CN101302306B - Preparation of high temperature resistant, anti-precipitation liquid rare earth/barium/zinc composite heat stabilizer - Google Patents
Preparation of high temperature resistant, anti-precipitation liquid rare earth/barium/zinc composite heat stabilizer Download PDFInfo
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- CN101302306B CN101302306B CN2008101224201A CN200810122420A CN101302306B CN 101302306 B CN101302306 B CN 101302306B CN 2008101224201 A CN2008101224201 A CN 2008101224201A CN 200810122420 A CN200810122420 A CN 200810122420A CN 101302306 B CN101302306 B CN 101302306B
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Abstract
The invention provides a method for preparing a rare earth/barium/zinc compound heat stabilizer having the advantages of high temperature resistance and liquid dropout resistance, belonging to the heat stabilizer technical field. In the heat stabilizer of the invention, rare earth organic acid salts are doped with liquefied barium and zinc and added with anti-sediment components and auxiliary stabilizers, so that the heat stabilizer of the invention achieves effects of high temperature resistance and liquid dropout resistance. The method has the advantages of simple manufacturing process and no generation of waste water and gas; moreover, the method realizes the clean production under the condition of no water, and the heat stabilizer is obviously better than liquefied barium and zinc and liquefied calcium and zinc in high temperature resistance performance, and the heat stabilizer is hard to drop out deposits while storing, so that the heat stabilizer belongs to the non-toxic and environment friendly product.
Description
Technical field
The present invention relates to that a kind of cleaner production is high temperature resistant under anhydrous condition, anti-precipitation liquid rare earth/barium is native/preparation method of barium/Zn composite heat stabilizer, belong to the thermo-stabilizer technical field.
Background technology
Polyvinyl chloride resin is at chemical industry, building materials, and automobile, electronics, fields such as packing have widespread use, yet use leaded, cadmium type thermal stabilizing agent because of they are a large amount of in the course of processing, have brought comparatively serious environmental issue.Many countries have formulated strict limit standard to the processing aid in the PVC plastics, have brought serious impact for PVC plastic working industry.Therefore, exploitation low toxicity, pollution-free, compound and thermo-stabilizer efficiently substitute use plumbous, cadmium stabilizer, are that the additives for plastics industry needs the urgent problem that solves.
Liquid composition metal soap class stablizer, because of it is produced with application process no dust pollution, clean environment firendly, is convenient to metering, cheap, obtained application more and more widely, be particularly useful for soft transparent PVC material, as transparent cable, soft toy, medicine equipment, food packaging film, artificial leather product etc.Wherein, liquid barium zinc is because of its thermostability height, and the transparency is good, is widely used in flexible PVC.
Preparation method about liquid base earth metals composite thermal stabilizer has had relevant record in United States Patent (USP) U.S.Pat.No.7078459, its principal character is that liquid calcium barium zinc ternary is compound, composite with various auxiliary stabilizers simultaneously to reach the purpose that improves thermostability, the initial stage Heat stability is good of products obtained therefrom, the transparency is good, and is difficult for separating out; U.S.Pat.No.5,322,872 disclose the anti-production method of composite alkaling earth metal base thermo-stabilizer of separating out of a kind of liquid, concrete grammar is the stability in storage that improves heat stabilizing system by the interpolation sequestrant, and these sequestrants can be phosphoric acid ester, phosphorous acid ester, prussiate, atmosphere class material etc.This patent is based on the characteristics of above patent, by improving organic acid structure, refinement rare earth/barium/zinc compound proportion, improve one package stabilizer preparation technology, adding novel anti precipitation agent and novel auxiliary stabilizer, solved liquid composite thermal stabilizer high thermal resistance deficiency, preparation technology is loaded down with trivial details, the shortcoming that storage cycle is short provides the novel preparation method of a kind of liquid rare earth/barium/zinc ternary composite thermal stabilizer.
