CN107141643B - A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application - Google Patents
A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application Download PDFInfo
- Publication number
- CN107141643B CN107141643B CN201710383706.4A CN201710383706A CN107141643B CN 107141643 B CN107141643 B CN 107141643B CN 201710383706 A CN201710383706 A CN 201710383706A CN 107141643 B CN107141643 B CN 107141643B
- Authority
- CN
- China
- Prior art keywords
- barium
- acid
- zinc
- salt
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to heat stabilizer field, it is related to a kind of barium-zinc liquid heat stabilizer and preparation method thereof, application.The barium-zinc liquid heat stabilizer includes at least following raw material: the first zinc salt 30~50 in parts by weight；Second zinc salt 45~70；First barium salt 280~375；Second barium salt 300~400；Light stabilizer 35~55；Calcium zinc stabilizer 10~20；Magnalium complexes 1~3；Phosphite ester 80~175；Polyglycerol polyricinoleate 8~35；Anti- precipitation agent 30~100；Kerosene 20~80.
Description
Technical field
The invention belongs to heat stabilizer field, it is related to a kind of barium-zinc liquid heat stabilizer and preparation method thereof, application.
Background technique
Polyvinyl chloride (PVC) is one of five big general-purpose plastics, and global yield is only second to polyethylene (PE) and occupies second, phase
For other resins for universal use, in thermal stability it is poor, product in machine-shaping be easy color burn, property
It can decline, so limiting its own application and development, therefore to add heat stabilizer appropriate in process.Mesh
Before, widely used PVC heat stabilizer has lead salts, organic tin, metal soap and terres rares etc..In face of increasingly strict ring
Regulation is protected, research and development novel environment protection PVC heat stabilizer has become inexorable trend.
The heat stabilizer used earliest in polyvinyl chloride (PVC) product process is Lead salt thermal stabilizer, but can not be used
Transparent article is produced, and lead salt is toxic, dust pollution is serious, and liquid barium Zn composite heat stabilizer is because of its production and application process
Without dust pollution, clean and environmental protection is cheap, and can be applied in transparent article, is more and more widely used.
Thus, it is highly desirable through the improvement of technique to develop a liquid barium with preferable thermostable effect
Zn composite heat stabilizer.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of barium-zinc liquid heat stabilizer, with
Parts by weight meter includes at least following raw material:
First zinc salt the preparation method is as follows:
By isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:1.2:2:2 is uniformly mixed, and is obtained
To the first mixed liquor；Zinc oxide is added into the first mixed liquor again, wherein n (zinc oxide): [n (isooctyl acid)+n (neodecanoic acid)]
=1:(1~2)；By the first mixed liquor stir 5~after ten minutes, be warming up to 100 DEG C~140 DEG C, be again stirring for reaction 50~80
Minute, after completion of the reaction, decompression dehydration is carried out, is filtered after cooling to 100 DEG C~120 DEG C, obtains the first zinc salt；
Second zinc salt the preparation method is as follows:
By benzoic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:2:
1.5:1.5:1.5 being uniformly mixed, the second mixed liquor is obtained；Zinc oxide is added into the second mixed liquor again, wherein n (zinc oxide):
=1:(1~2 [n (benzoic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；Second mixed liquor is stirred 5~10 minutes
Afterwards, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, decompression dehydration is carried out, cools to
It is filtered after 100 DEG C~120 DEG C, obtains the second zinc salt；
First barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether according to weight ratio are as follows: 2:1:0.5:1 is mixed
It closes uniformly, obtains third mixed liquor；Barium monohydrate is added into third mixed liquor again, wherein n (barium monohydrate):
=1:(1.5~2 [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；Third mixed liquor is stirred 5~10 minutes
Afterwards, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, decompression dehydration is carried out, cools to 80
DEG C, the different monooctyl ester of phosphorous acid hexichol one, kerosene are then added, stirring after ten minutes, obtains the first barium salt；
Second barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, kerosene, diethylene glycol monobutyl ether according to weight ratio are as follows: 3:1:3:
1.3:2.5 is uniformly mixed, and obtains the 4th mixed liquor；Barium monohydrate is added into the 4th mixed liquor again, wherein a n (water hydrogen
Barium monoxide) :=1:(1.5~2 [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；4th mixed liquor is stirred 5
~after ten minutes, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, carries out decompression dehydration,
80 DEG C are cooled to, the different monooctyl ester of phosphorous acid hexichol one is then added, stirring after ten minutes, obtains the second barium salt.
As a preferred technical solution of the present invention, the light stabilizer is benzotriazole light stabilizer, benzophenone
Class light stabilizer, triazines as light stabilizer, any one or a few the mixing in hindered amine light stabilizer.
As a preferred technical solution of the present invention, the preparation method of the magnalium complexes includes at least following step
It is rapid:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to molar ratio Mg2+: A13+=2~2.2:1 is configured to gold
Belong to salting liquid；The metal salt includes magnesium salts and aluminium salt；
(2) preparation of water soluble alkali solution: control n (OH-): (n (Mg2+)+n(A13+))=2:1, n (CO3 2-): n (A13 +)=1:1 controls the amount of sodium hydroxide and sodium carbonate according to such ratio to prepare water soluble alkali solution；
(3) dropwise addition of metal salt solution and water soluble alkali solution: being added water, neopelex in reaction kettle,
In the case where temperature is 25 DEG C, after mixing evenly, it is made into neopelex solution, then to neopelex solution
In be added dropwise the metal salt solution, water soluble alkali solution, hyperbranched amido silicon oil measured simultaneously, control pH value exists during being added dropwise
9~10, titration, which finishes, to be continued to stir 1h, obtains mixed liquor；
(4) crystallization, washing, drying: at a temperature of aging 4~8h by mixed liquor at 150 DEG C, it is washed, be dried to obtain magnesium
Aluminium compound.
As a preferred technical solution of the present invention, the phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one, phosphorous
Sour a benzene di-isooctyl, phenyl diisodecyl ester, triisodecyl phosphite ester, Conditions of Trilauryl Phosphite Ester, diphenyl phosphorous
Any one or a few mixing in acid esters.
It further include hyper branched polyphosphate in the barium-zinc liquid heat stabilizer as a preferred technical solution of the present invention
Ester.
As a preferred technical solution of the present invention, the anti-precipitation agent is selected from: carbon atom number be 10~28 it is advanced
Fatty alcohol.
