CN109824943A - A kind of composite thermal stabilizer and its application containing organotin, magnesium and titanium - Google Patents
A kind of composite thermal stabilizer and its application containing organotin, magnesium and titanium Download PDFInfo
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- CN109824943A CN109824943A CN201811530346.7A CN201811530346A CN109824943A CN 109824943 A CN109824943 A CN 109824943A CN 201811530346 A CN201811530346 A CN 201811530346A CN 109824943 A CN109824943 A CN 109824943A
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- thermal stabilizer
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Abstract
The invention discloses a kind of composite thermal stabilizer containing organotin, magnesium and titanium and its applications, wherein composite thermal stabilizer is compounded by main stabilizer and auxiliary stabilizer, wherein main stabilizer is selected from thiol methyl tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate, and auxiliary stabilizer is magnesium stearate, dipentaerythritol, butyl titanate and nano-titanium dioxide.The present invention passes through optimal screening, obtain a kind of composite thermal stabilizer with synergy containing organotin, magnesium stearate, dipentaerythritol, nano-titanium dioxide and coupling agent, it is applied in PVC, it can be obviously improved the thermal stability of material, and have the degradable property of potential environment.
Description
Technical field
It is specifically a kind of containing the compound of organotin, magnesium and titanium the present invention relates to a kind of processing of high molecular material auxiliary agent
Heat stabilizer and its application.
Background technique
Polyvinyl chloride and its product are China's annual outputs close to 18,000,000 tons of important high molecular material, due to carbon chlorine key key
It can be that 243kJ/mol is smaller, it usually needs heat stabilizer such as lead salt, composition metal soap, organotin, rare earth, organic etc. is added.
Lead salt is since toxicity is superseded greatly, and heat stabilizer is excellent and degradable towards nontoxic, efficient, multi-functional, cost performance at present
Direction is developed.Thiol methyl tin occupies an important position in polrvinyl chloride product heat stabilizer at present, it has heat resistance, transparent
Property and colour shallow advantage, nontoxic, security article is regarded as by world health supervisory organ.But thiol methyl tin price is high
It is expensive, have a peculiar smell, therefore reduce usage amount and use cost, find synergistic effect and degradability, become the task of top priority, therefore add
Auxiliary stabilizer such as magnesium stearate and nano-titanium dioxide explore possible synergistic effect and environmental-friendly, are of great significance.
Magnesium stearate has both metal salt and stearic double grading, the intrinsic fatty character of stearic acid include lubricity and
Repellency has the inorganic core and 2 linear long hydrocarbon chains of 1 charge high degree of dispersion in structure；Fusing point is high, has dispersed phase, fills out
Filling property, homogenieity and compatibility, white or milky uniform powder, large specific surface area have extremely strong suction-operated and moisture absorption
Property, nontoxic, tasteless, non-combustible, fusing point is 88.5 DEG C, does not dissolve in alcohol, ether, is slightly soluble in water, dissolves in hot ethanol, and property is stablized,
It is widely used in the additive of medical lubricant, paint and plastics；Have the effects that lubrication, it is anti-stick, help stream, manufactured particle tool
There are good mobility and compressibility, be used for the heat stabilizer of polyvinyl chloride and the drier of paint with calcium soap, zinc soap cooperation,
Release agent, outer smoothing preparation as plastic products；Magnesium stearate is the excellent lubrication stably dispersing auxiliary agent of plastic, rubber, plastics system
The high temperature resistant powder mould agent of the release agent, rubber product of product, is alternatively arranged as PVC heat stabilizer, increases the transparent or semitransparent of product
Degree.Magnesium stearate can prevent from decomposing with the heated hydrochloric acid effect decomposited of PVC；Magnesium stearate has fire-retardant in plastic, rubber
Effect.Magnesium stearate can also be used as the fire retardant of inorganic material, and magnesium stearate has hydrophobic because containing organo-functional group
Property.Because magnesium stearate has amphiphilic structure, according to the attracting principle of the same sex, non-polar end can be directed toward oily phase or air, pole
Water or homologue are stretched in property end, when repulsive interaction of the surfactant by apolar substance, while encountering its homologue or pole
Property molecule when, from drop low-surface-energy and surface tension angle analysis, polar end can actively stretch to polar molecule, on its surface
Enrichment, to reach modified purpose.
