improved affinity between the two when PVC mixes with heat stabilizer, reachesMolecular level diffusion mixes, and heat stabilizer can not form two-phase after mixing with polyvinyl chloride resin under molten condition, therebyMake PVC goods there is the higher transparency. The long-acting heat endurance that has strengthened again goods, has goods simultaneouslyLong service life.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated. Should be appreciated that described hereinSpecific embodiment only, in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Present embodiment has disclosed a kind of PVC compound stabilizer, and this compound stabilizer is 85-95% by mass fractionMain stabilizer and mass fraction be 5-15% auxiliary stabilizer composition, in present embodiment, can select quality to divideNumber is that 60% main stabilizer and mass fraction are 40% auxiliary stabilizer, certainly, can also be multiple any modelCombination in enclosing, the auxiliary stabilizer that the main stabilizer that for example mass fraction is 70% and mass fraction are 30%,Mass fraction is that 75% main stabilizer and mass fraction are 25% auxiliary stabilizer; Main stabilizer is by polyethylene pyrrolePyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na), calcium disodium chelate(C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) composition, auxiliary stabilizer is two hard by vinylAcyl amine (C38H76N2O2), pentaerythritol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6)Composition. Wherein, polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na), second twoAmine tetraacethyl disodium calcium (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) account for compound stabilizer matterAmount mark is respectively: 20%, 25%, 32%, 8%; Vinyl bis-stearamides (C38H76N2O2), pentaerythriteStearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6) account for compound stabilizer mass fractionBe respectively: 2%, 6%, 4%, 3%.
In addition, in above-mentioned formula system, in order further to optimize the performance of PVC compound stabilizer, all rightAdditional mode is added into rare-earth stabilizer, and additional rare-earth stabilizer accounts for described PVC compound stabilizer quality3%; Additional rare-earth stabilizer is any one of Lanthanum Stearate or maleamic acid lanthanum or isooctyl acid lanthanum, also canThe mixture of thinking Lanthanum Stearate and maleamic acid lanthanum, the ratio of both mixtures specifically can be 1.5-5:1,Be preferably 2.5:1; Also can be the mixture that comprises Lanthanum Stearate and isooctyl acid lanthanum, the ratio of both mixturesSpecifically can be 1-3.5:1, be preferably 1.5:1, can also be for comprising Lanthanum Stearate, maleamic acid lanthanum and differentSad lanthanum three's mixture, the ratio of mixture specifically can be 2.5-4:1:1.5, is preferably 2.5:1:1.5.In addition, go back the outer modifier indium acetate that is added with in this PVC compound stabilizer, it is compound steady that modifier indium acetate accounts for PVCDetermine 1.2% of agent quality, why selecting to add indium acetate is modifier, can effectively overcome the PVC containing rare earthThe problem that the anti-initial coloring of compound stabilizer is poor, and can obviously improve the heat endurance of PVC, can improveThe shock resistance of PVC goods, the PVC goods of preparation have good inside and outside lubricity, and processing can be protectedHold stably and carry out, and any other modifier adds any amount, all there is no such effect.
As further preferred, in this PVC compound stabilizer, there is aggretion type surface modifier FC4432,The mass fraction that surface modifier FC4432 accounts for PVC compound stabilizer is 0.6%.
Embodiment 2
Its recipe ingredient is with embodiment 1. Be with the difference of embodiment 1: in this PVC compound stabilizer,Polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na), disodium ethylene diamine tetraacetateCalcium (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) account for compound stabilizer mass fractionBe respectively: 15%, 25%, 45%, 10%; Vinyl bis-stearamides (C38H76N2O2), pentaerythrite are hardResin acid ester (C77H148O8), epoxy linseed oil, mannitol (C6H14O6) account for compound stabilizer qualityMark is respectively: 1%, 2%, 1%, 1%.
As further preferred, this PVC compound stabilizer is added with rare-earth stabilizer outward, and rare-earth stabilizer accounts forPVC compound stabilizer quality is 6%, and wherein, rare-earth stabilizer is yttrium stearate or maleamic acid yttrium or different pungentAcid yttrium. Additional rare-earth stabilizer is any one of yttrium stearate or maleamic acid yttrium or isooctyl acid yttrium, alsoCan be the mixture of yttrium stearate and maleamic acid yttrium, the ratio of both mixtures specifically can be 1.5-5:1, be preferably 2.5:1; Also can be the mixture that comprises yttrium stearate and isooctyl acid yttrium, both mixturesRatio specifically can be 1-3.5:1, is preferably 1.5:1, can also be for comprising yttrium stearate, maleamic acid yttriumWith isooctyl acid yttrium three's mixture, the ratio of mixture specifically can be 2.5-4:1:1.5, is preferably2.5:1:1.5。
In addition,, in order further to optimize the performance of PVC compound stabilizer, in this PVC compound stabilizer, also outer being added with changesProperty agent indium acetate, modifier indium acetate accounts for 3.6% of PVC compound stabilizer quality.