The second aspect of the invention provides a kind of preparation method of barium-zinc liquid heat stabilizer, includes at least following step
It is rapid:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10~30 minutes, are then warming up to 90 DEG C again, are stirred 50~80 minutes, will
Reaction system is cooled to 60 DEG C, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene is then added, by reaction system liter
Temperature stirs 10~20 minutes to 80 DEG C.
The third aspect of the invention provides PVC composition, in parts by weight, includes at least following raw material,
100 parts of polyvinyl chloride resin；
1~3 part of barium-zinc liquid heat stabilizer；
2~6 parts of nano silica.
As a preferred technical solution of the present invention, the nano silica is aminosilane coupling agent modifying nanometer
Silica.
The fourth aspect of the invention provides the preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5~20 minutes on the double roll mill, PVC composition can be obtained.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understand
Open content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device." optional " or " optionally " refer to and describe thereafter
Item or event may or may not occur, and the description includes the situation and the situation that does not occur of event that event occurs.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of barium-zinc liquid heat stabilizer, with
Parts by weight meter includes at least following raw material:
First zinc salt the preparation method is as follows:
By isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:1.2:2:2 is uniformly mixed, and is obtained
To the first mixed liquor；Zinc oxide is added into the first mixed liquor again, wherein n (zinc oxide): [n (isooctyl acid)+n (neodecanoic acid)]
=1:(1~2)；By the first mixed liquor stir 5~after ten minutes, be warming up to 100 DEG C~140 DEG C, be again stirring for reaction 50~80
Minute, after completion of the reaction, decompression dehydration is carried out, is filtered after cooling to 100 DEG C~120 DEG C, obtains the first zinc salt；
Second zinc salt the preparation method is as follows:
By benzoic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:2:
1.5:1.5:1.5 being uniformly mixed, the second mixed liquor is obtained；Zinc oxide is added into the second mixed liquor again, wherein n (zinc oxide):
=1:(1~2 [n (benzoic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；Second mixed liquor is stirred 5~10 minutes
Afterwards, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, decompression dehydration is carried out, cools to
It is filtered after 100 DEG C~120 DEG C, obtains the second zinc salt；
First barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether according to weight ratio are as follows: 2:1:0.5:1 is mixed
It closes uniformly, obtains third mixed liquor；Barium monohydrate is added into third mixed liquor again, wherein n (barium monohydrate):
=1:(1.5~2 [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；Third mixed liquor is stirred 5~10 minutes
Afterwards, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, decompression dehydration is carried out, cools to 80
DEG C, the different monooctyl ester of phosphorous acid hexichol one, kerosene are then added, stirring after ten minutes, obtains the first barium salt；
Second barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, kerosene, diethylene glycol monobutyl ether according to weight ratio are as follows: 3:1:3:
1.3:2.5 is uniformly mixed, and obtains the 4th mixed liquor；Barium monohydrate is added into the 4th mixed liquor again, wherein a n (water hydrogen
Barium monoxide) :=1:(1.5~2 [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；By the 4th mixed liquor stir 5~
After ten minutes, 100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, carries out decompression dehydration, drop
Then temperature adds the different monooctyl ester of phosphorous acid hexichol one to 80 DEG C, stirring after ten minutes, obtains the second barium salt.
Term " n (zinc oxide) " refers to the amount of the substance of zinc oxide, and n (isooctyl acid) refers to the amount of the substance of isooctyl acid, n
(neodecanoic acid) refers to the amount of the substance of neodecanoic acid；[n (isooctyl acid)+n (neodecanoic acid)] refers to the substance of isooctyl acid and neodecanoic acid
The sum of amount；[n (benzoic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)] refers to benzoic acid, neodecanoic acid, to tert-butyl benzene first
The sum of the amount of substance of acid；N (barium monohydrate) refers to the amount of the substance of barium monohydrate；[n (oleic acid)+n (neodecanoic acid)
+ n (p-tert-butyl benzoic acid)] refer to the sum of the amount of substance of oleic acid, neodecanoic acid, p-tert-butyl benzoic acid.
As a preferred technical solution of the present invention, the light stabilizer is benzotriazole light stabilizer, benzophenone
Class light stabilizer, triazines as light stabilizer, any one or a few the mixing in hindered amine light stabilizer.
What the benzotriazole light stabilizer can be enumerated has: Tinuvin213, UV327, UV328, UV320, UV-
P,Tinuvin571；What the Benzophenones light stabilizer can be enumerated has: UV-531；The triazines as light stabilizer can arrange
That lifts has: UV-1164；What the hindered amine light stabilizer can be enumerated has: ADEKASTABLA-52, LA-57, LA-62,
LA-67, LA-63, LA-68, LA-77, LA-82, LA-87 (Japanese Ai Dike Co., Ltd.), Tinuvin622,
Tinuvin770, Chisorb622LD, SanolLS-765 and SanolLS-292 (Taiwan Double Bond Chemical Ind.,Co.,Ltd.).
As a preferred technical solution of the present invention, the preparation method of the magnalium complexes includes at least following step
It is rapid:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to molar ratio Mg2+: A13+=2~2.2:1 is configured to gold
Belong to salting liquid；The metal salt includes magnesium salts and aluminium salt；
(2) preparation of water soluble alkali solution: control n (OH-): (n (Mg2+)+n(A13+))=2:1, n (CO3 2-): n (A13 +)=1:1 controls the amount of sodium hydroxide and sodium carbonate according to such ratio to prepare water soluble alkali solution；
(3) dropwise addition of metal salt solution and water soluble alkali solution: being added water, neopelex in reaction kettle,
In the case where temperature is 25 DEG C, after mixing evenly, it is made into neopelex solution, then to neopelex solution
In be added dropwise the metal salt solution, water soluble alkali solution, hyperbranched amido silicon oil measured simultaneously, control pH value exists during being added dropwise
9~10, titration, which finishes, to be continued to stir 1h, obtains mixed liquor；
(4) crystallization, washing, drying: at a temperature of aging 4~8h by mixed liquor at 150 DEG C, it is washed, be dried to obtain magnesium
Aluminium compound.
Term " hyperbranched amido silicon oil " refers to hyperbranched amino modified polysiloxane, in the application, used over-expense
The preparation method for changing amino modified polysiloxane is same " preparation and application study of hyperbranched amino modified polysiloxane ", and 2014
It is published in printing and dyeing assistant periodical December.