Thiol methyl tin be widely used in PVC squeeze out, calendering, blow molding and injection molding each based article in, with it is excellent just
Phase coloring, the transparency and thermal stability are the products such as polyvinyl chloride film, sheet material, plate, pellet, tubing, pipe fitting and profile
Key assistant.Thiol methyl tin is authenticated through U.S. FDA approval and Germany BGA, can be used for packaging material for food and upper hose etc.,
Safety is reliable.Because of its function admirable, the food-grade hard transparent product processing of high processing request can be used for.
Thiol methyl tin excellent effect at present, but it is expensive and have peculiar smell, and calcium-zinc composite stabilizing agent, effect is not
Good, no stablizing effect, nano-titanium dioxide and polyvinyl chloride macromolecule material is used alone in pentaerythrite or dipentaerythritol
Compatibility is poor, and adds a certain amount of butyl titanate coupling agent, and nano titanium oxide inorganic particle and polychlorostyrene second can be enhanced
Compatibility between alkene macromolecule, therefore the present invention is directed to standing state, and it is steady to propose a kind of compound thermal containing organotin, magnesium and titanium
Determine agent and its application.
Summary of the invention
The present invention is directed to above-mentioned deficiency of the prior art, it is desirable to provide a kind of containing the compound of organotin, magnesium and titanium
Heat stabilizer and its application.
Composite thermal stabilizer of the present invention containing organotin, magnesium and titanium, is compounded by main stabilizer and auxiliary stabilizer；
Wherein main stabilizer (A) is selected from thiol methyl tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate etc., preferably
Thiol methyl tin；Auxiliary stabilizer is magnesium stearate (B), dipentaerythritol (C), butyl titanate (D) and nano-titanium dioxide
(E)。
Composite thermal stabilizer of the present invention containing organotin, magnesium and titanium, each component are constituted as follows by mass fraction:
Each component is constituted preferably as follows by mass fraction:
Wherein dipentaerythritol can be substituted with pentaerythrite.
The application of composite thermal stabilizer of the present invention containing organotin, magnesium and titanium is added to as thermostabilization auxiliary agent
In polyvinyl chloride, to improve the thermal stability of material.
Proportion is constituted as follows when composite thermal stabilizer of the present invention is added to PVC:
Evaluating composite thermal stabilizer of the present invention is using Congo Red test, i.e., at PVC to the effect of PVC thermal stability
Grain overhung Congored test paper, is heated to 195 DEG C of constant temperature, observes and records Congored test paper and initially becomes the blue time and become blue completely
Time.PVC can sharply decompose release hydrogen chloride gas at about 170-180 DEG C, and Congored test paper and hcl reaction become blue.
Heat stabilizer is added, it is suppressed that it is decomposed, and can determine whether composite thermal stabilizer effect by the initial and complete length for becoming the blue time
Superiority and inferiority.
The present invention is obtained a kind of containing organotin, magnesium stearate, dipentaerythritol, nanometer titanium dioxide by optimal screening
The composite thermal stabilizer with synergy of titanium and coupling agent, is applied in PVC, and the heat that can be obviously improved material is steady
Qualitative energy, and have the degradable property of potential environment.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention is stablized using the collaboration of thiol methyl tin, magnesium stearate, dipentaerythritol, nano-titanium dioxide and is made
With the usage amount of thiol methyl tin can be reduced, effect effectively improves PVC better than thiol methyl tin stabilizer is used alone
Thermal stability；
2, magnesium stearate (B) is used as potential fire retardant, can promote the flame retardant effect of polyvinyl chloride；
3, butyl titanate (D) can promote tin, magnesium metal and nano-titanium dioxide and polyvinyl chloride molecule as coupling agent
Between electrostatic attraction and chemical bond force generation, potential light point when furthermore titanium salt is also used as polyvinyl chloride end-of-life
Promotor is solved, it is made to accelerate light degradation in the environment.
