CN110372914A - Calcium zinc stabilizer and preparation method thereof for PVC pipe - Google Patents
Calcium zinc stabilizer and preparation method thereof for PVC pipe Download PDFInfo
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- 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
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- C08L2203/18—Applications used for pipes
Abstract
The present invention relates to stabilizer technical fields, disclose a kind of calcium zinc stabilizer and preparation method thereof for PVC pipe.Calcium zinc stabilizer includes following components by weight: 10-30 parts of calcium stearate, 10-30 parts of zinc stearate, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, dibenzoyl methane -1-5 parts of quaternary amine chitosan-loaded nanocrystal composition, 1-3 parts of pentaerythrite, 1-3 parts of phosphite ester, 1-3 parts of bisphenol-A.The present invention by stabilizer dibenzoyl methane and quaternary ammonium salt it is compound, dibenzoyl methane and quaternary ammonium compound is set to show positive electricity, positively charged dibenzoyl methane repels with quaternary ammonium compound and positively charged ferric ion, become red complex to prevent dibenzoyl methane and ferric ion from being complexed, avoids PVC pipe from presenting red.
Description
Technical field
The present invention relates to stabilizer technical fields, more particularly, to a kind of calcium zinc stabilizer and its system for PVC pipe
Preparation Method.
Background technique
Polyvinyl chloride (PVC) is one of five big general-purpose plastics, its advantage is that PVC product is widely used, be mainly used for industry,
The fields such as building, agricultural, still, disadvantage is equally obvious, and the thermal stability of polyvinyl chloride resin is poor, product colour after heat ageing is decomposed
It deepens, each performance indicator decline can not be processed directly, so process must add heat stabilizer to improve ageing properties.
Currently used heat stabilizer mainly has inorganic lead salt, metallic soap and organotin etc., but inorganic lead salt is toxic, has
Machine tin smell is too heavy, seriously limits the application range of PVC product.For improvement people's health health, environment is protected, in recent years Europe
Country, the prosperity such as beauty state has successively formulateeed and implemented limitation using the regulation of toxic heat stabilizer, and the country was issued on July 1st, 2017
Cloth implements GB/T33284-2017 standard, it is specified that lead content≤100mg/Kg in PVC-U profile.Environmental protection is main trend, is remained
Under the products such as PVC pipe to prohibit lead be also inevitable.
Calcium zinc stabilizer is cooperated nontoxic made of a variety of organic auxiliary heat stabilizers based on the metallic soaps such as calcium, zinc
Stabilizer.The beta-diketone compounds such as dibenzoyl methane (DBM) as the nontoxic auxiliary heat stabilizer of the preferable zinc-base of effect,
Product initial stage color and thermostable effect can be significantly improved, the important component of stabilizer has been become.But using contain β-two
After the calcium zinc stabilizer of ketone, the vacuum tank material of production process extruder is iron, can discharge trivalent in the material into vacuum tank
Dibenzoyl methane in iron ion, ferric ion and stabilizer forms red complex, so as to cause the object in vacuum tank
Material becomes blood red, and then causes pipe finished that red also can also be presented, and is unfavorable for the popularization and application of product.Chinese patent discloses
Number CN105315574 discloses a kind of PVC calcium zinc heat stabilizer and its application, main stabilizer and auxiliary stabilizer composition, main
Stabilizer is made of quinolone zinc salt and quinolone calcium salt, and auxiliary stabilizer is hard by triphenyl phosphite, epoxidized soybean oil, epoxy
Resin acid monooctyl ester, pentaerythrite, dipentaerythritol, D-sorbite, trimethylolpropane, dibenzoyl methane, stearoyl benzoyl
The compound of any proportion of one or more of methane, uracil, the stabilizer is for producing PVC plastic process
In, the vacuum tank material of production process extruder cannot be iron, because of the dibenzoyl methane in ferric ion and stabilizer
It is capable of forming red complex, causes PVC plastic finished product to present red, so, it can only the higher other materials of use cost
Vacuum tank, and the production line for the production PVC plastic that enterprise uses is commercially available from outside, vacuum tank is to be mostly
Irony, if needing for vacuum tank to be changed to other materials using the stabilizer containing dibenzoyl methane, it is troublesome in poeration and
And increase cost.
Summary of the invention
The present invention be in order to overcome the dibenzoyl methane in the calcareous stabilizer of the prior art in irony vacuum tank with
Ferric ion complexing reddens the problem of influencing product colour, provides a kind of calcium zinc stabilizer for PVC pipe, and the present invention will
Dibenzoyl methane and quaternary ammonium salt in stabilizer is compound, is connected on nitrogen-atoms with four alkyl since quaternary ammonium salt obtains, and one, band
The positive charge of unit makes dibenzoyl methane and quaternary ammonium compound show positive electricity, positively charged dibenzoyl methane and quaternary ammonium salt
Compound repels with positively charged ferric ion, so that preventing dibenzoyl methane from being complexed with ferric ion becomes red
Color complex compound avoids PVC pipe from presenting red.
The present invention also provides a kind of preparation methods of calcium zinc stabilizer for PVC pipe.
To achieve the goals above, the invention adopts the following technical scheme:
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 10-30 parts of calcium stearate, zinc stearate
10-30 parts, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded
1-5 parts of nanocrystal composition, 1-3 parts of pentaerythrite, 1-3 parts of phosphite ester, 1-3 parts of bisphenol-A.
The present invention is main stabilizer using calcium stearate and zinc stearate, and auxiliary stabilizer is calcium acetylacetonate, hexichol first
Acyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and bisphenol-A improves stabilizer using hydrotalcite
The transparency, zeolite are conducive to improve the glossiness and transparency of product.Main stabilizer, auxiliary stabilizer, hydrotalcite and zeolite are multiple
With the calcium zinc stabilizer for being exclusively used in PVC plastic pipeline is formed, thermostabilization, the anti-aging property of PVC plastic pipeline can not only be improved,
Also has the effect that has a certain upgrade to the intensity of tubing.
The vacuum tank material of extruder is iron in PVC pipe production, can discharge ferric iron in the material into vacuum tank
Dibenzoyl methane in ion, ferric ion and stabilizer forms red complex, so as to cause the material in vacuum tank
Become blood red, and then cause pipe finished that red also can also be presented, change the color of PVC pipe, is unfavorable for the popularization of product
Using.Team of the present invention improves for the dibenzoyl methane in stabilizer, by stabilizer dibenzoyl methane with
Quaternary ammonium salt is compound, and due to being connected on the nitrogen-atoms of quaternary ammonium salt with four alkyl, the positive charge of one unit of band makes dibenzoyl first
Alkane and quaternary ammonium compound show positive electricity, positively charged dibenzoyl methane and quaternary ammonium compound and positively charged ferric ion
Repel, so that preventing dibenzoyl methane and ferric ion from being complexed becomes red complex, avoids PVC pipe from presenting red
Color.
Preferably, the dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method includes following step
It is rapid:
It is 2-5wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By two
It is 5-10wt% hexichol first that benzoyl methane addition mass concentration, which is that dissolution is configured to concentration in 10-20wt% sodium hydroxide solution,
Ethyl acetate is added into dibenzoyl methane solution in acyl dichloromethane, stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled mixed
It closes in liquid and stirs simultaneously, form chitosan microball；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 2-5h is carried out in the sodium tripolyphosphate solution of 3-6wt%, is filtered, dry dibenzoyl methane-chitosan complexes；It will
The 2,3- glycidyl front three for being configured to that concentration is 20-30wt% is added in deionized water in 2,3- epoxypropyltrimethylchloride chloride
2,3- epoxypropyltrimethylchloride chloride aqueous solution is added in dibenzoyl methane-chitosan complexes by ammonium chloride aqueous solution
In, the insulation reaction 1.5-3h at 40-45 DEG C is filtered, washing, dry that dibenzoyl methane-quaternary amine chitin carrier is multiple
Close object.
Carboxymethyl chitosan is added drop-wise in mixed liquor by the present invention, and the sodium hydroxide in mixed liquor serves not only as dibenzoyl
The solvent of methane also compounds the condensation water as carboxymethyl chitosan with ethyl acetate, carboxymethyl chitosan solution is added drop-wise to
Carboxymethyl chitosan drop slowly becomes microspheroidal in mixed liquor, and dibenzoyl methane is gradually diffused into carboxylic under the action of stirring
Then the inside of methyl chitosan carries out crosslinking Treatment to carboxymethyl chitosan using sodium tripolyphosphate crosslinking agent, makes carboxymethyl
Chitosan forms three-dimensional netted cross-linked structure, and dibenzoyl methane is embedded in the interior of three-dimensional netted carboxymethyl chitosan macromolecular
Portion is not easy to be detached from carboxymethyl chitosan microsphere；2,3- epoxypropyl trimethylammonium chloride is added in carboxymethyl chitosan microsphere again
The carboxyl in epoxy group and carboxymethyl chitosan microsphere in ammonium quaternary amine salting liquid, on 2,3- epoxypropyltrimethylchloride chlorides
Or ring-opening reaction occurs for hydroxyl, so that 3- epoxypropyltrimethylchloride chloride is grafted to the table of carboxymethyl chitosan microsphere by 2
Face, carboxymethyl chitosan play the role of " bridging ", and both 2,3- epoxypropyltrimethylchloride chloride and dibenzoyl methane is multiple
It closes, forms dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
Preferably, the additive amount of the ethyl acetate is the 2-5wt% of dibenzoyl methane solution.
Preferably, the dripping quantity of the carboxymethyl chitosan is the 15-30wt% of mixed liquor.
Preferably, dibenzoyl methane-the chitosan complexes and 2, the matter of 3- epoxypropyltrimethylchloride chloride
Amount is than being 1:0.3-0.6.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer at 60-80 DEG C
Lower stirring 1-3h；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 50-60 DEG C of stirring 20-30min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A be added step 2) in stirring after material in, at 50-60 DEG C stir 2-4h to get.
Preferably, step 1) the mixing speed control is in 1400-1500r/min；Mixing speed controls in step 2)
In 1200-1400r/min；Control mixing speed is in 1000-1100r/min in the step 3).
Therefore, the invention has the following beneficial effects: (1) main stabilizer, auxiliary stabilizer, hydrotalcite and zeolites to compound shape
At the calcium zinc stabilizer for being exclusively used in PVC plastic pipeline, thermostabilization, the anti-aging property of PVC plastic pipeline can not only be improved, it is also right
The intensity of tubing has the effect that has a certain upgrade；(2) by stabilizer dibenzoyl methane and quaternary ammonium salt it is compound, due to quaternary ammonium
Salt, which obtains, to be connected on nitrogen-atoms with four alkyl, the positive charge of one unit of band, keeps dibenzoyl methane and quaternary ammonium compound aobvious
Positive electricity, positively charged dibenzoyl methane repels with quaternary ammonium compound and positively charged ferric ion, to prevent
Dibenzoyl methane and ferric ion complexing become red complex, avoid PVC pipe from presenting red.
Specific embodiment
Below by specific embodiment, technical scheme is described further.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art,
Method in embodiment is unless otherwise instructed the conventional method of this field.
Embodiment 1
Dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method the following steps are included:
It is 3wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is that 8wt% dibenzoyl methane is molten that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 15wt% sodium hydroxide solution,
Liquid, ethyl acetate is added into dibenzoyl methane solution, and the additive amount of ethyl acetate is dibenzoyl methane solution
4wt% stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled in mixed liquor and is stirred simultaneously, chitosan microball, carboxymethyl are formed
The dripping quantity of chitosan is the 20wt% of mixed liquor；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 4h is carried out in the sodium tripolyphosphate solution of 5wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,3-
The 2,3- epoxypropyl trimethylammonium chloride for being configured to that concentration is 25wt% is added in deionized water in epoxypropyltrimethylchloride chloride
Aqueous ammonium dibenzoyl methane-chitosan complexes is added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution, hexichol
Formyl methane-chitosan complexes and 2, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 1:0.5, are kept the temperature at 40 DEG C anti-
3h is answered, is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 15 parts of calcium stearate, stearic acid
20 parts of zinc, 15 parts of hydrotalcite, 12 parts of zeolite, 3 parts of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition 3
Part, 2 parts of pentaerythrite, 2 parts of phosphite ester, 1 part of bisphenol-A；Wherein hydrotalcite is MgO/Al2O3Molar ratio is the magnalium two of 4:1
First hydrotalcite.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer and stirred at 70 DEG C
2h is mixed, mixing speed is controlled in 1400r/min；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 55 DEG C of stirring 25min, mixing speed
Control is in 1300r/min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A is added in the material in step 2) after stirring, stirs 3h at 55 DEG C, control mixing speed 1000r/min to get.
Embodiment 2
Dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method the following steps are included:
It is 2wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is that 6wt% dibenzoyl methane is molten that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 15wt% sodium hydroxide solution,
Liquid, ethyl acetate is added into dibenzoyl methane solution, and the additive amount of ethyl acetate is dibenzoyl methane solution
3wt% stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled in mixed liquor and is stirred simultaneously, chitosan microball, carboxymethyl are formed
The dripping quantity of chitosan is the 15wt% of mixed liquor；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 3h is carried out in the sodium tripolyphosphate solution of 5wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,3-
The 2,3- epoxypropyl trimethylammonium chloride for being configured to that concentration is 30wt% is added in deionized water in epoxypropyltrimethylchloride chloride
Aqueous ammonium dibenzoyl methane-chitosan complexes is added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution, hexichol
Formyl methane-chitosan complexes and 2, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 1:0.5, are kept the temperature at 45 DEG C anti-
1.5h is answered, is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 20 parts of calcium stearate, stearic acid
10 parts of zinc, 15 parts of hydrotalcite, 10 parts of zeolite, 3 parts of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition 3
Part, 2 parts of pentaerythrite, 1 part of phosphite ester, 2 parts of bisphenol-A；Wherein hydrotalcite is MgO/Al2O3Molar ratio is the magnalium binary of 4:1
Hydrotalcite.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer and stirred at 60 DEG C
2h is mixed, mixing speed is controlled in 1500r/min；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 55 DEG C of stirring 25min, mixing speed
Control is in 1300r/min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A is added in the material in step 2) after stirring, stirs 3h at 55 DEG C, control mixing speed 1100r/min to get.
Embodiment 3
Dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method the following steps are included:
It is 3wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is 10wt% dibenzoyl methane that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 20wt% sodium hydroxide solution,
Solution, ethyl acetate is added into dibenzoyl methane solution, and the additive amount of ethyl acetate is dibenzoyl methane solution
3wt% stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled in mixed liquor and is stirred simultaneously, chitosan microball, carboxymethyl are formed
The dripping quantity of chitosan is the 25wt% of mixed liquor；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 5h is carried out in the sodium tripolyphosphate solution of 5wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,3-
The 2,3- epoxypropyl trimethylammonium chloride for being configured to that concentration is 25wt% is added in deionized water in epoxypropyltrimethylchloride chloride
Aqueous ammonium dibenzoyl methane-chitosan complexes is added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution, hexichol
Formyl methane-chitosan complexes and 2, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 1:0.3, are kept the temperature at 40 DEG C anti-
3h is answered, is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 25 parts of calcium stearate, stearic acid
25 parts of zinc, 15 parts of hydrotalcite, 10 parts of zeolite, 4 parts of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition 3
Part, 2 parts of pentaerythrite, 2 parts of phosphite ester, 2 parts of bisphenol-A；Wherein hydrotalcite is MgO/Al2O3Molar ratio is the magnalium binary of 4:1
Hydrotalcite.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer and stirred at 80 DEG C
1h is mixed, mixing speed is controlled in 1400r/min；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 55 DEG C of stirring 25min, mixing speed
Control is in 1300r/min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A is added in the material in step 2) after stirring, stirs 3h at 55 DEG C, control mixing speed 1100r/min to get.
Embodiment 4
Dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method the following steps are included:
It is 5wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is 10wt% dibenzoyl methane that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 20wt% sodium hydroxide solution,
Solution, ethyl acetate is added into dibenzoyl methane solution, and the additive amount of ethyl acetate is dibenzoyl methane solution
5wt% stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled in mixed liquor and is stirred simultaneously, chitosan microball, carboxymethyl are formed
The dripping quantity of chitosan is the 30wt% of mixed liquor；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 5h is carried out in the sodium tripolyphosphate solution of 6wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,3-
The 2,3- epoxypropyl trimethylammonium chloride for being configured to that concentration is 30wt% is added in deionized water in epoxypropyltrimethylchloride chloride
Aqueous ammonium dibenzoyl methane-chitosan complexes is added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution, hexichol
Formyl methane-chitosan complexes and 2, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 1:0.6, are kept the temperature at 45 DEG C anti-
1.5h is answered, is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 30 parts of calcium stearate, stearic acid
30 parts of zinc, 20 parts of hydrotalcite, 15 parts of zeolite, 5 parts of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition 5
Part, 3 parts of pentaerythrite, 3 parts of phosphite ester, 3 parts of bisphenol-A；Wherein hydrotalcite is MgO/Al2O3Molar ratio is the magnalium two of 4:1
First hydrotalcite.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer and stirred at 80 DEG C
1h is mixed, mixing speed is controlled in 1500r/min；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 60 DEG C of stirring 20min, mixing speed
Control is in 1400r/min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A is added in the material in step 2) after stirring, stirs 2h at 60 DEG C, control mixing speed 1100r/min to get.
Embodiment 5
Dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition preparation method the following steps are included:
It is 2wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is that 5wt% dibenzoyl methane is molten that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 10wt% sodium hydroxide solution,
Liquid, ethyl acetate is added into dibenzoyl methane solution, and the additive amount of ethyl acetate is dibenzoyl methane solution
2wt% stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled in mixed liquor and is stirred simultaneously, chitosan microball, carboxymethyl are formed
The dripping quantity of chitosan is the 15wt% of mixed liquor；Concentration is added after chitosan microball is cleaned with deionized water to neutrality is
Crosslinking 2h is carried out in the sodium tripolyphosphate solution of 3wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,3-
The 2,3- epoxypropyl trimethylammonium chloride for being configured to that concentration is 20wt% is added in deionized water in epoxypropyltrimethylchloride chloride
Aqueous ammonium dibenzoyl methane-chitosan complexes is added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution, hexichol
Formyl methane-chitosan complexes and 2, the mass ratio of 3- epoxypropyltrimethylchloride chloride are 1:0.3, are kept the temperature at 40 DEG C anti-
3h is answered, is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition.
For the calcium zinc stabilizer of PVC pipe, including following components by weight: 10 parts of calcium stearate, stearic acid
10 parts of zinc, 10 parts of hydrotalcite, 10 parts of zeolite, 1 part of calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition 1
Part, 1 part of pentaerythrite, 1 part of phosphite ester, 1 part of bisphenol-A；Wherein hydrotalcite is MgO/Al2O3Molar ratio is the magnalium two of 4:1
First hydrotalcite.
The preparation method of calcium zinc stabilizer for PVC pipe, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer and stirred at 60 DEG C
3h is mixed, mixing speed is controlled in 1400r/min；
2) calcium stearate and zinc stearate are added in the material in step 1) after stirring, in 50 DEG C of stirring 30min, mixing speed
Control is in 1200r/min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A is added in the material in step 2) after stirring, stirs 4h at 50 DEG C, control mixing speed 1000r/min to get.
Experimental test:
Calcium zinc stabilizer in embodiment 1-5 is weighed 1g to be added in beaker respectively, 50mL dehydrated alcohol is then taken, is sufficiently stirred
Uniformly, 10min is stood, supernatant 5mL is taken to be added in test tube, a drop ammonium ferric sulfate solution is then added dropwise, observes color change.
To compare convenient for test effect, control group 1 and control group 2,1 calcium zinc stabilizer of control group and embodiment 1 are set
Difference is to replace with dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition into the dibenzoyl methane of equivalent；Control group 2
The difference of calcium zinc stabilizer and embodiment 1 is without containing dibenzoyl methane.By 2 calcium zinc stabilizer of control group 1 and control group
1g is weighed respectively to be added in beaker, 50mL dehydrated alcohol is then taken, stirs, and stands 10min, supernatant 5mL is taken to add
Enter in test tube, a drop ammonium ferric sulfate solution is then added dropwise, observes color change.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Control group 1 | Control group 2 | |
| Color | It is transparent | It is transparent | It is transparent | It is transparent | It is transparent | It reddens | It is transparent |
The calcium zinc stabilizer that experiment results proved contains dibenzoyl methane can redden color in conjunction with iron ion, the present invention couple
Dibenzoyl methane and quaternary ammonium salt in stabilizer is compound, is connected on nitrogen-atoms with four alkyl since quaternary ammonium salt obtains, and one, band
The positive charge of unit makes dibenzoyl methane and quaternary ammonium compound show positive electricity, positively charged dibenzoyl methane and quaternary ammonium salt
Compound repels with positively charged ferric ion, so that preventing dibenzoyl methane from being complexed with ferric ion becomes red
Color complex compound.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
It is right according to the technical essence of the invention for the equivalent embodiment of equivalent variations, but without departing from the technical solutions of the present invention
Any simple modification, equivalent change and modification made by above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (7)
1. being used for the calcium zinc stabilizer of PVC pipe, which is characterized in that including following components by weight: calcium stearate 10-
30 parts, 10-30 parts of zinc stearate, 10-20 parts of hydrotalcite, 10-15 parts of zeolite, 1-5 parts of calcium acetylacetonate, dibenzoyl methane-
1-5 parts of quaternary amine chitosan-loaded nanocrystal composition, 1-3 parts of pentaerythrite, 1-3 parts of phosphite ester, 1-3 parts of bisphenol-A.
2. the calcium zinc stabilizer according to claim 1 for PVC pipe, which is characterized in that the dibenzoyl methane-
The preparation method of quaternary amine chitosan-loaded nanocrystal composition the following steps are included:
It is 2-5wt% carboxymethyl chitosan solution that carboxymethyl chitosan, which is added dissolution in deionized water to be configured to concentration,；By hexichol
It is 5-10wt% dibenzoyl first that formyl methane addition mass concentration, which is that dissolution is configured to concentration in 10-20wt% sodium hydroxide solution,
Ethyl acetate is added into dibenzoyl methane solution in alkane solution, stirs to obtain mixed liquor；Carboxymethyl chitosan is instilled into mixed liquor
In and stir simultaneously, formation chitosan microball；It is 3- that concentration is added after chitosan microball is cleaned with deionized water to neutrality
Crosslinking 2-5h is carried out in the sodium tripolyphosphate solution of 6wt%, is filtered, dry dibenzoyl methane-chitosan complexes；By 2,
The 2,3- epoxy for being configured to that concentration is 20-30wt% is added in deionized water in 3- epoxypropyltrimethylchloride chloride
Dibenzoyl methane-chitosan complexes are added in 2,3- epoxypropyltrimethylchloride chloride aqueous solution aqueous ammonium chloride solution,
The insulation reaction 1.5-3h at 40-45 DEG C is filtered, washing, dry dibenzoyl methane-quaternary amine chitosan-loaded bluk recombination
Object.
3. the calcium zinc stabilizer according to claim 2 for PVC pipe, which is characterized in that the ethyl acetate adds
Dosage is the 2-5wt% of dibenzoyl methane solution.
4. the calcium zinc stabilizer according to claim 2 for PVC pipe, which is characterized in that the carboxymethyl chitosan
Dripping quantity be mixed liquor 15-30wt%.
5. the calcium zinc stabilizer according to claim 2 for PVC pipe, which is characterized in that the dibenzoyl methane-
The mass ratio of chitosan complexes and 2,3- epoxypropyltrimethylchloride chloride is 1:0.3-0.6.
6. the preparation method of the calcium zinc stabilizer for PVC pipe as described in claim 1-5 any claim, feature
It is, comprising the following steps:
1) raw material according to the ratio weighs to recipe ingredient, hydrotalcite and zeolite is added in high-speed mixer at 60-80 DEG C
Lower stirring 1-3h；
2) calcium stearate and zinc stearate are added in the material after stirring in step 1), in 50-60 DEG C of stirring 20-30min；
3) by calcium acetylacetonate, dibenzoyl methane-quaternary amine chitosan-loaded nanocrystal composition, pentaerythrite, phosphite ester and double
Phenol A be added step 2 in stir after material in, at 50-60 DEG C stir 2-4h to get.
7. the preparation method of the calcium zinc stabilizer according to claim 6 for PVC pipe, which is characterized in that the step
Rapid 1) mixing speed control is in 1400-1500r/min；Mixing speed control is in 1200-1400r/min in step 2；The step
Rapid 3) middle control mixing speed is in 1000-1100r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793307A (en) * | 2020-08-13 | 2020-10-20 | 惠州市志海新威科技有限公司 | Hyperbranched polymer-containing high-flame-retardance PVC (polyvinyl chloride) product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066460A (en) * | 2007-06-07 | 2007-11-07 | 上海交通大学 | Synthesis of quaternary ammonium salt modified nucleophilic NO donor |
| WO2009027971A2 (en) * | 2007-08-27 | 2009-03-05 | H2Q Water Industries Ltd. | Antimicrobial polymers |
| CN102321276A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Transparent environment-friendly calcium zinc stabilizer and preparation method thereof |
| CN105802192A (en) * | 2016-04-29 | 2016-07-27 | 苏州林华医疗器械股份有限公司 | Novel material applied to indwelling needle catheter and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
-
2019
- 2019-06-27 CN CN201910568230.0A patent/CN110372914B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066460A (en) * | 2007-06-07 | 2007-11-07 | 上海交通大学 | Synthesis of quaternary ammonium salt modified nucleophilic NO donor |
| WO2009027971A2 (en) * | 2007-08-27 | 2009-03-05 | H2Q Water Industries Ltd. | Antimicrobial polymers |
| CN102321276A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Transparent environment-friendly calcium zinc stabilizer and preparation method thereof |
| CN105802192A (en) * | 2016-04-29 | 2016-07-27 | 苏州林华医疗器械股份有限公司 | Novel material applied to indwelling needle catheter and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
Non-Patent Citations (1)
| Title |
|---|
| 吴茂英: "含β-二酮填充PVC塑料发红现象的原因与解决办法", 《塑料工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793307A (en) * | 2020-08-13 | 2020-10-20 | 惠州市志海新威科技有限公司 | Hyperbranched polymer-containing high-flame-retardance PVC (polyvinyl chloride) product |
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