CN101942160B - Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof - Google Patents
Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof Download PDFInfo
- Publication number
- CN101942160B CN101942160B CN2010102987452A CN201010298745A CN101942160B CN 101942160 B CN101942160 B CN 101942160B CN 2010102987452 A CN2010102987452 A CN 2010102987452A CN 201010298745 A CN201010298745 A CN 201010298745A CN 101942160 B CN101942160 B CN 101942160B
- Authority
- CN
- China
- Prior art keywords
- zinc
- thermal stabilizer
- pvc
- rare
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to an aluminum zinc rare-earth hydrotalcite compound thermal stabilizer for PVC and application thereof. The compound thermal stabilizer is compounded from aluminum zinc rare-earth hydrotalcite and proper amounts of calcium soap and beta-diketone in optimal proportions. A sodium stearate wet process is used for modifying the aluminum zinc rare-earth hydrotalcite and enhances the compatibility thereof with the PVC; the invention firstly adds the compounded modified aluminum zinc rare-earth hydrotalcite, the calcium soap and the beta-diketone into the PVC to serve as the compound thermal stabilizer. The static thermal ageing test indicates that the thermal stabilization time (the turning-black time of a sample) of the optimally compounded thermal stabilizer reaches more than 240 minutes. The thermal stabilizer can enhance the product transparence, has the advantages of favorable stability, simple and practicable preparation process, no toxicity, high efficiency and favorable weatherability, and effectively prevents zinc erosion.
Description
Technical field
The present invention relates to a kind of zinc-aluminium rare-earth hydrotalcite composite thermal stabilizer and application that is used for SE, belong to the material Application Areas.
Background technology
SE (PVC) can take off the catalytic degradation reaction of HCl under the influence of the high heat of high temperature, thereby its performance is affected and brings difficulty to processing.So must add certain thermo-stabilizer before use, alleviate its degraded within a certain period of time.The kind of thermo-stabilizer is a lot, but is poisonous mostly or costs an arm and a leg, thus develop a kind of cheapness, nontoxic, thermo-stabilizer is significant efficiently.
The hydrotalcite thermo-stabilizer is one type of nontoxic inorganic auxiliary stabilizer of the Japanese Japan Kyowa chemical company exploitation eighties in 20th century.Because its particular structure and performance receive domestic and international investigator's great attention, has very big development prospect.
Japanese Patent JP60184536 report, with prescription PVC100 part, 1.6 parts of hydrotalcites and 0.3 part of diaphragm of processing of dibutyltin maleate polymkeric substance are only emitted slight smell in the course of processing, during 200 ℃ of heating, begin variable color after 1 hour.
And for example patent JP60165158 reports; By containing 1% hydrotalcite and 2.18% double isooctyl mercaptoacetate, two bay tin or tri-thiol 2-ethyl hexyl ethanoate two bay tin jointly as the PVC material of thermo-stabilizer; 200 ℃ of 35 minutes resolving times, this explanation is very big to influences such as PVC thermostabilitys with the kind of the organotin that hydrotalcite is used.
Can find out that thus hydrotalcite is significant to the heat stabilization of PVC, this maybe be relevant with the hydrotalcite special construction.Two hydroxy metal oxide compounds (LDHs) are one type of anion type laminated structured materials with acidity, alkalescence and ion-exchange performance, and chemical constitution is [M
1-x IIM
x III(OH)
2]
X+(A
N-)
X/nMH
2O, M
2+And M
3+Represent divalence and trivalent metal ion respectively, A
N-Represent negatively charged ion.Different M
2+And M
3+, different interstitial anion A
N-, just can form different houghites.Absorb big calorimetric during the LDHs decomposes, can reduce the temperature of material surface, the thermolysis of plastics and rate of combustion are reduced greatly; Decompose the water and the carbon dioxide gas physical efficiency that discharge and dilute, intercept inflammable gas; Product after the decomposition is alkaline porous mass, and specific surface is big, can adsorb particularly sour gas of obnoxious flavour, and the carbonizing production of frosting combined to generate protective membrane when it was with burning simultaneously, cut off the intrusion of heat energy and oxygen.
