CN110330686A - Rare earth composite stabilizer and its preparation method and application - Google Patents
Rare earth composite stabilizer and its preparation method and application Download PDFInfo
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- CN110330686A CN110330686A CN201910385425.1A CN201910385425A CN110330686A CN 110330686 A CN110330686 A CN 110330686A CN 201910385425 A CN201910385425 A CN 201910385425A CN 110330686 A CN110330686 A CN 110330686A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of rare earth composite stabilizers and its preparation method and application.The rare earth composite stabilizer includes praseodymium-benzophenone complex and stearate；Praseodymium-benzophenone complex is reacted to obtain by water-soluble praseodymium salt with benzophenone compound；Stearate is selected from stearate, the stearate of Section III A group metal or the stearate of Section II B group metal of Section II A group metal.Rare earth composite stabilizer of the invention can make chliorinated polyvinyl chloride composition have both excellent thermal stability and photostability.
Description
Technical field
The present invention relates to a kind of rare earth composite stabilizers and its preparation method and application.
Background technique
Chlorinated polyvinyl chloride second dilute (hereinafter referred to as CPVC) is that polyvinyl chloride (hereinafter referred to as PVC) is novel through chlorination modified obtained one kind
High molecular material.Due to the chlorinty ratio PVC high of CPVC, resistance to ag(e)ing, corrosion resistance, weatherability, deformability and solvable
Solution property etc. increases than PVC.However, causing CPVC in process there is various structures defect in CPVC strand
And it is unstable in long-term outdoor use process, it is easy to degrade under light, heat effect.
CN104829999B discloses a kind of method for improving CPVC resin processing performance, by CPVC toner, modification
The raw materials such as processing aid and heat stabilizer are uniformly mixed, and are kneaded in kneading machine, then add lubricant, polystyrene
After continue mixing and molding.This method uses Ca-Zn composite heat stabilizer, is mainly used for reducing plasticization temperature and the modeling of CPVC resin
Change the time and improve handling ease degree, is not improved the thermal stability and light stability of its product.
CN105295271B discloses a kind of heat-resisting high transparency CPVC composition, and Methyl stannum mercaptide, butanethiol tin, octyl is respectively adopted
Tin mercaptides etc. are used as heat stabilizer, and hindered amine light stabilizer, benzotriazole are as UV absorbers, for improving CPVC
The thermal stability of resin, however organic tin stabilizer is expensive, there are peculiar smell in use process.
Rare earth composite stabilizer is mainly used for improving light stability, the transparency and the tinting strength, tinting power etc. of macromolecule resin.It
The toxic stabilizer such as lead cadmium salt class and organic tin can be replaced.Rare earth composite stabilizer is by the fatty acid salt of rare earth element and dilute
Earth metal element composition.Existing rare earth composite stabilizer is limited to the performance improvement of resin matrix.CN11730454A is disclosed
A kind of O-hydroxyl-diphenyl ketone-rare earth complex is used to improve the stability of polyolefin, but it is more difficult take into account thermal stability and
Photostability.
Summary of the invention
It is an object of the present invention to provide a kind of rare earth composite stabilizers, are used for chliorinated polyvinyl chloride, can be with
So that chliorinated polyvinyl chloride composition has both excellent thermal stability and photostability.
It is another object of the present invention to provide a kind of preparation methods of rare earth composite stabilizer, and simple process can
Steadily to obtain rare earth composite stabilizer.
It is yet a further object of the present invention to provide a kind of applications of rare earth composite stabilizer, can make chlorinated polyvinyl chloride second
Ene compositions have both excellent thermal stability and photostability.
Yet another object of the invention is that provide a kind of chliorinated polyvinyl chloride composition, have both excellent thermal stability and
Photostability.
The present invention adopts the following technical scheme that realization above-mentioned purpose.
The present invention provides a kind of rare earth composite stabilizer, including praseodymium-benzophenone complex and stearate；It is described
Praseodymium-benzophenone complex is reacted to obtain by water-soluble praseodymium salt with formula (I) compound represented:
Wherein, R is the alkyl that carbon atom number is 1~12；Stearate is selected from the stearate of Section II A group metal, the
The stearate of IIIA group metal or the stearate of Section II B group metal.
Rare earth composite stabilizer according to the present invention, it is preferable that R is the alkyl that carbon atom number is 6~10；And stearate
Selected from one of zinc stearate, calcium stearate, magnesium stearate, aluminum stearate or barium stearate or a variety of.
Rare earth composite stabilizer according to the present invention, it is preferable that R is iso-octyl, and stearate is zinc stearate.
Rare earth composite stabilizer according to the present invention, it is preferable that the praseodymium-benzophenone complex and stearate
Weight ratio is 1:1~10.
Rare earth composite stabilizer according to the present invention, it is preferable that the rare earth composite stabilizer further includes antioxidant, auxiliary
Stabilizer, lubricant and auxiliary material；The antioxidant is in irgasfos 168, antioxidant 215, antioxidant 1010, antioxidant 1076
It is one or more；The auxiliary stabilizer is selected from one of dipentaerythritol, stearoyl benzoyl methane, epoxidized soybean oil
Or it is a variety of；The lubricant is selected from one of polyethylene wax, Fischer-Tropsch wax, oxidized polyethylene wax, stearic acid or a variety of；It is described auxiliary
Material is selected from one of precipitated calcium carbonate, kaolin, talcum powder, zeolite or a variety of.