At present, liquid barium zinc type thermal stabilizing agent mainly is the metallic soap based on isocaprylic acid, but the isocaprylic acid soap easily separates out in high temperature process, and its high temperature resistant property is relatively poor, deposits precipitation easily takes place in the process to separate out, and has influenced the use properties of product.Usual method is to introduce the high-molecular weight organic acid therein, as oleic acid.But high-molecular weight organic acid soap long-term storage is easily separated out precipitation, and its usage quantity is restricted; Analyzing it and separate out sedimentary reason, mainly is because product tiny nucleus in depositing process grows up into deposit seeds and sedimentation gradually.Be to stop the formation of deposit seeds, can prevent effectively that by adding the antisolvent precipitation precipitation agent particulate from growing up.Anti-precipitation agent molecular structure must have than the large space steric hindrance, with at the outer layer protective layer that coats of nucleus, has stoped growing up of nucleus, thereby has prevented that the liquid composite thermal stabilizer precipitation from separating out.
By adding the 3rd component such as rare earth organic acid salt, be used for improving the permanent stability and the resistance to elevated temperatures of thermo-stabilizer by trielement synergistic, be a kind of effective ways that solve liquid barium zinc heat stabilizer poor stability, simultaneously, the adding of rare earth can reduce the content of barium metal in the barium zinc, has reduced the toxicity of product.
Why rare earth thermally-stabilised has above-mentioned performance to be determined by their electronic structure if being.From the quantum chemistry angle analysis, rare earth ion all has many 4f and the empty electronic level (electronic orbit) of 5d, they can accept the lone electron pair of 6-12 ligand as the coordination center ion, they have bigger ionic radius simultaneously, thereby might form the coordinate bond that 6-12 bond energy do not wait, i.e. complex bonds.This characteristic makes it have following function: except forming the ionic linkage with 3 or 4 HCl, also may adsorb if form the complex compound that bond energy does not wait in individual HCl molecule, effectively reduced concentration, thereby reduced HCl catalytic degradation reaction speed effectively as thermal destruction catalyzer HCl; Rare earth can also with the unstable chlorine atom complexing on the PVC chain, be stable structure effectively just at the initial stage of being heated with active chlorine atomic substitutions.Therefore, the consumption of HCl to the barium soap has effectively been alleviated in the introducing of rare earth, has also obviously reduced the concentration of the inner HCl of PVC, and in addition, rare earth is reduction ZnCl effectively
2Be zinc soap, further alleviated zinc and burnt phenomenon, improved the use temperature of thermo-stabilizer; In addition, rare earth has unique coupling effect, can improve liquid barium zinc stabilizer with the consistency between the PVC, in being subjected to thermal process can also with PVC molecule generation coupling, played the effect that high temperature is separated out that suppresses.
Different with the solid thermal stablizer is, rare earth adds in the mode of liquid and need prepare the rare earth organic acid salt in advance and be dissolved in the organic solvent, simultaneously, needs to keep the color and luster and the viscosity of product.Traditional liquid rare earth preparation is with double decomposition, carries out in water surrounding, has brought a large amount of waste water that contains rare earth ion, deals with the comparison difficulty, and comparatively complicated in the operation.And liquid rare earth also can't simply prepare by direct method; By, in mixed fatty acid, add a certain amount of special catalyst, directly in solvent oil, react then and can single stage method obtain the liquid rare earth soap.
Summary of the invention
The objective of the invention is to performance, and then improve the thermostability that barium zinc is used the PVC goods, reduce its toxicity by rareearth doped modified liquid barium/Zn composite heat stabilizer; Replace isocaprylic acid to improve the resistance to elevated temperatures of product with long chain fatty acid simultaneously, also improve the stability in storage of product by adding anti-precipitation agent, provide a kind of clean produce high temperature resistant, anti-precipitation liquid rare earth/barium is native/novel method of the preparation of barium/zinc ternary composite thermal stabilizer.
