CN103923433A - Halogen-free flame retardant and heat resistant ABS (acrylonitrile butadiene styrene copolymers) plastic for automotive interior trim parts and preparation method thereof - Google Patents
Halogen-free flame retardant and heat resistant ABS (acrylonitrile butadiene styrene copolymers) plastic for automotive interior trim parts and preparation method thereof Download PDFInfo
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- CN103923433A CN103923433A CN201410181195.4A CN201410181195A CN103923433A CN 103923433 A CN103923433 A CN 103923433A CN 201410181195 A CN201410181195 A CN 201410181195A CN 103923433 A CN103923433 A CN 103923433A
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Abstract
The invention discloses a halogen-free flame retardant and heat resistant ABS (acrylonitrile butadiene styrene copolymers) plastic for automotive interior trim parts and a preparation method thereof. The halogen-free flame retardant and heat resistant ABS plastic comprises the following components in parts by weight: 100 parts of ABS resin, 60-90 parts of PVC (polyvinyl chloride) resin, 2-15 parts of flame retardant and 1-8 parts of heat resistant agent, wherein preferably, the flame retardant is one of or a mixture of more of ammonium polyphosphate, montmorillonite, melamine cyanurate and aluminium hydroxide; the heat resistant agent is one of or a mixture of more of magnesium stearate, methyltin tris(isooctyl thioglycollate), dibutyltin dilaurate and tris(4-nonylphenyl)phosphite. The halogen-free flame retardant and heat resistant ABS plastic is low in production cost, has good processability, flame retardance and heat resistance, is environment-friendly, and is particularly suitable for preparing various automotive interior trim parts through injection molding.
Description
Technical field
The invention belongs to chemical material technical field, be specifically related to a kind of modified ABS plastics and preparation method thereof, relate in particular to a kind of automotive upholstery halogen-free flameproof heat-proof ABS plastics and preparation method thereof.
Background technology
ABS resin (acrylonitrile-butadiene-styrene copolymer, ABS is the acronym of Acrylonitrile Butadiene Styrene) is that a kind of intensity is high, good toughness, be easy to thermoplastics type's Polymer Materials ' Structure of machine-shaping.
ABS resin is the graft copolymer of vinyl cyanide, 1,3-butadiene and three kinds of monomers of vinylbenzene.Its molecular formula can be written as (C
8h
8c
4h
6c
3h
3n) x, but in fact often containing the graft copolymer of divinyl and the mixture of acrylonitritrile-styrene resin, wherein, vinyl cyanide accounts for 15～35%, divinyl accounts for 5～30%, and vinylbenzene accounts for 40～60%, and the modal ratio of emulsion method ABS is A:B:S=22:17:61, and the ratio of B is often lower in substance law ABS, be about 13%.
ABS is the general thermoplastic engineering plastic growing up 1940's, it is a plastics variety that comprehensive mechanical property is very outstanding, not only there is good rigidity, hardness and processing fluidity, and there is high tenacity feature, can injection moulding, extrude or thermoforming.
Most of trolley part is all with injection molding forming method processing, and the advantage of ABS resin is that impact-resistance, sound-proofing, scratch-resistant are better, more attractive in appearance than PP, is specially adapted to the comparatively strict parts of horizontal impact-resistance and use temperature.ABS resin is to use and be only second to Polyurethane and polyacrylic the third-largest resin in automobile.ABS resin can be used for Che Nei and car outer enclosure, the widgets such as bearing circle, oil guide pipe and handle and button, and car outside comprises front radiator grill and lampshade etc.
ABS resin is easily processed, finish size stability and surface luster are good, easily application, painted, can also carry out metallize, plating, welding and the suitability for secondary processing such as bonding, can be widely used in field of electronics, comprise various offices and consumer electronics/electrical equipment, office electrical equipment comprises electronic data processing machine, office equipment.
Thermostability and the thermal shock resistance of ABS resin are not so good.These shortcomings have seriously limited the application of ABS resin.
In recent years, Special Products becomes the emphasis of ABS product development.ABS product newly developed can be competed with engineering resin in some Application Areas, the used quality product of some ratios is much higher, instrument and consumer appliances are one of ever-increasing market of ABS product, comprise automotive upholstery, miniature instrument, refrigerator inwall and internals, housing of TV set, air supply rate, business machine and recording picture recording tape cassete.ABS resin has replaced the high engineering plastics of valency in a lot of fields, but the heat-resisting and flame retardant properties of ABS resin is not so good, and these shortcomings have seriously limited the application of ABS resin.
