CN101747533A - Modification clay and clay-high polymer composite - Google Patents
Modification clay and clay-high polymer composite Download PDFInfo
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- CN101747533A CN101747533A CN200810184308A CN200810184308A CN101747533A CN 101747533 A CN101747533 A CN 101747533A CN 200810184308 A CN200810184308 A CN 200810184308A CN 200810184308 A CN200810184308 A CN 200810184308A CN 101747533 A CN101747533 A CN 101747533A
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Abstract
The invention provides a modification clay and a clay-high polymer composite. The modification lamellar clay comprises lamellar clay material of which the intercalation is provided with modifier, the modifier has conjugated double bond structure and can produce a free radical after heated. The clay-polymer composite of the invention comprises high polymer substrate and the modification lamellar clay, wherein the modification lamellar clay is dispersed in the high polymer substrate, and at least parts of high polymer substrate are stripped; the modifier produces the free radical during heating so as to capture the free radical produced when high polymer substrate is thermally cracked or burnt, thus avoiding the phenomenon that the high polymer substrate is further cracked in short time.
Description
Technical field
The invention relates to upgrading type book clay, and utilize this upgrading type book clay in the making of flame retardancy clay-polymer composite.
Background technology
Macromolecular material is with a wide range of applications, and for example can be applicable to electronic product, material of construction, automotive material, reaches daily living article etc.With the example that is applied as of electronic packaging aspect, electronic packaging is in order to integrate assembling with many semiconductor integrated circuit, and the function that mainly provides comprises electric energy transmission, signal transmission, heat energy dissipation, reaches protection support etc.Wherein thermosetting resin (for example Resins, epoxy) is normal in the application of electronic packaging, as the base material of printed circuit board (PCB).Usually, printed circuit board (PCB) adopts the matrix material basal plate, is reinforcing fiber (for example glass fibre) to be bonded in the resin form.Matrix material can provide excellent physical strength and dimensional stability.
Yet,, be subjected to thermal softening or burning easily and cause disaster based on the material behavior of macromolecular material itself.In order to solve the macromolecular material incendiary problem of being heated easily, prior art is to add the very high incombustible agent of bromine content, for example brominated resins (Brominated Resin) in macromolecular material.Have suitable effect though add brominated resins to fire-retardant, its amount of being fuming is big and can produce tool corrodibility and toxic hydrogen halide or dioxin, and is very huge for environmental hazard.Based on the maintenance of environment, adopt the mode of non-halogen non-phosphate to improve the inflammable problem of macromolecular material, become inevitable development trend.
U.S. Pat .Pat.4708975 and US.Pat.4826899 disclose a kind of co-polymer, comprise organically clay (organophilic clay) of halogen-containing incombustible agent and parent, by clay being added the formation that can increase coke layer in the co-polymer.U.S. Pat .Pat.6414070 disclose to add organic upgrading clay and put out effect to promote certainly in the MVSS-302 test in co-polymer.
Other also comprises US.Pat.6011087 relevant for clay being used to promote the difficult United States Patent (USP) of examining that fires characteristic, US.Pat.6414070, US.Pat.5779775, US.Pat.6025421, US.Pat.6180695, US.Pat.4708975, US.Pat.4826899, US.Pat.4582866, US.Pat.6610770, US.Pat.5104735, US.Pat.4107376, US.Pat.6207085, US.Pat.4273879, US.Pat.5886072, US.Pat.4981521, US.Pat.5686514, US.Pat.5473007, US.Pat.4472538, US.Pat.3953565, US.Pat.4070315, US.Pat.5863974, US.Pat.5773502, US.Pat.5204395, US.Pat.5294654, US.Pat.5153251, US.Pat.4639486, US.Pat.4386027, US.Pat.4373047, or US.Pat.4280949 etc.In these patents, increase flame retardancy matter nothing more than having added halogen system, phosphorus system or three oxidations, two single, though clay can produce coke layer, the lifting of flame retardancy matter mainly is to reach by adding other inorganics or incombustible agent.
Summary of the invention
The invention provides a kind of upgrading type book clay, comprise the book clay material of the organic modification agent of intercalation, modification agent has conjugated double bond structures, can produce free radical after being heated.
The present invention also provides a kind of clay-polymer composite, comprise polymer base material and described upgrading type book clay, wherein upgrading type book clay is scattered in the polymer base material and goes stratification to small part, and modification agent produces free radical to catch polymer base material thermo-cracking or free radical that burning was produced when being heated, avoid the further cracking of polymer base material.
Description of drawings
For above and other objects of the present invention, feature and advantage can be become apparent, below conjunction with figs. is elaborated to preferred embodiment of the present invention, wherein:
Figure 1A shows the upgrading type book clay of embodiment 1 and composes without the XRD figure of upgrading clay.
Figure 1B shows the XRD figure spectrum of clay-polymer composite of embodiment 1.
Fig. 1 C shows the TEM photo of clay-polymer composite of embodiment 1.
