WO2024108383A1 - Easily dispersible hydrotalcite-based composite material for polymer, and preparation method therefor - Google Patents
Easily dispersible hydrotalcite-based composite material for polymer, and preparation method therefor Download PDFInfo
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- WO2024108383A1 WO2024108383A1 PCT/CN2022/133505 CN2022133505W WO2024108383A1 WO 2024108383 A1 WO2024108383 A1 WO 2024108383A1 CN 2022133505 W CN2022133505 W CN 2022133505W WO 2024108383 A1 WO2024108383 A1 WO 2024108383A1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 72
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 64
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 claims abstract description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 107
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 159000000003 magnesium salts Chemical class 0.000 claims description 12
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 27
- -1 and mixing NaAlO 2 Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940035893 uracil Drugs 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 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 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 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
- 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
-
- 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
- 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
- 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
Definitions
- the invention relates to an easily dispersible hydrotalcite-based composite material for polymer and a preparation method thereof.
- the Chinese invention patent application (application number: CN202110698946.X, application date: 2021-06-23) discloses a modified hydrotalcite and its preparation method, PVC heat stabilizer and application, wherein the modified hydrotalcite is synthesized in situ by uracil, epoxy acid, metal salt and other additives.
- the present invention can not only improve the ability of the modified hydrotalcite to absorb HCl and replace unstable chlorine atoms by intercalating uracil epoxy acid with excellent absorption of HCl and replacement of unstable chlorine atoms between the hydrotalcite layers, but also can complex the metal strong oxide in the layer to absorb HCl, such as AlCl 3 and MgCl 2 , which can replace Zn byproducts, and block the replacement of zinc ions in zinc salt heat stabilizers such as AlCl 3 and MgCl 2 ; the modified hydrotalcite can be used as a PVC heat stabilizer in PVC products after compounding with zinc salt, and the resulting product has excellent initial whiteness and long-term thermal stability.
- the invention relates to an easily dispersible hydrotalcite-based composite material for polymers, the composition of which is characterized in that the mass ratio of magnesium aluminum hydrotalcite: cerium stearate: aluminum hydroxide is 1: 0.03-0.05: 0.02-0.08.
- Example 5 Weigh 4.559 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL of NaOH solution and 0.12 g/mL of Al 2 (SO 4 ) 3 ⁇ 18H 2 O solution; at room temperature, pour solution A into a reactor and start a stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor and stir for 10 min to obtain a mixed solution; adjust the pH to 11.5 by dropping NaOH solution, 0.05 kg of an aqueous solution prepared with polyethylene glycol 1000 was added dropwise, and the mixture was stirred for 10 min to obtain a hydrotalcite precursor solution; the mixture was then reacted in a hydrothermal reactor at 140° C.
- the hydrotalcite solution in the reactor was diluted three times and poured into another reactor, and 0.025 kg of an aqueous solution prepared with sodium dodecyl sulfate was added at 85° C., and the mixture was stirred for 10 min. Then 0.15 kg of cerium stearate was added and the mixture was stirred for another 10 min.
- the pH value was adjusted to 7.00 by adding Al 2 (SO 4 ) 3 ⁇ 18H 2 O solution, and the addition time was about 1 h.
- the product was filtered, washed, dried at 90° C., and crushed to obtain an easily dispersible hydrotalcite-based composite material product 5.
- Test experiment 1 After the Mg-Al hydrotalcite-based composite material produced by this process was mixed with PVC, the heat resistance was tested using the Congo red method. 5g pure PVC + 0.2g Mg-Al hydrotalcite was tested at 200°C. The comparison of the heat resistance test results with pure PVC is shown in Table 1.
- Test experiment 2 To test the dispersibility of the synthesized hydrotalcite-based composite material, 0.01 g of the product was weighed and added to 10 mL of acetone, ultrasonicated for 5 min, and the absorbance at 350 nm was tested under a UV-visible spectrophotometer to compare the absorbance of the suspension. The test results are shown in Table 1. The higher the absorbance, the better the dispersibility.
