CN101289550B - Rare earth complex heat stabilizer for PVC and method for preparing same - Google Patents
Rare earth complex heat stabilizer for PVC and method for preparing same Download PDFInfo
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- CN101289550B CN101289550B CN2008100712049A CN200810071204A CN101289550B CN 101289550 B CN101289550 B CN 101289550B CN 2008100712049 A CN2008100712049 A CN 2008100712049A CN 200810071204 A CN200810071204 A CN 200810071204A CN 101289550 B CN101289550 B CN 101289550B
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- rare earth
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- salt
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Abstract
The invention provides a PVC rare-earth composite heat stabilizer and a method for making the same. The heat stabilizer is a wool acid metal rare-earth soap stabilizer and has a general chemical equation of xRE.yCa.zZn.(OOCR)n or x'RE.y'Ba.z'Zn.(OOCR)n. The method for making the heat stabilizer comprises the following steps that: sodium hydroxide is dissolved into an ethanol water solution and is stirred as well as is condensed and flowed back, the melting common and braid wool acid is added to adjust the pH value and decrease the temperature; water, chlorination rare-earth salt solution and salt are added in sequence to be pumped, filtered, washed by ethanol and water, dried and grinded into a product. The stabilizer adopts the common and braid wool acid as the raw material, thereby having wide resources, low cost, reasonable and scientific preparation method and great maneuverability; the product is straw yellow powder and has good primary and long-term heat stabilization performance of PVC and good effects in the aspects of material process and mechanical performance, is nontoxic and protects the environment, and can be applied to the processing and forming aspects of PVC water supply and drainage pipes and have evident social and economical benefits.
Description
Technical field
The invention belongs to PVC and make the field, more specifically relate to a kind of PVC rare earth complex heat stabilizer and preparation method thereof with thermo-stabilizer.
Background technology
China is rare earth big country, at present, to having valence variation element in the stabilization of PVC simultaneously, the rare earth thermal stabilizer of effect of metalloid soap and rare earth complex effect more and more becomes the focus of concern, how based on rare earth organic monoacid salt stabilizing agent, they are better than lead salts and other metallic soap classes to the long-term thermal stability of PVC, has long-term thermal stability preferably, and and other kind stablizers between synergistic effect is widely arranged, has good tolerability, be not subjected to the pollution of S, stable storing, toxicity is hanged down the advantage with environmental protection, also has coupling when lubricity is good, increase-volume, toughness reinforcing, improve material fluidity, improve effects such as PVC goods mechanical property.But, the organic monoacid salt such as rare-earth stearate of recent years development have shown effect preferably at PVC aspect thermally-stabilised, but the primary stability of material can be not good enough when using rare-earth stabilizer separately, it is low to show as the initial coloration performance, can adopt rare-earth stabilizer and other metal(lic)stabilizers to carry out the composite rare earth complex heat stabilizer that makes.
Lanolin fatty acid is the mixing acid of more than 150 kind of fatty acid monomer, uses it for the synthetic effect that can bring into play the multiple fatty acid soaps of metal of the same race of metallic soap.At present the alternative stearic acid of lanolin fatty acid is used for cosmetic field, and its metallic soap can be used as the rust-preventive agent of metal, and it is applied to the still belonging to the first time of thermo-stabilizer of PVC.
Summary of the invention
The purpose of this invention is to provide a kind of PVC rare earth complex heat stabilizer and preparation method thereof, this PVC rare earth complex heat stabilizer is a lanolin fatty acid rare earth metal soap class stablizer, adopting common and braid wool acid is one of raw material, raw material sources are extensive, with low cost, the preparation method is scientific and reasonable, workable, preparation process is consuming time shorter than wool grease rare earth complex heat stabilizer preparation process, the product that is prepared into does not have the stink of lanolin fatty acid and is pale yellow powder, PVC had initial stage and long-term thermal stability energy preferably, showing effect preferably aspect materials processing and the mechanical property, and asepsis environment-protecting can be applicable to the aspects such as machine-shaping of PVC plumbing tubing, has the significant social economic benefit.
PVC rare earth complex heat stabilizer of the present invention, it is characterized in that: described PVC rare earth complex heat stabilizer is a lanolin fatty acid rare earth metal soap class stablizer, adopting common and braid wool acid is one of raw material, the chemical general formula of described lanolin fatty acid rare earth metal soap class stablizer is: xREyCazZn (OOCR) n or x ' REy ' Baz ' Zn (OOCR) n '. wherein, x, y, z, n, x ', y ', z ', n ' is respectively the stoichiometric number of metallic element and wool acid group, and x=x '=1, y=y '=1～3, z=z '=1～1.5, n=n '=3～12, RE is scandium Sc, yttrium Y and lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, any element in samarium Sm or the europium Eu rare earth element.