It is specific the preparation method is as follows:
By n (both-end epoxy group polysiloxanes): n (diethylenetriamine removed water)=1.5:1 is added to be filled with equipped with nitrogen
In the drying four-hole boiling flask of device, reflux condensing tube and blender, solvent isopropanol is added, dosage is reactant gross mass
30%, be warming up to 80 DEG C after mixing evenly, insulation reaction for a period of time after, vacuum distillation removes solvent to get pale yellow transparent
The hyperbranched amino modified polysiloxane of liquid.
As a preferred technical solution of the present invention, the phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one, phosphorous
Sour a benzene di-isooctyl, phenyl diisodecyl ester, triisodecyl phosphite ester, Conditions of Trilauryl Phosphite Ester, diphenyl phosphorous
Any one or a few mixing in acid esters.
It further include hyper branched polyphosphate in the barium-zinc liquid heat stabilizer as a preferred technical solution of the present invention
Ester.
Term " hyper branched polyphosphate ester " refers to the high molecular weight that heat resistant type nitrogen-containing heterocycle is skeleton preparation, high activity, low
It volatilizees, the faint yellow terminal hydroxy group nitrogen hyper branched polyphosphate ester of high flame-retardant property.In the application, used hyper branched polyphosphate
Ester is commercially available acquisition, is purchased from Wuhan hyperbranched resin Science and Technology Ltd., product grade are as follows: HPP-102.
Applicants have discovered that hyper branched polyphosphate ester, which is added, can play jointly and compound with zinc salt, barium salt, magnalium complexes
Effect, further improves thermal stability, prevents the appearance for burning zinc phenomenon, plays the beneficial effect of the application.Overspend simultaneously
Fire-retardant effect can also be played with compounding for magnalium complexes by changing polyphosphate.
As a preferred technical solution of the present invention, the anti-precipitation agent is selected from: carbon atom number be 10~28 it is advanced
Fatty alcohol.
The higher aliphatic include branch and straight chain.These fatty alcohols are used alone or are made with arbitrary proportion mixing
With.
What can be enumerated has: laruyl alcohol, tetradecanol, cetanol, stearyl alcohol, oleyl alcohol, eicosanol, docosanol, two
Tetradecanol etc..
The second aspect of the invention provides a kind of preparation method of barium-zinc liquid heat stabilizer, includes at least following step
It is rapid:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10~30 minutes, are then warming up to 90 DEG C again, are stirred 50~80 minutes, will
Reaction system is cooled to 60 DEG C, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene is then added, by reaction system liter
Temperature stirs 10~20 minutes to 80 DEG C.
The third aspect of the invention provides PVC composition, in parts by weight, includes at least following raw material,
100 parts of polyvinyl chloride resin；
1~3 part of barium-zinc liquid heat stabilizer；
2~6 parts of nano silica.
As a preferred technical solution of the present invention, the nano silica is aminosilane coupling agent modifying nanometer
Silica.
In a preferred embodiment, the preparation method of the aminosilane coupling agent modifying nano silica is such as
Under:
In the reactor, solvent 300ml toluene is added and then 10g nano silica, ultrasonic disperse 30min is added
1g KH-550 silane coupling agent, add 20mL volumetric concentration be 20% triethylamine solution, the back flow reaction 5h at 100 DEG C,
Through filtering, ethanol washing 3 times, aminosilane coupling agent modifying nano silica is obtained.
It in a preferred embodiment, further include auxiliary agent in the environment-friendly type PVC composition.
What the auxiliary agent can be enumerated has: antioxidant, plasticizer, fire retardant, filler, ultraviolet absorbing agent, antibacterial agent, face
Expect, enter delustering agent, weather resisting agent, antistatic agent, anti-coloring agent etc..
What the antioxidant can be enumerated has: phenolic antioxidant, phosphite ester antioxidant, containing in sulphur ester antioxidant
It is at least one.
Phenolic antioxidant can be enumerated: 1- hydroxy-3-methyl -4- cumene, 2,6- DI-tert-butylphenol compounds, 2,6- bis-
Tert-butyl -4- ethyl -phenol, 2,6-di-tert-butyl p-cresol, 2,6- di-t-butyl -4- normal-butyl phenol, 4- methylol -2,6-
DI-tert-butylphenol compounds, butylhydroxy anisole, 2- (1- methylcyclohexyl) -4,6- xylenol, 2,4- dimethyl -6- uncle
Butylphenol, 2- methyl -4,6- dinonyl phenol, 2,6- di-t-butyl-α-dimethylamino-p-cresol, 2,4,6- tri-terts
Phenol, 6- (4- hydroxyl -3,5- di-tert-butyl amido) bis- (octylsulfo) -1,3,5-triazines of -2,4-, bis- (the 4- hydroxyls of 4,6-
Base -3,5- di-t-butyl phenoxy group) -2- n-octylthio -1,3,5-triazines, β-(3,5- di-tert-butyl-hydroxy phenyl) third
Sour methyl esters, β-(4-hydroxyls-3,5-di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester, styrenated phenol, 4,4 '-dihydroxies
Base biphenyl, butylated octylated phenol, butylated stytrene cresols, 2,2 '-methylene bis (4- methyl-6-tert-butylphenol) or
2,2 '-methylene bis (6- tert-butyl -4- cresols), 2,2 '-methylene bis (4- ethyl -6- tert-butyl phenol), 2,2 '-methylene bis (4-
Methyl -6- cyclohexylphenol), 4,4 '-methylene bis (2,6- DI-tert-butylphenol compounds), (6- α-methylbenzyl is to first for 2,2 '-methylene bis
Phenol), 1,1- bis- (4- hydroxy benzenes) hexamethylenes, 2,2 '-methylene bis (4- methyl -6- (Alpha-Methyl cyclohexyl) phenol) or 2,2 '-two
Hydroxyl -3,3 '-two (Alpha-Methyl cyclohexyl) -5,5 '-dimethyl diphenylmethanes, 1,3,5- trimethyls -2,4,6- tri- (3,5-
Di-tert-butyl-4-hydroxyl benzyl) benzene, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, four (3- (3 ' 5 ' -
Di-t-butyl -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, 4,4 '-thiobis (6- tert-butyl -3- methylphenol) or 4,4 ' -
Thiobis (6- tert-butyl-m-cresol), 4,4 '-thiobis (2- methyl-6-tert-butylphenol) or 4,4 '-thiobis (the tertiary fourth of 6-
Base o-cresol), 2,2 '-thiobis (4- methyl -6- tert-butyl phenol), bis- (β-(3, the 5- di-t-butyl -4- hydroxy benzenes of hexylene glycol
Base) propionic ester), 2,2 '-thiobis (3 ,-(3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate), N, N '-hexamethylene it is bis- (3,
5- di-t-butyl-4- hydroxyl hydrocinnamamide), 1,3,5- tri- (4- tert-butyl-3- hydroxyl-2,6- dimethyl benzyls) 1,3,5-three
Piperazine -2,4,6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) guanamines, 4,6- (1H,
3H, 5H) triketone or isocyanuric acid three (3,5- di-tert-butyl-4-hydroxyl benzyl ester), [β-(3, the 5- bis- tertiary fourths of isocyanuric acid three
Base -4- hydroxy phenyl) propionyloxy ethyl ester], bis- [3,3- bis- (3 '--4 '-hydroxy phenyl of tert-butyl) butyric acid] glycol esters, 1,
1 '-thiobis (beta naphthal), bis- (3,5- di-tert-butyl-4-hydroxyl benzyl) thioethers, 2,5- di-tert-butyl hydroquinone, 2,5- bis-
Tertiary pentyl hydroquinone, 3,5- di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (18) ester, 3,5- di-tert-butyl-4-hydroxyl benzyl
In double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters of diethyl phosphate, triethylene glycol, hydroquinone dibenzyl ether
It is a kind of.
