CN102634213B - High-toughness high-temperature-resistant hybridized polymer resin and preparation method, shaping method and application of premixture comprising composition - Google Patents
High-toughness high-temperature-resistant hybridized polymer resin and preparation method, shaping method and application of premixture comprising composition Download PDFInfo
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- CN102634213B CN102634213B CN 201210134032 CN201210134032A CN102634213B CN 102634213 B CN102634213 B CN 102634213B CN 201210134032 CN201210134032 CN 201210134032 CN 201210134032 A CN201210134032 A CN 201210134032A CN 102634213 B CN102634213 B CN 102634213B
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Abstract
The invention discloses high-strength high-toughness high-temperature-resistant hybridized polymer resin, and a preparation method, shaping method and application of a premixture comprising the composition, relates to high temperature of 350-450 DEG C high-temperature-resistant high-strength high-toughness hybridized polymer resin, the preparation method, the shaping method and application of the premixture comprising the composition, and provides high-strength high-toughness high-temperature-resistant hybridized polymer resin which can be adapted to the temperature environment in the operation of an aluminum electrolytic cell, further can keep enough strength and toughness under the environment temperature, and can seal the aluminum electrolytic cell, the preparation method, the shaping method and application of the premixture comprising the composition. The preparation method of the high-strength high-toughness high-temperature-resistant hybridized polymer resin provided by the invention comprises the following processing steps: 1) preparing a polymer; 2) preparing resin; and 3) finishing. According to the invention, the composition with high cost performance is obtained by a low-cost preparation method, the high-strength high-toughness high-temperature-resistant hybridized polymer resin is especially suitable for being used as a high-temperature-resistant (450 DEG C) seal insulation element, and can be used for elastic seal insulation under the environment.
Description
Technical field
The present invention relates to anti-350-450 ℃ of high temperature obdurability hybrid polymer resin, the preparation method who comprises the pre-composition of said composition, forming method and application.
Background technology
In aluminium electrolysis process, temperature is very high in the aluminium cell, reaches 350-600 ℃.The U-shaped plate that has had insulation, sealing function in the electrolyzer.Under this temperature, adopt near the aluminium cell notch structural part of common high molecular materials processing can decomposition, carbonization, brokenly fall, and reduce or lose insulating property; Cause the fluctuation of groove condition unusually anode effect to take place, finally influence the work-ing life of ordinary production and electrolyzer.In addition, in the aluminium electrolysis process, have and decomposite many obnoxious flavoures (as CO, CO
2, CF
4, C
2F
6Deng gas, HF severe toxicity gas particularly), near U-shaped plate Yin Gaowen in aluminium cell (notch temperature 350-400 ℃) can carbonization, brokenly fall, damaging the back makes whole sealing property descend, cause a large amount of obnoxious flavoures to enter the operating space, infringement operator's health, pollutant atmosphere reduce the obnoxious flavour rate of recovery.
Summary of the invention
The present invention is directed to above problem, provide a kind of and can adapt to the aluminium cell temperature environment in when work, and then can under this envrionment temperature, keep enough intensity, toughness, realize the high temperature resistant hybrid polymer resin of high-strong toughness, the preparation method who comprises the pre-composition of said composition, forming method and application to the aluminium cell sealing.
The preparation method of high-strong toughness of the present invention is high temperature resistant hybrid polymer resin, processing according to the following steps:
1), preparation polymkeric substance; Get organosilicon and phosphoric acid, in molar ratio (2+ δ): 2, mix under 32-48 ℃ of temperature wherein (1/10≤δ≤3/10); Immediately under temperature 90-110 ℃ shielding gas atmosphere, progressively be warming up to 240-260 ℃ and be incubated 0.8-1.2 hour, carry out the hybrid inorganic-organic polyreaction; Get colloidal low cross-linking hybridized polymer;
2), preparation resin; Aforementioned low cross-linking hybridized polymer is cooled to 18-30 ℃, add bivalent metal oxide immediately in described low cross-linking hybridized polymer, add-on is the 5-8% of described low cross-linking hybridized polymer weight, in the interpolation process, evenly stir, get transparent colloidal resin;
3), finish.