Fig. 2 A shows the upgrading type book clay of embodiment 2 and composes without the XRD figure of upgrading clay.
Fig. 2 B shows the XRD figure spectrum of clay-polymer composite of embodiment 2.
Fig. 2 C shows the TEM photo of clay-polymer composite of embodiment 2.
Fig. 3 A shows the upgrading type book clay of embodiment 3 and composes without the XRD figure of upgrading clay.
Fig. 3 B shows the XRD figure spectrum of clay-polymer composite of embodiment 3.
Fig. 3 C shows the TEM photo of clay-polymer composite of embodiment 3.
Fig. 4 shows the TEM photo of clay-polymer composite of embodiment 4.
Fig. 5 shows the TEM photo of clay-polymer composite of an embodiment.
Embodiment
Upgrading type book clay of the present invention is to get by the modification agent intercalation upgrading with conjugated double bond structures.In clay-polymer composite of the present invention, be dispersed with described upgrading type book clay, and upgrading type book clay to small part is gone stratification.Go to the clay surface after the stratification to be connected to modification agent, can produce free radical after the modification agent of tool conjugated double bond structures is heated and catch the free radical that clay-polymer composite is produced when thermo-cracking or burning, the free radical of avoiding thermo-cracking or burning to produce causes the scission reaction of polymer base material and destroys structural integrity, promotes the flame retardancy matter of clay-polymer composite.
General macromolecular material or polymer composite, in temperature near thermo-cracking temperature or when burning, macromolecular material produces various free radicals because of scission of link or burning easily, for example hydroperoxyl radical H or hydroxyl free radical OH, these free radicals will be attacked macromolecular material and cause cracking, thereby the structural integrity of destruction macromolecular material, and the flame retardancy of reduction macromolecular material.Therefore, the structure of existing macromolecular material or polymer composite all easily is heated and softening or disintegration, and good thermal resistance effect can't be provided.The present invention sees through importing upgrading type book clay in polymer base material and forms clay-polymer composite to improve described problem.
Be fit to book clay material of the present invention and can be natural clay or synthetic inorganic lamellar material, silicon aluminite class clay (smectite clay), vermiculite (vermiculite), tubulose kaolin (halloysite), sericite (sericite), mica (mica), interlayer double-hydroxide, zirconium phosphorus derivative compound or aforesaid combination are for example arranged.In one embodiment, the book clay material is cationic exchange type (being the inorganic lamellar material of tool interlayer cation exchange capacity), and its cationic exchange equivalent is about 50～300meq/100g.In another embodiment, the book clay material also can be anionresin type (being the inorganic lamellar material of tool interlayer anion exchange capacity), and its anionresin equivalent is about 50～1000meq/100g.
Be fit to modification agent of the present invention and have conjugated double bond structures, after being heated, can produce free radical.The conjugated double bond structures of modification agent of the present invention can comprise carbon-carbon double bond, the two keys of nitrogen carbon, the two keys of nitrogen nitrogen, the two keys of carbon oxygen or aforesaid combination.The modification agent that is fit to for example has upgrading carbon 60, upgrading nano carbon microsphere, upgrading CNT (carbon nano-tube), upgrading graphite or described combination.Materials such as carbon 60, nano carbon microsphere, CNT (carbon nano-tube) or graphite have good radical-scavenging ability owing to have many carbon-carbon double bonds.For example, described carbon-carbon double bond can be under suitable temperature scission of link and produce free radical, the free radical that is produced can be in order to catch the free radical that polymer base material is produced when thermo-cracking or the burning, to avoid or to stop polymer base material because of chain scission reaction that free radical was caused, to keep the structural integrity of clay-macromolecular material, reach blocking heat source and increase the effect of flame retardancy matter.
Modification agent of the present invention produces free radical than Canon near the thermo-cracking temperature of polymer base material the time.Generally speaking, the thermo-cracking temperature of macromolecular material is about between 250 ℃～500 ℃, therefore the used preferable free radical that produces after being heated to more than 300 ℃ of modification agent of the present invention for example can produce free radical (as upgrading type carbon 60) between 340 ℃～450 ℃.Therefore, person skilled in the art scholar is from complying with the suitable modification agent of high molecular thermo-cracking temperature collocation.
Upgrading type book clay of the present invention can utilize positively charged ion or the negatively charged ion on the modification agent and the book clay material carries out ion-exchange and make modification agent bond intercalation in the book clay material.The modification agent content of described intercalation is about 20～120 percent ion-exchange equivalent, and preferable with about 50～70% ion-exchange equivalent again.
