CN107057218B - A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer - Google Patents
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer Download PDFInfo
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- CN107057218B CN107057218B CN201710027051.7A CN201710027051A CN107057218B CN 107057218 B CN107057218 B CN 107057218B CN 201710027051 A CN201710027051 A CN 201710027051A CN 107057218 B CN107057218 B CN 107057218B
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- stabilizer
- composite thermal
- phthalic acid
- pvc
- fatty acid
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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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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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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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer, belongs to technical field of polymer materials.It is compounded by main stabilizer and auxiliary stabilizer, main stabilizer is phthalic acid monoesters metalloid salt, and auxiliary stabilizer is fatty acid zinc;Wherein main stabilizer: the mass ratio of auxiliary stabilizer is (1~4): (1~4);The structural formula of main stabilizer are as follows:
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of PVC phthalic acid monoesters metalloid salt/fat
Sour Zn composite heat stabilizer.
Background technique
Polyvinyl chloride (PVC) is one of five big resins for universal use, and annual output is only second to polyethylene, because of its excellent performance and
Cheap price and the various aspects for being widely used in our lives.But due to " defect " of PVC self structure, such as exist
The unstable chlorines structures such as allyl chloride, tertiary fourth chlorine are heated in process and are easy to happen dehydrochlorination reaction and degrade.Therefore
It must be added to heat stabilizer in PVC process.
Currently used PVC heat stabilizer mainly has lead salts, metal soap, organic tin and rare earth type thermal stabilizing agent.
Currently, lead salt stabilizer has good thermostable effect and excellent processing performance, but toxic, gradually it is eliminated;Metallic soap
Class stabilizer is usually that metallic compound is produced with organic acid saponification, but thermostable effect is poor;Organic tin stabilizer has efficient
Thermostable effect, be the main substitute products of lead salt stabilizer, but there are peculiar smell;Rare earth type thermal stabilizing agent mainly includes rare earth
Lanthanum, cerium, neodymium organic monoacid salt and inorganic salts, there is preferable long-term thermal stability, but higher cost.Though these heat stabilizers
Have the advantages that it is respective, but there is or toxic or thermostabilization inefficient or it is expensive the disadvantages of.Therefore, exploitation environmental protection, price
Rationally, the high-efficient heat stabilizer of thermostabilization is very necessary.
In Environment-friendlyheat heat stabilizer, calcium/zinc class composite thermal stabilizer by feat of it is nontoxic, environmentally friendly and cheap the advantages that at
For the hot spot in the research of domestic and international heat stabilizer, but the disadvantages of it is poor there is also thermostable effect.Therefore efficient, ring is studied
The composite thermal stabilizer of guarantor is very necessary.In the present invention, phthalic acid monoesters metalloid salt and fatty acid zinc composite thermal stabilizer are not
It is only environmentally friendly, and the two has preferable synergistic effect, the heat stabilizer for compounding composition has excellent thermal stability, thermostabilization effect
Fruit is better than traditional calcium/zinc salt heat stabilizer.
Summary of the invention
The purpose of the present invention is to solve current calcium/zinc salt composite thermal stabilizer stability is bad, and one provided
Kind phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer, obtains the excellent novel PVC thermostabilization of thermostable effect
Agent.
To achieve the purpose of the present invention, it is solved by following technology:
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer, it is characterised in that: described compound
Heat stabilizer is compounded by main stabilizer and auxiliary stabilizer, and main stabilizer is phthalic acid monoesters metalloid salt, and auxiliary is stablized
Agent is fatty acid zinc;Wherein main stabilizer: the mass ratio of auxiliary stabilizer is (1~4): (1~4), the use of composite thermal stabilizer
Amount is that 1~4 mass parts composite thermal stabilizer is added in every 100 mass parts PVC.
In the composite thermal stabilizer, the structural formula of main stabilizer are as follows:
In formula, R is carboxylate radical substance, such as-COO-、-CH2COO-Deng;M is metal, selected from Mg, Al, Ca, Zn, Sn, Sb,
Ba, La, Ce etc.;N is the chemical valence of the metal.
In the composite thermal stabilizer, auxiliary stabilizer is appointing in the fatty acid zincs such as zinc stearate, zinc oleate, zinc laurate
It anticipates one kind.
The evaluation present invention is Congo Red test to the method for PVC thermal stability, it may be assumed that Congo red in PVC powder overhung
Test paper is heated to 170 DEG C of constant temperature, observes and records Congored test paper Coloring Time.PVC can sharply decompose release at about 170 DEG C
Hydrogen chloride gas, Congored test paper and hcl reaction become blue.Heat stabilizer is added, it is suppressed that it is decomposed, and passes through Coloring Time
Length can determine whether the superiority and inferiority of heat stabilizer effect.
The present invention can make heat-stable time maximum extension of the PVC at 170 DEG C to about 4h, far superior to traditional calcium/zinc
Salt composite thermal stabilizer.
Compared with prior art, the beneficial effects of the present invention are:
(1) phthalic acid monoesters metalloid salt/fatty acid zinc synergistic stability effect is utilized, the heat of PVC can be effectively improved
Stability, and due to traditional calcium/zinc salt composite thermal stabilizer.
(2) the aromatic organic acid salt in system and fatty acid zinc belong to low toxic and environment-friendly type thermal stabilizing agent, comply fully with and work as
This life bound pair has wide practical use in the trend of ecological requirements.
Specific embodiment
Present invention will be further explained below with reference to specific examples, but the present invention is not limited to following embodiments.