In order to improve the thermal stability of PVC, much human has been studied synthetic, modification, the intercalation and composite of magnesium aluminum-hydrotalcite, and the preparation and the application of ternary, quaternary hydrotalcite are also arranged.
Application number is that the patent of 200810052676.X discloses a kind of preparation of Mg-Ca-Zn-Al quaternary hydrotalcite and in the application of PVC thermostability.The result shows, compares with Mg-Al binary hydrotalcite, and under 180 ± 1 ℃, heat-stable time has prolonged 29～54%.
Document [1]: people [Cu-Ni-Mg-Al-CO such as Feng Yongjun
3Synthetic and the structural analysis of quaternary hydrotalcite, chemical journal, 2003,61 (1) 78～83] adopt nucleation/crystallization isolation method to synthesize Cu-Ni-Mg-Al-CO
3The quaternary hydrotalcite has been prepared the regular M (II) of crystalline structure through changing the ion proportioning
4M (III)
2(OH)
12CO
34H2O type hydrotalcite.But, when synthesizing four-component hydrotalcite,, and form multiple oxyhydroxide impurity easily often because of metallic element too much causes the difficult control of reaction conditions.
The ternary houghite preparation condition is controlled well than four-component hydrotalcite, and is not easy to generate oxyhydroxide impurity.
Document [1]: Yanjun Lin; People [Layered and intercalated hydrotalcite-like materials as thermal stabilizers in PVC resin, Journal of Physics and Chemistry of Solids 67 (2006) 998-1001] such as Jianrong Wang have prepared MgZnAl-CO
3-LDH detects discovery through thermal stability, and this ternary hydrotalcite improves than the Mg-Al-CO3-LDH thermostability greatly, and long-term tint permanence of initial stage is all more shallow.
Document [2]: agricultural blue equality people [the synthetic and catalysis phenyl aldehyde H of cupric ternary houghite
2O
2The applied research of oxidation, chemical-biological and engineering, 2006,23 (9) 18～20] adopt variation pH value method and supersaturation constant pH method in the coprecipitation method to prepare the cupric ternary houghite compound.And this houghite is applied to phenyl aldehyde H
2O
2Oxidation in.
Document [3]: Emilian Angelescu, people [Cyanoethylation of ethanol on Mg-Alhydrotalcites promoted by Y such as Octavian Dumitru Pavel
3+And La
3+Catalysis Communications 5 (2004) 647-651] pass through coprecipitation method with Y
3+, La
3+Plasma adds to respectively on the hydrotalcite laminate, successfully synthesizes the rare-earth hydrotalcite with hydrotalcite structure.
The ternary RE houghite of bibliographical information all is to be applied to catalyzer and fluorescence luminescent material aspect basically; Though patent 200910303613.1 is arranged adds among the PVC Mg-Al rare-earth hydrotalcite as thermo-stabilizer to; But Mg-Al houghite thermostability in early stage is relatively poor; Coloring effect is poor, because the reason of Mg element self causes when it adds among the PVC, can making the sample transparency to weaken color jaundice, has satisfied not in the foodstuffs industry requirement to the plastics colorless and odorless to a great extent.The Zn-Al hydrotalcite transparency is good, and early stage, thermostability was also better, but to the later stage phenomenon of zinc burning can take place.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly can strengthen the product transparency, good stability prevents that effectively zinc from burning, and preparation flow is simple, non-toxic efficient, good weatherability, composite thermal stabilizer and the application method thereof compatible splendid with PVC.
The objective of the invention is to realize in the following manner.