4, above-mentioned organotin, magnesium stearate, dipentaerythritol and nano-titanium dioxide belong to asepsis environment-protecting substance, complete
Meet the demand for development for environmental protection both at home and abroad entirely, has a wide range of applications.
Specific embodiment
Polyvinyl chloride resin model S-65 used in the present embodiment.
Embodiment 1:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate, dipentaerythritol 1.0
Part, 0.5 part of butyl titanate, thiol methyl tin liquid are uniformly mixed with DOTP liquid, then by magnesium stearate, dipentaerythritol
The solution mixed is added with butyl titanate, is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added to
In polyvinyl chloride resin, stirring mixes it uniformly, and high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is 170-
It 180 DEG C, discharges after 2~3min of mixing, then uses vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 2:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate, dipentaerythritol 1.0
Part, 1.0 parts of butyl titanate, thiol methyl tin liquid are uniformly mixed with DOTP liquid, then by magnesium stearate, dipentaerythritol
The solution mixed is added with butyl titanate, is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added to
In polyvinyl chloride resin, stirring mixes it uniformly, and high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is 170-
It 180 DEG C, discharges after 2~3min of mixing, then uses vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 3:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate, dipentaerythritol 1.0
Part, thiol methyl tin liquid is uniformly mixed with DOTP liquid, is then mixed magnesium stearate, dipentaerythritol addition molten
Liquid is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirs, mixes it uniformly
It closing, high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is 170-180 DEG C, it discharges after 2~3min of mixing,
Then vulcanizing press tabletting is used, that is, sample thin slice is made.
Embodiment 4:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate are weighed, by thiol methyl tin
Liquid is uniformly mixed with DOTP liquid, and then magnesium stearate is added to the solution mixed, be stirred well to uniformly mixed.It will be complete
The stabiliser solution of fully dissolved is slowly added in polyvinyl chloride resin, and stirring mixes it uniformly, and it is close that high speed is added in the feed powder mixed
Mill hopper, control smelting temperature are 170-180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting, that is, make
At sample thin slice.
Embodiment 5:
100 parts of polyvinyl chloride resin, DOTP50 parts, 1.0 parts of thiol methyl tin are weighed, by thiol methyl tin liquid and DOTP liquid
It is uniformly mixed, is stirred well to uniformly mixed, the stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stir, make it
High speed mixer hopper is added in uniformly mixing, the feed powder mixed, and control smelting temperature is 170-180 DEG C, after 2~3min of mixing
Then discharging uses vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 6:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of dipentaerythritol are weighed, by thiol methyl
Tin liquor body is uniformly mixed with DOTP liquid, and the solution that mixes then is added in dipentaerythritol, be stirred well to it is uniformly mixed,
The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirs, mixes it uniformly, the feed powder mixed is added high
Fast mixer hopper, control smelting temperature are 170-180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting,
Sample thin slice is made.
Embodiment 7:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate, dipentaerythritol 1.0
Part, 5.0 parts of nano-titanium dioxide, 1.0 parts of butyl titanate using nano-titanium dioxide and butyl titanate and are used as auxiliary stabilization
Agent and photocatalytic degradation agent；
(1) thiol methyl tin liquid is uniformly mixed with DOTP liquid, then magnesium stearate, dipentaerythritol is added mixed
The solution got togather is thoroughly mixed uniformly to being completely dissolved, and (2) are by 1.0 parts of butyl titanate and nano-TiO25.0 parts of powder in
80 DEG C of heating mixing, stir 30min.
Uniformly mixed stabilizer (1) and (2) are slowly added into polyvinyl chloride resin, stirring mixes them thoroughly, and then will
Compound powder is added in high speed mixer hopper, and control smelting temperature is 170-180 DEG C, is discharged after 2~3min of mixing, then
With vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 8:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 1.0 parts of dipentaerythritol are weighed, by thiol methyl
Tin liquor body is uniformly mixed with DOTP liquid, and the solution that mixes then is added in dipentaerythritol, be stirred well to it is uniformly mixed,
The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirs, mixes it uniformly, the feed powder mixed is added high
Fast mixer hopper, control smelting temperature are 170-180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting,
Sample thin slice is made.
