CN107964193A - A kind of modified hydrocalumite base PVC composite heat stabilizer - Google Patents
A kind of modified hydrocalumite base PVC composite heat stabilizer Download PDFInfo
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- CN107964193A CN107964193A CN201711386509.4A CN201711386509A CN107964193A CN 107964193 A CN107964193 A CN 107964193A CN 201711386509 A CN201711386509 A CN 201711386509A CN 107964193 A CN107964193 A CN 107964193A
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- hydrocalumite
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K5/07—Aldehydes; Ketones
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to a kind of modified hydrocalumite base PVC composite heat stabilizer, which includes the component of following mass fraction：Modified hydrocalumite：50-80%, zinc stearate：10-30%, 1,3 dimethyl, 6 semicarbazides pyrimidine：3-8%,βDiketone type compound：1-5%, antioxidant：1-3%, lubricant：6-20%.For technical solution of the present invention to be modified major constituent of the hydrocalumite as PVC composite heat stabilizer, simple production process is of low cost, good with the compatibility of PVC, and with zinc stearate, 1,3 dimethyl, 6 semicarbazides pyrimidine,βThe components such as diketone type compound have extraordinary synergistic effect.This composite thermal stabilizer has excellent suppression PVC initial colorations performance and preferable long-term thermal stability performance.
Description
Technical field
The present invention relates to PVC heat stabilizer, more particularly to a kind of modified hydrocalumite base PVC composite heat stabilizer, belongs to
Material processing aid field.
Background technology
PVC easily decomposes at processing temperatures, causes product color burn, and structure and property change.Therefore, exist
In the process of PVC, it is necessary to heat stabilizer is added, to prevent or reduce its decomposition.At present, common heat stabilizer includes lead
Salt, organic tin, metal soap and composite thermal stabilizer.Lead salt type thermal stabilizing agent is to develop earliest and have good thermostabilization
The PVC heat stabilizer of performance.However, since lead salts compound has stronger toxicity, human body and Environmental security are formed and endangered
Evil, countries in the world are just gradually limiting the use of lead salt type thermal stabilizing agent.The heat endurance and the transparency of organic tin heat stabilizer
Preferably, small toxicity, is the PVC heat stabilizer of a kind of high comprehensive performance, but production cost is higher, is restricted its application.
Therefore, developing low-cost, high-performance environmentally-friendly type PVC heat stabilizer, to substitute lead salt type thermal stabilizing agent, promote PVC industries
" unleaded ", tool is of great significance.
Hydrocalumite, is one kind of layered composite metal hydroxides, and the carbanion between its laminate can be with chlorion
Exchange, laminate itself can also absorb the discharged hydrogen chloride of PVC degradeds, suppress its self-catalysis degraded, so as to improve PVC's
Thermal stability.Compared with magnalium hydrotalcite, the base strength on hydrocalumite surface is slightly higher, is more easy to absorbing hydrogen chloride, makes its suppression
The initial performance of PVC is more excellent.Peng Zhaolin, week happiness etc. disclose a kind of hydrocalumite base PVC in patent CN 104150518 and answer
Heat stabilizer is closed, it is mixed using unmodified hydrocalumite as major constituent by following raw material：Hydrocalumite 15-65%, calcium
Soap 10-56%, zinc soap 5-50%, lubricant 15-35%, chelating agent 3-10%, antioxidant 1-5%.Jiang Ping equalitys（Chinese Plastics,
2016,30（9）：75-81；CN 105802070）Also a kind of PVC prepared using unmodified hydrocalumite as major constituent is reported
Heat stabilizer, it includes following components：Hydrocalumite：Zinc stearate：Semicarbazides pyrimidine=3：0-0.5：1.5-2, has PVC
There is preferable thermal stability, but ratio of the semicarbazides pyrimidine of higher price in PVC heat stabilizer reaches 30-40%, makes it
Cost is higher, and scale application is restricted.
The content of the invention
The object of the present invention is to provide a kind of modified hydrocalumite base PVC composite heat stabilizer, the composite thermal stabilizer with
Modified hydrocalumite be main component, not comprising heavy metal and other toxic materials, with asepsis environment-protecting, easily prepared low with cost
Honest and clean advantage, and the heat endurance in PVC process can be significantly improved.
In order to realize the above object the present invention adopts the technical scheme that a kind of modified hydrocalumite base PVC of offer is compound
Heat stabilizer, includes the component of following mass content：
Modified hydrocalumite：50-80%；
Zinc stearate：10-30%；
1,3- dimethyl -6- semicarbazides pyrimidines：3-8%；
β- diketone type compound：1-5%；
Antioxidant：1-3%；
Lubricant：6-20%；
The modified hydrocalumite is to use polyethylene glycol or zinc stearate as modifying agent, to hydrocalumite progress surface modification
Prepare.
It is describedβ- diketone type compound is calcium acetylacetonate, zinc acetylacetonate, stearoyl benzoyl methane or dibenzoyl
Methane.
The antioxidant is antioxidant 1010, antioxidant 689, antioxidant 264 or antioxidant 1076.
The lubricant is Tissuemat E or solid paraffin.
The preparation process of the modified hydrocalumite is as follows：Hydrocalumite is dispersed in water, adds polyethylene glycol or hard
Resin acid zinc is modifying agent, wherein, the mass ratio of modifying agent and hydrocalumite is 3-10：100, reaction is stirred at 60-90 DEG C
When 0.5-2 is small, then through press filtration, dry and crushing.
The present invention is using the modification hydrocalumite being surface-treated by polyethylene glycol or zinc stearate as PVC composite heat stabilizer
Major constituent.Compared with traditional modification magnalium hydrotalcite, the initial coloration performance that modified hydrocalumite suppresses PVC is more excellent；With
Unmodified hydrocalumite is compared, and modified hydrocalumite is more preferable to the long-term thermal stability performance of PVC, and with the compatibility of PVC compared with
It is good.Even if content of the modified hydrocalumite in PVC composite heat stabilizer is up to 50-80%, corresponding PVC mixing materials are processed
It will not be separated out in journey.In addition, the simple production process of modified hydrocalumite, of low cost.Pass through many experiments, invention
People find modified water bovite and zinc stearate, 1,3- dimethyl -6- semicarbazides pyrimidine,βThe components such as-diketone type compound have
Extraordinary synergistic effect, composite thermal stabilizer are excellent to the thermal stability of PVC.
Embodiment
The embodiment of the present invention is described in further detail below.For those of skill in the art
For member, from detailed description of the invention, above and other objects, features and advantages of the invention will be evident.
The preferred preparation of modified hydrocalumite：
Modified hydrocalumite is to use polyethylene glycol or zinc stearate as modifying agent, and surface modification is carried out to hydrocalumite and is made
It is standby.Its preferred preparation process is：Hydrocalumite is dispersed in water, it is modifying agent to add polyethylene glycol or zinc stearate, wherein,
The mass ratio of modifying agent and hydrocalumite is 6：100；When stirring reaction 1 is small at 80 DEG C, then filtered, dry and crushing.
Embodiment 1：
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction：Modified hydrocalumite：60%, zinc stearate：
20%, 1,3- dimethyl -6- semicarbazides pyrimidines：5%, calcium acetylacetonate：3%, antioxidant 1010：2%, Tissuemat E：10%.
Embodiment 2：
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction：Modified hydrocalumite：70%, zinc stearate：
15%, 1,3- dimethyl -6- semicarbazides pyrimidines：3%, zinc acetylacetonate：3%, antioxidant 1076：1%, Tissuemat E：8%.
Embodiment 3：
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction：Modified hydrocalumite：80%, zinc stearate：
10%, 1,3- dimethyl -6- semicarbazides pyrimidines：2%, stearoyl benzoyl methane：1%, antioxidant 689：1%, solid paraffin：6%.
Embodiment 4：
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction：Modified hydrocalumite：50%, zinc stearate：
30%, 1,3- dimethyl -6- semicarbazides pyrimidines：8%, dibenzoyl methane：2%, antioxidant 689：3%, Tissuemat E：7%.
Embodiment 5：
The composite thermal stabilizer of the present embodiment includes the component of following mass fraction：Modified hydrocalumite：55%, zinc stearate：
15%, 1,3- dimethyl -6- semicarbazides pyrimidines：3%, calcium acetylacetonate：5%, antioxidant 264：2%, Tissuemat E：20%.
Comparative example 1：
The composite thermal stabilizer of this comparative example includes the component of following mass fraction：Modified magnalium hydrotalcite：60%, zinc stearate：
20%, 1,3- dimethyl -6- semicarbazides pyrimidines：5%, calcium acetylacetonate：3%, antioxidant 1010：2%, Tissuemat E：10%.Wherein,
The preparation method of modified magnalium hydrotalcite is similar to modified hydrocalumite, and raw material hydrocalumite only is changed to magnalium neatly
Stone.
Comparative example 2：
The composite thermal stabilizer of this comparative example includes the component of following mass fraction：Hydrocalumite：60%, zinc stearate：20%, 1,
3- dimethyl -6- semicarbazides pyrimidines：5%, calcium acetylacetonate：3%, antioxidant 1010：2%, Tissuemat E：10%.