Described organosilicon is dimethyldichlorosilane(DMCS) (R
2SiCl
2) or METHYL TRICHLORO SILANE (RSiCl
3).
Described bivalent metal oxide is CaO, CuO or ZnO.
Described shielding gas is nitrogen or rare gas element.
The preparation method of pre-composition of the present invention, described pre-composition comprises that described transparent colloidal resin 23-28%, low contraction material 10-15%, tert-butyl ester 1.0-1.5% and Zinic stearas 0.6-1.2% mix, are stirred to evenly under 20-35 ℃; Add glass fibre 15-25% and filler 40-50% then, evenly mediate, get bulk plasticity pre-composition; Make.
Described filler is Al
2O
3Powder and mica powder, ratio are (0-100): (100-0).
Also be added with the divalent metal oxyhydroxide of using as solidifying agent in the described pre-composition, add-on is the 0.1-1.5% of described pre-composition gross weight; Described divalent metal oxyhydroxide is calcium hydroxide or magnesium hydroxide.
It is evenly mixed by the 2:1 weight ratio that described low contraction material is liquid phenenyl ethene and granules of polystyrene.
Forming method of the present invention drops into the surface with described bulk plasticity pre-composition and scribbles in the metal molding die of polyether-ether-ketone, and hot pressing under 140-160 ℃ of environment makes profiled member.
Application of the present invention after described transparent gluey preparation of compositions is bulk plasticity pre-composition, by forming process, gets the U-shaped plate of doing the insulation sealing member on the aluminium cell.
It is main raw material that hybrid polymer resin of the present invention adopts organosilicon and phosphoric acid, by the control to mol ratio, and after the party reaction, the low cross-linking hybridized polymer with certain linearity of formation, this polymkeric substance self has anti-370 ℃ ability.Add bivalent metal oxide in this polymkeric substance after, bivalent metal oxide is evenly distributed in the polymkeric substance with molecular structure.The formation pre-composition also is shaped to after the structural part, when envrionment temperature surpasses 370 ℃ (the general work envrionment temperature is at 370-450 ℃), R group in the former low cross-linking hybridized polymer with certain linearity decomposes, and product can lose the weight of 5-8%, and toughness descends simultaneously.But since aforementioned bivalent metal oxide with molecular form, " physics attitude " be distributed in the linear structure inside of material, bivalent metal oxide can part substitute R
2SiCl
2Monomer is at high temperature kept chain-like structure.And then make structural part still have certain intensity and toughness.The present invention has obtained the composition of high performance-price ratio with preparation means cheaply, is particularly suitable for doing high temperature resistant (450 ℃) sealing insulator, does to realize the resilient seal insulation under this environment.
Description of drawings
Fig. 1 be the present invention at the schematic arrangement below 350 ℃,
Fig. 2 be the present invention at the schematic arrangement more than 350 ℃,
Fig. 3 is the synoptic diagram one of background technology of the present invention,
Fig. 4 is the synoptic diagram two of background technology of the present invention;
Me represents metal ion among the figure.
Embodiment
Embodiment one
The preparation method of high-strong toughness of the present invention is high temperature resistant hybrid polymer resin, processing according to the following steps:
1), preparation polymkeric substance; Get dimethyldichlorosilane(DMCS) and phosphoric acid, 2.1:2 mixes under 48 ℃ of temperature in molar ratio; Immediately under the nitrogen atmosphere environment of 110 ℃ of temperature, progressively be warming up to 260 ℃ and be incubated 0.8 hour, carry out polyreaction; Get colloidal low cross-linking hybridized polymer; Molecular structure as shown in Figure 1.The preparation principle of hybrid inorganic-organic polymkeric substance is as follows: dimethyldichlorosilane(DMCS) (R
2SiCl
2) and phosphoric acid (H
3PO
4) polycondensation under suitable condition, according to H
3PO
4With R
2SiCl
2The difference of mol ratio x, can obtain in theory as shown in Figure 3 tripolymer and linear hybridized polymer long-chain as shown in Figure 4.But after having increased δ (being the molar ratio 2.1=2+ δ of dimethyldichlorosilane(DMCS)), make linear hybridized polymer long-chain form crosslinking structure, increased structural strength, toughness after forming.