Technical scheme of the present invention: a kind of high temperature resistant, the preparation method of anti-precipitation liquid rare earth/barium soil/barium/Zn composite heat stabilizer: in solvent oil, use special catalyst to prepare rare earth/barium/zinc mixing acid soap, add anti-precipitation agent and auxiliary heat stabilizer again, mixing after-filtration makes high temperature resistant, anti-precipitation liquid rare earth/barium soil/barium/Zn composite heat stabilizer, its main ingredient is counted with the quality percentage: content of rare earth 5%～10%, Ba content 10%～15%, Zn content 1%～5%, anti-precipitation agent content 5%～10%, auxiliary heat stabilizer content 20%～60%, surplus are solvent oil; Technology is::
(1) preparation rare earth acid soap: earlier the organic acid of 7-16 weight part, the solvent oil of 15-20 weight part and the special catalyst of 0.4-1 weight part are added in the reactor, start to stir and be warming up to 90 ℃, the rare earth that adds the 2.5-4 weight part, reaction 2-3h makes rare earth acid soap;
(2) preparation rare earth/zinc mixing acid soap: continue to add the zinc oxide of 1 weight part, 90 ℃ of reaction 2-2.5h make rare earth/zinc mixing acid soap;
(3) preparation rare earth/barium/zinc mixing acid soap: add the organic acid of 11 weight parts, the hydrated barta of 3-3.5 weight part again, 90 ℃ of reaction 2-2.5h make rare earth/barium/zinc mixing acid soap;
(4) preparation liquid rare earth/barium/Zn composite heat stabilizer: system is warming up to 110 ℃, and underpressure distillation is deviate to anhydrous; System is cooled to 90 ℃, adds 8-18 parts by weight solvent oil, the anti-precipitation agent of 0.8-1.0 weight part, be stirred to dissolving, continue heated and stirred 0.5h, be cooled to 70 ℃, add the auxiliary heat stabilizer of 5-15 weight part again, thorough mixing is even, and heated and stirred is dissolved until solid matter;
(5) aftertreatment of product: while hot above product is filtered, need decolour more deeply as product colour; Finished product is placed sealed plastic container, avoid contact wetting and a large amount of air, standby;
Described solvent oil is selected from a kind of in 200# solvent oil, 25# transformer oil, tasteless kerosene, white oil, whiteruss, non-toxic plasticizer or the vegetables oil or their mixture;
Described mixing acid is selected from a kind of in oleic acid, linolic acid, lauric acid, capric acid, pelargonic acid, isocaprylic acid, Whitfield's ointment, phenylformic acid, the methacrylic acid or their mixture;
Described special catalyst is selected from a kind of in phosphorous acid, concentrated hydrochloric acid, polyphosphoric acid, the p-methyl benzenesulfonic acid or their mixture;
Described anti-precipitation agent is selected from a kind of in high fatty alcohol, benzoic ether, the alkyl substituted benzoic acid ester or their mixture;
Described auxiliary stabilizer is selected from a kind of in polyol ester, phosphorous acid ester, beta-diketon, epoxy aliphatic ester, thiobarbituricacid and the derivative thereof or their mixture.
Used rare earth is selected from oxyhydroxide, oxide compound or their mixture of lanthanum, cerium, praseodymium, neodymium, yttrium.
High fatty alcohol is selected from isooctyl alcohol, decyl alcohol, lauryl alcohol, hexylene glycol or their mixture.
Described alkyl substituted benzoic acid ester be selected from the neighbour,, the positive butyl ester of contraposition alkyl substituted benzoic acid or different monooctyl ester, wherein alkyl is methyl, ethyl, sec.-propyl, the tertiary butyl, iso-octyl and/or octyl group.
Concrete preparation process is as follows:
(1) preparation of liquid mixing soap:
In being arranged, the stainless steel cauldron of agitator adds C by proportioning
4～C
10Organic acid, combination of acidic catalyzer, solvent oil are warming up to 90 ℃, add hydroxide or rare earth oxide compound in batches, and reaction 2～3h continues to add zinc oxide in batches, 90 ℃ of reaction 2-2.5h; Continue to add C
16～C
18Lipid acid, hydrated barta, 90 ℃ are continued reaction 2-2.5h down, are warming up to 110 ℃, decompression dehydration after reaction is finished.
(2) interpolation of auxiliary agent and anti-precipitation agent:
Above product is cooled to 90 ℃, adds a certain proportion of anti-precipitation agent, start stirring, treat that anti-precipitation agent dissolves fully, continue stir about 0.5h, be cooled to 70 ℃, add the auxiliary heat stabilizer of metering ratio, stir and dissolve until solid matter.
(3) aftertreatment of product:
While hot above product is filtered, need decolour more deeply as product colour.Finished product is placed sealed plastic container, avoid contact wetting and a large amount of air.