In order further to optimize the performance of PVC compound stabilizer, be added with aggretion type table in these PVC compound stabilizer China and foreign countriesFace modifier FC4432, the mass fraction that surface modifier FC4432 accounts for PVC compound stabilizer is 1.8%.
Embodiment 3
Its recipe ingredient is with embodiment 1. Be with the difference of embodiment 1: in this PVC compound stabilizer,
Polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na), ethylenediamine tetra-acetic acidCalcium disodium (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) account for compound stabilizer qualityMark is respectively: 15%, 25%, 35%, 15%; Vinyl bis-stearamides (C38H76N2O2), Ji WusiAlcohol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6) account for compound stabilizerMass fraction is respectively: 2%, 3%, 2%, 3%.
This PVC compound stabilizer is outer rare-earth stabilizer and the modifier indium acetate of being added with also: rare-earth stabilizer be yttrium stearate,The mixture of maleamic acid yttrium, isooctyl acid yttrium, rare-earth stabilizer accounts for 4.2% of PVC compound stabilizer quality,The logical embodiment 2 of its composition and component ratio. Additional modifier indium acetate accounts for PVC compound stabilizer quality2.2％。
In order further to optimize the performance of PVC compound stabilizer, these PVC compound stabilizer China and foreign countries are added with aggretion type surfaceModifier FC4432, the mass fraction that surface modifier FC4432 accounts for PVC compound stabilizer is 1.2%.
Embodiment 4
The calcium-zinc composite stabilizing agent that PVC uses, by the above-mentioned PVC compound stabilizer of mass fraction 70-90%,The fatty acid calcium of mass fraction 4-15% or fatty acid zinc or both mixtures, mass fraction 4-10%'s is auxiliaryThe lubricant composition of agent, mass fraction 2-8%. In this PVC compound stabilizer component, contain 90% master steadyDetermine agent and 10% auxiliary stabilizer and the additional rare-earth stabilizer, 1.5% that accounts for this PVC compound stabilizer gross mass 4%Indium acetate, 0.9% surface modifier FC4432. Rare-earth stabilizer is Lanthanum Stearate, yttrium stearate, horseCarry out at least one in amic acid lanthanum, maleamic acid yttrium, isooctyl acid lanthanum, isooctyl acid yttrium. And, main stableAgent by account for PVC compound stabilizer gross mass mark be respectively 15% polyvinylpyrrolidone ((C6H9NO) n),25% zinc pyrrolidone carboxylate (PCA-Na), 35% calcium disodium chelate (C10H12CaN2Na2O8)、15% tetra isopropyl titanate (C12H28O4Ti) composition, auxiliary stabilizer is by total by accounting for PVC compound stabilizerMass fraction is respectively 2% vinyl bis-stearamides (C38H76N2O2), 3% pentaerythritol stearate(C77H148O8), 2% epoxy linseed oil, 3% mannitol (C6H14O6) composition.
In the formula of the present embodiment, fatty acid calcium is that carbon atoms number is 6 to 20 straight chain fatty acid rootWith the calcium salt that calcium ion forms, fatty acid zinc is that carbon atoms number is 6 to 20 straight chain fatty acid root and zincThe zinc salt that ion forms. Lubricant is following compound: paraffin, Tissuemat E, Fischer-Tropsch synthetic wax, aliphatic acid,At least one in fatty acid ester, fatty acid alcohol and fatty acid amide. Adjuvant is pentaerythritol resin, sub-phosphorusAcid esters antioxidant, beta-diketon, Sai Ke, uracil and uracil zinc salt, hydrotalcite, zeolite, alkali formula calciumAt least one in these compounds of aluminium phosphite and calcium hydroxide; Wherein beta-diketon is dibenzoyl firstAlkane, stearoyl benzoyl methane, dibenzoyl methane calcium, dibenzoyl methane zinc, stearoyl benzoyl methaneAt least one in magnesium, stearoyl benzoyl methane zinc, calcium acetylacetonate and these compounds of zinc acetylacetonate.Embodiment 5
A preparation method for PVC compound stabilizer, comprises the following steps:
1) preparation of main stabilizer: in mass ratio example take respectively polyvinylpyrrolidone ((C6H9NO) n), pyrrolesAlkane keto carboxylic acid zinc (PCA-Na), calcium disodium chelate (C10H12CaN2Na2O8), tetra isopropyl metatitanic acidEster (C12H28O4Ti), mix and blend at the temperature of 50 DEG C;
2) preparation of auxiliary stabilizer: example takes respectively vinyl bis-stearamides (C in mass ratio38H76N2O2), seasonPenta tetrol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6), mixing and stirring,Make auxiliary stabilizer;
3) successively rare-earth stabilizer and indium acetate are joined in the mixed solution of ethylenediamine and water composition, at 90 DEG CAt temperature, heating water bath 2 hours, is then added into surface modifier FC4432, and disperses at ultrasonic wave30 minutes, make additive agent mixture;
4) above-mentioned stabilizer blend and additive agent mixture are put into planetary ball mill tank, by batch mixing: nothingWater-ethanol mixes for the ratio of 1:2 by volume, moves 20 minutes with the rotating speed of 200-300r/min,Take out mixture and be placed in cold wind suction filtration container, suction filtration is dry, makes PVC compound stabilizer.
