CN1651508A - Preparation method of ABS (acrilonitrile-butadiene-phenyl ethylene copolymer) functional filling mother particle - Google Patents
Preparation method of ABS (acrilonitrile-butadiene-phenyl ethylene copolymer) functional filling mother particle Download PDFInfo
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- CN1651508A CN1651508A CN 200410039086 CN200410039086A CN1651508A CN 1651508 A CN1651508 A CN 1651508A CN 200410039086 CN200410039086 CN 200410039086 CN 200410039086 A CN200410039086 A CN 200410039086A CN 1651508 A CN1651508 A CN 1651508A
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- 238000002360 preparation method Methods 0.000 title claims description 16
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- 238000005728 strengthening Methods 0.000 claims abstract description 9
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 17
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- 238000000034 method Methods 0.000 claims description 9
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
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- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical class NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 claims 1
- ALLIERSUYDVYQJ-UHFFFAOYSA-N furan-2,5-dione octadecanoic acid Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)O.C1(C=C/C(=O)O1)=O ALLIERSUYDVYQJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 39
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 25
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 24
- 239000000945 filler Substances 0.000 abstract description 3
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- 235000021355 Stearic acid Nutrition 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
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- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A strengthening and toughening filler particle and a flame-retarding filler particle are respectively prepared from inorganic powder, functional assistant and resin carrier. The can be respectively mixed with acrylonitrile-butadiene-styrene (ABS) copolymer to obtain relative ABS with high mechanical performance or flame-retarding function.
Description
Technical field:
The present invention relates to the preparation method of the filling-modified functional agglomerate of a kind of ABS of being used for engineering plastics.Be the inorganic powder that aboundresources is cheap specifically, be prepared into functional filler parent granule by the technology of the present invention, again with master batch and ABS resin by a certain percentage melt blending make inorganic powder filling-modified ABS plastic goods, different according to selected inorganic powder, functional aid and vector resin, can make ABS goods with strengthening and toughening function and without halide ABS goods respectively with flame retardant resistance function.
Background technology:
Be used for polyolefine filling modified parent particles production technology, existing multinomial both at home and abroad patent documentation report, apply extremely extensive, and receive remarkable economic efficiency and social benefit, for saving petroleum resources, satisfy the different performance requirement, improving the performance of plastics and increase kind and made major contribution.Because the singularity of the The Nomenclature Composition and Structure of Complexes of ABS resin is different with polyolefin resin, and is bigger with inorganic powder filling-modified difficulty, the patent of this respect report is few at present, and practical application is more rare.
ABS resin is to be formed by acrylonitrile, divinyl and three kinds of monomer copolymerizations of vinylbenzene, and from microtexture, being the polybutadiene rubber particulate is evenly dispersed in the external phase of acrylonitrile-styrene resin with the form on " island ".ABS resin has rigidity, surface hardness and the height chemical stability of polyacrylonitrile concurrently, the good workability of polystyrene and glossiness, and the shock resistance of polyhutadiene, toughness and elasticity, be widely used in car industry and electric industry as universal thermoplastic engineering plastic.
ABS resin is in being applied to automotive industry and electric industry process, toughness, shock resistance usually do not satisfy requirement, mostly the way of employing and other resin such as blending and modifyings such as PA, PC, PPO improves its toughness and shock resistance at present, but the cost height exceeds more than 20% than pure ABS.Another defective of ABS resin is that flame retardant properties is poor, easy firing, and automotive industry and electric industry are high especially to the flame retardant properties requirement of material, solve the way of ABS resin flame retardant resistance at present, the general method that adopts the production PP Pipe Compound, be about to fire retardant earlier by a certain percentage with the ABS resin mixing granulation, make the flame retardant type PP Pipe Compound, make goods with PP Pipe Compound.There is the high problem of cost equally in this method, and organic halogen compound is generally adopted in used group of combustion agent, will produce harmful halide gas during burning.The present invention can solve ABS existing the problems referred to above in application preferably.
Summary of the invention:
The present invention relates to a kind of preparation method that universal thermoplastic abs engineering plastics are filled out the modification functional agglomerate that is used for.Inorganic powder content is that 70～84wt%, functional aid are that 4～10wt%, vector resin are 12～20wt% in the master batch.Different according to selected inorganic powder, functional aid and vector resin, adopt identical production technique, can prepare filling modified parent particles respectively with strengthening and toughening function and two kinds of different performances of anti-flaming function.With strengthening and toughening type functional agglomerate with 15～30wt% ratio and ABS resin mixed the every mechanical performance index of goods near or surpass pure ABS, wherein elongation at break can improve 2.1 times, notched Izod impact strength improves 3 times.With having ratio and the ABS resin mixed goods that get of flame retardant type functional agglomerate with 40～50wt%, under the condition that satisfies the use properties requirement, flame retardant properties can reach the UL94V-1 level, and when burning non-halogen thing obnoxious flavour produce, product cost can reduce by 15～20% than pure ABS.
