CN101665610A - Alloy material composition and alloy material - Google Patents
Alloy material composition and alloy material Download PDFInfo
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- CN101665610A CN101665610A CN200810141843A CN200810141843A CN101665610A CN 101665610 A CN101665610 A CN 101665610A CN 200810141843 A CN200810141843 A CN 200810141843A CN 200810141843 A CN200810141843 A CN 200810141843A CN 101665610 A CN101665610 A CN 101665610A
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Abstract
The invention discloses an alloy material composition, which comprises acrylonitrile-butadiene-styrene copolymer (ABS), polycaprolactam (PA6), an antioxidant and a compatible substance. The alloy material composition is characterized in that: the compatible substance contains repeat units shown in a formula 1 and a formula 2, wherein R1 is selected from straight-chain paraffin with carbon atomic number between 2 and 6; R2, R3 and R4 are respectively selected from H, Cl, CH3 and (CH3)3 independently; m is an integer between 2 and 20; and n is an integer between 2 and 20. The invention also discloses an alloy material. The combination between the PA6 component and the ABS component are improved by adding the compatible substance. The alloy material maintains mechanical properties of the material and obviously improves thermal stability, thermal ageing resistance and notch impact strength of the alloy material at the same time.
Description
[technical field]
The material, particularly a kind of polycaprolactam/acrylonitrile-butadiene-styrene copolymer alloy material compositions and the polycaprolactam/acrylonitrile-butadiene-styrene copolymer alloy material that the present invention relates to a kind of alloy material composition and prepare by said composition.
[background technology]
Polycaprolactam (PA6) claim nylon 6 or polyamide 6 again, is to contain repeating unit in a kind of molecular chain
Macromolecular material.Because of it has advantages such as wear-resisting, anti-solvent, oil resistant, Applicable temperature scope wide (40-100 ℃) and melt viscosity are low, be widely used in fields such as machinery, instrument, automobile, electronics, packing.But shortcomings such as simultaneously the polycaprolactam material exists also that water-intake rate is big, poor dimensional stability, low temperature and dry state shock strength are low have limited its application greatly.
Acrylonitrile-butadiene-styrene copolymer (ABS) is made by vinyl cyanide, Succinic Acid, three kinds of monomer copolymerizations of vinylbenzene.The dimensional stability of ABS material is good, good heat resistance, melt viscosity is higher and mechanical property is excellent, but its heat-resisting and weather resisteant can be poor.
The PA6/ABS alloy material that above two kinds of material blend make can be brought into play the advantage of polycaprolactam and ABS, and have good flowing property and graceful outward appearance, Application Areas is boundless.Yet, there are problems such as high interfacial energy and consistency difference between PA6 and the ABS, cause material each several part performance heterogeneity, mechanical property and resistant to thermal aging performance are undesirable.The common method that addresses these problems is exactly the compatilizer that adds block or graft copolymerization.
A kind of PA6/ABS alloy material and preparation method thereof is disclosed in the prior art.Alloy material comprises: PA6, ABS, compatilizer, lubricant, oxidation inhibitor and composite flame-retardant agent.Described compatilizer is styrene-acrylonitrile-maleic anhydride (MAH), styrene-ethylene-butylene-styrene multipolymer (SEBS)-MAH or ABS-MAH.This invention has given material certain flame retardant properties by adding composite flame-retardant agent.And the material that makes has, and good mechanical performance, dimensional stabilizing, intensity height, outward appearance are good, good fluidity and good advantages such as chemical resistance, but the thermostability of the PA6/ABS alloy material of this disclosure of the Invention is not high, heat aging property is poor, has limited its application to a certain extent.
[summary of the invention]
In order to overcome existing P A6/ABS alloy material thermostability, heat aging property and the relatively poor problem of notched Izod impact strength, the invention provides a kind of gold copper-base alloy composition, the alloy material that makes by said composition also has very excellent thermostability, heat aging property and notched Izod impact strength when keeping excellent mechanical performances.
