CN1462777A - Parent material containing high organic montmorillonite, and its prepn. method - Google Patents
Parent material containing high organic montmorillonite, and its prepn. method Download PDFInfo
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- CN1462777A CN1462777A CN 03137638 CN03137638A CN1462777A CN 1462777 A CN1462777 A CN 1462777A CN 03137638 CN03137638 CN 03137638 CN 03137638 A CN03137638 A CN 03137638A CN 1462777 A CN1462777 A CN 1462777A
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- 229910017059 organic montmorillonite Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 title description 11
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 238000010008 shearing Methods 0.000 claims abstract description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 58
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 56
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 20
- 239000011229 interlayer Substances 0.000 claims description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 10
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 10
- 229920002292 Nylon 6 Polymers 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- -1 polypropylene Polymers 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 abstract 1
- 229920002674 hyaluronan Polymers 0.000 abstract 1
- 229960003160 hyaluronic acid Drugs 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 23
- 238000009830 intercalation Methods 0.000 description 17
- 230000002687 intercalation Effects 0.000 description 17
- 239000002131 composite material Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 150000002892 organic cations Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910001411 inorganic cation Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical class CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 description 1
- FWLORMQUOWCQPO-UHFFFAOYSA-N benzyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 FWLORMQUOWCQPO-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Abstract
A mother material with high content of organic montmorillonite for modifying polyvinyl chloride, polypropylene, or nylon 6 is prepared through proportionally mixing organic montmorillonite, epoxy oligomer and organic hyaluronic acid and shearing and pugging at 150-200 deg.C.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a montmorillonite modified master batch for modifying polyvinyl chloride, polyolefin and engineering plastics and a preparation method thereof.
Background Art 1 organized treatment of montmorillonite
Montmorillonite or bentonite and clay, and the theoretical structural formula isas follows: (1/2Ca, Na)x(Al2-x、Mgx)(Si4O10)(OH)nH2O, the unit cell of which is composed of two layers of silicon-oxygen tetrahedra sandwiching a layer of aluminum octahedra, is a 2: 1 layered phyllosilicate. The montmorillonite crystal plate has negative electricity, and a great amount of Na + and Ca can be adsorbed between layers2+，Mg2+Etc. to maintain the electrical neutrality of the crystal. These cations can be exchanged by other organic or inorganic cations. The cation exchange capacity of the montmorillonite is called as Cation Exchange Capacity (CEC), and the cation exchange capacity of the montmorillonite suitable for modifying the composite material is 70-130 mmol/100g of montmorillonite.
When a large amount of inorganic cations are attached between montmorillonite layers, the montmorillonite is remote from organic matters, the metal cations are exchanged by organic cations by utilizing the exchangeability of the metal cations between the montmorillonite layers to organize the montmorillonite, and the organized montmorillonite has good affinity with organic polymers or organic low-molecular compounds serving as intercalation agents, namely the organic compounds can be easily inserted between the layers of the organic montmorillonite.
Common organic cation exchange materials are long chain fatty alkane quaternary ammonium salts such as: dodecyl trimethyl ammonium salt; cetyl trimethylammonium salt; octadecyl dimethyl benzyl ammonium salt; dodecyl dimethyl benzyl ammonium salt; and some organic amines and amides.
The reaction formula of the organic process is as follows:
wherein R is: -H, -CH3X is: cl-, Br-, I-M is: na +, Ca2+，Mg2+ Mont is: and (4) montmorillonite.
The interlayer spacing of montmorillonite is increased after organic treatment. The interlayer spacing d001 can be increased to more than 1.5nm by X-ray diffraction (XDR) analysis.
Depending on the ion exchange capacity of the montmorillonite, different organic cations, and different treatment methods, the organic cations may be arranged in different ways between layers of the montmorillonite. There are three main types: single layer arrangement, double layer arrangement and oblique arrangement. 2. Intercalation of epoxy oligomer in organic montmorillonite
The intermiscibility of the epoxy oligomer and the organic montmorillonite is excellent, a uniform and stable semitransparent mixture can be obtained by adopting a direct mixing method and a solution mixing method, and XDR analysis proves that the epoxy oligomer molecules are inserted between montmorillonite layers. After the organic montmorillonite is intercalated by the epoxy oligomer, the interlayer spacing is related to the chain length of the epoxy oligomer among montmorillonite layers, and is basically unrelated to the original interlayer spacing of the organic montmorillonite. The organic cations are arranged in different arrangement modes among the montmorillonite layers, so that different interlayer spacings exist, after epoxy intercalation, the affinity between epoxy molecules and organic amine is good, and the epoxy oligomers and the organic cations are arranged in an upright mode among the montmorillonite layers. 3. Dispersion of organic montmorillonite in organic polymer
The full stripping of the organic montmorillonite in the polymer is a key technology for realizing the modification of the composite material. One is an in-situ intercalation polymerization technology which can obtain a peeling-off type composite material, and the other is a melting intercalation technology which can only obtain an intercalation type composite material generally.
