CN101434745B - Polymer alloy and preparation thereof - Google Patents
Polymer alloy and preparation thereof Download PDFInfo
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- CN101434745B CN101434745B CN2007101871387A CN200710187138A CN101434745B CN 101434745 B CN101434745 B CN 101434745B CN 2007101871387 A CN2007101871387 A CN 2007101871387A CN 200710187138 A CN200710187138 A CN 200710187138A CN 101434745 B CN101434745 B CN 101434745B
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Abstract
The invention relates to a polymer alloy material and a preparation method thereof. The polymer alloy material is a product obtained by mixing polycarbonate, polyethylene glycol terephthalate, an inorganic additive contacting with an intercalator, a lubricant and an antioxidant selectively contained at the temperature that can melt the polycarbonate and polyethylene glycol terephthalate; the inorganic additive is one or more than one of phyllosilicates, nano inorganic oxides, hydroxides, carbonate and sulfate; the intercalator comprises a reactive type intercalator; the addition of the inorganic additive contacting with the intercalator can remarkably raise the melting point of the polymer alloy material so as to widen the using range, lead the processing temperature of PC resin to be more close to PET resin and lead the reaction temperature to be controlled more easily; the toughness, gas isolation performance and melting resistance of an alloy prepared are obviously promoted and the processing performance thereof is remarkably improved.
Description
Technical field
The present invention relates to a kind of polymer alloy and preparation method thereof.
Background technology
Polycarbonate (PC) is a kind of unformed hard thermoplastic plastics, have advantages such as good, heat-resisting, transparent, the nontoxic energy of shock strength height, creep resistance and dimensional stability is good, of many uses in fields such as electric, automotive industry, medicine equipment, building and lighting apparatuss.Yet, PC also exist processing fluidity poor, easily stress cracking, to shortcomings such as breach sensitivity, wearing and tearing easily, the chemical proofing of anti-the solvent are poor, on the high side, these shortcomings are restricted its application in a lot of fields.
Polyethylene terephthalate (PET) is a kind of crystallizable thermoplastics, has characteristics such as high strength, high rigidity, good thermotolerance, good dimensional stability, the chemical proofing of anti-the solvent as engineering plastics.It is that crystallization velocity is slow excessively as the difficulty of plastic applications, can not be suitable for the forming processing technology of general-purpose plastics, and shock-resistance also has much room for improvement.In addition, its heat-drawn wire is low, and shortcomings such as barrier properties for gases difference have also limited its range of application.
Alloy is made in PC and PET blend can learn from other's strong points to offset one's weaknesses, thereby has than excellent comprehensive performances, as disclosed manufacture method among the CN 101007893A.But transesterification reaction can take place in inevitably in the preparation process of PC/PET alloy, causes problems such as the reduction of blend fusing point, degree of crystallinity decline, nucleation rate reduction, thereby reduces the mechanical property of material, and makes extrusion moulding become difficult.
Montmorillonite is early to be used to one of inorganic materials of polymer modification.Because the double electrical layers of montmorillonite crystal layer inside, upper layer with the big organic cation of the easy adsorption specific surface area of negative charge near crystal layer, original positively charged ion between final substituted layer forms more stable laminate structure.The organic cation of large volume, both be easy to support big montmorillonite layer spacing, help forming stable intercalation composite minerals again, make the montmorillonite surfaces externally and internally become hydrophobicly, can make between the compound insertion montmorillonite layer of organic solvent, polymer monomer or polymkeric substance to form various montmorillonite/polymer nanocomposites by hydrophilic.Intercalator is divided into response type (active group is arranged) and non-response type (non-activity group) two classes by having or not active group in the structure.
Disclose a kind of polyester/phyllosilicate nano-composite material in CN 1465621A, its preparation method comprises: intercalator is contacted with layered silicate, obtain modified sheet silicate; With modified sheet silicate and polyester melting mixing extruding pelletization, obtain polyester/phyllosilicate nano-composite material.Described polyester is PET, polybutylene terephthalate (PBT), PC, copolyester or its mixture.Used intercalator is non-response type intercalator, comprises lauryl amine, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide or octadecyl benzyl dimethyl brometo de amonio.Though the material that this method is made has made the clay seam spacing change, this intercalator molecule does not possess the organic group that can react, thereby does not have the effect of the reinforcement that reaches by the formation macromole.
For the alloy of PC and PET, if only select non-response type intercalator for use, the end-blocking effect that is produced in the time of can't bringing into play the intercalator reaction.Thereby, can not fundamentally improve toughness, barrier properties for gases, solvent resistance and the processing characteristics of alloy material.