The invention discloses a kind of alloy material composition, comprise acrylonitrile-butadiene-styrene copolymer, polycaprolactam, oxidation inhibitor and compatibiliser, it is characterized in that: contain the repeating unit shown in formula 1 and the formula 2 in the described compatibiliser:
Formula 1:
Formula 2:
Wherein, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, R
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more;
M is the integer of 2-20, and n is the integer of 2-20.
Described compatibiliser is to contain repeating unit shown in the formula 1 and do not contain first compatilizer of repeating unit shown in the formula 2 simultaneously and contain repeating unit shown in the formula 2 and do not contain second compatilizer of repeating unit shown in the formula 1 simultaneously.
Described compatibiliser also can be for containing the compound compatilizer of repeating unit shown in described formula 1 and the formula 2 simultaneously in the molecule.
The invention also discloses a kind of alloy material, it is characterized in that: contain the repeating unit shown in repeating unit shown in the above-mentioned formula 1 and the formula 2 in the described alloy material.
The invention also discloses a kind of alloy material, make by the alloy material composition is mixed 1-5min down at 200-235 ℃, it is characterized in that: described composition is a foregoing.
Added compatibiliser in the alloy material disclosed by the invention, effect by compatibiliser, strengthened the combination between PA6 component and the ABS component, when keeping material mechanical performance, thermostability, heat aging property and the notched Izod impact strength of alloy material have been significantly improved.
[embodiment]
The invention discloses a kind of alloy material composition, comprise acrylonitrile-butadiene-styrene copolymer, polycaprolactam, oxidation inhibitor and compatibiliser, it is characterized in that: contain the repeating unit shown in formula 1 and the formula 2 in the described compatibiliser:
Formula 1:
Formula 2:
Wherein, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, R
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more;
M is the integer of 2-20, and n is the integer of 2-20.
Described polycaprolactam (PA6) is conventionally known to one of skill in the art, can be obtained by ε-Ji Neixianan open loop polycondensation.Among the present invention, described polycaprolactam weight-average molecular weight is 1.5 ten thousand-30,000, and its relative viscosity is 2.85.Described polycaprolactam can be commercially available, as the PA6 YH800H of Ba Ling petro-chemical corporation production.
Described ABS also is conventionally known to one of skill in the art, can be made by vinyl cyanide, Succinic Acid, three kinds of monomer copolymerizations of vinylbenzene, and among the present invention, described ABS weight-average molecular weight is 50,000-150,000.Described ABS can be commercially available, as the ABS 747 of Taiwan Qi Mei company production.
Described compatibiliser is to contain repeating unit shown in the formula 1 and do not contain first compatilizer of repeating unit shown in the formula 2 simultaneously and contain repeating unit shown in the formula 2 and do not contain second compatilizer of repeating unit shown in the formula 1 simultaneously.
R in described first compatilizer
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, m is the integer of 2-20, and weight-average molecular weight is 400-5000.Under the preferable case, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-4 one or more, m is the integer of 5-8, and weight-average molecular weight is 1000-3000.
Described first compatilizer can obtain by self-control, as making solvent with dehydrated alcohol, 4-hydroxybenzoyl hydrazine and propionic aldehyde is mixed in dehydrated alcohol, reacts 3 hours down at 40 ℃, uses hot water and washing with alcohol then, gets final product in 24 hours 55 ℃ of following vacuum-dryings.
R in described second compatilizer
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more, n is the integer of 2-20, weight-average molecular weight is 600-8000.Under the preferable case, R
2, R
3, R
4Independently be selected from H, Cl or CH separately
3In one or more, n is the integer of 5-8, weight-average molecular weight is 2000-4000.
Described second compatilizer can obtain by self-control, as making solvent with dehydrated alcohol, 4-hydroxybenzoyl hydrazine and 2-hydroxy benzaldehyde are mixed in dehydrated alcohol, reacted 3 hours down at 65 ℃, use hot water and washing with alcohol then, got final product in 24 hours 95 ℃ of following vacuum-dryings.