Beneficial effect of the present invention: technological process of the present invention is simple relatively, product is formed steady quality, metal oxide or oxyhydroxide can be finished between 80～120 ℃ with mixed organic acid direct reaction temperature, be reflected within 5～8h and finish, with short production cycle, thermal stability is better than the commercial like product; Product can reach 100min 180 ℃ of static-aging test xanthochromia times, and 190 ℃ of static-aging test xanthochromia times can reach 80min, and 200 ℃ of static-aging test xanthochromia times can reach 60min, and product frozen for storage time under-5 ℃ of low temperature can reach 1 year.
Advantages such as the rare earth/barium that the present invention relates to/zinc ternary composite thermal stabilizer has efficiently, low toxicity, preparation technology simple, good processability, high-temperature resistant result are good, be difficult for separating out, have wide range of applications, production process does not relate to wastewater treatment, and production cost is lower.This product is applicable to the flexible PVC goods, and as PVC leatheroid, cable, automotive trim, plastics film etc., performance is better than commercially available liquid composite stabilizing agent.Fig. 1 is preparing product of the present invention and commercially available liquid calcium zinc under 200 ℃ of conditions, the contrast of liquid barium zinc thermostable effect.As shown in the figure, under 200 ℃ of conditions, the PVC test piece of adding this product can keep stability preferably in the time of 60～70min of being heated, and only can keep about 50min with the commercially available liquid barium zinc of price under identical addition, liquid calcium zinc result of use is the poorest, only keeps about 20min.Hence one can see that, and the high thermal resistance of this product obviously is better than barium zinc and calcium zinc binary composite prod.Simultaneously, because the use of rare earth element more can improve The comprehensive performance, make its toxicity be lower than liquid barium zinc, effect then is much better than liquid calcium zinc.
Description of drawings
Fig. 1 is preparing product of the present invention and commercially available liquid calcium zinc under 200 ℃ of conditions, the contrast of liquid barium zinc thermostable effect.
Embodiment
Embodiment 1
In the stainless steel cauldron that the 500L band stirs, add: isocaprylic acid 30kg, methacrylic acid 33.4kg, butyl carbitol 30kg, tasteless kerosene 100kg, composite catalyst (phosphorous acid and concentrated hydrochloric acid) 3.9kg starts stirring and is warming up to 90 ℃, divide four times and add lanthanum hydroxide 24.6kg, reaction 2h continues to divide to add ZnO 8.4kg four times reaction 2h; Add oleic acid 92.6kg, and divide four times to add hydrated barta 28kg, react about 2h, be warming up to 110 ℃, underpressure distillation is extremely anhydrous deviates from.System is cooled to 90 ℃, adds tasteless kerosene 150kg, and the different monooctyl ester 7.5kg of p-tert-butyl benzoic acid is stirred to dissolving, be cooled to 70 ℃, add beta-diketon 8.4kg, triphenyl phosphite 45kg, thorough mixing is even, filters the product sealed storage while hot through plate-and-frame filter press.
Its main ingredient is counted with the quality percentage: content of rare earth 5%～10%, and Ba content 10%～15%, Zn content 1%～5%, anti-precipitation agent content 5%～10%, auxiliary stabilizer content 20%～60%, surplus is a solvent oil.
Embodiment 2
In the stainless steel cauldron that the 500L band stirs, add: phenylformic acid 25.4kg, methacrylic acid 33.4kg, butyl carbitol 30kg, tasteless kerosene 120kg, composite catalyst (concentrated hydrochloric acid and polyphosphoric acid) 5.8kg, start stirring and be warming up to 90 ℃, divide four times and add lanthanum hydroxide 12.3kg, praseodymium hydroxide 12.5kg, reaction 3h, continue to divide to add ZnO 8.4kg four times reaction 2h; Add oleic acid 92.6kg, and divide four times to add hydrated barta 28kg, react about 2h, be warming up to 110 ℃, underpressure distillation is extremely anhydrous deviates from; System is cooled to 90 ℃, adds tasteless kerosene 75kg, and anti-precipitation agent 7.5kg is stirred to dissolving, is cooled to 70 ℃, adds epoxy soybean oil 36kg, triphenyl phosphite 67.5kg, and thorough mixing is even, filters the product sealed storage while hot through plate-and-frame filter press.
