CN109456546A - A kind of plastic heat stabilizer and preparation method thereof with long-term thermal stability - Google Patents
A kind of plastic heat stabilizer and preparation method thereof with long-term thermal stability Download PDFInfo
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- CN109456546A CN109456546A CN201811141281.7A CN201811141281A CN109456546A CN 109456546 A CN109456546 A CN 109456546A CN 201811141281 A CN201811141281 A CN 201811141281A CN 109456546 A CN109456546 A CN 109456546A
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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
- 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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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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Abstract
The invention discloses a kind of plastic heat stabilizer and preparation method thereof with long-term thermal stability, according to mass fraction, raw material includes 1~12 part of lactate, 6~15 parts of calcium stearates, 10~40 parts of zinc stearates, 15~40 parts of auxiliary heat stabilizers, 4~8 parts of antioxidant and 10~25 parts of lubricants.It is used to prepare the solid calcium zinc heat stabilizer of polyvinyl chloride (PVC) plastics, lactate is added in raw material, lactate has double hydroxyl structures, the hydroxyl quantity of raw material can be increased, be conducive to improve long-term thermal stability, it is not less than 70min using transformation period of its PVC plastic in static burn in experiment, Congo red test Coloring Time is not less than 59min.
Description
Technical field
The present invention relates to field of plastics processing more particularly to a kind of plastic heat stabilizer with long-term thermal stability and its
Preparation method.
Background technique
Polyvinyl chloride (PVC) is second large general-purpose plastics that yield is only second to polyethylene (PE), has intensity height, can increase
The advantages that modeling, corrosion-resistant, fire retardant, good insulating, high transparency, by the way that additive appropriate is added, using technique appropriate and
Equipment, can produce the boardy products such as miscellaneous plastic products, including plate, tubing, pipe fitting, profile shapes and film, pipe, shoes,
The soft goods such as toy, CABLE MATERIALS, artificial leather are widely used in the fields such as industrial building, agricultural, daily necessities, packaging.But PVC
Thermal stability it is poor, it is degradable, thus heat stabilizer be PVC processing necessary additive.
Solid calcium zinc heat stabilizer is chiefly used in PVC processing, is a kind of nontoxic environmentally friendly heat stabilizer, but existing
Solid calcium zinc heat stabilizer poor heat resistance, prevent the thermal stability of existing solid calcium zinc heat stabilizer makes from keeping for a long time
It obtains PVC product its thermal stability decline in use for some time or loses.
Summary of the invention
It is environment amenable that there is long term thermal it is an object of the invention to propose that one kind is conducive to improve long-term thermal stability
Plastic heat stabilizer of stability and preparation method thereof.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of plastic heat stabilizer with long-term thermal stability, according to mass fraction, raw material include 1~12 part of lactate, 6~
15 parts of calcium stearates, 10~40 parts of zinc stearates, 15~40 parts of auxiliary heat stabilizers, 4~8 parts of antioxidant and 10~25 parts of lubrications
Agent.
Preferably, the lactate is one of sodium lactate, calcium lactate, zinc lactate, magnesium lactate and barium lactate or a variety of.
The lactate can carry out multiple combinations according to the metal ion needed for plastic heat stabilizer, quote different metal ions and make
Plastic heat stabilizer shows different effects, versatile and flexible.The lactate is sodium lactate, calcium lactate, zinc lactate, magnesium lactate
With one of barium lactate or a variety of, the present invention is not defined its specific combination and component ratio, and specific group
It closes and component ratio does not impact the long-term thermal stability of plastic heat stabilizer of the invention.
Preferably, the lubricant is made of in-lubricant and external lubricant, and the in-lubricant is stearic acid, single tristearin
One of acid glyceride, butyl stearate, oleamide and ethylene bis stearamide are a variety of, and the external lubricant is husky rope
Wax, one of paraffin and polyethylene wax or a variety of.