The in-situ intercalation polymer means that polymer precursor small molecules are firstly intercalated between montmorillonite layers, the small molecules are polymerized between the montmorillonite layers, and the intercalation action of the polymerized small molecules in the montmorillonite is attributed to the diffusivity of the small molecules and the affinity of organized space of the montmorillonite. In-situ polymerization releases a large amount of heat during polymerization, so that montmorillonite expands to obtain the peel-off composite material.
The patent publication of the Chinese academy of sciences is: CN1289786A, an in-situ intercalation polymerization preparation method of nano montmorillonite filled polyolefin, discloses a method for preparing nano montmorillonite directly filled polyolefin by in-situ intercalation polymerization. The method inserts ethylene oligomerization, dimerization or polymerization catalyst into the montmorillonite layers, and adds proper cocatalyst to make ethylene continuously adsorbed in the montmorillonite layers at 30-80 ℃ within 0.1-2 hours, and simultaneously polymerize to form the polyolefin/montmorillonite composite material. The method selects H-montmorillonite, has long polymerization reaction time, needs washing and drying after reaction, is generally used for polyolefin modification, such as processing into master batch, and has low content of montmorillonite.
The patent publication No. CN1374346A discloses a method for preparing nano montmorillonite composite, which adopts an anion intercalation composite polymerization method that caprolactam monomer is inserted into montmorillonite to prepare nylon/montmorillonite composite material in a double screw reaction extruder.
The molten intercalation polymer means that the macromolecular chain of the molten organic high molecular polymer is inserted between the layers of the organic montmorillonite under the action of high temperature and high shearing force, and generally only the intercalation composite material can be obtained. XRD analysis shows that the interlayer spacing of the molten intercalated composite material is 2.5-3.5, so that the completely stripped montmorillonite composite material is difficult to obtain. 4. Limitations of the prior art
The in-situ intercalation polymerization technology can obtain the high-performance exfoliated montmorillonite composite material, but has higher technical requirements on the organic intercalating agent and the montmorillonite, and has large industrial investment, long period and difficult popularization and application. The melt intercalation can be carried out in common plastic mixing equipment, the processing is convenient, but the organic intercalation agent is easy to decompose and discolor under the action of high temperature, high pressure and high shearing force, the thermal decomposition of the polyvinyl chloride is aggravated particularly in the processing process of the polyvinyl chloride, and the montmorillonite composite material which is completely stripped is not easy to obtain, thereby restricting the application of the montmorillonite in a plurality of organic polymer materials.
Disclosure of Invention
The invention provides a master batch with high content of organic montmorillonite, which has the advantages of simple processing, low cost and wide application range.
The invention utilizes the characteristic that epoxy oligomer has excellent intermiscibility with organic montmorillonite and can be directly inserted into the organic montmorillonite layers under the mixing conditions of high temperature and high shearing force to produce the master batch with high organic montmorillonite content.
H of organic protonic acid released therefrom+Can react with the epoxy oligomer and further react with organic cations among the organic montmorillonite layers, and can reduce the mixing temperature of the epoxy oligomer and the organic montmorillonite.
The master batch with high organic montmorillonite content comprises the following components: (in weight percent)
Organic montmorillonite: 50 to 75 percent
Epoxy oligomer: 20 to 50 percent
Organic protonic acid: 0 to 5 percent
The organic montmorillonite is subjected to intercalation treatment of alkyl organic quaternary ammonium salt with cation exchange capacity of 70-130 mmol/100g, and the interlayer spacing is larger than 1.5 nm.
The epoxy oligomer is as follows: one of bisphenol a epoxy resin, novolac epoxy resin, brominated bisphenol a epoxy resin, acrylic bisphenol a epoxy resin, and methacrylic bisphenol a epoxy resin.
The organic protonic acid is acrylic acid or methacrylic acid.
The processing method of the master batch comprises the following steps: weighing organic nano montmorillonite, epoxy oligomer and organic protonic acid according to a certain proportion, uniformly mixing, shearing and mixing at the temperature of 150-200 ℃ to obtain a powdery master batch.
The masterbatch with high content of organic montmorillonite has montmorillonite content of more than 50 percent and montmorillonite interlamellar spacing of more than 3.5 nm. The montmorillonite modified masterbatch can be used as modified masterbatch of general plastics such as polyvinyl chloride and polypropylene and engineering plastics such as nylon 6, and can be addedinto common mixing equipment in common plastic processing enterprises to prepare high-performance exfoliated montmorillonite composite materials. Tests show that the modification material added with the master batch has no 001 diffraction peak within 1-15 degrees of 2 theta angle through XRD tests, which shows that montmorillonite is completely peeled off in a high polymer material, and the heat resistance, tensile strength, impact strength, barrier property and flame retardance of the modification material are obviously improved.