Embodiment 3
In the stainless steel cauldron that the 500L band stirs, add: capric acid 36.4kg, Whitfield's ointment 76.4kg, butyl carbitol 30kg, tasteless kerosene 145kg, composite catalyst (polyphosphoric acid and p-methyl benzenesulfonic acid) 7.8kg, start stirring and be warming up to 90 ℃, divide four times and add lanthanum hydroxide 18.5kg, cerous hydroxide 13.4kg, reaction 2h, continue to divide to add ZnO 8.4kg four times reaction 2h; Add oleic acid 92.6kg, and divide four times to add hydrated barta 28kg, react about 2h, be warming up to 110 ℃, underpressure distillation is extremely anhydrous deviates from; System is cooled to 90 ℃, adds tasteless kerosene 75kg, and anti-precipitation agent 7.5kg is stirred to dissolving, be cooled to 70 ℃, add thiobarbituricacid 5g, epoxy soybean oil 30kg, triphenyl phosphite 62.5kg, thorough mixing is even, filters the product sealed storage while hot through plate-and-frame filter press.
Embodiment 4
In the stainless steel cauldron that the 500L band stirs, add: neodecanoic acid 36.4kg, lauric acid 98kg, butyl carbitol 45kg, tasteless kerosene 105kg, composite catalyst (phosphorous acid and p-methyl benzenesulfonic acid) 4.5kg starts stirring and is warming up to 90 ℃, divide four times and add lanthanum hydroxide 30.5kg, reaction 2.5h continues to divide to add ZnO 8.4kg four times reaction 2h; Add oleic acid 92.6kg, and divide four times to add hydrated barta 28kg, react about 2h, be warming up to 110 ℃, underpressure distillation is extremely anhydrous deviates from; System is cooled to 90 ℃, adds tasteless coal 125kg, and anti-precipitation agent 7.5kg is stirred to dissolving, is cooled to 70 ℃, adds thiobarbituricacid 9g, triphenyl phosphite 67.5kg, and thorough mixing is even, filters the product sealed storage while hot through plate-and-frame filter press.
Claims (3)
- One kind high temperature resistant, the preparation method of anti-precipitation liquid rare earth/barium soil/barium/Zn composite heat stabilizer, it is characterized in that: in solvent oil, use special catalyst to prepare rare earth/barium/zinc mixing acid soap, add anti-precipitation agent and auxiliary heat stabilizer again, mixing after-filtration makes high temperature resistant, anti-precipitation liquid rare earth/barium soil/barium/Zn composite heat stabilizer, its main ingredient is counted with the quality percentage: content of rare earth 5%～10%, Ba content 10%～15%, Zn content 1%～5%, anti-precipitation agent content 5%～10%, auxiliary heat stabilizer content 20%～60%, surplus are solvent oil; Technology is:(1) preparation rare earth acid soap: earlier the organic acid of 7-16 weight part, the solvent oil of 15-22 weight part and the special catalyst of 0.4-1 weight part are added in the reactor, start to stir and be warming up to 90 ℃, the rare earth that adds the 2.5-4 weight part, reaction 2-3h makes rare earth acid soap;(2) preparation rare earth/zinc mixing acid soap: continue to add the zinc oxide of 1 weight part, 90 ℃ of reaction 2-2.5h make rare earth/zinc mixing acid soap;(3) preparation rare earth/barium/zinc mixing acid soap: add the organic acid of 11 weight parts, the hydrated barta of 3-3.5 weight part again, 90 ℃ of reaction 2-2.5h make rare earth/barium/zinc mixing acid soap;(4) preparation liquid rare earth/barium/Zn composite heat stabilizer: system is warming up to 110 ℃, and underpressure distillation is deviate to anhydrous; System is cooled to 90 ℃, adds 8-18 parts by weight solvent oil, the anti-precipitation agent of 0.8-1.0 weight part, be stirred to dissolving, continue to stir 0.5h, be cooled to 70 ℃, add the auxiliary heat stabilizer of 5-15 weight part again, thorough mixing is even, stirs to dissolve until solid matter;(5) aftertreatment of product: while hot above product is filtered, need decolour more deeply as product colour; Finished product is placed sealed plastic container, avoid contact wetting and a large amount of air, standby;Described solvent oil is selected from a kind of in 200# solvent oil, 25# transformer oil, tasteless kerosene, white oil, whiteruss or the vegetables oil or their mixture;Described organic acid is selected from a kind of in oleic acid, linolic acid, lauric acid, capric acid, pelargonic acid, isocaprylic acid, Whitfield's ointment, phenylformic acid, the methacrylic acid or their mixture;Described special catalyst is selected from a kind of in phosphorous acid, concentrated hydrochloric acid, polyphosphoric acid, the p-methyl benzenesulfonic acid or their mixture;Described anti-precipitation agent is selected from a kind of in high fatty alcohol, benzoic ether, the alkyl substituted benzoic acid ester or their mixture;Described auxiliary stabilizer is selected from a kind of in polyol ester, phosphorous acid ester, beta-diketon, epoxy aliphatic ester, the thiobarbituricacid or their mixture;Used rare earth is selected from praseodymium hydroxide, lanthanum hydroxide, cerous hydroxide or their mixture.
