CN109354807A - A kind of environment-friendly type water bovite base PVC composite heat stabilizer - Google Patents
A kind of environment-friendly type water bovite base PVC composite heat stabilizer Download PDFInfo
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- CN109354807A CN109354807A CN201811370788.XA CN201811370788A CN109354807A CN 109354807 A CN109354807 A CN 109354807A CN 201811370788 A CN201811370788 A CN 201811370788A CN 109354807 A CN109354807 A CN 109354807A
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- hydrocalumite
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- antioxidant
- zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of environment-friendly type water bovite base PVC composite heat stabilizers, the composite thermal stabilizer includes the component of following mass fraction: modified hydrocalumite: 20-50%, zinc stearate: 20-40%, zinc acetylacetonate: 2-6%, calcium stearate: 6-10%, antioxidant: 2-6%, lubricant: 10-20%.Technical solution of the present invention is to be modified major constituent of the hydrocalumite as PVC composite heat stabilizer, and simple production process is low in cost, non-environmental-pollution, good with the compatibility of PVC, and has very excellent synergistic effect with zinc acetylacetonate.This composite thermal stabilizer has excellent inhibition PVC initial coloration performance and preferable long-term thermal stability performance.
Description
Technical field
The present invention relates to PVC heat stabilizer, in particular to a kind of environment-friendly type water bovite base PVC composite heat stabilizer belongs to
In material processing aid field.
Background technique
PVC is one of big general-purpose plastics in the world five, widely used.However, polyvinyl chloride resin is in process, it is easy to carry out
Dechlorination reaction releases self-catalysis agent HC1, causes to change colour, so that changing physics and chemical property.PVC is adding in order to prevent
Occur to degrade due to high temperature in work and use process or be crosslinked, it is necessary to thermostabilization addition be added in its processing and manufacturing process
Agent.Currently, common heat stabilizer includes lead salts, organic tin, metal soap and composite thermal stabilizer.Lead salts thermostabilization
Agent is to develop earliest and have the PVC heat stabilizer of good thermal stability energy.However, lead is a heavy metal species, have to organism
There is very strong toxicity, process dust easily generated in use process, countries in the world are just gradually limiting the use of lead salt type thermal stabilizing agent.
The thermal stability and the transparency of organic tin heat stabilizer are preferable, small toxicity, but can generate bad smell after processing for several times, make it
Using being restricted.Therefore, a kind of environment-friendly type PVC heat stabilizer haveing excellent performance is developed, it is right to replace lead salt type thermal stabilizing agent
" unleaded " for promoting PVC industry, has a very important significance.
The general structure of hydrocalumite are as follows: [ Ca2Al( OH) 6?+[ AN- 1/n·mH2O ], wherein AN-What is represented is interlayer
Anion, such as Cl?, CO3 2-, OH?, NO3 ?, SO4 2-, V2O7 2-, CrO4 2-Deng when anion therebetween is CO3 2-When, structural formula
Are as follows: Ca4Al2( OH) 12 CO3·nH2O.The interlamellar spacing of hydrocalumite depends on the type of anion therebetween, for water aluminium
Calcium stone type thermal stabilizing agent, wherein the effect of inorganic laminate is more embodied in the capture and absorption of the HC1 generated to PVC degradation with aging,
And the effect of interlayer anion is more embodied in and reacts with HCl and activity Cl?Capture exchange on, the two is combined and is prepared
Hydrocalumite heat stabilizer is used in compounding with zinc acetylacetonate, can show good synergy and excellent thermal stability
Energy.Lin Yanjun etc. (105348682 A of CN) reports a kind of calcium based hydrotalcite PVC composite heat stabilizer, (CN such as Peng Zhaolin
104150518) a kind of hydrocalumite base PVC composite heat stabilizer is also disclosed.However, stearic acid is only added in the above method
Zinc, calcium stearate cooperate with material as main compounding, and the performance of composite thermal stabilizer remains to be further improved.In addition, they
Using the hydrocalumite of salting liquid coprecipitation production as major constituent, there are a large amount of brine wastes of discharge in preparation process.