Halogen containing polymers or have good flame retardant properties with the flame-retardant mixture that halogen containing flame-retardant combines, Zeng Zuowei resistance alkene material is widely used.
But when fire occurs, this class Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas, cause into secondary harm.Therefore the flame-retardant system of invention Halogen, when burning, the amount of being fuming is little, does not produce poisonous, corrosive gases, has important practical significance.
Summary of the invention
For above shortcomings in prior art, technical problem to be solved by this invention is to provide a kind of automotive upholstery halogen-free flameproof heat-proof ABS plastics, has good anti-flame retardant resistance and thermotolerance, and the amount of being fuming is little when burning, do not produce poisonous, corrosive gases, avoid secondary pollution.
The present invention seeks to be achieved through the following technical solutions:
Halogen-free flameproof heat-proof ABS plastics for a kind of automotive upholstery, comprise the component of following weight parts:
Preferably, described automotive upholstery comprises the component of following weight parts with halogen-free flameproof heat-proof ABS plastics:
Preferably,
Described fire retardant is one or more the mixture in ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide;
Described heat-resistant agent is one or more the mixture in Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester;
It is further preferred,
Described fire retardant is made up of the component of following weight parts:
It is further preferred,
Described heat-resistant agent is made up of the component of following weight parts:
It is preferred,
Halogen-free flameproof heat-proof ABS plastics for described automotive upholstery, is characterized in that, comprise the component of following weight parts:
The present invention also provides the preparation method of above-mentioned automotive upholstery halogen-free flameproof heat-proof ABS plastics, and it comprises the following steps: take raw material by proportioning, fully mix after 5-10 minute at a high speed, add twin screw extruder, at 170-200 DEG C of extruding pelletization.
Obviously, for improving other performances of product, can also add adaptively other auxiliary agents, as heat-resistant agent, antiaging agent, scratch resistant agent, lubricant, photostabilizer, oxidation inhibitor, nucleator, softening agent, tinting material and static inhibitor etc. in the present invention.
In the present invention,
Polyvinyl chloride resin, i.e. polyvinyl chloride (PVC) RESINS.
Ammonium polyphosphate, claims again ammonium polyphosphate or polycondensation ammonium phosphate, is called for short APP, English name: ammonium polyphosphate; Polyphosphoric acids ammonium salts, CAS numbering: 68333-79-9.The branchiess long chain polymer of ammonium polyphosphate, the polymerization degree is preferably 21-26.
Polynite, English name: Montmorillonite, No. CAS: 1318-93-0.
Melamine cyanurate, No. CAS: 37640-57-6.
Aluminium hydroxide, No. CAS: 21645-51-2.
Magnesium Stearate, No. CAS: 557-04-0.
Methyl tin three (isooctyl mercaptoacetate), No. CAS: 57583-34-3.
Dibutyl tin laurate, No. CAS: 77-58-7.
Three (4-nonyl phenyl) phosphorous acid ester, No. CAS: 3050-88-2.
Contriver finds by great many of experiments, use fire retardant of the present invention and heat-resistant agent, the effectively flame retardant properties of reinforced ABS and resistance toheat, especially use the compound flame retardant of ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide, have the flame retardant effect of synergy, and do not contain haloid element in compound flame retardant, when burning, the amount of being fuming is little, do not produce poisonous, corrosive gases, avoid secondary pollution.Use the composite heat-resistant agent of Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester, have collaborative heat-resisting effect, its mechanism need the further research and inquirement of contriver.Meanwhile, it draws high the conventional parameters such as intensity, flexural strength, modulus in flexure and notched Izod impact strength and all meets the demands.
The preparation technology of this product is simple, and product cost is low, and the over-all properties of product is more excellent.Automotive upholstery of the present invention flame-proof heat-resistant ABS plastic, can be processed into easily by Shooting Technique the part of different shape, can be used for making automobile inside gadget.
Embodiment
Below in conjunction with embodiment, the invention will be further described.The ABS resin that the ABS resin using in the embodiment of the present invention and comparative example is 0215A for the Jilin Petrochemical company trade mark; Polyvinyl chloride resin is that Ning Botai moulds the polyvinyl chloride resin that Chemical Co., Ltd.'s trade mark is C65V.
