CN103304948A - Maleic anhydride grafted polypropylene aqueous dispersion and preparation method and application thereof - Google Patents

Abstract

The invention discloses a maleic anhydride grafted polypropylene aqueous dispersion and a preparation method and an application thereof, belonging to the field of interdisciplinary science of chemical industry and high molecular materials. The maleic anhydride grafted polypropylene aqueous dispersion is composed of the following raw materials: 5-35wt% of maleic anhydride grafted polypropylene with weight average molecular weight of 20000-60000, 0.5-20wt% of non-ionic surface active agent, 0.5-20wt% of carboxylic acid auxiliary surfactant, alkali accounting for 0-120% of total sum of neutralizing the acid values of the maleic anhydride grafted polypropylene and carboxylic acid auxiliary surfactant, and the balance of water, wherein the average particle diameter of particles in the aqueous dispersion is 1-50 microns. The preparation method comprises the following steps of: uniformly mixing the raw materials according to a proportion, stirring and preserving the temperature at 170-200 DEG C for 0.5-2 hours, and cooling the mixture to the room temperature to obtain the maleic anhydride grafted polypropylene aqueous dispersion. The maleic anhydride grafted polypropylene aqueous dispersion disclosed by the invention can be used for improving the hydrophilicity and antistatic property of the material surface and the affinity with PP (Propene Polymer) materials and can be used as a surfactant of a polypropylene material or a reinforcement material for polypropylene. Meanwhile, the maleic anhydride grafted polypropylene aqueous dispersion can be also applied in toughening modification of polypropylene.

Description

Maleic anhydride inoculated polypropylene aqueous dispersion and its preparation method and application

Technical field

The invention belongs to chemical industry and macromolecular material interdisciplinary science field, be specifically related to a kind of maleic anhydride inoculated polypropylene aqueous dispersion, also relate to the preparation method and application of this aqueous dispersion simultaneously.

Background technology

Polypropylene and polyethylene, polyvinyl chloride also claim three big interchangeable heat plastic resins, and it is cheap, and is of many uses; Compare with polyethylene, polyacrylic intensity, hardness, heat-drawn wire are higher; Compare with polyvinyl chloride, owing to do not contain chlorine, thereby high high-temp stability is better.

For stressed bigger Application Areas, polyacrylic intensity, rigidity etc. are still not enough, can not with engineering thermoplastic resin, compare such as nylon, polycarbonate etc., but by after the enhancings such as glass, particle, the mechanical property of polypropylene composite material can compare favourably with nylon, polycarbonate etc., and price is lower, these contents are commonly referred to the resins for universal use through engineering approaches, and this field has become the focus in the industry, document [Zhang Xiaoming, Liu Xiongya.Fiber reinforced thermolplastic composite material and application thereof.Beijing: Chemical Industry Press, 2007] describe the content of various fiber reinforced polypropylene in detail, as SFT-PP, LFT-PP, CFT-PP, GMT-PP, NMT-PP etc., they are respectively short glass fiber, roving glass fiber, continuous glass-fiber, glass felt, natural fiber felt Reinforced Polypropylene, particle Reinforced Polypropylene aspect comprises mica, talcum powder, calcium carbonate enhancing etc., also has nanometer enhancing etc. in addition.

Polypropylene belongs to nonpolar and hydrophobic material, polar functionalities not, and the surface resistivity height, thus limit it in the application of wetting ability, static resistance; The polypropylene material impact resistance is lower, needs toughening modifying to improve its impact resistance.

MAH-g-PP aqueous dispersion of the present invention is adapted to above-mentioned field, to improve relevant performance, in former study, relates to though everyway had, and does not have a kind of product can adapt to above-mentioned multiple field, explanation respectively below.

Aspect fiber, mica Reinforced Polypropylene material: adopt MAH-g-PP aqueous dispersion (in case of necessity in conjunction with amino silicane coupling agent) to anticipate fiber, mica, make strongthener and MAH-g-PP form the good interface bonding, then that treated strongthener and polypropylene is compound, improve strongthener and disperse at polypropylene matrix, the corresponding raising of composite property.

Aspect polypropylene material wetting ability, static resistance: adopt MAH-g-PP aqueous dispersion (adding carbon black and other additives in case of necessity) to be coated in the polypropylene material surface, adopt heating, pressing mode, make that the surface congruent melting of MAH-g-PP aqueous dispersion and polypropylene material is melted, cocrystallization, thereby improve correlated performance.