Zhang Kais etc. (fine chemistry industry, 2016,30 (9), 75-81) report hydrocalumite and compound synergistic effect with DMAU, but DMAU is added
It measures bigger than normal, causes production cost higher, limit its large-scale application.
The present invention compounds the excellent acetyl of synergistic effect to clean synthesis modification hydrocalumite base heat stabilizer as major constituent
Acetone zinc, this composite thermal stabilizer have excellent inhibition PVC initial coloration performance and preferable long-term thermal stability performance, cost
It is cheap, it can large-scale promotion use.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly type water bovite base PVC composite heat stabilizer, the composite thermal stabilizers
To be modified hydrocalumite as main component, it is equipped with the significant zinc acetylacetonate of synergistic effect, does not include heavy metal and other toxic materials
Material has asepsis environment-protecting, easily prepared and low-cost advantage, and can significantly improve the thermal stability in PVC process.
In order to achieve the goal above, the technical solution adopted by the present invention is that provide a kind of environment-friendly type water bovite base PVC multiple
Heat stabilizer is closed, the component comprising following mass content:
Modified hydrocalumite: 20-50%；
Zinc stearate: 20-40%；
Zinc acetylacetonate: 2-6%；
Calcium stearate: 6-10%；
Antioxidant: 2-6%；
Lubricant: 10-20%；
The modified hydrocalumite is to be prepared using stearic acid or zinc stearate to the modification of hydrocalumite surface.
Further, the preparation process of the modified hydrocalumite is as follows:
(1) calcium hydroxide, aluminium hydroxide and sodium carbonate are added in the reactor equipped with water, wherein calcium hydroxide and hydroxide
The molar ratio of aluminium is 1.8-2.4:1, and the molar ratio of aluminium hydroxide and sodium carbonate is 1.8-2.2:1, the matter of water and calcium hydroxide
Amount is stirred to react 0.5-2 hours than being 10-50:1 at 60-100 DEG C；
(2) stearic acid is added in step (1) products therefrom or zinc stearate is modifying agent, wherein modifying agent and hydrocalumite
Mass ratio be 3-10:100, be stirred to react at 60-100 DEG C 1-3 hours；
(3) stop stirring, the reaction was continued at 60-100 DEG C 10-20 hours, then through dehydration, drying and crushing.
Further, the antioxidant is antioxidant 1010, irgasfos 168 or antioxidant 1076.
Further, the lubricant is polyethylene wax or solid paraffin.
The present invention is using the modification hydrocalumite through perstearic acid or zinc stearate surface treatment as PVC composite heat stabilizer
Major constituent.Compared with traditional modification magnalium hydrotalcite, modified hydrocalumite inhibits the initial coloration performance of PVC more excellent, and with
The compatibility of PVC is more preferable, and PVC mixing material will not be precipitated in high temperature working processes.In addition, the life of modified hydrocalumite
Production. art is simple, low in cost.By many experiments, inventors have found that being different from hydrocalumite compounds a large amount of zinc stearates, hard
Resin acid calcium can be only achieved good thermostable effect, and hydrocalumite, which need to only compound a small amount of zinc acetylacetonate, can reach excellent first
Phase whiteness and preferable long-acting thermal stability.Therefore, modified hydrocalumite cooperates with work with very excellent with zinc acetylacetonate
With composite thermal stabilizer is excellent to the thermal stability of PVC.
Specific embodiment
The following examples are that of the invention is further described, however, the present invention is not limited thereto.For technical field
Technical staff for, from detailed description of the invention, above and other objects, features and advantages of the invention will it is aobvious and
It is clear to.