A kind of PVC comprises the component of following mass content with zinc-aluminium rare-earth hydrotalcite composite thermal stabilizer,
Zinc-aluminium rare-earth hydrotalcite 10%～88%
Calcium soap 2%～45%
Beta-diketon 10%～50%
This stablizer preferably includes the component of following mass content,
Zinc-aluminium rare-earth hydrotalcite 30%～79%
Calcium soap 8%～35%
Beta-diketon 12%～37%
Rare earth ion in the described zinc-aluminium rare-earth hydrotalcite is Ce
3+, La
3+, Pr
3+And Nd
3+In one or more.
Described calcium soap is a calcium stearate, calcium laurate, and calcium oleate, a kind of in the calcium palmitate is preferably calcium stearate, calcium oleate.
The application of described composite thermal stabilizer: in 100 parts of PVC powders, add 20～80 parts of dinoctyl phthalates, 0.2～5 part of composite thermal stabilizer; Mixed at high speed is 4～5 minutes then, and the back got final product in two roller mills in 170 ℃～200 ℃ in mixing 4～5 minutes.
The preparation process of composite thermal stabilizer of the present invention is following:
1) preparation of zinc-aluminium rare-earth hydrotalcite and modification
Divalent salts (zinc salt) and trivalent salt (aluminium salt and rare-earth salts) are pressed M
2+/ M
3+=2: 1～3: 1 mol ratio is made into mixing solutions, M in the solution
3+Total concn be 0.2～2.0mol/L, [RE
3+]/[M
3+]=0.03～0.6, wherein RE
3+Represent rare earth ion Ce
3+Or La
3+, M
3+Represent all trivalent metal ions in the solution.According to
The requirement of (0.2≤x≤0.33,0≤m≤2), weighing sodium carbonate and sodium hydroxide are made into mixing solutions, wherein n (CO
3 2-)/n (M
3+)=0.5～3, n (NaOH)/n (M
2++ M
3+)=1～4; Be added drop-wise to two kinds of solution in the deionized water respectively; Keep pH value between 6.0～8.0,, dropwise continued and stirred 1～2 hour 65 ℃～100 ℃ stirring reactions 2～3 hours; Then 45 ℃～120 ℃ following ageings 4～28 hours; Filter, wash, obtain zinc-aluminium rare-earth hydrotalcite filter cake (the wet cake water cut is 50%～80%) to PH=7.In wet cake, add entry; Water/wet cake mass ratio is 30～50, is warming up to 60 ℃～100 ℃, adds 0.3%～7% the properties-correcting agent (properties-correcting agent is StNa) account for the wet cake quality; Stirred 1～4 hour; Filter, and dry under 80 ℃～100 ℃, obtain through the wet-process modified zinc-aluminium rare-earth hydrotalcite of StNa.
2) zinc-aluminium rare-earth hydrotalcite and calcium soap, beta-diketon is composite
Zinc-aluminium rare-earth hydrotalcite after the modification and a spot of calcium soap, beta-diketon are carried out composite (being mass percent) in following ratio:
Zinc-aluminium rare-earth hydrotalcite 10%～88%
Calcium soap 2%～45%
Beta-diketon 10%～50%
3) composite thermal stabilizer is applied among the PVC, and carries out heat stability test through the static heat weathering test
In 100 parts of PVC powders, add 20～80 parts of dinoctyl phthalates (DOP), 0.2～5 part of composite thermal stabilizer; Mixed at high speed is 4～5 minutes then.Then in 170 ℃～200 ℃ in two roller mills mixing 4～5 minutes, and pull into the sample that thickness is 1.0mm, be cut into the small sample of 3cm * 2cm, put into 180 ± 1 ℃ of baking ovens and carry out the static heat senile experiment, whenever observe change in color at a distance from 10min.