The PVC of the present invention preparation method of rare earth complex heat stabilizer, it is characterized in that: quality proportioning sour according to common and braid wool and sodium hydroxide is 5.3～8: 1 amount, is that 75～78 ℃ of volumetric concentrations are in 80～90% the aqueous ethanolic solution with dissolution of sodium hydroxide in temperature, starts and stirs and condensation reflux unit; In the acid of 60～80 ℃ of following fusion common and braid wools, then common and braid wool acid 10～25g is joined gradually in the above-mentioned sodium hydroxide ethanolic soln that is in whipped state, stir saponification reaction 1.5～2h down at 75～78 ℃; The pH that adjusts reaction solution while hot is 7.0～9.0, be cooled to 50～60 ℃ then, add temperature in turn and be warm water 30～60ml of 50～60 ℃, rare earth chloride salts solution 10～30ml, calcium salt 1.5～2.5g or barium salt 3.4～5.2g and zinc salt 2.0～7.0g, reaction 0.5～2h after product is washed 3～4 times, washing 3～4 times through suction filtration, alcohol, 60～80 ℃ down oven dry be finished product after grinding.
Remarkable advantage of the present invention is:
1. product appearance of the present invention is white or pale yellow powder, and product does not have the appearance of black and the stink of raw material lanolin fatty acid.Can be well compatible with PVC, good heat stability, and product surface is smooth, snappiness is good etc., PVC had initial stage and long-term thermal stability energy preferably, show effect preferably aspect materials processing and the mechanical property, and asepsis environment-protecting, can be applicable to the aspects such as machine-shaping of PVC plumbing tubing.Solved the problem that domestic and international each stabilizer for plastics manufacturer presses for solution; Have advantages such as economic environmental protection, superior performance and technology are simple when turning waste into wealth concurrently, therefore developing this series products has extensive market prospects and favorable social and economic benefits.
2. lanolin fatty acid rare earth metal soap class stablizer of the present invention, adopting common and braid wool acid is one of raw material, raw material sources are wide, with low cost, the preparation method is scientific and reasonable, and is workable, compares with product performance with the reparation technology of wool grease rare earth, the compound soap of the synthetic a plurality of metallic soaps of single stage method is adopted in the preparation of lanolin fatty acid rare earth compound soap, and shorter and performance compound soap consuming time can be better than single wool grease rare earth soap.
3. product of the present invention is nontoxic, environmental protection and have lubricity concurrently, lanolin fatty acid is used for fields such as makeup and leather more, be the mixing acid of multiple fatty acid monomer, the nontoxic and Hydrolyzed Protein lubricity of lanolin fatty acid itself is described, the thermo-stabilizer of using it for PVC still belongs to the first time.
Embodiment
According to the quality proportioning of common and braid wool acid and sodium hydroxide is that 5.3～8: 1 amount takes by weighing raw material; The principle of reaction is RCOOH+NaOH → RCOONa+H
2O, wherein RCOOH is a lanolin fatty acid.
1) is that 75～78 ℃ of volumetric concentrations are in 80～90% the aqueous ethanolic solution with dissolution of sodium hydroxide in temperature, starts and stir and condensation reflux unit;
2) in the acid of 60～80 ℃ of following fusion common and braid wools, then common and braid wool acid 10～25g is joined gradually in the above-mentioned sodium hydroxide ethanolic soln that is in whipped state, stir saponification reaction 1.5～2h down at 75～78 ℃;
3) pH that adjusts reaction solution while hot is 7.0～9.0, be cooled to 50～60 ℃ then, add temperature in turn and be warm water 30～60ml of 50～60 ℃, rare earth chloride salts solution 10～30ml, calcium salt 1.5～2.5g or barium salt 3.4～5.2g and zinc salt 2.0～7.0g, reaction 0.5～2h after product is washed 3～4 times, washing 3～4 times through suction filtration, alcohol, 60～80 ℃ down oven dry be finished product after grinding.
The concentration of described rare earth chloride salts solution is 0.3～1mol/L, and described rare earth element is any in scandium Sc, yttrium Y and lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm or the europium Eu rare earth element muriate.
Described calcium salt is a calcium chloride, and described barium salt is the bariumchloride with two crystal water, and described zinc salt is a Zinc Sulphate Heptahydrate; The quality proportioning of described calcium chloride and Zinc Sulphate Heptahydrate is 1: 1～5, and the quality proportioning of bariumchloride and Zinc Sulphate Heptahydrate is 1～5: 2.