In above-mentioned steps, main stabilizer accounts for the 85-95% of compound stabilizer gross weight, and auxiliary stabilizer accounts for main steadyDetermine the 5-15% of agent weight, polyvinylpyrrolidone ((C6H9NO) n), zinc pyrrolidone carboxylate (PCA-Na),Calcium disodium chelate (C10H12CaN2Na2O8), tetra isopropyl titanate (C12H28O4Ti) account for stable compositionAgent mass fraction is respectively: 15-22%, 25-34%, 32-45%, 8-15%; Vinyl bis-stearamides (C38H76N2O2)、Pentaerythritol stearate (C77H148O8), epoxy linseed oil, mannitol (C6H14O6) account for compound stabilizerMass fraction is respectively: 1-3%, 1-6%, 1-4%, 1-5%.
Step 3) in, the ratio of the volume of the mixed solution of rare-earth stabilizer and indium acetate and ethylenediamine and water compositionFor 1:5, rare-earth stabilizer is Lanthanum Stearate, yttrium stearate, maleamic acid lanthanum, maleamic acid yttrium, differentOne or more in sad lanthanum, isooctyl acid yttrium; Rare-earth stabilizer accounts for the 3-6% of PVC compound stabilizer quality;Indium acetate accounts for the 1.2-3.6% of PVC compound stabilizer quality; Surface modifier FC4432 accounts for PVC stable compositionThe mass fraction of agent is 0.6-1.8%.
For further promoting PVC compound stabilizer performance, can also be by step 4) by compound the PVC making steadyDetermine agent and carry out slaking, the condition of slaking is 60 DEG C of-90 DEG C of temperature 2 hours.
In the prior art, the shortcoming of traditional calcium zinc heat stabilizer is that its heat endurance efficiency is not high, more plumbousThe heat endurance of the heat stabilizers such as salt is low. Inventor first sets about from improving formula, adopts main stabilizer and auxiliaryStabilizing agent fit system, the PVC compound stabilizer of preparation can obtain good heat stabilizer, but has light transmittanceThe problem that uniformity is not high. Through practice, inventor again to formula be optimized, introduced rare-earth stabilizer,Acetic acid, improves its heat endurance, has overcome the poor problem of initial coloring. By surface modifier FC4432Improve affinity between the two when PVC mixes with heat stabilizer, improved the transparency that makes PVC goods.
Compared with prior art: PVC compound stabilizer of the present invention has the spies such as nontoxic, environmental protection, lubricity be goodPoint; Can make the plasticizing of PVC compound evenly, be easy to processing; Have higher heat endurance, the higher transparency,Impact strength and section bar fillet weld strength; Can reduce the destruction of ultraviolet light to PVC molecule, the open air of improving goodsAgeing properties. Also there is good inside and outside lubricity, make the carrying out that processing can held stationary.
For more clearly explaining the technique effect of PVC compound stabilizer of the present invention, inventor adopts experimental techniquePVC stabilizing agent in above-mentioned formula is carried out to thermally-stabilised analysis, adopted Congo red test to add all kinds of formulasThe thermal stability of PVC, its testing procedure is, mixes with heat stabilizer through polyvinyl chloride resin powder, putsEnter in the small test tube of 10mm × 100mm, be immersed in the oil bath of 180 ± 1 DEG C, take out one every 3minIndividual sample, record the variable color situation of PVC in test tube, and the method can be used for simple more different heat stabilizersThermal stability.
The heat endurance experiment contrast of table 1PVC stabilizing agent
Find out from upper table, compared with prior art, the thermal stability of PVC stabilizing agent of the present invention is better, andAnd the formula that is added with the un-added indium acetate modifier of recipe ratio of indium acetate modifier has more excellent heatStability. And added the formula of surface modifier FC4432, change color is the slowest, heat enduranceCan be best.
Above-mentioned explanation illustrates and has described the preferred embodiments of the present invention, as previously mentioned, is to be understood that the present invention alsoNon-ly be confined to disclosed herein form, should do not regard the eliminating to other embodiment as, and can be used for various itsHis combination, amendment and environment, and can be in invention contemplated scope described herein, by above-mentioned instruction or relevantTechnology or the knowledge in field are changed. And the change that those skilled in the art carry out and variation do not depart from of the present inventionSpirit and scope, all should be in the protection domain of claims of the present invention.