Embodiment 1
Take each flame retardant compositions according to embodiment 1 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 1;
Get 5 kilograms of 80 parts of 100 kilograms of ABS resin, polyvinyl chloride resins, Magnesium Stearates after drying treatment and the compound flame retardant of embodiment 1, fully mix after 10 minutes at a high speed, add the spout of twin screw extruder; Control the rotating speed of twin screw extruder at 300rpm, temperature, at 200 DEG C, by twin screw extruder extruding pelletization, obtains the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 1.
Table 1: the ABS plastic fire retardant formula table unit of embodiment 1-7: kilogram
| ? | Ammonium polyphosphate | Polynite | Melamine cyanurate | Aluminium hydroxide |
| Embodiment 1 | 1.5 | 2 | 5 | 2 |
| Embodiment 2 | 1 | 2.5 | 4 | 3 |
| Embodiment 3 | 1.5 | 2 | 7 | / |
| Embodiment 4 | 6.5 | 2 | / | 2 |
| Embodiment 5 | 3.5 | / | 5 | 2 |
| Embodiment 6 | / | 3.5 | 5 | 2 |
| Embodiment 7 | 10.5 | / | / | / |
Embodiment 2
Take each flame retardant compositions according to embodiment 2 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 2;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 2.
Embodiment 3
Take each flame retardant compositions according to embodiment 3 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 3;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 3.
Embodiment 4
Take each flame retardant compositions according to embodiment 4 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 4;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 4.
Embodiment 5
Take each flame retardant compositions according to embodiment 5 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 5;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 5.
Embodiment 6
Take each flame retardant compositions according to embodiment 6 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 6;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 6.
Embodiment 7
Take each flame retardant compositions according to embodiment 7 data corresponding in table 1, after fully mixing, obtain the compound flame retardant of embodiment 7;
According to method described in embodiment 1, obtain the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 7.
Test case 1
The flame retardant resistance of the ABS plastic to embodiment 1-7 is tested, and test result is in table 2.
Table 2: the ABS plastic flame retardant resistance test chart of embodiment 1-7
| ? | UL-94 flame retardant rating, (1.6mm) | LOI，％ | Smoke density, m 2/kg |
| Embodiment 1 | V0 | 33.2 | 958 |
| Embodiment 2 | V0 | 32.8 | 974 |
| Embodiment 3 | V1 | 27.9 | 998 |
| Embodiment 4 | V0 | 29.0 | 1008 |
| Embodiment 5 | V1 | 28.2 | 1037 |
| Embodiment 6 | V0 | 30.4 | 1020 |
| Embodiment 7 | V2 | 25.5 | 1165 |
The flame retardant resistance of the ABS plastic to embodiment 1-7 is tested, found that the ABS plastic that embodiment 1-7 makes all has certain flame retardant resistance, especially embodiment 1-2 has used the compound flame retardant that ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide are made, be compared to embodiment 3-7, in the situation that adding same ratio fire retardant, oxygen index LOI value is brought up to 32.8%-33.2% from 25.5%-30.4%, and smoke density is from 998-1165m
2/ kg has been reduced to 958-974m
2/ kg, flame retardant effect is very obvious, special more excellent for the flame retardant effect of ABS plastic.
Embodiment 8
Take various heat-resistant agent components according to embodiment 8 data corresponding in table 3, get 10.5 kilograms of the compound flame retardants of 80 parts of 100 kilograms of ABS resin, polyvinyl chloride resins after drying treatment and embodiment 1, fully mix at a high speed after 10 minutes, they are added from the spout of twin screw extruder, control the rotating speed of screw extrusion press at 300rpm, temperature, at 200 DEG C, by screw extrusion press extruding pelletization, obtains the automotive upholstery halogen-free flameproof heat-proof ABS plastics of embodiment 8.
Table 3: the ABS plastic heat-resistant agent formula table unit of embodiment 8-13: kilogram
| ? | Magnesium Stearate | Methyl tin three (isooctyl mercaptoacetate) | Dibutyl tin laurate | Three (4-nonyl phenyl) phosphorous acid ester |
| Embodiment 8 | 1 | 1 | 2 | 1 |
| Embodiment 9 | 1 | 1 | 3 | / |
| Embodiment 10 | 1 | 1 | / | 3 |
| Embodiment 11 | 2 | / | 2 | 1 |
| Embodiment 12 | / | 2 | 2 | 1 |
| Embodiment 13 | 5 | / | / | / |
Embodiment 9
Take various heat-resistant agent components according to embodiment 9 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant ABS plastic of embodiment 9.
Embodiment 10
Take various heat-resistant agent components according to embodiment 10 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant ABS plastic of embodiment 10.
Embodiment 11
Take various heat-resistant agent components according to embodiment 11 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant ABS plastic of embodiment 11.
Embodiment 12
Take various heat-resistant agent components according to embodiment 12 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant ABS plastic of embodiment 12.
Embodiment 13
Take various heat-resistant agent components according to embodiment 13 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant ABS plastic of embodiment 13.
Test case 2
The resistance toheat of the ABS plastic to embodiment 8-13 is tested, and tests its heat-drawn wire (HDT, 1.8MPa), and test result is in table 4.
Table 4: the ABS plastic thermotolerance test chart of embodiment 8-13
| ? | Heat-drawn wire/DEG C |
| Embodiment 8 | 159 |
| Embodiment 9 | 132 |
| Embodiment 10 | 140 |
| Embodiment 11 | 129 |
| Embodiment 12 | 112 |
| Embodiment 13 | 109 |
By the test result in table 4, the heat-drawn wire of the ABS plastic that embodiment 8-13 makes is all significantly improved, especially embodiment 8 has used the composite heat-resistant agent of Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester, be compared to embodiment 9-13, in the case of using the heat-resistant agent of equal consumption, heat-drawn wire is higher, has strengthened more significantly the resistance toheat of ABS plastic.
Therefore, halogen-free flameproof heat-proof ABS plastics of the present invention can significantly improve flame retardant resistance, thermotolerance, and preparation technology is simple, and product cost is low, and the over-all properties of product is more excellent.Can also add adaptively other auxiliary agents, as antiaging agent, lubricant, photostabilizer, oxidation inhibitor, nucleator, softening agent, tinting material and static inhibitor etc., in order to improve other aspect performances.
Automotive upholstery of the present invention flame-proof heat-resistant ABS plastic, can be processed into easily by Shooting Technique the part of different shape, can be used for making automobile inside gadget.
The above; it is only the specific embodiment of the present invention; but protection scope of the present invention is not limited to this; any those of ordinary skill in the art are in the disclosed technical scope of the present invention; the variation that can expect without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (9)
1. halogen-free flameproof heat-proof ABS plastics for automotive upholstery, is characterized in that, comprise the component of following weight parts:
2. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 1, is characterized in that, comprise the component of following weight parts:
3. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 1, is characterized in that, described fire retardant is one or more the mixture in ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide.
4. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 3, is characterized in that, described fire retardant is made up of the component of following weight parts:
5. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 3, is characterized in that, the polymerization degree of described ammonium polyphosphate is 21-26.
6. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 1, it is characterized in that, described heat-resistant agent is one or more the mixture in Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester.
7. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 6, is characterized in that, described heat-resistant agent is made up of the component of following weight parts:
8. halogen-free flameproof heat-proof ABS plastics for automotive upholstery as claimed in claim 1, is characterized in that, comprise the component of following weight parts:
9. the preparation method of halogen-free flameproof heat-proof ABS plastics for the automotive upholstery as described in any one in claim 1-8, it is characterized in that, comprise the following steps: take raw material by proportioning, fully mix at a high speed after 5-10 minute, add twin screw extruder, at 170-200 DEG C of extruding pelletization.
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| CN104927291A (en) * | 2015-07-13 | 2015-09-23 | 苏州新区华士达工程塑胶有限公司 | Fragrant automobile interior trim panel plastic |
| CN104987649A (en) * | 2015-07-28 | 2015-10-21 | 苏州荣昌复合材料有限公司 | Corrosion-resistant ABS (acrylonitrile butadiene styrene) modified plastic |
| CN105602183A (en) * | 2015-12-30 | 2016-05-25 | 苏州乔布注塑工业有限公司 | Stable compound injection molding material |
| CN106519553A (en) * | 2016-11-22 | 2017-03-22 | 郑州仁宏医药科技有限公司 | ABS flame retardant plastic and preparation method thereof |
| CN108117706A (en) * | 2017-11-24 | 2018-06-05 | 上海金章高分子装饰材料有限公司 | A kind of novel flame-retardant material for car interior trim parts and its production technology and automotive upholstery |
| CN113897023A (en) * | 2021-09-18 | 2022-01-07 | 北京嘉诚瑞鑫科技有限公司 | Non-metal automobile body environment-friendly covering piece and manufacturing method thereof |
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