CN107200963A - Ca-Zn composite heat stabilizer for surface high glaze PVC spool material and preparation method thereof - Google Patents
Ca-Zn composite heat stabilizer for surface high glaze PVC spool material and preparation method thereof Download PDFInfo
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- CN107200963A CN107200963A CN201710528180.4A CN201710528180A CN107200963A CN 107200963 A CN107200963 A CN 107200963A CN 201710528180 A CN201710528180 A CN 201710528180A CN 107200963 A CN107200963 A CN 107200963A
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- heat stabilizer
- composite heat
- high glaze
- pvc
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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
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of Ca-Zn composite heat stabilizer for surface high glaze PVC spool material, it is made up of the raw material of following mass percent：Zinc stearate 10 40%, calcium acetylacetonate 5 20%, beta diketone 1 15%, zeolite 10 40%, hydrotalcite 5 15%, calcium carbonate 0 50%, antioxidant 1 15%, lubricant 0 30%.The present invention chooses the higher raw material of fineness and prepares heat stabilizer, or the raw material fusing point in formula is less than the processing temperature of PVC spools, fineness is less than 1250 mesh, contrasted by many experiments, it was found that the product surface glossiness produced using the higher material of fineness is high, by proportion optimizing, and the method being simply blended prepares a kind of higher powdered Ca-Zn composite heat stabilizer of fineness.
Description
Technical field
The present invention relates to heat stabilizer preparation field, more particularly to a kind of calcium zinc for surface high glaze PVC spool material
Composite thermal stabilizer and preparation method thereof.
Background technology
Igelite (PVC) is the maximum thermoplastic of current consumption, and its excellent performance is with low cost, extensively
Applied to each field.But, the reason for PVC is because of molecular structure, heat resistance is poor, at a temperature of more than 100 degrees Celsius
Degraded along with dehydrochlorination reaction, and routine PVC processing temperature is in 170 degrees centigrades, at this temperature, degraded speed
Faster, performance degradation is serious, and this characteristic constrains PVC application for degree.
For this solution it is required that a certain amount of heat stabilizer is added in processing suppresses its degraded, currently used for PVC
Heat stabilizer mainly have lead salt, organotin, antimony organic, terres rares, metal soap, etc..Lead salts is exploitation earliest and imitated
Fruit preferably PVC heat stabilizer, but the lead contained by it is poisonous, and environment is exerted heavy pressures on, current each state is all strictly limiting
The use of Lead salt thermal stabilizer processed.Ca-Zn composite heat stabilizer due to it is nontoxic, efficient the characteristics of, become reflex in recent years
Close most active field and most competitive product in stabilizer.
On the other hand, due to social development and growth in the living standard, requirement of the consumer to product quality is increasingly increased,
The outward appearance of product is also the key factor for influenceing consumer spending to determine, rakish product has more the market competitiveness.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of excellent performance, with low cost, the calcium zinc of simple production process
Composite thermal stabilizer, the problem of heat resistance is poor in process solving PVC, the stabilizer that the present invention is developed is in choosing
The material stage, the Ca-Zn composite heat stabilizer prepared can produce the PVC products of high glaze using the higher raw material of fineness.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of Ca-Zn composite heat stabilizer for surface high glaze PVC spool material, it is characterised in that：
It is made up of the raw material of following mass percent：
Zinc stearate 10-40%
Calcium acetylacetonate 5-20%
Beta-diketon 1-15%
Zeolite 10-40%
Hydrotalcite 5-15%
Calcium carbonate 0-50%
Antioxidant 1-15%
Lubricant 0-30%.
Preferably, the structural formula of described zinc stearate is [CH3(CH2)16]2Zn, its fusing point is at 100~140 DEG C.
Preferably, described calcium acetylacetonate structural formula is Ca (C5H7O2)2, its fusing point is 250~300 DEG C, and fineness is
1000~1500 mesh.
Preferably, its fusing point of described beta-diketon is 50~60 DEG C.
Preferably, the structural formula of described zeolite is A(x/q)[(AlO2)x(SiO2)y]n(H2O), wherein, A be Ca, Na,
The cations such as K, Ba, q is cationic compound valency, and n is moisture subnumber, and x is Al atomicities, and y is Si atomicities, through perstearic acid table
The non-toxic inorganic thing that face is modified, described zeolite fineness is less than 2000 mesh.