Wherein the rare earth chloride salts solution is generated by rare earth oxide and hydrochloric acid reaction, and the quality proportioning of rare earth oxide and Zinc Sulphate Heptahydrate is 1: 1～7:
The principle of reaction is: La
2O
3+ 6HCl → 2LaCl
3+ 3H
2O
3RCOONa+LaCl
3→(RCOO)
3La+3NaCl；
2RCOONa+CaCl
2→(RCOO)
2Ca+2NaCl
Or 2RCOONa+BaCl
2→ (RCOO)
2Ba+2NaCl;
2RCOONa+ZnSO
4→ (RCOO)
2Zn+2NaCl, wherein RCOO-is the wool acid group.
Below be 2 specific embodiments of the present invention, further set forth the present invention, but the present invention be not limited only to this
Embodiment 1
The preparation of lanolin fatty acid rare earth calcium zinc composite thermal stabilizer
1. the saponification reaction of lanolin fatty acid: take by weighing the sodium hydroxide of 2～4g, under 75～78 ℃, it is dissolved in volumetric concentration then and is in 80～90% the aqueous ethanolic solution, then while stirring to the fusion common and braid wool acid that wherein adds 10～25g, stirring reaction 1.5～2h.
2. the preparation of rare earth chloride salts solution: the RE that takes by weighing about 0.005～0.010mol
2O
3, adding concentration then is hydrochloric acid soln 2～5ml of 0.015～0.03mol/L, the dissolving of limit heating edge, and after waiting to clarify, dilution is settled to 10～30ml.
3. the replacement(metathesis)reaction of lanolin fatty acid soda soap: the pH that adjusts saponification liquor while hot is 7.0～9.0, is cooled to 60 ℃ then, adds 60～70 ℃ warm water, treat that saponification liquor stirs after, to the RECl that wherein adds step 10～30ml 2.
3The CaCl of solution, 1.5-2.5g
2ZnSO with 2.0-7.0g
47H
2O, with the product suction filtration, alcohol is washed 3-4 time then, washes 3-4 time behind the reaction 1-1.5h, after 60-80 ℃ of oven dry, grinding gets product.
Embodiment 2
The preparation of lanolin fatty acid rare earth barium zinc heat stabilizer
1. the saponification reaction of lanolin fatty acid takes by weighing the sodium hydroxide of 2-4g, it is dissolved in volumetric concentration then under 75～78 ℃ and is in 80～90% the aqueous ethanolic solution, then while stirring to the fusion common and braid wool acid that wherein adds 10-25g, stirring reaction 1.5-2h.
2. the preparation of rare earth chloride salts solution: the RE that takes by weighing about 0.005～0.010mol
2O
3, adding concentration then is hydrochloric acid soln 2～5ml of 0.015～0.03mol/L, the dissolving of limit heating edge, and after waiting to clarify, dilution is settled to 10～30ml.
3. the pH that adjusts saponification liquor while hot is 7.0～9.0, is cooled to 60 ℃ then, adds 60～70 ℃ warm water, treat that saponification liquor stirs after, to the RECl that wherein add to add step 10～30ml 2.
3The BaCl of solution, 3.4-5.2g
22H
2The ZnSO of O and 2.0-7.0g
47H
2O, with the product suction filtration, alcohol is washed 3-4 time then, washes 3-4 time behind reaction 1～1.5h, after 60-80 ℃ of oven dry, grinding gets product.
The thermal stability test comparison of this product and other thermo-stabilizers
Experimental result is as follows:
Table 1: the experiment test result of product of the present invention and several thermo-stabilizers relatively
| Thermo-stabilizer (content in PVC is 3%) | Congo red experiment static heat steady time/min | The duplex roller is tested dynamic heat-stable time/min |
| The lanolin fatty acid Ca-Zn composite heat stabilizer | 14.8 | 39 |
| Lanolin fatty acid lanthanum Ca-Zn composite heat stabilizer | 22.7 | 40 |
| Dustless complex lead salt | 42.7 | 50 |
| Stearic acid lanthanum Ca-Zn composite heat stabilizer | 14.9 | 38 |
Data as can be seen from table, dustless complex lead salt has all shown stabilising effect preferably in static and dynamic thermally-stabilised experiment, the stabilising effect of lanolin fatty acid lanthanum Ca-Zn composite heat stabilizer obviously is better than stearic acid lanthanum Ca-Zn composite heat stabilizer and lanolin fatty acid Ca-Zn composite heat stabilizer in the static test; Above-mentioned three's steady time is approaching in the dynamic test, find in the experiment, it no matter is glutinous roller molding effect, lubricity or stabilising effect from the sample variation that comprises initial stage and time steady in a long-term and color sample etc., on the whole, the stabilising effect of lanolin fatty acid lanthanum Ca-Zn composite heat stabilizer all is better than other both, and it is with low cost, the compound soap of a plurality of metallic soaps of the simple and disposable production of preparation technology, asepsis environment-protecting will be so this product will produce the enormous industrialization benefit if drop into to use.
Claims (3)
1. PVC rare earth complex heat stabilizer, it is characterized in that: described PVC rare earth complex heat stabilizer is a lanolin fatty acid rare earth metal soap class stablizer, adopting common and braid wool acid is one of raw material, the chemical general formula of described lanolin fatty acid rare earth metal soap class stablizer is: xREyCazZn (OOCR) n or x ' REy ' Baz ' Zn (OOCR) n '. wherein, x, y, z, n, x ', y ', z ', n ' are respectively the stoichiometric number of metallic element and wool acid group, and x=x '=1, y=y '=1～3, z=z '=1～1.5, n=n '=3～12; RE is any element in scandium Sc, yttrium Y, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm or the europium Eu rare earth element.
2. a PVC as claimed in claim 1 is with the preparation method of rare earth complex heat stabilizer, it is characterized in that: quality proportioning sour according to common and braid wool and sodium hydroxide is 5.3～8: 1 amount, is that 75～78 ℃ of volumetric concentrations are in 80～90% the aqueous ethanolic solution with dissolution of sodium hydroxide in temperature, starts and stirs and condensation reflux unit; In the acid of 60～80 ℃ of following fusion common and braid wools, then common and braid wool acid 10～25g is joined gradually in the above-mentioned sodium hydroxide ethanolic soln that is in whipped state, stir saponification reaction 1.5～2h down at 75～78 ℃; The pH that adjusts reaction solution while hot is 7.0～9.0, be cooled to 50～60 ℃ then, add temperature in turn and be warm water 30～60ml of 50～60 ℃, rare earth chloride salts solution 10～30ml, calcium salt 1.5～2.5g or barium salt 3.4～5.2g and zinc salt 2.0～7.0g, reaction 0.5～2h after product is washed 3～4 times, washing 3～4 times through suction filtration, alcohol, 60～80 ℃ down oven dry be finished product after grinding; The concentration of described rare earth chloride salts solution is 0.3～1mol/L; Described calcium salt is a calcium chloride, and described barium salt is the bariumchloride with two crystal water, and described zinc salt is a Zinc Sulphate Heptahydrate.
3. the PVC according to claim 2 preparation method of rare earth complex heat stabilizer, it is characterized in that: the quality proportioning of described calcium chloride and Zinc Sulphate Heptahydrate is 1: 1～5, the quality proportioning of bariumchloride and Zinc Sulphate Heptahydrate is 1～5: 2.
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| CN2008100712049A CN101289550B (en) | 2008-06-13 | 2008-06-13 | Rare earth complex heat stabilizer for PVC and method for preparing same |
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| CN2008100712049A CN101289550B (en) | 2008-06-13 | 2008-06-13 | Rare earth complex heat stabilizer for PVC and method for preparing same |
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| CN101289550B true CN101289550B (en) | 2010-12-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104893184B (en) * | 2015-06-27 | 2016-08-17 | 邵阳学院 | A kind of zinc-containing hydroxyapatite base PVC composite heat stabilizer and application |
| CN107793674B (en) * | 2017-11-10 | 2020-10-30 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC and preparation method thereof |
| CN109535610A (en) * | 2018-12-19 | 2019-03-29 | 南京清研新材料研究院有限公司 | A kind of chemicals processing technology can increase plastics stability and reaction kettle |
| CN110128738B (en) * | 2019-05-17 | 2023-05-26 | 浙江太湖远大新材料股份有限公司 | Tracking-resistant polyethylene sheath material |
| CN111533641A (en) * | 2020-05-16 | 2020-08-14 | 内蒙古联丰稀土化工研究院有限公司 | Preparation method of glycerin rare earth |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100362A (en) * | 1986-01-21 | 1987-08-05 | 中国人民解放军总后军械维修研究所 | From lanolin, produce lanolin fatty acid two valency metallic soaps |
| CN1539939A (en) * | 2003-10-25 | 2004-10-27 | 福州大学 | Method for fabricating thermal stablilizer made from wool ester, rare earth in use for PVC |
-
2008
- 2008-06-13 CN CN2008100712049A patent/CN101289550B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100362A (en) * | 1986-01-21 | 1987-08-05 | 中国人民解放军总后军械维修研究所 | From lanolin, produce lanolin fatty acid two valency metallic soaps |
| CN1539939A (en) * | 2003-10-25 | 2004-10-27 | 福州大学 | Method for fabricating thermal stablilizer made from wool ester, rare earth in use for PVC |
Non-Patent Citations (1)
| Title |
|---|
| JP昭57-117598A 1982.07.22 |
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