- the above comparison results show that after physical mixing with Mg-Al hydrotalcite, the heat resistance time is greatly improved.
- the heat resistance time of pure PVC is 3.42 minutes, and after adding 0.2g of Mg-Al hydrotalcite, the heat resistance time rises to 31.13min at most, and the heat resistance is significantly improved; and the product prepared in Example 2 has the best dispersibility (the absorbance of acetone solution at 350nm can reach 1.68), which is slightly better than the hydrotalcite DHT-4A product of Japan Kyowa Company (heat resistance 30.35min, dispersibility 350nm absorbance is 1.65).
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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)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to an easily dispersible hydrotalcite-based composite material for a polymer. The composition of the composite material is characterized in that the mass ratio of magnesium-aluminum hydrotalcite to cerium stearate to aluminum hydroxide is 1 : 0.03-0.05 : 0.02-0.08. In the product, the magnesium-aluminum hydrotalcite is prepared by means of a hydrothermal method, and aluminum hydroxide is deposited on the surface after cerium stearate surface modification, so as to form a composite material taking hydrotalcite as a main body. The composite material, taking the organic modified magnesium-aluminum hydrotalcite as the main body, synthesized in the present invention, is used in a PVC heat stabilizer, has the advantages of good heat stability, being easily dispersible, etc., and has the advantages of a green and environmentally friendly production process, a simple preparation method, a low production cost, being convenient for industrialization, etc.
Description
本发明涉及一种聚合物用易分散型水滑石基复合材料及其制备方法。The invention relates to an easily dispersible hydrotalcite-based composite material for polymer and a preparation method thereof.
水滑石，又称层状复合金属氢氧化物(Layered double hydroxides，LDHs)，是一类典型的阴离子型主客体层状结构化合物。其基本的化学组成可表示为[M
2+
1–xM
3+
x(OH)
2]
x+(A
n–
x/n)·mH
2O。其在阻燃、能源、环境、防腐以及生物医学等领域受到了越来越多的关注，相关研究在国际期刊上的发文量呈逐年上升的趋势。此外，LDHs结构可调，且可通过阳离子掺杂、阴离子插层、表面改性等多种途径来进一步提升其功能特性。水滑石具有层状结构和吸酸性能，能够有效地吸附和吸收PVC受热降解释放的氯化氢气体，阻止了PVC进一步的自催化分解，从而提高了PVC的耐热性能。相比较其他的传统的铅盐类，钙锌皂类和有机锡类热稳定剂，水滑石可作为一种无毒，价廉的PVC热稳定剂。
Hydrotalcite, also known as layered double hydroxides (LDHs), is a typical anionic host-guest layered structure compound. Its basic chemical composition can be expressed as [M 2+ 1–x M 3+ x (OH) 2 ] x+ (A n– x/n )·mH 2 O. It has received increasing attention in the fields of flame retardancy, energy, environment, anti-corrosion and biomedicine, and the number of related research papers published in international journals has been increasing year by year. In addition, the structure of LDHs is adjustable, and its functional properties can be further improved through various methods such as cation doping, anion intercalation, and surface modification. Hydrotalcite has a layered structure and acid absorption properties, which can effectively adsorb and absorb the hydrogen chloride gas released by the thermal degradation of PVC, preventing the further autocatalytic decomposition of PVC, thereby improving the heat resistance of PVC. Compared with other traditional lead salts, calcium zinc soaps and organotin heat stabilizers, hydrotalcite can be used as a non-toxic and inexpensive PVC heat stabilizer.