2.0 × 2.0 × 1.0mm size is made in sample, according to according to standard GB/T/T 2917.1-2002, measurement is rigid
Arnotto heat-stable time, test temperature are 195 DEG C, and Congored test paper lower end is shown in Table 1 apart from powder 2cm, test result.
1 Congo red test result of table
Note: A- thiol methyl tin；B- magnesium stearate；C- dipentaerythritol；D- butyl titanate；E- nano-titanium dioxide；Oil
195 DEG C of bath temperature；Embodiment 7 is butyl titanate coupling agent cladding titanium dioxide；Ti- initially becomes the blue time；When Tc- becomes blue completely
Between；Blank sample be 100 parts of PVC, 50 parts of DOTP, the same embodiment of preparation method.
From table 1 it follows that the PVC of 100 parts of the use of embodiment 7,50 parts of DOTP, 0.5 part of thiol methyl tin,
0.5 part of magnesium stearate, 1.0 parts of dipentaerythritol, 1.0 parts of butyl titanates coat 5.0 parts of nano-titanium dioxide, prepared
Polyvinyl chloride film initially become the blue time up to 54 minutes, become the blue time completely as 71 minutes, there is excellent heat resistance, it is stable
Property is best；For comparison, blank sample becomes the blue time initially as 5 minutes, becomes blue into 7 minutes completely, thermo-labile；Embodiment 3 uses
Polyvinyl chloride film prepared by 0.5 part of thiol methyl tin, 0.5 part of magnesium stearate and 1.0 parts of dipentaerythritol is initial
Become the blue time as 45 minutes, becomes the blue time completely as 75 minutes, be slightly better than embodiment 5, using 1 part of thiol methyl tin thermostabilization
Agent.The embodiment that compares 1,2,4, initial change blue time are close with the complete change blue time, it is seen that use magnesium stearate auxiliary agent, generation
It is used for 0.5 part of thiol methyl tin, the raising of film heat resistance can be promoted；And 0.5-1.0 parts of butyl titanate fails to mention
The heat resistance of high Examples 1 and 2 polyvinyl chloride film.
The above content is combining specific embodiment, to the further description done of the present invention, but it is of the invention
Embodiment is simultaneously not restricted to the described embodiments, and others are any to be done without departing from Spirit Essence or principle of the invention
Change, replacement modification combination and simplify in protection scope of the present invention.
Claims (7)
1. a kind of composite thermal stabilizer containing organotin, magnesium and titanium, it is characterised in that:
The composite thermal stabilizer is compounded by main stabilizer and auxiliary stabilizer, and wherein main stabilizer is selected from thiol methyl
Tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate, auxiliary stabilizer are magnesium stearate, dipentaerythritol, metatitanic acid
Butyl ester and nano-titanium dioxide.
2. composite thermal stabilizer according to claim 1, it is characterised in that:
The main stabilizer is thiol methyl tin.
3. composite thermal stabilizer according to claim 1 or 2, it is characterised in that each component is pressed in the composite thermal stabilizer
Mass fraction constitutes as follows:
4. composite thermal stabilizer according to claim 3, it is characterised in that each component presses matter in the composite thermal stabilizer
It is as follows to measure number composition:
5. a kind of application of composite thermal stabilizer described in claims 1 or 2, it is characterised in that: be as thermostabilization
Auxiliary agent is added in polyvinyl chloride, to improve the thermal stability of material.
6. application according to claim 5, it is characterised in that proportion is constituted such as when the composite thermal stabilizer is added to PVC
Under:
7. application according to claim 6, it is characterised in that proportion is constituted such as when the composite thermal stabilizer is added to PVC
Under:
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| CN201811530346.7A CN109824943A (en) | 2018-12-14 | 2018-12-14 | A kind of composite thermal stabilizer and its application containing organotin, magnesium and titanium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885513A (en) * | 2019-12-16 | 2020-03-17 | 安徽理工大学 | Folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885513A (en) * | 2019-12-16 | 2020-03-17 | 安徽理工大学 | Folic acid modified nano titanium dioxide composite heat stabilizer for PVC and application thereof |
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Application publication date: 20190531 |