CN101845241B - Preparation method of exfoliated hydrotalcite and application thereof - Google Patents
Preparation method of exfoliated hydrotalcite and application thereof Download PDFInfo
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- CN101845241B CN101845241B CN 200910312944 CN200910312944A CN101845241B CN 101845241 B CN101845241 B CN 101845241B CN 200910312944 CN200910312944 CN 200910312944 CN 200910312944 A CN200910312944 A CN 200910312944A CN 101845241 B CN101845241 B CN 101845241B
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Abstract
The invention discloses a preparation method of an exfoliated hydrotalcite and the application thereof; hydrotalcite LDH-CO3 with an interlayer anion as CO32- serves as the prosoma; the intercalated exfoliated hydrotalcite is prepared through an ultrasonic technology for the first time, and the preparation method has the advantages of simple process, low cost, easy preparation and mild reaction conditions. On the other hand, the hydrotalcite with the interlayer anion as C032- is pre-treated and is mixed with ethylene acrylic acid random copolymer, extruded in a screw extruder to obtain the melting exfoliated hydrotalcite; and the surface of an obtained exfoliated hydrotalcite layer contains an ethylene acrylic acid random copolymer chain segment, so that the compatibility with polyolefin is greatly improved. These two types of exfoliated hydrotalcite are quite good flame retardant and enhancer, and significantly improve the mechanical performance of polymer. Compared with the prior art, the invention fully exfoliates the hydrotalcite.
Description
Technical field
The present invention relates to the hydrotalcite technical field, particularly relate to a kind of preparation method and application thereof of exfoliated hydrotalcite.
Background technology
Hydrotalcite has another name called layered double hydroxide (Layered Double Hydroxides, LDH), has laminate structure, and its basic structure layer is by M
2+-OH, M
3+-OH is octahedra to be formed, and forms positively charged laminate, has filled anion layer and water molecules between structural sheet, the anionic clay that therefore is otherwise known as, and its lamellar crystalline texture has good filling enhancement to plastic material.Modal hydrotalcite is Mg-Al composite oxyhydroxide, and its representative chemical structural formula is: [MgAl (OH)
8]
2CO
3H
2O.When hydrotalcite is heated to 190～250 ℃, for the first time thermolysis occurs, crystal water discharges with the water vapour form and takes away amount of heat, and generally about 210 ℃, rate of weight loss is 12～15% for the peak temperature of this reaction, and the heat absorption value reaches as high as more than the 410J/g.Because electric density is large between the LDH laminate, interfloor distance is little, and polyolefine polarity is little, is difficult to so that LDH peels off in polyolefin substrate with general method.So, have not yet to see any patent and LDH can be peeled off and be dispersed in the polyolefin substrate.
Document Arira Ookubo, kenta Ooi and Hiromu Hayashi.Langmuir, 1993,9.1418-1422 and A.Legrouri, M.Barroug, A.De Roy, and J.P.Besse.Journal of MaterialsScience Letters, 1999,18,1077-1079 all adopts ion exchange method, under alkaline condition, respectively with Mg-Al-Cl LDHs, Zn-Al-NO
3LDHs is presoma, and the preparation interlayer anion is the intercalated houghite (LDHs) of phosphoric acid one hydrogen root.Front a kind of preparation method's weak point is: intercalation presoma Mg-Al-Cl hydrotalcite and intercalation Mg-Al-HPO
4The preparation condition of hydrotalcite is harsh, needs to regulate pH value, and for a long time reaction under the low temperature, and can not get exfoliated hydrotalcite; The weak point of rear a kind of method is: protect complicated operation with N2, and pH value easy-regulating not, intercalation product regularity is relatively poor.
A kind of preparation method of phosphate pillared ht is disclosed in publication number CN 1475535A.This method is to utilize the preparation of ion-exchange graft process, and its interlayer anion mainly is to exist with the phosphate radical dihydro-form.But the phosphate radical of its interlayer two hydride ions mainly are the forms with physical adsorption and electrostatic force is present in the hydrotalcite sheets interlayer, do not form stable chemical bond, so migration out easily, the flame retardant effect that does not reach, and hydrotalcite is not peeled off fully, can not bring into play the superior nano effect of hydrotalcite nanoscale twins.
A kind of preparation method of inorganic combustion inhibitor of polyphosphoric acid radical column supported hydrotalcite is disclosed in publication number CN101284994A.This method is to utilize the two-step approach preparation, and process is more loaded down with trivial details.Same polyphosphoric acid radical ion just is present in the hydrotalcite sheets interlayer with the form of physical adsorption and electrostatic force, and the polymerization degree of the ammonium polyphosphate that wherein adopts is lower, and the polymerization degree only reaches about 20.Same hydrotalcite is not peeled off, and can not bring into play the superior nano effect of hydrotalcite nanoscale twins, and the hydrotalcite surface is bad with polyolefinic consistency not through processing.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that existing hydrotalcite can not be peeled off fully, a kind of preparation method and application thereof of exfoliated hydrotalcite are provided, this exfoliated hydrotalcite can be in polyolefine well disperses, improve its flame retardant properties and with polyolefinic consistency.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
The preparation method of exfoliated hydrotalcite provided by the invention: take interlayer anion as CO
3 2-Hydrotalcite LDH-CO
3Make precursor, mix with the ethylene acrylic random copolymers after pretreatment, in screw extrusion press, extrude to get the melting exfoliated hydrotalcite.
In above-mentioned preparation method, each preferred parameter is: pretreated hydrotalcite LDH-CO
3With the weight ratio of ethylene acrylic random copolymers be 1: 2～3.When extruding in screw extrusion press, screw speed is 60～120rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃ and 200 ℃.
Among the aforementioned preparation method, wherein a kind of pretreatment process of hydrotalcite is: described pre-treatment is with hydrotalcite LDH-CO
3Processed 6～10 hours at 80～200 ℃.The hydrotalcite of processing with this pretreatment process and the hydrotalcite of ethylene acrylic random copolymers extrusion reaction gained are the melting exfoliated hydrotalcite, but it is to utilize hydrotalcite to have the performances such as intercalation assembling, memory reduction, and the highly active hydroxyl in hydrotalcite surface can prepare the exfoliated hydrotalcite material at hydrotalcite melt surface grafted ethene vinylformic acid random copolymers with carboxyl generation esterification.
The present invention also provides another pretreatment process of hydrotalcite: with hydrotalcite LDH-CO
3Processed 6～10 hours at 200 ℃～500 ℃; Then add in the acid ammonium polyphosphate hot solution, reacted under ultrasonic environment 10～30 minutes, then stirring reaction 3～5 days under 60 ℃～70 ℃ conditions filters, and grinds after dry.
The preferred parameter of the second hydrotalcite pretreatment process is: the mass percentage concentration of described acid ammonium polyphosphate solution is that 1～10%, pH value is 4.8～5.2, is heated to 80 ℃～90 ℃.Stirring reaction filtered with semi-permeable membranes after 3～5 days under 60 ℃～70 ℃ conditions, and to the filtrate water white transparency, filter residue descended dry 12～24 hours at 60～80 ℃, ground with 80～100 ℃ deionized water wash.The present invention is applied to ultrasonic technology the intercalation field first, and hyperacoustic sonochemical effect is so that contain ammonium polyphosphate and the aqueous solution of hydrotalcite can reach the high temperature, 10 of about 5000K in the part
8The high pressure of Pa and 10
9The rate of temperature change of K/s, and follow strong shockwave and the speed per hour of 400Km, ultrasonic technology realizes that under general condition being difficult to the chemical reaction that maybe can not realize provides a kind of new very special physicochemical environment.
The hydrotalcite that the hydrotalcite that obtains with the second pretreatment process and ethylene acrylic random copolymers extrusion reaction obtain is the functionalization exfoliated hydrotalcite.The method is to keep under the condition of former laminate structure at hydrotalcite, with the H of powerful hot-fluid with hydrotalcite layers
2O and CO
3 2-Evaporate, when these materials evaporate, strutted the interfloor distance of hydrotalcite, and improved the specific surface energy area of hydrotalcite, can promote carrying out smoothly of next step intercalation.When the intercalation ammonium polyphosphate reacts, utilize ultrasonic technology, promote carrying out smoothly of intercalation, this special Local physical chemical environment of ultrasonic wave is so that ammonium polyphosphate is easier enters hydrotalcite layers and be grafted on the hydrotalcite lamella, on the other hand, hyperacoustic effect so that around the hydrotalcite lamella fragile part be subject to destruction, thereby so that hydrotalcite particles has obtained refinement.Intercalation the hydrotalcite of ammonium polyphosphate in the process of extruding with the ethylene acrylic random copolymers, because also exist hydroxyl on the hydrotalcite surface behind the intercalation, and with the ammonium polyphosphate macromolecular chain, so that the degree of peeling off of hydrotalcite is larger.
The application in polyolefine as fire retardant and toughener of aforementioned exfoliated hydrotalcite.The hydrotalcite of aforesaid method preparation is owing to obtained peeling off fully, itself and polyolefinic consistency have been improved, can well be dispersed in the polyolefine, improve polyolefinic mechanical strength and flame retardant properties, and also played to a certain extent the cigarette effect that presses down, solved common expansibility flame-proof agent in the large situation of its addition, the problem that composite materials property is poor.
In the technique scheme, in the process of extruding with screw extrusion press, high viscosity, highly active ethylene acrylic random copolymers (EAA) carry out fusion-grafting with hydrotalcite on the one hand, the also intercalation laminated structure that enters hydrotalcite of the long molecular chain of EAA on the other hand is so that hydrotalcite is peeled off fully.Through the FT-IR characteristic group characterize, the checking of XRD interfloor distance, two kinds of hydrotalcites have all successfully obtained peeling off, and on the functionalization exfoliated hydrotalcite laminated structure successful grafting ammonium polyphosphate and ethylene acrylic random copolymers.
Compared with prior art, the present invention has carried out peeling off fully to hydrotalcite, and having carried out the grafted functional group at the hydrotalcite of peeling off first processes, and utilize first ultrasonic technology successfully to prepare the intercalation exfoliated hydrotalcite, preparation method's technique is simple, cost is low, easy to operate, reaction conditions is gentle.The exfoliated hydrotalcite sheet surfaces of gained contains ethylene acrylic random copolymers segment, so that itself and polyolefinic consistency increase substantially, is a kind of preferably fire retardant and toughener, and more remarkable to the raising of mechanical properties of polymer.
Description of drawings
Fig. 1 is the SEM figure of various hydrotalcites; Wherein (1) is the SEM photo of raw material LDH; The SEM photo of LDH after dry 6 hours under (2) 400 ℃ of conditions; (3) the SEM photo of example 2 intercal type LDH; (4) the SEM photo of example 1 exfoliated LDH.
Fig. 2 is the EDS data plot; Wherein (1) is raw material LDH, and (2) are the intercal type LDH of example 2, and (3) are the exfoliated LDH of example 1.
Fig. 3 .1 is the XRD figure of various hydrotalcites; Wherein, a is the functionalization exfoliated hydrotalcite of embodiment 1 gained, and b is the intercalated houghite of embodiment 2 gained, and c is the hydrotalcites of 400 ℃ of thermal treatments after 6 hours, and d is the raw water talcum.
Fig. 3 .2 is the XRD figure of various fusion hydrotalcites; Wherein (a) is embodiment 4 products, (b) is embodiment 5 products, (c) is embodiment 6 products.
Fig. 4 .1 is the FT-IR figure of various hydrotalcites; Wherein, wherein a is the exfoliated hydrotalcite of embodiment 1 gained, and b is the intercalated houghite of embodiment 2 gained, and c is the raw water talcum, and d is ammonium polyphosphate.
Fig. 4 .2 is the FT-IR figure of various melting hydrotalcites; Wherein: a is unmodified LDH, and b is embodiment 6 products obtained therefroms, and c is EAA, and d is embodiment 5 products obtained therefroms, and e is embodiment 4 products obtained therefroms.
Embodiment
Embodiment 1: the preparation of functionalization exfoliated hydrotalcite
Adopting business-like interlayer anion is CO
3 2-Hydrotalcite LDH-CO
3Make precursor, drying is 6 hours under 400 ℃ of conditions, other gets the beaker of 2000ml, adding the 50g polymerization degree is 50 ammonium polyphosphates, and adding 1200ml deionized water is heated to 80 ℃, so that ammonium polyphosphate dissolves fully, with the PH=4.8 of dilute hydrochloric acid regulator solution～5.2, in solution, add dried hydrotalcite 100g, use again dilute hydrochloric acid regulator solution PH=4.8～5.2, fully stir into white milky solution, then this milk sap is put into ultrasonic wave and react 10min, take out, solution was put into 60 ℃ of oil bath stirring reactions with magnetic stirring apparatus after 4 days, filter with semi-permeable membranes, and with 100 ℃ deionized water wash to the filtrate water white transparency, filter residue grinds 80 ℃ of dryings 12 hours, obtains exfoliated hydrotalcite.Again this exfoliated hydrotalcite and ethylene acrylic random copolymers are extruded (screw speed is as 100rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃ and 200 ℃) take weight ratio fusion-grafting in single screw extrusion machine of 1: 2, and get final product.
Embodiment 2: ion exchange method prepares the intercal type hydrotalcite
Adopting business-like interlayer anion is CO
3 2-Hydrotalcite LDH-CO
3Make precursor, the adding 50g polymerization degree is 50 ammonium polyphosphate in the beaker of 2000ml, and the deionized water that adds 1200ml is heated to 80 ℃, so that APP dissolves fully, with dilute hydrochloric acid regulator solution PH=4.8～5.2, add hydrotalcite 100g, use again dilute hydrochloric acid regulator solution PH=4.8～5.2, fully stir into white milky solution, then this milk sap is put into ultrasonic wave and react 10min, take out, put into again 60 ℃ of oil bath stirring reactions with magnetic stirring apparatus after 4 days, utilize semi-permeable membranes to filter, and tens of inferior with 100 ℃ deionized water wash, drying is ground, and obtains the intercal type hydrotalcite.Again with this intercal type hydrotalcite and the ethylene acrylic random copolymers weight ratio fusion-grafting in single screw extrusion machine with 1: 2, (screw speed is 100rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃ and 200 ℃), and get final product.
The analysis of embodiment 1 and embodiment 2:
Can find out from accompanying drawing 3.1, (embodiment 1, and interlamellar spacing a) obviously increases, and its (003) crystal face diffraction peak intensity is very low for the functionalization exfoliated hydrotalcite, hydrotalcite has obtained fully peeling off, and hydrotalcite particles has obtained refinement (refinement the results are shown in accompanying drawing 1).And intercalated houghite (embodiment 2, only have in b) LDH (003) crystal face of part to Small angle skew to occur, and this has illustrated to only have the LDH interlayer of part to contain ammonium polyphosphate; And (003) crystal face of the LDH of (embodiment 1) is all to the skew of little angular direction after Overheating Treatment, and intensity becomes very weak, and it is unordered that the LDH that this method gained is described has very major part be in, and reaches the state of peeling off.Can be found out by SEM photo among Fig. 1 (d), the lamella particle diameter of the LDH that embodiment 1 method obtains has also obtained significantly refinement simultaneously, accompanying drawing 2 data show that the ammonium polyphosphate content of LDH grafting is respectively 19.6% and 13.8% among embodiment 1 and the embodiment 2.This explanation thermal treatment can make the content of hydrotalcite grafting ammonium polyphosphate be improved.Can be found out by Fig. 4 .1 that more the ammonium polyphosphate with interlayer in the hydrotalcite of ammonium polyphosphate that two embodiment prepare is not with simple physisorption, but is grafted on the LDH lamella.By upper surface analysis gained: heat treated effect not only can improve the content of LDH grafting ammonium polyphosphate, and can make the LDH lamella obtain refinement, promotes to be peeled off between the LDH lamella.
In accompanying drawing 4.1,1630cm
-1, 930cm
-1Be respectively P (=O)-asymmetrical stretching vibration and symmetrical stretching vibration in the O-Al bridged bond, and the P among the APP (=O)-O-N bridged bond stretching vibration peak is at 1245cm
-1The place.APP sloughs first NH under acidic conditions
4+Generation P (=O)-OH, P (=O)-OH again with the LDH surface-OH condensation under acidic conditions generate P (=O)-the O-Al key, this has illustrated that the combination of APP and LDH is not simple physisorption, but combines with the form of chemical bond.Can be at 1386cm in LDH (c)
-1About see a very strong and wide peak, this is CO among the LDH
3 2-The vibration peak of middle C=O (b) be can not see this peak among the figure, the CO of LDH interlayer in the intercalated compound of ion exchange method preparation is described
3 2-Cemented out fully by APP; At (a) but in herein peak die down more sharply, this has illustrated that reason owing to heating is so that the CO among the LDH
3 2-Some is decomposed out, but some is attracted on the LDH, makes more firm that it is combined with LDH, also may be owing under hyperacoustic environmental activity, not have the CO of decomposition
3 2-With by the Mg of LDH lamella weakness
2+Or Al
3+Generated other salt.At a, b, among the d at 1075cm
-1A very strong and wide absorption peak can be seen by the place, be herein P (=O)-O-P in the vibration absorption peak of P-O-P, this peak has illustrated that also the APP of intercalation in LDH do not decompose, or complete long-chain.
Embodiment 3: with high density polyethylene(HDPE): ammonium polyphosphate: ethylene glycol: trimeric cyanamide: embodiment 1 or embodiment 2 products by 61: 19: 6: 5: 9 weight ratio is fully mixed, (screw speed 300rpm, extrusion temperature is: 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 230 ℃ with the twin screw extruder extruding pelletization.) the preparation standard batten, it is as shown in table 1 to test its flame retardant properties and mechanical property.
Table 1
| | Embodiment | 1 | |
| Tensile strength | 25MPa | 27.2MPa | |
| The fault growth rate | 173％ | 378％ | |
| Flexural strength | 31.2 | 32.2 | |
| Modulus in flexure | 1.27GPa | 1.27GPa | |
| Notched Izod impact strength | 19.06KJ/m 2 | 9.6KJ/m 2 | |
| Vertically | FV-0 | FV-1 |
As can be seen from Table 1, the functionalization exfoliated hydrotalcite that example 1 is prepared has improved the flame retardant properties of matrix material to a great extent, and its fire-retardant rank has reached the FV-0 level; Its notched Izod impact strength doubles than the performance that use-case 2 usefulness ion exchange methods prepare intercal type hydrotalcite gained matrix material, and other mechanical property is suitable.This be because, on the thin and lamella of the functionalization exfoliated hydrotalcite particle diameter that example 1 is prepared grafting the ammonium polyphosphate molecular chain.Simultaneously on the lamella also with ethylene acrylic random copolymers (EAA) molecular chain so that this kind exfoliated hydrotalcite disperses is more even, can give full play of the fire-retardant and toughness reinforcing performance of this kind functionalization exfoliated hydrotalcite in matrix material.
Embodiment 4: the preparation of high density polyethylene(HDPE) (HDPE) fusion intercalation type LDH
The interlayer anion that adopts Korea S capital letter business Co., Ltd. to provide is CO
3 2-The surface through stearic acid modified hydrotalcite LDH-CO
3With HDPE be that the mixture of 1: 2 ratio is put into the screw extrusion press fusion intercalation in mass ratio.The control screw speed is 60rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃, 200 ℃.
Embodiment 5: the preparation of high-density polycthylene grafted maleic anhydride (HDPE-g-MA) fusion intercalation type LDH
The interlayer anion that adopting Xiangfan City of Hubei Province oil to build chemical industry company limited provides is CO
3 2-The hydrotalcite LDH-CO of not correcting one's mistakes property of surface
3Make presoma, and processed 6 hours at 200 ℃.Be the LDH after this processing and HDPE-g-MA that the mixture of 1: 2 ratio is put into the screw extrusion press fusion intercalation in mass ratio again.The control screw speed is 60rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃, 200 ℃.
Embodiment 6: the preparation of the exfoliated LDH of ethylene acrylic random copolymers (EAA) melting
The interlayer anion that adopting Xiangfan City of Hubei Province oil to build chemical industry company limited provides is CO
3 2-Surperficial unmodified hydrotalcite LDH-CO
3Make presoma, and processed 6 hours at 200 ℃.Be the LDH after this processing and EAA that the mixture of 1: 2 ratio is put into the screw extrusion press fusion intercalation in mass ratio again.The control screw speed is 60rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃, 200 ℃.
The interpretation of result of example 4, example 5 and example 6:
From Fig. 4 .2, can find out EAA through extruding with LDH reaction after (example 6, b), the 1706cm in the EAA system
-1(V
C=O ( OH)) absorption peak located disappears; Yet EAA/LDH melt extrudes product at 1608cm
-1A new peak occurred, this peak is with identical with stearic acid modified LDH (e) position, and swarming has occured, and this is the characteristic peak of carboxylate salt.From top 2 hydroxyls that can judge the carboxyl the EAA segment and LDH surface fusion-grafting has occured, and this key can be judged to be (V
C=O (OMg)Or V
C=O (OAl)) absorption peak.In order to estimate the activity of EAA and LDH reaction, we use again HDPE-g-MA under identical processing condition, have carried out melt extruding that (example 5, d), discovery is still newly-generated 1608cm in the product with identical direction and LDH
-1The peak.But can find out that from the FT-IR collection of illustrative plates absorption intensity at peak is more sharp-pointed herein than the LDH of HDPE-g-MA/LDH and surface modification for the EAA/LDH that melt extrudes, span is larger; Illustrated that indirectly EAA has larger activity than HDPE-g-MA in this reaction process.
Example 7, composite manufacture
High density polyethylene(HDPE) is fully mixed with embodiment 4,5 and 6 products obtained therefroms respectively, (screw speed 300rpm, extrusion temperature is: 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 230 ℃ to use respectively the twin screw extruder extruding pelletization again.) the preparation standard batten, test its mechanical property respectively shown in table 2, table 3 and table 4.
The mechanical property of table 2 standard batten (preparation of embodiment 4 products)
| LDH content | Tensile strength (MPa) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) |
| 0％ | 24.6 | 18.2 | 0.43 | 48.76 |
| 1％ | 34.04 | 18.08 | 0.39 | 44.82 |
| 3％ | 33.21 | 17.09 | 0.306 | 50.24 |
| 5％ | 32.09 | 17.17 | 0.454 | 49.88 |
The mechanical property of table 3 standard batten (preparation of embodiment 5 products)
| LDH content | Tensile strength (MPa) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) |
| 0％ | 24.6 | 18.2 | 0.43 | 48.76 |
| 1％ | 30.13 | 17.03 | 0.42 | 48.68 |
| 3％ | 29.35 | 17 | 0.41 | 43.77 |
| 5％ | 29.13 | 17.15 | 0.41 | 37.75 |
The mechanical property of table 4 standard batten (preparation of embodiment 6 products)
| LDH content | Tensile strength (MPa) | Flexural strength (MPa) | Modulus in flexure (GPa) | Notched Izod impact strength (KJ/m 2) |
| 0％ | 24.6 | 18.2 | 0.43 | 48.76 |
| 1％ | 33.6 | 25.02 | 0.63 | 45.69 |
| 3％ | 33.13 | 22.2 | 0.78 | 61.01 |
| 5％ | 33 | 22.97 | 0.81 | 55.05 |
| 7％ | 32.2 | 21.27 | 0.75 | 56.28 |
| 10％ | 32.33 | 22.47 | 0.86 | 44.09 |
| 15％ | 33.27 | 22.4 | 0.85 | 35.98 |
Can find out in the XRD data from accompanying drawing 3.2, HDPE and the surface modification hydrotalcite matrix material (example 4 prepared of molten state in forcing machine, a) in (003) crystal face diffraction peak of LDH still exist and intensity also larger, this peak is not offset to low angle yet simultaneously, this explanation is not peeled off (it decreases than pure LDH diffraction peak intensity, is because the fewer cause of its content in matrix material) fully with the LDH of this method preparation.The HDPE/LDH matrix material of being prepared by HDPE-g-MA fusion intercalation LDH method (example 5, b) in (003) crystal face diffraction peak of LDH equally also exist; Simultaneously this peak only has seldom that a part is offset to low angle, and this explanation is not equally peeled off with example 4 fully with the LDH of this method preparation, only has partly to be in intercalated state.Peel off the HDPE/LDH matrix material (example 6 that the LDH method is prepared by the EAA melting, when the massfraction at LDH c) is (1%, 3%, 5%, 7%, 10%), its (003) crystal face diffraction peak exists hardly, do not find simultaneously the diffraction peak of this crystal face at low angle yet, illustrate that this method can prepare a kind of exfoliated LDH fully.When LDH content is 15%, a very weak diffraction peak appears at (003) crystal face, and this is because the difficulty that the too high levels of LDH also can cause LDH to peel off in the matrix material becomes large.The LDH that example 6 usefulness EAA meltings are prepared can make LDH peel off, and is because the carboxyl on the EAA chain can reaction occur with the hydroxyl that LDH shows, has formed covalent linkage, and this covalent linkage has played very important effect in the LDH stripping process.And the quantity few (FTIR intensity can characterize indirectly in by figure) of this type of covalent linkage that forms in HDPE-g-MA and surface modification, deficiency is so that the LDH limellar stripping.
Can be found out by table 2, table 3 and table 4, account at hydrotalcite under the condition of composite system identical weight mark, flexural strength, modulus in flexure and the notched Izod impact strength of the matrix material of being prepared by the example 6 products all value than the matrix material of being prepared by example 4 and example 5 products is high.The melting exfoliated hydrotalcite that this explanation is prepared by example 6 can increase substantially the mechanical property of polyolefin substrate.
Claims (6)
1. the preparation method of an exfoliated hydrotalcite is characterized in that: take interlayer anion as CO
3 2-Hydrotalcite LDH-CO
3Make precursor, mix with the ethylene acrylic random copolymers after pretreatment, extrude to get exfoliated hydrotalcite in screw extrusion press, wherein, described pre-treatment is:
(1) with hydrotalcite LDH-CO
3Processed 6～10 hours at 80～200 ℃;
Or (2) are with hydrotalcite LDH-CO
3Processed 6～10 hours at 200 ℃～500 ℃; Then add in the acid ammonium polyphosphate hot solution, reacted under ultrasonic environment 10～30 minutes, then stirring reaction 3～5 days under 60 ℃～70 ℃ conditions filters, and grinds after dry.
2. according to the preparation method of the described exfoliated hydrotalcite of claim 1, it is characterized in that: pretreated hydrotalcite LDH-CO
3With the weight ratio of ethylene acrylic random copolymers be 1:2～3.
3. according to the preparation method of the described exfoliated hydrotalcite of claim 1, it is characterized in that: when extruding in screw extrusion press, screw speed is 60～200rpm, and extrusion temperature is controlled to be 170 ℃, 180 ℃, 190 ℃ and 200 ℃.
4. according to the preparation method of the described exfoliated hydrotalcite of claim 1, it is characterized in that: the mass percentage concentration of described acid ammonium polyphosphate solution is that 1～10%, pH value is 4.8～5.2, is heated to 80 ℃～90 ℃.
5. according to the preparation method of the described exfoliated hydrotalcite of claim 1, it is characterized in that: stirring reaction is after 3～5 days under 60 ℃～70 ℃ conditions, filter with semi-permeable membranes, with 80～100 ℃ deionized water wash to the filtrate water white transparency, filter residue descended dry 12～24 hours at 60～80 ℃, ground.
6. each described exfoliated hydrotalcite of claim 1 to 5 application in polyolefine as fire retardant and toughener.
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| CN102321274B (en) * | 2011-06-21 | 2012-12-12 | 浙江工业大学 | Hydrotalcite-ammonium polyphosphate halogen-free flame retardant and preparation method thereof |
| CN102827398B (en) * | 2012-09-22 | 2014-04-16 | 山东农业大学 | Core-shell-structure phosphorus-nitrogen compound modified hydrotalcite-like flame retardant and preparation method thereof |
| CN103387757B (en) * | 2013-07-25 | 2016-02-10 | 北京市建筑工程研究院有限责任公司 | A kind of preparation method of overcritical middle hydrotalcite grafting fire retardant |
| CN105400117B (en) * | 2015-11-23 | 2019-12-13 | 厦门理工学院 | anti-droplet expansion flame-retardant poly (butylene succinate) and preparation method thereof |
| CN105482252B (en) * | 2015-12-30 | 2018-03-20 | 衢州学院 | A kind of Halogen smoke-inhibiting flame retardant PP composite material and preparation method thereof |
| CN108623973A (en) * | 2018-05-30 | 2018-10-09 | 雷春生 | It is a kind of using talcum powder as plastic additive of matrix and preparation method thereof |
| CN113043691A (en) * | 2021-03-15 | 2021-06-29 | 四川汇利实业有限公司 | Oral liquid multilayer composite hard tablet and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287967A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Surface preparation of layered dihydroxy composite metal oxide powder |
| CN1563179A (en) * | 2004-04-21 | 2005-01-12 | 浙江大学 | Nano composite resin of polyvinyl chloride/hydrotalcite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287967A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Surface preparation of layered dihydroxy composite metal oxide powder |
| CN1563179A (en) * | 2004-04-21 | 2005-01-12 | 浙江大学 | Nano composite resin of polyvinyl chloride/hydrotalcite |
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