中国发明专利申请(申请号：CN201710129104.6，申请日：2017-03-06)公开了一种用于PVC热稳定剂的改性水滑石及其制备方法。该方法包括：(1)将聚乙二醇、可溶性的镁盐及水混合配成盐溶液,将NaAlO
2、NaOH、Na
2CO
3及水混合配成碱溶液；(2)将盐溶液和碱溶液混合,并在混合液中加入氰尿酸盐,将反应得到的沉淀物脱水干燥后,得到改性水滑石。通过聚乙二醇和氰尿酸盐的协同作用,本发明得到的复合改性水滑石对PVC的热稳定性显著优于传统的未改性或经单一改性剂改性的水滑石。
The Chinese invention patent application (application number: CN201710129104.6, application date: 2017-03-06) discloses a modified hydrotalcite used as a PVC heat stabilizer and a preparation method thereof. The method comprises: (1) mixing polyethylene glycol, a soluble magnesium salt and water to form a salt solution, and mixing NaAlO 2 , NaOH, Na 2 CO 3 and water to form an alkaline solution; (2) mixing the salt solution and the alkaline solution, and adding cyanurate to the mixed solution, and dehydrating and drying the precipitate obtained by the reaction to obtain a modified hydrotalcite. Through the synergistic effect of polyethylene glycol and cyanurate, the composite modified hydrotalcite obtained by the present invention has significantly better thermal stability to PVC than the traditional unmodified hydrotalcite or hydrotalcite modified by a single modifier.
中国发明专利申请(申请号：CN202110698946.X,申请日：2021-06-23)公开了一种改性水滑石及其制备方法、PVC热稳定剂及应用,所述改性水滑石由脲嘧啶、环氧酸、金属盐以及其他助剂原位合成获得。本发明通过在水滑石层间插层具有优异的吸收HCl、取代不稳定氯原子的脲嘧啶环氧酸,不仅能够提升改性水滑石吸收HCl和取代不稳定氯原子的能力,而且可以络合层内金属强氧化物吸收HCl后的AlCl
3和MgCl
2等可置换Zn的副产物,阻断AlCl
3和MgCl
2等置换锌盐热稳定剂中的锌离子；改性水滑石与锌盐复配后可以作为PVC热稳定剂应用在PVC产品中,所得产品具有优异初期白度和长期热稳定性。
The Chinese invention patent application (application number: CN202110698946.X, application date: 2021-06-23) discloses a modified hydrotalcite and its preparation method, PVC heat stabilizer and application, wherein the modified hydrotalcite is synthesized in situ by uracil, epoxy acid, metal salt and other additives. The present invention can not only improve the ability of the modified hydrotalcite to absorb HCl and replace unstable chlorine atoms by intercalating uracil epoxy acid with excellent absorption of HCl and replacement of unstable chlorine atoms between the hydrotalcite layers, but also can complex the metal strong oxide in the layer to absorb HCl, such as AlCl 3 and MgCl 2 , which can replace Zn byproducts, and block the replacement of zinc ions in zinc salt heat stabilizers such as AlCl 3 and MgCl 2 ; the modified hydrotalcite can be used as a PVC heat stabilizer in PVC products after compounding with zinc salt, and the resulting product has excellent initial whiteness and long-term thermal stability.
传统共沉淀法制备的水滑石颗粒较小、易团聚，分散性较差；而水热合成水滑石后期改性较难，产品分散性差。本发明一方面筛选聚乙二醇1000作为合成助剂加入水滑石水热合成步骤中，成功控制了产品的粒径和分散性；另一方面，再后期改性阶段，加入阴离子表面活性剂以及硬脂酸铈，双重调控产品分散性和耐热性，并为中和产物反应液的高pH值，在水滑石片层结构上沉积氢氧化铝形成纳米片阵列，形成水滑石基复合材料将有利于提升其PVC热稳定性。The hydrotalcite prepared by the traditional coprecipitation method has small particles, is easy to agglomerate, and has poor dispersibility; while the hydrothermally synthesized hydrotalcite is difficult to modify in the later stage, and the product has poor dispersibility. On the one hand, the present invention selects polyethylene glycol 1000 as a synthesis aid and adds it to the hydrothermal synthesis step of the hydrotalcite, successfully controlling the particle size and dispersibility of the product; on the other hand, in the later modification stage, anionic surfactants and cerium stearate are added to dually regulate the dispersibility and heat resistance of the product, and in order to neutralize the high pH value of the product reaction liquid, aluminum hydroxide is deposited on the hydrotalcite sheet structure to form a nanosheet array, forming a hydrotalcite-based composite material, which will be beneficial to improve its PVC thermal stability.
