CN109135102A - A kind of compound FWR stabilizer of polymolecularity rare earth and its preparation process - Google Patents
A kind of compound FWR stabilizer of polymolecularity rare earth and its preparation process Download PDFInfo
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Abstract
The invention proposes a kind of compound FWR stabilizer of polymolecularity rare earth and its preparation processes, the stabilizer includes following parts by weight component: 15-30 parts of lead salt stabilizer, 5-9 parts of rare-earth stabilizer, 1-5 parts of mercaptoethanol, 3-6 parts of hydroxycyclohexan benzophenone, modified 3-10 parts of cladding material, the modified cladding material is the clay modified cladding hydroxyapatite fiber of amino, hydroxyapatite fiber accounting is 18-33wt% in modified cladding material, it further include 3-8 parts of auxiliary stabilizer, the present invention passes through reasonable raw material choice, effectively increase the dispersibility of stabilizer, thermal stability significantly improves, and there is certain absorption treatment effect certainly containing lead stabilizer compared to tradition, thermostabilization timeliness is longer, safety is more preferably.
Description
Technical field
The present invention relates to plastics-production additives for process technical fields, and in particular to a kind of compound FWR of polymolecularity rare earth
Stabilizer and its preparation process.
Background technique
Polyvinyl chloride (PVC) is one of big synthetic resin of dosage maximum five in the world, is by vinyl chloride monomer through freedom
The thermoplastic linear polymer that base polymerization reaction generates.PVC material has high-intensitive, cheap, and chemical corrosion resistance is good, electric
The advantages that good insulating and difficult to burn, and be easily worked, it can be processed by the various ways such as molding, laminated, injection molding,
It is widely used in the hard and soft goods of the industries such as engineering construction, food packaging, electrical.
Although PVC itself has superior performance, due to containing branch point, double bond in PVC polymer chain structure and drawing
The presence of the unstable factors such as hair agent residue is heated to 140 DEG C so that the chlorosity on PVC strand is easily deviate from from strand
When will decompose and release hydrogen chloride.As extending heating time or temperature increase, hydrogen chloride is largely deviate from and is accumulated in material
In material, since hydrogen chloride has catalytic action to PVC degradation, so that PVC degradation speed is greatly speeded up, deviate from molecule after hydrogen chloride
The phenomenon that largely being formed in chain has the conjugated double bond added lustre to, and color, which occurs, in product sharply to be deepened, and physical mechanical property declines, very
To carbonization until use value of dying.Therefore, when PVC product carries out processing and forming, it is necessary to use heat stabilizer.
More commonly used heat stabilizer has lead salt, organic tin, metal soap, terres rares and calcium zinc class in PVC industry
Equal stabilizers.China is rare earth big country, currently, in the stabilization of PVC simultaneously have valence variation element, the effect of metalloid soap and
The rare earth thermal stabilizer of rare earth comprehensive function is increasingly focus of attention, mostly based on rare earth organic monoacid salt stabilizing agent, it
Lead salts and other metal soaps are better than to the long-term thermal stability of PVC, have preferable long-term thermal stability, and with it is other
Have extensive synergistic effect between type stabilizer, there is good tolerance, not by the pollution of S, stable storing, toxicity it is low and
The advantage of environmental protection also has coupling, increase-volume, toughening, improves material fluidity, improves PVC product power while greasy property is good
The effects of learning performance.But the organic monoacids salt such as rare-earth stearate developed recent years is shown in terms of PVC thermal stability
Preferable effect, but the primary stability of material can be not good enough when rare-earth stabilizer is used alone, and shows as initial coloration performance
It is low, it can carry out compounding obtained rare earth using rare-earth stabilizer and other metallic stabilizers and meet heat stabilizer.
Summary of the invention
In view of the above problems, the invention proposes a kind of polymolecularity rare earths to answer FWR stabilizer and its preparation work
Skill effectively increases the dispersibility of stabilizer by reasonable raw material choice, and thermal stability significantly improves, and compared to tradition
There is certain absorption treatment effect certainly containing lead stabilizer, thermostabilization timeliness is longer, and safety is more preferably.
In order to achieve the above purpose, the following technical solution is employed by the present invention:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 15-30 parts of lead salt stabilizer,
5-9 parts of rare-earth stabilizer, 1-5 parts of mercaptoethanol, 3-6 parts of hydroxycyclohexan benzophenone, 3-10 parts of cladding material modified, the modified packet
Covering material is the clay modified cladding hydroxyapatite fiber of amino, and hydroxyapatite fiber accounting is 18- in modified cladding material
33wt%.
It preferably, further include 3-8 parts of auxiliary stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa-methylene four
Amine, pentaerythritol stearate, double dodecyl methyl tertiary amines composition.
Preferably, the lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:0.5-2.
Preferably, the rare-earth stabilizer uses rare-earth stearate stabilizer, salicylic acid rare-earth stabilizer, lemon acid rare earth
One of stabilizer or numerous compositions, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, and it is 1 that three, which adds mole ratio:
1-3:0.5-1.5, and cerium content is twice of shirt content.
Preferably, modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball mill
Middle ball-milling treatment 3-4h, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed in ball mill again
5-10h is finally dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5- of amino clay and 2-4 times of quality
Then fiber material is added thereto by 10min, high-speed stirred 5-10min, subsequent low speed insulated and stirred 0.5-1h are stored at room temperature 1-
2h, being re-fed into vacuum drier dry, pulverize, and must be modified cladding material.
Preferably, the polyvinyl alcohol water solution mass content is 1-1.5wt%, and soaking temperature is 65 ± 2 DEG C, when immersion
Between be 90-150min.
Preferably, the gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, and gaseous mixture intake is
1L/h。
Preferably, high-speed stirred revolving speed is 1500-1800rpm, and low speed insulated and stirred revolving speed is 200-300rpm, heat preservation temperature
Degree is 50-55 DEG C.
Preferably, the compound FWR stabilizer of polymolecularity rare earth, preparation process are as follows:
1) by two parts of lead salt stabilizer equal part, portion is blended with rare-earth stabilizer, is placed in high-speed mixer, 1000-
5-10min is stirred under the conditions of 1200rpm, 75-80 DEG C, obtains mixing one；
2) another is blended with remaining unclassified stores, is placed in elder generation 1500rpm in high-speed mixer, is stirred under the conditions of 70 DEG C
3-5min is mixed, 1000rpm, 50 DEG C of stirring 10-15min is being down to, is obtaining mixing two；
3) mixing one, mixing two are blended, are placed in high-speed mixer, 1000-1500rpm, 55-60 DEG C of stirring 5-
10min.
Due to using above-mentioned technical solution, the beneficial effects of the present invention are: the present invention has by reasonable raw material choice
Effect improves the dispersibility of stabilizer, and thermal stability significantly improves, and has certain self-priming containing lead stabilizer compared to tradition
Attached treatment effect, thermostabilization timeliness is longer, and safety is more preferably.
The present invention compounds lead salt stabilizer with rare-earth stabilizer, and comprehensive thermal stability is stronger.Expect added with modified cladding,
On the one hand there is excellent mechanical property, thermal stability is not only increased in PVC production process, while significantly improving anti-impact
Hit intensity, obdurability improve 5-10%, on the other hand, have in excellent reactivity, with compound stabilizer Blending Processes,
It is good that associativity is bonded between raw material, dispersed homogeneous degree height is compounded compared to simple lead salt stabilizer, rare-earth stabilizer, and efficiency mentions
Liter property is good, and stability improves 18% or more, in PVC production process, replaces with active chlorine atom fast reaction, meanwhile, it is right
There is the hydrogen chloride of generation good adsorptivity and heavy metal ion therein also to have certain absorption sequestering, comprehensive
Benefit is strong, highly-safe.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described.Based on the embodiment of the present invention, the common skill in this field
Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 15 parts of lead salt stabilizer, dilute
8 parts of soil stabilizer, 4 parts of mercaptoethanol, 4 parts of hydroxycyclohexan benzophenone, modified cladding expect 6 parts, and the modified cladding material is amino
Clay modified cladding hydroxyapatite fiber, being modified hydroxyapatite fiber accounting in cladding material is 18wt%；It further include auxiliary
6 parts of stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecanes
The composition of ylmethyl tertiary amine.
Wherein, lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:0.5；Rare-earth stabilizer is adopted
With rare-earth stearate stabilizer, salicylic acid rare-earth stabilizer composition, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, three
Addition mole ratio is 1:1:0.5, and cerium content is twice of shirt content.
Modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball milling in ball mill
3h is handled, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed 5h in ball mill again, finally exists
It is dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then will
Fiber material is added thereto, high-speed stirred 5-10min, and subsequent low speed insulated and stirred 0.5h is stored at room temperature 1h, is re-fed into vacuum drying
It dry, pulverize in machine, cladding material must be modified.
Wherein, polyvinyl alcohol water solution mass content is 1.5wt%, and soaking temperature is 65 ± 2 DEG C, and soaking time is
90min；Gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, gaseous mixture intake is 1L/h；High-speed stirred
Revolving speed is 1500rpm, and low speed insulated and stirred revolving speed is 200rpm, and holding temperature is 50-55 DEG C.
The compound FWR stabilizer of polymolecularity rare earth, preparation process are as follows:
1) by two parts of lead salt stabilizer equal part, portion is blended with rare-earth stabilizer, is placed in high-speed mixer, 1000-
5-10min is stirred under the conditions of 1200rpm, 75-80 DEG C, obtains mixing one；
2) another is blended with remaining unclassified stores, is placed in elder generation 1500rpm in high-speed mixer, is stirred under the conditions of 70 DEG C
3-5min is mixed, 1000rpm, 50 DEG C of stirring 10-15min is being down to, is obtaining mixing two；
3) mixing one, mixing two are blended, are placed in high-speed mixer, 1000-1500rpm, 55-60 DEG C of stirring 5-
10min.
Embodiment 2:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 22 parts of lead salt stabilizer, dilute
6 parts of soil stabilizer, 3 parts of mercaptoethanol, 3 parts of hydroxycyclohexan benzophenone, modified cladding expect 6 parts, and the modified cladding material is amino
Clay modified cladding hydroxyapatite fiber, being modified hydroxyapatite fiber accounting in cladding material is 25wt%；It further include auxiliary
6 parts of stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecanes
The composition of ylmethyl tertiary amine.
Wherein, lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:2；Rare-earth stabilizer uses
Rare-earth stearate stabilizer, salicylic acid rare-earth stabilizer composition, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, San Zhetian
Adding mole ratio is 1:2:1, and cerium content is twice of shirt content.
Modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball milling in ball mill
4h is handled, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed 10h in ball mill again, finally
It is dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then
Fiber material is added thereto, high-speed stirred 5-10min, subsequent low speed insulated and stirred 1h is stored at room temperature 2h, is re-fed into vacuum drying
It dry, pulverize in machine, cladding material must be modified.
Wherein, polyvinyl alcohol water solution mass content is 1wt%, and soaking temperature is 65 ± 2 DEG C, and soaking time is
120min；Gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, gaseous mixture intake is 1L/h；High-speed stirring
Mixing revolving speed is 1600rpm, and low speed insulated and stirred revolving speed is 300rpm, and holding temperature is 50-55 DEG C.
The compound FWR stabilizer of polymolecularity rare earth, preparation process is the same as embodiment 1.
Embodiment 3:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 25 parts of lead salt stabilizer, dilute
5 parts of soil stabilizer, 2 parts of mercaptoethanol, 4 parts of hydroxycyclohexan benzophenone, modified cladding expect 5 parts, and the modified cladding material is amino
Clay modified cladding hydroxyapatite fiber, being modified hydroxyapatite fiber accounting in cladding material is 30wt%；It further include auxiliary
5 parts of stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecanes
The composition of ylmethyl tertiary amine.
Wherein, lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:1；Rare-earth stabilizer uses
Salicylic acid rare-earth stabilizer, citric acid rare-earth stabilizer composition, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, San Zhetian
Adding mole ratio is 1:2.6:1.3, and cerium content is twice of shirt content.
Modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball milling in ball mill
3h is handled, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed 6h in ball mill again, finally exists
It is dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then will
Fiber material is added thereto, high-speed stirred 5-10min, and subsequent low speed insulated and stirred 0.5h is stored at room temperature 2h, is re-fed into vacuum drying
It dry, pulverize in machine, cladding material must be modified.
Wherein, polyvinyl alcohol water solution mass content is 1wt%, and soaking temperature is 65 ± 2 DEG C, and soaking time is
150min；Gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, gaseous mixture intake is 1L/h；High-speed stirring
Mixing revolving speed is 1800rpm, and low speed insulated and stirred revolving speed is 300rpm, and holding temperature is 50-55 DEG C.
The compound FWR stabilizer of polymolecularity rare earth, preparation process is the same as embodiment 1.
Embodiment 4:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 30 parts of lead salt stabilizer, dilute
9 parts of soil stabilizer, 1 part of mercaptoethanol, 5 parts of hydroxycyclohexan benzophenone, modified cladding expect 3 parts, and the modified cladding material is amino
Clay modified cladding hydroxyapatite fiber, being modified hydroxyapatite fiber accounting in cladding material is 20wt%；It further include auxiliary
3 parts of stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecanes
The composition of ylmethyl tertiary amine.
Wherein, lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:1.5；Rare-earth stabilizer is adopted
With salicylic acid rare-earth stabilizer, citric acid rare-earth stabilizer composition, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, three
Addition mole ratio is 1:3:1.5, and cerium content is twice of shirt content.
Modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball milling in ball mill
3h is handled, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed 5h in ball mill again, finally exists
It is dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then will
Fiber material is added thereto, high-speed stirred 5-10min, and subsequent low speed insulated and stirred 0.5h is stored at room temperature 2h, is re-fed into vacuum drying
It dry, pulverize in machine, cladding material must be modified.
Wherein, polyvinyl alcohol water solution mass content is 1wt%, and soaking temperature is 65 ± 2 DEG C, and soaking time is
100min；Gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, gaseous mixture intake is 1L/h；High-speed stirring
Mixing revolving speed is 1600rpm, and low speed insulated and stirred revolving speed is 250rpm, and holding temperature is 50-55 DEG C.
The compound FWR stabilizer of polymolecularity rare earth, for example lower same embodiment 1 of preparation process.
Embodiment 5:
A kind of compound FWR stabilizer of polymolecularity rare earth, including following parts by weight component: 20 parts of lead salt stabilizer, dilute
6 parts of soil stabilizer, 5 parts of mercaptoethanol, 6 parts of hydroxycyclohexan benzophenone, modified cladding expect 10 parts, and the modified cladding material is amino
Clay modified cladding hydroxyapatite fiber, being modified hydroxyapatite fiber accounting in cladding material is 33wt%；It further include auxiliary
8 parts of stabilizer, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecanes
The composition of ylmethyl tertiary amine.
Wherein, lead salt stabilizer uses lead stearate, the dibasic lead phosphite of molar ratio 1:1.5；Rare-earth stabilizer is adopted
With salicylic acid rare-earth stabilizer, citric acid rare-earth stabilizer composition, wherein rare earth is selected from the composition of lanthanum, cerium, shirt, three
Addition mole ratio is 1:1.8:0.9, and cerium content is twice of shirt content.
Modified cladding material preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball milling in ball mill
4h is handled, taking-up, which is placed in polyvinyl alcohol water solution, impregnates, and is then placed in secondary milled processed 8h in ball mill again, finally exists
It is dry that fiber material is spare in gaseous mixture；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then will
Fiber material is added thereto, high-speed stirred 5-10min, and subsequent low speed insulated and stirred 1h is stored at room temperature 1h, is re-fed into vacuum drier
It inside dry, pulverize, cladding material must be modified.
Wherein, polyvinyl alcohol water solution mass content is 1.5wt%, and soaking temperature is 65 ± 2 DEG C, and soaking time is
120min；Gaseous mixture is the gaseous mixture of nitrogen, hydrogen, and the two is passed through than for 1:0.2, gaseous mixture intake is 1L/h；High-speed stirring
Mixing revolving speed is 1500rpm, and low speed insulated and stirred revolving speed is 200rpm, and holding temperature is 50-55 DEG C.
The compound FWR stabilizer of polymolecularity rare earth, for example lower same embodiment 1 of preparation process.
The product that the embodiment of the present invention is worth is used for PVC production, product obtained is tested for the property, data are such as
Under:
Wherein (based on embodiment 1):
Comparative example 1: containing only lead salt stabilizer；
Comparative example 2: containing only rare-earth stabilizer；
Comparative example 3: lead salt stabilizer is compound with rare-earth stabilizer；
Comparative example 4: without modified cladding material.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (9)
1. a kind of compound FWR stabilizer of polymolecularity rare earth, which is characterized in that including following parts by weight component: lead salt is stablized
15-30 parts of agent, 5-9 parts of rare-earth stabilizer, 1-5 parts of mercaptoethanol, 3-6 parts of hydroxycyclohexan benzophenone, modified cladding expect 3-10 parts,
The modified cladding material is the clay modified cladding hydroxyapatite fiber of amino, hydroxyapatite fiber accounting in modified cladding material
For 18-33wt%.
2. the compound FWR stabilizer of polymolecularity rare earth according to claim 1, it is characterised in that: further include that auxiliary is stablized
3-8 parts of agent, the auxiliary stabilizer uses mass ratio 2:5:4 hexa, pentaerythritol stearate, double dodecyls
The composition of methyl tertiary amine.
3. the compound FWR stabilizer of polymolecularity rare earth according to claim 1, it is characterised in that: the lead salt stabilizer
Using the lead stearate of molar ratio 1:0.5-2, dibasic lead phosphite.
4. the compound FWR stabilizer of polymolecularity rare earth according to claim 1, it is characterised in that: the rare-earth stabilizer
Using one of rare-earth stearate stabilizer, salicylic acid rare-earth stabilizer, citric acid rare-earth stabilizer or numerous compositions,
In, rare earth is selected from the composition of lanthanum, cerium, shirt, and it is 1:1-3:0.5-1.5 that three, which adds mole ratio, and cerium content is shirt content
Twice.
5. the compound FWR stabilizer of polymolecularity rare earth according to claim 1, which is characterized in that the modified cladding material
Preparation step are as follows: first by weight feeding, hydroxyapatite fiber is placed in ball-milling treatment 3-4h in ball mill, taking-up is placed on
It is impregnated in polyvinyl alcohol water solution, is then placed in secondary milled processed 5-10h in ball mill again, it is finally dry in gaseous mixture
Fiber material is spare；By the distilled water blending and stirring 5-10min of amino clay and 2-4 times of quality, then fiber material is added thereto,
High-speed stirred 5-10min, subsequent low speed insulated and stirred 0.5-1h are stored at room temperature 1-2h, are re-fed into vacuum drier dry, powder
It is broken, cladding material must be modified.
6. the compound FWR stabilizer of polymolecularity rare earth according to claim 5, it is characterised in that: the polyvinyl alcohol water
Solution quality content is 1-1.5wt%, and soaking temperature is 65 ± 2 DEG C, soaking time 90-150min.
7. the compound FWR stabilizer of polymolecularity rare earth according to claim 5, it is characterised in that: the gaseous mixture is nitrogen
The gaseous mixture of gas, hydrogen, the two are passed through than for 1:0.2, gaseous mixture intake is 1L/h.
8. the compound FWR stabilizer of polymolecularity rare earth according to claim 5, it is characterised in that: the high-speed stirred turns
Speed is 1500-1800rpm, and low speed insulated and stirred revolving speed is 200-300rpm, and holding temperature is 50-55 DEG C.
9. the compound FWR stabilizer of polymolecularity rare earth according to claim 1-8, which is characterized in that preparation work
Skill is as follows:
1) by two parts of lead salt stabilizer equal part, portion is blended with rare-earth stabilizer, is placed in high-speed mixer, 1000-
5-10min is stirred under the conditions of 1200rpm, 75-80 DEG C, obtains mixing one；
2) another is blended with remaining unclassified stores, is placed in elder generation 1500rpm in high-speed mixer, is stirred 3- under the conditions of 70 DEG C
5min is being down to 1000rpm, 50 DEG C of stirring 10-15min, is obtaining mixing two；
3) mixing one, mixing two are blended, are placed in high-speed mixer, 1000-1500rpm, 55-60 DEG C of stirring 5-10min, i.e.,
It can.
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| CN117105724A (en) * | 2023-08-25 | 2023-11-24 | 广州优卡思农业技术有限公司 | Rare earth-containing water-soluble fertilizer and processing technology thereof |
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2018
- 2018-07-09 CN CN201810747590.2A patent/CN109135102A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117105724A (en) * | 2023-08-25 | 2023-11-24 | 广州优卡思农业技术有限公司 | Rare earth-containing water-soluble fertilizer and processing technology thereof |
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