Through being introduced, REE synthesized the ternary RE houghite on the laminate, the preparation flow simple possible.When composite during as the PVC thermo-stabilizer with calcium soap, beta-diketon; Show good " synergy " REE and cl ions coordination and form stable complex compound, but the activation energy of REE complexing cl ions is higher, speed is slower; Show as initial coloring; And calcium soap just in contrast, and calcium salt and HCl reaction fast being difficult for generates long polyenoid sequence, so initial stage easy coloring not.But the muriate of calcium salt can quicken separating out of HCI, thereby impels the polyenoid sequence to increase, and therefore, the later stage can produce halochromism.Therefore can produce good synergy when it is restored the old order with rare earth.More single binary hydrotalcite, thermal stability increases greatly.
A large amount of Application Research show that rare earth complex heat stabilizer has coupling, increase-volume, toughness reinforcing to the PVC system, improve material fluidity; Improve the effect of PVC mechanical property, its reason ascribes the special construction of REE to, and REE has numerous unoccupied orbitals to accept the lone-pair electron of ligand as central ion; Rare earth ion has bigger ionic radius simultaneously; So, it can with the active chlorine coordination on the PVC, effectively prevented to take off HCl reaction.In addition, it can adsorb with in and HCl, eliminate catalyzed reaction, thereby alleviate degraded degraded.The present invention first with zinc-aluminium rare-earth hydrotalcite and a spot of calcium soap, beta-diketon composite after, add among the PVC as thermo-stabilizer, test-results shows that this thermo-stabilizer has improved the thermal stability of PVC greatly.
Mg-Al houghite early stage, thermostability was relatively poor, and coloring effect is poor because the reason of Mg element self causes when it adds among the PVC, can making the sample transparency to weaken the color jaundice, satisfied to a great extent not in the foodstuffs industry to the requirement of plastics colorless and odorless.The present invention just is being based on these shortcomings of Mg-Al hydrotalcite and is replacing with the Zn-Al hydrotalcite.The Zn-Al hydrotalcite transparency is good, and early stage, thermostability was also better, but to the later stage phenomenon of zinc burning can take place.The present invention restores the old order a certain amount of Ca-Zn composite heat stabilizer, beta-diketon and zinc-aluminium rare-earth hydrotalcite; Also promptly through the long-term thermal stability of REE and the initial coloration effect of zinc-aluminium hydrotalcite; The later stage of calcium soap and beta-diketon is painted mixes the restoration of the old order; Effectively stoped the zinc burning, all do not had zinc black among the 240min and occur.Wherein the calcium soap in the composite thermal stabilizer will cause the ZnCl of " zinc burning " phenomenon
2Be converted into zinc soap, reduce ZnCl
2Accumulation volume, delay " zinc burning ".Zinc soap just need not to add directly by ZnCl in addition like this
2Transform, this also is one of bright spot of the present invention.In addition; The restoration of the old order that beta-diketon has good initial coloring and Ca-Zn composite heat stabilizer has effectively prevented " zinc burning "; And the long-term thermal stability of PVC also had good improvement effect, and can improve the transparency of sample simultaneously, make the thermostability of sample bring up to 240min.
Description of drawings
Fig. 1 is that thermo-stabilizer of the present invention and other auxiliary heat stabilizers carry out relatively photo of static heat senile experiment;
The static heat senile experiment photo of a for carrying out composite application by embodiment 7 prescriptions;
The static heat senile experiment photo of b for carrying out composite application by embodiment 9 prescriptions.
The static heat senile experiment photo of c for carrying out composite application by embodiment 11 prescriptions;
The static heat senile experiment photo of d for carrying out composite application by embodiment 12 prescriptions.
Embodiment
Below in conjunction with embodiment the present invention is further specified, and can not limit the present invention.
