CN101759950A - Novel low-odor and low-emission ABS resin compound and preparation method thereof - Google Patents
Novel low-odor and low-emission ABS resin compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel low-odor and low-emission ABS resin compound which contains the following materials by weight proportion: 100 ABS, 1.0-5.0 hydrophobic odor adsorption master batch, 0.1-1.0 antioxidant and 0-5.0 other auxiliaries. The invention has the advantages that a hydrophobic odor adsorption system is adopted, so the low-odor and low-emission ABS resin compound prepared through the method can ensure the characteristic of low odor of the material, the processing of the material is not affected and the physical mechanical properties of the material are not affected.
Description
Technical field
The present invention relates to a kind of ABS resin mixture, be specially a kind of novel low-odor, low ABS resin mixture that distributes and preparation method thereof.
Background technology
ABS resin (Acrylnitrile-Butadiene-Styrene copolymer), it is the terpolymer of acrylonitrile-butadiene-styrene (ABS), be development and the kind that changes maximum in the styrene series resin, because preferable performance and relative cheap price, make it to compare with other resin, apodeictic advantage is arranged with competitive, therefore the ABS that has various characteristics constantly obtains exploitation and uses, this makes ABS become the kind of consumption maximum in the engineering plastics, is widely used in automotive industry, household electrical appliance, electrical instrumentation industry and the mechanical industry.
Yet, though having extremely widely, uses the ABS material, but the ABS material also can discharge some niff in varying degrees, and particularly for the various automotive trim products of being made by the ABS material, this problem has been subjected to the human consumer and has more and more queried.Along with people's environment protection health consciousness constantly strengthens, suffered challenge will be more and more serious on the one hand at this for the ABS material.For this reason, in order further to expand of the application of ABS material, must search out an effective way to prepare low smell, the low ABS material that distributes in association area.
A lot of work have been done about the smell problem people that how to reduce in the macromolecular material to be discharged.Basic skills comprises chemical reaction and physical adsorption two big classes.
Chemical reaction method is meant and adds the additive that can discharge small molecules reaction of smell with these in the middle of material prescription, by the reaction between these additives and the small molecules produce molecular weight big, use under the thermal environment normal, as less than 100 ℃, can from material, not evaporate the another kind of compound that produces peculiar smell, thereby reach the effect of eliminating peculiar smell.Though the related reaction of this method is extremely complicated,, therefore progressively caused people's interest in recent years owing to can control other performances that do not influence material on this theoretical method.At USP 6,297, introduced the ABS alloy molding that a kind of smell has improved as Eichenauer etc. in 307.By add the mixture of a kind of zinc oxide, magnesium oxide and at least a epoxy compounds in molding, the smell of this ABS alloy molding is improved.Yet by practice, we find that the interpolation of this mixture is very big to the impact property influence of the basic physical and mechanical property, particularly material of ABS alloy material, therefore do not possess very big practical value.
And physical adsorption can be adsorbed the small molecules and the organic compound of any generation smell or other fugitive constituents in theory, therefore an ideal effect might all be arranged to all respects that produce this problem.And along with the physical absorbent industrial expansion, multiple physical absorbent system has at present grown up.Mineral soil body systems such as gac system, silica gel system, molecular sieve system, attapulgite etc. have been comprised in the middle of this.Based on adsorption effect, when above-mentioned serial sorbent systems was distributed in resin matrix with a definite form, they all can adsorb the volatility organic molecule that produces in the resin material.Yet in the middle of the application of reality, they have deficiency separately again.For example, adopt traditional gac, can play adsorption to the organic compound that discharges smell in the macromolecular material fully, thereby reduce smell or other harmful fugitive constituent materials of material by the micropore in the gac as sorbent material.Yet, because gac make it can only be confined to use in the black material, so practical value is little from the cause as black.And, above-mentioned all sorbent systems exist all when being applied in the ABS material that a common defective---they all are the hydrophilic sorbent materials, when being their volatile small molecule and organic compound in the polymeric adsorbent material, also can adsorb in the lump together with the moisture that exists around the system inevitably, thereby may cause material surface when follow-up forming process to occur such as comparatively serious processing problems such as " spray ", " filamentary silvers ".