Phosphite ester antioxidant can be enumerated: triphenyl phosphite, phosphorous acid three (nonyl phenyl ester), phosphorous acid three are different pungent
Ester, triisodecyl phosphite ester, phosphorous acid benzene diisodecyl ester, trilauryl trithiophosphite, trilauryl phosphite, phosphorous acid
Three (octadecyl esters), diphosphorous acid pentaerythrite diisodecyl ester, diphosphorous acid pentaerythrite distearyl alcohol ester, 4,4 '-fourths fork are bis- (sub-
Phosphoric acid (3- methyl-6-tert butyl phenyl) two (tridecyl) esters), isooctyl diphenyl phosphite, phosphorous acid benzene di-isooctyl, Asia
Diphenyl octyl phosphate, diphenyl isophthalate, dioctyl phosphite, phosphorous acid dilauryl, dimethylphosphite, phosphorous acid
Double 13 esters of two oleyl alcohol esters, didecyl phosphite, dibutyl phosphite, phosphorous acid, phosphorous acid double 14 esters, phosphorous triethylenetetraminehexaacetic acid
Ester, tributyl phosphite, triisopropyl phosphite, three monooctyl ester of phosphorous acid or phosphorous acid three (2- ethylhexyl), phosphorous acid-benzene are double
One of (nonyl benzene) ester, phosphorous acid hexichol nonyl phenyl ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
It can be enumerated containing sulphur ester antioxidant: dilauryl thiodipropionate, thio-2 acid 2 stearyl ester or thio
Dipropionic acid two (octadecyl ester), β, thio two butyric acid two (18) ester of β '-, thio-2 acid laurel octadecyl ester, thio-2 acid two
(13) ester, thio-2 acid two (14) ester are medium.
The plasticizer can be enumerated: dioctyl phthalate, diisooctyl phthalate, terephthalic acid (TPA) two are pungent
One of ester, trioctyl trimellitate (TOTM) or dioctyl sebacate are a variety of.And then preferred cold resistant plasticizer DOS (decanedioic acid
Dioctyl ester) or DOP (dioctyl phthalate) etc..
The fire retardant can be enumerated: brominated organic based flame retardant, phosphoric acid based flame retardant, antimony trioxide, magnesium hydroxide, red
Phosphorus etc..
The filler can be enumerated: silica, aluminium oxide, kaolinite, wollastonite, mica, talcum, clay, sericite,
Magnesium carbonate, magnesium sulfate, calcium oxide, silicon carbide, antimony trisulphide, artificial gold, copper sulfide, iron sulfide, bismuth sulfide, zinc sulphide, metal
Powder, glass powder, glass flake, montmorillonite, glass microballoon etc..
What the ultraviolet absorbing agent can be enumerated has: 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2- (2- hydroxyl
Base -5- butyl phenyl) benzotriazole, 2- (2- hydroxyl -5- octyl phenyl) benzotriazole, 2- (3- tert-butyl -2- hydroxy-5-methyl
Base phenyl) the enumerate BTA systems ultraviolet light such as -5- chlorobenzotriazole, 2- (3,5- bis- tertiary pentyl -2- hydroxy phenyl) benzotriazole inhales
Receive agent；The benzophenone series ultraviolet lights such as ESCALOL 567,2- hydroxyl -4- n-octyl oxygroup benzophenone are inhaled
Receive agent；2- [4,6- bis- (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases] -5- (octyl oxygroup) phenol, 2- (4,6- hexichol
Base -1,3,5-triazines -2- base) the triazines system ultraviolet absorbing agent such as -5- (hexyl oxygroup) phenol；P-t-butylphenyl salicylate,
The salicylates such as phenyl salicylate system ultraviolet absorbing agent etc..
What the antibacterial agent can be enumerated has: silver ion class antibacterial agent, zinc oxide, copper oxide, ammonium dihydrogen phosphate, carbonic acid
Lithium, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols formic acid, sorbic acid, has anilid class
Machine iodine, nitrile, sulphur cyanogen, copper agent, three halogenation allyl compounds, organic nitrogen sulfur compound, chitin, mustard, castor oil, horseradish
Deng.
The fourth aspect of the invention provides the preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5~20 minutes on the double roll mill, PVC composition can be obtained.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment 1:
The present embodiment 1 provides a kind of barium-zinc liquid heat stabilizer, in parts by weight, includes at least following raw material:
First zinc salt the preparation method is as follows:
By isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:1.2:2:2 is uniformly mixed, and is obtained
To the first mixed liquor；Zinc oxide is added into the first mixed liquor again, wherein n (zinc oxide): [n (isooctyl acid)+n (neodecanoic acid)]
=1:2；After ten minutes by the stirring of the first mixed liquor, 140 DEG C are warming up to, are again stirring for reaction 50 minutes, after completion of the reaction, carried out
Decompression dehydration filters after cooling to 120 DEG C, obtains the first zinc salt；
Second zinc salt the preparation method is as follows:
By benzoic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:2:
1.5:1.5:1.5 being uniformly mixed, the second mixed liquor is obtained；Zinc oxide is added into the second mixed liquor again, wherein n (zinc oxide):
[n (benzoic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)]=1:2；After ten minutes by the stirring of the second mixed liquor, it is warming up to
140 DEG C, it is again stirring for reaction 80 minutes, after completion of the reaction, decompression dehydration is carried out, is filtered after cooling to 120 DEG C, obtain the second zinc
Salt；
First barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether according to weight ratio are as follows: 2:1:0.5:1 is mixed
It closes uniformly, obtains third mixed liquor；Barium monohydrate is added into third mixed liquor again, wherein n (barium monohydrate):
[n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)]=1:2；After ten minutes by the stirring of third mixed liquor, 140 are warming up to
DEG C, it is again stirring for reaction 50 minutes, after completion of the reaction, decompression dehydration is carried out, cools to 80 DEG C, then add phosphorous acid hexichol
One different monooctyl ester, kerosene, stirring after ten minutes, obtain the first barium salt；
Second barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, kerosene, diethylene glycol monobutyl ether according to weight ratio are as follows: 3:1:3:
1.3:2.5 is uniformly mixed, and obtains the 4th mixed liquor；Barium monohydrate is added into the 4th mixed liquor again, wherein a n (water hydrogen
Barium monoxide): [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)]=1:2；After ten minutes by the stirring of the 4th mixed liquor,
100 DEG C are warming up to, reaction 80 minutes is again stirring for, after completion of the reaction, decompression dehydration is carried out, cools to 80 DEG C, then add
The different monooctyl ester of phosphorous acid hexichol one, stirring after ten minutes, obtain the second barium salt.
The light stabilizer is selected from: BASF BASF hindered amine light stabilizer Tinuvin 622；
The calcium zinc stabilizer is selected from: Nantong Ai Dewang calcium zinc stabilizer；
The preparation method of the magnalium complexes, at least includes the following steps:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to molar ratio Mg2+: A13+=that 2:1 is configured to metal salt is molten
Liquid；The metal salt includes magnesium salts and aluminium salt；The magnesium salts is magnesium sulfate；The aluminium salt is aluminium hydroxide；The aluminium hydroxide
Molal quantity be 1000；
(2) preparation of water soluble alkali solution: control n (OH-): (n (Mg2+)+n(A13+))=2:1, n (CO3 2-): n (A13 +)=1:1 controls the amount of sodium hydroxide and sodium carbonate according to such ratio to prepare water soluble alkali solution；
(3) 1000kg water, detergent alkylate sulphur the dropwise addition of metal salt solution and water soluble alkali solution: are added in reaction kettle
Sour sodium after mixing evenly, is made into neopelex solution, then to dodecyl benzene sulfonic acid in the case where temperature is 25 DEG C
The metal salt solution, water soluble alkali solution, hyperbranched amido silicon oil measured is added dropwise in sodium solution simultaneously, is controlled during being added dropwise
9, titration finishes to be continued to stir 1h pH value, obtains mixed liquor；The weight ratio of the neopelex and metal salt are as follows:
1:18；
(4) crystallization, washing, drying: the at a temperature of aging 4h by mixed liquor at 150 DEG C, it is washed, to be dried to obtain magnalium multiple
Close object.
Hyperbranched amido silicon oil it is specific the preparation method is as follows:
By n (both-end epoxy group polysiloxanes): n (diethylenetriamine removed water)=1.5:1 is added to be filled with equipped with nitrogen
In the drying four-hole boiling flask of device, reflux condensing tube and blender, solvent isopropanol is added, dosage is reactant gross mass
30%, be warming up to 80 DEG C after mixing evenly, insulation reaction for a period of time after, vacuum distillation removes solvent to get pale yellow transparent
The hyperbranched amino modified polysiloxane of liquid.The weight ratio of the hyperbranched amido silicon oil and metal salt are as follows: 1:40.
The phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one；
The polyglycerol polyricinoleate is purchased from Shandong Xi Tang Biotechnology Co., Ltd；
The anti-precipitation agent is selected from: stearyl alcohol；
The preparation method of the barium-zinc liquid heat stabilizer, at least includes the following steps:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10 minutes, are then warming up to 90 DEG C again, are stirred 80 minutes, by reaction system
60 DEG C are cooled to, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene is then added, reaction system is warming up to 80
DEG C, it stirs 20 minutes.
A kind of PVC composition includes at least following raw material in parts by weight,
100 parts of polyvinyl chloride resin；
1 part of barium-zinc liquid heat stabilizer described in embodiment 1；
2 parts of nano silica.
The aminosilane coupling agent modifying nano silica the preparation method is as follows:
In the reactor, solvent 300ml toluene is added and then 10g nano silica, ultrasonic disperse 30min is added
1g KH-550 silane coupling agent, add 20mL volumetric concentration be 20% triethylamine solution, the back flow reaction 5h at 100 DEG C,
Through filtering, ethanol washing 3 times, aminosilane coupling agent modifying nano silica is obtained.
The preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5 minutes on the double roll mill, PVC composition can be obtained.
Embodiment 2:
The present embodiment 2 provides a kind of barium-zinc liquid heat stabilizer, in parts by weight, includes at least following raw material:
First zinc salt, the second zinc salt, the first barium salt, the preparation method is the same as that of Example 1 for the second barium salt.
The preparation method is the same as that of Example 1 for the magnalium complexes.
The light stabilizer is selected from: BASF BASF hindered amine light stabilizer Tinuvin 622；
The calcium zinc stabilizer is selected from: Nantong Ai Dewang calcium zinc stabilizer；
The phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one；
The polyglycerol polyricinoleate is purchased from Shandong Xi Tang Biotechnology Co., Ltd；
The anti-precipitation agent is selected from: stearyl alcohol；
The preparation method of the barium-zinc liquid heat stabilizer, at least includes the following steps:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10 minutes, are then warming up to 90 DEG C again, are stirred 80 minutes, by reaction system
60 DEG C are cooled to, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene is then added, reaction system is warming up to 80
DEG C, it stirs 20 minutes.
A kind of PVC composition includes at least following raw material in parts by weight,
100 parts of polyvinyl chloride resin；
1 part of barium-zinc liquid heat stabilizer described in embodiment 1；
2 parts of nano silica.
The aminosilane coupling agent modifying nano silica the preparation method is as follows:
In the reactor, solvent 300ml toluene is added and then 10g nano silica, ultrasonic disperse 30min is added
1g KH-550 silane coupling agent, add 20mL volumetric concentration be 20% triethylamine solution, the back flow reaction 5h at 100 DEG C,
Through filtering, ethanol washing 3 times, aminosilane coupling agent modifying nano silica is obtained.
The preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5 minutes on the double roll mill, PVC composition can be obtained.
Embodiment 3:
The present embodiment 3 provides a kind of barium-zinc liquid heat stabilizer, in parts by weight, includes at least following raw material:
First zinc salt, the second zinc salt, the first barium salt, the preparation method is the same as that of Example 1 for the second barium salt.
The preparation method is the same as that of Example 1 for the magnalium complexes.
The light stabilizer is selected from: BASF BASF hindered amine light stabilizer Tinuvin 622；
The calcium zinc stabilizer is selected from: Nantong Ai Dewang calcium zinc stabilizer；
The phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one；
The polyglycerol polyricinoleate is purchased from Shandong Xi Tang Biotechnology Co., Ltd；
The anti-precipitation agent is selected from: stearyl alcohol；
The preparation method of the barium-zinc liquid heat stabilizer, at least includes the following steps:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10 minutes, are then warming up to 90 DEG C again, are stirred 80 minutes, by reaction system
60 DEG C are cooled to, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene is then added, reaction system is warming up to 80
DEG C, it stirs 20 minutes.
A kind of PVC composition includes at least following raw material in parts by weight,
100 parts of polyvinyl chloride resin；
1 part of barium-zinc liquid heat stabilizer described in embodiment 1；
2 parts of nano silica.
The aminosilane coupling agent modifying nano silica the preparation method is as follows:
In the reactor, solvent 300ml toluene is added and then 10g nano silica, ultrasonic disperse 30min is added
1g KH-550 silane coupling agent, add 20mL volumetric concentration be 20% triethylamine solution, the back flow reaction 5h at 100 DEG C,
Through filtering, ethanol washing 3 times, aminosilane coupling agent modifying nano silica is obtained.
The preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5 minutes on the double roll mill, PVC composition can be obtained.
Embodiment 4:
The present embodiment 4 provides a kind of barium-zinc liquid heat stabilizer, in parts by weight, includes at least following raw material:
First zinc salt, the second zinc salt, the first barium salt, the preparation method is the same as that of Example 1 for the second barium salt.
The preparation method is the same as that of Example 1 for the magnalium complexes.
The light stabilizer is selected from: BASF BASF hindered amine light stabilizer Tinuvin 622；
The calcium zinc stabilizer is selected from: Nantong Ai Dewang calcium zinc stabilizer；
The phosphite ester is selected from: the different monooctyl ester of phosphorous acid hexichol one；
The polyglycerol polyricinoleate is purchased from Shandong Xi Tang Biotechnology Co., Ltd；
The anti-precipitation agent is selected from: stearyl alcohol；
The preparation method of the barium-zinc liquid heat stabilizer, at least includes the following steps:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc are stablized
Agent, magnalium complexes are added in reactor, are stirred 10 minutes, are then warming up to 90 DEG C again, are stirred 80 minutes, by reaction system
60 DEG C are cooled to, phosphite ester, polyglycerol polyricinoleate, anti-precipitation agent, kerosene, hyper branched polyphosphate ester is then added, it will be anti-
It answers system to be warming up to 80 DEG C, stirs 20 minutes.
A kind of PVC composition includes at least following raw material in parts by weight,
100 parts of polyvinyl chloride resin；
1 part of barium-zinc liquid heat stabilizer described in embodiment 1；
2 parts of nano silica.
The aminosilane coupling agent modifying nano silica the preparation method is as follows:
In the reactor, solvent 300ml toluene is added and then 10g nano silica, ultrasonic disperse 30min is added
1g KH-550 silane coupling agent, add 20mL volumetric concentration be 20% triethylamine solution, the back flow reaction 5h at 100 DEG C,
Through filtering, ethanol washing 3 times, aminosilane coupling agent modifying nano silica is obtained.
The preparation method of PVC composition, at least includes the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added to high-speed mixer
In, after evenly mixing, it is then placed in 200 DEG C again and is kneaded 5 minutes on the double roll mill, PVC composition can be obtained.
Comparative example 1:
1 detailed process of comparative example is with embodiment 3, the difference lies in that not including the first zinc salt.
Comparative example 2:
2 detailed process of comparative example is with embodiment 3, the difference lies in that not including the second zinc salt.
Comparative example 3:
3 detailed process of comparative example is with embodiment 3, the difference lies in that not including the first barium salt.
Comparative example 4:
4 detailed process of comparative example is with embodiment 3, the difference lies in that not including the second barium salt.
Comparative example 5:
5 detailed process of comparative example is with embodiment 3, the difference lies in that not including magnalium complexes.
Comparative example 6:
6 detailed process of comparative example is with embodiment 3, the difference lies in that hyperbranched amido silicon oil is replaced with alkyl-silicone oil, purchases
In Guangzhou Si Luoke Chemical Co., Ltd, product grade is
Comparative example 7:
7 detailed process of comparative example is with embodiment 3, the difference lies in that not including polyglycerol polyricinoleate.
Comparative example 8:
8 detailed process of comparative example with embodiment 3, the difference lies in that " by isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether,
Kerosene is according to weight ratio are as follows: 1:1.2:2:2 is uniformly mixed, and obtains the first mixed liquor；Zinc oxide is added into the first mixed liquor again "
It is changed to and " by isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether, kerosene, zinc oxide while mixing addition."
Comparative example 9:
9 detailed process of comparative example is with embodiment 4, the difference lies in that it is more that hyper branched polyphosphate ester is changed to melamine
Polyphosphate, the melamine condensed phosphate are purchased from Zhengzhou Sen Yao Chemical Co., Ltd..
Test method:
1, the product in embodiment and comparative example length and width are cut into put for 3cm × 2cm with a thickness of the sample of 1.0mm
Enter and carry out static thermal ageing test in 180 ± 1 DEG C of baking ovens, every the variation of 10min observation color, until sample start to occur it is black
The time of point is set to heat-stable time.
2, congo red method: the product in embodiment and comparative example is measured according to GB2917-82, is placed in 180 ± 1 DEG C
In glycerol bath, measurement Congored test paper starts to turn the blue time, is defined as heat-stable time.
3, horizontal vertical burning is tested according to UL94 horizontal vertical combustion method.
4, the dynamic stability time tested under the conditions of 200 DEG C of temperature with the mixing of Haake rheometer.
