CN107057218A - A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers - Google Patents
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers Download PDFInfo
- Publication number
- CN107057218A CN107057218A CN201710027051.7A CN201710027051A CN107057218A CN 107057218 A CN107057218 A CN 107057218A CN 201710027051 A CN201710027051 A CN 201710027051A CN 107057218 A CN107057218 A CN 107057218A
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- Prior art keywords
- stabilizer
- composite thermal
- phthalic acid
- fatty acid
- pvc
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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
-
- 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
-
- 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
Abstract
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers, belong to technical field of polymer materials.Formed by main stabilizer and auxiliary stabilizer compounding, 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 is：
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 technology
Polyvinyl chloride (PVC) is one of five big resins for universal use, and its annual production 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 it is due to " defect " of PVC self structures, such as exists
The unstable chlorine structures such as allyl chloride, tertiary fourth chlorine, are heated and easily occur dehydrochlorination reaction and degrade in process.Therefore
Heat stabilizer is must be added in PVC process.
Currently used PVC heat stabilizer mainly has lead salts, metal soap, organic tin and rare earth type thermal stabilizing agent.
At present, lead salt stabilizer has good thermostable effect and excellent processing characteristics, but toxic, is progressively 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 is peculiar smell；Rare earth type thermal stabilizing agent mainly includes rare earth
Lanthanum, cerium, the organic monoacid salt and inorganic salts of neodymium, with preferable long-term thermal stability, but cost is higher.Though these heat stabilizers
The shortcomings of having a respective advantage, but there is poisonous or thermally-stabilised inefficient or be expensive.Therefore, environmental protection, price are developed
Rationally, the heat stabilizer of thermally-stabilised efficiency high 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 of into
Focus in being studied for domestic and international heat stabilizer, but it there is also thermostable effect it is poor the shortcomings of.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 both have preferable cooperative effect, the heat stabilizer of compounding composition has excellent heat endurance, thermally-stabilised effect
Fruit is better than traditional calcium/zinc salt heat stabilizer.
The content of the invention
The invention aims to the stability for solving current calcium/zinc salt composite thermal stabilizer is not good, and one provided
Phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer is planted, the excellent novel PVC of thermostable effect is obtained thermally-stabilised
Agent.
To realize the purpose of the present invention, solved by following technology：
A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers, it is characterised in that：It is described compound
Heat stabilizer is formed by main stabilizer and auxiliary stabilizer compounding, and main stabilizer is phthalic acid monoesters metalloid salt, and auxiliary is stable
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
Measure to add 1~4 mass parts composite thermal stabilizer in every 100 mass parts PVC.
In the composite thermal stabilizer, the structural formula of main stabilizer is：
In formula, R is carboxylate radical class material, 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 times in the fatty acid zincs such as zinc stearate, zinc oleate, zinc laurate
Meaning is a kind of.
It is Congo Red test to the method for PVC heat endurances to evaluate the present invention, i.e.,：It is Congo red in PVC powder overhung
Test paper, is heated to 170 DEG C of constant temperature, observed and recorded Congored test paper Coloring Time.PVC can drastically decompose release at about 170 DEG C
Hydrogen chloride gas, Congored test paper becomes blue with hcl reaction.Add heat stabilizer, it is suppressed that it is decomposed, and passes through Coloring Time
Length can determine whether the quality of heat stabilizer effect.
The present invention can make heat-stable time maximum extensions 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 invention are as follows：
(1) the synergistic stability effect of phthalic acid monoesters metalloid salt/fatty acid zinc is utilized, PVC heat can be effectively improved
Stability, and due to traditional calcium/zinc salt composite thermal stabilizer.
(2) the aromatic organic acid salt and fatty acid zinc in system 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.
Embodiment
With reference to specific embodiment, the present invention is expanded on further, but the present invention is not limited to following examples.
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 reaction 1h~3h under 40 DEG C~80 DEG C, constant temperature stirring condition is warming up to, room temperature is subsequently cooled to, is filtered, dries, produces
To phthalic acid list tetramethyl piperidine alcohol ester solid；
(2) phthalic acid list tetramethyl piperidine alcohol esters of a. obtained by step (1), sodium hydroxide are in organic solvent or organic molten
Reacted in agent and water, then add metal salt and occur metathesis reaction generation target product；
Or phthalic acid list tetramethyl piperidine alcohol ester, metal hydroxides or the metal oxide obtained by b. steps (1) 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, the gross mass of fixed composite thermal stabilizer changes two
The proportioning of person, is evaluated to phthalic acid list tetramethyl piperidine alcohol ester calcium salt/zinc stearate composite thermal stabilizer effect,
As a result it is as shown in table 1.
The phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table 1/zinc stearate composite thermal stabilizer
Embodiment 2
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 25：1, the gross mass of fixed composite thermal stabilizer changes two
The proportioning of person, is evaluated to phthalic acid list tetramethyl piperidine alcohol ester lanthanum salt/zinc stearate composite thermal stabilizer effect,
As a result it is as shown in table 2.
The phthalic acid list tetramethyl piperidine alcohol ester lanthanum salt of table 2/zinc stearate composite thermal stabilizer
Embodiment 3
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 25：1, the gross mass of fixed composite thermal stabilizer changes two
The proportioning of person, is evaluated to phthalic acid list tetramethyl piperidine alcohol ester cerium salt/zinc stearate composite thermal stabilizer effect,
As a result it is as shown in table 3.
The phthalic acid list tetramethyl piperidine alcohol ester cerium salt of table 3/zinc stearate composite thermal stabilizer
Embodiment 4
The mass ratio for selecting polyvinyl chloride resin and stabilizer total amount is 50：1, the gross mass of fixed composite thermal stabilizer changes two
The proportioning 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.
The phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table 4/oleic acid Zn composite heat stabilizer
Embodiment 5
It is respectively 30 to select polyvinyl chloride resin and the mass ratio of stabilizer total amount:1、37.5:1、50:1、67.5:1、75:1, Gu
Determine polyvinyl chloride resin content, carried out to phthalic acid list tetramethyl piperidine alcohol ester calcium salt/zinc stearate composite thermal stabilizer effect
Evaluate, as a result as shown in table 5.
The phthalic acid list tetramethyl piperidine alcohol ester calcium salt of table 5/zinc stearate composite thermal stabilizer
As can be seen that the composite thermal stabilizer is respectively provided with good cooperative effect from embodiment 1~4；Embodiment 1~
In 3, preferably, optimum proportioning is 5 to the composite thermal stabilizer effect in embodiment 1:5, secondly to be compound thermally-stabilised in embodiment 2
Agent, optimum proportioning is 5:5, it is finally the composite thermal stabilizer of embodiment 3, optimum proportioning is 7:3；Compound thermal in embodiment 4
The optimum proportioning of stabilizer is 5:5；In embodiment 5, with the content increase of composite thermal stabilizer, thermostable effect is better.
It is described above, only specific embodiments of the present invention, but protection scope of the present invention is not limited thereto.Readding
Read after 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
Change or change, these equivalent form of values 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 stabilizers, it is characterised in that：The compound thermal
Stabilizer is formed by main stabilizer and auxiliary stabilizer compounding, 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 is：
In formula, R is carboxylate radical class material；M is metal, and n is the chemical valence of the metal.
2. according to a kind of phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers of PVC described in claim 1, its
It is characterised by：R is-COO-、-CH2COO-。
3. according to a kind of phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers of PVC described in claim 1, its
It is characterised by：M is selected from Mg, Al, Ca, Zn, Sn, Sb, Ba, La, Ce.
4. according to a kind of phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizers of PVC described in claim 1, its
It is characterised by：Auxiliary stabilizer is any one in the fatty acid zincs such as zinc stearate, zinc oleate, zinc laurate.
5. 1~4 mass parts compound thermal is added in the purposes of the composite thermal stabilizer described in claim 1, every 100 mass parts PVC
Stabilizer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710027051.7A CN107057218B (en) | 2017-01-15 | 2017-01-15 | A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer |
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| CN201710027051.7A CN107057218B (en) | 2017-01-15 | 2017-01-15 | A kind of PVC phthalic acid monoesters metalloid salt/fatty acid zinc composite thermal stabilizer |
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| CN107057218A true CN107057218A (en) | 2017-08-18 |
| CN107057218B CN107057218B (en) | 2019-04-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341665A (en) * | 2020-11-26 | 2021-02-09 | 江苏视科新材料股份有限公司 | Ultraviolet-proof and blue-light-proof optical material and preparation method thereof |
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 |
-
2017
- 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341665A (en) * | 2020-11-26 | 2021-02-09 | 江苏视科新材料股份有限公司 | Ultraviolet-proof and blue-light-proof optical material and preparation method thereof |
| CN112341665B (en) * | 2020-11-26 | 2022-06-03 | 江苏视科新材料股份有限公司 | Ultraviolet-proof and blue-light-proof optical material and preparation method thereof |
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| CN107057218B (en) | 2019-04-26 |
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