The raw material of above-mentioned preparation first and second compatilizers can be commercially available, as the 4-hydroxybenzoyl hydrazine of Nanjing method nurse laboratory production.
When described described first compatilizer of compatibiliser while and described second compatilizer, the weight ratio of first compatilizer and second compatilizer is 0.3-3: 1, be preferably 0.5-2: 1.The weight ratio of described first compatilizer and second compatilizer is meant the weight ratio when not containing the undocumented material of the present invention in described first compatilizer and/or second compatilizer.When containing the undocumented material of the present invention in described first compatilizer and/or second compatilizer, the weight of this undocumented material without limits.
Described compatibiliser disclosed by the invention is also for containing the compound compatilizer of repeating unit shown in described formula 1 and the formula 2 simultaneously in the molecule.In the described compound compatilizer, repeating unit shown in the formula 1 can directly link to each other with the repeating unit shown in the formula 2 and also can directly not link to each other, under the preferable case, repeating unit shown in the described formula 1 is directly to link to each other with the repeating unit shown in the formula 2, further preferred described compound compatilizer is the material that contains structure shown in the formula 3
Formula 3:
Wherein, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, R
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more;
X is the integer of 2-20, and y is the integer of 2-20.
The preparation method of described compound compatilizer is: with second raw material of repeating unit shown in described first raw material that contains repeating unit shown in the formula 1 and the formula 2, under the condition that initiator exists, stir 1-5h down in 50-75 ℃.
The process of polyreaction is as follows:
With described first raw material weight is benchmark, and described second material content is 25-75wt%, and described initiator content is 0.3-0.5wt%.Under the preferable case, described second material content is 40-60wt%, and described initiator content is 0.3-0.4wt%.The weight of above-described first raw material and second raw material is the weight when not containing the undocumented material of the present invention in described first raw material and second raw material.When containing the undocumented material of the present invention in described first raw material and/or second raw material, the weight of this undocumented material without limits.
R in described first raw material that contains repeating unit shown in the formula 1
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, m is the integer of 2-20, and weight-average molecular weight is 400-5000.Under the preferable case, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-4 one or more, m is the integer of 5-8, and weight-average molecular weight is 1000-3000.
Described first raw material can by with 4-hydroxybenzoyl hydrazine and propionic aldehyde with weight ratio 0.98-1.02: 1 mixes, react 1-5h down at 35-50 ℃, use hot water and washing with alcohol then, make at 50-60 ℃ of following vacuum-drying 12-36h, for example: make solvent with dehydrated alcohol, 4-hydroxybenzoyl hydrazine and 2-hydroxy benzaldehyde are mixed in dehydrated alcohol, reacted 3 hours down at 40 ℃, use hot water and washing with alcohol then, got final product in 24 hours 55 ℃ of following vacuum-dryings.
R in described second raw material that contains repeating unit shown in the formula 2
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more, n is the integer of 2-20, weight-average molecular weight is 600-8000.Under the preferable case, R
2, R
3, R
4Independently be selected from H, Cl or CH separately
3In one or more, n is the integer of 5-8, weight-average molecular weight is 2000-4000.
Described second raw material can by with 4-hydroxybenzoyl hydrazine and 2-hydroxy benzaldehyde with weight ratio 0.98-1.02: 1 mixes, react 1-5h down at 55-75 ℃, use hot water and washing with alcohol then, make at 85-100 ℃ of following vacuum-drying 12-36h, for example: make solvent with dehydrated alcohol, 4-hydroxybenzoyl hydrazine and propionic aldehyde are mixed in dehydrated alcohol, reacted 3 hours down at 65 ℃, use hot water and washing with alcohol then, got final product in 24 hours 95 ℃ of following vacuum-dryings.
Above-mentioned number of repeat unit m that contains formula 1 and formula 2 described repeating units and the x in n and the compound compatilizer and y value can record by SH/T 0108-1992.