1 characterization test of table
From table 1 it follows that there is extraordinary thermal stability in the application, have extraordinary static heat steady
It fixes time, dynamic heat-stable time, in addition to this, the application also has preferable flame retardant property.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (10)
1. a kind of barium-zinc liquid heat stabilizer, which is characterized in that in parts by weight, include at least following raw material:
First zinc salt the preparation method is as follows:
By isooctyl acid, neodecanoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:1.2:2:2 is uniformly mixed, and obtains the
One mixed liquor；Zinc oxide is added into the first mixed liquor again, wherein n (zinc oxide): [n (isooctyl acid)+n (neodecanoic acid)]=1:
(1~2)；By the first mixed liquor stir 5~after ten minutes, be warming up to 100 DEG C~140 DEG C, be again stirring for reaction 50~80 minutes,
After completion of the reaction, decompression dehydration is carried out, is filtered after cooling to 100 DEG C~120 DEG C, obtains the first zinc salt；
Second zinc salt the preparation method is as follows:
By benzoic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether, kerosene according to weight ratio are as follows: 1:2:1.5:
1.5:1.5 being uniformly mixed, the second mixed liquor is obtained；Zinc oxide is added into the second mixed liquor again, wherein n (zinc oxide): [n
(benzoic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)]=1:(1~2)；By the second mixed liquor stir 5~after ten minutes,
100 DEG C~140 DEG C are warming up to, is again stirring for reaction 50~80 minutes, after completion of the reaction, decompression dehydration is carried out, cools to 100 DEG C
It is filtered after~120 DEG C, obtains the second zinc salt；
First barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, diethylene glycol monobutyl ether according to weight ratio are as follows: 2:1:0.5:1 mixing is equal
It is even, obtain third mixed liquor；Barium monohydrate is added into third mixed liquor again, wherein n (barium monohydrate): [n (oil
Acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)]=1:(1.5~2)；By third mixed liquor stir 5~after ten minutes, heating
To 100 DEG C~140 DEG C, it is again stirring for reaction 50~80 minutes, after completion of the reaction, carries out decompression dehydration, cool to 80 DEG C, then
The different monooctyl ester of phosphorous acid hexichol one, kerosene are added, stirring after ten minutes, obtains the first barium salt；
Second barium salt the preparation method is as follows:
By oleic acid, neodecanoic acid, p-tert-butyl benzoic acid, kerosene, diethylene glycol monobutyl ether according to weight ratio are as follows: 3:1:3:1.3:
2.5 are uniformly mixed, and obtain the 4th mixed liquor；Barium monohydrate is added into the 4th mixed liquor again, wherein a n (water hydroxide
Barium) :=1:(1.5~2 [n (oleic acid)+n (neodecanoic acid)+n (p-tert-butyl benzoic acid)])；4th mixed liquor is stirred 5~10 points
Zhong Hou is warming up to 100 DEG C~140 DEG C, is again stirring for reaction 50~80 minutes, after completion of the reaction, carries out decompression dehydration, cools to
80 DEG C, the different monooctyl ester of phosphorous acid hexichol one is then added, stirring after ten minutes, obtains the second barium salt.
2. barium-zinc liquid heat stabilizer as described in claim 1, which is characterized in that the light stabilizer is benzotriazole light
Stabilizer, Benzophenones light stabilizer, triazines as light stabilizer, any one or a few mixed in hindered amine light stabilizer
It closes.
3. barium-zinc liquid heat stabilizer as described in claim 1, which is characterized in that the preparation method of the magnalium complexes,
It at least includes the following steps:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to molar ratio Mg2+: A13+It is molten that=2~2.2:1 is configured to metal salt
Liquid；The metal salt includes magnesium salts and aluminium salt；
(2) preparation of water soluble alkali solution: control n (OH-): (n (Mg2+)+n(A13+))=2:1, n (CO3 2-): n (A13+)=1:
1, the amount of sodium hydroxide and sodium carbonate is controlled according to such ratio to prepare water soluble alkali solution；
(3) dropwise addition of metal salt solution and water soluble alkali solution: water, neopelex are added in reaction kettle, in temperature
Degree is after mixing evenly, to be made into neopelex solution at 25 DEG C, then same into neopelex solution
When the metal salt solution, water soluble alkali solution, the hyperbranched amido silicon oil that measure is added dropwise, during being added dropwise control pH value 9~
10, titration, which finishes, to be continued to stir 1h, obtains mixed liquor；
(4) crystallization, washing, drying: at a temperature of aging 4~8h by mixed liquor at 150 DEG C, it is washed, to be dried to obtain magnalium multiple
Close object.
4. barium-zinc liquid heat stabilizer as described in claim 1, which is characterized in that the phosphite ester is selected from: phosphorous acid two
The different monooctyl ester of benzene one, diisooctyl phenyl phosphite, phenyl diisodecyl ester, triisodecyl phosphite ester, three laurel of phosphorous acid
Any one or a few mixing in alcohol ester, diphenylphosphite.
5. barium-zinc liquid heat stabilizer as described in claim 1, which is characterized in that also wrapped in the barium-zinc liquid heat stabilizer
Include hyper branched polyphosphate ester.
6. barium-zinc liquid heat stabilizer as described in claim 1, which is characterized in that the anti-precipitation agent is selected from: carbon atom number
For 10~28 higher aliphatic.
7. the preparation method of barium-zinc liquid heat stabilizer as described in any one of claims 1 to 6, which is characterized in that at least wrap
Include following steps:
First zinc salt of corresponding parts by weight, the second zinc salt, the first barium salt, the second barium salt, light stabilizer, calcium zinc stabilizer are added
It into reactor, stirs 10~30 minutes, is then warming up to 90 DEG C again, stir 50~80 minutes, reaction system is cooled to 60
DEG C, phosphite ester, anti-precipitation agent, kerosene is then added, reaction system is warming up to 80 DEG C, is stirred 10~20 minutes.
8. a kind of PVC composition, which is characterized in that in parts by weight, following raw material is included at least,
100 parts of polyvinyl chloride resin；
1~3 part of barium-zinc liquid heat stabilizer；
2~6 parts of nano silica；
The barium-zinc liquid heat stabilizer is the described in any item barium-zinc liquid stabilizers of claim 1~6.
9. PVC composition as claimed in claim 8, which is characterized in that the nano silica is amino silicane coupling agent
Modified manometer silicon dioxide.
