CN115232363B - Composite calcium-zinc heat stabilizer composition and preparation method and application thereof - Google Patents
Composite calcium-zinc heat stabilizer composition and preparation method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- 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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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The application discloses a composite calcium-zinc heat stabilizer composition, a preparation method and application thereof. The composite calcium-zinc heat stabilizer composition comprises the following components in parts by weight: 10 parts of calcium zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate; the modified fumed silica is fumed silica modified by a silane coupling agent. The hydroxyl-terminated pentaerythritol adipate has good compatibility with PVC, and can reduce precipitation of heat stabilizer while improving heat stability; the surface of the modified fumed silica modified by the silane coupling agent is provided with silanol groups, so that the modified fumed silica is very easy to adsorb substances which can form hydrogen bonds with the silanol groups. According to the application, the composite calcium zinc heat stabilizer composition with excellent heat stability is obtained through the cooperation and the synergistic effect of the modified fumed silica, the hydroxyl-terminated pentaerythritol adipate and the calcium zinc heat stabilizer.
Description
Technical Field
The application relates to the technical field of PVC heat stabilizers, in particular to a composite calcium zinc heat stabilizer composition, a preparation method and application thereof.
Background
The PVC pipeline has excellent flame retardance, wear resistance, chemical corrosion resistance, mechanical property,Electrical insulation property and the like, and is widely applied to the fields of industry, construction, municipal administration, agriculture and the like. The PVC molecular chain has a tertiary chlorine and tertiary hydrogen structure, has lower bond energy, is easy to remove HCl to generate free radicals, causes unstable PVC molecular chain and has the following characteristics in O 2 Degradation and aging can be carried out under high temperature and illumination conditions. The decomposition temperature of the PVC resin is about 130 ℃, but the molding temperature of the PVC resin is 180 ℃ or higher, so that in order to achieve the workability of the PVC resin, it is necessary to add a heat stabilizer to the PVC material system.
The calcium-zinc stabilizer is a recognized nontoxic and environment-friendly heat stabilizer, and in the actual production process of the PVC pipeline, the calcium-zinc heat stabilizer is added to improve the heat stability of the PVC resin and slow down the degradation and discoloration processes of the PVC resin. Chinese patent application CN1624040A discloses a granule of UPVC pipe fitting for water supply, which consists of PVC resin, calcium zinc heat stabilizer, processing aid, lubricant, impact modifier and the like, and improves the heat stability of PVC-U material.
However, calcium zinc heat stabilizer, while effective in inhibiting the initial degradation and coloration of PVC materials, has the following drawbacks: under long-time hot processing, the calcium-zinc heat stabilizer is extremely easy to separate out to form scaling of a mold runner and sizing sleeve frost, so that the appearance and physical and mechanical properties of the pipe are seriously affected, and the heat stability of the PVC material is further deteriorated; znCl generated by the calcium-zinc heat stabilizer in the later stage of hot working 2 Has extremely strong catalytic HCl removal effect, so that the PVC molecular chain is unstable and easy to degrade, and the color of the material is deepened. Therefore, the long-acting heat stability of PVC is improved only by using the calcium-zinc heat stabilizer, and the composite calcium-zinc heat stabilizer composition needs to be developed, so that the heat stability time of PVC pipeline materials can be effectively prolonged.
Disclosure of Invention
The application provides a composite calcium-zinc heat stabilizer composition, which comprises modified fumed silica, hydroxyl-terminated pentaerythritol adipate and a calcium-zinc heat stabilizer, can effectively prolong the heat stability time of PVC pipeline materials, and has excellent long-acting heat stability effect on PVC.
The application also aims to provide a preparation method of the composite calcium-zinc heat stabilizer composition.
The application further aims to provide application of the composite calcium zinc heat stabilizer composition in PVC pipeline materials.
In order to solve the technical problems, the application adopts the following technical scheme:
the composite calcium-zinc heat stabilizer composition comprises the following components in parts by weight:
10 parts of calcium zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate;
the modified fumed silica is fumed silica modified by a silane coupling agent.