Embodiment 1:
(mol ratio is zinc-aluminium cerium houghite: M
2+/ M
3+=2: 1, Ce
3+/ M
3+=0.2) preparation and modification.Take by weighing 12.82g Mg (NO respectively
3)
26H
2O (0.050moL), 7.50g Al (NO
3)
39H
2O (0.02moL), 2.171gCe (NO
3)
36H
2O (0.005moL) mixes the back and adds the 40mL deionized water; Take by weighing 1.325gNa
2CO
3(0.013moL) and 6.0gNaOH (0.150moL), mix the back and add the 40mL deionized water; Above-mentioned two kinds of solution are added drop-wise to respectively in the 30mL deionized water, keep pH value to be about 8, at 85 ℃ of following stirring reactions; Dropwise continued and stirred 2 hours,, filter then 65 ℃ of following ageings 20 hours; Wash to PH=7, obtain magnesium aluminum-hydrotalcite filter cake (the wet cake water cut is about 75%).In wet cake, add entry, water/wet cake mass ratio is 50: 1, is warming up to 80 ℃; Add 2% the properties-correcting agent (properties-correcting agent is StNa) account for the wet cake quality, stirred filtration 2 hours; And, obtain through the wet-process modified zinc-aluminium cerium houghite of StNa at 80 ℃ of following dry 24h.
Embodiment 2:
Making mol ratio according to the method for embodiment 1 is M
2+/ M
3+=3: 1, Ce
3+/ M
3+=0.075 zinc-aluminium cerium houghite.
Embodiment 3:
Making mol ratio according to the method for embodiment 1 is M
2+/ M
3+=2: 1, La
3+/ M
3+=0.1 zinc-aluminium lanthanum houghite.
Embodiment 4:
Making mol ratio according to the method for embodiment 1 is M
2+/ M
3+=3: 1, La
3+/ M
3+=0.05 zinc-aluminium lanthanum houghite.
Embodiment 5:
Making mol ratio according to the method for embodiment 1 is M
2+/ M
3+=3: 1, Pr
3+/ M
3+=0.05 zinc-aluminium praseodymium houghite.
Embodiment 6:
Making mol ratio according to the method for embodiment 1 is M
2+/ M
3+=3: 1, Nd
3+/ M
3+=0.1 zinc-aluminium neodymium houghite.
Embodiment 7:
Zinc-aluminium cerium houghite and calcium stearate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium cerium houghite and a certain amount of calcium stearate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium cerium houghite 71%, calcium stearate 11%, beta-diketon 18%.
Embodiment 8:
Zinc-aluminium cerium houghite and calcium stearate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium cerium houghite and a certain amount of calcium stearate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium cerium houghite 68%, calcium stearate 10%, beta-diketon 22%.
Embodiment 9:
Zinc-aluminium cerium houghite and calcium oleate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium cerium houghite and a certain amount of calcium oleate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium cerium houghite 78%, calcium oleate 9%, beta-diketon 13%.
Embodiment 10:
Zinc-aluminium lanthanum houghite and calcium stearate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium lanthanum houghite and a certain amount of calcium stearate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium lanthanum houghite 55%, calcium stearate 28%, beta-diketon 17%.
Embodiment 11:
Zinc-aluminium lanthanum houghite and calcium stearate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium lanthanum houghite and a certain amount of calcium stearate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium lanthanum houghite 70%, calcium stearate 11%, beta-diketon 19%.
Embodiment 12:
Zinc-aluminium lanthanum houghite and calcium oleate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium lanthanum houghite and a certain amount of calcium oleate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium lanthanum houghite 62%, calcium oleate 22%, beta-diketon 16%.
Embodiment 13:
Zinc-aluminium praseodymium houghite and calcium oleate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium praseodymium houghite and a certain amount of calcium oleate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium praseodymium houghite 62%, calcium oleate 22%, beta-diketon 16%.
Embodiment 14:
Zinc-aluminium neodymium houghite and calcium stearate, the composite composite thermal stabilizer that makes of beta-diketon
Zinc-aluminium neodymium houghite and a certain amount of calcium stearate, beta-diketon are carried out composite (being mass percent) in following ratio: zinc-aluminium neodymium houghite 55%, calcium stearate 28%, beta-diketon 17%.