The plastic heat stabilizer increases in-lubricant, allows and reduces polymerization in process using its PVC plastic
The lubrication of object molecule interchain internal friction；The stearic acid, glycerin monostearate, butyl stearate, oleamide and ethylene are double
Stearmide is commercially available gained, and good with PVC compatibility, can be evenly spread between strand, to reduce molecule
The interior friction of chain improves the mobility of polymer, improves product surface finish.The in-lubricant is stearic acid, single tristearin
One of acid glyceride, butyl stearate, oleamide and ethylene bis stearamide are a variety of, and the present invention does not have it
Body combination and component ratio are defined, and specific combination and component ratio be not to the interior profit of plastic heat stabilizer of the invention
Slip impacts.
The plastic heat stabilizer increases external lubricant, and allowing is reduced using its PVC plastic and added in processing and forming
The interface friction of work mechanical surface；The sand rope wax, paraffin and polyethylene wax are commercially available gained, and very with PVC compatibility
It is small, it is easy in process from the interior shifting of PVC to surface, forms a lubricant molecular layer in interface.It is described
External lubricant is husky rope wax, one of paraffin and polyethylene wax or a variety of, the present invention not to its specific combination and at
Point ratio is defined, and specific combination and component ratio do not cause shadow to the outer lubricity of plastic heat stabilizer of the invention
It rings.
Preferably, according to mass ratio, the in-lubricant: external lubricant is 1~3:2~5.In-lubricant and external lubricant
Mass ratio be set as 1~3:2~5, can accelerate the fusion time of PVC, reduce counter balance torque, allow PVC plastic using it
Counter balance torque is not higher than 16.3 Nm.
Preferably, the auxiliary heat stabilizer is by dipentaerythritol, 1,3,5- tri- (2- ethoxy) cyanuric acids, zeolite, water
Talcum and beta-diketon composition.
Preferably, according to mass ratio, dipentaerythritol: 1,3,5- tri- (2- ethoxy) cyanuric acid: zeolite: hydrotalcite: β-
Diketone is 1~6:2~10:10~30:4~10:2~5.
Above-mentioned mass ratio is arranged in the auxiliary heat stabilizer, is used cooperatively with lactate, can greatly improve thermal stability.
The dipentaerythritol, 1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons are used cooperatively, and are had fabulous
Synergistic effect, dipentaerythritol can prevent chloride catalytic degradation, while in the presence of metallic soap with chelated metal ions
Under, allyl chloride can be replaced, so that PVC be made to stablize.In addition, the more hydroxyl of dipentaerythritol can be formed with metal ion
Colourless ligand prevents metal ion and PVC polyene structure to cooperate to alleviate the catalysis acceleration of zinc stearate
Coloured ligand formation, play auxiliary stabilization, and lactate also provides great amount of hydroxy group, make dipentaerythritol stablize
Effect increases.
Preferably, the antioxidant is sub- by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and two
Phosphoric acid pentaerythrite distearyl alcohol ester composition.The antioxidant can delay the oxidative degradation of PVC, β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester be applied in combination, generate adduction effect, and cream
Hydrochlorate is used cooperatively, and ensure that the intrinsic stability and presentation quality of PVC plastic.
Preferably, the preparation method of the plastic heat stabilizer with long-term thermal stability, according to mass fraction, by 1
~12 parts of lactates, 6~15 parts of calcium stearates, 10~40 parts of zinc stearates, 15~40 parts of auxiliary heat stabilizers, 4~8 parts of antioxygens
Agent and 10~25 parts of lubricants are added to mixing in high speed mixer and take out after 30 seconds, are made described with long-term thermal stability
Plastic heat stabilizer.The preparation method of the plastic heat stabilizer with long-term thermal stability only needs raw material high-speed stirred is equal
Even, preparation difficulty is low, at low cost, high production efficiency.