发明内容Summary of the invention
本发明涉及一种聚合物用易分散型水滑石基复合材料，其组成特征为镁铝水滑石：硬脂酸铈：氢氧化铝的质量比为1:0.03-0.05：0.02-0.08。The invention relates to an easily dispersible hydrotalcite-based composite material for polymers, the composition of which is characterized in that the mass ratio of magnesium aluminum hydrotalcite: cerium stearate: aluminum hydroxide is 1: 0.03-0.05: 0.02-0.08.
作为优选，所述的易分散型水滑石基复合材料，其制备方法为：Preferably, the easily dispersible hydrotalcite-based composite material is prepared by:
1)称取一定质量的镁盐、偏铝酸钠、碳酸钠配置成溶液，其中n(镁盐)：n(偏铝酸钠)：n(碳酸钠)的摩尔比为2-3:1:0.5；室温下，按镁盐溶液、偏铝酸钠溶液、碳酸钠溶液的顺序在搅拌下依次加入反应釜并搅拌10-30min；然后通过滴加NaOH溶液调至溶液pH＝10-13，缓慢加入预计水滑石质量0.1-2％的聚乙二醇1000配置的水溶液，继续搅拌10-30min得到反应液；1) weighing a certain mass of magnesium salt, sodium aluminate, and sodium carbonate to prepare a solution, wherein the molar ratio of n (magnesium salt): n (sodium aluminate): n (sodium carbonate) is 2-3:1:0.5; adding the magnesium salt solution, sodium aluminate solution, and sodium carbonate solution to a reaction kettle in the order of stirring at room temperature and stirring for 10-30 minutes; then adding a NaOH solution dropwise to adjust the solution pH to 10-13, slowly adding an aqueous solution prepared with polyethylene glycol 1000 in an amount of 0.1-2% of the estimated weight of the hydrotalcite, and continuing stirring for 10-30 minutes to obtain a reaction solution;
2)然后在水热反应釜110-160℃条件下反应2-16h；2) then reacting in a hydrothermal reactor at 110-160°C for 2-16h;
3)将产物转移入另一个反应器中，加入1-3倍的水稀释，然后加热到60-90℃，加入预计水滑石质量0.5％的十二烷基硫酸钠水溶液，搅拌10min，再加入预计水滑石质量3-5％的硬脂酸铈，再搅拌10min；3) The product is transferred into another reactor, diluted with 1-3 times of water, then heated to 60-90° C., an aqueous sodium dodecyl sulfate solution of 0.5% of the expected hydrotalcite mass is added, stirred for 10 min, and then cerium stearate of 3-5% of the expected hydrotalcite mass is added, and stirred for another 10 min;
4)缓慢滴加硫酸铝溶液反应1-2h，将产物调节pH值至7-8之间；4) Slowly add aluminum sulfate solution and react for 1-2 hours to adjust the pH value of the product to between 7 and 8;
5)产物经压滤、洗涤、70-120℃烘干、粉碎，得到易分散型水滑石基复合材料产品。5) The product is filtered, washed, dried at 70-120° C., and crushed to obtain an easily dispersible hydrotalcite-based composite material product.
作为优选，所述的易分散型水滑石基复合材料的制备方法，所述的镁盐为氯化镁、硝酸镁、硫酸镁的一种或多种。Preferably, in the method for preparing the easily dispersible hydrotalcite-based composite material, the magnesium salt is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate.