Embodiment 15:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 0.2 part of composite thermal stabilizer (wherein each constituent mass mark is respectively: zinc-aluminium cerium houghite 68%, calcium stearate 10%, beta-diketon 22%), mixed at high speed is 5 minutes then.
Embodiment 16:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 40 parts of dinoctyl phthalates (DOP), 2.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium cerium houghite 78%, calcium oleate 9%, beta-diketon 13%), mixed at high speed is 5 minutes then.
Embodiment 17:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 3.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium lanthanum houghite 78%, calcium stearate 9%, beta-diketon 13%), mixed at high speed is 5 minutes then.
Embodiment 18:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 4.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium lanthanum houghite 76%, calcium oleate 11%, beta-diketon 13%), mixed at high speed is 5 minutes then.
Embodiment 19:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 4.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium praseodymium houghite 76%, calcium oleate 11%, beta-diketon 13%), mixed at high speed is 5 minutes then.
Embodiment 20:
The composite application of composite thermal stabilizer and PVC powder
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 4.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium neodymium houghite 78%, calcium stearate 10%, beta-diketon 12%), mixed at high speed is 5 minutes then.
Embodiment 21:
The static heat weathering test is to the test of thermal stability
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 3.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium cerium houghite 71%, calcium stearate 11%, beta-diketon 18%); Mixed at high speed is 5 minutes then.Then in 180 ℃ in two roller mills mixing 5 minutes, and pull into the sample that thickness is 1.0mm, be cut into the small sample of 3cm * 2cm, put into 180 ± 1 ℃ of baking ovens and carry out the static heat senile experiment, whenever observe change in color at a distance from 10min.
Embodiment 22:
The static heat weathering test is to the test of thermal stability
In 100 parts of PVC powders, add 50 parts of dinoctyl phthalates (DOP), 2.0 parts of composite thermal stabilizers (wherein each constituent mass mark is respectively: zinc-aluminium lanthanum houghite 78%, calcium stearate 9%, beta-diketon 13%); Mixed at high speed is 5 minutes then.Then in 180 ℃ in two roller mills mixing 5 minutes, and pull into the sample that thickness is 1.0mm, be cut into the small sample of 3cm * 2cm, put into 180 ± 1 ℃ of baking ovens and carry out the static heat senile experiment, whenever observe change in color at a distance from 10min.
The time ratio that table 1 carries out Congo red experiment for thermo-stabilizer of the present invention and other auxiliary heat stabilizers;
Table 1
The Congo red experimental period of A for carrying out composite application by embodiment 7 prescriptions;
The Congo red experimental period of B for carrying out composite application by embodiment 9 prescriptions.
The Congo red experimental period of C for carrying out composite application by embodiment 11 prescriptions;
The Congo red experimental period of D for carrying out composite application by embodiment 12 prescriptions.
Claims (5)
1. a PVC is characterized in that with zinc-aluminium rare-earth hydrotalcite composite thermal stabilizer, comprises the component of following mass content,
Zinc-aluminium rare-earth hydrotalcite 10%～88%
Calcium soap 2%～45%
Beta-diketon 10%～50%
The preparation and the modifying process of zinc-aluminium rare-earth hydrotalcite are following:
Divalent salts and trivalent salt are pressed M
2+/ M
3+=2: 1～3: 1 mol ratio is made into mixing solutions, and wherein divalent salts is a zinc salt, and trivalent salt is aluminium salt and rare-earth salts, M in the solution
3+Total concn be 0.2～2.0mol/L, [RE
3+]/[M
3+]=0.03～0.6, wherein RE
3+Represent rare earth ion Ce
3+, La
3+, Pr
3+, Nd
3+In one or more, M
3+Represent all trivalent metal ions in the solution, according to
0.2 the requirement of≤x≤0.33,0≤m≤2, weighing sodium carbonate and sodium hydroxide are made into mixing solutions, wherein n (CO
3 2-)/n (M
3+)=0.5～3, n (NaOH)/n (M
2++ M
3+)=1～4; Two kinds of solution are added drop-wise to respectively in the deionized water, keep the pH value between 6.0～8.0,65 ℃～100 ℃ stirring reactions 2～3 hours; Dropwise continued and stirred 1～2 hour,, filter then 45 ℃～120 ℃ following ageings 4～28 hours; Wash to pH=7, obtain zinc-aluminium rare-earth hydrotalcite filter cake, the wet cake water cut is 50%～80%; In wet cake, add entry, water/wet cake mass ratio is 30～50, is warming up to 60 ℃～100 ℃; Add 0.3%～7% the properties-correcting agent account for the wet cake quality, properties-correcting agent is StNa, stirs 1～4 hour; Filter, and dry under 80 ℃～100 ℃, obtain through the wet-process modified zinc-aluminium rare-earth hydrotalcite of StNa.