The present invention is that micro interface is induced under the guide of theory in toughness reinforcing theory of rigid particles and matrix material, the inorganic powder particle is adopted double-contracting film activation treatment technology, make the inorganic powder particle surface form one deck and can produce strong bonding force with inorganic particulate, again can with the elastica that combines with chemical bond or strong Van der Waals force between the vector resin, this elastica by coupling agent and reactive auxiliary agent acting in conjunction after and form, that is to say to have only the double-contracting membrane technique just can have this effect.Double-contracting film inorganic particulate can be distributed in the matrix resin equably, does the time spent when material is subjected to external force, and elastica can play the effect of buffering and dispersive stress, thereby improves the toughness and the shock resistance of goods.
The flame retardant properties of functional filler parent granule mainly comes from the inorganic powder-aluminium hydroxide with flame retardant properties, brucite powder and antimonous oxide and the synergy that composite back is produced between them.The inorganic powder fire retardant is compared with organic halogen containing flame-retardant, cost is low, do not produce deleterious halide gas during burning, but loading level must be big, just can have better flame retardant effect, inorganic powder filled amount main point influences the mechanical property of ABS, adopts double-contracting membrane technique of the present invention, just can this contradictory problems of fine solution.
The present invention produce the used material of main part of the functional filler parent granule of ABS be particle diameter be 2Mm～12Mm inorganic powder they are one or both and two or more mixtures in kaolin, talcum powder, water-ground limestone, light calcium carbonate, wollastonite powder, brucite powder, wilkinite, aluminium hydroxide and the antimonous oxide.Different inorganic powders will be given the master batch difference in functionality.The strengthening and toughening master batch selects the big inorganic powder of length-to-diameter ratio effective, and is more effective than single powder with two or more powder mix.The flame retardant type master batch should select to have the inorganic powder of flame retardant properties, is 2Mm～12Mm as particle diameters such as brucite powder, aluminium hydroxide and antimonous oxides.Different flame retardant resistance inorganic powders can produce synergy by rational proportion, to reach the optimum resistance combustion effect.
Functional aid is the key of the functional filler parent granule performance of ABS of influence wood invention production.The effect of coupling agent is directly to form thin film at inorganic powder surface with chemistry or physical force; Have in the reactive auxiliary agent molecule these active genes of active gene be easy to coupling agent or vector resin molecule in active gene, chemical reaction takes place, make that the form with elastic interface is combined into one securely between inorganic powder and the vector resin.The effect of lubricating type dispersion agent can also impel functional master batch to be evenly dispersed in the matrix resin with ABS matrix resin melt blending the time except that guarantee that inorganic powder better disperses in vector resin.
The used coupling agent of the present invention is: one or both and two or more compound in silane compound, metatitanic acid fat, aluminic acid lipoprotein and the acid phosphite.Consumption is 1～2wt% of functional agglomerate quality, different coupling agents or different amounts effect difference.Two kinds and two or more compound are more effective than single coupling agent.Reactive auxiliary agent has: one or both in maleic anhydride, epoxy type lipid acid and the epoxy type natural fats and oils and two or more compound.Consumption is 2～6wt% of functional master batch quality.Reactive auxiliary agent is to be used for inorganic powder secondary coating, different coupling agents, and the different carriers resin, used reactive auxiliary agent should be different to some extent with consumption.The lubricating type dispersion agent has: one or both in whiteruss, solid paraffin, polyethylene wax, Poly Propylene Wax, soap, the NN '-ethylenebisstearamide and two or more compound.Consumption is 1～2wt% of functional agglomerate quality.
Different with preparation polyolefine filler parent granule, ABS resin is not an one-component, but is formed by three kinds of absolutely different component copolymerization of performance.For understanding makes functional agglomerate homodisperse in matrix resin ABS, and form single homogeneous system with it, the selection of preparation functional agglomerate vector resin is one of core technology of the present invention.Vector resin should and coating after the inorganic powder particle between form strong bonding force, has consistency preferably with the matrix ABS resin again, and vector resin itself also will have good mobility, dispersiveness and workability, single or unmodified a certain resin is difficult to satisfy simultaneously above-mentioned many performance requriementss, must adopt the compound of modified resin or several different performance resins, utilize between them performance complement or mutual synergy to satisfy the vector resin performance requriements.Used carrier resin of the present invention has: EVA, EAA, MBS, AS, ABS, PVAC, PS/PMMA embedding are with one or both and two or more compound in multipolymer or graft copolymer, second-third rubber and the chlorinatedpolyethylene, and the content of vector resin is 12～20wt% in the functional agglomerate.
