CN113773552A - Dihydropyridine PVC composite heat stabilizer and preparation method thereof - Google Patents

Dihydropyridine PVC composite heat stabilizer and preparation method thereof Download PDF

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Publication number
CN113773552A
CN113773552A CN202111139735.9A CN202111139735A CN113773552A CN 113773552 A CN113773552 A CN 113773552A CN 202111139735 A CN202111139735 A CN 202111139735A CN 113773552 A CN113773552 A CN 113773552A
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dihydropyridine
heat stabilizer
composite heat
parts
molecular sieve
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唐守余
曹伟
李廷希
张海昌
李德刚
杨朝平
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SHANDONG HUIKE ADDITIVES CO Ltd
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SHANDONG HUIKE ADDITIVES CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432Six-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

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  • 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 belongs to the technical field of chemical synthesis, and particularly relates to a dihydropyridine PVC composite heat stabilizer and a preparation method thereof, wherein the composite heat stabilizer is prepared from the following raw materials in parts by weight: 20-30 parts of dihydropyridine; 5-10 parts of an antioxidant; 5-10 parts of a plasticizer; 20-45 parts of a modified molecular sieve; 10-20 parts of zinc stearate; 5-10 parts of calcium stearate. The calcium-zinc composite stabilizer is prepared by compounding dihydropyridine and a sodium perchlorate modified molecular sieve, replaces components such as beta-diketone, bisphenol A, pentaerythritol and the like in the formula of the traditional calcium-zinc stabilizer, and reduces the dosage of hard calcium, hard zinc and calcium stearate. The PVC composite material has excellent synergistic effect and lubricating effect, can improve the thermal stability time of PVC products, prevent precipitation and blooming, improve later weather resistance and reduce production cost.

Description

Dihydropyridine PVC composite heat stabilizer and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a dihydropyridine PVC composite heat stabilizer and a preparation method thereof.
Background
PVC is a short name for polyvinyl chloride resin. Is a thermoplastic linear polymer produced by free radical polymerization of vinyl chloride monomer. The industrial product is white or light yellow powder, has a relative density of 1.36, and has a chlorine content of 56-58%. Has the advantages of alkali resistance, wear resistance, good electrical insulation, flame retardancy, self-extinguishing property and the like. However, PVC has poor thermal stability, and when the PVC is heated to 140 ℃, hydrogen chloride is released to degrade, so that the processability is lost. The processing temperature is usually above 160-180 ℃, so that a heat stabilizer must be added during the PVC molding processing. PVC heat stabilizers are essential in PVC processing.
In order to solve the problem of poor thermal stability of PVC, a thermal stabilizer must be added during the PVC processing process to prevent thermal degradation. The heat stabilizer applied to PVC has various types, and mainly comprises a monomer stabilizer, a composite lead salt stabilizer, an organic tin heat stabilizer, an environment-friendly calcium-zinc stabilizer and the like. It plays the main roles of:
1. not only can effectively inhibit the initial coloring of the PVC ingredients, but also can keep the stability of the ingredients in the processing and using processes.
2. The ingredients have proper plasticizing rate and internal and external lubricity, so that the processing can be stably carried out.
3. Does not have antagonistic action with other adjuvants.
Among them, the most widely used stabilizer at present is an environment-friendly calcium zinc stabilizer. The environment-friendly calcium zinc stabilizer has the advantages of environmental protection, no toxicity, low price, easy obtainment of raw materials and the like, overcomes the defects of other heat stabilizers, becomes the mainstream heat stabilizer used at present, and has the problem of unstable processing later stage.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the dihydropyridine PVC composite heat stabilizer and the preparation method thereof overcome the defects of the prior art, and the dihydropyridine and perchlorate modified molecular sieve are added to improve the stability of initial whiteness, and zinc stearate is reduced as a raw material for improving the initial whiteness, so that the formula cost of the traditional calcium zinc stabilizer is reduced.
The dihydropyridine PVC composite heat stabilizer provided by the invention comprises the following raw materials in parts by weight:
Figure BDA0003283328320000011
Figure BDA0003283328320000021
wherein:
the modified molecular sieve is prepared according to the following method:
and (3) carrying out water removal treatment on the 4A type molecular sieve in an industrial microwave oven, taking out the 4A type molecular sieve, mixing the obtained product with perchlorate, cooling to room temperature, and fully grinding to obtain the modified molecular sieve. Wherein: the drying temperature is 350-.
The mass ratio of the perchlorate to the dried 4A type molecular sieve is 2: 3.
The plasticizer is preferably di-n-octyl phthalate.
The antioxidant is preferably an antioxidant 1076.
The preparation method of the dihydropyridine PVC composite heat stabilizer comprises the following steps:
adding dihydropyridine into a high-speed mixer, heating to 80-90 ℃, continuously adding the modified molecular sieve, keeping the temperature at 120 ℃, continuously stirring, adding an antioxidant, a plasticizer, calcium stearate and zinc stearate, uniformly stirring the materials, and discharging the materials to obtain the product.
Dihydropyridines can be prepared by co-heating (1 hour) ethyl acetoacetate and urotropine in an ethanol solution of ammonium acetate; cooling the obtained liquid to precipitate crystals, filtering, washing with ethanol, and drying in air to obtain yellowish powdery dihydropyridine.
The invention adopts dihydropyridine as a main stabilizer, wherein the dihydropyridine has a chemical formula of C13H19NO4Is a natural antioxidant. Has certain initial stability effect, and can improve the initial stability and initial whiteness of PVC products. In the products, dihydropyridine is used for solving the problems of initial whiteness and initial thermal stability of PVC processing, so that the products with lower price and excellent performance are designed.
Dihydropyridine of the formula:
Figure BDA0003283328320000022
compared with the prior art, the invention has the following beneficial effects:
1. the dihydropyridine composite heat stabilizer is prepared by compounding dihydropyridine and a sodium perchlorate modified molecular sieve, replaces components such as beta-diketone, bisphenol A, pentaerythritol and the like in the formula of the traditional calcium-zinc stabilizer, and reduces the dosage of hard calcium, hard zinc and calcium stearate. The PVC composite material has excellent synergistic effect and lubricating effect, can improve the thermal stability time of PVC products, prevent precipitation and blooming, improve later weather resistance and reduce production cost.
2. According to the national standard GB2113-82 'plastic whiteness experiment method', compared with the traditional calcium-zinc stabilizer, the dihydropyridine composite heat stabilizer prepared by the invention has excellent initial whiteness and better heat stability. From the comparison test of dynamic stability, it can also be found that the dihydropyridine composite heat stabilizer prepared by the invention can enhance the plasticizing capacity of PVC plastics and obviously prolong the dynamic thermal stability time. Through Congo red experiments, the static thermal stability of the stabilizer is obviously superior to that of the domestic environment-friendly stabilizer.
Detailed Description
The present invention will be further described with reference to the following examples.
Examples 1 to 3
Preparation of sodium perchlorate modified molecular sieve
And (3) carrying out water removal treatment on the 4A type molecular sieve in an industrial microwave oven, taking out the 4A type molecular sieve, mixing the obtained product with perchlorate, cooling to room temperature, and fully grinding to obtain the modified molecular sieve. The drying temperature is 375 +/-25 ℃, the drying time is 3h, and the mixing time is 20 min.
The mass ratio of the perchlorate to the dried 4A type molecular sieve is 2: 3.
Preparation of dihydropyridine PVC composite heat stabilizer:
dihydropyridines can be prepared by co-heating (1 hour) ethyl acetoacetate and urotropine in an ethanol solution of ammonium acetate; cooling the obtained liquid to precipitate crystals, filtering, washing with ethanol, and drying in air to obtain yellowish powdery dihydropyridine.
Adding dihydropyridine into a high-speed mixer, heating to 80-90 ℃, continuously adding the sodium perchlorate modified molecular sieve, keeping the temperature at 120 ℃, continuously stirring, adding the antioxidant, the plasticizer, the zinc stearate and the calcium stearate, uniformly stirring the materials, and discharging the materials to obtain the product.
The formulations of examples 1-3 are shown in Table 1.
TABLE 1 (in parts by weight)
Raw materials Example 1 Example 2 Example 3
Dihydropyridines 20 25 30
Modified molecular sieve 30 30 30
Antioxidant agent 5 5 5
Plasticizer 10 10 10
Zinc stearate 20 20 20
Calcium stearate 5 10 10
Table 2 shows a comparison of the formulations of specific PVC pipes produced using the dihydropyridine PVC composite heat stabilizer produced in examples 1-3.
TABLE 2 (in g)
Figure BDA0003283328320000041
The four PVC plastics prepared in table 2 were subjected to a heat-resistant whiteness test, and table 3 is a relative whiteness value measured by placing a test piece in a whiteness meter examined with a standard whiteness board having a whiteness of 85%. From table 3, it can be found that the calcium zinc stabilizer added with the dihydropyridine PVC composite heat stabilizer has superior heat stability compared with the equivalent traditional calcium zinc stabilizer.
It can also be found from the comparison experiment of dynamic thermal stability performance that the dynamic thermal stability time of PVC plastics can be obviously increased by using the dihydropyridine PVC composite thermal stabilizer (see Table 3).
TABLE 3
Figure BDA0003283328320000042
The plasticizing process at each stage of the formulation was analyzed from the rheology curves and is detailed in table 4.
TABLE 4
Figure BDA0003283328320000051
Test example
The dosage of the following sample formulas, comparative example 1 and comparative example 2 are parts by weight; the processing aid ACR-801 is purchased from Shandong Ruifeng chemical Co., Ltd.
The test formula is as follows: 100 parts of PVC resin, 0.8 part of polyethylene wax, 4 parts of plasticizer DOP, 4 parts of processing aid ACR-8013 and 4 parts of stabilizer prepared in example 1;
comparative example 1: 100 parts of PVC resin, 0.8 part of polyethylene wax, 4 parts of plasticizer DOP, 893 parts of processing aid ACR-8013 and 4 parts of environment-friendly stabilizer of certain well-known enterprise in China;
comparative example 2: 100 parts of PVC resin, 0.8 part of polyethylene wax, 4 parts of plasticizer DOP, 3 parts of processing aid ACR-8013 and 4 parts of British Samminsen environment-friendly stabilizer;
the components of the test formulation, comparative example 1 and comparative example 2 were mixed uniformly under the same test conditions, and then tested by the Congo Red test method (GB 2917-82) which is a polyvinyl chloride thermal stability test method, wherein the Congo Red time at 190 ℃ was 54 minutes (test formulation), 48 minutes (comparative example 1) and 55 minutes (comparative example 2), and the Congo Red time at 200 ℃ was 46 minutes (test formulation), 36 minutes (comparative example 1) and 46 minutes (comparative example 2).
The test data show that the thermal stability of the stabilizer is obviously superior to that of a certain well-known enterprise at home, and the performance of the stabilizer is basically close to that of similar products at home and abroad.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.

Claims (8)

1. A dihydropyridine PVC composite heat stabilizer is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003283328310000011
2. the dihydropyridine PVC composite heat stabilizer according to claim 1, characterized in that: the modified molecular sieve is prepared according to the following method:
and (3) carrying out water removal treatment on the 4A type molecular sieve in an industrial microwave oven, taking out the 4A type molecular sieve, mixing the obtained product with perchlorate, cooling to room temperature, and fully grinding to obtain the modified molecular sieve.
3. The dihydropyridine PVC composite heat stabilizer according to claim 2, characterized in that: the drying temperature is 350-.
4. The dihydropyridine PVC composite heat stabilizer according to claim 2, characterized in that: the mass ratio of the perchlorate to the dried 4A type molecular sieve is 2: 3.
5. The dihydropyridine PVC composite heat stabilizer according to claim 1, characterized in that: the plasticizer is di-n-octyl phthalate.
6. The dihydropyridine PVC composite heat stabilizer according to claim 1, characterized in that: the antioxidant is antioxidant 1076.
7. A method for preparing dihydropyridine PVC composite heat stabilizer according to any one of claims 1 to 6, which is characterized in that: adding dihydropyridine into a high-speed mixer, heating, continuing to add the modified molecular sieve, keeping the temperature, continuously stirring, adding the antioxidant, the plasticizer, the zinc stearate and the calcium stearate, uniformly stirring the materials, and discharging the materials to obtain the product.
8. The preparation method of the dihydropyridine PVC composite heat stabilizer according to claim 7, characterized in that: the temperature is increased to 80-90 ℃, and the heat preservation temperature is 120 ℃.
CN202111139735.9A 2021-09-27 2021-09-27 Dihydropyridine PVC composite heat stabilizer and preparation method thereof Pending CN113773552A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671447A (en) * 2008-09-11 2010-03-17 杭州新新塑料助剂科研有限公司 Liquid heat stabilizer special for cable wires
CN102875930A (en) * 2012-10-22 2013-01-16 南通新邦化工科技有限公司 Preparation method of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride)
CN107936300A (en) * 2017-12-20 2018-04-20 山东慧科助剂股份有限公司 Perchlorate modified molecular screen stabilizer and preparation method thereof
CN108892631A (en) * 2018-08-09 2018-11-27 广州臻莱迈新材料科技有限公司 A kind of heat stabilizer and its synthetic method for PVC

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671447A (en) * 2008-09-11 2010-03-17 杭州新新塑料助剂科研有限公司 Liquid heat stabilizer special for cable wires
CN102875930A (en) * 2012-10-22 2013-01-16 南通新邦化工科技有限公司 Preparation method of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride)
CN107936300A (en) * 2017-12-20 2018-04-20 山东慧科助剂股份有限公司 Perchlorate modified molecular screen stabilizer and preparation method thereof
CN108892631A (en) * 2018-08-09 2018-11-27 广州臻莱迈新材料科技有限公司 A kind of heat stabilizer and its synthetic method for PVC

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
蓝凤祥: "《聚氯乙烯生产与加工应用手册》", 30 November 1995 *

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