In addition, if modification agent directly intercalation to the book clay material, can optionally carry out upgrading to modification agent.For example, can be earlier with carbon 60 water-solubleization and make to have and carry out ion-exchange with the book clay material and the ability of intercalation to the book clay material.In one embodiment, be to utilize formaldehyde (CH
2O) with N-methyl aminoacetic acid (N-methylglycine) upgrading carbon 60, and make upgrading carbon 60 see through cationic exchange and the bond intercalation in the book clay material.In another embodiment, except with formaldehyde and the N-methyl aminoacetic acid upgrading carbon 60, also can add Benzene Chloride diformazan hydrocarbon ammonium (Benzalkonium Chloride) again and come upgrading carbon 60.Materials such as nano carbon microsphere, CNT (carbon nano-tube) or graphite can also be similar the mode upgrading, but the upgrading mode is not limited to described mode of giving an example, such as any surface that can make described material have can with the functional group's of book clay material intercalation bond (for example seeing through ion-exchange) upgrading mode, all applicable to the present invention.For example, the top layer that can utilize oxidation reduction process, cycloaddition reaction or free radical addition to react on described material form as alcohol radical, ketone group, aldehyde radical, carboxylic acid group ,-the NHAr base ,-N
+(CH
3)
2Ar base, Ammonia ,=CCl
2Base ,-OSO
3 -The base or-C (CH
3)
2CN base etc., with auxiliary described modification agent smoothly intercalation to book clay.
The modification agent of the embodiment of the invention except use has the compound of carbon-carbon double bond, also can use have carbon-to-nitrogen double bon, the conjugated double bond compound of the two keys of nitrogen nitrogen or the two keys of carbon oxygen, for example imidazolium compounds, melamine compound or described combination.Imidazolium compounds for example has 4,5-imidazole-2-carboxylic acid (4,5-Imidazole dicarboxylicacid), Imidazole-2-carboxaldehyde or 4-(Imidazol-1-yl) phenol etc.Melamine compound for example has melamine cyanurate (melamine cyanurate), tris (2-Hydroxyethyl)-1,3,5-triazinetrione, trimeric cyanamide, melamino-formaldehyde (melamine-formaldehyde), butoxymethylmelamine, hexamethoxymethylmelamine, methyl melamine (methyl melamine), methoxymethyl melamine or methoxymethyl methylol melamine etc.Wherein, the modification agent (for example 4,5-imidazole-2-carboxylic acid) of part directly intercalation to the book clay material, do not need further upgrading.
The modification agent that the present invention was suitable for is not limited to described compound, and intercalation and can discharge free radical to end or to suppress polymer scission reaction person, all in the scope that the present invention is contained to book clay under proper temperature smoothly such as.
The book clay material at intercalation behind the modification agent, its interlayer spacing can be strutted, its spacing for example approximately greater than
The upgrading type book clay that the interlayer spacing struts can form clay-polymer composite jointly with polymer base material, and the upgrading type book clay that the interlayer spacing is bigger can go stratification (exfoliated) more easily in polymer base material, and is scattered in the polymer base material.
In the clay-polymer composite of the embodiment of the invention, the content of upgrading type book clay is benchmark with the polymer base material of 100 weight parts, can be about 1～10 weight part, and preferable with about 3～7 weight parts again.It should be noted that the content of upgrading type book clay can adjust according to circumstances in the clay-polymer composite of the embodiment of the invention, is not limited to described content range.
The generation type of the clay-polymer composite of the embodiment of the invention for example can be mixed upgrading type book clay with the monomer of polymer base material, the monomer that utilizes polymer base material is polymerization reaction take place (for example see through heat or add catalyzer) in the interlayer spacing of upgrading type book clay.When monomer forms polymer base material by polyreaction, help to make upgrading type book clay to go stratification and be scattered in the polymer base material.For example, in one embodiment, described upgrading type book clay is dissolved in the solvent, then the monomer (as novolac epoxy, Bisphenol-A novolac epoxy) with Resins, epoxy adds in the upgrading type book clay solution and dispersed with stirring.Gained solution extract by solvent with thermal treatment after (for example in Hotaircirculatingoven in 190 ℃ of down sclerosis 90 minutes), the monomer of Resins, epoxy just can form the Resins, epoxy base material by polyreaction, and makes upgrading type book clay go stratification and be scattered in the Resins, epoxy base material.
On the other hand, clay-polymer composite of the present invention also can by upgrading type book clay directly and polymer base material mix and form, for example can adopt melt blending (melt blending) or solution blending (solutionblending).Generally speaking, melt blending can be carried out in a closed system, for example can utilize surging mixing facilities such as single screw rod or multiscrew extruding machine, Banbury Banbury mixer, twin-screw mixer machine, single screw mixing machine, ten thousand horsepowers of machines, continuous mixer, Kneader kneader, under enough high temperature, both be carried out melting mixing and get final product.The temperature of melt blending is about 290～310 ℃.As for the solution blending, be upgrading type book clay to be added be dissolved with in the organic solvent of polymer base material, high-speed stirring is even, and the mixture of gained can obtain clay-polymer composite after removing organic solvent.For example, can be directly directly to place mixing facilities to carry out polymeric Resins, epoxy base material and upgrading type book clay mixing, and because mixing facilities surging mixing, upgrading type book clay also can go stratification and is scattered in the Resins, epoxy base material to small part.
According to the made clay-polymer composite of described method, can penetrate molded, extrude molded or modes such as compression molding are directly made various moulding product, or before molded earlier and other polymkeric substance blending.
Be applicable to that polymer base material of the present invention or its corresponding monomer can be thermosetting macromolecule, thermoplastics type's polymer or aforesaid combination, for example can be materials such as Resins, epoxy, nylon, urethane, polystyrene, polyethylene, polyvinyl chloride, described corresponding monomer or aforesaid combination.Clay-the polymer composite of the embodiment of the invention is owing to comprise the upgrading type book clay that is scattered in wherein and goes stratification to small part, except book clay thermal source capable of blocking itself and blocking-up oxygen enter and improve the rerum natura and flame retardancy matter of polymer base material, also can catch in the polymer base material free radical that produces because of thermo-cracking or burning with clay dispersive modification agent, avoid polymer base material attacked and the initiation scission reaction by free radical, make the structure of polymer base material keep integrity, further improve the flame retardancy matter of clay-polymer composite effectively to block thermal source.In one embodiment, the heat release rate of clay-polymer composite reduces between 50～150kw/m2 approximately than the polymer base material that does not comprise upgrading type book clay.In addition, in one embodiment, the limiting oxygen index(LOI) of clay-polymer composite increases between 3～10 approximately than the polymer base material that does not comprise upgrading type book clay.
In addition, clay-polymer composite of finishing in said system also can add other composition, as malleableize agent, stiffening agent, fireproofing agent, compatible agent, organic-inorganic weighting agent, UV absorption agent, photostabilizer, static inhibitor, fluidizer, lubrication prescription or antioxidant etc., look closely needed application and decide.
Below, enumerate several embodiment to further specify embodiments of the present invention.
[embodiment 1]
With water-soluble carbon 60 upgrading natural clays (polynite)
At first, form water-soluble carbon 60 powder.10 gram carbon 60 are added 0.414 gram formaldehyde (CH
2O) and in 2.416 grams N-methyl aminoacetic acids (N-methylglycine), and refluxed 2 hours in 110 ℃, the oven dry back obtains water-soluble carbon 60 powder.Then, reach 5.934 gram Benzene Chloride diformazan hydrocarbon ammoniums (Benzalkonium Chloride) and stirring and dissolving in the 0.1N hydrochloric acid (HCl) with 16.7 milliliters of 1.305 gram water-soluble carbons, 60 addings and form modification agent.
2.89 gram natural clays were added in 50 times of deionized waters swelling 24 hours, and gained clay solution slowly splashed into carry out cationic exchange in the modification agent.If the cationic exchange equivalent of this natural clay is about 116meq/100ml.Adjust its pH value between 3～4 with 1N hydrochloric acid, and stir and spend the night.
With above-mentioned solution centrifugal and take off a layer clay.With deionized water swelling stirring and centrifugal repeatedly, splash into Silver Nitrate (AgNO again until upper solution
3) till no silver chloride (AgCl) white precipitate of back.After centrifugal lower floor's clay of finishing put into refrigerator, put into freeze drier again and wait for complete drying.Behind the complete drying, the lower floor clay pulverized and drying for standby and obtain upgrading type book clay.
Figure 1A shows the upgrading type book clay of embodiment 1 and composes without the XRD figure of upgrading clay that wherein curve 1AM represents the XRD figure spectrum of gained upgrading type book clay among the embodiment 1, and curve 1A represents the XRD figure spectrum without the upgrading natural clay.Shown in Figure 1A, upgrading natural clay (curve 1A) representative (001) planar diffraction peak is not behind upgrading, to left, it represents the successful intercalation of water-soluble carbon 60 to the stratiform natural clay and strut book clay, makes to have bigger (001) interplanar spacing (d-spacing).The interlayer spacing of the book clay behind the upgrading is by originally
Strut to
Then, form clay-polymer composite with embodiment 1 described upgrading type book clay.At first, (be Propylene glycol methyl ether, PM) stirring solvent is dissolved it fully to get an amount of upgrading clay adding propyleneglycoles methyl ether.Then, (Bisphenol-A novolac epoxy) adds above-mentioned solution with an amount of novolac epoxy, and stirring makes its dispersion.Afterwards, pour finely dispersed Resins, epoxy into mould, and dry in vacuum drying oven.Be put in the Hotaircirculatingoven taking out the Resins, epoxy that desolvates, in 190 ℃ down sclerosis take out after about 90～180 minutes and Resins, epoxy bulk (being the clay-polymer composite of one embodiment of the invention).
Figure 1B shows the XRD figure spectrum of clay-polymer composite of embodiment 1, wherein curve a represents not add the XRD figure spectrum of upgrading type book clay in wherein Resins, epoxy bulk, and curve a1, a3, a5 represent upgrading type book clay addition be respectively 1%, 3%, and the XRD figure of clay-polymer composite of 5% compose.Can't find shown in Figure 1A, to correspond to (001) planar diffraction peak of natural clay among Figure 1B, show upgrading type book clay after adding novolac epoxy and further drying is hardened to bulk, go stratification and make interplanar spacing excessive or grain-size is too small and can't manifest the diffraction peak in the XRD figure spectrum to small part.Fig. 1 C shows the TEM photo of clay-polymer composite of embodiment 1.Shown in the TEM photo of Fig. 1 C, can find that really the upgrading type book clay of part has gone stratification, and be scattered in the novolac epoxy base material.
[embodiment 2]
With 4, double-hydroxide between 5-imidazole-2-carboxylic acid upgrading lithium aluminium lamination
At first, double-hydroxide ([LiAl between preparation lithium aluminium lamination
2] LDH).With mixture 7.28 gram nitric hydrate lithium (LiNO
33H
2O) and 78.82 gram nitric hydrate aluminium (Al (NO
3)
39H
2O) be dissolved in 400 ml deionized water, and then add 50.4 gram sodium hydroxide (NaOH).Above-mentioned mixed solution was stirred one hour and keep the pH value in 13.Then, mixed solution is inserted autoclave in 100 ℃ of reactions 24 hours.Centrifugal several and with washed with de-ionized water lower floor clay, after grinding by oven dry again double-hydroxide powder (Li-Al LDH) between the lithium aluminium lamination.The anionresin equivalent of double-hydroxide powder is about 420meq/100g between gained lithium aluminium lamination.
With 4,5-imidazole-2-carboxylic acid (4,5-Imidazole dicarboxylic acid) is dissolved in 200 ml deionized water with as modification agent.With double-hydroxide powder between 6.3 gram lithium aluminium laminations with 50 times of deionized water dissolvings and stirred 24 hours.Then, gained clay solution slowly added carry out anionresin in the modification agent, and kept 2 days in 50 ℃.Then, with described solution centrifugal for several times, and, get upgrading type book clay after grinding by oven dry again with washed with de-ionized water lower floor clay.
Fig. 2 A shows the upgrading type book clay of embodiment 2 and composes without the XRD figure of upgrading clay that wherein curve 2AM represents the XRD figure spectrum of gained upgrading type book clay among the embodiment 2, and curve 2A represents the XRD figure spectrum without double-hydroxide between upgrading lithium aluminium lamination.Shown in Fig. 2 A, double-hydroxide (curve 2A) does not represent (002) planar diffraction peak behind upgrading between upgrading lithium aluminium lamination, to left, it represents 4, the successful intercalation of 5-imidazole-2-carboxylic acid makes to have bigger (002) interplanar spacing (d-spacing) to double-hydroxide between the lithium aluminium lamination and strut book clay.The interlayer spacing of the book clay behind the upgrading is by originally
Strut to
Then, form clay-polymer composite with embodiment 2 described upgrading type book clays.At first, getting an amount of upgrading clay adding PM stirring solvent dissolves it fully.Then, (Bisphenol-A novolac epoxy) adds described solution with an amount of novolac epoxy, and stirring makes its dispersion.Afterwards, pour finely dispersed Resins, epoxy into mould, and dry in vacuum drying oven.Be put in the Hotaircirculatingoven taking out the Resins, epoxy that desolvates, in 190 ℃ down sclerosis take out after 90～180 minutes and Resins, epoxy bulk (being the clay-polymer composite of one embodiment of the invention).
Fig. 2 B shows the XRD figure spectrum of clay-polymer composite of embodiment 2, wherein curve b represents not add the XRD figure spectrum of upgrading type book clay in wherein Resins, epoxy bulk, and curve b1, b3, b5 represent upgrading type book clay addition be respectively 1%, 3%, and the XRD figure of clay-polymer composite of 5% compose.Can't find shown in Fig. 2 A, to correspond to (002) planar diffraction peak of double-hydroxide between the lithium aluminium lamination among Fig. 2 B, show upgrading type book clay after adding novolac epoxy and further drying is hardened to bulk, go stratification and make interplanar spacing excessive or grain-size is too small and can't manifest the diffraction peak in the XRD figure spectrum to small part.Fig. 2 C shows the TEM photo of clay-polymer composite of embodiment 2.(the less enlargement ratio in the left side, the big enlargement ratio in the right) can be found that really the upgrading type book clay of part has gone stratification, and be scattered in the novolac epoxy base material shown in the TEM photo of Fig. 2 C.
[embodiment 3]
With water-soluble carbon 60 upgrading natural clays (polynite)
Embodiment 3 is similar to embodiment 1, and main difference is to implement not use in 3 Benzene Chloride diformazan hydrocarbon ammonium to carry out upgrading.At first, form water-soluble carbon 60 powder.10 gram carbon 60 are added 0.414 gram formaldehyde (CH
2O) and in 2.416 grams N-methyl aminoacetic acids (N-methylglycine), and refluxed 2 hours in 110 ℃, the oven dry back obtains water-soluble carbon 60 powder.Then, 2.612 gram water-soluble carbons 60 are added in 33.5 milliliters the 0.1N hydrochloric acid (HCl) and stirring and dissolving, and form modification agent.
2.89 gram natural clays were added in 50 times of deionized waters swelling 24 hours, and gained clay solution slowly splashed into carry out cationic exchange in the modification agent.The cationic exchange equivalent of natural clay is about 116meq/100ml.Adjust its pH value between 3～4 with 1N hydrochloric acid, and stir and spend the night.With above-mentioned solution centrifugal and take off a layer clay.With deionized water swelling stirring and centrifugal repeatedly, splash into Silver Nitrate (AgNO again until upper solution
3) till no silver chloride (AgCl) white precipitate of back.After centrifugal lower floor's clay of finishing put into refrigerator, put into freeze drier again and wait for complete drying.Behind the complete drying, the lower floor clay pulverized and drying for standby and obtain upgrading type book clay.
Fig. 3 A shows the upgrading type book clay of embodiment 3 and composes without the XRD figure of upgrading clay that wherein curve 3AM represents the XRD figure spectrum of gained upgrading type book clay among the embodiment 1, and curve 3A represents the XRD figure spectrum without the upgrading natural clay.As shown in Figure 3A, upgrading natural clay (curve 3A) representative (001) planar diffraction peak is not behind upgrading, to left, it represents the successful intercalation of water-soluble carbon 60 to the book clay natural clay and strut book clay, makes to have bigger (001) interplanar spacing (d-spacing).The interlayer spacing of the book clay behind the upgrading is by originally
Strut to
Then, form clay-polymer composite with embodiment 3 described upgrading type book clays.At first, get an amount of upgrading clay and add PM, propylene glycol monomethyl ether (propylene glycol methyl ether) stirring solvent is dissolved it fully.Then, (Bisphenol-A novolac epoxy) adds above-mentioned solution with an amount of novolac epoxy, and stirring makes its dispersion.Afterwards, pour finely dispersed Resins, epoxy into mould, and dry in vacuum drying oven.Be put in the Hotaircirculatingoven taking out the Resins, epoxy that desolvates, in 190 ℃ down sclerosis take out after 90 minutes and Resins, epoxy bulk (being the clay-polymer composite of one embodiment of the invention).
Fig. 3 B shows the XRD figure spectrum of clay-polymer composite of embodiment 3, wherein curve c represents not add the XRD figure spectrum of upgrading type book clay in wherein Resins, epoxy bulk, and curve c1, c3, c5 represent upgrading type book clay addition be respectively 1%, 3%, and the XRD figure of clay-polymer composite of 5% compose.Can't find to correspond to as shown in Figure 3A (001) planar diffraction peak of natural clay among Fig. 3 B, show upgrading type book clay after adding novolac epoxy and further drying is hardened to bulk, go stratification and make interplanar spacing excessive or grain-size is too small and can't manifest the diffraction peak in the XRD figure spectrum to small part.Fig. 3 C shows the TEM photo of clay-polymer composite of embodiment 1.(the big enlargement ratio in the left side, the less enlargement ratio in the right) can be found that really the upgrading type book clay of part has gone stratification, and be scattered in the novolac epoxy base material shown in the TEM photo of Fig. 3 C.And in the TEM photo of big multiplying power (Fig. 3 C left side), also can find the carbon six ten of intercalation on the clay of delamination.
[embodiment 4]
With 4, double-hydroxide between 5-imidazole-2-carboxylic acid upgrading lithium aluminium lamination
Embodiment 4 is similar to embodiment 2, and it is that magnalium interlayer double-hydroxide is carried out upgrading that main difference is to implement 4.At first, with magnalium interlayer double-hydroxide (Mg-Al-LDH) in 500 ℃ of following calcination 5 hours.With 4,5-imidazole-2-carboxylic acid (4,5-Imidazole dicarboxylic acid) is dissolved in 200 ml deionized water with as modification agent.With the magnalium interlayer double-hydroxide powder of 6.3 grams after the thermal treatments with 50 times of deionized water dissolvings and stirred 24 hours.Then, gained clay solution slowly added carry out anionresin in the modification agent, and kept 2 days in 50 ℃.Then, with described solution centrifugal for several times, and, get upgrading type book clay after grinding by oven dry again with washed with de-ionized water lower floor clay.
Then, form clay-polymer composite with embodiment 4 described upgrading type book clays.At first, getting an amount of upgrading clay adding PM stirring solvent dissolves it fully.Then, (Bisphenol-A novolac epoxy) adds above-mentioned solution with an amount of novolac epoxy, and stirring makes its dispersion.Afterwards, pour finely dispersed Resins, epoxy into mould, and dry in vacuum drying oven.Be put in the Hotaircirculatingoven taking out the Resins, epoxy that desolvates, in 190 ℃ down sclerosis take out after 90 minutes and Resins, epoxy bulk (being the clay-polymer composite of one embodiment of the invention).
Fig. 4 shows the TEM photo of clay-polymer composite of embodiment 4.(the less enlargement ratio in the left side, the big enlargement ratio in the right) can be found that really the upgrading type book clay of part has gone stratification, and be scattered in the novolac epoxy base material shown in the TEM photo of Fig. 4.
Table one shows the flame retardancy matter of clay-polymer composite of embodiment 1～4, and the addition of its upgrading type book clay is all 3wt%.Comparative example refers to pure novolac epoxy base material, does not add any upgrading type book clay.
Table one
Wherein, limiting oxygen index(LOI) (Limiting oxygen index) is in order to the difficulty combustion effect of decision material.When utilizing the flame retardancy matter of oxygen limit index instrument (oxygen index flammability tester) test clay-polymer composite, burning things which may cause a fire disaster by test piece to be measured (be about 3.8 centimetres, wide about 2.4 centimetres, and thick about 0.2 centimetre) light on the top and oxygen flow from bottom to top provides.See through to adjust the oxygen in the oxygen limit index instrument and the dividing potential drop of nitrogen, can find out the oxygen partial pressure amount that test piece to be measured takes fire required and determine limiting oxygen index(LOI).The limiting oxygen index(LOI) reduction formula is as follows:
Limiting oxygen index(LOI)=oxygen volume/(oxygen volume+nitrogen volume)
Therefore, the high more expression of limiting oxygen index(LOI) test piece to be measured take fire required amount of oxygen more Gao Eryue be not easy the burning.In addition, table one is also listed clay-polymer composite measured thermorodiative property under circular cone calorimeter (Conecalorimeter) of embodiment 1～4.Test piece to be measured is put heating with level, and radiation heat flux is 50kW/m
2, test piece to be measured be about 10 centimetres, wide about 10 centimetres, and thick about 0.5 centimetre.
Can be found out that by table one limiting oxygen index(LOI) of the clay-polymer composite of the embodiment of the invention all is higher than comparative example, between 6～9, its flame retardancy matter is improved its increasing amount approximately.And the evenly heat release rate of each embodiment, total heat discharge, reach the average quality scatter ratio, scatter and disappear ratio all less than comparative example.Wherein, the evenly heat release rate reduces by 60～110kW/m approximately
2
Though described embodiment 1～4 is all upgrading type book clay is imported in the thermosetting polymer, yet the invention is not restricted to this.Upgrading type book clay of the present invention also can import and change its flame retardancy matter of loosing in the thermal plastic high polymer.Fig. 5 shows the TEM photo of clay-polymer composite of an embodiment, the polymer base material that uses be thermal plastic high polymer nylon (Nylon).As shown in Figure 5, can find that the upgrading type book clay of part has gone stratification, and be scattered in the nylon base.Table two shows pure nylon and the flame retardancy matter (addition of upgrading type book clay is 2phr with respect to nylon) that is added with the clay-nylon composite materials of upgrading type book clay.
Table two
| Sample | Evenly heat release rate (kW/m 2) | Total heat discharges (MJ/m 2) | Average quality scatter ratio, scatter and disappear ratio (g/s) |
| Nylon | ??386.96 | ??158.67 | ??17.327 |
| Clay-nylon composite materials | ??242.16 | ??106.81 | ??49.342 |
By Fig. 5 and table two as can be known, upgrading type book clay of the present invention is also applicable to thermal plastic high polymer, and also can reduce its evenly heat release rate and total heat discharges.
In sum, the embodiment of the invention sees through the modification agent intercalation is formed upgrading type book clay to the book clay material.The upgrading type book clay of the embodiment of the invention can effectively increase the flame retardancy matter of clay-polymer composite, can improve the inflammable problem of macromolecular material.See through and to have the modification agent intercalation of conjugated double bond structures in book clay, can make modification agent along with the upgrading type book clay that goes stratification to small part, be scattered in the polymer base material, these dispersive modification agents can produce free radical and catch polymer base material thermo-cracking or free radical that burning produced when being heated, avoid the further cracking of polymer base material, promote the whole flame resistivity matter of clay-polymer composite.
Though the present invention discloses as above with several preferred embodiments; right its is not in order to limit the present invention; have in the technical field under any and know the knowledgeable usually; without departing from the spirit and scope of the present invention; when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking accompanying the claim person of defining.
Claims (22)
1. upgrading type book clay is characterized in that comprising:
One stratiform clay material, its intercalation has a modification agent, and this modification agent has conjugated double bond structures, can produce free radical after being heated.
2. upgrading type book clay according to claim 1 is characterized in that this book clay material comprises the inorganic lamellar material with interlayer cation exchange capacity or has the inorganic lamellar material of interlayer anion exchange capacity.
3. upgrading type book clay according to claim 1 is characterized in that this book clay material comprises natural clay or synthetic inorganic lamellar material.