Pentaerythritol is an excellent auxiliary heat stabilizer, and the mechanism for improving the heat stability of a PVC material system is as follows: the oxygen atoms in the hydroxyl groups of the pentaerythritol have lone pair electrons, so that zinc chloride generated by zinc salts in the calcium zinc heat stabilizer is easily complexed, and the catalytic decomposition of the zinc chloride on PVC is further delayed. Although pentaerythritol and a calcium-zinc heat stabilizer are used simultaneously, a certain synergistic effect can be generated, so that a better heat stability effect is obtained; however, due to poor compatibility of pentaerythritol and PVC, pentaerythritol is easy to separate out, so that the pentaerythritol is independently added into a PVC system to limit the synergistic effect of the pentaerythritol on the thermal stability of the PVC material.
According to the application, hydroxyl-terminated adipic acid and pentaerythritol are used for introducing ester groups through esterification reaction, on one hand, after the pentaerythritol is esterified, the compatibility with PVC is obviously improved, and the pentaerythritol is not easy to separate out in the hot working process; on the other hand, through esterification reaction, hydroxyl in hydroxyl-terminated adipic acid is reserved, the hydroxyl reacted in pentaerythritol molecules is compensated, and oxygen atoms in the hydroxyl can promote complexing zinc chloride, so that the synergistic effect of the composite calcium-zinc heat stabilizer composition on PVC heat stability is further improved. Wherein the hydroxyl-terminated adipic acid is 2-hydroxy adipic acid, and CAS number is 18294-85-4.
Meanwhile, in the process of preparing the modified fumed silica, alkoxy groups in the silane coupling agent are hydrolyzed to generate hydroxyl groups, wherein one part of hydroxyl groups react with silicon hydroxyl groups on the surface of the fumed silica, and the other part of hydroxyl groups remain, namely after the modified fumed silica is modified by the silane coupling agent, the compatibility between the modified fumed silica and PVC can be increased, silanol groups (silicon hydroxyl groups) can be formed on the surface of the fumed silica, and the modified fumed silica is very easy to adsorb substances capable of forming hydrogen bonds with the silanol groups. Therefore, the modified fumed silica has a rapid adsorption effect on HCl removed by degradation of PVC, and desorption is not easy to occur. HCl is timely adsorbed and removed through the modified fumed silica, so that the autocatalysis degradation effect of HCl on PVC molecules is effectively blocked, and the degradation of PVC molecules is slowed down.
Therefore, the modified fumed silica and the hydroxyl-terminated pentaerythritol adipate in the composite calcium-zinc heat stabilizer composition provided by the application act together to synergistically enhance the effect, so that an excellent heat stabilization effect is achieved.
Through the synergistic effect of modified fumed silica, hydroxyl-terminated pentaerythritol adipate and a calcium-zinc heat stabilizer, the composite calcium-zinc heat stabilizer composition with excellent long-acting heat stabilization effect on PVC materials can be obtained.
The hydroxyl-terminated adipic acid pentaerythritol ester is obtained by esterification reaction of hydroxyl-terminated adipic acid and pentaerythritol.
Preferably, the molar ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is (1-1.5) to 2.
Preferably, the acid value of the hydroxyl-terminated pentaerythritol adipate is less than or equal to 0.5mg KOH/g, and the hydroxyl value is 70-90 mg KOH/g.
Preferably, the preparation method of the modified fumed silica comprises the following steps:
dispersing the fumed silica and the silane coupling agent in an organic solvent, carrying out reflux reaction for 2-4 hours at 60-80 ℃, and carrying out post-treatment to obtain the modified fumed silica.
Preferably, the mass ratio of the fumed silica to the silane coupling agent is (40-50): (20-30).
Preferably, the organic solvent is one or more of acetone, methanol, ethanol and ethyl acetate.
Preferably, the silane coupling agent is one or more of KH570, KH560 and KH 171.