Drawings
FIG. 1 is an XRD pattern of the masterbatch of the invention having an organo montmorillonite content of 75%.
Figure 2 is an XRD pattern of a rigid PVC modified blend with 8% master batch of the present invention added.
Figure 3 is an XRD pattern of a PP modified blend with 15% addition of masterbatch of the invention.
FIG. 4 is an XRD diagram of a nylon 6/ABS alloy resin modified blend material added with 8% of the master batch of the invention.
Detailed description example 1:
75 parts of organic montmorillonite; 20 parts of bisphenol A epoxy resin with an epoxy value of 0.4-0.5; 5 parts of acrylic acid are uniformly mixed, added into a double-roller mixing roll with the surface temperature of 150 ℃ and mixed for 5-20 minutes to obtain a powdery product, and the interlayer spacing of the montmorillonite is larger than 3.5nm through XRD analysis.
Example 2:
55 parts of organic montmorillonite and 45 parts of bisphenol A epoxy resin with the epoxy value of 0.18-0.22; adding 5 parts of a mixture of methacrylic acid into a double-screwmixing extruder, setting the temperature of a charging barrel to be 180-200 ℃, extruding the mixture by the double-screw extruder to obtain a powdery substance, and analyzing the interlayer spacing of montmorillonite to be more than 3.5nm by XRD diffraction.
Example 3
75 parts of organic montmorillonite; 25 parts of acrylic bisphenol A epoxy resin; and (3) uniformly mixing, adding the mixture into a double-roller mixing mill with the surface temperature of 160 ℃, mixing for 5-20 minutes to obtain a powdery product, and analyzing by XRD (X-ray diffraction) to ensure that the interlayer spacing of the montmorillonite is more than 3.5 nm.
Example 4:
75 parts of organic montmorillonite; 25 parts of bisphenol A methacrylate epoxy resin; and (3) uniformly mixing, adding the mixture into a double-roller mixing mill with the surface temperature of 160 ℃, mixing for 5-20 minutes to obtain a powdery product, and analyzing by XRD (X-ray diffraction) to ensure that the interlayer spacing of the montmorillonite is more than 3.5 nm.
Example 5:
50 parts of organic montmorillonite and 40 parts of novolac epoxy resin with the epoxy value of 0.4-0.5; adding 5 parts of acrylic acid mixture into a double-screw mixing extruder, setting the temperature of a charging barrel to be 180-200 ℃, mixing and extruding by using double screws to obtain a powdery substance, and analyzing the interlayer spacing of montmorillonite to be more than 3.5nm by XRD diffraction. Example 6:
50 parts of organic montmorillonite; 47 parts of brominated bisphenol A epoxy resin with the epoxy value of 0.16-0.19 and the bromine content of 21-23%; 3 parts of acrylic acid are uniformly mixed, then the mixture is added into a double-screw mixing extruder, the temperature of a charging barrel is set tobe 180-200 ℃, a powdery substance is obtained after double-screw mixing extrusion, and the interlayer spacing of montmorillonite is larger than 3.5nm through XRD diffraction analysis.
Application example 1
8 parts of the master batch with high content of organic montmorillonite in example 1 is added into 100 parts of rigid PVC premix, the mixture is mixed for 8 minutes on a two-roll mill at 170 ℃, the PVC sheet does not have color change, and the mixture is mixed for 8 minutes, and a tab is pulled as shown in figure 2. the XRD test shows that the 2 theta angle does not have 001 diffraction peak within 1-15 degrees, which indicates that the montmorillonite is completely stripped in the rigid PVC. And directly adding untreated organic montmorillonite, mixing under the same condition, and yellowing PVC sheet.
Application example 2
15 parts of the master batch with high content of organic montmorillonite in example 2 is added into 100 parts of PP material containing PP-g-MAH 5%, and extruded and granulated by a double screw extruder, the granules have no color change, and the granules are sampled by tabletting, and tested by XRD, as shown in figure 3, the diffraction peak of 001 does not appear in 2 theta angle of 1-15 degrees, which indicates that the montmorillonite is completely stripped. And the addition of untreated organic montmorillonite turns yellow under the same conditions.
Application example 3
8 parts of the master batch with high organic montmorillonite content in the example 3 is added into 100 parts of nylon 6 resin, and extruded and granulated by a double-screw extruder, the granules have no color change, and the tabletting is proved to be completely stripped by XRD test.
Application example 4
8 parts of the master batch with high organic montmorillonite content in the example 4 is added into 100 parts of nylon 6/ABS alloy resin, the mixture is extruded and granulated by a double-screw extruder, the granules have no color change, and the tabletting is tested by XRD (X-ray diffraction), as shown in figure 4, the montmorillonite is completely stripped.
Application example 5
8 parts of the master batch with high organic montmorillonite content in the example 1 is added into 100 parts of nylon 6/PP alloy resin, and extruded and granulated by a double-screw extruder, the granules have no color change, and the tabletting is proved by XRD test that the montmorillonite is completely stripped.
Claims (8)
1. A master batch with high content of organic montmorillonite is characterized in that: epoxy oligomer is inserted between the layers of the organic montmorillonite through mixing to form a master batch.
2. The master batch with high content of organic montmorillonite as claimed in claim 1, which is characterized in that: organic protonic acid is also added during the mixing of the master batch.
3. The master batch with high content of organic montmorillonite as claimed in claim 1, which is characterized in that: the master batch comprises the following components in percentage by weight: 50-75% of organic montmorillonite and 20-50% of epoxy oligomer.
4. The master batch with high content of organic montmorillonite as claimed in claim 2, which is characterized in that: the master batch comprises the following components in percentage by weight: 50-75% of organic montmorillonite, 20-50% of epoxy oligomer and 0-5% of organic protonic acid.
5. The master batch with high content of organic montmorillonite as claimed in claim 1, which is characterized in that: the organic montmorillonite is treated by organic quaternary ammonium salt, the cation exchange capacity is 70-130 mmol/100g, and the interlayer spacing is more than 1.5 nm.
6. The master batch with high content of organic montmorillonite as claimed in claim 1, which is characterized in that: the epoxy oligomer is as follows: one of bisphenol a epoxy resin, novolac epoxy resin, brominated bisphenol a epoxy resin, acrylic bisphenol a epoxy resin, and methacrylic bisphenol a epoxy resin.
7. The master batch with high content of organic montmorillonite as claimed in claim 1, which is characterized in that: the organic protonic acid is acrylic acid or methacrylic acid.
8. A preparation method of a master batch with high content of organic montmorillonite comprises the following steps: weighing organic nano montmorillonite, epoxy oligomer and organic protonic acid according to a certain proportion, uniformly mixing, shearing and mixing at the temperature of 150-200 ℃ to obtain a powdery master batch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137638 CN1212347C (en) | 2003-06-09 | 2003-06-09 | Parent material containing high organic montmorillonite, and its prepn. method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137638 CN1212347C (en) | 2003-06-09 | 2003-06-09 | Parent material containing high organic montmorillonite, and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
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| CN1462777A true CN1462777A (en) | 2003-12-24 |
| CN1212347C CN1212347C (en) | 2005-07-27 |
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| CN102061061A (en) * | 2010-12-17 | 2011-05-18 | 无锡阿科力化工有限公司 | Preparation method of exfoliated montmorillonite-epoxy resin composite |
| CN101735604B (en) * | 2009-12-25 | 2012-05-23 | 杭州鸿雁电器有限公司 | Montmorillonoid modified Pa6/ABS alloy material and preparation method thereof |
| CN102993564A (en) * | 2012-11-29 | 2013-03-27 | 浙江吉利汽车研究院有限公司杭州分公司 | Flame retardant material and preparation method thereof and automobile engine trim cover |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN111807808A (en) * | 2020-08-11 | 2020-10-23 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant heat-insulation composite material |
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2003
- 2003-06-09 CN CN 03137638 patent/CN1212347C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735604B (en) * | 2009-12-25 | 2012-05-23 | 杭州鸿雁电器有限公司 | Montmorillonoid modified Pa6/ABS alloy material and preparation method thereof |
| CN102061061A (en) * | 2010-12-17 | 2011-05-18 | 无锡阿科力化工有限公司 | Preparation method of exfoliated montmorillonite-epoxy resin composite |
| CN102061061B (en) * | 2010-12-17 | 2012-02-22 | 无锡阿科力化工有限公司 | Preparation method of exfoliated montmorillonite-epoxy resin composite |
| CN102993564A (en) * | 2012-11-29 | 2013-03-27 | 浙江吉利汽车研究院有限公司杭州分公司 | Flame retardant material and preparation method thereof and automobile engine trim cover |
| CN102993564B (en) * | 2012-11-29 | 2014-10-15 | 浙江吉利汽车研究院有限公司杭州分公司 | Flame retardant material and preparation method thereof and automobile engine trim cover |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
| CN111807808A (en) * | 2020-08-11 | 2020-10-23 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant heat-insulation composite material |
| CN111807808B (en) * | 2020-08-11 | 2022-04-22 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant heat-insulation composite material |
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