Rare earth composite stabilizer according to the present invention, it is preferable that including 1 parts by weight praseodymium-benzophenone complex, 1~
10 weight part of stearate, 0.1~1 parts by weight antioxidant, 1~5 parts by weight auxiliary stabilizer, 1~5 parts by weight lubricant and 2
~10 parts by weight auxiliary materials.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned rare earth composite stabilizer, include the following steps:
(1) aqueous solution of water-soluble praseodymium salt is mixed with the ethanol solution of formula (I) compound represented, using 0.1~
It is 6~7 that the ammonia spirit of 1.0mol/L, which adjusts pH value, and 1~10h is then reacted at 20~35 DEG C, obtains praseodymium-benzophenone
Complex；
(2) raw material including praseodymium-benzophenone complex and stearate is uniformly mixed, obtains rare earth stable composition
Agent.
Preparation method according to the present invention, it is preferable that the praseodymium of water-soluble praseodymium salt and the molar ratio of formula (I) compound represented
For 1:1~5；The concentration of water-soluble praseodymium salt in aqueous solution is 0.1~0.5mol/L, chemical combination shown in formula (I) in ethanol solution
The concentration of object is 0.3~1.5mol/L.
In another aspect, the present invention provide a kind of rare earth composite stabilizer and meanwhile improve chliorinated polyvinyl chloride thermal stability and
Application in photostability.
Another aspect, the present invention provide a kind of chliorinated polyvinyl chloride composition, including 100 parts by weight chliorinated polyvinyl chlorides,
In 10~20 parts by weight precipitated calcium carbonates, 2~15 parts by weight haloflexes, 1~5 parts by weight titanium dioxide and 1~15 parts by weight
State rare earth composite stabilizer.
Rare earth composite stabilizer of the invention can improve the thermal stability and photostability of CPVC simultaneously；For example, can be with
Mechanical property and color after improving CPVC strong illumination.Compared with the modified CPVC product of traditional organic tin stabilizer
Compared with more significantly the present invention can improve the mechanical property of the CPVC product after strong ultraviolet radiation.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
< rare earth composite stabilizer >
Rare earth composite stabilizer of the invention includes praseodymium-benzophenone complex and stearate.Optionally, of the invention
Rare earth composite stabilizer can also include antioxidant, auxiliary stabilizer, lubricant and auxiliary material etc..Praseodymium-benzophenone cooperation
Object and stearate synergistic effect, so that rare earth composite stabilizer has both the function of the thermal stability and photostability that improve CPVC
Can, and performance is more excellent.
Praseodymium of the invention-benzophenone complex is reacted to obtain by water-soluble praseodymium salt with formula (I) compound represented:
Wherein, R is the alkyl that carbon atom number is 1~12.
In the present invention, the example of the substituent R of formula (I) compound represented includes but is not limited to n-propyl, isopropyl,
Normal-butyl, isobutyl group, n-pentyl, isopentyl, neopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl,
Nonyl, decyl etc..Preferably, R is the alkyl that carbon atom number is 6~10, it is highly preferred that R is the alkyl that carbon atom number is 8~9,
Most preferably, R is iso-octyl.
The example of formula (I) compound represented includes but is not limited to 2- hydroxyl -4- n-octyl benzophenone, 2- hydroxyl -4--
Iso-octyl-benzophenone, 2- hydroxyl -4- n-hexyl benzophenone, 2- hydroxyl -4- isohesyl benzophenone, the positive fourth of 2- hydroxyl -4-
Base benzophenone, 2- hydroxyl -4- isobutyl group benzophenone, 2- hydroxyl -4- n-propyl benzophenone, 2- hydroxyl -4- isopropyl two
Benzophenone.Preferably, formula (I) compound represented is selected from 2- hydroxyl -4- n-octyl benzophenone, 2- hydroxyl -4-- iso-octyl -
Benzophenone, 2- hydroxyl -4- n-hexyl benzophenone or 2- hydroxyl -4- isohesyl benzophenone；More preferably 2- hydroxyl -4- is just
Octyl benzophenone or 2- hydroxyl -4-- iso-octyl-benzophenone.The light that selection above compound is conducive to take into account CPVC is stablized
Property and thermal stability.
In the present invention, water-soluble praseodymium salt is the praseodymium salt that can be dissolved in water, and specific example includes but is not limited to praseodymium chloride,
Praseodymium nitrate, praseodymium acetate, praseodymium sulfate, praseodymium carbonate etc.；Preferably praseodymium chloride or praseodymium nitrate.