The preferred preparation process of modified hydrocalumite:
Calcium hydroxide, aluminium hydroxide and sodium carbonate are added in the reactor equipped with water, wherein calcium hydroxide and aluminium hydroxide
Molar ratio is 2:1, and the molar ratio of aluminium hydroxide and sodium carbonate is 2:1, and the mass ratio of water and calcium hydroxide is 30:1, at 80 DEG C
It is stirred to react 1 hour；Stearic acid is added or zinc stearate is modifying agent, wherein the mass ratio of modifying agent and hydrocalumite is 6:
100, it is stirred to react at 80 DEG C 2 hours；Stop stirring, the reaction was continued at 80 DEG C 17 hours, then through dehydration, drying and powder
It is broken to be modified hydrocalumite to get to product.
Embodiment 1:
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction: modified hydrocalumite: 50%, zinc stearate: 20
%, calcium stearate: 10%, zinc acetylacetonate: 6%, antioxidant 1076: 2%, polyethylene wax: 12%.
Embodiment 2:
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction: modified hydrocalumite: 50%, zinc stearate:
24%, calcium stearate: 10%, zinc acetylacetonate: 2%, antioxidant 1076: 2%, polyethylene wax: 12%.
Embodiment 3:
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction: modified hydrocalumite: 45%, zinc stearate:
25%, calcium stearate: 10%, zinc acetylacetonate: 6%, antioxidant 1076: 2%, solid paraffin: 12%.
Embodiment 4:
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction: modified hydrocalumite: 40%, zinc stearate:
30%, calcium stearate: 10%, zinc acetylacetonate: 4%, antioxidant 1076: 4%, polyethylene wax: 12%.
Embodiment 5:
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction: modified hydrocalumite: 20%, zinc stearate:
40%, calcium stearate: 10%, zinc acetylacetonate: 4%, irgasfos 168: 6%, polyethylene wax: 20%.
Comparative example 1:
The composite thermal stabilizer of this comparative example includes the component of following mass fraction: modified magnalium hydrotalcite: 50%, zinc stearate:
20%, calcium stearate: 10%, zinc acetylacetonate: 6%, antioxidant 1076: 2%, polyethylene wax: 12%.
Comparative example 2:
The composite thermal stabilizer of this comparative example includes the component of following mass fraction: hydrocalumite: 50%, zinc stearate: and 26%, firmly
Resin acid calcium: 10%, antioxidant 1076: 2%, polyethylene wax: 12%.
Comparative example 3:
The composite thermal stabilizer of this comparative example includes the component of following mass fraction: modified hydrocalumite: 50%, zinc stearate:
20%, calcium stearate: 10%, zinc acetylacetonate: 6%, antioxidant 1076: 2%, polyethylene wax: 12%.Wherein, modified hydrocalumite with
Calcium chloride, sodium metaaluminate, sodium hydroxide and sodium carbonate are raw material, are prepared by coprecipitation.
Thermal stability test
Test condition: the performance of composite thermal stabilizer 190 DEG C of material temperature, is tested using general RM-200A torque rheometer test is breathed out
5 kg of load, 35 rpm of revolving speed.Test sample composition: 48 parts of PVC (SG-5 type) resins, 1.4 parts of composite thermal stabilizers, 9 parts
CaCO3, 3.5 parts of CPE, 1.3 parts of titanium dioxides, 0.1 part of pentaerythritol monostearate, 0.1 part of PE wax, 1 part of ACR.Test method:
It is kneaded in torque rheometer and takes out sample after ten minutes, initial stage whiteness is tested using color difference meter, and in addition sampling and testing dynamic
Heat-stable time.Test result is shown in Table 1.
The heat stabilization test result of table 1:PVC sample.
According to the result of table 1, the present invention is prepared for a kind of novel hydrocalumite base heat stabilizer, shows superior thermal stability
Can, the defect of other non-heavy metal type thermal stabilizing agent performances is breached, and be not susceptible to zinc burning.With commercially available magnalium hydrotalcite
Heat stabilizer is compared, and performance substantially improves, and shows that hydrocalumite base heat stabilizer and zinc acetylacetonate produce good collaboration
Effect.Even if content of the modified hydrocalumite in PVC composite heat stabilizer is up to 50%, corresponding PVC mixing material is in process
In will not be precipitated.