4. upgrading type book clay according to claim 1 is characterized in that this modification agent produces free radical through being heated to after (removal) more than 300 ℃.
5. upgrading type book clay according to claim 1 is characterized in that the temperature range of this modification agent through heating main generation free radical is between 340 ℃～450 ℃.
6. upgrading type book clay according to claim 1 is characterized in that this modification agent comprises carbon-carbon double bond, the two keys of nitrogen carbon, the two keys of nitrogen nitrogen, the two keys of carbon oxygen or aforesaid combination.
7. upgrading type book clay according to claim 1 is characterized in that the material of this book clay material comprises silicon aluminite class clay, vermiculite, tubulose kaolin, sericite, mica, interlayer double-hydroxide, zirconium phosphorus derivative compound or aforesaid combination.
8. upgrading type book clay according to claim 1 is characterized in that this modification agent comprises upgrading carbon 60, upgrading nano carbon microsphere, upgrading CNT (carbon nano-tube), upgrading graphite or aforesaid combination.
9. upgrading type book clay according to claim 8 is characterized in that this modification agent is to get by formaldehyde and N-methyl aminoacetic acid upgrading.
10. upgrading type book clay according to claim 8, it is characterized in that this modification agent be by formaldehyde, N-methyl aminoacetic acid, and Benzene Chloride diformazan hydrocarbon ammonium upgrading get.
11. upgrading type book clay according to claim 1 is characterized in that this modification agent comprises imidazolium compounds, melamine compound or aforesaid combination.
12. upgrading type book clay according to claim 1, it is characterized in that its interlayer spacing approximately greater than
13. upgrading type book clay according to claim 1 is characterized in that the cationic exchange equivalent of this book clay is about 50～300meq/100g.
14. upgrading type book clay according to claim 1 is characterized in that the anionresin equivalent of this book clay is about 50～1000meq/100g.
15. a clay-polymer composite is characterized in that comprising:
One polymer base material; And
One upgrading type book clay according to claim 1, wherein this upgrading type book clay is scattered in this polymer base material and goes stratification to small part, and this modification agent produces free radical to catch this polymer base material thermo-cracking or free radical that burning was produced, to avoid the further cracking of this polymer base material when being heated.
16. clay-polymer composite according to claim 15 is characterized in that the thermo-cracking temperature of this polymer base material is about between 250 ℃-500 ℃.
17. clay-polymer composite according to claim 15 is characterized in that this modification agent produces free radical after being heated to more than 300 ℃.
18. clay-polymer composite according to claim 15 is characterized in that this modification agent produces free radical after being heated between 340 ℃～380 ℃.
19. clay-polymer composite according to claim 15 is characterized in that this polymer base material comprises thermosetting polymer, thermal plastic high polymer or aforesaid combination.
20. clay-polymer composite according to claim 15 is characterized in that this polymer base material comprises Resins, epoxy, nylon, urethane, polystyrene, polyethylene, polyvinyl chloride or aforesaid combination.
21. clay-polymer composite according to claim 15 is characterized in that its average (removal) heat release rate reduces between 50～150kw/m2 approximately than the polymer base material that does not comprise this upgrading type book clay.
22. clay-polymer composite according to claim 15, it is characterized in that its limiting oxygen index(LOI) increases between 3～10 approximately than the polymer base material that does not comprise this upgrading type book clay.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952393A (en) * | 2011-08-29 | 2013-03-06 | 奇菱科技股份有限公司 | Organic modification laminated composite material |
| CN111574768A (en) * | 2020-04-09 | 2020-08-25 | 杭州联通管业有限公司 | Lightning-proof optical fiber communication pipeline and preparation method thereof |
| CN111690197A (en) * | 2020-07-02 | 2020-09-22 | 南京工程学院 | Melamine-containing direct intercalation g-C3N4Flame-retardant cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958676A (en) * | 2005-11-03 | 2007-05-09 | 私立中原大学 | Modification type clay, composite material of novolac epoxy resin of containing the clay, and predation method |
| TWI353342B (en) * | 2007-04-24 | 2011-12-01 | Ind Tech Res Inst | Carbon nanocapsules-layered silicate hybrid and pr |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952393A (en) * | 2011-08-29 | 2013-03-06 | 奇菱科技股份有限公司 | Organic modification laminated composite material |
| CN111574768A (en) * | 2020-04-09 | 2020-08-25 | 杭州联通管业有限公司 | Lightning-proof optical fiber communication pipeline and preparation method thereof |
| CN111690197A (en) * | 2020-07-02 | 2020-09-22 | 南京工程学院 | Melamine-containing direct intercalation g-C3N4Flame-retardant cable material and preparation method thereof |
| CN111690197B (en) * | 2020-07-02 | 2022-09-13 | 南京工程学院 | Melamine-containing direct intercalation g-C 3 N 4 Flame-retardant cable material and preparation method thereof |
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