本发明合成的有机改性镁铝水滑石为主体的复合材料，用于PVC热稳定剂，具有热稳定性好、易分散等优点，并具有生产工艺绿色环保、制备方法简单、生产成本低、便于产业化等优点。The composite material with organic modified magnesium aluminum hydrotalcite as the main body synthesized by the invention is used as a PVC heat stabilizer and has the advantages of good thermal stability and easy dispersion, and also has the advantages of green and environmentally friendly production process, simple preparation method, low production cost, and easy industrialization.
下面通过具体的实验对本发明作进一步的说明：The present invention will be further described below through specific experiments:
实施例1：称取无水MgCl
2 3.320Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝12.5，滴加0.03Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，90℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.20Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约1h，产物经压滤，洗涤，90℃烘干，粉碎，得到易分散型水滑石基复合材料产品1。
Example 1: Weigh 3.320 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 12.5, drop 0.03Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 140°C for 8h; pour the hydrotalcite solution in the reactor into another reactor at a three-fold dilution, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 90°C, stir for 10min, then add 0.20Kg of cerium stearate, stir for another 10min, adjust pH = 7.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 1h, the product is filtered, washed, dried at 90°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 1.
实施例2：称取无水MgCl
2 3.73Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝13.0，滴加0.05Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，85℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.20Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝8.00，滴加时间约1h，产物经压滤，洗涤，70℃烘干，粉碎，得到易分散型水滑石基复合材料产品2。
Example 2: Weigh 3.73 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 13.0, drop 0.05Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 140°C for 8h; pour the hydrotalcite solution in the reactor into another reactor with a three-fold dilution, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 85°C, stir for 10min, then add 0.20Kg of cerium stearate, stir for another 10min, adjust pH = 8.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 1h, the product is filtered, washed, dried at 70°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 2.
实施例3：称取无水MgCl
2 4.140Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝13.0，滴加0.08Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜130℃条件下反应6h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，85℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.20Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约2h，产物经压滤，洗涤，110℃烘干，粉碎，得到易分散型水滑石基复合材料产品3。
Example 3: Weigh 4.140 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 13.0, drop 0.08Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 130°C for 6 hours; pour the hydrotalcite solution in the three-fold diluted reactor into another reactor, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 85°C, stir for 10 minutes, then add 0.20Kg of cerium stearate, stir for another 10 minutes, adjust pH = 7.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 2 hours, the product is filtered, washed, dried at 110°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 3.
实施例4：称取无水MgCl
2 4.559Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝13.0，滴加0.05Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，85℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.20Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约1h，产物经压滤，洗涤，70℃烘干，粉碎，得到易分散型水滑石基复合材料产品4。
Example 4: Weigh 4.559 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 13.0, drop 0.05Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 140°C for 8h; pour the hydrotalcite solution in the three-fold diluted reactor into another reactor, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 85°C, stir for 10min, then add 0.20Kg of cerium stearate, stir for another 10min, adjust pH = 7.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 1h, the product is filtered, washed, dried at 70°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 4.
实施例5：称取无水MgCl
2 4.559Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝11.5， 滴加0.05Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，85℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.15Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约1h，产物经压滤，洗涤，90℃烘干，粉碎，得到易分散型水滑石基复合材料产品5。
Example 5: Weigh 4.559 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL of NaOH solution and 0.12 g/mL of Al 2 (SO 4 ) 3 ·18H 2 O solution; at room temperature, pour solution A into a reactor and start a stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor and stir for 10 min to obtain a mixed solution; adjust the pH to 11.5 by dropping NaOH solution, 0.05 kg of an aqueous solution prepared with polyethylene glycol 1000 was added dropwise, and the mixture was stirred for 10 min to obtain a hydrotalcite precursor solution; the mixture was then reacted in a hydrothermal reactor at 140° C. for 8 h; the hydrotalcite solution in the reactor was diluted three times and poured into another reactor, and 0.025 kg of an aqueous solution prepared with sodium dodecyl sulfate was added at 85° C., and the mixture was stirred for 10 min. Then 0.15 kg of cerium stearate was added and the mixture was stirred for another 10 min. The pH value was adjusted to 7.00 by adding Al 2 (SO 4 ) 3 ·18H 2 O solution, and the addition time was about 1 h. The product was filtered, washed, dried at 90° C., and crushed to obtain an easily dispersible hydrotalcite-based composite material product 5.