Preferably, the silanol group density of the modified fumed silica surface is 3 to 5SiOH/nm 2 . More preferably, the silanol group density of the modified fumed silica surface is 3.1 to 4.8SiOH/nm 2 . In particular, the silanol group density of the modified fumed silica surface can be 3.1SiOH/nm 2 、4.1SiOH/nm 2 、4.8SiOH/nm 2 。
Preferably, the specific surface area of the modified fumed silica is 250-350 m 2 /g。
Preferably, the calcium zinc heat stabilizer is a mixture of calcium stearate and zinc stearate.
More preferably, the mass ratio of the calcium stearate to the zinc stearate is (15-30) to (10-20).
Preferably, the composite calcium zinc heat stabilizer composition comprises the following components in parts by weight:
8-10 parts of calcium zinc heat stabilizer, 0.4-0.8 part of modified fumed silica and 0.3-0.6 part of hydroxyl-terminated pentaerythritol adipate.
The application also provides a preparation method of the composite calcium-zinc heat stabilizer composition, which comprises the following steps:
and uniformly mixing the calcium-zinc heat stabilizer, the modified fumed silica and the hydroxyl-terminated pentaerythritol adipate to obtain the composite calcium-zinc heat stabilizer composition.
The application also protects the application of the composite calcium zinc heat stabilizer composition in PVC composite materials.
Preferably, the PVC composite material comprises the following components in parts by weight:
80-100 parts of polyvinyl chloride, 5-30 parts of inorganic filler, 1-3 parts of titanium dioxide and 5-12 parts of the composite calcium-zinc heat stabilizer composition.
Preferably, the PVC composite material also comprises 6.5 to 17 parts by weight of other auxiliary agents.
Preferably, the other auxiliary agents include lubricants, impact modifiers, processing aids.
Preferably, the lubricant in the other auxiliary agents is 1-5 parts, the impact modifier is 5-10 parts, and the processing auxiliary agent is 0.5-2 parts.
Optionally, the lubricant is PE wax and/or monoglyceride.
Optionally, the impact modifier is Chlorinated Polyethylene (CPE) and/or methyl methacrylate-butadiene-styrene terpolymer (MBS).
Optionally, the processing aid is an acrylic copolymer.
The processing aid can promote the plasticizing effect of the PVC-U material to be better.
Compared with the prior art, the application has the beneficial effects that:
according to the application, through the synergistic effect of modified fumed silica, hydroxyl-terminated pentaerythritol adipate and a calcium-zinc heat stabilizer, the composite calcium-zinc heat stabilizer composition with excellent long-acting heat stabilization effect on PVC materials is developed.
Drawings
FIG. 1 is a Fourier infrared spectrum of pentaerythritol hydroxy-terminated adipate A of the present application.
Detailed Description
The application is further described below in connection with the following detailed description.
The starting materials in both examples and comparative examples are commercially available, wherein:
the calcium-zinc heat stabilizer A is prepared from calcium stearate and zinc stearate according to the mass ratio of 20:12 a compounded mixture;
the calcium-zinc heat stabilizer B is prepared from calcium stearate and zinc stearate according to the mass ratio of 15:20 a compounded mixture;
the calcium-zinc heat stabilizer C is prepared from calcium stearate and zinc stearate according to the mass ratio of 30:10 a compounded mixture;
the calcium zinc heat stabilizer D is purchased from a new material of Jiashan three benefit, and W520.
