CN102443192A - Composite plastic processing agent and preparation method thereof - Google Patents
Composite plastic processing agent and preparation method thereof Download PDFInfo
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- CN102443192A CN102443192A CN201110314918XA CN201110314918A CN102443192A CN 102443192 A CN102443192 A CN 102443192A CN 201110314918X A CN201110314918X A CN 201110314918XA CN 201110314918 A CN201110314918 A CN 201110314918A CN 102443192 A CN102443192 A CN 102443192A
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Abstract
The invention discloses a composite plastic processing agent and a preparation method thereof. The processing agent comprises the following raw material components in parts by weight: 90 to 100 parts of light calcium carbonate powder, 3 to 5 parts of kaoline, 2 to 2 parts of mica powder, 1 to 2 parts of straw ash, 3 to 5 parts of activated zinc oxide, 3 to 5 parts of fumed silica, 1 to 2 parts of polymer of methacrylate, 1 to 2 parts of polyethylene wax, 1 to 2 parts of sodium dodecyl sulfonate, and 1 to 2 parts of silicone oil. The preparation method comprises the following steps of: baking the light calcium carbonate until the moisture weight is lower than 0.3 percent; adding into a high-speed kneading machine; adding other materials in the prescription according to the weight proportion; heating to a temperature of between 100 and 130 DEG C; and preserving the temperature and stirring for 8 to 10 minutes, and discharging to obtain a finished product. According to the composite plastic processing agent prepared by adopting the method disclosed by the invention, the surface energy among the particles is reduced, the compatibility and diffusion of the plastic are reinforced; the polymer material plasticization is promoted, the melt viscosity is reduced, and the processing fluidity is improved; and impact degree, rigidity, heat resistance and dimension stability of the composite plastic processing agent are improved. The composite plastic processing agent has the characteristics of energy saving, consumption reduction, environmental friendliness, no toxicity and no 'three wastes'.
Description
Technical field
The present invention relates to field of plastics processing, specifically is a kind of composite plastic processing aid and preparation method thereof.
Background technology
The properties-correcting agent of China's plastic working multifunction still is in developmental stage, and is no matter bigger with external gap on kind, output, quality and modification function.
The producer that produces plastic processing modifier in the world is a lot, mainly contains U.S. Rohmandhass (ROHM AND HAAS) company and ATOCHEM company, Japanese clock deep pool chemical company etc.Rhom and Hass has developed first acrylic acid or the like impact modifier at middle nineteen sixties; Serial trade mark products such as ParaloidKM323B, KM330, KM334, KM335 have been developed later in succession; Wherein ParaloidKM355 is a product of new generation, and superior performance is arranged.At present, Rhom and Hass has become the main provider of plastics additive in the world wide.Japan Wu Yu company is at the Pacific region and other area and Rhom and Hass's joint sales PVC impact modifier and processing aids in the world.The cooperation of above-mentioned two companies is produced ACR class properties-correcting agent in Singapore by Wu Yu chemistry (Singapore) private limited partnership, and its product grade is that the goods of ParalOidKM355P put goods on the market, and YO is 100,000 tons.More external ACR anti-impacts change the agent trade mark and see table 1.
The external several A CR impact modifier trade mark of table 1
Core-shell type ACR class impact modifier uses extensively, and multifunctionality is arranged, and application prospect is extensive.At present; High-performance and the most dependence on import of tailored version nuclear-shell ACR class impact modifier that China uses; Minority manufacturer production such as domestic only Qilu Petrochemical, Shanxi chemical institute, Shanghai Shanhu Chemical Factory, Shanghai, and kind is single, far can not satisfy the needs of different model PVC plastics.
Different properties-correcting agent performances are relatively seen table 2.
Three kinds of properties-correcting agent of table 2 relatively
Annotate: from 1 to 5, performance is from bad to excellent
In addition, except several kinds of above-mentioned impact modifying agents, also have many plastic processing functional properties-correcting agent that can be used for.For example, CPE grafting vinyl chloride multipolymer, EVA grafting vinyl chloride multipolymer, ACR grafting vinyl chloride multipolymer, EPR (second third glue) grafting vinyl chloride multipolymer, vinylchlorid grafted ethene-Yodo Sol GH 28 and EVACO multipolymer (ethane-acetic acid ethyenyl vinegar-CO terpolymer) etc.In recent years, also obtained remarkable progress, as with CPE/ACR, CPE/MBS composite toughening PVC with the research of two kinds of elastomer composite toughening PVCs.Result of study shows that the impact effect that the synergy of two kinds of toughner produces is superior to single toughner.Except using elastic body toughening PVC, as with organic rigid-particle (PMMA, AS etc.), inorganic rigid particle (ultra-fine CaCO
3) report of toughening PVC, these inelastic body co-mixing systems also can be used as plastic processing modifier.Use the report of elastomerics and non-resilient composite toughening in addition, as with CPE/PS, the ultra-fine CaCO of CPE/
3, composite toughening PVC.And China PVC nanometer CaCO
3The composite study exploitation had obtained remarkable break-throughs over the past two years.