In order to solve this difficult problem, publication number is odor adsorption master batch and the sealing that the patent of CN1730544 has adopted elder generation smell inhibitor and matrix resin to be made high density, and it is even master batch and material mixing again to add man-hour at forming materials, during by forming process the melting mixing of body material and smell inhibitor with the smell inhibitor disperse equably with material in the middle of.Though this method can avoid the smell inhibitor to suck moisture in the blend extrusion, make that also the follow-up contour machining procedure of material is complicated more.If for example the odor adsorption master batch is just to add immediately to mix after the blend of ABS material is extruded, then the sealing preservation even the transportation of mixing the back material all proposed strict demand, wanted to make the material that is added with the odor adsorption master batch to have good processing properties and just must guarantee that it can not touch moist environment in whole storage and transportation; And if the odor adsorption master batch is to add to mix before material is about to forming process again, then requiring again will have suitable mixing equipment at the forming process scene of material, and require consumption to forming process to have comparatively accurately to estimate, otherwise how effectively sealing to preserve the unnecessary material that is mixed with the odor adsorption master batch also be the problem that can not avoid.In a word, this method makes that the subsequent treatment process of material is very complicated, and the client uses this material also very inconvenient.
Therefore, must find and a kind ofly can fully take into account above-mentioned each side factor, solve the simple effective ways of above-mentioned various smell problems and following process problem comprehensively, just can make this class adopt the low smell of physical adsorption mechanism, the low ABS material that distributes really to have Practical significance.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, a kind of novel low smell is provided, hangs down and distribute ABS resin mixture and preparation method, can improve its smell and total carbon emitting performance effectively, do not influence Drawing abillity simultaneously again.
The present invention with hydrophobic type odor adsorption master batch as hydrophobic type odor adsorption system, be used for preparing low smell, low total carbon emitting ABS resin mixture, this hydrophobic type odor adsorption system energy active adsorption produces the various volatile small molecule and the organic compound of smell, be difficult for simultaneously adsorption moisture again, thereby can prepare a kind of novel low smell, the low ABS resin mixture that distributes, still can keep its materials processing performance simultaneously.
This novel low smell, the low ABS resin mixture that distributes comprise the raw material of following weight part:
ABS??????????????????????100
Hydrophobic type odor adsorption master batch 1.0-5.0
Oxidation inhibitor 0.1-1.0
Other auxiliary agents 0-5.0.
Described ABS can difference be heat-resisting, the general ABS of different shock resistances in order to have, and production company and kind are not had strict demand.Butadiene unit content on the industrial production in the general control ABS resin is that 5-30% (massfraction), acrylonitrile unit content are that 10-30% (massfraction), styrene units content are 40-70% (massfraction).
Described oxidation inhibitor be triglycol two-one or both combination in 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide and three (2, the 4-di-tert-butylphenol) phosphorous acid ester.
Described other auxiliary agent can be one or more a composition in lubricant, fire retardant, photostabilizer, toughner and the tinting material.
Described hydrophobic type odor adsorption master batch is by being mixed with by following materials of weight proportions: ABS resin 50-80% and hydrophobicity odor adsorption agent 20-50%.The preparation method of this hydrophobic type odor adsorption master batch is as follows:
(1) takes by weighing raw material by weight ratio;
(2) ABS resin and the agent of hydrophobic type odor adsorption were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation, its technology is: a district 200-210 ℃, two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
(4) with the hydrophobic type odor adsorption master batch aluminium foil vacuum-sealing for preparing, stand-by.
Described ABS resin can difference be heat-resisting, the general ABS resin of different shock resistances in order to have, and production company and kind are not had strict demand.Butadiene unit content on the industrial production in the general control ABS resin is that 5-30% (massfraction), acrylonitrile unit content are that 10-30% (massfraction), styrene units content are 40-70% (massfraction).