2), preparation resin; Aforementioned low cross-linking hybridized polymer is cooled to 30 ℃, adds CaO immediately in described low cross-linking hybridized polymer, add-on is 8% of described low cross-linking hybridized polymer weight, in the interpolation process, evenly stirs, and gets transparent colloidal resin; This moment, calcium oxide was blended between the aforementioned crosslinked linear hybridized polymer long-chain with molecular form " physics attitude ".
3), finish.
The preparation method of pre-composition of the present invention, described pre-composition comprises that described transparent colloidal resin 23%, liquid phenenyl ethene mix under 20 ℃ with low contraction material 10%, the tert-butyl ester 1.0% and the Zinic stearas 0.6% that granules of polystyrene mixes by the 2:1 weight ratio, are stirred to evenly; Add glass fibre 15% and Al then
2O
3Powder 50% is evenly mediated, and gets bulk plasticity pre-composition; Make.Al
2O
3Powder is processed as 325 order powders.
Also be added with the divalent metal oxyhydroxide of using as solidifying agent in the described pre-composition, add-on is 0.1% of described pre-composition gross weight; Described divalent metal oxyhydroxide is calcium hydroxide.
Forming method of the present invention drops into the surface with described bulk plasticity pre-composition and scribbles in the metal molding die of polyether-ether-ketone, and hot pressing under 140 ℃ of environment makes profiled member.
Application of the present invention after described transparent gluey preparation of compositions is bulk plasticity pre-composition, by forming process, gets the U-shaped plate of doing the insulation sealing member on the aluminium cell.
Embodiment two
The preparation method of high-strong toughness of the present invention is high temperature resistant hybrid polymer resin, processing according to the following steps:
1), preparation polymkeric substance; Get METHYL TRICHLORO SILANE (RSiCl
3) and phosphoric acid, (2+ δ): 2, wherein mix under 32 ℃ of temperature δ=3/10; Immediately under the helium atmosphere environment of 90 ℃ of temperature, progressively be warming up to 240 ℃ and be incubated 1.2 hours, carry out polyreaction; Get colloidal low cross-linking hybridized polymer; Molecular structure as shown in Figure 1.The preparation principle of hybrid inorganic-organic polymkeric substance is as follows: dimethyldichlorosilane(DMCS) (R
2SiCl
2) and phosphoric acid (H
3PO
4) polycondensation under suitable condition, according to H
3PO
4With R
2SiCl
2The difference of mol ratio x, can obtain in theory as shown in Figure 3 tripolymer and linear hybridized polymer long-chain as shown in Figure 4.But after having increased δ, make linear hybridized polymer long-chain form crosslinking structure, increased structural strength, toughness after forming.
2), preparation resin; Aforementioned low cross-linking hybridized polymer is cooled to 18 ℃, adds CuO immediately in described low cross-linking hybridized polymer, add-on is 5% of described low cross-linking hybridized polymer weight, in the interpolation process, evenly stirs, and gets transparent colloidal resin;
3), finish.
The preparation method of pre-composition of the present invention, described pre-composition comprises that described transparent colloidal resin 28%, liquid phenenyl ethene mix under 35 ℃ with low contraction material 15%, the tert-butyl ester 1.5% and the Zinic stearas 1.2% that granules of polystyrene mixes by the 2:1 weight ratio, are stirred to evenly; Add glass fibre 25% and mica powder 40% then, evenly mediate, get bulk plasticity pre-composition; Make.
Also be added with the magnesium hydroxide of using as solidifying agent in the described pre-composition, add-on is 1.5% of described pre-composition gross weight.
Forming method of the present invention drops into the surface with described bulk plasticity pre-composition and scribbles in the metal molding die of polyether-ether-ketone, and hot pressing under 160 ℃ of environment makes profiled member.
Application of the present invention after described transparent gluey preparation of compositions is bulk plasticity pre-composition, by forming process, gets the U-shaped plate of doing the insulation sealing member on the aluminium cell.
Embodiment three
The preparation method of high-strong toughness of the present invention is high temperature resistant hybrid polymer resin, processing according to the following steps:
1), preparation polymkeric substance; Get METHYL TRICHLORO SILANE (RSiCl
3) and phosphoric acid, (2+ δ) in molar ratio: 2, mix under 38 ℃ of temperature wherein (δ=0.2); Immediately under the argon gas atmosphere environment of 100 ℃ of temperature, progressively be warming up to 250 ℃ and be incubated 1 hour, carry out polyreaction; Get colloidal low cross-linking hybridized polymer;
2), preparation resin; Aforementioned low cross-linking hybridized polymer is cooled to 24 ℃, adds ZnO immediately in described low cross-linking hybridized polymer, add-on is 6% of described low cross-linking hybridized polymer weight, in the interpolation process, evenly stirs, and gets transparent colloidal resin;
3), finish.
The preparation method of pre-composition of the present invention, described pre-composition comprises that described transparent colloidal resin 25.5%, liquid phenenyl ethene mix under 28 ℃ with low contraction material 12.5%, the tert-butyl ester 1.2% and the Zinic stearas 1% that granules of polystyrene mixes by the 2:1 weight ratio, are stirred to evenly; Add glass fibre 20% and filler 45% then, evenly mediate, get bulk plasticity pre-composition; Make.
Described filler is Al
2O
3Powder and mica powder, ratio are 50:50.(mica powder 400 orders, Al
2O
3325 orders)
Also be added with the calcium hydroxide of using as solidifying agent in the described pre-composition, add-on is 0.7% of described pre-composition gross weight.
Forming method of the present invention drops into the surface with described bulk plasticity pre-composition and scribbles in the metal molding die of polyether-ether-ketone, and hot pressing under 150 ℃ of environment makes profiled member.
Application of the present invention after described transparent gluey preparation of compositions is bulk plasticity pre-composition, by forming process, gets the U-shaped plate of doing the insulation sealing member on the aluminium cell.
The present invention in use, when envrionment temperature reached 350-370 ℃, the R group decomposed, product can lose the weight of 5-8%, toughness descends simultaneously.This is that after the substituent R thermolysis of organic moiety on the molecular chain was left away, Si had more two active reaction points, and is very easily crosslinked with other parts or other chains of chain because the Si atom is 4 valencys, forms with [SiO
4] tetrahedron is the crystalline structure of structural unit, thereby lost the kindliness of chain molecule, in order to overcome this shortcoming, when synthetic, need add bivalent metal oxides such as a certain proportion of CaO, CuO or ZnO, substitute R with part
2SiCl
2Monomer is at high temperature kept chain-like structure.As shown in Figure 2.The heatproof bonded adhesives of this structure and commonly used phosphoric acid-cupric oxide series (can anti-high temperature more than 800 ℃) similar, but contain the part silicone ingredients.The existence of organosilicon part has improved stability and the rheological of resin (glue) when room temperature, the convenient use.Test shows that the product of this modification can be for a long time 370-700 ℃ of work down, toughness is only lower slightly than the hybridized polymer among Fig. 1, shape is translucent, but it must cooperate competence exertion effectiveness with suitable filler in use, this is because of the hydroxyl instability on the phosphorus atom under the high temperature, easily dewater and pyrophosphorylation, this is equivalent to increase degree of crosslinking, and material is become fragile.In filler, add the low glass modifier of a certain amount of valence state or the metal oxide of organizer for this reason, these metal oxides and hydroxyl reaction under working temperature, generate dangling bonds, reduce the number of P-O-P bridging oxygen key, can make structure at high temperature keep the kindliness of chain-like structure to greatest extent like this, make bonded adhesives keep toughness.Hydroxyl on the phosphorus atom still is the key of adhesive curing.Selection has the divalent metal oxyhydroxide of alkalescence, as Ca (OH)
2, make solidifying agent, can be near room temperature and the P-OH radical reaction, bonded adhesives because increasing, degree of crosslinking is solidified.
If the resin among the present invention (bonded adhesives) is solidified the back calcining, can obtain the similar structure that is used as the low melting glass of electronic package material.Ultimate principle of the present invention can be summarized as: when low-temperature working, the bonded adhesives molecule is identical with organic polymer; When at high temperature working, organic moiety is decomposed, for preventing degradation production SiO
2, POx forms the inorganic crystal phase of fragility, in molecular structure or in filler, add the low glass modifier of valence state or the metal oxide of organizer, to reduce the number of Si-O-Si or P-O-P bridging oxygen key, make degradation production form the low melting glass attitude of thickness, continued bonding effect.
The present invention creatively proposes organic and inorganic " hybrid polymer " concept.Ultimate principle can be summarized as: when low temperature (below 370 ℃) was worked, the hybrid polymer resin was identical with organic polymer; When high temperature (370-520 ℃) was worked down, organic moiety was decomposed, for preventing degradation production SiO
2, PO
xForm the inorganic crystal phase of fragility, in molecular structure or in filler, add the low glass modifier of valence state or the metal oxide of organizer, to reduce the number of Si-O-Si or P-O-P bridging oxygen key, make degradation production form the low melting glass attitude of thickness, continued bonding effect.
Claims (5)
1. the preparation method of the resin premixed thing of the high temperature resistant hybrid polymer of high-strong toughness, process earlier described resin according to the following steps:
1), preparation polymkeric substance; Get organosilicon and phosphoric acid, in molar ratio (2+ δ): 2, wherein mix under 32-48 ℃ of temperature 1/10≤δ≤3/10; Immediately under temperature 90-110 ℃ shielding gas atmosphere, progressively be warming up to 240-260 ℃ and be incubated 0.8-1.2 hour, carry out the hybrid inorganic-organic polyreaction; Get colloidal low cross-linking hybridized polymer;
2), preparation resin; Aforementioned low cross-linking hybridized polymer is cooled to 18-30 ℃, add bivalent metal oxide immediately in described low cross-linking hybridized polymer, add-on is the 5-8% of described low cross-linking hybridized polymer weight, in the interpolation process, evenly stir, get transparent colloidal resin; It is characterized in that,
Then, preparation pre-composition, described pre-composition comprise described transparent colloidal resin 23-28%, low material 10-15%, tert-butyl ester 1.0-1.5% and the Zinic stearas 0.6-1.2% of shrinking, and mix under 20-35 ℃, be stirred to evenly; Add glass fibre 15-25% and filler 40-50% then, evenly mediate, get bulk plasticity pre-composition; Make;
Also be added with the divalent metal oxyhydroxide of using as solidifying agent in the described pre-composition, add-on is the 0.1-1.5% of described pre-composition gross weight; Described divalent metal oxyhydroxide is calcium hydroxide or magnesium hydroxide;
Wherein, to be liquid phenenyl ethene and granules of polystyrene evenly mixed by the 2:1 weight ratio for described low contraction material;
Described organosilicon is dimethyldichlorosilane(DMCS) or METHYL TRICHLORO SILANE.
2. the preparation method of the resin premixed thing of the high temperature resistant hybrid polymer of a kind of high-strong toughness according to claim 1 is characterized in that, described bivalent metal oxide is CaO, CuO or ZnO.
3. the preparation method of the resin premixed thing of the high temperature resistant hybrid polymer of a kind of high-strong toughness according to claim 1 is characterized in that, described shielding gas is nitrogen or rare gas element.
4. the preparation method of the resin premixed thing of the high temperature resistant hybrid polymer of a kind of high-strong toughness according to claim 1 is characterized in that, described filler is Al
2O
3Powder and mica powder, ratio are (0-100): (100-0).
5. forming method that adopts the resin premixed thing of the claim 1 high temperature resistant hybrid polymer of described a kind of high-strong toughness, it is characterized in that, described bulk plasticity pre-composition is dropped into the surface scribble in the metal molding die of polyether-ether-ketone, hot pressing under 140-160 ℃ of environment makes profiled member.
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