" nuclear " of ACR generally is the esters of acrylic acid rubber polymer of low cross-linking, and " shell " layer can be one deck or bilayer, so anti-impact type ACR has the branch of double-deck and three layers of " nuclear-shell " structure.Its basic process is first with letex polymerization manufactured seed emulsion particle, and appropriately crosslinked in the presence of linking agent, drips other monomers then, makes it carry out graft copolymerization on seed emulsion particle top layer.The skin of double-deck " nuclear-shell " structure ACR mainly is the multipolymer of methyl methacrylate polymer or TEB 3K and propenoate; Three layers of " nuclear-shell " structure ACR can be divided into time skin and outermost layer again, and secondly outer is styrene polymer often.According to the needs of using, except that stratum nucleare be certainly lightly crosslinked, other layers can be divided into line style or crosslinked again.No matter double-deck or three layers of " nuclear-shell " structure ACR; The IPN that polymer chain is arranged between its stratum nucleare and the shell; So ACR is in fact again one type of latex IPN, according to the mensuration of electron microscope observation and dynamic viscoelasticity spectrum appearance, all provable ACR is the heterogeneous structure system.
Its toughening mechanism is comparatively common with crazing-shear zone theoretical explanation usually.The effect of " nuclear-shell " type rubber particles on the one hand as the stress concentration center, is brought out matrix and is produced a large amount of crazings and shear zone, and the generation of its crazing or shear zone and development need to consume significant amount of energy, thereby significantly improves the shock resistance of material.Simultaneously; Through bearing part three axial stresses, controlled the development of crazing, and crazing is in time stopped and unlikelyly developed into destructive crackle at crazing and rubber separation surface; The most advanced and sophisticated stress field of crazing can be brought out the generation of shear zone, and shear zone also can stop further developing of crazing.
" nuclear-shell " structure modifier is often carried out crosslinkedly through the covalent linkage that adds typical cross-linking monomer, its nuclear core has good elasticity; Shell is the superpolymer that has than high glass transition temperature, and separate easily between particle can be dispersed to the PVC base material uniformly; And ability and the interaction of PVC base material; Thereby this type particle also plays the effect of similar ACR processing aid, promotion polyvinyl chloride resin gelation and plasticizing except that can improving the PVC erosion-resisting characteristics.The major advantage of ACR class impact modifier has: good impact modification effect, wider processing temperature scope, the bloated property of low mould, product size are stablized, are had concurrently the processing aid characteristics, can shorten the fusion plastification time of compound, improve the co-mixing system moulding processability, have better weather.
Lime carbonate belongs to the inorganic non-metallic mineral; The surface has many hydroxyls, easy adsorption moisture, the hydrophilic oleophobic of not surface treated calcium carbonate powder particle surface; Be strong polarity; Thereby can not with macromolecule organic generation chemically crosslinkeds such as plastics, rubber, in organic medium, be difficult to homodisperse, the interface is difficult to form good bonding.In addition, the calcium carbonate superfine powder particle diameter is little, has great specific surface area and higher specific surface energy; Particle coalescence, reunion very easily take place in preparation and last handling process; Form offspring, make grain diameter become big, in application process, lose the function that ultrafine particulate possesses; Thereby influence practical application effect, can not play the effect of functional stuffing; On the contrary, can reduce some physicals of goods to a certain extent because of boundary defect.
Summary of the invention
The invention provides a kind of composite plastic processing aid and preparation method thereof, the prepared composite plastic processing additives has reduced intergranular surface energy, has strengthened the consistency and the dispersiveness of plastics; Promote high polymer material plasticizing, reduced melt viscosity, improved processing fluidity; Improve goods shock extent, rigidity, thermotolerance and dimensional stability, have energy-saving and cost-reducing, environmental protection, nontoxic, the characteristics of not having " three wastes ".
Technical scheme of the present invention is:
A kind of composite plastic processing aid is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, kaolin 3-5, mica powder 2-2, stalk ashes 1-2, active zinc flower 3-5, aerosil 3-5, the polymkeric substance 1-2 of methacrylic ester, polyethylene wax 1-2, sodium laurylsulfonate 1-2, silicone oil 1-2.
The preparation method of described composite plastic processing aid; It is characterized in that: light calcium carbonate is dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding kaolin, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium laurylsulfonate, silicone oil; After having added; Be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Polynary composite theory is meant: in modifying plastics, can not rely on single method; According to different resins, different plastics goods and different use occasion and different sorts; The mineral filler (powder) of different loading levels; After using properties-correcting agent, also to use one or more methods to carry out modifying plastics to reach better modification actual effect.Wherein replacing the binary compound (polymer/inorganic powder) of inorganic powder and plastics with the ternary of inorganic powder, rubber (elastomerics), plastics compound (polymkeric substance/elastomerics/inorganic powder) is main method.
Beneficial effect of the present invention: the present invention selects the tensio-active agent of multiple function to mix, and reduces the surface energy and the IT of particle significantly, prevents the autohemagglutination of miniaturization particle effectively; Increase its consistency and dispersiveness in rubber, plastics, can promote high polymer material plasticizing, reduce melt viscosity; Improve processing fluidity; Improve goods shock extent, rigidity, thermotolerance and dimensional stability, thereby can realize the increment filling, reduce the goods cost.
Embodiment
Composite plastic processing aid, each feed composition are by weight than being: the polymkeric substance 2 of light calcium carbonate powder 100, kaolin 4, mica powder 2, stalk ashes 2, active zinc flower 4, aerosil 4, methacrylic ester, polyethylene wax 1, sodium laurylsulfonate 1, silicone oil 2.
The preparation method of composite plastic processing aid; Light calcium carbonate dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding kaolin, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium laurylsulfonate, silicone oil; After having added; Be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Calcium carbonate modified front and back microscopic pattern compares:
Ordinary calcium carbonate particle distribution scope is wide, and how the forms with state of aggregation exist, though and the amounts of particles under Electronic Speculum of the calcium carbonate particles after composite plastic processing aid-modification of the present invention is more; But can obviously find out after surface modification treatment; Surface energy is low, and agglomeration does not take place, and reaches homodisperse; How to exist with the primary partical state; Wherein part is to have (particle diameter is less than 100nm) with the nanoparticle state, thereby it can reach better dispersion in the PVC plastics, plays toughened and reinforced effect.
Calcium carbonate powder particle after composite plastic processing aid-modification of the present invention is many to be existed with similar circle or fusiform, and such powder adds in the plastics, and is more liquid, can play toughened and reinforced effect.But the ordinary calcium carbonate powder, then surperficial corner angle are more, cause rheological poor easily, problems such as easy fracture.
Respectively by the prescription batch mixing, room temperature is carried out rheological experiment at PLE331 type torque rheometer after placing 8h with the lime carbonate after ordinary calcium carbonate and the composite plastic processing aid-modification of the present invention, and the result is as shown in table 3:
Table 3 rheological experiment result
| Title | Peak torque/N.m | Balancing torque/N.n | Fusion time/S | Melt temperature/℃ |
| Common CaCO 3 | 37.4 | 25.0 | 150 | 187 |
| Modification CaCO 3 | 35.3 | 22.8 | 114 | 186 |
Prescription: 100 parts of PVC, 5 parts of one package stabilizers, 6 parts of KM355P, common CaCO
3Or modification CaCO
315 parts
Can find out that from table 3 add the composite plastic processing aid and compare with ordinary calcium carbonate, moment of torsion reduces; Fusion time obviously shortens, and melt temperature descends, and plasticizing rate accelerates; Explain that composite plastic processing aid and PVC plastics system consistency are good; Help processing, can improve extruded velocity, make the smooth exquisiteness of products appearance.This is because the properties-correcting agent and the PVC plastics of composite plastic processing aid surface chemistry bonding have excellent compatibility, shows strong interior lubrication, thereby has weakened the intermolecular reactive force of PVC, makes system rheological performance change.Explain under equal conditions also that simultaneously the composite plastic processing aid can increase loading level, also can reach good processing properties.
Calcium carbonate-filled PVC Mechanics Performance Testing before and after the modification:
PVC test piece test result compares:
With raw materials such as polyvinyl chloride resin, one package stabilizer, DOP, ordinary calcium carbonate or composite plastic processing aids, by the prescription batching, thorough mixing 10min discharging is subsequent use in high-speed mixer.Compound is plasticated at double roller plastic-making device, and film is at 165 ℃ of abundant down plasticizing 6min, and hard sheet is processed the thick thin slice of 0.5mm at 190 ℃ of abundant plasticizing 8min, and room temperature cuts into dumbbell specimen test fully after transferring 24h.
Ordinary calcium carbonate and composite plastic processing aid are produced hard, soft test piece respectively, on INSTRON 4466 type universal testing machines, test, the result sees table 4, table 5.
Table 4 rheological experiment result
| Title | Ys/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 50.835 | 21.364 | 46.569 | 2666.59 |
| Modification CaCO 3 | 53.952 | 42.456 | 103.360 | 2748.27 |
Prescription: 5 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
320 parts
Table 5 soft pvc plastic test piece test result relatively
| Title | Ys/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 7.09 | 6.91 | 48.7 | 75.7 |
| Modification CaCO 3 | 4.51 | 7.25 | 106.1 | 61.7 |
Prescription: 50 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
3120 parts
Can find out from table 4, table 5, under the situation of same addition, hard, the flexible article of PVC no matter; Use the composite plastic processing aid, the elongation at break that the mechanical property of test piece all obviously is superior to ordinary calcium carbonate, particularly test piece doubles many; And material is prone to plasticizing; Roll banding not, surface brightness is high, and processing characteristics is good.This is that surface energy is high because the ordinary calcium carbonate surface polarity is strong, in polyvinyl chloride resin, is easy to reunite, and is difficult for disperseing, thereby influences the goods processibility, and destroy the mechanical property of goods.And composite plastic processing aid surface organic modification; Surface energy significantly reduces; Being difficult for reuniting, is to be distributed in the polyvinyl chloride resin with the primary partical state basically, and passes through the molecule crane span structure effect of organic modifiers; On the interface, produce strong adhesive effect, and wherein part is penetrated in the polyvinyl chloride resin three-dimensional net structure with nanometer state dispersive rigid particles.According to inelastic body toughening modifying viewpoint, rigidity nanometer grade calcium carbonate particle surface defective is few, and the non-matching atom is many; Combine firmly with polyvinyl chloride resin, do the time spent receiving external force, cause matrix resin crazing absorption energy; Crisp-tough transformation takes place; Thereby avoid cracking of stress raisers, make matrix material reach toughened and reinforced effect, have mechanical property preferably.
Lime carbonate after composite plastic processing aid-modification of the present invention is at wave number 2979cm
-1, 2917cm
-1, 2512cm
-1, 1797cm
-1, 875cm
-1, etc. locate stretching vibration absorption band width and obviously widen, and displacement has taken place, show between the lime carbonate after the modification to have formed firm chemical bond.
Claims (2)
1. composite plastic processing aid, it is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, kaolin 3-5, mica powder 2-2, stalk ashes 1-2, active zinc flower 3-5, aerosil 3-5, the polymkeric substance 1-2 of methacrylic ester, polyethylene wax 1-2, sodium laurylsulfonate 1-2, silicone oil 1-2.
2. the preparation method of the described composite plastic processing aid of claim 1; It is characterized in that: light calcium carbonate is dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding kaolin, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium laurylsulfonate, silicone oil; After having added; Be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
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Cited By (6)
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| CN103509225A (en) * | 2013-09-24 | 2014-01-15 | 安徽省三乐门窗幕墙工程有限公司 | Flame retardant high strength wood-plastic sectional material and preparation method thereof |
| CN104497637A (en) * | 2014-12-16 | 2015-04-08 | 湖北羿廷化工科技有限公司 | Modified calcium carbonate and preparation method thereof |
| CN105419334A (en) * | 2015-12-29 | 2016-03-23 | 王丽萍 | High-performance plastic processing auxiliary agent |
| CN105419059A (en) * | 2015-12-29 | 2016-03-23 | 李栋军 | Novel plastic additive |
| CN105482486A (en) * | 2015-12-29 | 2016-04-13 | 王丽萍 | Novel high-performance plastic additive |
| CN108822546A (en) * | 2018-05-25 | 2018-11-16 | 佛山市高明区生产力促进中心 | A kind of plastic additive with fire retardation |
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| CN103509225A (en) * | 2013-09-24 | 2014-01-15 | 安徽省三乐门窗幕墙工程有限公司 | Flame retardant high strength wood-plastic sectional material and preparation method thereof |
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