The agent of described hydrophobic type odor adsorption is the attapulgite through the quaternary ammonium salt cationic surfactant modification.Attapulgite is a kind of rich magnesium silicate clay mineral, and its ideal structure formula is Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, its crystalline structure belongs to the duplex structure of silicate and the transition type of laminate structure.Because it has unique laminate structure, thereby has good adsorption and ion-exchange performance.But the specific surface area of attapulgite itself is big, surfactivity is high, easily reunite, and its surface contains a large amount of silicon hydroxyls, so the attapulgite of non-modified still belongs to the hydrophilic sorbent material, improve it and organic affinity just must be carried out organically-modified to it.
The purity of described attapulgite is greater than 30% (weight ratio).The particle size distribution of the attapulgite more than at least 95% is at the 200-1250 order.The exchangeable cation amount (CEC) of described attapulgite is 2.5-15mmol/100g.
Following method preparation is adopted in the agent of described hydrophobic type odor adsorption:
(1) take by weighing attapulgite, add appropriate amount of deionized water according to weight percent 0.01%-10%, high-speed stirring mixes aaerosol solution;
(2) high-speed stirring under 20-95 ℃ of condition drips an amount of quaternary ammonium salt cationic surfactant solution simultaneously, keeps high-speed stirring 1-6h;
(3) suction filtration, washing after vacuum-drying, activate 1-4h, crushing screening down at 80-300 ℃ for several times then repeatedly with reaction product.
Quaternary ammonium salt cationic surfactant described in the aforesaid method, its molecular structural formula is:
R1, R2, R3, R4 are alkyl, wherein have at least one to be that carbonatoms is the long carbochain alkyl of 6-18, and it is methyl, ethyl, the tertiary butyl or benzyl that remaining alkyl is selected from.X is haloid element or other anionic groups such as fluorine, bromine, chlorine.
The concentration of the quaternary ammonium salt cationic surfactant solution described in the aforesaid method can be water (or organic solvent) solution of 0.01-1g/ml quality volume percent.The dripping quantity of the quaternary ammonium salt cationic surfactant solution described in the aforesaid method is 0.5-2 times (mol ratio) of the cation exchange capacity (CEC) of attapulgite.
Owing to exist a large amount of exchangeable cation between the attapulgite layer mineral, as Na
+, Mg
2+Deng, thus the organic cation in the quaternary ammonium salt cationic surfactant will and layer mineral between positively charged ion carry out ion-exchange and advance between people's layer mineral.Attapulgite after the modification can think and be made of two " phases " that one is former mineral silicate " inorganic phase " part mutually, and another forms " organic phase " by advancing people's mineral lattice interlayer by the modifier molecules alkyl chain mutually.Though for the long carbochain alkyl that carbonatoms is 15-18, because of its molecule more often is difficult to reach ion-exchange completely, but they still can be attached in the attapulgite by hydrophobic alkyl interchain Intermolecular Forces with the organic cation that has been exchanged again.Therefore along with the growth of surfactant molecule alkyl chain, the organic phase ratio of the attapulgite of modification (organic carbon amount) will significantly increase.And along with the raising of organic phase ratio in attapulgite modified, its organic adsorptive power to periphery also enlarges markedly.And because the growth of tensio-active agent carbochain will make that on the one hand attapulgite modified layer mineral spacing increases, and the size of interlamellar spacing is an important factor that influences saturated adsorption capacity; The growth of carbochain on the other hand also makes attapulgite modified hydrophobicity strengthen, and therefore it also strengthen organic adsorptive power and distributional effects.The carbochain that is cats product is longer, and attapulgite modified is nonpolar just strong more, and it is just bigger to organic saturated adsorption capacity.
Therefore with the long chain quaternary positively charged ion make attapulgite modified in the alkyl organic phase have obvious hydrophobic, water molecules is difficult to be present in the interlayer of this class organic clay, and various organic compound are very easily adsorbed by its alkyl organic phase, thereby make the attapulgite of modification become the fabulous sorbent material of various organic molecules.
Prepare above-mentioned novel low smell, the method for hanging down the ABS resin mixture of total carbon emitting, its step is as follows:
(1) weighs raw material by weight ratio;
(2) ABS and hydrophobic type odor adsorption master batch, oxidation inhibitor and other auxiliary agents were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation obtains the PC/ABS alloy material, and its technology is: a district 220-230 ℃, and two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The invention has the advantages that the odor adsorption system of having used a kind of hydrophobic type, prepared low smell, the low ABS resin mixture that distributes are when guaranteeing the low odor property of material, the forming process of material is unaffected, and every physical and mechanical property of material is unaffected simultaneously.