Thermal stability is tested
The performance of composite thermal stabilizer is tested using general RM-200A torque rheometers are breathed out, test condition：190 DEG C of material temperature, experiment carry
5 kg of lotus, 35 rpm of rotating speed.Test sample forms：54 parts of PVC (SG-3 types) resins, 1.6 parts of composite thermal stabilizers, 12 parts
CaCO3, 5 parts of CPE, 1.6 parts of titanium dioxides, 0.2 part of pentaerythritol monostearate, 0.2 part of PE wax, 1 part of ACR.Test method：
It is kneaded in torque rheometer and takes out sample after ten minutes, whiteness at initial stage, and in addition sampling and testing Dynamic Thermal is tested using color difference meter
Stabilization time.Test result is shown in Table 1.
Table 1：The heat stabilization test result of PVC sample.
According to table 1 as a result, modified hydrocalumite based composite heat stabilizer provided by the invention shows PVC excellent heat surely
It is qualitative can, there is extraordinary synergistic effect between each component.Compared with traditional modification magnalium hydrotalcite, modified hydrocalumite
The initial coloration performance for suppressing PVC is more excellent；Compared with unmodified hydrocalumite, modified hydrocalumite is steady to the long term thermal of PVC
Qualitative energy is more preferable and preferable with the compatibility of PVC.Even if content of the modified hydrocalumite in PVC composite heat stabilizer is up to
50-80%, corresponding PVC mixing materials will not separate out in process.
It should be appreciated that although the present invention has carried out clear explanation by above example, but without departing substantially from the present invention
In the case of spirit and its essence, person of ordinary skill in the field make in accordance with the present invention various corresponding changes and
Correct, but these corresponding variations and modifications should all belong to the scope of the claims of the present invention.
Claims (5)
1. a kind of modified hydrocalumite base PVC composite heat stabilizer, it is characterised in that include the component of following mass content：
Modified hydrocalumite：50-80%；
Zinc stearate：10-30%；
1,3- dimethyl -6- semicarbazides pyrimidines：3-8%；
β- diketone type compound：1-5%；
Antioxidant：1-3%；
Lubricant：6-20%；
The modified hydrocalumite is to use polyethylene glycol or zinc stearate as modifying agent, to hydrocalumite progress surface modification
Prepare.
2. composite thermal stabilizer according to claim 1, it is characterised in that describedβ- diketone type compound is acetylacetone,2,4-pentanedione
Calcium, zinc acetylacetonate, stearoyl benzoyl methane or dibenzoyl methane.
3. composite thermal stabilizer according to claim 1, it is characterised in that the antioxidant is antioxidant 1010, antioxygen
Agent 689, antioxidant 264 or antioxidant 1076.
4. composite thermal stabilizer according to claim 1, it is characterised in that the lubricant is Tissuemat E or solid stone
Wax.
5. composite thermal stabilizer according to claim 1, it is characterised in that the preparation process of the modified hydrocalumite is such as
Under：Hydrocalumite is dispersed in water, it is modifying agent to add polyethylene glycol or zinc stearate, wherein, modifying agent and hydrocalumite
Mass ratio be 3-10：100, when stirring reaction 0.5-2 is small at 60-90 DEG C, then through press filtration, dry and crushing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711386509.4A CN107964193A (en) | 2017-12-20 | 2017-12-20 | A kind of modified hydrocalumite base PVC composite heat stabilizer |
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| CN201711386509.4A CN107964193A (en) | 2017-12-20 | 2017-12-20 | A kind of modified hydrocalumite base PVC composite heat stabilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034075A (en) * | 2017-12-29 | 2018-05-15 | 东莞市汉维科技股份有限公司 | A kind of preparation process of PVC base color masterbatch processing aid |
| CN109354807A (en) * | 2018-11-18 | 2019-02-19 | 邵阳天堂助剂化工有限公司 | A kind of environment-friendly type water bovite base PVC composite heat stabilizer |
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| 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 |
| CN106867030A (en) * | 2017-03-06 | 2017-06-20 | 邵阳天堂助剂化工有限公司 | A kind of composite modified hydrotalcite for PVC heat stabilizer and preparation method thereof |
| CN107312273A (en) * | 2017-08-17 | 2017-11-03 | 浙江秦山电缆有限公司 | A kind of 70 DEG C of sheaths level soft polyvinyl chloride plastic for trunking |
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2017
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| CN104150518A (en) * | 2014-08-05 | 2014-11-19 | 邵阳天堂助剂化工有限公司 | Synthesis method for hydrocalumites and hydrocalumites based PVC complex heat stabilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034075A (en) * | 2017-12-29 | 2018-05-15 | 东莞市汉维科技股份有限公司 | A kind of preparation process of PVC base color masterbatch processing aid |
| CN109354807A (en) * | 2018-11-18 | 2019-02-19 | 邵阳天堂助剂化工有限公司 | A kind of environment-friendly type water bovite base PVC composite heat stabilizer |
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Application publication date: 20180427 |