Described initiator is this area initiator commonly used, as Sodium Persulfate, Potassium Persulphate, the persulfuric acid lithium, Diisopropyl azodicarboxylate, benzoyl peroxide, dichlorobenzoyl peroxide, nitrogen peroxide, cumene hydroperoxide and t-butylperoxyl benzoate, the diisopropyl benzene hydrogen peroxide, t-butyl perbenzoate, cross sec.-propyl carbonic acid tertiary butyl ester, cross the isopropylformic acid tertiary butyl ester, cross sad tertiary butyl ester, cross two dimethyl isopropyl esters, cross in two carbonic acid two (2-ethylhexyl) ester and the ferrous ion-b diammonium edta one or more, perhaps sodium formaldehyde sulphoxylate, S-WAT, in sodium bisulfite and the saccharosonic acid one or more.Described initiator can be commercially available, the LQ-BPO that the auxiliary reagent factory, Lanzhou produces.
When described compatibiliser is when containing the compound compatilizer of repeating unit shown in described formula 1 and the formula 2 in the molecule simultaneously, can also contain secondary compatilizer in the described composition, described secondary compatilizer contains the first secondary compatilizer and/or the second secondary compatilizer; The described first secondary compatilizer contains repeating unit shown in the formula 1 and does not contain repeating unit shown in the formula 2 simultaneously, and the described second secondary compatilizer contains repeating unit shown in the formula 2 and do not contain repeating unit shown in the formula 1 simultaneously; With described compound compatilizer weight is benchmark, and it is 25-75wt% that described parafacies holds agent content, and when containing the first secondary compatilizer and the second secondary compatilizer in the secondary compatilizer simultaneously, it doesn't matter for the two content, only needs total amount to get final product in above-mentioned scope.The weight of the above-described first secondary compatilizer and the second secondary compatilizer is the weight when not containing the undocumented material of the present invention in the described first secondary compatilizer and the second secondary compatilizer.When containing the undocumented material of the present invention in the described first secondary compatilizer and/or the second secondary compatilizer, the weight of this undocumented material without limits.
The method for preparing the described first secondary compatilizer is identical with above-mentioned first raw material with material, and the method for preparing the described second secondary compatilizer is identical with above-mentioned second raw material with material, does not repeat them here.The described first secondary compatilizer and first raw material, the second secondary compatilizer and second raw material can be identical or different respectively.For making more convenient operation, adding first and/or second properties-correcting agent is directly to use first and/or second raw material.
Owing to during organic synthesis, from the reactant to the product, have transformation efficiency, in the present invention, transformation efficiency there are not special requirement, the reactant content that only need prepare required product falls into separately and gets final product in the content range.
Described oxidation inhibitor is this area oxidation inhibitor commonly used, as butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several; Under the preferable case, described oxidation inhibitor is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.Above-mentioned oxidation inhibitor can be commercially available, as the Irganox 1098 of CIBA company production.
With acrylonitrile-butadiene-styrene copolymer weight is benchmark, and the content of described polycaprolactam is that the content of 10-50wt%, oxidation inhibitor is that the content of 0.2-0.6wt%, compatibiliser is 2-20wt%.Under the preferable case, the content of described polycaprolactam is that the content of 20-30wt%, oxidation inhibitor is that the content of 0.3-0.5wt%, compatibiliser is 5-15wt%.The weight of the above compatibiliser is the weight when not containing the undocumented material of the present invention in the described compatibiliser.When containing the undocumented material of the present invention in the described compatibiliser, the weight of this undocumented material without limits.
The invention also discloses a kind of alloy material, contain the repeating unit shown in repeating unit shown in the above-mentioned formula 1 and the formula 2 in the described alloy material.Repeating unit shown in repeating unit shown in the described formula 1 and the formula 2 can obtain by fourier transform infrared spectroscopy (FT-IR) test, can be GB/T6040-2002 infrared spectrum analysis general rule as testing method.
A kind of alloy material disclosed by the invention can make by above-mentioned alloy material composition is mixed 1-5min down at 210-235 ℃.