Embodiment
In embodiment and Comparative Examples composite-material formula, the ABS resin that ABS selects for use BASF AG to produce, the resin trade mark is GP22; Attapulgite is that Xuyi Jiangsu attapulgite clay company produces, purity 80%, and grain diameter 300 orders, commutative calcium ion amount is 12mmol/100g; Quaternary ammonium salt cationic surfactant is chemical pure cetyl trimethylammonium bromide, and company limited provides by the Shanghai chemical reagent; Primary antioxidant be triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide, Switzerland Ciba company produces, trade names are Irganox 245; Auxiliary antioxidant is three (2, the 4-di-tert-butylphenol) phosphorous acid ester, and Switzerland Ciba company produces, and trade names are Irganox 168.In Comparative Examples, also selected a kind of odor adsorption agent---molecular sieve of general hydrophilic for use, be specially the 13X molecular sieve activation powder of microporous molecular sieve aperture greater than 10 dusts.
The preparation of hydrophobic type odor adsorption agent: take by weighing attapulgite 200g, add the 2500ml deionized water, high-speed stirring mixes aaerosol solution; High-speed stirring 3h under 80 ℃ of conditions drips the cetyl trimethylammonium bromide aqueous solution 75ml of 0.1g/ml simultaneously; Suction filtration, washing after vacuum-drying, activate 2h, crushing screening down at 200 ℃ for several times then repeatedly with reaction product.
Embodiment 1
The preparation of hydrophobic type odor adsorption master batch: take by weighing ABS 60%, hydrophobic type odor adsorption agent 40% and in super mixer, did mixed 3-5 minute, again in twin screw extruder through melt extruding, granulation, aluminium foil vacuum-sealing, stand-by, its expressing technique is: a district 200-210 ℃, and two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The preparation of low smell ABS resin mixture: with 100 parts of ABS, 1 part of hydrophobic type odor adsorption master batch, 0.2 part antioxidant 1010 and 0.1 part of oxidation inhibitor 168 are done in super mixer and were mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Embodiment 2
The preparation of hydrophobic type odor adsorption master batch: take by weighing ABS 60%, hydrophobic type odor adsorption agent 40% and in super mixer, did mixed 3-5 minute, again in twin screw extruder through melt extruding, granulation, aluminium foil vacuum-sealing, stand-by, its expressing technique is: a district 200-210 ℃, and two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The preparation of low smell ABS resin mixture: with 100 parts of ABS, 3 parts of hydrophobic type odor adsorption master batches, 0.2 part antioxidant 1010 and 0.1 part of oxidation inhibitor 168 are done in super mixer and were mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Embodiment 3
The preparation of hydrophobic type odor adsorption master batch: take by weighing ABS 60%, hydrophobic type odor adsorption agent 40% and in super mixer, did mixed 3-5 minute, again in twin screw extruder through melt extruding, granulation, aluminium foil vacuum-sealing, stand-by, its expressing technique is: a district 200-210 ℃, and two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The preparation of low smell ABS resin mixture: with 100 parts of ABS, 5 parts of hydrophobic type odor adsorption master batches, 0.2 part antioxidant 1010 and 0.1% oxidation inhibitor 168 are done in super mixer and were mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Embodiment 4
The preparation of hydrophobic type odor adsorption master batch: take by weighing ABS 80%, hydrophobic type odor adsorption agent 20% and in super mixer, did mixed 3-5 minute, again in twin screw extruder through melt extruding, granulation, aluminium foil vacuum-sealing, stand-by, its expressing technique is: a district 200-210 ℃, and two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The preparation of low smell ABS resin mixture: with 100 parts of ABS, 6 parts of hydrophobic type odor adsorption master batches, 0.2 part antioxidant 1010 and 0.1% oxidation inhibitor 168 are done in super mixer and were mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Embodiment 5
The preparation of hydrophobic type odor adsorption master batch: take by weighing ABS 80%, hydrophobic type odor adsorption agent 20% and in super mixer, did mixed 3-5 minute, again in twin screw extruder through melt extruding, granulation, aluminium foil vacuum-sealing, stand-by, its expressing technique is: a district 200-210 ℃, and two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
The preparation of low smell ABS resin mixture: with 100 parts of ABS, 10 parts of hydrophobic type odor adsorption master batches, 0.2 part antioxidant 1010 and 0.1% oxidation inhibitor 168 are done in super mixer and were mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Comparative Examples 1
With 100 parts of ABS, 3 parts of 13X molecular sieve activation powder, 0.2 part antioxidant 1010,0.1 part oxidation inhibitor 168, in super mixer, do to mix 3～5 minutes, again in twin screw extruder through melt extruding granulation, its technology is: a district 220-230 ℃, two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 8-10MPa.
Comparative Examples 2
100 parts of ABS, 0.2 part of antioxidant 1010,0.1 part of oxidation inhibitor 168, operation that all the other do to mix in super mixer and extruding in twin screw extruder, granulation are operated with embodiment 1.。
Get embodiment 1-5 and Comparative Examples 1,2 resulting products, carry out performance evaluation.
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*6*4mm, and notch depth is 1/3rd of a sample thickness; Vicat softening point temperature is undertaken by ISO 306, and specimen size is 10*10*4mm, and load is 5Kg; The odor property of material is tested by the PV3900 of Volkswagen, and sample mass is 40～60g, and the vessel content size is 1 liter; Material organic compound volatility is tested by self-defined standard, and sample mass is 10, and laying temperature is 100 ℃, and be 16 hours storage period; The total carbon emitting characteristic of material is tested with capillary gas chromatograph by the PV3341 of Volkswagen, and sample is the 1g pellet.
Comprehensive mechanical performance is passed through the tensile strength of test gained, elongation at break, and modulus in flexure, the numerical value of thermal denaturation temperature and shock strength is passed judgment on; The odor property of material is divided into according to standard code: 1 grade: odorlessness, 2 grades: scent of, but non interference smell, 3 grades: obvious smell is arranged, but the non interference smell, 4 grades: the interference smell is arranged, 5 grades: strong interference smell is arranged, 6 grades: insupportable smell is arranged; The material emission characteristics obtains according to formula: total carbon emitting amount E
GEvaluation COEFFICIENT K * 2 * 0.6204 that=(total peak area-peak area blank value that sample obtains)/acetone is identified, unit is μ gC/g (being every g sample volatilization μ g carbon), the high more expression material of the numerical value total carbon volatilization of calculating gained is big more, and emission characteristics is poor more, otherwise then emission characteristics is good more.
Embodiment 1-5 and Comparative Examples 1-2 experimental formula see Table 1, and every The performance test results sees Table 2.
Table 1 embodiment 1-5 and Comparative Examples 1,2 material prescription tables (weight part)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 1 | Comparative Examples 2 | |
| ??ABS?GP22 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| Hydrophobic type odor adsorption master batch | ??1 | ??3 | ??5 | ??2 | ??6 | ??10 | ??- | ??- |
| Oxidation inhibitor 245 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Oxidation inhibitor 168 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 1 | Comparative Examples 2 | |
| 13X molecular sieve activation powder | ??- | ??- | ??- | ??- | ??- | ??- | ??3 | ??- |
Table 2 embodiment 1-5 and Comparative Examples 1,2 product test results
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 1 | Comparative Examples 2 | |
| Shock strength (kJ/m 2) | ??NB | ??NB | ??NB | ??NB | ??NB | ??NB | ??NB | ??NB |
| Notched Izod impact strength (kJ/m 2) | ??17.3 | ??16.5 | ??14.8 | ??17.1 | ??16 | ??14.3 | ??14.5 | ??17.8 |
| Vicat softening point (℃) | ??95 | ??94.5 | ??94.2 | ??95.6 | ??95 | ??94.7 | ??92.8 | ??96 |
| Tensile strength (MPa) | ??40 | ??39 | ??37.6 | ??41.8 | ??38.2 | ??37 | ??39.6 | ??43 |
| Flexural strength (MPa) | ??65 | ??65 | ??65.7 | ??65.4 | ??65 | ??64.5 | ??64 | ??66 |
| Modulus in flexure (MPa) | ??2250 | ??2290 | ??2310 | ??2300 | ??2295 | ??2285 | ??2400 | ??2210 |
| Oder levels | 4.5 level | 4 grades | 3.5 level | 4 grades | 3.5 level | 3 grades | 3.5 level | 5 grades |
| Total carbon volatilization value (μ gC/g) | ??45 | ??32 | ??29 | ??38 | ??24 | ??21 | ??35 | ??85 |
| Whether follow-up forming process surface " spray " phenomenon occurs | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Do not have |
Can find from the contrast of embodiment 1-6 and Comparative Examples 1,2, adding hydrophobic type smell master batch can significantly reduce the smell and the total carbon emitting of ABS material really, and, also can further reduce the smell and the total carbon emitting of ABS material simultaneously along with the increase of smell master batch deal to the not tangible influence of the physicals of ABS material.In ABS, add the Comparative Examples 1 that the 13X molecular sieve activates powder and adopt, though also can obviously reduce the smell and the total carbon emitting of ABS material, but molecular sieve is easy to adsorption moisture, material is affected easily in follow-up forming process, therefore this method requires relatively harshness to the material environment for use, does not adopt the method for hydrophobic type smell master batch to use conveniently.
Can also find from the mutual contrast of embodiment 4,5,6 and embodiment 1,2,3 in addition, the odor adsorption master batch (embodiment 4,5,6) that employing 80%ABS and 20% hydrophobic type odor adsorption agent are made is to the smell of reduction ABS material and the better effects if of total carbon emitting, this moment, material not only possessed better smell and total carbon emitting performance, and the basic physical and mechanical property and the thermomechanical property of material also can keep preferably simultaneously.
Claims (14)
1. a novel low smell, the low ABS resin mixture that distributes comprise the raw material of following weight part:
ABS????????????????????????????????100
Hydrophobic type odor adsorption master batch 1.0-5.0
Oxidation inhibitor 0.1-1.0
Other auxiliary agents 0-5.0.
2. a kind of novel low smell according to claim 1, the low ABS resin mixture that distributes, it is characterized in that: by massfraction, the butadiene unit content in the ABS resin is that 5-30%, acrylonitrile unit content are that 10-30%, styrene units content are 40-70%.
3. a kind of novel low smell according to claim 1, the low ABS resin mixture that distributes, it is characterized in that: described oxidation inhibitor be triglycol two-one or both combination in 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide and three (2, the 4-di-tert-butylphenol) phosphorous acid ester.
4. a kind of novel low smell according to claim 1, the low ABS resin mixture that distributes is characterized in that: described other auxiliary agent is one or more a composition in lubricant, fire retardant, photostabilizer, toughner and the tinting material.
5. a kind of novel low smell according to claim 1, the low ABS resin mixture that distributes, it is characterized in that: described hydrophobic type odor adsorption master batch is by being mixed with by following raw materials by weight percent: ABS resin 50-80% and hydrophobicity odor adsorption agent 20-50%.
6. a kind of novel low smell according to claim 1, the low ABS resin mixture that distributes, it is characterized in that: the preparation method of described hydrophobic type odor adsorption master batch is as follows:
(1) takes by weighing raw material by weight ratio;
(2) ABS resin and the agent of hydrophobic type odor adsorption were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation, its technology is: a district 200-210 ℃, two district 210-220 ℃, three district 210-220 ℃, four district 205-215 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MPa.
(4) with the hydrophobic type odor adsorption master batch aluminium foil vacuum-sealing for preparing, stand-by.
7. according to claim 5 or 6 described a kind of novel low smells, the low ABS resin mixture that distributes, it is characterized in that: by massfraction, the butadiene unit content in the described ABS resin is that 5-30%, acrylonitrile unit content are that 10-30%, styrene units content are 40-70%.
8. according to claim 5 or 6 described a kind of novel low smells, the low ABS resin mixture that distributes, it is characterized in that: the agent of described hydrophobic type odor adsorption is the attapulgite through the quaternary ammonium salt cationic surfactant modification, and its structural formula is Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, its crystalline structure belongs to the duplex structure of silicate and the transition type of laminate structure.
9. a kind of novel low smell according to claim 8, the low ABS resin mixture that distributes, it is characterized in that: by weight, the purity of described attapulgite is greater than 30%, the particle size distribution of the attapulgite more than at least 95% is at the 200-1250 order, and the exchangeable cation amount is 2.5-15mmol/100g.
10. a kind of novel low smell according to claim 8, the low ABS resin mixture that distributes is characterized in that: following method preparation is adopted in the agent of described hydrophobic type odor adsorption:
1) take by weighing attapulgite, add appropriate amount of deionized water according to weight percent 0.01%-10%, high-speed stirring mixes aaerosol solution;
2) high-speed stirring under 20-95 ℃ of condition drips an amount of quaternary ammonium salt cationic surfactant solution simultaneously, keeps high-speed stirring 1-6h;
3) suction filtration, washing after vacuum-drying, activate 1-4h, crushing screening down at 80-300 ℃ for several times then repeatedly with reaction product.
11. according to Claim 8 or 10 described a kind of novel low smells, the low ABS resin mixture that distributes, it is characterized in that: described quaternary ammonium salt cationic surfactant, its molecular structural formula is:
Wherein, R1, R2, R3, R4 are alkyl, wherein have at least one to be that carbonatoms is the long carbochain alkyl of 6-18, and it is methyl, ethyl, the tertiary butyl or benzyl that remaining alkyl is selected from, and X is haloid element or other anionic groups.
12. a kind of novel low smell according to claim 10, the low ABS resin mixture that distributes, it is characterized in that: the concentration of described quaternary ammonium salt cationic surfactant solution is the water or the organic solvent solution of 0.01-1g/ml quality volume percent.
13. a kind of novel low smell according to claim 10, the low ABS resin mixture that distributes is characterized in that: meter in molar ratio, the dripping quantity of described quaternary ammonium salt cationic surfactant solution be attapulgite cation exchange capacity 0.5-2 doubly.
14. one kind prepares the described novel low smell of claim 1, the method for the low ABS resin mixture that distributes, its step is as follows: (1) weighs raw material by claim 1 proportioning;
(2) ABS and hydrophobic type odor adsorption master batch, oxidation inhibitor and other auxiliary agents were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation obtains the PC/ABS alloy material, and its technology is: a district 220-230 ℃, and two district 230-240 ℃, three district 230-240 ℃, four district 215-225 ℃; The residence time of whole extrusion is 1-2 minute, and pressure is 12-18MP.
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| CN102627830A (en) * | 2012-03-23 | 2012-08-08 | 宁波康氏塑料科技有限公司 | ABS / attapulgite composite material and preparation method thereof |
| CN103861464A (en) * | 2012-12-10 | 2014-06-18 | 天津工业大学 | Preparation method of molecular sieve micro powder-modified polyvinylidene fluoride membrane |
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| CN114573877A (en) * | 2022-03-14 | 2022-06-03 | 宁波福尔达智能科技股份有限公司 | Composition for adsorbing and degrading organic volatile matters and master batch |
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| CA2320988A1 (en) * | 1998-02-13 | 1999-08-19 | Solutia Inc. | Polymer nanocomposite composition |
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| CN103861464A (en) * | 2012-12-10 | 2014-06-18 | 天津工业大学 | Preparation method of molecular sieve micro powder-modified polyvinylidene fluoride membrane |
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| CN114573877A (en) * | 2022-03-14 | 2022-06-03 | 宁波福尔达智能科技股份有限公司 | Composition for adsorbing and degrading organic volatile matters and master batch |
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| CN116574352A (en) * | 2023-06-26 | 2023-08-11 | 深圳市富恒新材料股份有限公司 | High-performance low-precipitation low-odor ABS material and preparation method thereof |
| CN116574352B (en) * | 2023-06-26 | 2023-11-14 | 深圳市富恒新材料股份有限公司 | High-performance low-precipitation low-odor ABS material and preparation method thereof |
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