2. composite thermal stabilizer according to claim 1 is characterized in that, comprises the component of following mass content,
Zinc-aluminium rare-earth hydrotalcite 30%～79%
Calcium soap 8%～35%
Beta-diketon 12%～37%.
3. composite thermal stabilizer according to claim 1 and 2 is characterized in that, described calcium soap is a calcium stearate, calcium laurate, calcium oleate, a kind of in the calcium palmitate.
4. composite thermal stabilizer according to claim 3 is characterized in that, described calcium soap is calcium stearate or calcium oleate.
5. the application of the described composite thermal stabilizer of claim 1 is characterized in that, in 100 parts of PVC powders, adds 20～80 parts of dinoctyl phthalates, 0.2～5 part of composite thermal stabilizer; Mixed at high speed is 4～5 minutes then, and the back got final product in two roller mills in 170 ℃～200 ℃ in mixing 4～5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102987452A CN101942160B (en) | 2010-09-30 | 2010-09-30 | Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102987452A CN101942160B (en) | 2010-09-30 | 2010-09-30 | Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101942160A CN101942160A (en) | 2011-01-12 |
| CN101942160B true CN101942160B (en) | 2012-06-27 |
Family
ID=43434378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102987452A Expired - Fee Related CN101942160B (en) | 2010-09-30 | 2010-09-30 | Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101942160B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740004B (en) * | 2014-01-16 | 2015-09-09 | 唐山师范学院 | Light rare-earth hydrotalcite-curcumicomposite composite heat-stable assistant and preparation method thereof |
| CN104558970B (en) * | 2015-01-30 | 2016-09-28 | 唐山师范学院 | PVC rare-earth hydrotalcite composite thermal stabilizer and preparation method thereof |
| CN105001447B (en) * | 2015-08-03 | 2017-11-14 | 盐城科迈特新材料有限公司 | A kind of preparation method of NEW TYPE OF COMPOSITE heat stabilizer |
| CN105295244A (en) * | 2015-11-18 | 2016-02-03 | 安徽华塑股份有限公司 | Hydrotalcite-organic tin composite environmental protection stabilizer for PVC, and preparation method thereof |
| CN105255064A (en) * | 2015-11-18 | 2016-01-20 | 安徽华塑股份有限公司 | Hydrotalcite citric acid rare earth composite environment-friendly stabilizer for PVC and preparing method thereof |
| CN105295248A (en) * | 2015-11-18 | 2016-02-03 | 安徽华塑股份有限公司 | Hydrotalcite-dimer acid lanthanum composite environmental protection stabilizer for PVC, and preparation method thereof |
| CN105295251A (en) * | 2015-11-18 | 2016-02-03 | 安徽华塑股份有限公司 | Hydrotalcite-maleic acid rare earth composite environmental protection stabilizer for PVC, and preparation method thereof |
| CN110204789B (en) * | 2019-06-24 | 2021-03-19 | 东莞市尚诺新材料有限公司 | Stabilizer for transparent tube and preparation method thereof |
| CN115260596A (en) * | 2022-09-29 | 2022-11-01 | 圣地亚科技(江苏)有限公司 | Moistureproof environment-friendly calcium-zinc stabilizer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565512A (en) * | 2008-08-29 | 2009-10-28 | 内蒙古皓海化工有限责任公司 | Nanometer rare-earth calcium-zinc-magnesium-aluminum PVC composite stabilizer |
| CN101492548B (en) * | 2009-02-20 | 2011-05-18 | 中南大学 | Composite heat stabilizer for PVC, preparation and application thereof |
