CN109836613B - Organic acid zinc alkanolamine compound and heat stabilizer application thereof - Google Patents
Organic acid zinc alkanolamine compound and heat stabilizer application thereof Download PDFInfo
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- CN109836613B CN109836613B CN201910057764.7A CN201910057764A CN109836613B CN 109836613 B CN109836613 B CN 109836613B CN 201910057764 A CN201910057764 A CN 201910057764A CN 109836613 B CN109836613 B CN 109836613B
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Abstract
The invention discloses an organic acid zinc alkanolamine compound and the application of a heat stabilizer thereof, wherein alkanolamine and organic acid zinc salt are reacted in an aqueous medium according to the molar ratio of 1-2:1, so as to obtain the organic acid zinc alkanolamine compound, and a catalyst can be added if necessary; the product obtained by the reaction has good thermal stability, and the problem of zinc burning is solved to a certain extent or completely, so that the cost of the existing calcium-zinc stabilizer is reduced, and the product is popularized and applied more widely.
Description
Technical Field
The invention relates to the technical field of chlorine-containing polymeric materials, in particular to an organic acid zinc alkanolamine compound and application of a heat stabilizer thereof.
Background
Chlorine-containing polymers, such as polyvinyl chloride (PVC), copolymers of vinyl chloride and vinyl acetate, and poly (1, 1-dichloroethylene), and the like, are commonly used in the manufacture of many articles such as pipes, window profiles, baffles, bottles, wall coverings, and packaging films. Many attempts have been made to improve the color retention of polymer resins, particularly during processing, such as during initial processing and during any subsequent reprocessing, by adding stabilizers to the chlorine-containing polymers. Most stabilizer compositions in use today contain metals such as tin, barium, cadmium and even lead. While these stabilizer compositions are effective in reducing discoloration during initial processing as well as any subsequent reprocessing, there is increasing interest in developing stabilizers that do not contain tin, barium, cadmium, and/or lead for environmental and other reasons.
In China, the development and popularization of calcium-zinc heat stabilizers are vigorously carried out. Combinations of zinc and calcium carboxylates have been used as stabilizers, however most use alone or in combination as chlorine-containing polymer stabilizers results in rapid degradation or "zinc burn" of the zinc compound after a short period of good color. In order to obtain acceptable stability performance from the zinc-calcium combination, many additives or co-stabilizers must be used, thereby increasing the cost of the stabilizer system. Therefore, it is urgently required to find a new heat stabilizer.
Disclosure of Invention
In order to solve the technical problems, the invention provides an organic acid zinc alkanolamine compound and application of a heat stabilizer thereof, wherein the organic acid zinc alkanolamine compound has good heat stability and certain zinc burning resistance.
The technical scheme is as follows: the organic acid zinc alkanolamine complex is characterized by being prepared in the following way: reacting an alkanolamine with an organic acid zinc salt in an aqueous medium in a molar ratio of 1-2:1 to obtain an organic acid zinc alkanolamine complex, the alkanolamine having the general structural formula:
wherein R is methyl, ethyl or hydroxymethyl.
The reaction product obtained by adopting the technical scheme can be directly used as a stabilizing agent without purification by removing water through reduced pressure distillation and/or removing water through simple separation, so the product is called as a 'compound', meanwhile, the reactant alkanolamines can be two or more, the obtained product is not a single substance, and the 'compound' obtained by the method has good thermal stability and good zinc burning resistance.
As further preferred:
the reaction is carried out at 70-80 deg.C, and the pH of the reaction system is less than or equal to 7.
And a catalyst can be added into the reaction system, wherein the catalyst is sulfuric acid, nitric acid, hydrochloric acid or acetic acid, and the dosage of the catalyst is 0.1-2% of the mass of the zinc salt of the organic acid. The catalyst to be added may be 0.1%, 0.3%, 0.5%, 1%, 2%, or the like.
The zinc salt of organic acid is zinc acetate, zinc propionate, zinc lactate, zinc benzoate, zinc 6-acetamido hexanoate, zinc gluconate or zinc citrate.
The alkanolamine is 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol or trihydroxymethylaminomethane.
The alkanolamine is trihydroxymethylaminomethane.
The heat stabilizer application of the organic acid zinc alkanolamine compound is characterized in that: the organic acid zinc alkanolamine compound prepared in the step of adding the organic acid zinc alkanolamine compound as a heat stabilizer in the process of processing the chlorine-containing polymer. After the organic acid zinc alkanolamine complex prepared by the invention is added, the chlorine-containing polymer has better thermal stability and zinc burning resistance.
The key point of the preparation method of the organic acid zinc alkanolamine compound is that the organic acid zinc alkanolamine compound is obtained by the preparation method and controlling the temperature of a reaction system to be 70-80 ℃ and the pH value to be less than or equal to 7.
Has the advantages that: the reaction process is carried out at a lower temperature, no three wastes are released in the reaction process, and the distilled water of the product after the reaction or the water liquid separated by simple separation can be recycled, so that the advantage of the preparation process of the organic acid zinc alkanolamine compound is reflected; the product obtained by the reaction has good thermal stability, and the problem of zinc burning is solved to a certain extent or completely, so that the cost of the existing calcium-zinc stabilizer is reduced, and the product is popularized and applied more widely.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of organic acid zinc alkanolamine compound
Alkanolamines useful in the practice of this invention have the general structure:
including 2-amino-2-methyl-1, 3-propanediol (AMPD), 2-amino-2-ethyl-1, 3-propanediol (AEPD), and trihydroxymethyl aminomethane (THAM), which are commercially available in conventional commercial grades suitable for use in the practice of the present invention. It can also be prepared conventionally by condensation of nitroalkanes with aldehydes, followed by a reduction treatment.
The (I) used in the present invention has good solubility in both water and ethanol: trihydroxymethyl aminomethane powder with a solubility of 500g/L in water and 22g/L in 95% ethanol at 25 ℃; 2-amino-2-methyl-1, 3-propanediol crystal powder, the solubility of which in water is 2500g/L at 20 ℃, is dissolved in ethanol; the 2-amino-2-ethyl-1, 3-propanediol is a pale yellow viscous liquid which is easily dissolved in water and ethanol.
The invention (I) is alkaline when dissolved in water and ethanol: 0.1mol of THAM aqueous solution with the pH value of 10.4; 0.1mol of AMPD aqueous solution, the pH value is 10.8; 0.1mol of AEPD in water at a pH of 10.8. The good solubility is beneficial to the reaction and the alkali reaction control and end point judgment after the dissolution.
Zinc carboxylates are known as components of calcium zinc stabilizers to thermally stabilize chlorine-containing polymers against thermal degradation. Practice has shown that most of the zinc carboxylates used alone or in combination as stabilizers for chlorine-containing polymers lead to zinc compounds which degrade or "burn" rapidly after a very short good color or do not show sufficient stability to the chlorine-containing polymer. Among the organic acid zinc salts used in the present invention, water-soluble ones are: zinc acetate (30 g/100 at 20 ℃ and also soluble in alcohol), zinc lactate (soluble in water and slightly soluble in ethanol), zinc benzoate (needle-like crystal soluble in water and ethanol), zinc 6-acetamido hexanoate (soluble in boiling water and slightly soluble in cold water), and zinc gluconate (soluble in hot water); slightly soluble in water are: zinc citrate, and the like. These compounds are commercially available and are of conventional commercial grade suitable for use in the practice of the present invention, although the zinc salts of organic acids used in the present invention are not limited to those mentioned above and include other zinc salts of organic acids which are soluble in hot or cold water or sparingly soluble in water and have boiling points and decomposition temperatures greater than the processing temperature of the chlorine-containing polymer, which temperature generally does not exceed 250 ℃, and the basic properties of the resulting complex of these zinc salts of organic acids reacted with alkanolamine do not differ significantly from the product properties of the aforementioned zinc salts of organic acids.
Example 1, acetic acid (THAM)2Preparation of zinc complex (1):
tris (hydroxymethyl) aminomethane is supplied by Suzhou subfamily science and technology Co., Ltd and Shandong Ying Lang chemical Co., Ltd; the rest raw materials are purchased from the market and are in chemical pure grade. The mass g of the reaction raw materials is 100 percent of the content.
Dissolving 12.0g (0.1mol) of THAM in 30ml of distilled water at normal temperature or slightly under heating while stirring to obtain a transparent pale yellow solution, and filling the solution into a dropping funnel for later use;
in a 250ml three-necked round-bottomed flask, 9.2g (0.05mol) of zinc acetate was dissolved in 120ml of water with stirring under heating to give a colorless transparent solution. Heating to 75 ℃, dropwise adding the prepared THAM aqueous solution, keeping the temperature at 70-80 ℃ in the dropwise adding process, and keeping the pH value less than or equal to 7; after the dropwise addition (about 30min), the temperature is reduced to 50 ℃ after keeping for 2 hours, and the water is removed by vacuum pumping to obtain a transparent colloid, namely acetic acid (THAM)2A zinc complex (1).
Example 2, zinc acetate (THAM) complex (2) preparation:
operating as in example 1, but replacing 0.05mol of zinc acetate by 0.1mol of zinc acetate, a white wet solid, namely zinc acetate (THAM) complex (2), was obtained.
Example 3 gluconic acid (THAM)2Preparation of zinc complex (3):
operating as in example 1, but replacing 9.2g (0.05mol) of zinc acetate with 22.8g (0.05mol) of zinc gluconate, a pale yellow colloid, gluconic acid (THAM), is obtained2A zinc complex (3).
Example 4, preparation of zinc gluconate (THAM) complex (4):
operating as in example 1, but replacing 0.1mol of THAM by 0.05mol of THAM, a yellowish colloid, namely zinc gluconate (THAM) complex (4), was obtained.
Example 5 citric acid (THAM)2Preparation of zinc complex (5):
dissolving 12.0g (0.1mol) of THAM in 30ml of distilled water at normal temperature or slightly under stirring to obtain a transparent pale yellow solution, and filling the solution into a dropping funnel for later use;
adding 28.8g (0.05mol) of zinc citrate and 0.14g of nitric acid (0.5% by mass of zinc citrate) as a catalyst into 120ml of water in a 250ml three-necked round-bottomed flask, heating to 70 ℃ with stirring, and acidifying for 2 hr; dropwise adding the prepared THAM aqueous solution, wherein the temperature is kept at 70-80 ℃ in the dropwise adding process, and the PH is kept to be less than or equal to 7; after the dropwise addition (about 3hr), the solution is keptMaintaining for more than 2hr, cooling to 50 deg.C, and vacuum-pumping to remove water to obtain white solid citric acid (THAM)2A zinc complex (5).
The catalyst nitric acid in the preparation process can be replaced by sulfuric acid, hydrochloric acid or acetic acid, and the like, and the added catalyst can be any numerical value between 0.1 and 2 percent of the mass of the zinc salt of the organic acid, so that the normal operation of the reaction is not influenced.
Example 6, citric acid (THAM) zinc complex (6) preparation:
operating as in example 5, but replacing 0.1mol of THAM by 0.05mol of THAM, a white solid zinc citrate (THAM) complex (6) was obtained.
Other examples, with reference to the procedure of example 1 and the corresponding parameters, acetic Acid (AEPD) was prepared2Zinc complex, lactic Acid (AEPD)2Zinc complex, gluconic Acid (AEPD)2Zinc complex, acetic Acid (AMPD)2Zinc complex and citric Acid (AEPD)2A zinc complex; referring to example 2 procedures and corresponding parameters, zinc Acetate (AEPD) complex, zinc lactate (AEPD) complex, zinc gluconate (AEPD) complex, zinc Acetate (AMPD) complex, zinc gluconate (AEPD) complex, and zinc citrate (AEPD) complex were prepared.
Second, thermal stability experiment and anti-zinc burning experiment
(1) The thermal stability test uses the following test materials and equipment:
a rheometer: model XSS-300 Torque rheometer, manufactured by Shanghai scientific rubber and plastic machinery, Inc.; parameters are as follows: torque 35rpm, temperature 180 ℃ and time 5 min.
Testing equipment: model NS800 colorimeter, manufactured by 3NH technologies ltd.
The formula of the base material is shown in table 1, the organic acid zinc alkanolamine prepared in the embodiment of the invention is added into the base material to be used as a stabilizer to prepare a mixture for testing, THAM, AEPD, AMPD, zinc acetate, zinc lactate, zinc gluconate and zinc citrate are respectively added into the base material to be used as stabilizers to prepare a mixture for comparison, and the formula of the mixture is shown in table 2:
TABLE 1 base material formulation
| Name of material | Quantity (weight meter) |
| PVC-SG5(K value) | 100 portions of |
| CaCO3 | 20 portions of |
| Rutile titanium dioxide | 1.5 parts of |
| CPE 135 | 4.5 parts of |
TABLE 2 blend formula
| Name of material | Weight (g) |
| Base material | 68 |
| Lubricant (PE wax) | 1 |
| Stabilizer | 1 |
| Total of | 70 |
The testing steps are as follows: and uniformly mixing the materials according to the formula of the mixture, adding the mixture when a rheometer is stabilized at 180 ℃ and the torque is 35rpm, performing rheological operation for 5min, taking out a sample, and flattening to obtain a sample sheet to be tested.
The test judgment method comprises the following steps: the sample pieces were tested three times with a color tester to obtain the average b value for each sample piece. The larger the value of b, the worse the thermal stability; the smaller the b value, the better the thermal stability, and the test results are shown in table 3:
TABLE 3 thermal stability test results
| Serial number | Stabilizers added to the sample pieces | Corresponding to the b value of the sample piece |
| 1 | THAM | 9.79 |
| 2 | AEPD | 19.76 |
| 3 | AMPD | 19.87 |
| 4 | Zinc acetate | 15.10 |
| 5 | Zinc acetate (THAM) complexes | 10.70 |
| 6 | Acetic acid (THAM)2Zinc complexes | 9.07 |
| 7 | Zinc Acetate (AEPD) complexes | 12.21 |
| 8 | Acetic Acid (AEPD)2Zinc complexes | 10.90 |
| 9 | Zinc Acetate (AMPD) complexes | 12.58 |
| 10 | Acetic Acid (AMPD)2Zinc complexes | 11.13 |
| 11 | Zinc lactate | 15.85 |
| 12 | Lactic Acid (AEPD) zinc complexes | 11.62 |
| 13 | Lactic Acid (AEPD)2Zinc complexes | 13.23 |
| 14 | Zinc gluconate | 20.26 |
| 15 | Zinc gluconate (THAM) complexes | 15.06 |
| 16 | Gluconic acid (THAM)2Zinc complexes | 13.31 |
Table 3 continues:
| serial number | Stabilizers added to the sample pieces | Corresponding to the b value of the sample piece |
| 17 | Zinc gluconate (AEPD) complexes | 15.28 |
| 18 | Gluconic Acid (AEPD)2Zinc complexes | 13.79 |
| 19 | Zinc citrate | 18.58 |
| 20 | Zinc citrate (THAM) complexes | 13.20 |
| 21 | Citric acid (THAM)2Zinc complexes | 9.34 |
| 22 | Zinc citrate (AEPD) complexes | 14.36 |
| 23 | Citric Acid (AEPD)2Zinc complexes | 11.55 |
From the test result, AMPD, AEPD, THAM, zinc acetate, zinc lactate, zinc gluconate, zinc citrate and other raw materials have certain thermal stability; (ii) the thermal stability of THAM > AEPD > AMPD in the feedstock; the thermal stability of the product organic acid zinc alkanolamine complex is better than that of the reaction raw material, and the thermal stability of the product organic acid zinc alkanolamine complex is increased along with the increase of alkanolamine in the raw material; in the product organic acid zinc alkanolamine complex, along with the increase of the proportion of THAM and AEPD in the raw materials, the product organic acid zinc alkanolamine complex has better thermal stability; the reaction raw material is preferably THAM from the viewpoint of thermal stability of the product.
(2) In the anti-zinc burning experiment, THAM is similar to AMPD and AEPD in structure and property, and products have similarity, only THAM is selected to illustrate the anti-zinc burning performance of the products, and the anti-zinc burning performance of the products obtained by reacting AMPD and AEPD with organic acid zinc is similar to the products, so that the description is omitted.
The experimental materials and equipment used were as follows:
a rheometer: model XSS-300 Torque rheometer, manufactured by Shanghai scientific rubber and plastic machinery, Inc.; parameters are as follows: the torque was 35rpm, the temperature 180 ℃ and the time 3.5 min.
Testing equipment: model NS800 colorimeter, manufactured by 3NH technologies ltd.
The formula of the base material is shown in table 4, zinc acetylacetonate is simply added into the base material as a stabilizer (contrast), or a mixture of organic acid zinc alkanolamine and zinc acetylacetonate prepared in the embodiment of the invention is added into the base material as a stabilizer to prepare a mixture, and the formula of the mixture is shown in table 5:
TABLE 4 base material formulation
| Name of material | Quantity (weight meter) |
| PVC-SG5(K value) | 100 portions of |
| CaCO3 | 20 portions of |
| Rutile titanium dioxide | 1.5 parts of |
| CPE 135 | 4.5 parts of |
TABLE 5 blend formula
The testing steps are as follows: and uniformly mixing the materials according to the formula of the mixture, adding the mixture when a rheometer is stabilized at 180 ℃ and the torque is 35rpm, performing rheological operation for 3.5min, taking out a sample, and flattening to obtain a sample sheet to be tested.
The test judgment method comprises the following steps: the sample pieces were tested three times with a color tester to obtain the average L value for each sample piece. The larger the L value is, the better the zinc burning resistance is; the smaller the L value, the poorer the zinc burn resistance, and the test results are shown in Table 6 below:
TABLE 6 anti-Zinc burn test results
From the test results, the organic acid zinc alkanolamine complex prepared by the invention has certain zinc burning resistance, and the zinc burning resistance of the product organic acid zinc alkanolamine complex is increased along with the increase of the proportion of alkanolamine serving as a complexing agent in reaction raw materials.
In conclusion, after the organic acid zinc alkanolamine compound prepared by the invention is used in the processing of chlorine-containing polymers, the thermal stability and the zinc burning resistance of the chlorine-containing polymers can be effectively improved.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (6)
1. A preparation method of organic acid zinc alkanolamine compound comprises the following steps: characterized in that alkanolamine and organic acid zinc salt are reacted in an aqueous medium according to the molar ratio of 1-2:1, the reaction is carried out at 70-80 ℃, the pH of the reaction system is less than or equal to 7, and organic acid zinc-alkanolamine complex is obtained, wherein the alkanolamine has the following general structural formula:
wherein R is methyl, ethyl or hydroxymethyl.
2. A method of preparing a zinc alkanolamine complex of organic acids as claimed in claim 1, characterized in that: and a catalyst can be added into the reaction system, wherein the catalyst is sulfuric acid, nitric acid, hydrochloric acid or acetic acid, and the dosage of the catalyst is 0.1-2% of the mass of the zinc salt of the organic acid.
3. A method of preparing a zinc alkanolamine complex of organic acids as claimed in claim 2, characterized in that: the zinc salt of the organic acid is zinc acetate, zinc propionate, zinc lactate, zinc benzoate, zinc 6-acetamido hexanoate, zinc gluconate or zinc citrate.
4. A method of preparing a zinc alkanolamine complex of organic acids as claimed in claim 3, characterized in that: the alkanolamine is 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol or trishydroxymethylaminomethane.
5. A method of preparing a zinc alkanolamine complex of organic acids as claimed in claim 1, characterized in that: the alkanolamine is trihydroxymethyl aminomethane.
6. The use of the organic acid zinc alkanolamine compound as a heat stabilizer is characterized in that: adding the organic acid zinc alkanolamine complex obtained by the preparation method of any one of claims 1-5 into the chlorine-containing polymer processing process as a heat stabilizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61231041A (en) * | 1985-04-05 | 1986-10-15 | Akishima Kagaku Kogyo Kk | Method fro thermally stabilizing chlorine-containing resin composition |
| JP3816697B2 (en) * | 1999-07-07 | 2006-08-30 | 大日精化工業株式会社 | Functional agent bound with polymer, method for producing the same, method for using them, and article using the same |
| BR0215972A (en) * | 2002-12-19 | 2005-09-13 | Arch Chem Inc | Pyrithione biocides enhanced by zinc mental ions and organic amines |
| DE10318910A1 (en) * | 2003-04-26 | 2004-11-11 | Crompton Vinyl Additives Gmbh | Stabilizer system for stabilizing halogen-containing polymers |
| CN105086293B (en) * | 2015-09-23 | 2017-11-17 | 清华大学深圳研究生院 | A kind of polyvinyl-chloride use zinc-base heat stabilizer, composition and application |
| CN105482218B (en) * | 2015-12-07 | 2017-12-12 | 重庆太岳新材料科技有限公司 | A kind of composite thermal stabilizer production technology using cyanuric acid zinc calcium as matrix |
| CN105949508B (en) * | 2016-05-23 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | A kind of heat stabilizer for PVC and its preparation method and application |
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