Summary of the invention
The objective of the invention is to overcome the relatively poor shortcoming of toughness, barrier properties for gases, solvent resistance and processing characteristics of the PC/PET alloy that prior art makes, a kind of polymer alloy material with processing characteristics of high toughness, barrier properties for gases and solvent resistance and improvement is provided.
Another object of the present invention provides the preparation method of this polymer alloy material.
The invention provides a kind of polymer alloy material, wherein, this material is by PC, PET, makes the product that mixes under PC and the PET fused temperature and obtain with lubricant and antioxidant that contacted inorganic additives of intercalator and selectivity contain, and described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator is the response type intercalator.
The present invention also provides a kind of preparation method of polymer alloy material, wherein, this method comprises that lubricant that PC, PET, the inorganic additives that contacts with intercalator and selectivity are contained and antioxidant mix making under PC and the PET fused temperature, and described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator comprises the response type intercalator.
Utilize the active group in the response type intercalator to react with inorganic additives, polycondensation forms stablizes this mechanism of cross-linked macromolecular, can allow this intercalator serve as parents' tensio-active agent on the one hand, makes between organic phase and the inorganic phase compatible better; It can bring into play the effect of end-capping reagent on the other hand, reduces the group that transesterification reaction takes place in the polyester easily, avoids generating the third product that has a strong impact on the alloy material performance.
Material provided by the invention and existing P C/PET alloy phase ratio, toughness, barrier properties for gases and solvent resistance obviously improve and processing characteristics is significantly improved.Adding with the contacted inorganic additives of response type intercalator makes the fusing point of this polymer alloy material significantly improve, and has widened use range, and the processing temperature that makes the PC resin makes temperature of reaction be more prone to control more near the PET resin.
Embodiment
PC with 100 weight parts is a benchmark, and the content of each component is: PET is the 30-70 weight part; The inorganic additives contacted with intercalator is the 4-30 weight part; Lubricant is the 0-3 weight part, is preferably the 0.5-2 weight part; Antioxidant is the 0-3 weight part, is preferably the 0.5-2 weight part.Described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator comprises the response type intercalator.
Described PC can be the various PC that are used to prepare polymer alloy of routine.In the present invention, the weight-average molecular weight of PC is preferably 30000-50000.The melt temperature of PC is generally 220-230 ℃, and decomposition temperature is generally 350-370 ℃.
Described PET can be the various PET that are used to prepare polymer alloy of routine.In the present invention, the weight-average molecular weight of PET is preferably 20000-35000.The melt temperature of PET is generally 250-270 ℃, and decomposition temperature is generally 360-380 ℃.
Described PC and the PET fused temperature of making for example, can be 220-270 ℃ for more than or equal to the melt temperature of PC and PET and less than the decomposition temperature of PC and PET.
Layered silicate can be various layered silicates, be preferably in rectorite, fluorine hectorite, hectorite, rich magnesium montmorillonite, montmorillonite, wilkinite and the rectorite leng one or more, more preferably polynite content is the above layered silicate of 85% weight; Described inorganic oxide is one or more in aluminum oxide, zirconium white, the silicon-dioxide; Described oxyhydroxide is magnesium hydroxide and/or aluminium hydroxide; Described carbonate is lime carbonate and/or magnesiumcarbonate; Described vitriol is barium sulfate and/or calcium sulfate.
More even in order to make various components mix ground, the average particle diameter of described inorganic additives is preferably 0.5-200nm, more preferably 1-50nm.
The amount that is used for the intercalator that contacts with inorganic additives is the 1-5 weight % of inorganic additives, is preferably 1.5-2.5 weight %.The inorganic additives contacted with intercalator can be by contacting inorganic additives (for example with the solution that contains described intercalator, inorganic additives is immersed in the solution that contains described intercalator), the temperature of contact can be 40-80 ℃, be preferably 65-75 ℃, can be 1-5 hour duration of contact, be preferably 2-4 hour, take out then and dry and make.