It should be appreciated that although the present invention has carried out clear explanation by above embodiments, without departing substantially from the present invention
Spirit and its essence in the case where, person of ordinary skill in the field make in accordance with the present invention it is various it is corresponding variation and
Amendment, but these corresponding variations and modifications all should belong to scope of protection of the claims of the invention.
Claims (4)
1. a kind of environment-friendly type water bovite base PVC composite heat stabilizer, which is characterized in that the component comprising following mass content:
Modified hydrocalumite: 20-50%；
Zinc stearate: 20-40%；
Zinc acetylacetonate: 2-6%；
Calcium stearate: 6-10%；
Antioxidant: 2-6%；
Lubricant: 10-20%；
The modified hydrocalumite is to be prepared using stearic acid or zinc stearate to the modification of hydrocalumite surface.
2. composite thermal stabilizer according to claim 1, which is characterized in that the preparation process of the modified hydrocalumite is such as
Under:
(1) calcium hydroxide, aluminium hydroxide and sodium carbonate are added in the reactor equipped with water, wherein calcium hydroxide and hydroxide
The molar ratio of aluminium is 1.8-2.4:1, and the molar ratio of aluminium hydroxide and sodium carbonate is 1.8-2.2:1, the matter of water and calcium hydroxide
Amount is stirred to react 0.5-2 hours than being 10-50:1 at 60-100 DEG C；
(2) stearic acid is added in step (1) products therefrom or zinc stearate is modifying agent, wherein modifying agent and hydrocalumite
Mass ratio be 3-10:100, be stirred to react at 60-100 DEG C 1-3 hours；
(3) stop stirring, the reaction was continued at 60-100 DEG C 10-20 hours, then through dehydration, drying and crushing.
3. composite thermal stabilizer according to claim 1, which is characterized in that the antioxidant is antioxidant 1010, antioxygen
Agent 168 or antioxidant 1076.
4. composite thermal stabilizer according to claim 1, which is characterized in that the lubricant is polyethylene wax or solid stone
Wax.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811370788.XA CN109354807A (en) | 2018-11-18 | 2018-11-18 | A kind of environment-friendly type water bovite base PVC composite heat stabilizer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811370788.XA CN109354807A (en) | 2018-11-18 | 2018-11-18 | A kind of environment-friendly type water bovite base PVC composite heat stabilizer |
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| CN201811370788.XA Pending CN109354807A (en) | 2018-11-18 | 2018-11-18 | A kind of environment-friendly type water bovite base PVC composite heat stabilizer |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802070A (en) * | 2016-04-13 | 2016-07-27 | 江南大学 | Method for preparing hydrocalumite based heat stabilizer from calcium-aluminum hydroxide and application of hydrocalumite based heat stabilizer |
| CN107964193A (en) * | 2017-12-20 | 2018-04-27 | 邵阳天堂助剂化工有限公司 | A kind of modified hydrocalumite base PVC composite heat stabilizer |
-
2018
- 2018-11-18 CN CN201811370788.XA patent/CN109354807A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802070A (en) * | 2016-04-13 | 2016-07-27 | 江南大学 | Method for preparing hydrocalumite based heat stabilizer from calcium-aluminum hydroxide and application of hydrocalumite based heat stabilizer |
| CN107964193A (en) * | 2017-12-20 | 2018-04-27 | 邵阳天堂助剂化工有限公司 | A kind of modified hydrocalumite base PVC composite heat stabilizer |
Non-Patent Citations (1)
| Title |
|---|
| 谢梦姣等: "改性水铝钙石的清洁制备及其对PVC的热稳定性能研究", 《邵阳学院学报（自然科学版）》 * |
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Application publication date: 20190219 |