Stearate of the invention is selected from the stearate of Section II A group metal, the stearate of Section III A group metal or the
The stearate of IIB group metal.Section II A group metal includes but is not limited to magnesium, calcium, barium and strontium；Section III A group metal includes but not
It is limited to aluminium, indium and thallium；Section II B group metal includes but is not limited to zinc and cadmium.Preferably, stearate is selected from zinc stearate, tristearin
One of sour calcium, magnesium stearate, aluminum stearate or barium stearate are a variety of；It is highly preferred that stearate be selected from zinc stearate,
One of magnesium stearate or aluminum stearate are a variety of.A specific embodiment according to the present invention, stearate are tristearin
Sour zinc.
It is a discovery of the invention that praseodymium-benzophenone complex and stearate synergistic effect, so that rare earth composite stabilizer is simultaneous
Tool improves the thermal stability of CPVC and the function of photostability, and performance is more excellent.When praseodymium-benzophenone complex is 2-
The complex that hydroxyl -4-- iso-octyl-benzophenone and soluble praseodymium salt are formed can be more when stearate is zinc stearate
It is obviously improved the thermal stability and photostability of CPVC.Rare earth composite stabilizer of the invention is in the thermal stability side for improving CPVC
Face is suitable with organic tin stabilizer, in terms of improving photostability, is then substantially better than organic tin stabilizer.Experiment shows
The CPVC composition of rare earth composite stabilizer of the invention, the tensile strength after strong ultraviolet light slightly improve.
In the present invention, the weight ratio of praseodymium-benzophenone complex and stearate is 1:1~10；Preferably, praseodymium-
The weight ratio of benzophenone complex and stearate is 1:2~8；It is highly preferred that praseodymium-benzophenone complex and tristearin
The weight ratio of hydrochlorate is 1:4~6.Using the rare earth composite stabilizer in above range, the photostability of CPVC is further increased
Energy and thermal stability.
Rare earth composite stabilizer of the invention can also include antioxidant, auxiliary stabilizer, lubricant and auxiliary material etc..Using
Above-mentioned antioxidant, auxiliary stabilizer, lubricant and auxiliary material can make rare earth composite stabilizer favorable dispersibility in CPVC, be not easy
It is precipitated.
Antioxidant of the invention can be selected from one in irgasfos 168, antioxidant 215, antioxidant 1010, antioxidant 1076
Kind is a variety of；Preferably one of antioxidant 215, antioxidant 1010, antioxidant 1076 or a variety of；More preferably antioxidant
1010。
Auxiliary stabilizer of the invention can be in dipentaerythritol, stearoyl benzoyl methane, epoxidized soybean oil
It is one or more；It is one or more to be preferably selected from dipentaerythritol, stearoyl benzoyl methane；More preferably dipentaerythritol.
Lubricant of the invention can be in polyethylene (PE) wax, Fischer-Tropsch wax, oxidic polyethylene (OPE) wax, stearic acid
It is one or more；Be preferably selected from polyethylene wax, Fischer-Tropsch wax, oxidized polyethylene wax it is one or more；More preferably polyethylene
Wax, oxidized polyethylene wax 316 and oxidized polyethylene wax 629.
Auxiliary material of the invention can be selected from one of precipitated calcium carbonate, kaolin, talcum powder, zeolite or a variety of；It is preferred that
Selected from one of precipitated calcium carbonate, kaolin, zeolite or a variety of；The more preferably combination of kaolin and zeolite.
In certain embodiments, rare earth composite stabilizer includes 1 parts by weight praseodymium-benzophenone complex, 1~10 weight
Measure part stearate, 0.1~1 parts by weight antioxidant, 1~5 parts by weight auxiliary stabilizer, 1~5 parts by weight lubricant and 2~10
Parts by weight auxiliary material；Preferably, rare earth composite stabilizer includes 1 parts by weight praseodymium-benzophenone complex, 2~8 parts by weight tristearin
Hydrochlorate, 0.2~0.8 parts by weight antioxidant, 1.5~4 parts by weight auxiliary stabilizers, 2~4.5 parts by weight lubricants and 4~8 weight
Part auxiliary material；It is highly preferred that rare earth composite stabilizer includes 1 parts by weight praseodymium-benzophenone complex, 4~6 parts by weight stearic acid
Salt, 0.4~0.6 parts by weight antioxidant, 2.5~4 parts by weight auxiliary stabilizers, 3~4 parts by weight lubricants and 5~7 parts by weight are auxiliary
Material.By the rare earth composite stabilizer of each component control within the above range, it can be further improved rare earth composite stabilizer and exist
Dispersibility in CPVC is allowed to be not easy to be precipitated；And the thermal stability of rare earth composite stabilizer raising CPVC can be assisted
And light stability.
According to embodiment of the present invention, rare earth composite stabilizer includes 1 parts by weight praseodymium-benzophenone cooperation
Object, 1~10 parts by weight zinc stearate, 0.1~1 parts by weight antioxidant 1010,1~5 parts by weight dipentaerythritol, 1~3 parts by weight
Polyethylene wax, 1~5 parts by weight oxidized polyethylene wax, 3~7 parts by weight kaolin clay and 1~3 parts by weight zeolite.It is according to the present invention
One preferred embodiment, rare earth composite stabilizer include 1 parts by weight praseodymium-benzophenone complex, 2~8 parts by weight tristearin
Sour zinc, 0.2~0.8 parts by weight antioxidant 1010,1~5 parts by weight dipentaerythritol, 1~3 weight account polyethylene wax, 1~3 weight
Measure part oxidized polyethylene wax 316,1~3 parts by weight oxidized polyethylene wax 629,3~7 parts by weight kaolin clay and the boiling of 1~3 parts by weight
Stone.
The preparation method > of < rare earth composite stabilizer
The preparation method of rare earth composite stabilizer of the invention includes (1) praseodymium-benzophenone complex preparation step
(2) forming step of stabilizer.
In step (1), the aqueous solution of water-soluble praseodymium salt is mixed with the ethanol solution of formula (I) compound represented, is used
Ammonia spirit adjusts pH value, then reacts, obtains praseodymium-benzophenone complex.Shown in the praseodymium and formula (I) of water-soluble praseodymium salt
The molar ratio of compound is 1:1~5, it is preferable that the molar ratio of the praseodymium of water-soluble praseodymium salt and formula (I) compound represented is 1:1
~4；The praseodymium of water-soluble praseodymium salt and the molar ratio of formula (I) compound represented are 1:1~3.
In step (1), the concentration of the water-soluble praseodymium salt in aqueous solution can be 0.1~0.5mol/L, ethanol solution Chinese style
(I) concentration of compound represented is 0.3~1.5mol/L.Preferably, the concentration of the water-soluble praseodymium salt in aqueous solution is 0.15
~0.35mol/L, the concentration of formula (I) compound represented is 0.4~1mol/L in ethanol solution.It is highly preferred that in aqueous solution
The concentration of water-soluble praseodymium salt be 0.2~0.25mol/L, in ethanol solution the concentration of formula (I) compound represented be 0.5~
0.6mol/L。
In step (1), the example of the substituent R of formula (I) compound represented includes but is not limited to n-propyl, isopropyl,
Normal-butyl, isobutyl group, n-pentyl, isopentyl, neopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl,
Nonyl, decyl etc..Preferably, R is the alkyl that carbon atom number is 6~10, it is highly preferred that R is the alkyl that carbon atom number is 8~9,
Most preferably, R is iso-octyl.
In step (1), the example of formula (I) compound represented includes but is not limited to 2- hydroxyl -4- n-octyl benzophenone,
2- hydroxyl -4-- iso-octyl-benzophenone, 2- hydroxyl -4- n-hexyl benzophenone, 2- hydroxyl -4- isohesyl benzophenone, 2-
Hydroxyl -4- normal-butyl benzophenone, 2- hydroxyl -4- isobutyl group benzophenone, 2- hydroxyl -4- n-propyl benzophenone, 2- hydroxyl -
4- isopropyl diphenyl ketone.Preferably, formula (I) compound represented is selected from 2- hydroxyl -4- n-octyl benzophenone, 2- hydroxyl -
4-- iso-octyl-benzophenone, 2- hydroxyl -4- n-hexyl benzophenone or 2- hydroxyl -4- isohesyl benzophenone；More preferably
2- hydroxyl -4- n-octyl benzophenone or 2- hydroxyl -4-- iso-octyl-benzophenone.Selection above compound is conducive to take into account
The photostability and thermal stability of CPVC.
In step (1), water-soluble praseodymium salt is the praseodymium salt that can be dissolved in water, and specific example includes but is not limited to praseodymium chloride,
Praseodymium nitrate, praseodymium acetate, praseodymium sulfate, praseodymium carbonate etc.；Preferably praseodymium chloride or praseodymium nitrate.
In step (1), stearate be selected from the stearate of Section II A group metal, Section III A group metal stearate or
The stearate of Section II B group metal；Preferably, stearate is selected from zinc stearate, calcium stearate, magnesium stearate, aluminum stearate
Or one of barium stearate or a variety of.A specific embodiment according to the present invention, stearate is zinc stearate.
In step (1), the weight ratio of praseodymium-benzophenone complex and stearate is 1:1~10；Preferably, praseodymium-two
The weight ratio of Benzophenone class complex and stearate is 1:2~8；It is highly preferred that praseodymium-benzophenone complex and stearic acid
The weight ratio of salt is 1:4~6.Using the rare earth composite stabilizer in above range, the light stability of CPVC is further increased
And thermal stability.
In step (1), the concentration of ammonia spirit is 0.1~1.0mol/L；Preferably, the concentration of ammonia spirit be 0.2~
0.8mol/L；It is highly preferred that the concentration of ammonia spirit is 0.4~0.6mol/L；Adjusting pH value by ammonia spirit is 6~7；It is excellent
Selection of land, adjusting pH value by ammonia spirit is 6.2~6.8；It is highly preferred that adjusting pH value by ammonia spirit is 6.4~6.6.
Reaction condition is that 1~10h is reacted at 20~35 DEG C；Preferably, reaction condition is that 2~8h is reacted at 25~30 DEG C；It is highly preferred that
Reaction condition is that 2~3h is reacted at 25~28 DEG C.
In step (2), the raw material including praseodymium-benzophenone complex and stearate is uniformly mixed, rare earth is obtained
Compound stabilizer.The raw material of rare earth composite stabilizer of the invention can also include antioxidant, auxiliary stabilizer, lubricant and auxiliary
Material etc..It can make rare earth composite stabilizer in macromolecule resin using above-mentioned antioxidant, auxiliary stabilizer, lubricant and auxiliary material
Favorable dispersibility is not easy to be precipitated.
In step (2), antioxidant can be in irgasfos 168, antioxidant 215, antioxidant 1010, antioxidant 1076
It is one or more；Preferably one of antioxidant 215, antioxidant 1010, antioxidant 1076 or a variety of；More preferably antioxidant
1010。
In step (2), auxiliary stabilizer can be in dipentaerythritol, stearoyl benzoyl methane, epoxidized soybean oil
It is one or more；It is one or more to be preferably selected from dipentaerythritol, stearoyl benzoyl methane；More preferably double Ji Wusi
Alcohol.
In step (2), lubricant can be selected from polyethylene (PE) wax, Fischer-Tropsch wax, oxidic polyethylene (OPE) wax, stearic acid
One of or it is a variety of；Be preferably selected from polyethylene wax, Fischer-Tropsch wax, oxidized polyethylene wax it is one or more；More preferably poly- second
Alkene wax, oxidized polyethylene wax 316 and oxidized polyethylene wax 629.
In step (2), auxiliary material can be selected from one of precipitated calcium carbonate, kaolin, talcum powder, zeolite or a variety of；It is excellent
Choosing is selected from one of precipitated calcium carbonate, kaolin, zeolite or a variety of；The more preferably combination of kaolin and zeolite.
In certain embodiments, the praseodymium of praseodymium chloride and the molar ratio for the compound that R base shown in formula (I) is iso-octyl are
1:1~3；The concentration of praseodymium chloride in aqueous solution is 0.2~0.25mol/L, iso-octyl chemical combination shown in formula (I) in ethanol solution
The concentration of object is 0.5~0.6mol/L.The concentration of ammonia spirit is 0.4~0.6mol/L, adjusts pH value by ammonia spirit and is
6.4~6.6.2~5h is reacted at 25~28 DEG C obtains praseodymium-benzophenone complex.By praseodymium-benzophenone of 1 parts by weight
Class complex is uniformly mixed with the zinc stearate of 4~6 parts by weight both obtains rare earth composite stabilizer.
It will include praseodymium-benzophenone complex, stearate, antioxidant, auxiliary stabilizer, lubricant in step (2)
It is uniformly mixed with the raw material of auxiliary material, obtains rare earth composite stabilizer.In certain embodiments, raw material includes 1 parts by weight praseodymium-two
Benzophenone class complex, 1~10 weight part of stearate, 0.1~1 parts by weight antioxidant, 1~5 parts by weight auxiliary stabilizer, 1
~5 parts by weight lubricants and 2~10 parts by weight auxiliary materials；Preferably, raw material includes 1 parts by weight praseodymium-benzophenone complex, 2
~8 weight part of stearate, 0.2~0.8 parts by weight antioxidant, 1.5~4 parts by weight auxiliary stabilizers, 2~4.5 parts by weight profit
Lubrication prescription and 4~8 parts by weight auxiliary materials；It is highly preferred that raw material is hard including 1 parts by weight praseodymium-benzophenone complex, 4~6 parts by weight
Resin acid salt, 0.4~0.6 parts by weight antioxidant, 2.5~4 parts by weight auxiliary stabilizers, 3~4 parts by weight lubricants and 5~7 weight
Part auxiliary material.Above-mentioned raw materials are controlled in above range, can be further improved dispersion of the rare earth composite stabilizer in CPVC
Property, it is allowed to be not easy to be precipitated；And the thermal stability and light stability of rare earth composite stabilizer raising CPVC can be assisted.
According to embodiment of the present invention, raw material includes 1 parts by weight praseodymium-benzophenone complex, 1~10 weight
Part zinc stearate, 0.1~1 parts by weight antioxidant 1010,1~5 parts by weight dipentaerythritol, 1~3 weight account polyethylene wax, 1~
5 parts by weight oxidized polyethylene wax, 3~7 parts by weight kaolin clay and 1~3 parts by weight zeolite.A preferred implementation according to the present invention
Mode, raw material include 1 parts by weight praseodymium-benzophenone complex, 2~8 parts by weight zinc stearates, 0.2~0.8 parts by weight antioxygen
Agent 1010,1~5 parts by weight dipentaerythritol, 1~3 weight account polyethylene wax, 1~3 parts by weight oxidized polyethylene wax 316,1~3
Parts by weight oxidized polyethylene wax 629,3~7 parts by weight kaolin clay and 1~3 parts by weight zeolite.
< application and chliorinated polyvinyl chloride composition >
Rare earth composite stabilizer of the invention is used for chliorinated polyvinyl chloride can improve thermal stability and light stabilization simultaneously
Property.In the thermal stability and photostability for improving chliorinated polyvinyl chloride at the same time the present invention also provides above-mentioned rare earth composite stabilizer
Application.
Chliorinated polyvinyl chloride composition of the invention includes 100 parts by weight chliorinated polyvinyl chlorides, 10~20 parts by weight lightweights
Calcium carbonate, 2~15 parts by weight haloflexes, 1~5 parts by weight titanium dioxide and 1~15 parts by weight rare earth composite stabilizer.It is preferred that
Ground, chliorinated polyvinyl chloride composition of the invention include 100 parts by weight chliorinated polyvinyl chlorides, 12~18 parts by weight lightweight carbonic acid
Calcium, 4~12 parts by weight haloflexes, 1.5~4 parts by weight titanium dioxides and 4~12 parts by weight rare earth composite stabilizers.More preferably
Ground, chliorinated polyvinyl chloride composition of the invention include 100 parts by weight chliorinated polyvinyl chlorides, 14~16 parts by weight lightweight carbonic acid
Calcium, 6~10 parts by weight haloflexes, 2~3.5 parts by weight titanium dioxides and 6~10 parts by weight rare earth composite stabilizers.In this way may be used
Preferably to improve dispersibility of the rare earth composite stabilizer in chliorinated polyvinyl chloride, so that the heat for improving chliorinated polyvinyl chloride is steady
The mechanical property of product after qualitative energy and light stability, especially strong illumination.
Embodiment 1
By the praseodymium trichloride (PrCl of 0.01mol3) it is dissolved in 50ml water formation praseodymium trichloride aqueous solution.By the 2- of 0.03mol
Hydroxyl -4- iso-octyl-benzophenone is dissolved in 50ml ethyl alcohol and forms ethanol solution.By praseodymium trichloride aqueous solution and above-mentioned ethanol solution
It is uniformly mixed, pH to 6.5 is adjusted using the ammonia spirit of 0.5mol/L.In 25 DEG C of reaction 2h, pale yellow precipitate is generated.Through washing
It is praseodymium-benzophenone complex after washing, filter, drying.
By 1g praseodymium-benzophenone complex, 5g zinc stearate, 0.5g antioxidant 1010,2.8g dipentaerythritol, 1.5g
Polyethylene wax, 0.5g oxidized polyethylene wax 316,1.2g oxidized polyethylene wax 629,5g kaolin and 1.8g zeolite are uniformly mixed,
Up to rare earth composite stabilizer.
CPVC, 15g precipitated calcium carbonate of 100g, 8g haloflex, 3g titanium dioxide and 8g rare earth composite stabilizer are mixed
It closes uniformly, is placed in double roller plastic-making device (180 DEG C of roller temperature, roll spacing 1mm) 5min that plasticates, is cut into square sample.
Embodiment 2
By the praseodymium trichloride (PrCl of 0.01mol3) it is dissolved in 50ml water formation praseodymium trichloride aqueous solution.By the 2- of 0.03mol
- 4 isobutyl groups of hydroxyl-benzophenone is dissolved in 50ml ethyl alcohol and forms ethanol solution.By praseodymium trichloride aqueous solution and above-mentioned ethanol solution
It is uniformly mixed, pH to 6.5 is adjusted using the ammonia spirit of 0.5mol/L.In 25 DEG C of reaction 2h, pale yellow precipitate is generated.Through washing
It is praseodymium-benzophenone complex after washing, filter, drying.
By 1g praseodymium-benzophenone complex, 5g zinc stearate, 0.5g antioxidant 1010,2.8g dipentaerythritol, 1.5g
Polyethylene wax, 0.5g oxidized polyethylene wax 316,1.2g oxidized polyethylene wax 629,5g kaolin and 1.8g zeolite are uniformly mixed,
Up to rare earth composite stabilizer.
CPVC, 15g precipitated calcium carbonate of 100g, 8g haloflex, 3g titanium dioxide and 8g rare earth composite stabilizer are mixed
It closes uniformly, is placed in double roller plastic-making device (180 DEG C of roller temperature, roll spacing 1mm) 5min that plasticates, is cut into square sample.
Comparative example 1
Zinc stearate is replaced with into zinc salicylate, remaining condition is same as Example 1, obtains rare earth composite stabilizer.
CPVC, 15g precipitated calcium carbonate of 100g, 8g haloflex, 3g titanium dioxide and 8g rare earth composite stabilizer are mixed
It closes uniformly, is placed in double roller plastic-making device (180 DEG C of roller temperature, roll spacing 1mm) 5min that plasticates, is cut into square sample.
Comparative example 2
By CPVC, 15g precipitated calcium carbonate of 100g, 8g haloflex, 3g titanium dioxide and 8g organic tin stabilizer
(TM181) it is uniformly mixed, is placed in double roller plastic-making device (180 DEG C of roller temperature, roll spacing 1mm) 5min that plasticates, is cut into square sample.
Experimental example
1, hot-air exposure test
According to plastics hot-air exposure test method (GB/T7141-92), square sample is placed in ageing oven,
Senile experiment is carried out at 180 ± 1 DEG C.Sample is taken out every 10min, observes and records the variation of coloration, experimental result is shown in Table 1.
As seen from table, CPVC of the thermal stability better than addition organic tin stabilizer of the CPVC composition of rare earth complex heat stabilizer is added
The thermal stability of composition.Compared with zinc salicylate, zinc stearate and praseodymium-benzophenone complex cooperation can be more significant
Improve the thermal stability of CPVC composition.
Table 1, oven ageing result
| Ageing time (min) | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| 0 | White | White | White |
| 10 | It is yellowish | It is yellowish | It is yellowish |
| 20 | It is yellowish | Yellow | It is yellowish |
| 30 | Yellow | It is orange | It is deep yellow |
| 40 | Shallow orange | Brown | Brown |
| 50 | Brown | It is dark brown | It is greyish brown |
| 60 | It is dark brown | It is dark brown | It is greyish black |
2, torque rheology is tested
Contain the composite sample of CPVC by embodiment or comparative example group assignment system, and by 70 grams of samples on Haake torque rheometer
Torque rheology experiment is carried out, setting torque rheology temperature is 185 DEG C, revolving speed 50r/min.Experimental result is referring to table 2.It can by table
Know, adds CPVC composition of the thermal stability better than addition organic tin stabilizer of the CPVC composition of rare earth complex heat stabilizer
Thermal stability.
Table 2, torque rheology result
| Number | Embodiment 1 | Comparative example 2 |
| Fusion time/mn | 0.92 | 1.18 |
| Counter balance torque/Nm | 22.02 | 23.27 |
| Stablize time/min | 17.83 | 17.25 |
3, ultraviolet ageing is tested
Sample is cut into 4cm × 3cm, each sample cuts 8 samples, is put into QUV ultraviolet ageing case, carries out 168 hours
The experiment of QUV ultraviolet ageing.50 DEG C of experimental temperature, each sample took a sample every 24 hours, observes and is recorded by color difference meter
The variation of sample coloration (Lab value), and calculate the △ E value with initial color chips.Experimental result is referring to table 3.As seen from table, embodiment
1 △ E value changes minimum, and the △ E value in comparative example 2 changes maximum, shows: adding the CPVC combination of rare earth complex heat stabilizer
Photostability of the photostability of object better than the CPVC composition of addition organic tin stabilizer.Compared with zinc salicylate, stearic acid
Zinc and praseodymium-benzophenone complex cooperation can more significantly improve the photostability of CPVC composition.
Table 3, coloration △ E result of variations
| Irradiation time (h) | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| 0 | / | / | / |
| 24 | 1.63 | 1.83 | 4.66 |
| 48 | 2.40 | 2.15 | 5.27 |
| 72 | 2.29 | 2.45 | 5.67 |
| 96 | 2.41 | 2.98 | 6.24 |
| 120 | 2.80 | 3.15 | 6.86 |
| 144 | 3.08 | 3.86 | 6.90 |
| 168 | 3.98 | 4.32 | 8.05 |
According to plastic tensile method for testing performance (GB/T1040-2006), sample is cut into dumbbell shape, each sample cuts 6
A sample is divided equally into two groups.Every group is put into QUV ultraviolet ageing case, QUV ultraviolet ageing experiment in 168 hours is carried out.It surveys respectively
The tensile strength and tensile elongation variation of each sample aging front and back are tried, every group of each sample measurement three times, is averaged note
Record.Experimental result is referring to table 4.As seen from table: aging forward backward averaging tensile strength and average tensile elongation be not in embodiment 1
It decreased significantly；And aging forward backward averaging tensile strength and average tensile elongation are substantially reduced in comparative example 2, are illustrated in light
Its mechanical property is substantially reduced according under the conditions of, photostability decline.Therefore, the CPVC composition of rare earth complex heat stabilizer is added
Photostability better than addition organic tin stabilizer CPVC composition photostability.
Tensile strength and tensile elongation experimental result before and after table 4, aging
| Number | Embodiment 1 | Comparative example 2 |
| Average tensile strength/MPa before aging | 31.03 | 27.52 |
| Average tensile strength/MPa after aging | 30.52 | 15.22 |
| Average tensile elongation before aging | 17.65 | 17.30 |
| Average tensile elongation after aging | 15.27 | 10.53 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of rare earth composite stabilizer, which is characterized in that including praseodymium-benzophenone complex and stearate；The praseodymium-
Benzophenone complex is reacted to obtain by water-soluble praseodymium salt with formula (I) compound represented:
Wherein, R is the alkyl that carbon atom number is 1~12；Stearate is selected from the stearate of Section II A group metal, Section III A group
The stearate of metal or the stearate of Section II B group metal.
2. rare earth composite stabilizer according to claim 1, which is characterized in that R is the alkyl that carbon atom number is 6~10；
And stearate is selected from one of zinc stearate, calcium stearate, magnesium stearate, aluminum stearate or barium stearate or a variety of.
3. rare earth composite stabilizer according to claim 2, which is characterized in that R is iso-octyl, and stearate is tristearin
Sour zinc.