The production technique of the functional filler parent granule of ABS of the present invention is mainly three parts, i.e. inorganic powder surface activation treatment, batch mixing and twin screw extruder extruding pelletization.The inorganic powder surface activation treatment is to carry out twice coating in height stirs machine, it for the first time is coupling agent treatment with 1～2wt% of functional agglomerate quality, for the second time be that reactive auxiliary agent with 2～6wt% of functional agglomerate quality carries out coating by chemical reaction, temperature is 80～120 ℃, time 5min～10min, batch mixing is the inorganic powder and 1～2wt% lubricating type dispersion agent that accounts for functional master batch quality and the 12～20wt% vector resin that accounts for functional master batch quality after will activating in height stirs machine or blender, mixes.The barrel temperature of twin screw extruder extruding pelletization, engine speed and head temperature etc. will be decided according to vector resin, and the barrel temperature generally answers control ratio vector resin melt temperature high 5 ℃, and head is lower 5 ℃ than melt temperature.
The functional filler parent granule of the ABS that the present invention produced also can obviously reduce raw materials cost except that can giving ABS goods strengthening and toughening or anti-flaming function, have better economic benefit and social benefit.
Embodiment:
The functional master batch preparation of embodiment 1-strengthening and toughening type:
Get 60Kg 2250 orders (6.8Mm) water-ground limestone and 20Kg 1250 orders (12Mm) length-to-diameter ratio greater than 10 wollastonite powder, put into the 200L homogenizer, start and be stirred under the high-speed stirring, add 1.5Kg aluminium/titanium composite coupler, high-speed stirring 5min, add 1Kg stearic acid and 1.5Kg hexa-methylene isocyanic ester again, continue to stir 6～8min down at 90 ℃ and make double-contracting film activity lime carbonate/wollastonite powder.
With the above-mentioned treated carbonates/wollastonite powder that makes and 1Kg polyethylene wax, 0.5Kg NN '-ethylenebisstearamide, 2Kg EVA, 2.5Kg PA-g-MAA and 10Kg MBS resin, in stirring machine, height mixes under the normal temperature.
At 160～180 ℃ of following extruding pelletizations, make strengthening and toughening type ABS functional agglomerate with 1: 36 twin screw extruder of 75 type length-to-diameter ratios.
Be injection molded into the standard batten with the functional agglomerate that makes and ABS (LG/2/H) with 2: 8 mixed and compare with pure ABS, tensile strength improves 5%, and flexural strength improves 8%, and elongation at break improves 1.5 times, and notched Izod impact strength improves 2.6 times.
The preparation of embodiment 2-flame retardant type functional agglomerate
Get 60Kg 2250 order brucite powders, 12Kg 1250 order aluminium hydroxides and 8Kg1250 order antimonous oxide, join in the 200L homogenizer, start and be stirred under the high-speed stirring, add the 1.5Kg silane coupling agent, add the 0.5Kg maleic anhydride, 0.5Kg stearic acid and 2Kg epoxy linolic acid behind the stirring 5min, after 95 ℃ 10min is stirred in continuation down, just make the fire-retardant inorganic powder of double-contracting film activity.
With above-mentioned active flame-proof inorganic powder that makes and 0.5Kg solid paraffin, the 1Kg polyethylene wax, the 4Kg chlorinatedpolyethylene mixes in height stirs machine under 2Kg EAA and the 8Kg ABS resin normal temperature.
At 180～200 ℃ of following extruding pelletizations, make flame retardant type ABS functional agglomerate with 1: 36 twin screw extruder of 75 type length-to-diameter ratios.
With ratio and the ABS resin mixed ABS plastic goods that get of this master batch with 1: 1, its use properties is suitable with pure ABS, and flame retardant properties can reach the UL94V-1 level.
Claims (6)
1, the functional filler parent granule preparation method of a kind of ABS comprises the preparation technology of inorganic powder, functional aid, inorganic powder activating surface activating treatment process, vector resin and functional filler parent granule.Inorganic powder content is that 70～84wt%, functional aid are that 4～10wt%, vector resin are 12～20wt% in the functional filler parent granule.
2, according to the functional filler parent granule preparation method of the ABS of claim 1, wherein inorganic powder is: particle diameter is one or both and the two or more mixture in kaolin, talcum powder, water-ground limestone, light calcium carbonate, wollastonite powder, brucite powder, wilkinite, aluminium hydroxide and the antimonous oxide of 2Mm～12Mm.The inorganic powder total content is 70～84wt% in the functional agglomerate.
3, according to the functional filler parent granule preparation method of the ABS of claim 1,1. coupling agent of functional aid wherein: one or both in silane compound, titanic acid ester, aluminic acid ester and the acid phosphorous acid ester and two or more compound; 2. reactive auxiliary agent: one or both in maleic anhydride stearic acid, carbodiimide compound, carbimide type compound, epoxy type lipid acid and the epoxy type natural fats and oils and two or more compound; 3. lubricating type dispersion agent: one or both in whiteruss, solid paraffin, polyethylene wax, Poly Propylene Wax, soap, the NN '-ethylenebisstearamide and two or more compound.The total content of functional aid is 4～10wt% in the master batch, and wherein coupling agent is that 1～2wt%, reactive auxiliary agent are that 2～6wt%, lubricating type dispersion agent are 1～2wt%.
4, according to the functional filler parent granule preparation method of the ABS of claim 1, wherein the inorganic powder surface activating treatment process is to adopt the double-contracting membrane technique, specific practice is: earlier with 1～2wt% of function sexupara grain quality one or both and two or more compound in height stirs machine, by high-speed stirring inorganic powder surface is carried out the coating activation treatment, use the reactive auxiliary agent of 2～6wt% of function sexupara grain quality again, in height stirs machine under 80～120 ℃ of high-speed stirring conditions, by chemical reaction inorganic powder is carried out secondary coating activation treatment, make inorganic powder surface form the interfacial layer that one deck has certain elasticity and can produce strong affinity with inorganic powder and vector resin.
5, according to the functional filler parent granule preparation method of a kind of ABS of claim 1, wherein vector resin is: EVA (ethene-vinyl acetate copolymer), EAA (ethylene-acrylic acid copolymer), MBS (Methacrylate-butadiene-styrene), AS (propylene cyanogen-styrol copolymer), ABS, PVAC (polyvinyl acetate), the PS/PMAA embedding is with multipolymer or graft copolymer, the PA/PMAA embedding is with multipolymer or graft copolymer, in second-third rubber and the chlorinatedpolyethylene one or both and two or more compound, the content of vector resin is 12～20wt% in the master batch.
6, according to the functional filler parent granule preparation method of a kind of ABS of claim 1, functional agglomerate preparation technology wherein: 1. in height stirs machine, inorganic powder is carried out the surface-coating activation treatment with 1～2wt% of master batch quality one or both and two or more coupling agent compound earlier, use the reactive auxiliary agent of 2～6wt% of master batch quality again, under 80～120 ℃ of high-speed stirring conditions, by chemical reaction inorganic powder is carried out secondary coating activation treatment, make active inorganic powder.2. active inorganic powder and 1～2wt% lubricating type dispersion agent that accounts for the master batch quality respectively and the 12～20wt% vector resin that accounts for the master batch quality are mixed under the normal temperature in height stirs machine or in the blender.3. use twin screw extruder under 160～210 ℃, extruding pelletization makes the functional filler parent granule of ABS.Different according to used inorganic powder with functional agent and vector resin, can produce strengthening and toughening functional agglomerate and flame retardant resistance functional agglomerate respectively.
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| CN100366675C (en) * | 2005-12-30 | 2008-02-06 | 上海林达塑胶化工有限公司 | Method for preparing defoaming, dehumidifying and drying mother stock for ABS(acrylonitrile- butadiene-styrene copolymer) plastic processing |
| CN101210079B (en) * | 2006-12-31 | 2010-10-13 | 大连亚泰科技新材料有限公司 | Mg(OH)2 inorganic anti-flaming material and its preparing method and application |
| CN101220194B (en) * | 2007-10-15 | 2011-03-02 | 张发饶 | Production method for environment-protection flame-proof ABS system master batch |
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| CN1038421C (en) * | 1995-11-17 | 1998-05-20 | 南京化工大学 | Supertough master-pellets for polypropylene plastics and making method thereof |
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| CN106009781A (en) * | 2016-06-15 | 2016-10-12 | 江西广源化工有限责任公司 | Preparation method of aluminum hydroxide coated talc powder special for flame retardant cable material |
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| CN109438905A (en) * | 2018-09-30 | 2019-03-08 | 常州大学 | A kind of ABS quaternary blending modified material and preparation method thereof |
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| CN109354714A (en) * | 2018-11-15 | 2019-02-19 | 张金娥 | Antimony oxide reinforcing agent and its application in high-intensitive acryl plates |
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