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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- CN109135102A CN109135102A CN201810747590.2A CN201810747590A CN109135102A CN 109135102 A CN109135102 A CN 109135102A CN 201810747590 A CN201810747590 A CN 201810747590A CN 109135102 A CN109135102 A CN 109135102A
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- stabilizer
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- rare
- fwr
- polymolecularity
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 108
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 73
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005253 cladding Methods 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 23
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 23
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 18
- 239000004927 clay Substances 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- CUJPJTIBYGTKKC-UHFFFAOYSA-N cyclohexanol;diphenylmethanone Chemical compound OC1CCCCC1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 CUJPJTIBYGTKKC-UHFFFAOYSA-N 0.000 claims abstract description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008246 gaseous mixture Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 methyl tertiary amine Chemical class 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002657 fibrous material Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 7
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 239000004800 polyvinyl chloride Substances 0.000 description 16
- 229920000915 polyvinyl chloride Polymers 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 239000003583 soil stabilizing agent Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical class [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007786 learning performance Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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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Cited By (1)
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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 | A kind of water-soluble fertilizer containing rare earth and its processing technology |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 | A kind of water-soluble fertilizer containing rare earth and its processing technology |
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