The plastic heat stabilizer with long-term thermal stability is the solid calcium for being used to prepare polyvinyl chloride (PVC) plastics
Zinc heat stabilizer, lactate is added in raw material, and lactate has double hydroxyl structures, can increase the hydroxyl quantity of raw material, favorably
In raising long-term thermal stability.
It is a kind of anaerobic fermentation product that lactate, which cannot be simply considered that, more should be using it as an adjusting molecule, can
To adjust and integrate a plurality of metabolic pathway.Although lactate itself is not a kind of compound for having redox,
It takes part in glycolysis, biological oxidation and biosynthesis as a kind of important mesostate.Now, sodium lactate, lactic acid
Zinc, calcium lactate and magnesium lactate also can be widely used in dairy products, beverage, health care of food product as a kind of common food additives
Equal fields.It can be seen that lactate is a kind of nontoxic additive, have the function of to environment harmless.Lactate preferably has a left side
The Pfansteihl salt of structure is revolved, Pfansteihl salt does not have peculiar smell, and more environmentally friendly, the Pfansteihl salt is commercially available gained.
Lactate, auxiliary heat stabilizer and antioxidant interaction, so that the plastics heat with long-term thermal stability
Stabilizer has long-term thermal stability, improves heat resistance, reduces cost of material, is tested using its PVC plastic in static burn in
In transformation period be not less than 70min, Congo red test Coloring Time be not less than 59min.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
The raw material components and proportion of embodiment 1~11, as shown in table 1.
Table 1
In table 1, the raw material of embodiment 1 and embodiment 2: lactate is calcium lactate, and lubricant is the monostearate that mass ratio is 1:3
Glyceride and polyethylene wax, auxiliary heat stabilizer are dipentaerythritol, 1,3,5- tri- (the 2- hydroxyl second that mass ratio is 1:2:10:4:2
Base) cyanuric acid, zeolite, hydrotalcite and beta-diketon, antioxidant is β-(3, the 5- di-t-butyl -4- hydroxy benzenes that mass ratio is 1:1
Base) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester；
The raw material of embodiment 3: lactate is sodium lactate and magnesium lactate, and lubricant is the monostearate that mass ratio is 0.8:1.5:4
Glyceride, oleamide and polyethylene wax, auxiliary heat stabilizer are that mass ratio is the dipentaerythritol of 6:10:30:10:5,1,3,5-
Three (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons, antioxidant are β-(3, the 5- di-t-butyls-that mass ratio is 2:1
4- hydroxy phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester；
The raw material of embodiment 4 and embodiment 6: lactate is zinc lactate and barium lactate, and lubricant is that mass ratio is 0.3:0.8:
The stearic acid of 1.9:1.5:1.5, ethylene bis stearamide, butyl stearate, husky rope wax and polyethylene wax, auxiliary heat stabilizer are
Mass ratio is the dipentaerythritol of 3:5:20:7:4,1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons,
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid season that mass ratio is 2:3
Penta tetrol distearyl alcohol ester；
The raw material of embodiment 5 and embodiment 7: lactate is calcium lactate, zinc lactate and barium lactate, and lubricant is that mass ratio is 1:
Stearic acid, oleamide, paraffin, husky rope wax and the polyethylene wax of 1.5:0.6:2.5:1.7, auxiliary heat stabilizer is that mass ratio is 4:
The dipentaerythritol of 2:15:10:3,1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons, antioxidant is matter
Amount is harder than β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite two for being 4:1
Lipidol ester；
The raw material of embodiment 8: lactate is sodium lactate and magnesium lactate, and auxiliary heat stabilizer is that mass ratio is 6:10:30:10:5
Dipentaerythritol, 1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons, antioxidant are that mass ratio is 2:1
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester；
The raw material of embodiment 9: lactate is calcium lactate, and lubricant is the paraffin and polyethylene wax that mass ratio is 1:3, assists heat steady
It is the dipentaerythritol of 1:2:10:4:2,1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and β-that determine agent, which be mass ratio,
Diketone, antioxidant are β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and two phosphorous that mass ratio is 1:1
Sour pentaerythrite distearyl alcohol ester；
The raw material of embodiment 10: lactate is calcium lactate, and lubricant is the oleamide and ethylene stearic bicine diester that mass ratio is 1:3
Amine, auxiliary heat stabilizer are that mass ratio is the dipentaerythritol of 1:2:10:4:2,1,3,5- tri- (2- ethoxy) cyanuric acids, boiling
Stone, hydrotalcite and beta-diketon, antioxidant are β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid positive 18 that mass ratio is 1:1
Carbon alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester；
The raw material of embodiment 11: lactate is calcium lactate, and lubricant is the glycerin monostearate and polyethylene that mass ratio is 4:7
Wax, auxiliary heat stabilizer are that mass ratio is the dipentaerythritol of 1:2:10:4:2,1,3,5- tri- (2- ethoxy) cyanuric acids, boiling
Stone, hydrotalcite and beta-diketon, antioxidant are β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid positive 18 that mass ratio is 1:1
Carbon alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester.
