CN107090141A - Pvc heat stabilizer and preparation method thereof - Google Patents
Pvc heat stabilizer and preparation method thereof Download PDFInfo
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- CN107090141A CN107090141A CN201710272644.XA CN201710272644A CN107090141A CN 107090141 A CN107090141 A CN 107090141A CN 201710272644 A CN201710272644 A CN 201710272644A CN 107090141 A CN107090141 A CN 107090141A
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- heat stabilizer
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- pvc heat
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention relates to a kind of PVC heat stabilizer and preparation method thereof, the preparation method comprises the following steps：Tartaric acid solution is mixed with sodium hydroxide solution, insulation 0.5h~2h after 50 DEG C~80 DEG C is then heated to, then by the temperature adjustment of mixed solution to 60 DEG C~90 DEG C；Rare-earth salt solution is taken, is added drop-wise in mixed solution, until when the pH value of solution is 6.5~7.5, stopping being added dropwise, stirring reaction is then proceeded to, then carries out suction filtration, washing successively, dry, PVC heat stabilizer is obtained.The preparation method of the PVC heat stabilizer of the present invention, simple and easy to apply, whole process reaction condition is gentle, it is easy to operate.PVC heat stabilizer prepared by the inventive method is nontoxic, efficient, containing basic group and content of rare earth is higher, excellent performance, PVC heat-stable time can be greatly prolonged during exclusive use compared to other organic acid rare earths, with good synergy when being shared with other kinds of stabilizer.
Description
Technical field
The invention belongs to processing of high molecular material technical field, it is related to a kind of PVC heat stabilizer and preparation method thereof.
Background technology
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 is processed, because the effect of temperature and shearing force, PVC often degrades, catabolite HCl meetings again
PVC accelerated degradations are catalyzed, therefore PVC is in process, it is necessary to add heat stabilizer to prevent PVC degraded.Traditional heat is steady
Determining agent has lead class, metal soap, tin class and calcium/zinc class stabilizer etc..But lead salt has heavy metal pollution, more and more
Side has disabled lead salt；Tin stabilizer has peculiar smell when processing；The thermally-stabilised efficiency of calcium/zinc class stabilizer is unstable.
Rare earth is the peculiar resource of China, and rare earth thermal stabilizer is also a kind of heat stabilizer specific to China.Rare earth heat
Stabilizer because its long-term thermal stability is good, nontoxic and effect with coupling and plasticising and as current heat stabilizer industry
One of main study subject.There are abundant rare earth resources in China, therefore rare earth type thermal stabilizing agent has wide development in China
Prospect.
The content of the invention
It is an object of the present invention to propose a kind of preparation method of PVC heat stabilizer.
The preparation method of the PVC heat stabilizer of the present invention, comprises the following steps：S101：It is 0.8% by mass percentage concentration
~24% tartaric acid solution is mixed with mass percentage concentration for 1.4%~14% sodium hydroxide solution, under agitation
It is heated to after 50 DEG C~80 DEG C being incubated 0.5h~2h, then by temperature adjustment to 60 DEG C~90 DEG C；Wherein, tartaric acid and sodium hydroxide
Mol ratio be 1:(3.5~8)；S102：The rare-earth salt solution that molar concentration is 0.1mol/L~1.5mol/L is taken, 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 proceed to stirring reaction 1h~3h, then carry out suction filtration, washing successively, dry, obtain
To PVC heat stabilizer.
The preparation method of the PVC heat stabilizer of the present invention, simple and easy to apply, whole process reaction condition is gentle, it is easy to operate.
PVC heat stabilizer prepared by the inventive method 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 is accounted between the 45%-75% of stabilizer gross mass, excellent performance, and other are compared during exclusive use
The organic acid rare earth of alkali formula can greatly prolong PVC heat-stable time, and with good when being shared with other kinds of stabilizer
Synergy.
In addition, the preparation method of PVC heat stabilizer according to the above embodiment of the present invention, can also have what is added as follows
Technical characteristic：
Further, in the step S102, the speed 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 at least includes rare earth nitrate solution, rare-earth chloride solution or rare earth sulphur
One kind in 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 kind in holmium, erbium, thulium, ytterbium, lutetium and yttrium.
It is another object of the present invention to the PVC heat stabilizer for proposing prepared by described method.
Another object of the present invention is application of the PVC heat stabilizer in PVC process described in proposition.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
Embodiments of the invention are described below in detail, the embodiment is exemplary, it is intended to for explaining the present invention, and
It is not considered as limiting the invention.
It is an object of the present invention to propose a kind of preparation method of PVC heat stabilizer.
The preparation method of the PVC heat stabilizer of the present invention, comprises the following steps：S101：It is 0.8% by mass percentage concentration
~24% tartaric acid solution is mixed with mass percentage concentration for 1.4%~14% sodium hydroxide solution, under agitation
It is heated to after 50 DEG C~80 DEG C being incubated 0.5h~2h, then again by temperature adjustment to 60 DEG C~90 DEG C；Wherein, tartaric acid and hydrogen-oxygen
The mol ratio for changing sodium is 1:(3.5~8)；S102：The rare-earth salt solution for taking molar concentration to be 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 the pH value of solution for 6.5~
When 7.5, stop that the rare-earth salt solution is added dropwise, then proceed to stirring reaction 1h~3h, then carry out suction filtration, washing successively, dry,
Obtain PVC heat stabilizer.
The preparation method of the PVC heat stabilizer of the present invention, simple and easy to apply, whole process reaction condition is gentle, it is easy to operate.
PVC heat stabilizer prepared by the inventive method 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 is accounted between the 45%-75% of stabilizer gross mass, excellent performance, and other are compared during exclusive use
The organic acid rare earth of alkali formula can greatly prolong PVC heat-stable time, and with good when being shared with other kinds of stabilizer
Synergy.
It is another object of the present invention to the PVC heat stabilizer for proposing prepared by described method.
Another object of the present invention is application of the PVC heat stabilizer in PVC process described in proposition.
The present invention is described in detail below by specific embodiment.
Embodiment 1
Embodiment 1 proposes a kind of PVC heat stabilizer, and its preparation method comprises the following steps：
(1) it is the mass percentage concentration tartaric acid solution for being 0.8% and sodium hydroxide that mass percentage concentration is 14% is molten
Liquid is mixed, and is then heated to after 50 DEG C and is incubated 2h, then by temperature adjustment to 60 DEG C；Wherein, mole of tartaric acid and sodium hydroxide
Than for 1:3.5.
(2) the lanthanum nitrate cerium solution (La that molar concentration is 0.1mol/L is taken2O3/ Σ REO are 35.4%, CeO2/ Σ REO are
64.6%), the lanthanum nitrate cerium solution is added drop-wise in the solution that the step (1) is obtained while stirring, until solution
PH value when being 7.5, stop that the rare-earth salt solution is added dropwise, then proceed to stirring reaction 1h, then carry out suction filtration, washing successively,
Then dried at a temperature of 100 DEG C, obtain PVC heat stabilizer；Wherein, the speed when rare-earth salt solution is added dropwise is 0.2L/
min。
Embodiment 2
Embodiment 2 proposes a kind of PVC heat stabilizer, and its preparation method comprises the following steps：
(1) it is the mass percentage concentration tartaric acid solution for being 24% and sodium hydroxide that mass percentage concentration is 1.4% is molten
Liquid is mixed, and is then heated to after 80 DEG C and is incubated 0.5h, then by temperature adjustment to 90 DEG C；Wherein, tartaric acid and sodium hydroxide rub
You are than being 1:8.
(2) solution of cerium chloride by oxidation that molar concentration is 1.5mol/L is taken, the solution of cerium chloride by oxidation is added dropwise while stirring
In the solution obtained to the step (1), until when the pH value of solution is 6.5, stopping that the rare-earth salt solution, Ran Houji is added dropwise
Continuous stirring reaction 3h, then suction filtration, washing are carried out successively, then dried at a temperature of 60 DEG C, obtain PVC heat stabilizer；Wherein, drip
Plus the speed during rare-earth salt solution is 1L/min.
Embodiment 3
Embodiment 3 proposes a kind of PVC heat stabilizer, and its preparation method comprises the following steps：
(1) sodium hydroxide solution that the tartaric acid solution for being 12% by mass percentage concentration is 7% with mass percentage concentration
Mixing, is then heated to after 65 DEG C and is incubated 1.2h, then by temperature adjustment to 75 DEG C；Wherein, mole of tartaric acid and sodium hydroxide
Than for 1:5.7.
(2) lanthanum nitrate hexahydrate that molar concentration is 0.8mol/L is taken, the lanthanum nitrate hexahydrate is added dropwise while stirring
In the solution obtained to the step (1), until when the pH value of solution is 7.0, stopping that the rare-earth salt solution, Ran Houji is added dropwise
Continuous stirring reaction 2h, then suction filtration, washing are carried out successively, then dried at a temperature of 80 DEG C, obtain PVC heat stabilizer；Wherein, drip
Plus the speed during rare-earth salt solution is 0.6L/min.
Compare the thermal stability (being shown in Table 1) and anti-tarnishing ability of product and other heat stabilizers prepared by each embodiment
(being shown in Table 2).
Assay method is as follows：
Congo Red test (static stability experiment)：Determined according to national standard GB/T2917.1-2002 congo red methods, by PVC
Powder is 25 in mass ratio with heat stabilizer:After 1 is sufficiently mixed and (is fully ground in mortar), pour into test tube, test tube mouthful plug
A upper lower section hangs with the plug of Congored test paper, and it is highly about 25mm with PVC powder to keep Congored test paper.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 PVC heat-stable time.
Discoloration experiment：It is 25 in mass ratio by PVC powder and heat stabilizer:1 is sufficiently mixed and (is fully ground in mortar) it
Afterwards, sample average is divided into some deciles, be put in respectively in each porcelain Noah's ark, it is old that porcelain Noah's ark then is put into 180 DEG C of heat simultaneously
Change in baking oven, take 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
The PVC heat stabilizer that can be seen that the present invention from the data of Tables 1 and 2 possesses good static heat stability, its
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, 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 to apply, and whole process reaction condition is gentle, it is easy to
Operation.PVC heat stabilizer prepared by the inventive method is nontoxic, efficient, containing basic group and content of rare earth is higher, alkali formula winestone
The quality of acid rare earth stabilizer middle rare earth is accounted between the 45%-75% of stabilizer gross mass, and excellent performance is compared during exclusive use
Other organic acid rare earths of alkali formula can greatly prolong PVC heat-stable time, and have when being shared with other kinds of stabilizer good
Good synergy.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (7)
1. a kind of preparation method of PVC heat stabilizer, it is characterised in that comprise the following steps：
S101：The tartaric acid solution and mass percentage concentration for being 0.8%~24% by mass percentage concentration are 1.4%~14%
Sodium hydroxide solution is mixed, and is heated to after 50 DEG C~80 DEG C being incubated 0.5h~2h under agitation, then by temperature adjustment to 60
DEG C~90 DEG C；Wherein, the mol ratio of tartaric acid and sodium hydroxide is 1:(3.5~8)；
S102：The rare-earth salt solution that molar concentration is 0.1mol/L~1.5mol/L is taken, by the rare-earth salts while stirring
Solution is added drop-wise in the solution that the step S101 is obtained, until when the pH value of solution is 6.5~7.5, stopping dropwise addition described dilute
Earth salt solution, then proceedes to stirring reaction 1h~3h, then carries out suction filtration, washing successively, dries, and obtains PVC heat stabilizer.
2. the preparation method of PVC heat stabilizer according to claim 1, it is characterised in that in the step S102, drop
Plus the speed during rare-earth salt solution is 0.2L/min~1L/min.
3. the preparation method of PVC heat stabilizer according to claim 1, it is characterised in that in the step S102, institute
The temperature for stating drying process is 60 DEG C~100 DEG C.
4. the preparation method of PVC heat stabilizer according to claim 1, it is characterised in that the rare-earth salt solution is at least
Including one kind in rare earth nitrate solution, rare-earth chloride solution or rare earth sulfuric acid salting liquid.
5. the preparation method of PVC heat stabilizer according to claim 4, it is characterised in that in the rare-earth salt solution
Rare earth element is at least one kind in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium.
6. PVC heat stabilizer prepared by the method described in claim any one of 1-5.
7. application of the PVC heat stabilizer in PVC process described in claim 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107793674A (en) * | 2017-11-10 | 2018-03-13 | 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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Cited By (3)
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| CN107793674A (en) * | 2017-11-10 | 2018-03-13 | 内蒙古科技大学 | rare earth composite heat stabilizer for PVC and preparation method thereof |
| 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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| CN107090141B (en) | 2019-07-30 |
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