Under the preferable case, described blending means is in twin screw extruder, in length-to-diameter ratio is 50-30: 1, screw speed is 150-300r/min, each zone temperatures is respectively 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, the vacuum tightness of each section is to mix under the condition of 0.02-0.08MPa, extrudes then, obtains extruding product.Described vacuum tightness is pounds per square inch absolute (psia).Described twin screw extruder can be this area twin screw extruder commonly used, as the TSSJ25 twin screw extruder of strong company of morning twilight section production.
The described product of extruding is carried out tie rod, pelletizing and injection moulding and can obtain described alloy material.Described tie rod, pelletizing and injection moulding process are this area method commonly used; as extruding product by tank cooling carrying out tie rod; with dicing machine (machinery company limited of Zhangjagang City the United Nations General Assembly; model is QLJ-1) under rotating speed 350r/min, carry out pelletizing; after the oven dry of the micelle after cutting, carry out injection moulding with injection moulding machine.
The present invention is further illustrated below by embodiment.
Embodiment 1
Present embodiment is used to illustrate alloy material composition disclosed by the invention and this alloy material.
1, the preparation of first and second compatilizers
4-hydroxybenzoyl hydrazine and propionic aldehyde in dehydrated alcohol are mixed with weight ratio at 1: 1, stir, reacted 3 hours down, use hot water (55 ℃) and washing with alcohol then,, obtain first compatilizer 55 ℃ of following vacuum-dryings 24 hours at 40 ℃.The number of repeat unit m that records the described first compatilizer Chinese style, 1 described repeating unit by SH/T 0108-1992 is 15, and the weight-average molecular weight of described first compatilizer is 2000.
4-hydroxybenzoyl hydrazine and 2-hydroxy benzaldehyde in dehydrated alcohol are mixed with weight ratio at 1: 1, stir, reacted 3 hours down, use hot water (85 ℃) and washing with alcohol then,, obtain second compatilizer 95 ℃ of following vacuum-dryings 24 hours at 65 ℃.The number of repeat unit n that records the described second compatilizer Chinese style, 2 described repeating units by SH/T 0108-1992 is 12, and the weight-average molecular weight of described second compatilizer is 3000.
2, the preparation of alloy material
With acrylonitrile-butadiene-styrene copolymer weight is benchmark, with acrylonitrile-butadiene-styrene copolymer (747 of Qi Mei company production, weight-average molecular weight is 80,000), 12 weight parts, first compatilizer, 4 weight parts, second compatilizer, 40 weight part polycaprolactams (the PA6 800H that Ba Ling petro-chemical corporation produces, weight-average molecular weight is 20,000, relative viscosity is 2.85) and 0.3 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (CIBA company produce Irganox 1010) joins in the twin screw extruder, in length-to-diameter ratio is 40: 1, screw speed is 240r/min, each zone temperatures is respectively 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, the vacuum tightness of each section is to mix under the condition of 0.05MPa, extrude then, obtain extruding product.
3, tie rod, pelletizing, injection moulding
To extrude product by tank cooling carrying out tie rod, (machinery company limited of Zhangjagang City the United Nations General Assembly, model is QLJ-1) carries out pelletizing under rotating speed 350r/min with dicing machine, after the oven dry of the micelle after cutting, carries out injection moulding with injection moulding machine.Obtain alloy material A1.
Embodiment 2
Present embodiment is used to illustrate alloy material composition disclosed by the invention and this alloy material.
1, the preparation of first and second compatilizers
The preparation method of first compatilizer and second compatilizer is with embodiment 1, and different is to use butyraldehyde and 3 respectively, 5-di-tert-butyl salicylaldehyde replacement propionic aldehyde and 2-hydroxy benzaldehyde.
2, the preparation of alloy material
With acrylonitrile-butadiene-styrene copolymer weight is benchmark, with acrylonitrile-butadiene-styrene copolymer (747 of Qi Mei company production, weight-average molecular weight is 80,000), 4 weight parts, first compatilizer, 8 weight parts, second compatilizer, the 25 weight part polycaprolactams (PA6800H that Ba Ling petro-chemical corporation produces, weight-average molecular weight is 20,000, relative viscosity is 2.85), 0.3 weight part 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane alcohol ester (Irganox 1076 that CIBA company produces) and 0.3 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (CIBA company produce Irganox 1010) joins in the twin screw extruder, in length-to-diameter ratio is 40: 1, screw speed is 240r/min, each zone temperatures is respectively 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, the vacuum tightness of each section is to mix under the condition of 0.02MPa, extrude then, obtain extruding product.
3, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain alloy material A2 with embodiment 1.
Embodiment 3
Present embodiment is used to illustrate alloy material composition disclosed by the invention and this alloy material.
1, the preparation of first and second raw materials
4-hydroxybenzoyl hydrazine and 2-hydroxy benzaldehyde in dehydrated alcohol are mixed with weight ratio at 1: 1, stir, reacted 3 hours down, use hot water (55 ℃) and washing with alcohol then,, obtain first raw material 55 ℃ of following vacuum-dryings 24 hours at 40 ℃.
4-hydroxybenzoyl hydrazine and propionic aldehyde in dehydrated alcohol are mixed with weight ratio at 1: 1, stir, reacted 3 hours down, use hot water (85 ℃) and washing with alcohol then,, obtain second raw material 95 ℃ of following vacuum-dryings 24 hours at 65 ℃.
2, the preparation of compound compatilizer
(LQ-BPO that the auxiliary reagent factory, Lanzhou produces) mixes with first raw material, second raw material and benzoyl peroxide, stirs, and reaction 3h obtains compound compatilizer under 65 ℃.The number of repeat unit x that records described compound compatilizer Chinese style 1 described repeating unit by SH/T 0108-1992 is 13, and the number of repeat unit y of formula 1 described repeating unit is 8.
With described first raw material weight is benchmark, and described second material content is 75 weight parts, and described initiator content is 0.5 weight part.
3, the preparation of alloy material
With acrylonitrile-butadiene-styrene copolymer weight is benchmark, with acrylonitrile-butadiene-styrene copolymer (747 of Qi Mei company production, weight-average molecular weight is 80,000), the compound compatilizer of 10 weight parts, the 24 weight part polycaprolactams (PA6800H that Ba Ling petro-chemical corporation produces, weight-average molecular weight is 20,000, relative viscosity is 2.85) and 0.4 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (CIBA company produce Irganox 1010) joins in the twin screw extruder, in length-to-diameter ratio is 40: 1, screw speed is 240r/min, each zone temperatures is respectively 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, the vacuum tightness of each section is to mix under the condition of 0.02MPa, extrude then, obtain extruding product.
4, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain alloy material A3 with embodiment 1.
Embodiment 4
Present embodiment is used to illustrate alloy material composition disclosed by the invention and this alloy material.
1, the preparation of first and second raw materials
The preparation method of first raw material and second raw material is with embodiment 3.
2, the preparation of compound compatilizer
(LQ-BPO that the auxiliary reagent factory, Lanzhou produces) mixes with first raw material, second raw material and benzoyl peroxide, stirs, and reaction 3h obtains compound compatilizer under 65 ℃.
With described first raw material weight is benchmark, and described second material content is 50wt%, and described initiator content is 0.4 weight part.
3, the preparation of alloy material
With acrylonitrile-butadiene-styrene copolymer weight is benchmark, with acrylonitrile-butadiene-styrene copolymer (747 of Qi Mei company production, weight-average molecular weight is 80,000), the compound compatilizer of 10 weight parts, 5 weight parts, first raw material, the 25 weight part polycaprolactams (PA6800H that Ba Ling petro-chemical corporation produces, weight-average molecular weight is 20,000, relative viscosity is 2.85) and 0.4 weight part four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (CIBA company produce Irganox 1010) joins in the twin screw extruder, in length-to-diameter ratio is 40: 1, screw speed is 240r/min, each zone temperatures is respectively 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, the vacuum tightness of each section is to mix under the condition of 0.02MPa, extrude then, obtain extruding product.