Described response type intercalator is selected from one or more in the alkyl lactan that carbonatoms is the ammonium salt that forms of the alkyl diamines that contains 1-6 carbon carbon unsaturated link(age) of 10-70, carbonatoms is 10-70 alkyl amino acid and carbonatoms be 10-70.The negatively charged ion of the ammonium salt that described alkyl diamines forms can be the negatively charged ion of organic or inorganic, for example, can be Cl
-, CO
3 2-, SO
4 2-, PO
4 3-, COO
-, PhO
-, NO
3 -, C
2O
4 2-, SO
3 2-In one or more.The example of described response type intercalator includes but not limited to: CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2N (CH
3) H
2Cl, CH
3(CH
2)
11N (CH
2)
5-CO, CH
3(CH
2)
17N (CH
2)
5-CO, CH
3(CH
2)
15N (CH
2)
5-CO, CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2NH
3Cl, CH
3-(CH
2)
11-CH-NH
2-COOH, CH
3-(CH
2)
17-CH-NH
2-COOH, CH
3-(CH
2)
11-S-CH
2-CH-NH
2-COOH.
The nano inorganic additive of vast scale organises in order to allow more, and intercalator can also comprise non-response type intercalator.The weight ratio of response type intercalator and non-response type intercalator is 1: 2-3: 1, be preferably 1: 1-2: 1.Described non-response type intercalator is selected from one or more in the ammonium salt that kiber alkyl amine that carbonatoms is 10-70, secondary amine and tertiary amine form.The negatively charged ion of described ammonium salt can be the negatively charged ion of organic or inorganic, for example, can be Cl
-, CO
3 2-, SO
4 2-, PO
4 3-, COO
-, PhO
-, NO
3 -, C
2O
4 2-, SO
3 2-In one or more.The example of described non-response type intercalator includes but not limited to: CH
3-(CH
2)
17-NH
3Cl, CH
3-(CH
2)
17-N (CH
3)
2HCl, CH
3-(CH
2)
17-N (CH
3) H
2Cl, (CH
3-(CH
2)
17-NH
3)
2C
2O
4, (CH
3-(CH
2)
17-N (CH
3)
2H)
2SO
4
The response type intercalator can be handled inorganic additives as intercalator separately, also can mix with non-response type intercalator or successively inorganic additives be handled.Under the preferable case, after handling with the response type intercalator earlier, handle with non-response type intercalator again.
Described lubricant can be preferably silicone lubricant for the various lubricants that are used for polymer alloy of routine, and described silicone lubricant can be [C
5H
12SiO
2]
m, { [RO (CH
2CH
2O)
n]
4Si}
m(CH
3)
3Si[OSi (CH
3)
2]
p-C
3H
6-O-(CH
2CH
2O)
q-CH
3In one or more, R is that carbonatoms is replacement or the unsubstituted monovalence alkyl of 1-20, m is the integer of 30-100, n is the integer of 2-4, p is the integer of 30-100, q is the integer of 20-80.
Described antioxidant can be the various antioxidants that are used for polymer alloy of routine, be preferably four [methyl-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in pentaerythritol ester (be called for short 1010) and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (abbreviation 168) one or both.
The preparation method of polymer alloy material provided by the invention comprises that lubricant that PC, PET, the inorganic additives that contacts with intercalator and selectivity are contained and antioxidant mix making under polycarbonate and the polyethylene terephthalate fused temperature, and described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator comprises the response type intercalator.
PC with 100 weight parts is a benchmark, and the add-on of PET is the 30-70 weight part; With the add-on of the contacted inorganic additives of intercalator be the 4-30 weight part; The add-on of lubricant is the 0-3 weight part, is preferably the 0.5-2 weight part; The add-on of antioxidant is the 0-3 weight part, is preferably the 0.5-2 weight part.
Under the preferable case, the lubricant that contains with PC, PET, with contacted inorganic additives of intercalator and selectivity and antioxidant blended method comprise that the lubricant that earlier PC, the inorganic additives that contacts with intercalator and selectivity contained and antioxidant are blended in to make under the PC fused temperature and mix, and then the mixture that obtains mixed making under the PET fused temperature with PET again.According to this preferred implementation, can improve toughness, barrier properties for gases and solvent resistance and the processing characteristics of polymer alloy material better.
According to method of the present invention, make under PC and the PET fused temperature, lubricant and antioxidant blended process that inorganic additives of handling with PC, PET, with intercalator and selectivity contain can be carried out in the various device known in the art, as, can in twin screw extruder, mix and extruding pelletization then in stirrer for mixing.With method, condition and the used forcing machine of mixture extruding pelletization is conventionally known to one of skill in the art.The pellet of extruding can pass through the direct injection moulding of injection moulding machine.