Claims (10)
1. a PVC compound stabilizer, is characterized in that: described compound stabilizer is 85-95% by mass fractionMain stabilizer and mass fraction are 5-15% auxiliary stabilizer composition, described main stabilizer by polyvinylpyrrolidone,Zinc pyrrolidone carboxylate, calcium disodium chelate, tetra isopropyl titanate composition, described auxiliary stabilizerFormed by vinyl bis-stearamides, pentaerythritol stearate, epoxy linseed oil, mannitol.
2. PVC compound stabilizer according to claim 1, is characterized in that: described polyvinylpyrrolidone,Zinc pyrrolidone carboxylate, calcium disodium chelate, tetra isopropyl titanate account for compound stabilizer mass fractionBe respectively: 15-22%, 25-34%, 32-45%, 8-15%; Described vinyl bis-stearamides, pentaerythriteStearate, epoxy linseed oil, mannitol quality account for compound stabilizer mass fraction and are respectively: 1-3%,1-6％、1-4％、1-5％。
3. PVC compound stabilizer according to claim 1, is characterized in that: described PVC compound stabilizerThe also outer rare-earth stabilizer that is added with, described rare-earth stabilizer be Lanthanum Stearate, yttrium stearate, maleamic acid lanthanum,One or more in maleamic acid yttrium, isooctyl acid lanthanum, isooctyl acid yttrium, described in described rare-earth stabilizer accounts forThe 3-6% of PVC compound stabilizer quality.
4. PVC compound stabilizer according to claim 1, is characterized in that: described PVC compound stabilizerIn the outer modifier indium acetate that is added with also, described modifier indium acetate accounts for described PVC compound stabilizer quality1.2-3.6％。
5. according to the PVC compound stabilizer described in claim 1-4 any one, it is characterized in that: described PVC is multipleClose in stabilizing agent and be also added with aggretion type surface modifier FC4432 outward, described surface modifier FC4432 accounts for PVCThe mass fraction of compound stabilizer is 0.6-1.8%.
6. a preparation method for PVC compound stabilizer, is characterized in that: comprise the following steps:
1) preparation of main stabilizer: in mass ratio example take respectively polyvinylpyrrolidone, zinc pyrrolidone carboxylate,Calcium disodium chelate, tetra isopropyl titanate, mix and blend at the temperature of 50 DEG C;
2) preparation of auxiliary stabilizer: example takes respectively vinyl bis-stearamides, pentaerythrite tristearin in mass ratioAcid esters, epoxy linseed oil, mannitol, mixing and stirring, makes auxiliary stabilizer;
3) successively rare-earth stabilizer and indium acetate are joined in the mixed solution of ethylenediamine and water composition, at 90 DEG CAt temperature, heating water bath 2 hours, is then added into surface modifier FC4432, and disperses at ultrasonic wave30 minutes, make additive agent mixture;
4) above-mentioned stabilizer blend and additive agent mixture are put into planetary ball mill tank, by batch mixing: nothingWater-ethanol mixes for the ratio of 1:2 by volume, moves 20 minutes with the rotating speed of 200-300r/min,Take out mixture and be placed in cold wind suction filtration container, suction filtration is dry, makes PVC compound stabilizer.
7. the preparation method of PVC compound stabilizer according to claim 6, is characterized in that: described rare earthStabilizing agent is Lanthanum Stearate, yttrium stearate, maleamic acid lanthanum, maleamic acid yttrium, isooctyl acid lanthanum, different pungentOne or more in acid yttrium; Described rare-earth stabilizer accounts for the 3-6% of described PVC compound stabilizer quality.
8. the preparation method of PVC compound stabilizer according to claim 6, is characterized in that: described step4) rare-earth stabilizer described in and indium acetate with the ratio of the volume of the mixed solution of ethylenediamine and water mixed solution are1:5, described modifier indium acetate accounts for the 1.2-3.6% of described PVC compound stabilizer quality.
9. the preparation method of PVC compound stabilizer according to claim 6, is characterized in that: described surfaceThe mass fraction that modifier FC4432 accounts for PVC compound stabilizer is 0.6-1.8%.
10. the preparation method of PVC compound stabilizer according to claim 6, is characterized in that: also comprise stepRapid 5), the PVC compound stabilizer making is carried out to slaking, the condition of described slaking is at 60 DEG C of-90 DEG C of temperatureSlaking 2 hours.
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| CN106009412A (en) * | 2016-07-20 | 2016-10-12 | 合肥恒研智能科技有限公司 | PVC (polyvinyl chloride) cable material |
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| CN106009412B (en) * | 2016-07-20 | 2018-02-02 | 合肥恒研智能科技有限公司 | A kind of PVC cable material |
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