4, tie rod, pelletizing, injection moulding
Tie rod, pelletizing, injection moulding process obtain alloy material A4 with embodiment 1.
Embodiment 5
Present embodiment is used to illustrate alloy material composition disclosed by the invention and this alloy material.
The preparation method of alloy material is with embodiment 4, and different is: in step 3, add and adopt 2.5 weight parts, first raw material and 5 weight parts, second raw material substitution, 5 weight parts, first raw material.
Obtain alloy material A5.
Comparative Examples 1
This Comparative Examples is used to illustrate alloy material composition of the prior art and this alloy material.
Adopt disclosed material and method preparation among the embodiment 3, different is with 10 parts by weight of styrene-vinyl cyanide-maleic anhydride (the SAM 308HF that Shanghai Petroleum Chemical Engineering Institute produces) alternative composite compatilizer, to obtain alloy material D1.
Performance test
Adopt ASTM (U.S.'s test and materials association) standard and UL (American insurance merchant tests authentication) that above-mentioned poly-lactic acid material A1-A5 that makes and D1 are carried out following performance test:
1, tensile strength and elongation at break
Adopt ASTM D638 method to measure the tensile strength and the elongation at break of material;
2, flexural strength and modulus in flexure
Adopt ASTM D790 method to measure the flexural strength and the modulus in flexure of material;
3, notched Izod impact strength
Adopt ASTM D256 method to measure the notched Izod impact strength of material;
4, heat-drawn wire
Adopt ASTM D648 method to measure the heat-drawn wire of material;
5, Vicat softening point
Adopt ASTM D1525 method to measure the Vicat softening point of material;
6, heat aging property
After carrying out burin-in process by ISO 4892.2-1994, according to above correlation method test material tensile strength, notched Izod impact strength and heat-drawn wire.
Test result sees Table 1.
Test result from table 1 as can be seen, with in alloy material, add the performance that styrene-acrylonitrile-maleic anhydride improves material in the prior art and compare, the present invention can significantly improve the resistance toheat and the notched Izod impact strength of material by add compatibiliser disclosed in this invention in material.
The test result of comparative analysis A1, A2 and A3-A5 as can be known, by first raw material among the present invention and second raw material are made the performance that compound compatilizer can further improve material by reaction, and the first secondary compatilizer and/or the second secondary compatilizer and compound compatilizer acting in conjunction can significantly improve resistance toheat, heat aging property and the notched Izod impact strength of material equally.
Table 1
Claims (12)
1, a kind of alloy material composition comprises acrylonitrile-butadiene-styrene copolymer, polycaprolactam, oxidation inhibitor and compatibiliser, it is characterized in that: contain the repeating unit shown in formula 1 and the formula 2 in the described compatibiliser:
Formula 1:
Formula 2:
Wherein, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, R
2, R
3, R
4Independently be selected from H, Cl, CH separately
3Or C (CH
3)
3In one or more;
M is the integer of 2-20, and n is the integer of 2-20.
2, composition according to claim 1 is characterized in that: described compatibiliser is to contain repeating unit shown in the formula 1 and do not contain first compatilizer of repeating unit shown in the formula 2 simultaneously and contain repeating unit shown in the formula 2 and do not contain second compatilizer of repeating unit shown in the formula 1 simultaneously.
3, composition according to claim 2 is characterized in that: the weight ratio of described first compatilizer and second compatilizer is 0.3-3: 1.
4, composition according to claim 1 is characterized in that: described compatibiliser is the compound compatilizer that contains repeating unit shown in described formula 1 and the formula 2 in the molecule simultaneously.
5, composition according to claim 4 is characterized in that: described compound compatilizer is the material that contains structure shown in the formula 3,
Formula 3:
Wherein, R
1Be selected from the straight-chain paraffin that the C atomicity is 2-6 one or more, R
2, R
3, R
4Independently be selected from H, C1, CH separately
3Or C (CH
3)
3In one or more;
X is the integer of 2-20, and y is the integer of 2-20.
6, composition according to claim 4, it is characterized in that: also contain secondary compatilizer in the described composition, described secondary compatilizer contains the first secondary compatilizer and/or the second secondary compatilizer, the described first secondary compatilizer contains repeating unit shown in the formula 1 and does not contain repeating unit shown in the formula 2 simultaneously, and the described second secondary compatilizer contains repeating unit shown in the formula 2 and do not contain repeating unit shown in the formula 1 simultaneously; With described compound compatilizer weight is benchmark, and it is 25-75wt% that described parafacies holds agent content.
7, according to any described composition in the claim 4,5 or 6, it is characterized in that: the preparation method of described compound compatilizer is: second raw material of repeating unit shown in described first raw material that contains repeating unit shown in the formula 1 and the formula 2 under the condition that initiator exists, is stirred 1-5h down in 35-50 ℃; Described initiator is a Sodium Persulfate, Potassium Persulphate, the persulfuric acid lithium, Diisopropyl azodicarboxylate, benzoyl peroxide, dichlorobenzoyl peroxide, nitrogen peroxide, cumene hydroperoxide and t-butylperoxyl benzoate, the diisopropyl benzene hydrogen peroxide, t-butyl perbenzoate, cross sec.-propyl carbonic acid tertiary butyl ester, cross the isopropylformic acid tertiary butyl ester, cross sad tertiary butyl ester, cross two dimethyl isopropyl esters, cross in two carbonic acid two (2-ethylhexyl) ester and the ferrous ion-b diammonium edta one or more, perhaps sodium formaldehyde sulphoxylate, S-WAT, in sodium bisulfite and the saccharosonic acid one or more.
8, composition according to claim 7 is characterized in that: with described first raw material weight is benchmark, and described second material content is 98-102wt%, and described initiator content is 0.3-0.5wt%.
9, according to any described composition among the claim 1-6, it is characterized in that: with acrylonitrile-butadiene-styrene copolymer weight is benchmark, and the content of described polycaprolactam is that the content of 10-50wt%, oxidation inhibitor is that the content of 0.2-0.6wt%, compatibiliser is 2-20wt%.
10, composition according to claim 9, it is characterized in that: described oxidation inhibitor is butylated hydroxy anisole, butylated hydroxytoluene, tertiarybutylhydroquinone, phosphorous acid benzene two isodecyl esters, pentaerythritol bis-phosphite, [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in ten caprylates, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or several.
11, a kind of alloy material is characterized in that: contain repeating unit shown in the described formula 1 of claim 1 and the repeating unit shown in the formula 2 in the described alloy material.
12, a kind of alloy material makes by the alloy material composition is mixed 1-5min down at 200-235 ℃, and it is characterized in that: described composition is the described composition of claim 1-10.
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| CN102876017A (en) * | 2011-07-13 | 2013-01-16 | 黑龙江鑫达企业集团有限公司 | Core-shell toughened high-impact-toughness polyamide 6 (PA6) material and its preparation method |
| CN111511831A (en) * | 2017-07-26 | 2020-08-07 | 英力士苯领集团股份公司 | Scratch resistant styrenic copolymer compositions containing inorganic metal compound nanoparticles |
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| CN102876017A (en) * | 2011-07-13 | 2013-01-16 | 黑龙江鑫达企业集团有限公司 | Core-shell toughened high-impact-toughness polyamide 6 (PA6) material and its preparation method |
| CN111511831A (en) * | 2017-07-26 | 2020-08-07 | 英力士苯领集团股份公司 | Scratch resistant styrenic copolymer compositions containing inorganic metal compound nanoparticles |
| CN111511831B (en) * | 2017-07-26 | 2023-04-07 | 英力士苯领集团股份公司 | Scratch-resistant styrenic copolymer compositions containing nanoparticles of inorganic metal compounds |
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