Preferably, described hydrotalcite is the allusion quotation shape layer structure of having by Main Ingredients and Appearance of magnalium, through perstearic acid
The nontoxic inorganic matter that surface is modified, described zeolite fineness is less than 2000 mesh.
Preferably, described calcium carbonate is the non-toxic inorganic thing being modified through stearic acid surface, the fineness of the calcium carbonate
Less than 1250 mesh.
Formed preferably, described antioxidant is phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant compounding.
Formed preferably, described lubricant is Tissuemat E and stearic acid compounding.
The embodiment of the present invention also provides a kind of preparation of the Ca-Zn composite heat stabilizer for surface high glaze PVC spool material
Method, it is characterised in that：Comprise the following steps：
(1) zinc stearate is accurately weighed by formula rate, calcium acetylacetonate, beta-diketon, zeolite, hydrotalcite, calcium carbonate resists
Oxygen agent and lubricant, and each raw material components are put into high-speed mixer；
(2) running parameter of high-speed mixer is set, and running parameter is：Rotating speed 1500r/min, 25-40 DEG C of temperature, mixing
Time 3-10min；
(3) feed bin lid is locked, the blowing packed for standby use after material is well mixed.
The present invention has the advantages that compared with prior art：
The present invention is by experiment screening material, and the raw material that the higher raw material of selection fineness is prepared in heat stabilizer, formula will
Fusing point is less than the processing temperature of PVC spools, or fineness is less than 1250 mesh, is contrasted by many experiments, and discovery uses fineness
The product surface glossiness that higher material is produced is high, and by proportion optimizing, and the method being simply blended prepares one
Plant the higher powdered Ca-Zn composite heat stabilizer of fineness.
Brief description of the drawings
Fig. 1 is the rheological curve figure that the embodiment of the present invention is obtained under experimental conditions；
Fig. 2 is that the heat endurance of product is carried out by Oven Method according to the formula material and method in the embodiment of the present invention
The design sketch of inspection.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1：
Raw material is weighed according to following formula：
Zinc stearate 25%
Zeolite 15%
Calcium acetylacetonate 5%
Beta-diketon 10%
Hydrotalcite 6%
Antioxidant 5%
Calcium carbonate 24%
Lubricant 10%
For the preparation method of the Ca-Zn composite heat stabilizer of surface high glaze PVC spool material, comprise the following steps：
(1) zinc stearate, calcium acetylacetonate, beta-diketon, zeolite, hydrotalcite, carbon are accurately weighed according to above-mentioned formula rate
Sour calcium, antioxidant and lubricant, and each raw material components are put into high-speed mixer；
(2) running parameter of high-speed mixer is set, and running parameter is：Rotating speed 1500r/min, 25-40 DEG C of temperature, mixing
Time 3-10min；
(3) feed bin lid is locked, the blowing packed for standby use after material is well mixed.
Embodiment 2：
Raw material is weighed according to following formula：
Zinc stearate 15%
Zeolite 20%
Calcium acetylacetonate 10%
Beta-diketon 2%
Hydrotalcite 6%
Antioxidant 5%
Calcium carbonate 37%
Lubricant 5%.
For the preparation method of the Ca-Zn composite heat stabilizer of surface high glaze PVC spool material, comprise the following steps：
(1) zinc stearate, calcium acetylacetonate, beta-diketon, zeolite, hydrotalcite, carbon are accurately weighed according to above-mentioned formula rate
Sour calcium, antioxidant and lubricant, and each raw material components are put into high-speed mixer；
(2) running parameter of high-speed mixer is set, and running parameter is：Rotating speed 1500r/min, 25-40 DEG C of temperature, mixing
Time 3-10min；
(3) feed bin lid is locked, the blowing packed for standby use after material is well mixed.
Embodiment 3：
Raw material is weighed according to following formula：
Zinc stearate 22%
Zeolite 17%
Calcium acetylacetonate 7%
Beta-diketon 5%
Hydrotalcite 6%
Antioxidant 5%
Calcium carbonate 23%
Lubricant 15%.