Under the preferable case, preparation method's provided by the invention concrete steps are as follows:
(1) processing of inorganic additives.Per 100 gram inorganic additivess add 1.5-2.5 gram response type intercalators, and high-speed stirring is blended in 65-75 ℃ of effect 2-4 hour, through standby after solid-liquid separation, washing, centrifugal, the vacuum-drying.Get the said products and add 1-2 and restrain non-response type intercalator, high-speed stirring is blended in 65-75 ℃ of effect 4-6 hour, through standby after solid-liquid separation, washing, centrifugal, the vacuum-drying.
(2) lubricant and the antioxidant that contains with PC, with contacted inorganic additives of intercalator and selectivity mixes, and makes under the PC fused temperature, adopts the twin screw extruder extruding pelletization.Wherein, described twin screw extruder length-to-diameter ratio is 32-52: 1, and screw speed 150-400 rev/min, temperature can be 220-250 ℃.
(3) to join stirrer for mixing even for the pellet that PET and step (2) are obtained, and obtains mixture, and wherein, the temperature of blended under agitation can be 85-120 ℃, and the time of blended under agitation can be 1-30 minute, and the rotating speed of blended under agitation is 50-200 rev/min.
(4) adopt twin screw extruder, length-to-diameter ratio is 32-52: 1, and screw speed 150-400 rev/min, temperature is 240-270 ℃, with the mixture fusion and the extruding pelletization of step (3).
Before mixing, can be with PC and PET drying, to remove moisture wherein.The exsiccant temperature can be 85-100 ℃, and can be 4-6 hour time of drying.
The kind of PC, PET, the inorganic additives that contacts with intercalator and lubricant and antioxidant is described in detail hereinbefore, does not repeat them here.
Below will be described in more detail the present invention by embodiment.
Embodiment 1.
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
(1) handles polynite.
With response type intercalator CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2NH
3It is 20% ethanolic soln that Cl is made into massfraction.(Zhejiang Feng Hong, NANNOLIN DK4) puts into this solution with polynite, and per 100 gram montmorillonites use 1.5 gram intercalators, and high-speed stirring is blended in 70 ℃ of effects 3 hours.After the solid-liquid separation, with washing with alcohol 3 times (per 100 gram solid products are at every turn with 100 milliliters of ethanol), with 100 rev/mins centrifugal 20 minutes, standby after 2 hours 80 ℃ of following vacuum-dryings.Make above-mentioned product and non-response type intercalator CH then
3(CH
2)
17N (CH
3)
3The Cl effect.Earlier intercalator is made into massfraction and is 20% ethanolic soln, the above-mentioned product of per 100 grams adds the 1g intercalator, and high-speed stirring mixed suspension liquid, 70 ℃ of effects 5.5 hours.After the solid-liquid separation, with washing with alcohol 3 times (per 100 gram solid products are at every turn with 100 milliliters of ethanol), with 100 rev/mins centrifugal 20 minutes, standby after 2 hours 80 ℃ of following vacuum-dryings.
(2) preparation PC/ layered silicate alloy.
The polynite contacted that PC and step (1) are obtained with intercalator, 100 ℃ dry 4 hours down, the polynite that 100 weight part PC, 5 weight parts and intercalator is contacted, 1 weight part, 1010,1 weight part [C
5H
12SiO
2]
50Uniform mixing.Pass through the twin screw extruder extruding pelletization then, used twin screw extruder length-to-diameter ratio is 40: 1,260 rev/mins of screw speeds, and the controlled temperature scope is 225-235 ℃.
(3) to join stirrer for mixing even for the pellet that PET and step (2) are obtained, and obtains mixture, and wherein, mixture contains the contacted polynite of 100 weight part PC, 65 weight part PET, 5 weight parts and intercalator, 1 weight part, 1010,1 weight part [C
5H
12SiO
2]
50The temperature of blended under agitation is 100 ℃, and the time of blended under agitation is 5 minutes, and the rotating speed of blended under agitation is 200 rev/mins.
(4) adopt twin screw extruder, length-to-diameter ratio is 40: 1,260 rev/mins of screw speeds, and the controlled temperature scope is 245-255 ℃, with the mixture fusion and the extruding pelletization of step (3), note is made E1.
Embodiment 2
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
(1) handles polynite.
With response type intercalator CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2N (CH
3) H
2It is 20% ethanolic soln that Cl is made into massfraction.(Zhejiang Feng Hong, NANNOLIN DK4) puts into this solution with polynite, and 2.5 gram intercalators are used in per 100 gram polynites, and high-speed stirring is blended in 70 ℃ of effects 3 hours.After the solid-liquid separation, with washing with alcohol 3 times (per 100 gram solid products are at every turn with 100 milliliters of ethanol), with 100 rev/mins centrifugal 20 minutes, standby after 2 hours 80 ℃ of following vacuum-dryings.Make above-mentioned product and non-response type intercalator CH then
3(CH
2)
11N (CH
3)
3The massfraction that Cl is made into is 20% ethanolic soln effect, and the above-mentioned product of per 150 grams adds the 1.5g intercalator, and high-speed stirring mixed suspension liquid, 70 ℃ of effects 5.5 hours.After the solid-liquid separation, with washing with alcohol 3 times (per 100 gram solid products are at every turn with 100 milliliters of ethanol), with 100 rev/mins centrifugal 20 minutes, standby after 2 hours 80 ℃ of following vacuum-dryings.
(2) with PC and the polynite contacted with intercalator, drying is 4 hours under 85 ℃, the polynite that 100 weight part PC, 10 weight parts and intercalator is contacted, 2 weight parts, 1010,2 weight part [C
5H
12SiO
2]
50Uniform mixing.Pass through the twin screw extruder extruding pelletization then, used twin screw extruder length-to-diameter ratio is 40: 1,260 rev/mins of screw speeds, and the controlled temperature scope is 225-235 ℃.
(3) to join stirrer for mixing even for the pellet that PET and step (2) are obtained, and obtains mixture, and wherein, mixture contains the contacted polynite of 100 weight part PC, 50 weight part PET, 10 weight parts and intercalator, 2 weight parts, 1010,2 weight part [C
5H
12SiO
2]
50The temperature of blended under agitation is 100 ℃, and the time of blended under agitation is 5 minutes, and the rotating speed of blended under agitation is 200 rev/mins.
(4) with embodiment 1 step (4), the product note is made E2.
Embodiment 3
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
(1) handles nano zircite.
With with the identical method of embodiment 1 step (1), replace polynite with zirconium white (Nanjing Ai Purui), make the zirconium white contacted with intercalator.
(2) with PC and the zirconium white contacted with intercalator, drying is 4 hours under 85 ℃, the zirconium white that 100 weight part PC, 20 weight parts and intercalator is contacted, 1 weight part, 1010,1 weight part (CH
3)
3Si[OSi (CH
3)
2]
50-C
3H
6-O-(CH
2CH
2O)
30-CH
3Uniform mixing.Pass through the twin screw extruder extruding pelletization then, used twin screw extruder length-to-diameter ratio is 40: 1,260 rev/mins of screw speeds; The controlled temperature scope is 225-235 ℃.
(3) to join stirrer for mixing even for the pellet that PET and step (2) are obtained, and obtains mixture, and wherein, mixture contains the contacted zirconium white of 100 weight part PC, 50 weight part PET, 20 weight parts and intercalator, 1 weight part, 1010,1 weight part [C
5H1
2SiO
2]
50The temperature of blended under agitation is 100 ℃, and the time of blended under agitation is 5 minutes, and the rotating speed of blended under agitation is 200 rev/mins.
(4) with embodiment 1 step (4), note is made E3.
Embodiment 4
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
With the method identical with embodiment 1, different is, (river jumps with nano-aluminum hydroxide, 6000 orders) replace polynite, and do not add antioxidant and lubricant, mixture contains 100 weight part PC, 40 weight part PET, 25 weight parts and the contacted aluminium hydroxide of intercalator, and the product note is made E4.
Embodiment 5
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
Prepare alloy with the method identical with embodiment 1, different is, replaces polynite with nano barium sulfate (river that jumps, 12500 orders), and used response type intercalator is with CH
3-(CH
2)
11-CH-NH
2-COOH replaced C H
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2NH
3Cl, the product note is made E5.
Embodiment 6
Present embodiment is used to illustrate the preparation of PC/PET alloy of the present invention.
(1) handles nano-calcium carbonate.
Select the mixing intercalator for use, make response type intercalator CH
3(CH
2)
11N (CH
2)
5-CO and non-response type intercalator CH
3-(CH
2)
17-NH
3Cl mixes, and the weight ratio of two kinds of intercalators is: 1.5: 1, be made into massfraction and be 20% ethanolic soln.Add the above-mentioned mixing intercalator of 1.5g in per 100 gram lime carbonate (river that jumps, 12500 orders), mixed 3 hours 70 ℃ of high-speed stirring.After the solid-liquid separation, with washing with alcohol 3 times (per 100 gram solid products are at every turn with 100 milliliters of ethanol), with 100 rev/mins centrifugal 20 minutes, standby after 2 hours 80 ℃ of following vacuum-dryings.
Step (2), (3), (4) are with embodiment 3, and the product note is made E6.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation of prior art PC/PET alloy.
(1) PET sheet stock, PC pellet and methyl methacrylate are mixed, wherein contain the PC of 100 weight parts, the PET of 40 weight parts and the methyl methacrylate of 25 weight parts.The fineness of described PET section is 100 orders, and PC particulate fineness is 100 orders.
(2) first that above-mentioned compound is following dry 4 hours at 85 ℃.Adopt the twin screw extruder extruding pelletization, used twin screw extruder length-to-diameter ratio is 40: 1,260 rev/mins of screw speeds; The controlled temperature scope is 240-250 ℃, and the product note is made C1.
Comparative Examples 2
This Comparative Examples is used to illustrate the preparation of prior art polyester/phyllosilicate nano-composite material.
(1) handles polynite
With polynite 5 grams, add 200 milliliters of deionized waters, high-speed stirring was uniformly dispersed in 0.5 hour; Again 0.6 milliliter of concentrated hydrochloric acid and 2.6 gram hexadecyl brometo de amonios are added in 100 ml deionized water; The latter is slowly added in the montmorillonite suspension liquid, continue high-speed stirring and hand over and be warming up to 70 ℃, through standby after solid-liquid separation, washing, centrifugal, the vacuum-drying.
(2) 350 gram PC and 140 were restrained PET dry 5 hours, the product that obtains with step (1) mixes, and high-speed stirring uses twin screw extruder at 250 ℃ of extruding pelletizations then, and the product note is made C2.
Embodiment 7-12
Embodiment 7-12 is used to measure the performance of the PC/PET alloy that embodiment 1-6 makes.
Melt flow rate (MFR): ASTM D1238
Heat-drawn wire: ASTM D648
Vicat softening point: ASTM D1525
Tensile strength: ASTM D638
Flexural strength, modulus in flexure: ASTM D790
Notched Izod impact strength: ASTM D256
Barrier properties for gases: acc. (Adaptive Cruise Control Systems) ISO 2556, ISO 15106-1
Solvent resistance: under 23 ℃, sample strip is immersed in the trichloroethane solution 6 hours, the material of observe whether it occurs ftractureing, bubble, pitting, colour-change, existence being wiped easily, warpage, layering, impaired, phenomenon such as be partly dissolved, there is obvious phenomenon to be designated as T, do not see that phenomenon is designated as F, have slight phenomenon to be designated as S.
Comparative Examples 3,4
Comparative Examples 3 and 4 is used for the performance of the alloy that test comparison example 1 and 2 makes.
Measure the performance of the alloy that Comparative Examples 1 and 2 makes according to the method identical with embodiment 7-12, the result is as shown in table 1.
Table 1
| Project the numbering | Testing method | E1 | E2 | E3 | E4 | E5 | E6 | C1 | C2 |
| Melt flow rate (MFR)/g/10min | ASTM?D1238 | 23 | 15 | 17 | 12 | 27 | 17 | 10 | 20 |
| Notched Izod impact strength/J/m | ASTM?D256 | 780.53 | 750.18 | 703.16 | 601.04 | 680.13 | 701.35 | 289.53 | 330.20 |
| Flexural strength/MPa | ASTM?D790 | 83.53 | 83.2 | 84.10 | 80.85 | 79.6 | 79.2 | 70.53 | 77.3 |
| Modulus in flexure/MPa | ASTM?D790 | 3996.18 | 3057.9 | 4001.18 | 4241.72 | 3101 | 3215 | 1696.18 | 2250 |
| Tensile strength/MPa | ASTM?D638 | 53.43 | 57.36 | 55.62 | 50.40 | 53.43 | 57.36 | 47.43 | 50.02 |
| Heat-drawn wire/(0.455MPa)/℃ | ASTM?D648 | 112.2 | 109.1 | 108.3 | 103 | 110.5 | 104.1 | 92 | 99 |
| Heat-drawn wire/(1.82MPa)/℃ | ASTM?D648 | 93.1 | 94 | 92 | 90.2 | 93.1 | 94 | 73.1 | 85 |
| Vicat softening point/℃ | ASTM?D1525 | 122 | 120.1 | 120.5 | 117.3 | 108 | 119.1 | 108 | 112 |
| Water vapor transmission rate (WVTR)/g/ (m 2·24h) | ISO?15106-1 | 5.5 | 7.0 | 7.0 | 7.1 | 5.5 | 7.0 | 13 | 7.2 |
| OTR oxygen transmission rate/cm3/ (m224h*bar) | acc.ISO?2556 | 300 | 400 | 400 | 400 | 300 | 400 | 600 | 500 |
| Solvent resistance/0.5h | Trichloroethane | F | F | F | S | F | F | T | S |
By table 1 as can be seen, the present invention uses the inorganic nano additive after the response type intercalator is handled that the PC/PET alloy is carried out modification, compare with existing P C/PET alloy and with the lamella silicate modified polyester that non-response type intercalator is handled, the toughness of material, barrier properties for gases and solvent resistance are improved and processing characteristics is significantly improved.
Claims (22)
1. polymer alloy material, it is characterized in that this material is by polycarbonate, polyethylene terephthalate, makes the product that mixes under polycarbonate and the polyethylene terephthalate fused temperature and obtain with lubricant and antioxidant that contacted inorganic additives of intercalator and selectivity contain; Described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator comprises response type intercalator and non-response type intercalator.
2. polymer alloy material according to claim 1 wherein, is a benchmark with the polycarbonate of 100 weight parts, and the content of each component is: polyethylene terephthalate is the 30-70 weight part; The inorganic additives contacted with intercalator is the 4-30 weight part; Lubricant is the 0.5-2 weight part; Antioxidant is the 0.5-2 weight part.
3. polymer alloy material according to claim 1, wherein, comprise with the preparation method of the contacted inorganic additives of intercalator inorganic additives is contacted with intercalator, the temperature of contact is 65-75 ℃, the time of contact is 2-4 hour, and the consumption of intercalator is the 1-5 weight % of inorganic additives.
4. polymer alloy material according to claim 1, wherein, described response type intercalator is selected from one or more in the lactan that carbonatoms is the ammonium salt that forms of the alkyl diamines that contains 1-6 carbon carbon unsaturated link(age) of 10-70, carbonatoms is 10-70 alkyl amino acid and carbonatoms be 10-70.
5. polymer alloy material according to claim 4, wherein, the described ammonium salt that is formed by the alkyl diamines is CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2N (CH
3) H
2Cl and/or CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2NH
3Cl; Described alkyl amino acid is CH
3-(CH
2)
11-CH (NH
2)-COOH, CH
3-(CH
2)
11-S-CH
2-CH (NH
2)-COOH and CH
3-(CH
2)
17-S-CH
2-CH (NH
2Among the)-COOH one or more; Described alkyl lactan is
In one or more.
6. polymer alloy material according to claim 1 and 2, wherein, the weight ratio of described response type intercalator and non-response type intercalator is 1: 1-2: 1.
7. polymer alloy material according to claim 6, wherein, it is in the ammonium salt that forms of kiber alkyl amine, secondary amine and the tertiary amine of 10-70 one or more that described non-response type intercalator is selected from by carbonatoms.
8. polymer alloy material according to claim 1, wherein, layered silicate is one or more in rectorite, montmorillonite, wilkinite and the rectorite leng; Described inorganic oxide is one or more in aluminum oxide, zirconium white, the silicon-dioxide; Described oxyhydroxide is magnesium hydroxide and/or aluminium hydroxide; Described carbonate is lime carbonate and/or magnesiumcarbonate; Described vitriol is barium sulfate and/or calcium sulfate.
9. polymer alloy material according to claim 8, wherein, described montmorillonite is at least a in fluorine hectorite, hectorite, the rich magnesium montmorillonite.
10. polymer alloy material according to claim 1 and 2, wherein, described lubricant is (CH
3)
3Si[OSi (CH
3)
2]
p-C
3H
6-O-(CH
2CH
2O)
qCH
3, [RO (CH
2CH
2O)
n]
4Among the Si one or more, R are that carbonatoms is replacement or the unsubstituted monovalence alkyl of 1-20, and n is the integer of 2-4, and p is the integer of 30-100, and q is the integer of 20-80; Described antioxidant is four [methyl-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and/or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters.
11. the preparation method of the described polymer alloy material of claim 1, it is characterized in that, this method comprises that lubricant that polycarbonate, polyethylene terephthalate, the inorganic additives that contacts with intercalator and selectivity are contained and antioxidant mix making under polycarbonate and the polyethylene terephthalate fused temperature, and described inorganic additives is one or more in layered silicate, nano inorganic oxide, oxyhydroxide, carbonate and the vitriol; Described intercalator comprises response type intercalator and non-response type intercalator.
12. method according to claim 11, wherein, the lubricant that polycarbonate, polyethylene terephthalate, the inorganic additives that contacts with intercalator and selectivity are contained and antioxidant blended method comprise that the lubricant that earlier polycarbonate, the inorganic additives that contacts with intercalator and selectivity contained and antioxidant are blended under the temperature that makes polycarbonate melt and mix, and then the mixture that obtains mixed making under the polyethylene terephthalate fused temperature with polyethylene terephthalate again.
13. according to claim 11 or 12 described methods, wherein, be benchmark with the polycarbonate of 100 weight parts, the consumption of each component is: polyethylene terephthalate is the 30-70 weight part; The inorganic additives contacted with intercalator is the 4-30 weight part; Lubricant is the 0.5-2 weight part; Antioxidant is the 0.5-2 weight part.
14. according to claim 11 or 12 described methods, wherein, comprise with the preparation method of the contacted inorganic additives of intercalator inorganic additives is contacted with intercalator that the temperature of contact is 65-75 ℃, the time of contact is 2-4 hour, and the consumption of intercalator is the 1-5 weight % of inorganic additives.
15. according to claim 11 or 12 described methods, wherein, described response type intercalator is selected from one or more in the lactan that carbonatoms is the ammonium salt that forms of the alkyl diamines that contains 1-6 carbon carbon unsaturated link(age) of 10-70, carbonatoms is 10-70 alkyl amino acid and carbonatoms be 10-70.
16. polymer alloy material according to claim 15, wherein, the described ammonium salt that is formed by the alkyl diamines is CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2N (CH
3) H
2Cl and/or CH
3-C
4H
8-C
2H
2-NH-C
4H
8-C
2H
2NH
3Cl; Described alkyl amino acid is CH
3-(CH
2)
11-CH (NH
2)-COOH, CH
3-(CH
2)
11-S-CH
2-CH (NH
2)-COOH and CH
3-(CH
2)
17-S-CH
2-CH (NH
2Among the)-COOH one or more; Described alkyl lactan is
In one or more.
17. according to claim 11 or 12 described methods, wherein, the weight ratio of described response type intercalator and non-response type intercalator is 1: 1-2: 1.
18. polymer alloy material according to claim 17, wherein, it is in the ammonium salt that forms of kiber alkyl amine, secondary amine and the tertiary amine of 10-70 one or more that described non-response type intercalator is selected from by carbonatoms.
19. according to claim 11 or 12 described methods, wherein, layered silicate is one or more in rectorite, montmorillonite, wilkinite and the rectorite leng; Described inorganic oxide is one or more in aluminum oxide, zirconium white, the silicon-dioxide; Described oxyhydroxide is magnesium hydroxide and/or aluminium hydroxide; Described carbonate is lime carbonate and/or magnesiumcarbonate; Described vitriol is barium sulfate and/or calcium sulfate.
20. method according to claim 19, wherein, described montmorillonite is at least a in fluorine hectorite, hectorite, the rich magnesium montmorillonite.
21. according to claim 11 or 12 described methods, wherein, described lubricant is (CH
3)
3Si[OSi (CH
3)
2]
p-C
3H
6-O-(CH
2CH
2O)
q-CH
3, [RO (CH
2CH
2O)
n]
4Among the Si one or more, R are that carbonatoms is replacement or the unsubstituted monovalence alkyl of 1-20, and n is the integer of 2-4, and p is the integer of 30-100, and q is the integer of 20-80; Described antioxidant is one or both in four [methyl-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
22. according to claim 11 or 12 described methods, wherein, melt temperature is 220-270 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373775A (en) * | 1999-08-13 | 2002-10-09 | 索罗蒂亚公司 | Method for preparation of polyamide nanocomposite compositions by in situ polymerization |
| US20070161738A1 (en) * | 2006-01-09 | 2007-07-12 | Bayer Materialscience Llc | Thermoplastic composition containing polycarbonate-polyester and nanoclay |
| CN101031510A (en) * | 2004-08-27 | 2007-09-05 | 独立行政法人物质·材料研究机构 | Organic-inorganic composite and polymer composite material, and method for production thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373775A (en) * | 1999-08-13 | 2002-10-09 | 索罗蒂亚公司 | Method for preparation of polyamide nanocomposite compositions by in situ polymerization |
| CN101031510A (en) * | 2004-08-27 | 2007-09-05 | 独立行政法人物质·材料研究机构 | Organic-inorganic composite and polymer composite material, and method for production thereof |
| US20070161738A1 (en) * | 2006-01-09 | 2007-07-12 | Bayer Materialscience Llc | Thermoplastic composition containing polycarbonate-polyester and nanoclay |
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