CN115403830B - Preparation method of modified hydrotalcite for PVC heat stabilizer - Google Patents
Preparation method of modified hydrotalcite for PVC heat stabilizer Download PDFInfo
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- CN115403830B CN115403830B CN202211073127.7A CN202211073127A CN115403830B CN 115403830 B CN115403830 B CN 115403830B CN 202211073127 A CN202211073127 A CN 202211073127A CN 115403830 B CN115403830 B CN 115403830B
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- hydrotalcite
- ricinoleate
- preparation
- oleate
- vegetable
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 20
- 229940049964 oleate Drugs 0.000 claims abstract description 35
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 35
- 235000013311 vegetables Nutrition 0.000 claims abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 31
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 claims abstract description 18
- 229940066675 ricinoleate Drugs 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- GMIMAWFYOOIAQD-GNNYBVKZSA-L magnesium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [Mg+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GMIMAWFYOOIAQD-GNNYBVKZSA-L 0.000 claims abstract description 3
- TXSUIVPRHHQNTM-UHFFFAOYSA-N n'-(3-methylanilino)-n-phenyliminobenzenecarboximidamide Chemical compound CC1=CC=CC(NN=C(N=NC=2C=CC=CC=2)C=2C=CC=CC=2)=C1 TXSUIVPRHHQNTM-UHFFFAOYSA-N 0.000 claims abstract description 3
- VAKMIIPDYZXBEV-DPMBMXLASA-M potassium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [K+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O VAKMIIPDYZXBEV-DPMBMXLASA-M 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 claims abstract description 3
- 229940100530 zinc ricinoleate Drugs 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 26
- 229920000915 polyvinyl chloride Polymers 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 7
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- 229940035893 uracil Drugs 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- -1 mixing NaAlO 2 Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
Abstract
The invention provides a preparation method of modified hydrotalcite for a PVC heat stabilizer, and belongs to the technical field of PVC heat stabilizers. The preparation method of the modified hydrotalcite comprises the following steps: the modified hydrotalcite is obtained by cooling, filtering, washing and drying after the reaction with the modifier as a reaction medium and the hydrotalcite as a main agent; the modifier is vegetable oleate and ricinoleate; the vegetable oleate is one or more of potassium vegetable oleate, sodium vegetable oleate, zinc vegetable oleate, calcium vegetable oleate and magnesium vegetable oleate; the ricinoleate is one or more of potassium ricinoleate, sodium ricinoleate, zinc ricinoleate, calcium ricinoleate and magnesium ricinoleate. The preparation method provided by the invention has wide sources of raw materials, can obtain the modified hydrotalcite with good dispersion effect and good thermal stability in PVC, and is simple and easy to operate.
Description
Technical Field
The invention belongs to the technical field of PVC heat stabilizers, and particularly relates to a preparation method of modified hydrotalcite for a PVC heat stabilizer.
Background
Hydrotalcite and hydrotalcite-like compounds have attracted attention because of their excellent properties due to their special layered bimetallic structure. hydrotalcite-Like (LDHs) heat stabilizer is taken as a two-dimensional anionic layered compound, and is taken as a novel high-efficiency environment-friendly heat stabilizer, which has caused wide attention in domestic and foreign scientific research and industry, and is expected to gradually replace traditional toxic and harmful heat stabilizers such as lead salt and the like.
One of three general resins of polyvinyl chloride (PVC) is widely applied to various important fields of national economy. The molecular structure determines the properties and also influences the processing conditions. Polyvinyl chloride is prepared by vinyl chloride monomer according to a free radical polymerization mechanism, and a large number of C-Cl polar bonds exist in the chain, so that HCl is easily removed under the action of heat and shearing force, and the defects of poor thermal stability, poor processability and the like of the PVC are caused. The heat stabilizer commonly used in PVC processing comprises lead salts, metal soaps and organic tin, and along with the restriction of various environmental protection in foreign countries and the increasing demand of domestic environment protection, the trend of environmental protection of the heat stabilizer is more and more obvious, including the export of some policies. Hydrotalcite is used as a stabilizer in PVC, and is more and more researched, and because hydrotalcite is powder, agglomeration is easy to cause in PVC, and the uniformity of hydrotalcite dispersion attracts attention.
Patent CN 113444287A discloses a modified hydrotalcite, a preparation method thereof, a PVC heat stabilizer and application, wherein the modified hydrotalcite is obtained by in-situ synthesis of uracil, epoxy acid, metal salt and other auxiliary agents. The invention can not only promote the ability of modified hydrotalcite to absorb HCl and replace unstable chlorine atoms, but also complex AlCl after the metal strong oxide in the layer absorbs HCl by inserting and inserting the uracil epoxy acid with excellent HCl absorption and unstable chlorine atom substitution between hydrotalcite layers 3 And MgCl 2 By-products of Zn substitution and blocking AlCl 3 And MgCl 2 And replacing zinc ions in the zinc salt heat stabilizer; the modified hydrotalcite and zinc salt can be used as PVC heat stabilizer in PVC products after being compounded, and the obtained products have excellent initial whiteness and long-term heat stability. However, the preparation method provided in this patent does not solve the agglomeration problem.
Patent CN 106867030A discloses a composite modified hydrotalcite for PVC heat stabilizer and its preparation method. The method comprises the following steps: (1) Mixing polyethylene glycol, soluble magnesium salt and water to obtain salt solution, mixing NaAlO 2 、NaOH、Na 2 CO 3 Mixing water to prepare an alkali solution; (2) And mixing the salt solution with the alkali solution, adding uracil into the mixed solution, and dehydrating and drying the precipitate obtained by the reaction to obtain the composite modified hydrotalcite. The invention obtains the compound by the synergistic effect of polyethylene glycol and uracilThe thermal stability of the modified hydrotalcite to PVC is obviously superior to that of the traditional hydrotalcite which is not modified or modified by a single modifier. In addition, the preparation method of the composite modified hydrotalcite provided by the invention has simple flow, does not need special equipment, and is suitable for industrial application; however, there is also a problem of dispersion of hydrotalcite during processing.
Therefore, it is necessary to explore a preparation method of modified hydrotalcite with wide sources of raw materials, good dispersing effect and good thermal stability in PVC, and the operation is simple and easy.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of hydrotalcite co-modified by vegetable oleate and ricinoleate for PVC heat stabilizer, which is used for reducing the agglomeration degree of hydrotalcite in PVC, increasing the dispersion uniformity degree of hydrotalcite and increasing the heat stability of PVC. Simultaneously, the vegetable oleate and the ricinoleate are both heat stabilizers of the PVC, and the three are synergistic to improve the heat stability of the PVC. The method has no requirement on the concentration of the vegetable oleate and the ricinoleate, and has no requirement on the type of hydrotalcite.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, a preparation method of modified hydrotalcite is provided, which comprises the following steps: the modified hydrotalcite is obtained by cooling, filtering, washing and drying after the reaction with the modifier as a reaction medium and the hydrotalcite as a main agent;
the modifier is vegetable oleate and ricinoleate;
in the invention, the modifier is mixed by using the plant oleate and the ricinoleate, and the sequence of feeding can be that the plant oleate is added into the ricinoleate or that the ricinoleate is added into the plant oleate;
the vegetable oleate is one or more of potassium vegetable oleate, sodium vegetable oleate, zinc vegetable oleate, calcium vegetable oleate and magnesium vegetable oleate;
the ricinoleate is one or more of potassium ricinoleate, sodium ricinoleate, zinc ricinoleate, calcium ricinoleate and magnesium ricinoleate.
Further, the weight ratio of the modifier to the hydrotalcite is 0.1-30:100, preferably 5-25:100.
further, the weight percentage of the plant oleate in the total amount of the modifier is 0.01-99.99%, preferably 10-80%.
Further, the weight of the vegetable oleate accounts for 30-65% of the total weight of the modifier.
Further, the hydrotalcite is one or more of hydrotalcite, hydrotalcite-like compound and intercalated hydrotalcite. The hydrotalcite is directly added into a mixture of vegetable oleate and ricinoleate by taking the modifier as a reaction medium and taking hydrotalcite as a main agent.
Further, stirring is performed during the reaction, and the stirring speed is 1 to 3000rpm, preferably 20 to 1500rpm, and more preferably 30 to 800rpm.
Further, the temperature of the reaction is 40 to 90 ℃, preferably 50 to 80 ℃.
The reaction temperature can be maintained at the same reaction temperature in the whole reaction process, and heating can also be performed in a temperature programming mode, so long as the temperature of the end point of the temperature rise does not exceed the upper temperature limit of the reaction temperature. The temperature programming can be continuous temperature programming, namely one-stage temperature programming: heating at a certain rate by taking the temperature at the beginning of the reaction as a starting point until the temperature just reaches the end point temperature at the end of the reaction, or heating to the end point temperature in a certain time at a certain heating rate, and then continuing the reaction for a period of time; discontinuous temperature programming, i.e. staged temperature programming, can also be used, and the reaction is continued for a certain time after each stage of temperature programming. In the present invention, continuous temperature programming is preferable, and the temperature is controlled by an automatic instrument according to the total reaction temperature setting.
Further, the reaction time is 0.5 to 12 hours, preferably 2 to 9 hours.
Secondly, a modified hydrotalcite obtained by the preparation method is provided.
Finally, the modified hydrotalcite obtained by the preparation method or the application of the modified hydrotalcite in the preparation of the PVC heat stabilizer is provided.
Compared with the prior art, the invention has the following beneficial effects:
(1) Few using equipment and simple and easy operation;
(2) Hydrotalcite, vegetable oleate and ricinoleate are all environment-friendly stabilizers, and do not contain toxic and harmful substances;
(3) The vegetable oleate and the ricinoleate are both easily available products and have wide raw materials;
(4) The modified hydrotalcite has good dispersing effect, effectively reduces the agglomeration degree, has good thermal stability in PVC, and has longer thermal stability time than unmodified hydrotalcite;
(5) Hydrotalcite and ricinoleate also play roles in inhibiting smoke, retarding flame and the like in PVC.
Detailed Description
It is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
In the following examples, a 2000mL reactor was used, the hydrotalcite was 1000g, the hydrotalcite was magnesium aluminum hydrotalcite, the plant oleate was 20% solids, and the ricinoleate was 20% solids. The formulation ratios of the other raw material reagents added in the examples are shown in table 1, and the process conditions are shown in table 2.
Example 1
20g of potassium vegetable oleate (20%) and 180g of sodium ricinoleate (20%) are respectively added into a reaction kettle, hydrotalcite is added under the stirring of 800rpm, and the temperature is raised to 90 ℃ after the uniform stirring, and the reaction is carried out for 2 hours. Cooling, filtering, washing and drying to obtain the co-modified hydrotalcite.
Examples 2 to 10
Referring to the method described in example 1, according to the raw material formulation ratios and process workpiece parameters (example 1 corresponds to the data of group 1 in table 1-2) described in table 1-2, the data of groups 2 to 10 were replaced, respectively, that is, examples 2 to 10 were obtained.
Comparative examples 1 to 2
With reference to the process described in example 1, modified hydrotalcite was prepared according to the raw material formulation proportions and process workpiece parameters described in tables 1-2. Comparative example 1 used only vegetable oleate and comparative example 2 used only ricinoleate.
Table 1 formulation table
Table 2 Table 2
| Sequence number | Stirring speed, rpm | Reaction temperature, DEG C | Reaction time, h |
| 1 | 800 | 90 | 2 |
| 2 | 700 | 85 | 3 |
| 3 | 600 | 75 | 4 |
| 4 | 500 | 70 | 5 |
| 5 | 400 | 65 | 6.5 |
| 6 | 300 | 60 | 7 |
| 7 | 200 | 55 | 7.5 |
| 8 | 100 | 50 | 8 |
| 9 | 50 | 45 | 8.5 |
| 10 | 30 | 40 | 9 |
| Comparative example 1 | 200 | 55 | 7.5 |
| Comparative example 2 | 200 | 55 | 7.5 |
Experimental example
After fully mixing other auxiliary agents such as PVC, co-modified hydrotalcite, plasticizer and the like, mixing and plasticizing at 165 ℃ to prepare a sheet with the thickness of 1.0mm, cooling and cutting into small sample sheets with the thickness of 1.5cm x1.5 cm. Placing the sample in a thermal aging test box with the temperature of (190+/-1) ℃ for static thermal aging test, taking out 1 small sample piece every 20min to observe the color change, and taking the blackening time of the sample piece as the PVC static thermal aging time;
the congo red heat stability time of the samples at 200℃was determined according to GB/T8815-2008 standard.
Table 3 test results table
| Sequence number | Congo red, min | Static heat aging time, min |
| 1 | 56 | 230 |
| 2 | 57 | 250 |
| 3 | 62 | 310 |
| 4 | 64 | 350 |
| 5 | 66 | 330 |
| 6 | 63 | 300 |
| 7 | 64 | 320 |
| 8 | 65 | 304 |
| 9 | 64 | 310 |
| 10 | 63 | 315 |
| Comparative example 1 | 45 | 180 |
| Comparative example 2 | 40 | 165 |
From Table 3, it can be seen that the Congo red stabilization time and static heat aging time at 200 ℃ are both longer, which indicates that the co-modified hydrotalcite has good heat stabilization effect on PVC as a heat stabilizer.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (14)
1. The preparation method of the modified hydrotalcite is characterized by comprising the following steps of: the modified hydrotalcite is obtained by cooling, filtering, washing and drying after the reaction with the modifier as a reaction medium and the hydrotalcite as a main agent;
the modifier is vegetable oleate and ricinoleate;
the vegetable oleate is one or more of potassium vegetable oleate, sodium vegetable oleate, zinc vegetable oleate, calcium vegetable oleate and magnesium vegetable oleate;
the ricinoleate is one or more of potassium ricinoleate, sodium ricinoleate, zinc ricinoleate, calcium ricinoleate and magnesium ricinoleate;
the weight ratio of the modifier to the hydrotalcite is 0.1-30:100.
2. the preparation method according to claim 1, wherein the weight ratio of the modifier to hydrotalcite is 5-25:100.
3. the preparation method according to claim 1, wherein the weight of the vegetable oleate is 0.01-99.99% of the total modifier.
4. The preparation method according to claim 3, wherein the weight of the vegetable oleate is 10-80% of the total amount of modification.
5. The preparation method according to claim 4, wherein the weight of the vegetable oleate is 30-65% of the total modifier.
6. The preparation method according to claim 1, wherein the hydrotalcite is one or more of hydrotalcite, hydrotalcite-like compound and intercalated hydrotalcite.
7. The method according to claim 1, wherein stirring is performed during the reaction, and the stirring speed is 1-3000rpm.
8. The method of claim 7, wherein the stirring speed is 20-1500rpm.
9. The process of claim 1, wherein the temperature of the reaction is 40-90 ℃.
10. The process of claim 9, wherein the temperature of the reaction is 50-80 ℃.
11. The method of claim 1, wherein the reaction time is 0.5 to 12 hours.
12. The method of claim 11, wherein the reaction time is 2 to 9 hours.
13. The modified hydrotalcite obtained by the production process according to any one of claims 1 to 12.
14. Use of the modified hydrotalcite obtained by the preparation method according to any one of claims 1 to 12 or the modified hydrotalcite according to claim 13 in the preparation of PVC heat stabilizers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073127.7A CN115403830B (en) | 2022-09-02 | 2022-09-02 | Preparation method of modified hydrotalcite for PVC heat stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073127.7A CN115403830B (en) | 2022-09-02 | 2022-09-02 | Preparation method of modified hydrotalcite for PVC heat stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115403830A CN115403830A (en) | 2022-11-29 |
| CN115403830B true CN115403830B (en) | 2023-10-27 |
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| CN202211073127.7A Active CN115403830B (en) | 2022-09-02 | 2022-09-02 | Preparation method of modified hydrotalcite for PVC heat stabilizer |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0341142A (en) * | 1989-07-10 | 1991-02-21 | Adeka Argus Chem Co Ltd | Polyvinyl chloride resin composition for food package |
| JPH06100749A (en) * | 1992-09-22 | 1994-04-12 | Asahi Denka Kogyo Kk | Polyvinyl chloride-based resin composition for food warp |
| JP2005336305A (en) * | 2004-05-26 | 2005-12-08 | Okamoto Ind Inc | Vinyl chloride-based resin wrap film for food packaging |
| CN102516597A (en) * | 2011-12-13 | 2012-06-27 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN103467887A (en) * | 2013-09-11 | 2013-12-25 | 江南大学 | Preparation methods of castor oil base carboxylate radical intercalated hydrotalcite for PVC (Polyvinyl Chloride) and compound heat stabilizer thereof |
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2022
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0341142A (en) * | 1989-07-10 | 1991-02-21 | Adeka Argus Chem Co Ltd | Polyvinyl chloride resin composition for food package |
| JPH06100749A (en) * | 1992-09-22 | 1994-04-12 | Asahi Denka Kogyo Kk | Polyvinyl chloride-based resin composition for food warp |
| JP2005336305A (en) * | 2004-05-26 | 2005-12-08 | Okamoto Ind Inc | Vinyl chloride-based resin wrap film for food packaging |
| CN102516597A (en) * | 2011-12-13 | 2012-06-27 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN103467887A (en) * | 2013-09-11 | 2013-12-25 | 江南大学 | Preparation methods of castor oil base carboxylate radical intercalated hydrotalcite for PVC (Polyvinyl Chloride) and compound heat stabilizer thereof |
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