10. the preparation method of PVC composition as claimed in claim 8, which is characterized in that at least include the following steps:
The polyvinyl chloride resin of corresponding parts by weight, barium-zinc liquid heat stabilizer, nano silica are added in high-speed mixer,
After even mixing, it is then placed in 200 DEG C again and is kneaded 5~20 minutes on the double roll mill, PVC composition can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383706.4A CN107141643B (en) | 2017-05-26 | 2017-05-26 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383706.4A CN107141643B (en) | 2017-05-26 | 2017-05-26 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107141643A CN107141643A (en) | 2017-09-08 |
| CN107141643B true CN107141643B (en) | 2019-06-07 |
Family
ID=59779872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710383706.4A Active CN107141643B (en) | 2017-05-26 | 2017-05-26 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107141643B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573869B (en) * | 2022-03-17 | 2023-10-13 | 浙江传化华洋化工有限公司 | Barium zinc liquid stabilizer and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775153A (en) * | 2010-01-28 | 2010-07-14 | 德清县东来化学有限公司 | Barium-zinc liquid stabilizer, preparation method and application thereof |
| CN102532608A (en) * | 2011-12-15 | 2012-07-04 | 湖北犇星化工有限责任公司 | Heat stabilizer containing liquid barium and zinc, preparation method thereof and application thereof |
| CN103304847A (en) * | 2013-07-02 | 2013-09-18 | 上海浩缘环保材料有限公司 | Barium-zinc liquid stabilizer and preparation method thereof |
| CN103757911A (en) * | 2013-12-12 | 2014-04-30 | 福建思嘉环保材料科技有限公司 | Modified polyester fiber mesh cloth, PVC film structure material, and preparation method of modified polyester fiber mesh cloth and PVC film structure material |
| CN104309233A (en) * | 2014-10-28 | 2015-01-28 | 福建思嘉环保材料科技有限公司 | Gas mould material with excellent printing performance |
| CN104494264A (en) * | 2014-12-31 | 2015-04-08 | 思嘉环保材料科技（上海）有限公司 | Cold-resistant heat-insulating foaming material for tent, as well as preparation method thereof |
| CN104910414A (en) * | 2015-06-18 | 2015-09-16 | 巢湖香枫塑胶助剂有限公司 | Preparation method of liquid barium-zinc composite heat stabilizer |
-
2017
- 2017-05-26 CN CN201710383706.4A patent/CN107141643B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775153A (en) * | 2010-01-28 | 2010-07-14 | 德清县东来化学有限公司 | Barium-zinc liquid stabilizer, preparation method and application thereof |
| CN102532608A (en) * | 2011-12-15 | 2012-07-04 | 湖北犇星化工有限责任公司 | Heat stabilizer containing liquid barium and zinc, preparation method thereof and application thereof |
| CN103304847A (en) * | 2013-07-02 | 2013-09-18 | 上海浩缘环保材料有限公司 | Barium-zinc liquid stabilizer and preparation method thereof |
| CN103757911A (en) * | 2013-12-12 | 2014-04-30 | 福建思嘉环保材料科技有限公司 | Modified polyester fiber mesh cloth, PVC film structure material, and preparation method of modified polyester fiber mesh cloth and PVC film structure material |
| CN104309233A (en) * | 2014-10-28 | 2015-01-28 | 福建思嘉环保材料科技有限公司 | Gas mould material with excellent printing performance |
| CN104494264A (en) * | 2014-12-31 | 2015-04-08 | 思嘉环保材料科技（上海）有限公司 | Cold-resistant heat-insulating foaming material for tent, as well as preparation method thereof |
| CN104910414A (en) * | 2015-06-18 | 2015-09-16 | 巢湖香枫塑胶助剂有限公司 | Preparation method of liquid barium-zinc composite heat stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107141643A (en) | 2017-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107099104B (en) | Magnalium hydrotalcite composite thermal stabilizer and preparation method thereof, application | |
| CN100480309C (en) | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application thereof | |
| CN102504340B (en) | Nontoxic calcium and zinc thermal stabilizer | |
| CN102532608B (en) | Heat stabilizer containing liquid barium and zinc, preparation method thereof and application thereof | |
| CN109651826A (en) | A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer | |
| CN103194005A (en) | Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer | |
| CN105315574A (en) | Calcium and zinc heat stabilizer for PVC and application of calcium and zinc heat stabilizer | |
| DE2540066A1 (en) | STABILIZER COMPOSITION AND PLASTIC COMPOSITION IT CONTAINS | |
| CN104447647B (en) | 3-arylbenzofuranone compound and composition formed thereby | |
| CN107141643B (en) | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application | |
| CN102746595B (en) | Method for preparing modified liquid metal soap thermal stabilizer through potassium ion characteristic doping | |
| CN102725275A (en) | Bisbenzoxazinone compound | |
| CN106189235B (en) | A kind of sulfone polymer composition and the thermoplastic composition being made from it and application | |
| CN107163433B (en) | A kind of barium cadmium zinc liquid heat stabilizer and preparation method thereof, application | |
| Han et al. | Pentaerythritol stearate ester-based tin (II) metal alkoxides: A tri-functional organotin as poly (vinyl chloride) thermal stabilizers | |
| CN104761751B (en) | Zinc-containing metal soap heat stabilizer and the PVC composition comprising it | |
| CN107108961A (en) | Plasticizer composition, resin combination and preparation method thereof | |
| CN105885288A (en) | Auxiliary heat stabilizer for polyvinyl chloride and preparation method thereof | |
| CN103524945B (en) | Technology for preparing efficient environment-friendly compound heat stabilizer for polyvinyl chloride hard products | |
| CN106947111B (en) | Methyl stannum mercaptide complex composition and preparation method thereof | |
| CN102898751A (en) | Application of environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products | |
| CN106316899B (en) | A kind of mercaptobenzoic acid aliphatic alcohol ester barium and preparation method thereof, composition and application | |
| CN109836327A (en) | A kind of preparation method of glyceryl monostearate | |
| CN107540541A (en) | Colorless and odorless liquid plasticses lubricant and synthetic method | |
| CN104892653B (en) | The preparation method of curcumin rare earth compounding, hard PVC composite thermal stabilizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210823 Address after: 226200 Hezuo Shihai Town, Qidong City, Nantong City, Jiangsu Province Patentee after: Qidong Qiangqiang Trade Co.,Ltd. Address before: 226200 Binjiang fine chemical industry park, Qidong Economic Development Zone, Nantong City, Jiangsu Province Patentee before: NANTONG ADVANCE CHEMICALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |