CN107090141B - The preparation method of PVC heat stabilizer - Google Patents
The preparation method of PVC heat stabilizer Download PDFInfo
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- CN107090141B CN107090141B CN201710272644.XA CN201710272644A CN107090141B CN 107090141 B CN107090141 B CN 107090141B CN 201710272644 A CN201710272644 A CN 201710272644A CN 107090141 B CN107090141 B CN 107090141B
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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 present invention relates to a kind of preparation method of PVC heat stabilizer, include the following steps: to mix tartaric acid solution with sodium hydroxide solution, 0.5h~2h is kept the temperature after being then heated to 50 DEG C~80 DEG C, then the temperature of mixed solution is adjusted to 60 DEG C~90 DEG C；Rare-earth salt solution is taken, is added drop-wise in mixed solution, until stopping being added dropwise, then proceeding to be stirred to react, then successively filtered, washed, dried, obtain PVC heat stabilizer when the pH value of solution is 6.5~7.5.The preparation method of PVC heat stabilizer of the invention, simple and easy, whole process reaction condition is mild, easily operated.The PVC heat stabilizer of the method for the present invention preparation is nontoxic, efficient, containing basic group and content of rare earth it is higher, it has excellent performance, when exclusive use can greatly prolong the heat-stable time of PVC compared to other organic acid rare earths, have good synergistic effect when sharing with other kinds of stabilizer.
Description
Technical field
The invention belongs to technical field of polymer material processing, are related to a kind of preparation method of PVC heat stabilizer.
Background technique
Polyvinyl chloride is also known as PVC, is one of resin most popular on our times.Because PVC has excellent resistance to
Acid-base property, wearability, electrical insulating property and fire retardant, self-extinguishment etc., and it is widely used in the fields such as industry, agricultural, construction industry.So
And during PVC processing, because of the effect of temperature and shearing force, PVC often degrades, catabolite HCl meeting again
It is catalyzed PVC accelerated degradation, therefore PVC is in process, needs to add heat stabilizer to prevent the degradation of PVC.Traditional heat is steady
Determining agent has lead class, metal soap, tin class and calcium/zinc class stabilizer etc..However there are heavy metal pollutions for lead salt, more and more
Side has disabled lead salt；Tin stabilizer has peculiar smell when processing；Calcium/zinc class stabilizer thermostabilization efficiency is unstable.
Rare earth is the peculiar resource in China, and rare earth thermal stabilizer is also a kind of heat stabilizer specific to China.Rare earth heat
Stabilizer is good, nontoxic because of its long-term thermal stability and has the function of being coupled and being plasticized and as current heat stabilizer industry
One of main study subject.There are rare earth resources abundant in China, therefore rare earth type thermal stabilizing agent has wide development in China
Prospect.
Summary of the invention
An object of the present invention is to provide a kind of preparation methods of PVC heat stabilizer.
The preparation method of PVC heat stabilizer of the invention, includes the following steps: S101: being 0.8% by mass percentage concentration
~24% tartaric acid solution is mixed with the sodium hydroxide solution that mass percentage concentration is 1.4%~14%, under agitation
0.5h~2h is kept the temperature after being heated to 50 DEG C~80 DEG C, then the temperature was then adjusted to 60 DEG C~90 DEG C；Wherein, tartaric acid and sodium hydroxide
Molar ratio be 1:(3.5~8)；S102: taking molar concentration is the rare-earth salt solution of 0.1mol/L~1.5mol/L, in stirring
The rare-earth salt solution is added drop-wise in the solution that the step S101 is obtained simultaneously, until the pH value of solution is 6.5~7.5
When, stop that the rare-earth salt solution is added dropwise, then proceedes to be stirred to react 1h~3h, then successively filtered, washed, dried, obtain
To PVC heat stabilizer.
The preparation method of PVC heat stabilizer of the invention, simple and easy, whole process reaction condition is mild, easily operated.
The PVC heat stabilizer of the method for the present invention preparation is nontoxic, efficient, and basic group and rare earth are contained in alkali formula tartaric acid rare earth stabilizer
Content is higher, and the quality of rare earth accounts between the 45%-75% of stabilizer gross mass, has excellent performance, and compares other when exclusive use
The organic acid rare earth of alkali formula can greatly prolong the heat-stable time of PVC, and while being shared with other kinds of stabilizer have it is good
Synergistic effect.
In addition, the preparation method of PVC heat stabilizer according to the above embodiment of the present invention, can also have following additional
Technical characteristic:
Further, in the step S102, the rate when rare-earth salt solution is added dropwise is 0.2L/min~1L/
min。
Further, in the step S102, the temperature of the drying process is 60 DEG C~100 DEG C.
Further, the rare-earth salt solution includes at least rare earth nitrate solution, rare-earth chloride solution or rare earth sulphur
One of acid salt solution.
Further, the rare earth element in the rare-earth salt solution be at least lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium,
One of holmium, erbium, thulium, ytterbium, lutetium and yttrium.
It is another object of the present invention to the PVC heat stabilizers for proposing the method preparation.
Another object of the present invention is to propose application of the PVC heat stabilizer in PVC process.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail, the embodiment is exemplary, it is intended to it is used to explain the present invention, and
It is not considered as limiting the invention.
An object of the present invention is to provide a kind of preparation methods of PVC heat stabilizer.
The preparation method of PVC heat stabilizer of the invention, includes the following steps: S101: being 0.8% by mass percentage concentration
~24% tartaric acid solution is mixed with the sodium hydroxide solution that mass percentage concentration is 1.4%~14%, under agitation
0.5h~2h is kept the temperature after being heated to 50 DEG C~80 DEG C, then the temperature was then adjusted to 60 DEG C~90 DEG C again；Wherein, tartaric acid and hydrogen-oxygen
The molar ratio for changing sodium is 1:(3.5~8)；S102: taking molar concentration is the rare-earth salt solution of 0.1mol/L~1.5mol/L, is being stirred
The rare-earth salt solution is added drop-wise in the solution that the step S101 is obtained while mixing, until solution pH value be 6.5~
When 7.5, stops that the rare-earth salt solution is added dropwise, then proceedes to be stirred to react 1h~3h, then successively filtered, washed, dried,
Obtain PVC heat stabilizer.
The preparation method of PVC heat stabilizer of the invention, simple and easy, whole process reaction condition is mild, easily operated.
The PVC heat stabilizer of the method for the present invention preparation is nontoxic, efficient, and basic group and rare earth are contained in alkali formula tartaric acid rare earth stabilizer
Content is higher, and the quality of rare earth accounts between the 45%-75% of stabilizer gross mass, has excellent performance, and compares other when exclusive use
The organic acid rare earth of alkali formula can greatly prolong the heat-stable time of PVC, and while being shared with other kinds of stabilizer have it is good
Synergistic effect.
It is another object of the present invention to the PVC heat stabilizers for proposing the method preparation.
Another object of the present invention is to propose application of the PVC heat stabilizer in PVC process.
Below by specific embodiment the present invention is described in detail.
Embodiment 1
Embodiment 1 proposes a kind of PVC heat stabilizer, and preparation method includes the following steps:
(1) by tartaric acid solution and mass percentage concentration that mass percentage concentration is 0.8% be 14% sodium hydroxide it is molten
Liquid mixing, keeps the temperature 2h, then the temperature was then adjusted to 60 DEG C after being then heated to 50 DEG C；Wherein, mole of tartaric acid and sodium hydroxide
Than for 1:3.5.
(2) taking molar concentration is the lanthanum nitrate cerium solution (La of 0.1mol/L2O3/ Σ REO is 35.4%, CeO2/ Σ REO is
64.6%), the lanthanum nitrate cerium solution is added drop-wise in the solution that the step (1) obtains while agitating, until solution
PH value when being 7.5, stop that the rare-earth salt solution is added dropwise, then proceed to be stirred to react 1h, then successively filtered, washed,
Then dry at a temperature of 100 DEG C, obtain PVC heat stabilizer；Wherein, the rate when rare-earth salt solution is added dropwise is 0.2L/
min。
Embodiment 2
Embodiment 2 proposes a kind of PVC heat stabilizer, and preparation method includes the following steps:
(1) by tartaric acid solution and mass percentage concentration that mass percentage concentration is 24% be 1.4% sodium hydroxide it is molten
Liquid mixing, keeps the temperature 0.5h, then the temperature was then adjusted to 90 DEG C after being then heated to 80 DEG C；Wherein, tartaric acid and sodium hydroxide rub
You are than being 1:8.
(2) taking molar concentration is the solution of cerium chloride by oxidation of 1.5mol/L, and the solution of cerium chloride by oxidation is added dropwise while agitating
In the solution obtained to the step (1), until when the pH value of solution is 6.5 stop that the rare-earth salt solution is added dropwise, then after
It is continuous to be stirred to react 3h, then successively filtered, washed, it is then dry at a temperature of 60 DEG C, obtain PVC heat stabilizer；Wherein, it drips
Adding the rate when rare-earth salt solution is 1L/min.
Embodiment 3
Embodiment 3 proposes a kind of PVC heat stabilizer, and preparation method includes the following steps:
(1) sodium hydroxide solution for being 7% with mass percentage concentration by the tartaric acid solution that mass percentage concentration is 12%
Mixing, keeps the temperature 1.2h, then the temperature was then adjusted to 75 DEG C after being then heated to 65 DEG C；Wherein, mole of tartaric acid and sodium hydroxide
Than for 1:5.7.
(2) taking molar concentration is the lanthanum nitrate hexahydrate of 0.8mol/L, and the lanthanum nitrate hexahydrate is added dropwise while agitating
In the solution obtained to the step (1), until when the pH value of solution is 7.0 stop that the rare-earth salt solution is added dropwise, then after
It is continuous to be stirred to react 2h, then successively filtered, washed, it is then dry at a temperature of 80 DEG C, obtain PVC heat stabilizer；Wherein, it drips
Adding the rate when rare-earth salt solution is 0.6L/min.
Compare the product of each embodiment preparation and the thermal stability (being shown in Table 1) and anti-tarnishing ability of other heat stabilizers
(being shown in Table 2).
Measuring method is as follows:
Congo Red test (static stability experiment): it is measured according to national standard GB/T2917.1-2002 congo red method, by PVC
Powder and heat stabilizer are after 25:1 is sufficiently mixed and (is fully ground in mortar), to pour into test tube in mass ratio, test tube mouth plug
A upper lower section hangs with the plug of Congored test paper, keeps Congored test paper and PVC powder height is about 25mm.It will be added with PVC
Test tube be put into 180 DEG C of oil baths, start timing.Congored test paper color change is observed, when Congored test paper starts to become indigo plant,
Timing terminates, and this period is the heat-stable time of PVC.
Discoloration experiment: being that 25:1 is sufficiently mixed and (is fully ground in mortar) it by PVC powder and heat stabilizer in mass ratio
Afterwards, sample average is divided into several equal parts, is put in each porcelain Noah's ark respectively, it is old that porcelain Noah's ark is then put into 180 DEG C of heat simultaneously
Change in baking oven, takes out one every 5min, observe its discoloration.(note: take-off speed is fast, and closes baking oven rapidly
Door).
The heat-stable time of several heat stabilizers of table 1 compares
| Stabilizer | Congored test paper becomes indigo plant time/min |
| Calcium stearate | 35 |
| Lead stearate | 46 |
| Calcium stearate zinc composite stabilizer | 19 |
| Lanthanum Stearate | 21 |
| Embodiment 1 | 56 |
| Embodiment 2 | 51 |
| Embodiment 3 | 62 |
The comparison of the anti-tarnishing ability of several heat stabilizers of table 2
It can be seen that PVC heat stabilizer of the invention from the data of Tables 1 and 2 and possess good static heat stability,
Static heat-stable time is better than traditional lead stearate stabilizer, is much better than Lanthanum Stearate and calcium-zinc composite stabilizing agent.The present invention
The long-term anti-tarnishing ability of heat stabilizer is preferable, is better than Lanthanum Stearate and calcium-zinc composite stabilizing agent.
To sum up, the preparation method of PVC heat stabilizer of the invention, simple and easy, whole process reaction condition is mild, is easy to
Operation.The method of the present invention preparation PVC heat stabilizer it is nontoxic, efficient, containing basic group and content of rare earth it is higher, alkali formula winestone
The quality of rare earth accounts between the 45%-75% of stabilizer gross mass in acid rare earth stabilizer, has excellent performance, and when exclusive use is compared
Other organic acid rare earths of alkali formula can greatly prolong the heat-stable time of PVC, and while being shared with other kinds of stabilizer have it is good
Good synergistic effect.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (3)
1. a kind of preparation method of PVC heat stabilizer, which comprises the steps of:
S101: by mass percentage concentration be 0.8%~24% tartaric acid solution and mass percentage concentration be 1.4%~14%
Sodium hydroxide solution mixing, keeps the temperature 0.5h~2h, then the temperature was then adjusted to 60 after being heated to 50 DEG C~80 DEG C under agitation
DEG C~90 DEG C；Wherein, the molar ratio of tartaric acid and sodium hydroxide is 1:(3.5~8)；
S102: taking molar concentration is the rare-earth salt solution of 0.1mol/L~1.5mol/L, while agitating by the rare-earth salts
Solution is added drop-wise in the solution that the step S101 is obtained with the rate of 0.2L/min~1L/min, until the pH value of solution is
When 6.5~7.5, stops that the rare-earth salt solution is added dropwise, then proceed to be stirred to react 1h~3h, then successively filtered, washed,
It is dry, obtain PVC heat stabilizer；Wherein, the temperature of the drying process is 60 DEG C~100 DEG C；The rare-earth salt solution is at least
Including one of rare earth nitrate solution, rare-earth chloride solution or rare earth sulfuric acid salting liquid；In the rare-earth salt solution
Rare earth element is at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium.
2. the PVC heat stabilizer of method preparation described in claim 1.
3. application of the PVC heat stabilizer as claimed in claim 2 in PVC process.
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| CN107793674B (en) * | 2017-11-10 | 2020-10-30 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC and preparation method thereof |
| CN109251364A (en) * | 2018-08-14 | 2019-01-22 | 含山县胜发塑料制品有限公司 | Heat stabilizer is used in a kind of production and processing of PVC plastic |
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| CN104829961A (en) * | 2014-12-09 | 2015-08-12 | 周贤明 | Preparation method of rare earth thermal-stabilizer |
| CN106565993A (en) * | 2016-11-10 | 2017-04-19 | 周荣 | Preparation method of environment-friendly composite heat stabilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104829961A (en) * | 2014-12-09 | 2015-08-12 | 周贤明 | Preparation method of rare earth thermal-stabilizer |
| CN106565993A (en) * | 2016-11-10 | 2017-04-19 | 周荣 | Preparation method of environment-friendly composite heat stabilizer |
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| 碱式羧酸稀土热稳定剂及其协同效应的研究;曾冬铭等;《稀土》;20020831;第23卷(第4期);第20-22页 |
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