For the preparation method of the Ca-Zn composite heat stabilizer of surface high glaze PVC spool material, comprise the following steps：
(1) zinc stearate, calcium acetylacetonate, beta-diketon, zeolite, hydrotalcite, carbon are accurately weighed according to above-mentioned formula rate
Sour calcium, antioxidant and lubricant, and each raw material components are put into high-speed mixer；
(2) running parameter of high-speed mixer is set, and running parameter is：Rotating speed 1500r/min, 25-40 DEG C of temperature, mixing
Time 3-10min；
(3) feed bin lid is locked, the blowing packed for standby use after material is well mixed.
The embodiment of the present invention also provides a kind of method that application Ca-Zn composite heat stabilizer makes PVC, specific system
Make method as follows:
Weigh 100 parts of PVC resin powder, 35 parts of calcium carbonate, 10 parts of haloflex, ACR1.5 parts, 1 part of stearic acid, PE waxes 2
Part, 0.8 part of titanium dioxide, 3.2 parts of Ca-Zn composite heat stabilizer (product prepared by embodiment 1-3).By the production of PVC spool material
Technique hybrid process, carries out mark by the PVC spool material processed, is cooled to room temperature and packages spare.
Ready PVC spools material is subjected to mixing experiment, mixing time 10 minutes, by acquisition by twin-screw extruder
The PVC sheet-like articles that the heat stabilizer sample of PVC sheet-like articles and commercially available famous brand name is prepared using similarity condition are contrasted,
It was found that the whiteness of embodiment 1 is better than commercially available famous brand name, embodiment 2,3 quite, illustrates steady using the heat of the invention prepared therewith
Determine agent effect preferably, can play and suppress the degraded of polyvinyl chloride resin in process, improve the processing stability of PVC product.
Ready PVC spools material is produced into spool by the conical double screw extruder with cable tube die head, and adopted
PVC spool material are prepared with the heat stabilizer of commercially available famous brand name, spool is produced using same condition, found by contrasting, is used
The PVC spools surface gloss that heat stabilizer prepared by embodiment 1-3 is produced is prepared better than commercially available famous brand name heat stabilizer
PVC spools, illustrate that the heat stabilizer for preparing of the present invention coordinates corresponding formula and mould to prepare the PVC lines of high glaze
Pipe.
We have carried out table by various ways such as torque rheometer, baking oven, color difference meters to the calcium zinc stabilizer of the present invention
Levy, calcium zinc stabilizer of the present invention specify that than general calcium zinc stabilizer by experimental result, not only cost declines 20-30%, and
It is real to realize super quality and competitive price and performance is more excellent.By the production technology hybrid process of PVC spool material, by the PVC spool material processed
Mark is carried out, room temperature is cooled to and packages spare.Ready PVC spools material is tested by torque rheometer.
It is shown in Figure 1, it is calcium zinc stabilizer of the present invention in 195 DEG C of temperature, tests rotating speed 60r/min, setting time
Solid line is used for PVC for calcium zinc stabilizer prepared in embodiment in 10min experiment condition, the rheological curve figure of acquisition, Fig. 1
Stream varied curve, dotted line is the general calcium zinc stabilizer PVC stream varied curves of outsourcing under equal conditions.We can be with bright from Fig. 1
Aobvious finds out, no matter makes moment of torsion or fusion time, and calcium zinc stabilizer of the present invention is better than general calcium zinc stabilizer.
We have a look below, the Experimental Comparison number of calcium zinc stabilizer of the present invention and general calcium zinc stabilizer
According to as shown in table 1：
Table 1
It will be seen that combining the value of chromatism of obtained spool can significantly more judge that calcium zinc of the present invention is steady from table 1
Determine agent and be substantially better than general calcium zinc stabilizer.
It is shown in Figure 2, it is that the embodiment of the present invention carries out Experimental comparison by Oven Method to the heat endurance of product, from figure
As can be seen that under same time, calcium zinc stabilizer of the present invention is more excellent than the product heat endurance of general calcium zinc stabilizer in 2
It is good.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of Ca-Zn composite heat stabilizer for surface high glaze PVC spool material, it is characterised in that：It is by following quality
The raw material composition of percentage：
Zinc stearate 10-40%
Calcium acetylacetonate 5-20%
Beta-diketon 1-15%
Zeolite 10-40%
Hydrotalcite 5-15%
Calcium carbonate 0-50%
Antioxidant 1-15%
Lubricant 0-30%.
2. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：The structural formula of described zinc stearate is [CH3(CH2)16]2Zn, its fusing point is at 100~140 DEG C.
3. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：Described calcium acetylacetonate structural formula is Ca (C5H7O2)2, its fusing point is 250~300 DEG C, and fineness is 1000~1500 mesh.
4. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：Its fusing point of described beta-diketon is 50~60 DEG C.
5. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：The structural formula of described zeolite is A(x/q)[(AlO2)x(SiO2)y]n(H2O), wherein, A is the cation, q such as Ca, Na, K, Ba
For cationic compound valency, n is moisture subnumber, and x is Al atomicities, and y is Si atomicities, the nontoxic nothing being modified by stearic acid surface
Machine thing, described zeolite fineness is less than 2000 mesh.
6. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：Described hydrotalcite be by Main Ingredients and Appearance of magnalium have allusion quotation shape layer structure, by stearic acid surface be modified it is nontoxic
Inorganic matter, described zeolite fineness is less than 2000 mesh.
7. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：Described calcium carbonate is the non-toxic inorganic thing being modified through stearic acid surface, and the fineness of the calcium carbonate is less than 1250 mesh.
8. the Ca-Zn composite heat stabilizer according to claim 1 for surface high glaze PVC spool material, its feature exists
In：Described antioxidant is that phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant compounding are formed.
9. a kind of Ca-Zn composite heat stabilizer for surface high glaze PVC spool material according to claim 1, its feature
It is：Described lubricant is that Tissuemat E and stearic acid compounding are formed.
10. the Ca-Zn composite heat stabilizer for surface high glaze PVC spool material according to any one of claim 1 to 9
Preparation method, it is characterised in that：Comprise the following steps：
(1) zinc stearate, calcium acetylacetonate, beta-diketon, zeolite, hydrotalcite, calcium carbonate, antioxidant are accurately weighed by formula rate
And lubricant, and each raw material components are put into high-speed mixer；
(2) running parameter of high-speed mixer is set, and running parameter is：Rotating speed 1500r/min, 25-40 DEG C of temperature, incorporation time
3-10min；
(3) feed bin lid is locked, the blowing packed for standby use after material is well mixed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710528180.4A CN107200963A (en) | 2017-07-01 | 2017-07-01 | Ca-Zn composite heat stabilizer for surface high glaze PVC spool material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710528180.4A CN107200963A (en) | 2017-07-01 | 2017-07-01 | Ca-Zn composite heat stabilizer for surface high glaze PVC spool material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373596A (en) * | 2018-03-20 | 2018-08-07 | 山东三义实业股份有限公司 | A kind of hard PVC product environmentally friendly calcium-zinc composite stabilizing agent and preparation method thereof |
| CN110330741A (en) * | 2019-07-25 | 2019-10-15 | 东莞市柯益信息技术有限公司 | A kind of environmental protection high transparency leaded light PVC is stabilizing agent specially used and preparation method thereof |
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| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN102875916A (en) * | 2012-07-25 | 2013-01-16 | 肇庆市森德利化工实业有限公司 | Dedicated Mg-Al-Zn modified non-toxic compound stabilizer for PVC (Poly Vinyl Chloride) pipes |
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| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
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| CN103665668A (en) * | 2013-12-11 | 2014-03-26 | 甘肃大禹节水集团股份有限公司 | Magnesium-aluminium-zinc modified stabilizer for PVC (Poly Vinyl Chloride) pipe |
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Cited By (2)
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| CN108373596A (en) * | 2018-03-20 | 2018-08-07 | 山东三义实业股份有限公司 | A kind of hard PVC product environmentally friendly calcium-zinc composite stabilizing agent and preparation method thereof |
| CN110330741A (en) * | 2019-07-25 | 2019-10-15 | 东莞市柯益信息技术有限公司 | A kind of environmental protection high transparency leaded light PVC is stabilizing agent specially used and preparation method thereof |
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