The preparation method of main stabilizer:
(1) phthalic acid or acid anhydride are dissolved in solvent, 2,2,6,6- tetramethyl -4- piperidines is added portionwise within a certain period of time
Alcohol, and be warming up to 40 DEG C~80 DEG C reacts 1h~3h, then cools to room temperature under constant temperature stirring condition, filter, it is dry to get
To phthalic acid list tetramethyl piperidine alcohol ester solid;
(2) a. resulting phthalic acid list tetramethyl piperidine alcohol ester of step (1), sodium hydroxide are in organic solvent or organic molten
It is reacted in agent and water, then adds metal salt and metathesis reaction generation target product occurs;
Or the resulting phthalic acid list tetramethyl piperidine alcohol ester of b. step (1), metal hydroxides or metal oxide add
Thermal response directly generates target product.
Phthalic acid or acid anhydride areAcid or anhydride.
Embodiment 1
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 25:1, and the gross mass of fixed composite thermal stabilizer changes two
The proportion of person is evaluated to phthalic acid list tetramethyl piperidine alcohol ester calcium salt/zinc stearate composite thermal stabilizer effect,
The results are shown in Table 1.
1 phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table/zinc stearate composite thermal stabilizer
Embodiment 2
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 25:1, and the gross mass of fixed composite thermal stabilizer changes two
The proportion of person is evaluated to phthalic acid list tetramethyl piperidine alcohol ester lanthanum salt/zinc stearate composite thermal stabilizer effect,
The results are shown in Table 2.
2 phthalic acid list tetramethyl piperidine alcohol ester lanthanum salt of table/zinc stearate composite thermal stabilizer
Embodiment 3
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 25:1, and the gross mass of fixed composite thermal stabilizer changes two
The proportion of person is evaluated to phthalic acid list tetramethyl piperidine alcohol ester cerium salt/zinc stearate composite thermal stabilizer effect,
The results are shown in Table 3.
3 phthalic acid list tetramethyl piperidine alcohol ester cerium salt of table/zinc stearate composite thermal stabilizer
Embodiment 4
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 50:1, and the gross mass of fixed composite thermal stabilizer changes two
The proportion of person is evaluated to phthalic acid list tetramethyl piperidine alcohol ester calcium salt/oleic acid Zn composite heat stabilizer effect, knot
Fruit is as shown in table 4.
4 phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table/oleic acid Zn composite heat stabilizer
Embodiment 5
Selection polyvinyl chloride resin and the mass ratio of stabilizer total amount are respectively 30:1,37.5:1,50:1,67.5:1,75:1, Gu
Determine polyvinyl chloride resin content, is carried out to phthalic acid list tetramethyl piperidine alcohol ester calcium salt/zinc stearate composite thermal stabilizer effect
Evaluation, the results are shown in Table 5.
5 phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table/zinc stearate composite thermal stabilizer
As can be seen that the composite thermal stabilizer all has good synergistic effect from Examples 1 to 4;Embodiment 1~
In 3, the composite thermal stabilizer effect in embodiment 1 is best, optimum proportioning 5:5, is secondly the compound thermostabilization in embodiment 2
Agent, optimum proportioning 5:5 are finally the composite thermal stabilizer of embodiment 3, optimum proportioning 7:3;Compound thermal in embodiment 4
The optimum proportioning of stabilizer is 5:5;In embodiment 5, as the content of composite thermal stabilizer increases, thermostable effect is better.
The above, only specific embodiments of the present invention, but scope of protection of the present invention is not limited thereto.It is readding
After having read the content of the invention lectured, those skilled in the art can make various changes to the present invention with any same or similar means
It changes or modifies, such equivalent forms are similarly fallen under the scope of the present invention.
Claims (5)
1. a kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer, it is characterised in that: the compound thermal
Stabilizer is compounded by main stabilizer and auxiliary stabilizer, and main stabilizer is phthalic acid monoesters metalloid salt, auxiliary stabilizer
For fatty acid zinc;Wherein main stabilizer: the mass ratio of auxiliary stabilizer is (1~4): (1~4);
In the composite thermal stabilizer, the structural formula of main stabilizer are as follows:
In formula, R is carboxylate radical substance;M is metal, and n is the chemical valence of the metal.
2. a kind of PVC described in accordance with the claim 1 phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer,
Be characterized in that: R is-COO-、-CH2COO-。
3. a kind of PVC described in accordance with the claim 1 phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer,
Be characterized in that: M is selected from Mg, Al, Ca, Zn, Sn, Sb, Ba, La, Ce.
4. a kind of PVC described in accordance with the claim 1 phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer,
Be characterized in that: auxiliary stabilizer is zinc stearate, zinc oleate, any one in zinc laurate.
5. the purposes of composite thermal stabilizer described in claim 1,1~4 mass parts compound thermal is added in every 100 mass parts PVC
Stabilizer.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4101509A (en) * | 1976-03-29 | 1978-07-18 | Ciba-Geigy Corporation | Hindered piperidine carboxylic acids, metal salts thereof and stabilized compositions |
US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
JPH03188066A (en) * | 1989-12-15 | 1991-08-16 | Daicel Chem Ind Ltd | Production of 2,2,6,6-tetramethyl-4-oxomethyl-piperidine |
CN1328534A (en) * | 1998-11-23 | 2001-12-26 | 纳尔科/埃克森能源化学有限公司 | Stabilised compositions comprising olefins |
-
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- 2017-01-15 CN CN201710027051.7A patent/CN107057218B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
US4101509A (en) * | 1976-03-29 | 1978-07-18 | Ciba-Geigy Corporation | Hindered piperidine carboxylic acids, metal salts thereof and stabilized compositions |
JPH03188066A (en) * | 1989-12-15 | 1991-08-16 | Daicel Chem Ind Ltd | Production of 2,2,6,6-tetramethyl-4-oxomethyl-piperidine |
CN1328534A (en) * | 1998-11-23 | 2001-12-26 | 纳尔科/埃克森能源化学有限公司 | Stabilised compositions comprising olefins |
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