- 2. preparation method according to claim 1 is characterized in that: anti-precipitation agent high fatty alcohol is selected from isooctyl alcohol, decyl alcohol, lauryl alcohol, hexylene glycol or their mixture.
- 3. preparation method according to claim 1 is characterized in that: described anti-precipitation agent alkyl is gotFor benzoic ether be selected from the neighbour,, the positive butyl ester of contraposition alkyl substituted benzoic acid or different monooctyl ester, wherein alkyl is methyl, ethyl, sec.-propyl, the tertiary butyl or octyl group.
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| CN101575423B (en) * | 2008-12-26 | 2011-12-14 | 广东炜林纳功能材料有限公司 | Rare earth rubber aging inhibitor and application thereof |
| CN104629400A (en) * | 2015-01-29 | 2015-05-20 | 河北正洋建材有限公司 | Resin liquid and preparation method thereof |
| CN104910414A (en) * | 2015-06-18 | 2015-09-16 | 巢湖香枫塑胶助剂有限公司 | Preparation method of liquid barium-zinc composite heat stabilizer |
| CN105001447B (en) * | 2015-08-03 | 2017-11-14 | 盐城科迈特新材料有限公司 | A kind of preparation method of NEW TYPE OF COMPOSITE heat stabilizer |
| CN106084810A (en) * | 2016-08-26 | 2016-11-09 | 江苏联盟化学有限公司 | A kind of high-performance PVC (polyvinyl chloride) liquid composite thermal stabilizer |
| CN106751064B (en) * | 2016-12-10 | 2019-04-05 | 包头稀土研究院 | A kind of phosphorus or phosphonic acid ester rare earth compound PVC heat stabilizer |
| CN107057220B (en) * | 2017-04-18 | 2019-07-30 | 天津科技大学 | A kind of PVC transparent composite thermal stabilizer of liquid barium/zinc |
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| CN1277974A (en) * | 2000-06-12 | 2000-12-27 | 郑德� | Rare-earth multi-functional composite stabilizer for PVC and its processing method |
| CN1544520A (en) * | 2003-11-27 | 2004-11-10 | 衡水精信化工有限公司 | Preparation method and application for composite rare-earth stabilizer for PVC profiled bar |
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| CN1277974A (en) * | 2000-06-12 | 2000-12-27 | 郑德� | Rare-earth multi-functional composite stabilizer for PVC and its processing method |
| CN1544520A (en) * | 2003-11-27 | 2004-11-10 | 衡水精信化工有限公司 | Preparation method and application for composite rare-earth stabilizer for PVC profiled bar |
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Assignee: Xinyi Ceramic (China) Co., Ltd. Assignor: Jiangnan University Contract record no.: 2011320010132 Denomination of invention: Preparation of high temperature resistant, anti-precipitation liquid rare earth/barium/zinc composite heat stabilizer Granted publication date: 20101215 License type: Exclusive License Open date: 20081112 Record date: 20111221 |
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