CN113651999A - Solid calcium-zinc composite heat stabilizer for PVC (polyvinyl chloride) - Google Patents
Solid calcium-zinc composite heat stabilizer for PVC (polyvinyl chloride) Download PDFInfo
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- CN113651999A CN113651999A CN202111026428.XA CN202111026428A CN113651999A CN 113651999 A CN113651999 A CN 113651999A CN 202111026428 A CN202111026428 A CN 202111026428A CN 113651999 A CN113651999 A CN 113651999A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
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- 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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Abstract
The invention discloses a solid calcium-zinc composite heat stabilizer for PVC, which particularly belongs to the technical field of PVC modification, and comprises the following components in percentage by weight: 15-35% of calcium monomer, 10-25% of zinc monomer, 5-20% of beta-diketone, 0-5% of polyol, 0-20% of organic nitrogen-containing compound, 5-45% of hydrotalcite, 0-10% of lubricant and 0-5% of antioxidant. The solid calcium-zinc composite heat stabilizer for PVC has the advantages of good initial coloring, high transparency and excellent long-term heat resistance.
Description
Technical Field
The invention belongs to the technical field of PVC modification, and particularly relates to a solid calcium-zinc composite heat stabilizer for PVC.
Background
Polyvinyl chloride (PVC) is a high molecular material obtained by vinyl chloride through addition polymerization reaction, and is one of five synthetic resins commonly used in the world. The flame-retardant and corrosion-resistant composite material has the advantages of light weight, easiness in processing, excellent mechanical property, good flame retardance, good corrosion resistance and the like, so that the flame-retardant and corrosion-resistant composite material is widely applied to the fields of building materials, industrial products, daily necessities, pipes, wires and cables, packaging films, aerospace and the like.
However, the conventional PVC has the following disadvantages in use: the thermal stability is poor, and when the temperature is heated to 100 ℃, the decomposition starts to release hydrogen chloride gas. The presence of hydrogen chloride gas can catalyze the decomposition of polyvinyl chloride, so that the polyvinyl chloride is converted into polyene containing unsaturated conjugated double bond structure, the color of the polyene becomes darker from transparent, and in addition, the polyene structure is easy to be further oxidized and decomposed. In addition, the poor thermal stability of polyvinyl chloride results in the decrease of physical and chemical properties of polyvinyl chloride products, thereby limiting the application of polyvinyl chloride.
Disclosure of Invention
The invention aims to provide a solid calcium-zinc composite heat stabilizer for PVC, which has the advantages of good initial coloring, high transparency and excellent long-term heat resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
the solid calcium-zinc composite heat stabilizer for PVC comprises the following components in percentage by weight: 15-35% of calcium monomer, 10-20% of zinc monomer, 5-20% of beta-diketone, 0-5% of polyol, 0-20% of organic nitrogen-containing compound, 5-45% of hydrotalcite, 0-10% of lubricant and 0-5% of antioxidant.
The calcium salt and the zinc salt are used as main stabilizers, the calcium salt has good absorption capacity on hydrogen chloride, the generated calcium chloride has no catalytic action, and the calcium salt is matched with hydrotalcite to be used, so that the long-term thermal stability is good. Meanwhile, the zinc salt can absorb hydrogen chloride and inhibit the decomposition of PVC carbon chains, the effect is quick, the initial coloring is good, but the generated zinc chloride can catalyze and accelerate the degradation of PVC, and the zinc burning phenomenon is caused. Therefore, by adding the beta-diketone, the polyol and the organic nitrogen-containing compound as auxiliary heat stabilizers, the hydrogen chloride can be absorbed to play a role of a stabilizer, and the phenomenon of 'zinc burning' caused by adding the zinc salt can be effectively prevented.
Preferably, the solid calcium-zinc composite heat stabilizer for PVC comprises the following components in percentage by weight: 20-45% of calcium monomer, 10-20% of zinc monomer, 10-16% of beta-diketone, 0-3% of polyol, 5-20% of organic nitrogen-containing compound, 15-35% of hydrotalcite, 0-8% of lubricant and 0-3% of antioxidant.
Preferably, the solid calcium-zinc composite heat stabilizer for PVC comprises the following components in percentage by weight: 26% of calcium monomer, 10% of zinc monomer, 13% of beta-diketone, 1% of polyol, 15% of organic nitrogen-containing compound, 33% of hydrotalcite, 1% of lubricant and 1% of antioxidant.
Preferably, the calcium monomer is selected from any one of calcium stearate and calcium acetylacetonate, or a mixture thereof.
Preferably, the calcium monomer is selected from a mixture of calcium stearate and calcium acetylacetonate, and the mixing ratio of the calcium stearate to the calcium acetylacetonate is 0-1: 1.