Different plastic heat stabilizers is made according to following steps in raw material in table 1 by embodiment 1~11:
It is matched according to shown in table 1, by lactate, calcium stearate, zinc stearate, auxiliary heat stabilizer, antioxidant and lubricant
It is added to mixing in high speed mixer to take out after 30 seconds, the plastic heat stabilizer is made.
PVC plastic thin slice is prepared using plastic heat stabilizer made from embodiment 1~11 respectively:
According to mass fraction, plastic heat stabilizer made from 100 parts of PVC, 10 parts of calcium carbonate and 4 parts is taken, in a high speed mixer
It is sufficiently stirred, gained dry blend LRM-M-100 type open type dual-roller open mill, plasticate 5min at 185 DEG C, is pressed into thickness
For the PVC plastic thin slice of 1mm.
Following performance test is carried out to PVC plastic thin slice made from embodiment 1~11, the results are shown in Table 2:
(1) static burn in is tested: being tested, PVC plastic thin slice is placed in hot old according to the standard of ASTM D 2115-2010
Change in chamber, the heated at constant temperature at 180 DEG C, sampled every 10min, the color change of PVC plastic thin slice is observed, by PVC plastic
The time of material thin slice blackening is denoted as static burn in experiment transformation period；
(2) Congo red test: being tested according to the standard of GB/T 2917.1-2002, will be rigid controlled at 185 ± 1 DEG C
Arnotto test paper starts to become the Congo red Coloring Time for the blue time being denoted as PVC plastic thin slice；
(3) torque rheology is tested: being weighed 70g dry blend and is added in torque rheometer, in revolving speed be 35r/min and temperature is
Mixing rolls 15min under conditions of 185 DEG C, observes the variation of balancing moment.
| Transformation period (min) is tested in static burn in | Congo red test Coloring Time (min) | Counter balance torque (N m) | |
| Embodiment 1 | 70 | 59 | 16.3 |
| Embodiment 2 | 113 | 98 | 14.6 |
| Embodiment 3 | 82 | 75 | 13.4 |
| Embodiment 4 | 96 | 86 | 15.3 |
| Embodiment 5 | 108 | 93 | 13.9 |
| Embodiment 6 | 42 | 37 | 16.1 |
| Embodiment 7 | 54 | 41 | 14.5 |
| Embodiment 8 | 80 | 71 | 25.8 |
| Embodiment 9 | 110 | 96 | 24.3 |
| Embodiment 10 | 72 | 61 | 28.9 |
| Embodiment 11 | 114 | 97 | 24.7 |
Table 2
By analyzing the test data of Examples 1 to 5 it is found that the plastic heat stabilizer with long-term thermal stability has length
Phase thermal stability improves heat resistance, can accelerate the fusion time of PVC, reduces counter balance torque, allows using its PVC plastic quiet
Transformation period in state senile experiment is not less than 70min, and Congo red test Coloring Time is not less than 59min, and counter balance torque is not high
In 16.3 Nm.