实施例6：称取无水MgCl
2 4.559Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝10.5，滴加0.05Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，90℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.25Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约1h，产物经压滤，洗涤，90℃烘干，粉碎，得到易分散型水滑石基复合材料产品6。
Example 6: Weigh 4.559 kg of anhydrous MgCl 2 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 10.5, drop 0.05Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 140°C for 8h; pour the hydrotalcite solution in the three-fold diluted reactor into another reactor, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 90°C, stir for 10min, then add 0.25Kg of cerium stearate, stir for another 10min, adjust pH = 7.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 1h, the product is filtered, washed, dried at 90°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 6.
实施例7：称取无水MgSO
4 5.758Kg加20L水配成溶液A，称取NaAlO
2 1.431Kg加15L水配成溶液B，称取无水Na
2CO
3 0.925Kg加15L水配成溶液C；配置NaOH溶液0.2g/mL,配置Al
2(SO
4)
3·18H
2O溶液0.12g/mL；室温条件下，将溶液A倒入反应釜中，并开启搅拌器搅拌，将溶液B缓慢滴加入反应釜，再将C溶液缓慢滴加入反应釜，并搅拌10min，得到混合溶液；通过滴加NaOH溶液，调至pH＝13.0，滴加0.05Kg聚乙二醇1000配置的水溶液，搅拌10min得到水滑石前驱体溶液；然后在水热反应釜140℃条件下反应8h；三倍稀释反应釜中的水滑石溶液倒入另一个反应器中，90℃条件下，加入0.025Kg十二烷基硫酸钠配置的水溶液，搅拌10min，再加入0.25Kg硬脂酸铈，再搅拌10min，通过Al
2(SO
4)
3·18H
2O溶液调节pH＝7.00，滴加时间约1h，产物经压滤，洗涤，90℃烘干，粉碎，得到易分散型水滑石基 复合材料产品7。
Example 7: Weigh 5.758 kg of anhydrous MgSO 4 and add it to 20 L of water to prepare solution A, weigh 1.431 kg of NaAlO 2 and add it to 15 L of water to prepare solution B, weigh 0.925 kg of anhydrous Na 2 CO 3 and add it to 15 L of water to prepare solution C; prepare 0.2 g/mL NaOH solution, prepare Al 2 (SO 4 ) 3 ·18H 2 O solution 0.12g/mL; under room temperature, pour solution A into the reactor and start the stirrer to stir, slowly drop solution B into the reactor, then slowly drop solution C into the reactor, and stir for 10 minutes to obtain a mixed solution; by dropping NaOH solution, adjust to pH = 13.0, drop 0.05Kg of aqueous solution prepared by polyethylene glycol 1000, stir for 10 minutes to obtain a hydrotalcite precursor solution; then react in a hydrothermal reactor at 140°C for 8h; pour the hydrotalcite solution in the three-fold diluted reactor into another reactor, add 0.025Kg of aqueous solution prepared by sodium dodecyl sulfate at 90°C, stir for 10min, then add 0.25Kg of cerium stearate, stir for another 10min, adjust pH = 7.00 by Al2 ( SO4 ) 3 · 18H2O solution, the dropping time is about 1h, the product is filtered, washed, dried at 90°C, and crushed to obtain an easily dispersible hydrotalcite-based composite material product 7.
检测实验1：用此工艺生产的Mg-Al水滑石基复合材料与PVC混合后，用刚果红法进行耐热性测试，5g纯PVC+0.2gMg-Al水滑石，200℃条件下测试，与纯PVC耐热性测试结果对比见表1。Test experiment 1: After the Mg-Al hydrotalcite-based composite material produced by this process was mixed with PVC, the heat resistance was tested using the Congo red method. 5g pure PVC + 0.2g Mg-Al hydrotalcite was tested at 200°C. The comparison of the heat resistance test results with pure PVC is shown in Table 1.
检测实验2：为测试合成的水滑石基复合材料的分散性，称取产品0.01g加入10mL丙酮中，超声5min，在紫外-可见分光度计下，测试350nm处吸光度，对比悬浮液的吸光度。测试结果见表1，吸光度越高说明其分散性越好。Test experiment 2: To test the dispersibility of the synthesized hydrotalcite-based composite material, 0.01 g of the product was weighed and added to 10 mL of acetone, ultrasonicated for 5 min, and the absorbance at 350 nm was tested under a UV-visible spectrophotometer to compare the absorbance of the suspension. The test results are shown in Table 1. The higher the absorbance, the better the dispersibility.
表1水滑石基复合材料耐热和分散性指标测试结果Table 1 Test results of heat resistance and dispersibility of hydrotalcite-based composite materials
从以上比较结果显示，经过Mg-Al水滑石物理混合后，耐热时间大大提升。纯PVC耐热时间为3.42分钟，而加了0.2g的Mg-Al水滑石后，耐热时间最高上升到了31.13min，耐热性显著提高；并且实施例2所制产品其分散性也是最好的(丙酮溶液350nm吸光度可达1.68)，略优于日本协和公司水滑石DHT-4A产品(耐热30.35min,分散性350nm吸光度为1.65)。The above comparison results show that after physical mixing with Mg-Al hydrotalcite, the heat resistance time is greatly improved. The heat resistance time of pure PVC is 3.42 minutes, and after adding 0.2g of Mg-Al hydrotalcite, the heat resistance time rises to 31.13min at most, and the heat resistance is significantly improved; and the product prepared in Example 2 has the best dispersibility (the absorbance of acetone solution at 350nm can reach 1.68), which is slightly better than the hydrotalcite DHT-4A product of Japan Kyowa Company (heat resistance 30.35min, dispersibility 350nm absorbance is 1.65).
Claims (4)
- 一种聚合物用易分散型水滑石基复合材料，其特征在于组成为镁铝水滑石：硬脂酸铈：氢氧化铝的质量比为1:0.03-0.05：0.02-0.08。A readily dispersible hydrotalcite-based composite material for polymers, characterized in that the mass ratio of magnesium aluminum hydrotalcite: cerium stearate: aluminum hydroxide is 1: 0.03-0.05: 0.02-0.08.
- 一种如权利要求1所述的聚合物用易分散型水滑石基复合材料，其特征在于制备方法包括以下步骤：An easily dispersible hydrotalcite-based composite material for polymers as claimed in claim 1, characterized in that the preparation method comprises the following steps:1)称取一定质量的镁盐、偏铝酸钠、碳酸钠配置成溶液，其中n(镁盐)：n(偏铝酸钠)：n(碳酸钠)的摩尔比为2-3:1:0.5；室温下，按镁盐溶液、偏铝酸钠溶液、碳酸钠溶液的顺序在搅拌下依次加入反应釜并搅拌10-30min；然后调至溶液pH＝10-13，缓慢加入聚乙二醇1000配置的水溶液，继续搅拌10-30min得到反应液；1) Weigh a certain amount of magnesium salt, sodium aluminate, and sodium carbonate to prepare a solution, wherein the molar ratio of n (magnesium salt): n (sodium aluminate): n (sodium carbonate) is 2-3:1:0.5; at room temperature, add the magnesium salt solution, sodium aluminate solution, and sodium carbonate solution into a reaction kettle in the order of stirring and stir for 10-30 minutes; then adjust the solution pH to 10-13, slowly add the aqueous solution prepared with polyethylene glycol 1000, and continue stirring for 10-30 minutes to obtain a reaction solution;2)然后在水热反应釜110-160℃条件下反应2-16h；2) then reacting in a hydrothermal reactor at 110-160°C for 2-16h;3)将产物转移入另一个反应器中，加水稀释，然后加热到60-90℃，加入十二烷基硫酸钠水溶液，搅拌，再加入硬脂酸铈，再搅拌；3) The product is transferred into another reactor, diluted with water, then heated to 60-90° C., an aqueous solution of sodium dodecyl sulfate is added, stirred, and then cerium stearate is added, and stirred again;4)缓慢滴加硫酸铝溶液反应1-2h，将产物调节pH值至7-8之间；4) Slowly add aluminum sulfate solution and react for 1-2 hours to adjust the pH value of the product to between 7 and 8;5)产物经压滤、洗涤、70-120℃烘干、粉碎，得到易分散型水滑石基复合材料产品。5) The product is filtered, washed, dried at 70-120° C., and crushed to obtain an easily dispersible hydrotalcite-based composite material product.
- 如权利要求2所述的聚合物用易分散型水滑石基复合材料，其特征在于制备方法包括以下步骤：The easily dispersible hydrotalcite-based composite material for polymers as claimed in claim 2, characterized in that the preparation method comprises the following steps:1)称取一定质量的镁盐、偏铝酸钠、碳酸钠配置成溶液，其中n(镁盐)：n(偏铝酸钠)：n(碳酸钠)的摩尔比为2-3:1:0.5；室温下，按镁盐溶液、偏铝酸钠溶液、碳酸钠溶液的顺序在搅拌下依次加入反应釜并搅拌10-30min；然后通过滴加NaOH溶液调至溶液pH＝10-13，缓慢加入水滑石质量0.1-2％的聚乙二醇1000配置的水溶液，继续搅拌10-30min得到反应液；1) Weigh a certain mass of magnesium salt, sodium aluminate, and sodium carbonate to prepare a solution, wherein the molar ratio of n (magnesium salt): n (sodium aluminate): n (sodium carbonate) is 2-3:1:0.5; at room temperature, add the magnesium salt solution, sodium aluminate solution, and sodium carbonate solution into a reaction kettle in the order of stirring and stir for 10-30 minutes; then dropwise add NaOH solution to adjust the solution pH to 10-13, slowly add an aqueous solution prepared with polyethylene glycol 1000 in an amount of 0.1-2% by weight of the hydrotalcite, and continue stirring for 10-30 minutes to obtain a reaction solution;2)然后在水热反应釜110-160℃条件下反应2-16h；2) then reacting in a hydrothermal reactor at 110-160°C for 2-16h;3)将产物转移入另一个反应器中，加入1-3倍的水稀释，然后加热到60-90℃，加入水滑石质量0.5％的十二烷基硫酸钠水溶液，搅拌10min，再加入预计水滑石质量3-5％的硬脂酸铈，再搅拌10min；3) The product is transferred into another reactor, diluted with 1-3 times of water, then heated to 60-90°C, an aqueous sodium dodecyl sulfate solution of 0.5% of the mass of the hydrotalcite is added, stirred for 10 minutes, and then cerium stearate of 3-5% of the expected mass of the hydrotalcite is added, and stirred for another 10 minutes;4)缓慢滴加硫酸铝溶液反应1-2h，将产物调节pH值至7-8之间；4) Slowly add aluminum sulfate solution and react for 1-2 hours to adjust the pH value of the product to between 7 and 8;5)产物经压滤、洗涤、70-120℃烘干、粉碎，得到易分散型水滑石基复合材料产品。5) The product is filtered, washed, dried at 70-120° C., and crushed to obtain an easily dispersible hydrotalcite-based composite material product.
- 如权利要求2所述的聚合物用易分散型水滑石基复合材料的制备方法，其特征在于所述的镁盐为氯化镁、硝酸镁、硫酸镁的一种或多种。The method for preparing the easily dispersible hydrotalcite-based composite material for polymers as claimed in claim 2, characterized in that the magnesium salt is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate.
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