Preferably, the zinc monomer is selected from any one of zinc stearate and zinc acetylacetonate, or a mixture thereof.
Preferably, the zinc monomer is selected from a mixture of zinc stearate and zinc acetylacetonate, and the mixing ratio of the zinc stearate to the zinc acetylacetonate is 0-1: 1.
Preferably, the beta-diketone is selected from any one of stearoylbenzoylmethane, dibenzoylmethane, isovalerylbenzoylmethane, octanoylbenzoylmethane, or a mixture thereof.
Preferably, the polyol is selected from any one of pentaerythritol monostearate, tris (hydroxymethyl) aminomethane, tris (. alpha. -hydroxyethyl) isocyanurate, aluminum pentaerythritol, or a mixture thereof.
Preferably, the organic nitrogen-containing compound is any one selected from 1, 3-dimethyl-6-semicarbazide pyrimidine, barbituric acid, diphenylthiourea, melamine and triglycidyl isocyanurate, or a mixture thereof.
Preferably, the lubricant is selected from any one of glyceryl monostearate and ethylene bis stearamide, or a mixture thereof.
Preferably, the antioxidant is any one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and dilauryl thiodipropionate, or a mixture thereof.
Compared with the prior art, the invention has the beneficial effects that:
the main stabilizer and the auxiliary heat stabilizer have good synergistic effect, so that the obtained calcium-zinc composite heat stabilizer has good initial coloring, excellent transparency and long-term heat resistance, simple production process and low cost, and has good application prospect in the field of PVC transparent products with high environmental protection requirements.
Drawings
FIG. 1 is a schematic flow chart of the time from plasticization to decomposition of PVC according to the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
26g of calcium stearate, 10g of zinc stearate, 13g of dibenzoylmethane, 1g of tris (. alpha. -hydroxyethyl) isocyanurate, 15g of triglycidyl isocyanurate, 33g of hydrotalcite, 1g of ethylenebisstearamide and 1g of pentaerythritol tetrakis (. beta. - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) were stirred and mixed at room temperature.
Example 2
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
13g of calcium stearate, 13g of calcium acetylacetonate, 5g of zinc stearate, 5g of zinc acetylacetonate, 13g of dibenzoylmethane, 1g of tris (. alpha. -hydroxyethyl) isocyanurate, 15g of triglycidyl isocyanurate, 33g of hydrotalcite, 1g of ethylenebisstearamide and 1g of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester were stirred and mixed uniformly at room temperature.
Example 3
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
26g of calcium acetylacetonate, 10g of zinc acetylacetonate, 13g of dibenzoylmethane, 1g of tris (. alpha. -hydroxyethyl) isocyanurate, 15g of triglycidyl isocyanurate, 33g of hydrotalcite, 1g of ethylenebisstearamide and 1g of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] were mixed by stirring at room temperature.
Example 4
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
26g of calcium stearate, 10g of zinc stearate, 6g of dibenzoylmethane, 7g of stearoylbenzoylmethane, 1g of tris (. alpha. -hydroxyethyl) isocyanurate, 15g of triglycidyl isocyanurate, 33g of hydrotalcite, 1g of ethylenebisstearamide and 1g of pentaerythritol tetrakis (. beta. - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) were stirred and mixed at room temperature.
Example 5
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
26g of calcium stearate, 13g of zinc stearate, 16g of dibenzoylmethane, 11g of glycerol monostearate, 33g of hydrotalcite and 1g of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] were stirred and mixed uniformly at room temperature.
Example 6
A preparation method of the solid calcium-zinc composite heat stabilizer for PVC comprises the following steps:
33g of calcium stearate, 10g of zinc stearate, 13g of dibenzoylmethane, 1g of tris (. alpha. -hydroxyethyl) isocyanurate, 15g of triglycidyl isocyanurate, 26g of hydrotalcite, 1g of ethylenebisstearamide and 1g of pentaerythritol tetrakis (. beta. - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate were stirred and mixed at room temperature.
The comparison result of the solid calcium-zinc heat stability obtained by the formula of the above case and the heat stability time of the commercial calcium-zinc heat stabilizer 600A is as follows:
test example 1:
100g of PVC resin and 0.8g of the prepared calcium-zinc composite heat stabilizer are uniformly mixed, mixed on an open plasticator, the temperature is 195 +/-2 ℃, the rotor speed is 40r/min, the time from plasticizing to decomposing of the PVC is recorded, and the result shows that the mixing time is as long as 20 minutes.
Claims (10)
1. The solid calcium-zinc composite heat stabilizer for PVC is characterized by comprising the following components in percentage by weight: 15-35% of calcium monomer, 10-25% of zinc monomer, 5-20% of beta-diketone, 0-5% of polyol, 0-20% of organic nitrogen-containing compound, 5-45% of hydrotalcite, 0-10% of lubricant and 0-5% of antioxidant.
2. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, which comprises the following components in percentage by weight: 20-45% of calcium monomer, 10-16% of zinc monomer, 10-20% of beta-diketone, 0-3% of polyol, 5-20% of organic nitrogen-containing compound, 15-35% of hydrotalcite, 0-8% of lubricant and 0-3% of antioxidant.
3. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, which comprises the following components in percentage by weight: 26% of calcium monomer, 10% of zinc monomer, 13% of beta-diketone, 1% of polyol, 15% of organic nitrogen-containing compound, 33% of hydrotalcite, 1% of lubricant and 1% of antioxidant.
4. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, wherein the calcium monomer is selected from any one of calcium stearate and calcium acetylacetonate, or a mixture thereof.
5. The solid calcium-zinc composite heat stabilizer for PVC according to claim 4, wherein the calcium monomer is selected from a mixture of calcium stearate and calcium acetylacetonate, and the mixing ratio of the calcium stearate to the calcium acetylacetonate is 0-1: 1.
6. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, wherein the zinc monomer is selected from any one of zinc stearate and zinc acetylacetonate, or a mixture thereof.
7. The solid calcium-zinc composite heat stabilizer for PVC according to claim 6, wherein the zinc monomer is selected from a mixture of zinc stearate and zinc acetylacetonate, and the mixing ratio of the zinc stearate to the zinc acetylacetonate is 0-1: 1.
8. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, wherein the beta-diketone is selected from any one of stearoylbenzoylmethane, dibenzoylmethane, isovalerylbenzoylmethane, octanoylbenzoylmethane, or a mixture thereof.
9. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, wherein the polyol is selected from any one of pentaerythritol monostearate, tris (α -hydroxyethyl) isocyanurate, aluminum pentaerythritol, or a mixture thereof.
10. The solid calcium-zinc composite heat stabilizer for PVC according to claim 1, wherein the organic nitrogen-containing compound is selected from any one of 1, 3-dimethyl-6-semicarbazide pyrimidine, barbituric acid, diphenylthiourea, melamine and triglycidyl isocyanurate, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111026428.XA CN113651999A (en) | 2021-09-02 | 2021-09-02 | Solid calcium-zinc composite heat stabilizer for PVC (polyvinyl chloride) |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111026428.XA CN113651999A (en) | 2021-09-02 | 2021-09-02 | Solid calcium-zinc composite heat stabilizer for PVC (polyvinyl chloride) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558163A (en) * | 2022-11-17 | 2023-01-03 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
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| CN101942110A (en) * | 2010-09-06 | 2011-01-12 | 芜湖海螺型材科技股份有限公司 | Zn-Ca compound stabilizer |
| CN101967253A (en) * | 2010-10-26 | 2011-02-09 | 湘乡市贝特尔塑胶有限公司 | Environmentally-friendly PVC calcium zinc composite stabilizer |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN109575481A (en) * | 2018-12-19 | 2019-04-05 | 嘉兴若天新材料科技有限公司 | A kind of PVC floor wearing layer Environment-friendlyheat heat stabilizer |
| CN110283375A (en) * | 2019-07-26 | 2019-09-27 | 内蒙古佳运通智能环保新材料有限公司 | A kind of anti-prodegradant of Ca Zn composite thermostabilization and its preparation method and application |
| CN110564075A (en) * | 2019-09-11 | 2019-12-13 | 佛山市东豹化工有限公司 | PVC environment-friendly calcium-zinc composite stabilizer and preparation method thereof |
-
2021
- 2021-09-02 CN CN202111026428.XA patent/CN113651999A/en active Pending
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| CN101942110A (en) * | 2010-09-06 | 2011-01-12 | 芜湖海螺型材科技股份有限公司 | Zn-Ca compound stabilizer |
| CN101967253A (en) * | 2010-10-26 | 2011-02-09 | 湘乡市贝特尔塑胶有限公司 | Environmentally-friendly PVC calcium zinc composite stabilizer |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN109575481A (en) * | 2018-12-19 | 2019-04-05 | 嘉兴若天新材料科技有限公司 | A kind of PVC floor wearing layer Environment-friendlyheat heat stabilizer |
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| CN110564075A (en) * | 2019-09-11 | 2019-12-13 | 佛山市东豹化工有限公司 | PVC environment-friendly calcium-zinc composite stabilizer and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558163A (en) * | 2022-11-17 | 2023-01-03 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
| CN115558163B (en) * | 2022-11-17 | 2023-03-24 | 山东东临新材料股份有限公司 | Preparation method of composite heat stabilizer containing tris (glycidyl) isocyanurate |
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