By comparative example 4 and 6, comparative example 5 and 7 it is found that adding lactate in plastic heat stabilizer, can increase
The hydroxyl quantity for adding raw material is conducive to improve long-term thermal stability；If without lactate in plastic heat stabilizer, allow using its
Transformation period of the PVC plastic in static burn in experiment is lower than 70min, and Congo red test Coloring Time is lower than 59min, Bu Nengchang
Phase keeps thermal stability.
It can by comparative example 3 and 8, comparative example 2 and 9, comparative example 1 and 10, comparative example 2 and 11
Know, the mass ratio of in-lubricant and external lubricant is set as 1~3:2~5, can accelerate the fusion time of PVC, reduces balance and turns round
Square allows using the counter balance torque of its PVC plastic not higher than 16.3 Nm.If not adding in-lubricant in plastic heat stabilizer
And external lubricant, or no addition in-lubricant, or the mass ratio of external lubricant or lubricant and external lubricant is not added not upper
Range is stated, counter balance torque increases, and temperature of charge increases, and is easy thermal degradation blackening.It allows high using the counter balance torque of its PVC plastic
In 16.3 Nm.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field
Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within
Within protection scope of the present invention.
Claims (8)
1. a kind of plastic heat stabilizer with long-term thermal stability, it is characterised in that: according to mass fraction, raw material includes 1~
12 parts of lactates, 6~15 parts of calcium stearates, 10~40 parts of zinc stearates, 15~40 parts of auxiliary heat stabilizers, 4~8 parts of antioxidant
With 10~25 parts of lubricants.
2. the plastic heat stabilizer according to claim 1 with long-term thermal stability, it is characterised in that: the lactate
For one of sodium lactate, calcium lactate, zinc lactate, magnesium lactate and barium lactate or a variety of.
3. the plastic heat stabilizer according to claim 1 with long-term thermal stability, it is characterised in that: the lubricant
It is made of in-lubricant and external lubricant, the in-lubricant is stearic acid, glycerin monostearate, butyl stearate, oleoyl
One of amine and ethylene bis stearamide are a variety of, and the external lubricant is husky rope wax, one of paraffin and polyethylene wax
Or it is a variety of.
4. the plastic heat stabilizer according to claim 3 with long-term thermal stability, it is characterised in that: according to quality
Than the in-lubricant: external lubricant is 1~3:2~5.
5. the plastic heat stabilizer according to claim 1 with long-term thermal stability, it is characterised in that:
The auxiliary heat stabilizer is by dipentaerythritol, 1,3,5- tri- (2- ethoxy) cyanuric acid, zeolite, hydrotalcite and beta-diketons
Composition.
6. the plastic heat stabilizer according to claim 5 with long-term thermal stability, it is characterised in that: according to quality
Than dipentaerythritol: 1,3,5- tri- (2- ethoxy) cyanuric acid: zeolite: hydrotalcite: beta-diketon is 1~6:2~10:10~30:
4~10:2~5.
7. the plastic heat stabilizer according to claim 1 with long-term thermal stability, it is characterised in that: the antioxidant
By β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and diphosphorous acid pentaerythrite distearyl alcohol ester group
At.
8. the preparation method of the plastic heat stabilizer according to claim 1 with long-term thermal stability, it is characterised in that:
According to mass fraction, by 1~12 part of lactate, 6~15 parts of calcium stearates, 10~40 parts of zinc stearates, 15~40 parts of auxiliary heat
Stabilizer, 4~8 parts of antioxidant and 10~25 parts of lubricants are added to mixing in 24000r/min high speed mixer and take after 30 seconds
Out, the plastic heat stabilizer with long-term thermal stability is made.
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| CN114605701A (en) * | 2022-03-17 | 2022-06-10 | 浙江紫东新材料科技有限公司 | PVC plastic stabilizer and preparation method thereof |
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Application publication date: 20190312 |