4. described in any item rare earth composite stabilizers according to claim 1~3, which is characterized in that the praseodymium-benzophenone
The weight ratio of complex and stearate is 1:1~10.
5. described in any item rare earth composite stabilizers according to claim 1~3, which is characterized in that the rare earth stable composition
Agent further includes antioxidant, auxiliary stabilizer, lubricant and auxiliary material；The antioxidant is selected from irgasfos 168, antioxidant 215, antioxygen
One of agent 1010, antioxidant 1076 are a variety of；The auxiliary stabilizer is selected from dipentaerythritol, stearoyl benzoyl first
One of alkane, epoxidized soybean oil are a variety of；The lubricant is selected from polyethylene wax, Fischer-Tropsch wax, oxidized polyethylene wax, stearic acid
One of or it is a variety of；The auxiliary material is selected from one of precipitated calcium carbonate, kaolin, talcum powder, zeolite or a variety of.
6. rare earth composite stabilizer according to claim 5, which is characterized in that match including 1 parts by weight praseodymium-benzophenone
Close object, 1~10 weight part of stearate, 0.1~1 parts by weight antioxidant, 1~5 parts by weight auxiliary stabilizer, 1~5 parts by weight profit
Lubrication prescription and 2~10 parts by weight auxiliary materials.
7. the preparation method of described in any item rare earth composite stabilizers according to claim 1~6, which is characterized in that including such as
Lower step:
(1) aqueous solution of water-soluble praseodymium salt is mixed with the ethanol solution of formula (I) compound represented, using 0.1~1.0mol/
It is 6~7 that the ammonia spirit of L, which adjusts pH value, and 1~10h is then reacted at 20~35 DEG C, obtains praseodymium-benzophenone complex；
(2) raw material including praseodymium-benzophenone complex and stearate is uniformly mixed, obtains rare earth composite stabilizer.
8. preparation method according to claim 7, which is characterized in that chemical combination shown in the praseodymium and formula (I) of water-soluble praseodymium salt
The molar ratio of object is 1:1~5；The concentration of water-soluble praseodymium salt in aqueous solution is 0.1~0.5mol/L, formula (I) in ethanol solution
The concentration of compound represented is 0.3~1.5mol/L.
9. described in any item rare earth composite stabilizers improve the heat of chliorinated polyvinyl chloride surely at the same time according to claim 1~6
Application in qualitative and photostability.
10. a kind of chliorinated polyvinyl chloride composition, which is characterized in that including 100 parts by weight chliorinated polyvinyl chlorides, 10~20 weight
Part precipitated calcium carbonate, 2~15 parts by weight haloflexes, 1~5 parts by weight titanium dioxide and 1~15 parts by weight such as claim 1~
6 described in any item rare earth composite stabilizers.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277974A (en) * | 2000-06-12 | 2000-12-27 | 郑德� | Rare-earth multi-functional composite stabilizer for PVC and its processing method |
| CN1730454A (en) * | 2005-08-16 | 2006-02-08 | 广东工业大学 | O-hydroxyl-diphenyl ketone- rare earth complex and its preparation method and uses |
| CN101659605A (en) * | 2009-09-18 | 2010-03-03 | 广东工业大学 | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
| CN107778720A (en) * | 2017-11-09 | 2018-03-09 | 新沂市星辰新材料科技有限公司 | A kind of environment-protecting and non-poisonous PVC zinc stearate compound stabilizers |
| CN108948420A (en) * | 2018-07-10 | 2018-12-07 | 内蒙古科技大学 | Rare earth composite stabilizer and preparation method thereof for PVC |
-
2019
- 2019-05-09 CN CN201910385425.1A patent/CN110330686A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277974A (en) * | 2000-06-12 | 2000-12-27 | 郑德� | Rare-earth multi-functional composite stabilizer for PVC and its processing method |
| CN1730454A (en) * | 2005-08-16 | 2006-02-08 | 广东工业大学 | O-hydroxyl-diphenyl ketone- rare earth complex and its preparation method and uses |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
| CN101659605A (en) * | 2009-09-18 | 2010-03-03 | 广东工业大学 | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound |
| CN107778720A (en) * | 2017-11-09 | 2018-03-09 | 新沂市星辰新材料科技有限公司 | A kind of environment-protecting and non-poisonous PVC zinc stearate compound stabilizers |
| CN108948420A (en) * | 2018-07-10 | 2018-12-07 | 内蒙古科技大学 | Rare earth composite stabilizer and preparation method thereof for PVC |
Non-Patent Citations (1)
| Title |
|---|
| 胡应喜: "2-羟基-4-辛氧基二苯甲酮稀土配合物合成与表征", 《合成材料老化与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113444328A (en) * | 2021-07-20 | 2021-09-28 | 内蒙古科技大学 | PVC (polyvinyl chloride) main stabilizer, composite heat stabilizer for PVC and PVC |
| CN113444328B (en) * | 2021-07-20 | 2022-08-16 | 内蒙古科技大学 | PVC (polyvinyl chloride) main stabilizer, composite heat stabilizer for PVC and PVC |
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