| CN101575425B (en) * | 2009-06-25 | 2011-10-05 | 中南大学 | PVC compound heat stabilizer prepared from magnesium/aluminum rare-earth hydrotalcite and application thereof |
-
2010
- 2010-09-30 CN CN2010102987452A patent/CN101942160B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101942160A (en) | 2011-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101942160B (en) | Aluminum zinc rare-earth hydrotalcite thermal stabilizer for PVC and application thereof | |
| CN101575425B (en) | PVC compound heat stabilizer prepared from magnesium/aluminum rare-earth hydrotalcite and application thereof | |
| CN101492548B (en) | Composite heat stabilizer for PVC, preparation and application thereof | |
| CN101942111B (en) | Preparation method and application of zinc-aluminum-magnesium hydrotalcite-based PVC complex heat stabilizer | |
| CN102093654B (en) | Zinc-aluminium terres rares hydrotalcite compound heat stabilizer for polyvinyl chloride (PVC) as well as preparation and application of compound heat stabilizer | |
| JP4768562B2 (en) | Lithium / transition metal composite oxide, method for producing the same, and lithium battery using the same | |
| CN102259931B (en) | Method for preparing lithium manganese oxide battery material | |
| CN103172119B (en) | Preparation method of layered chemical manganese dioxide | |
| CN111498906B (en) | Transparent heat-shielding material, transparent heat-shielding microparticle dispersion, and production method and use thereof | |
| CN102795649A (en) | Preparation method for magnesium-aluminium hydrotalcite | |
| CN101284953A (en) | Mg-Ca-Zn-Al four-component hydrotalcite heat stabilizer | |
| CN106674598A (en) | Preparation method for efficient modified layered double-hydroxide flame retardant additive | |
| JP5370682B2 (en) | Zn-Mg-Al hydrotalcite-type particle powder and resin composition containing the Zn-Mg-Al hydrotalcite-type particle powder | |
| CN104277368A (en) | Rare earth type hydrotalcite composite heat stabilizer and heat-stable polyvinyl chloride | |
| CN104927086A (en) | Flame-retardant smoke-suppression agent and preparation method thereof | |
| JP2022537755A (en) | Transparent heat-shielding fine particles, fine particle dispersion, production method and use thereof | |
| CN101288821B (en) | Preparation method of calcium zincate and calcium zincate reclaiming agent at normal temperature | |
| CN102718986A (en) | Lignin modified layered double hydroxide and preparation method thereof and rubber composite | |
| CN110078103A (en) | A kind of calcium aluminium houghite and preparation method thereof | |
| CN110963513A (en) | Preparation method of magnesium-based hydrotalcite | |
| CN105038027B (en) | Metal oxide-hexanehexol compound heat stabilizer, preparation method and application in PVC | |
| CN102774873A (en) | Preparation method of calcium zincate and calcium zincate normal temperature desulfurizing agents | |
| CN103311536B (en) | β type covers the preparation method of cobalt hydroxy nickel oxide | |
| CN105329934A (en) | Preparation method of hydrotalcite-like compound used for electrophoretic paint | |
| CN102219964A (en) | Layered composite hydroxide used as polyvinyl chloride heat stabilizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120627 Termination date: 20170930 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |