CN112480564A - Environment-friendly PVC composite heat stabilizer - Google Patents
Environment-friendly PVC composite heat stabilizer Download PDFInfo
- Publication number
- CN112480564A CN112480564A CN202011315805.7A CN202011315805A CN112480564A CN 112480564 A CN112480564 A CN 112480564A CN 202011315805 A CN202011315805 A CN 202011315805A CN 112480564 A CN112480564 A CN 112480564A
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- China
- Prior art keywords
- bean dregs
- percent
- heat stabilizer
- composite heat
- modified
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims abstract description 48
- 244000046052 Phaseolus vulgaris Species 0.000 claims abstract description 48
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 6
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 claims abstract description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004040 coloring Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an environment-friendly PVC composite heat stabilizer which comprises the following components in parts by mass: modified bean dregs: 30-40%; zinc stearate: 30-40%; trishydroxyethyl isocyanurate: 10 to 15 percent; dipentaerythritol: 10 to 15 percent; calcium acetylacetonate: 3 to 7 percent; the modified bean dregs are prepared by oxidizing and alkali treating bean dregs. The composite heat stabilizer provided by the invention can obviously improve the heat stability of PVC, and has slight initial coloring and excellent long-term heat stability.
Description
Technical Field
The invention relates to a PVC heat stabilizer, in particular to an environment-friendly PVC composite heat stabilizer, belonging to the field of material processing aids.
Background
PVC is susceptible to decomposition at processing temperatures, resulting in darker products with altered structure and properties. Therefore, during the processing of PVC, heat stabilizers must be added to prevent or reduce its decomposition. Currently, commonly used heat stabilizers include lead salts, organotin compounds, metallic soaps, and complex heat stabilizers. Lead salt heat stabilizers were the earliest developed PVC heat stabilizers with good heat stability. However, lead salt compounds have strong toxicity and cause harm to human body and environmental safety, and the use of lead salt heat stabilizers is gradually limited in various countries in the world. The organic tin heat stabilizer has good thermal stability and transparency and low toxicity, is a PVC heat stabilizer with excellent comprehensive performance, but has high production cost, so that the application of the organic tin heat stabilizer is limited. Therefore, the development of the low-cost and high-performance environment-friendly PVC composite heat stabilizer to replace lead salt heat stabilizers and promote the lead-free property in the PVC industry has very important significance.
The bean dregs are main by-products in the bean product processing industry, and the yield of wet bean dregs reaches more than 2000 ten thousand tons every year. Because the fresh bean dregs have large water content and high protein content and are easy to decay and deteriorate, most of the bean dregs are directly discarded, so that the resource waste is caused and the environment is polluted. Although more researches on the reutilization of the bean dregs exist at present, most of the researches utilize the nutritive value of the bean dregs to produce food or extract beneficial components, the utilization amount is small, and the fundamental problem cannot be solved. The main components of the bean dregs comprise cellulose, protein and fat, and if the main components can be used as components of an environment-friendly PVC heat stabilizer, a feasible new method can be provided for large-scale resource utilization of the bean dregs.
Disclosure of Invention
The invention aims to provide an environment-friendly PVC composite heat stabilizer which takes modified bean dregs as a main component, has the advantages of no toxicity, environmental protection, good biocompatibility and low cost, and can obviously improve the heat stability in the PVC processing process.
In order to achieve the purpose, the invention adopts the technical scheme that an environment-friendly PVC composite heat stabilizer is provided, and comprises the following components in percentage by mass:
modified bean dregs: 30-40%;
zinc stearate: 30-40%;
trishydroxyethyl isocyanurate: 10 to 15 percent;
dipentaerythritol: 10 to 15 percent;
calcium acetylacetonate: 3 to 7 percent;
the modified bean dregs are prepared by oxidizing and alkali treating bean dregs.
The preparation process of the modified bean dregs comprises the following steps: dispersing bean dregs in water, adding hydrogen peroxide with the concentration of 25-50%, stirring and reacting for 0.5-2 hours, adding sodium hydroxide, and continuously stirring and reacting for 0.5-2 hours, wherein the mass ratio of hydrogen peroxide to bean dregs is 1-3: 1, the mass ratio of the sodium hydroxide to the bean dregs is 0.5-1.5: 1; and after the reaction is finished, centrifuging, drying and crushing to obtain the modified bean dregs.
The invention takes modified bean dregs as the main component of the PVC composite heat stabilizer. The bean dregs mainly comprise cellulose, protein and fat, and the modified bean dregs after oxidation treatment and alkali treatment contain a large amount of-COONa and-NH2and-OH groups. Modification of-COONa and-NH in Bean dregs2The group can absorb HCl released by PVC degradation and inhibit HCl from autocatalytic degradation of PVC, and the-OH group can react with Zn2+Coordinating and inhibiting 'zinc burning'. Through the above effects, the modified bean dregs have better thermal stability to PVC. The components have good synergistic effect, can obviously improve the thermal stability of PVC, and has slight initial coloring and excellent long-term thermal stability.
Detailed Description
The following provides a more detailed description of the present invention. The above and other objects, features and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the present invention.
The preferable preparation of the modified bean dregs comprises the following steps:
the modified bean dregs are prepared by oxidizing and alkali treating the bean dregs, and the preferable preparation process comprises the following steps: dispersing bean dregs in water, adding 27.5% hydrogen peroxide, stirring and reacting for 1.5 hours, adding sodium hydroxide, and continuously stirring and reacting for 1 hour, wherein the mass ratio of hydrogen peroxide to bean dregs is 1.5: 1, the mass ratio of the sodium hydroxide to the bean dregs is 0.8: 1; and after the reaction is finished, centrifuging, drying and crushing to obtain the modified bean dregs.
Example 1:
the composite heat stabilizer of the embodiment comprises the following components in percentage by mass: modified bean dregs: 35 percent; zinc stearate: 35 percent; trishydroxyethyl isocyanurate: 12 percent; dipentaerythritol: 13 percent; calcium acetylacetonate: 5 percent.
Example 2:
the composite heat stabilizer of the embodiment comprises the following components in percentage by mass: modified bean dregs: 40 percent; zinc stearate: 30 percent; trishydroxyethyl isocyanurate: 13 percent; dipentaerythritol: 10 percent; calcium acetylacetonate: 7 percent.
Example 3:
the composite heat stabilizer of the embodiment comprises the following components in percentage by mass: modified bean dregs: 30 percent; zinc stearate: 40 percent; trishydroxyethyl isocyanurate: 15 percent; dipentaerythritol: 12 percent; calcium acetylacetonate: 3 percent.
Test for thermal stability
The performance of the composite heat stabilizer is tested by a Harper RM-200A torque rheometer, and the test conditions are as follows: the material temperature is 190 ℃, the experimental load is 5 kg, and the rotating speed is 35 rpm. Test sample composition: 54 parts of PVC (SG-3 type) resin, 1.6 parts of composite heat stabilizer and 12 parts of CaCO35 parts of CPE, 1.6 parts of titanium dioxide, 0.2 part of pentaerythritol monostearate, 0.1 part of antioxidant 1010, 0.2 part of PE wax and 1 part of ACR. The test method comprises the following steps: and (3) mixing for 10 minutes in a torque rheometer, taking out a sample, testing initial whiteness by using a color difference meter, and additionally sampling to test dynamic thermal stability time. The test results are shown in Table 1.
Table 1: and (4) testing the thermal stability of the PVC sheet.
According to the results shown in Table 1, the environment-friendly PVC composite heat stabilizer taking the modified bean dregs as the main component can better inhibit the initial coloring of PVC, has good dynamic long-term thermal stability to PVC, and is a PVC composite heat stabilizer with excellent performance. In addition, the technical scheme provided by the invention also provides a feasible new method for resource utilization of the bean dregs, considering that the bean dregs are byproducts of the bean product processing industry.
It should be understood that although the present invention has been clearly illustrated by the foregoing examples, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.
Claims (2)
1. The environment-friendly PVC composite heat stabilizer is characterized by comprising the following components in percentage by mass:
modified bean dregs: 30-40%;
zinc stearate: 30-40%;
trishydroxyethyl isocyanurate: 10 to 15 percent;
dipentaerythritol: 10 to 15 percent;
calcium acetylacetonate: 3 to 7 percent;
the modified bean dregs are prepared by oxidizing and alkali treating bean dregs.
2. The composite heat stabilizer according to claim 1, wherein the modified bean dregs are prepared by the following steps: dispersing bean dregs in water, adding hydrogen peroxide with the concentration of 25-50%, stirring and reacting for 0.5-2 hours, adding sodium hydroxide, and continuously stirring and reacting for 0.5-2 hours, wherein the mass ratio of hydrogen peroxide to bean dregs is 1-3: 1, the mass ratio of the sodium hydroxide to the bean dregs is 0.5-1.5: 1; and after the reaction is finished, centrifuging, drying and crushing to obtain the modified bean dregs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011315805.7A CN112480564A (en) | 2020-11-22 | 2020-11-22 | Environment-friendly PVC composite heat stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011315805.7A CN112480564A (en) | 2020-11-22 | 2020-11-22 | Environment-friendly PVC composite heat stabilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112480564A true CN112480564A (en) | 2021-03-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011315805.7A Pending CN112480564A (en) | 2020-11-22 | 2020-11-22 | Environment-friendly PVC composite heat stabilizer |
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| CN (1) | CN112480564A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133751A (en) * | 2021-12-30 | 2022-03-04 | 湖南雄创新材料科技有限公司 | Preparation method of modified hydrotalcite-bean dreg heat stabilizer for PVC |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592682A (en) * | 2015-01-09 | 2015-05-06 | 芜湖航天特种电缆厂 | Flame-retardant PVC cable sleeve and preparation method thereof |
| CN106009379A (en) * | 2016-06-21 | 2016-10-12 | 肇庆市森德利化工实业有限公司 | Magnesium-aluminum-zinc environment-friendly stabilizer special for U-PVC calendered sheet |
| CN106977841A (en) * | 2017-03-28 | 2017-07-25 | 常州大学 | A kind of preparation method of PVC rare earth thermal stabilizers |
-
2020
- 2020-11-22 CN CN202011315805.7A patent/CN112480564A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592682A (en) * | 2015-01-09 | 2015-05-06 | 芜湖航天特种电缆厂 | Flame-retardant PVC cable sleeve and preparation method thereof |
| CN106009379A (en) * | 2016-06-21 | 2016-10-12 | 肇庆市森德利化工实业有限公司 | Magnesium-aluminum-zinc environment-friendly stabilizer special for U-PVC calendered sheet |
| CN106977841A (en) * | 2017-03-28 | 2017-07-25 | 常州大学 | A kind of preparation method of PVC rare earth thermal stabilizers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133751A (en) * | 2021-12-30 | 2022-03-04 | 湖南雄创新材料科技有限公司 | Preparation method of modified hydrotalcite-bean dreg heat stabilizer for PVC |
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Application publication date: 20210312 |