The modified fumed silica A is prepared by the following method:
the mass ratio is 50:20 and a silane coupling agent KH570 are dispersed in acetone, and the modified fumed silica A is obtained after the reaction temperature is 70 ℃ and the reaction time is 2 hours, separation and drying; the silanol group density of the modified fumed silica A was 3.1SiOH/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the modified fumed silica is 258m 2 /g；
The modified fumed silica B is prepared by the following method:
the mass ratio is 40:30 fumed silica and a silane coupling agent KH560 are dispersed in ethanol, and the modified fumed silica B is obtained after the reaction is carried out by reflux heating reaction at 70 ℃ for 2 hours, separation and drying; the silanol group density of the modified fumed silica B was 4.8SiOH/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the modified fumed silica is 277m 2 /g；
The modified fumed silica C is prepared by the following method:
dispersing fumed silica and a silane coupling agent KH171 in the mass ratio of 45:25 in dimethylbenzene, carrying out reflux heating reaction at 70 ℃ for 2 hours, separating and drying to obtain modified fumed silica C; the silanol group density of the modified fumed silica C was 4.1SiOH/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the modified fumed silica was 302m 2 /g；
The modified fumed silica D is prepared by the following method:
dispersing fumed silica and an aluminate coupling agent in a mass ratio of 50:20 in dimethylbenzene, carrying out reflux heating reaction at a reaction temperature of 70 ℃ for 2 hours, and separating and drying to obtain modified fumed silica D;
the hydroxyl-terminated pentaerythritol adipate is prepared by the following method:
under the action of concentrated sulfuric acid serving as a catalyst, adding hydroxyl-terminated adipic acid and pentaerythritol into a round-bottomed flask with a stirring device, and carrying out esterification reaction under the condition of vacuumizing to obtain hydroxyl-terminated adipic acid pentaerythritol ester;
wherein, in the preparation method of the hydroxyl-terminated pentaerythritol adipate A, the mol ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is 1:2, the esterification reaction temperature is 150 ℃, the reaction time is 4 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate A is 0.2mgKOH/g, and the hydroxyl value is 90mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate B, the molar ratio of hydroxyl-terminated adipic acid to pentaerythritol is 1.5:2, the esterification reaction temperature is 150 ℃, the reaction time is 4 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate B is 0.35mgKOH/g, and the hydroxyl value is 70mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate C, the molar ratio of hydroxyl-terminated adipic acid to pentaerythritol is 1:2, the esterification reaction temperature is 170 ℃, the reaction time is 2 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate C is 0.31mgKOH/g, and the hydroxyl value is 80mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate D, the molar ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is 1:2, the esterification reaction temperature is 130 ℃, the reaction time is 5 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate D is 0.25mgKOH/g, and the hydroxyl value is 86mgKOH/g.
Pentaerythritol stearate, purchased from Chengan biological Co., ltd, has an acid value of less than or equal to 0.5mgKOH/g and a hydroxyl value of 20-37 mgKOH/g.
Pentaerythritol oleate is purchased from biological processes in Anqing city, the acid value is less than or equal to 1mgKOH/g, and the hydroxyl value is less than or equal to 15mgKOH/g.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Examples 1 to 13
Examples 1-13 respectively provide a composite calcium zinc heat stabilizer composition, the contents of the components are shown in table 1, and the preparation method comprises the following steps: and uniformly mixing the components according to the table 1 to obtain the composite calcium zinc heat stabilizer composition.
Table 1 the component contents (parts by weight) of the composite calcium-zinc heat stabilizer compositions of examples 1 to 13
Comparative examples 1 to 8
Comparative examples 1 to 8 respectively provide a composite calcium zinc heat stabilizer composition, the contents of the components are shown in Table 2, and the preparation method comprises the following steps: and uniformly mixing the components according to the table 1 to obtain the composite calcium zinc heat stabilizer composition.
Table 2 component contents (parts by weight) of the composite calcium-zinc heat stabilizer compositions of comparative examples 1 to 8
Performance testing
(1) Fourier infrared spectroscopy test
The application is subjected to Fourier infrared spectrum test, the test result is shown in figure 1, and from the figure, it can be seen that the hydroxyl-terminated pentaerythritol adipate A is at 1726cm -1 The absorption peak of the ester carbonyl appears at 3400cm -1 A broad and strong-OH absorption peak was observed, and it was confirmed that 2-hydroxyadipic acid and pentaerythritol were esterified to produce a compound having both an ester group and a hydroxyl group. The Fourier infrared spectra of the hydroxyl-terminated pentaerythritol adipate B, the hydroxyl-terminated pentaerythritol adipate C and the hydroxyl-terminated pentaerythritol adipate D are basically the same as those of the hydroxyl-terminated pentaerythritol adipate A, and all the compounds containing both ester groups and hydroxyl groups are generated.
(2) Modified fumed silica surface silicon hydroxyl number test
The specific test method comprises the following steps: weighing a certain amount of modified fumed silica in a beaker, adding a certain amount of absolute ethyl alcohol and 10% NaCl solution, uniformly stirring, and adjusting the pH value to 4.0 by using 0.1mol/L HCl solution; slowly adding 0.1mol/L NaOH solution, adjusting the pH value to 9.0, maintaining for 30s, and maintaining the pH unchanged; then calculate each (nm) according to the following formula 2 Number of fumed silica hydroxyl groups (N):
N＝(C*V*NA*10 -3 )/(Sm)；
wherein C is NaOH concentration, V is the volume of NaOH (mL) consumed when the pH is raised from 4.0 to 9.0, NA is the A Fu Jiade Rockwell, S is the fumed silica specific surface area (nm 2 /g), m being the mass (g) of fumed silica.
The silanol group density of the modified fumed silica A of the application is 3.1SiOH/nm as determined by detection and calculation 2 The method comprises the steps of carrying out a first treatment on the surface of the The silanol group density of the modified fumed silica B was 4.8SiOH/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The silanol group density of the modified fumed silica C was 4.1SiOH/nm 2 。
(3) The calcium zinc heat stabilizer prepared in the embodiment and the comparative example is uniformly mixed according to the following weight parts: 100 parts of PVC, 8 parts of a composite calcium zinc heat stabilizer composition, 5 parts of calcium carbonate, 1 part of a lubricant, 5 parts of an impact modifier and 1 part of a processing aid to obtain PVC pipeline materials; and adding the PVC pipeline material into a double-screw extruder, performing melt extrusion, molding by a die, performing cooling shaping by using a cooling water tank, and cutting to obtain the PVC pipeline.
And (3) carrying out heat-resistant stability time test on the PVC pipeline material, and observing precipitation condition of the composite calcium-zinc heat stabilizer composition to evaluate the heat stability of the composite calcium-zinc heat stabilizer composition.
a. Heat resistant stabilization time: the torque rheometer is used for carrying out rheological experiments on the PVC pipeline material, the color change of the PVC pipeline material is tested by using the color difference meter at intervals, the time for changing the color from colorless to other colors is the heat-resistant stable time, and the specific test method is as follows:
weighing according to the formula of PVC, mixing by a small high-speed mixer, and pouring out for later use. The torque rheometer sets the temperature in advance, when the temperature is raised to the specified temperature and the rotating speed is stable, the weighed mixture is added into the processing box, the processing box is rapidly closed, and various parameters on a computer connected with the processing box are recorded, so that the rheometer is the rheological curve. After processing is complete, different appearance characteristics of the extrudate can also be obtained, such as whiteness, whether to form, smoothness, etc.
b. Heat stabilizer precipitation: and (3) carrying out pipe extrusion experiments on the PVC pipe material by using an extruder, continuously starting up for 4 hours, observing the precipitate at the die, and weighing the mass of the precipitate, wherein 1mg is grade I, 1-5 mg is grade II, and more than 5mg is grade III.
The test results of the examples and comparative examples are shown in Table 3.
According to the test results of the table, the composite calcium zinc heat stabilizer composition of each embodiment of the application has excellent heat stabilization effect on PVC, has long heat resistance stabilization time which is more than or equal to 30min, and has no heat stabilizer precipitation in the PVC pipeline preparation process.
In comparative example 1, the composite calcium zinc heat stabilizer composition did not contain modified fumed silica and pentaerythritol hydroxy-terminated adipate, the heat stability was poor, the heat stability time was only 20min, the sample had color change at 25min, and the precipitates were more. In comparative examples 2 and 3, the fumed silica added was not modified with the silane coupling agent, and the heat resistance stability time was only 25 minutes, and there was a certain degree of precipitate. In comparative examples 5 and 6, when pentaerythritol hydroxyl-terminated adipate was replaced with pentaerythritol stearate or pentaerythritol oleate, respectively, the pentaerythritol in the above two comparative examples was still added to the PVC system in the form of an ester group, but since stearic acid or oleic acid was an acid containing no hydroxyl group, the hydroxyl groups reacted in the pentaerythritol molecule could not be compensated, and further effective improvement of heat resistance could not be achieved, and there was some precipitation during production. In comparative example 7, pentaerythritol which is not esterified is used for replacing hydroxyl-terminated adipic acid pentaerythritol ester, so that the heat stability cannot meet the requirement, and the precipitates are more and reach class III. In comparative examples 4 and 8, the heat-resistant stabilization time was 25 minutes without adding modified fumed silica or pentaerythritol hydroxy-terminated adipate, and the excellent effect as in the examples of the present application could not be obtained.
It is to be understood that the above examples of the present application are provided by way of illustration only and not by way of limitation of the embodiments of the present application. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are desired to be protected by the following claims.
Claims (9)
1. The composite calcium-zinc heat stabilizer composition is characterized by comprising the following components in parts by weight:
10 parts of calcium zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate; the modified fumed silica is fumed silica modified by a silane coupling agent;
the hydroxyl-terminated adipic acid pentaerythritol ester is obtained by esterification reaction of hydroxyl-terminated adipic acid and pentaerythritol, and the molar ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is (1-1.5) to 2;
the hydroxyl-terminated adipic acid is 2-hydroxy adipic acid.
2. The composite calcium zinc heat stabilizer composition according to claim 1, wherein the acid value of the hydroxyl-terminated pentaerythritol adipate is not more than 0.5mg KOH/g and the hydroxyl value is 70-90 mg KOH/g.
3. The composite calcium zinc heat stabilizer composition according to claim 1, wherein the modified fumed silica is prepared by the following steps:
dispersing the fumed silica and the silane coupling agent in an organic solvent, carrying out reflux reaction for 2-4 hours at 60-80 ℃, and carrying out post-treatment to obtain the modified fumed silica.
4. A composite calcium zinc heat stabilizer composition according to claim 3, wherein the mass ratio of the fumed silica to the silane coupling agent is (40 to 50): (20-30).
5. The composite calcium zinc heat stabilizer according to claim 1The composition is characterized in that the silanol group density of the surface of the modified fumed silica is 3-5 SiOH/nm 2 。
6. The composite calcium zinc heat stabilizer composition according to claim 1, wherein the modified fumed silica has a specific surface area of 250 to 350m 2 /g。
7. The composite calcium zinc heat stabilizer composition according to claim 1, wherein the calcium zinc heat stabilizer is a mixture of calcium stearate and zinc stearate.
8. The method for preparing the composite calcium-zinc heat stabilizer composition according to any one of claims 1 to 7, characterized by comprising the steps of:
and uniformly mixing the calcium-zinc heat stabilizer, the modified fumed silica and the hydroxyl-terminated pentaerythritol adipate to obtain the composite calcium-zinc heat stabilizer composition.
9. Use of the composite calcium zinc heat stabilizer composition according to any one of claims 1 to 7 in PVC composite materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4202806A (en) * | 1977-04-22 | 1980-05-13 | Koei Chemical Co., Ltd. | Stabilization of chlorine-containing resins |
| 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 |
| CN105237942A (en) * | 2015-10-12 | 2016-01-13 | 神华集团有限责任公司 | Toughening polyformaldehyde composite material and preparation method thereof |
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| CN102093648A (en) * | 2010-12-10 | 2011-06-15 | 浙江海普顿化工科技有限公司 | Pasty calcium-zinc composite heat stabilizer and preparation method thereof |
| CN103613884B (en) * | 2013-12-05 | 2016-01-27 | 山东慧科助剂股份有限公司 | PVC efficient zinc-base composite thermal stabilizer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202806A (en) * | 1977-04-22 | 1980-05-13 | Koei Chemical Co., Ltd. | Stabilization of chlorine-containing resins |
| 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 |
| CN105237942A (en) * | 2015-10-12 | 2016-01-13 | 神华集团有限责任公司 | Toughening polyformaldehyde composite material and preparation method thereof |
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