Improve aspect its impact resistance at the polypropylene material toughening modifying: the MAH-g-PP aqueous dispersion is fully dehydrated becomes meal, with this meal and acrylic resin blend, melt extrudes granulation then, improves its impact resistance.

Mode and the effect of the certain applications of MAH-g-PP aqueous dispersion are seen [Zhao Ke.Functionalized polypropylene emulsion and application thereof, the 13 Surface Engineering innovated and practical technique exchanging meeting collection of thesis P128-133 2010 years Kaifengs; Yuan Yongyao, Zhao Ke.Functional poly propylene emulsion preparation method progress.Bonding, 2011,4:81-83; Http:// www.cnfrp.net/ns/echo.php id=40119] relevant report.

Foregoing all relates to several problems: (one) polypropylene and MAH-g-PP molecular structure, crystallinity, molecular weight, (two) polypropylene aqueous dispersion and preparation method thereof, the relation of (three) MAH-g-PP aqueous dispersion median size and its application.

(1) polypropylene and MAH-g-PP molecular structure, crystallinity, molecular weight:

Polyacrylic molecular structure is as follows

N represents the polymerization degree, contains side branched chain methyl-CH on the carbon backbone chain ₃From the molecular structure aspect, according to the residing position of methyl, there are four kinds of structures in polypropylene, isotactic → methyl is in a side (isotatic polypropylene), a rule → methyl alternately is in both sides (syndiotactic polypropylene), the irregular both sides (Atactic Polypropelene) that are in of random → methyl, in addition, also there is the polypropylene that possesses above-mentioned two kinds of structures on the molecular chain simultaneously, as metallocene polypropylene.

From molecular structure, isotatic polypropylene is owing to the methyl in the molecule is arranged in a side, and regularity is best, the easiest crystallization, and degree of crystallinity is higher, thereby the strength and stiffness of material are the highest.

Isotatic polypropylene be propylene monomer under certain temperature, pressure, formed by Qi Ge-Natta catalyst catalyzed polymerization; In addition, can form multipolymer between the propylene-ethylene, when adopting Qi Ge-Natta catalyst, copolymerization contains the small amount of ethylene monomer, and when forming Co-polypropylene, this multipolymer still has certain crystallizing power; But compare isotatic polypropylene, molecular weight near the time, the strength and stiffness of material descend relatively, but impelling strength increases.

For isotatic polypropylene, because tertiary carbon hydrogen is more active on the main chain, chemical reaction takes place easily, thereby also easily by grafting or atmospheric oxidation; For Co-polypropylene, similar chemical reaction also takes place easily.

MAH-g-PP(Maleic Anhydride grafted polypropylene), namely maleic anhydride inoculated polypropylene is to be the isotatic polypropylene chemical modification thing that forms behind the matrix grafted maleic anhydride with the isotatic polypropylene.

From the molecular weight aspect, have only isotatic polypropylene, Co-polypropylene can reach higher molecular weight, they can be used as material and use, and also can be enhanced material and strengthen; The isotatic polypropylene thermal destruction is isotatic polypropylene wax, and its essence is that n descends, and oxidation by air and be with acidic-group; The Co-polypropylene thermal destruction, the Co-polypropylene wax of formation, also oxidation by air and be with acidic-group; And a rule, the Atactic Polypropelene molecular weight is not high, often is called syndiotactic polypropylene wax, Atactic Polypropelene wax, and they do not contain acidic-group.

Metallocene polypropylene is class polypropylene newly developed, when molecular weight is not high, is called metallocene polypropylene wax, and with isotatic polypropylene wax phase ratio, the regularity that methyl is arranged in a side descends, and crystallizing power descends relatively, and does not contain acidic-group.

Poly Propylene Wax on the ordinary meaning comprises: isotatic polypropylene wax, Co-polypropylene wax, syndiotactic polypropylene wax, Atactic Polypropelene wax, metallocene polypropylene wax, because molecular weight is not high, they generally use as additive, interface treating agent.

(2) polypropylene aqueous dispersion and preparation method thereof:

For some special Application Areas, polypropylene need be dispersed in that the form with molecule re-uses in the water, this process is called polyacrylic Water-borne modification.From Water-borne modification difficulty or ease angle, according to " similar compatibility " principle, polypropylene polarity is more high, more easy Water-borne modification then, and its crystallinity makes the polypropylene microparticle trend grow into bigger crystalline particle and separates out from aqueous phase, and the more big Water-borne modification that then more is unfavorable for of molecular weight, and crystallinity, molecular weight, polarity are three class major influence factors, the isotatic polypropylene of high molecular, Co-polypropylene are difficult to Water-borne modification because molecular weight is big; When molecular weight within the specific limits owing to be grafted with maleic anhydride, then MAH-g-PP might Water-borne modification; Poly Propylene Wax, its weight-average molecular weight be below 10000, and contain certain polar group, then relatively easy Water-borne modification.

If five kinds of Poly Propylene Waxes (isotatic polypropylene wax, Co-polypropylene wax, syndiotactic polypropylene wax, Atactic Polypropelene wax, metallocene polypropylene wax) molecular weight, polarity are close, uncrystallizable and the easiest Water-borne modification of Atactic Polypropelene wax then, be difficult to most Water-borne modification and isotatic polypropylene wax crystallization ability is the strongest, Co-polypropylene wax, syndiotactic polypropylene wax, metallocene polypropylene wax mediate.

There are two class polypropylene wax emulsion in the market, one class is to be raw material with Atactic Polypropelene wax, by grafting polar group (as maleic anhydride, (methyl) vinylformic acid etc.) or oxidation, improve polarity, the wetting ability of Atactic Polypropelene wax, under normal pressure, add tensio-active agent and emulsification Atactic Polypropelene wax, this series products is mainly used in decorative kind, and it is attractive in appearance to give material; Another kind of is to be raw material with metallocene polypropylene wax, by solution mode grafting polar group (as maleic anhydride, (methyl) vinylformic acid etc.), be dissolved in the organic solvent again after then grafts being purified, under normal pressure, add tensio-active agent and metallocene polypropylene wax after the emulsification grafting, remove organic solvent at last again, this series products is mainly used in top coat, printing ink of polypropylene material etc., to improve polyacrylic dyeability, printing; In addition, also having a class is raw material with metallocene polypropylene wax, and through similar treatment process, the metallocene polypropylene wax emulsion of producing is used for glass and soaks into processing, and this glass is used for LFT-PP, GMT-PP, and the representative of this emulsion is the product that DSM N. V. produces.

Can two class polypropylene wax emulsion in the market be used for application purpose of the present invention? have why not enough?

(1) in the Atactic Polypropelene wax emulsion, its emulsion particle diameter can reach 0.1-1 μ m, the flexibility material that its main raw material Atactic Polypropelene wax is a kind of rubber like and uncrystallizable, handle strongthener with this emulsion, then because strongthener-polypropylene is difficult to crystallization at the interface, thereby can reduce strongthener-polypropylene interface binding ability, and strongthener-polypropylene interface is the tie that the Load Transfer that polypropylene is born is arrived strongthener, so the reinforced effects of strongthener can descend; In other respects, because Atactic Polypropelene wax is uncrystallizable, also limit its application.

(2) in the metallocene polypropylene wax emulsion (seeing Chinese patent CN1649954A and CN1798802A), there is some difference aspect molecular structure for its main raw material metallocene polypropylene wax and isotatic polypropylene, Co-polypropylene, can have influence on metallocene polypropylene wax and isotatic polypropylene, Co-polypropylene cocrystallization, it is strong inadequately to improve strongthener-polypropylene interface binding ability.

(3) in the metallocene polypropylene wax emulsion manufacturing processed, need to adopt the grafting solution method polar group earlier and purify, purify, then grafts is dissolved in the organic solvent, remove organic solvent after the emulsification again, this method organic solvent generally is difficult to remove fully totally, thereby has influence on application.

(4) metallocene polypropylene wax price is higher, raw material is bought has big difficulty, and, the complicate fabrication process of metallocene polypropylene wax emulsion, cost is higher, thereby its application is restricted.

(5) surface treatment of strongthener and the particle diameter in the emulsion have substantial connection.Metallocene polypropylene wax emulsion particle diameter about 1 μ m, relatively is suitable for trying out as the treating compound composition in the continuous glass-fiber wire drawing usually, and for other rich and varied strongtheners, this emulsion can not satisfy the demands.

(6) in other respects, since metallocene polypropylene wax emulsion, the also relevant application of restriction.

Select Atactic Polypropelene wax, the elder generation's grafting of metallocene polypropylene wax or oxidation, improve polarity, wetting ability, reduce the difficulty of emulsification, for the Atactic Polypropelene wax after the chemical modification, can directly emulsification under normal pressure; And for the metallocene polypropylene wax after the chemical modification, then owing to its characteristics of molecular structure, it need be dissolved in the organic solvent, and then emulsification, remove organic solvent at last again, but such production technique can be brought the serial problem of organic solvent; According to contriver's research, the manufacture craft of metallocene polypropylene wax emulsion can not be for the production of the MAH-g-PP aqueous dispersion, and this is because MAH-g-PP has stronger crystallinity, and polarity is lower, hydrophobicity is stronger, molecular weight is bigger.

(3) relation of MAH-g-PP aqueous dispersion median size and its application:

From MAH-g-PP molecular structure, crystallinity, molecular weight aspect, MAH-g-PP almost is identical or highly similar with polypropylene molecule structure, crystallinity aspect, when molecular weight in certain limit, and owing to contain maleic anhydride and increase its polarity, thereby make that MAH-g-PP can Water-borne modification, being used for multiple field, but there are substantial connection in the application in these fields and MAH-g-PP aqueous dispersion median size, the following describes.

The usage quantity of MAH-g-PP aqueous dispersion median size and tensio-active agent presents negative correlation, and namely amount of surfactant is more big, and then median size is more little, and aqueous dispersion is relatively more stable, and the water-absorbent after the MAH-g-PP aqueous dispersion film forming is more big; In depositing process, MAH-g-PP aqueous dispersion particle floats gradually and gathers also, and median size can increase gradually, thereby the MAH-g-PP aqueous dispersion product needed of preparation was used in the short as far as possible time; The MAH-g-PP aqueous dispersion needs corresponding median size in different Application Areass, the following describes.

Aspect fiber, mica Reinforced Polypropylene material: improving strongthener-polypropylene interface effective constituent is MAH-g-PP, and tensio-active agent and other additives then are disadvantageous to this; Soak into processing when being used for glass, require aqueous dispersion stability very high, MAH-g-PP aqueous dispersion median size is best near 1 μ m, but relative quantities such as tensio-active agent, other additives are more; For other application, MAH-g-PP aqueous dispersion median size need be at proper range, but should not surpass 50 μ m, and relative quantities such as tensio-active agent, other additives are less; In addition, reinforcement form, pretreatment mode and technology require different to MAH-g-PP aqueous dispersion median size.

Aspect polypropylene material wetting ability, static resistance: MAH-g-PP, tensio-active agent, other additives etc. all are conducive to improve polypropylene material wetting ability, static resistance, but action principle difference, MAH-g-PP can melt with the polypropylene congruent melting, cocrystallization, thereby play caking agent, when its content was very few, polypropylene material wetting ability, static resistance were difficult to keep for a long time; Tensio-active agent, other additives etc. are very big to polypropylene material wetting ability, static resistance influence; In addition, modified technique has influence on polypropylene material wetting ability, antistatic property; These contents are all relevant with MAH-g-PP aqueous dispersion median size, and median size and can be controlled median size between 1-50 μ m, can satisfy various requirement.

Improve aspect its impact resistance at the polypropylene material toughening modifying: MAH-g-PP, tensio-active agent, other additives etc. have influence on the effect that the polypropylene material toughening modifying is improved its impact resistance, and wherein MAH-g-PP plays the effect of compatilizer; Tensio-active agent, other additives etc. can have influence on the crystallizing power of isotatic polypropylene etc.; In addition, modified technique influences its effect; These contents are all relevant with MAH-g-PP aqueous dispersion median size, and median size and can be controlled median size between 1-50 μ m, can satisfy various requirement.

If in a set of equipment,, between 1-50 μ m, can control the median size size, and not contain organic solvent by control MAH-g-PP aqueous dispersion median size, to adapt to diversified application, then this method has certain advantage.This just the inventor be engaged in the motivation of the present invention, forefathers do not relate to this.

Forefathers' Water-borne modification polypropylene work summary:

High molecular functional poly propylene (weight-average molecular weight is more than 20000) is difficult to be because their high molecular, high melt viscosity, low melt flow index (MFR) or melt flow index (MFI), high hydrophobicity and relatively low polarity by Water-borne modification.And the high molecular functional poly propylene of isotactic is because its higher crystallization trend is more difficult by Water-borne modification, below from molecular weight angle analysis forefathers work in this regard.

(1) forefathers' Water-borne modification Poly Propylene Wax

Since nineteen fifties various functional polyolefins aqueous dispersion for commercial use, develop the method for Water-borne modification low-molecular-weight polyolefin (weight-average molecular weight is lower than 10000), and be applied to many fields.

It is 1000cP-5000cP maleinization Poly Propylene Wax that U.S. Patent No. 5290954 discloses a kind of 190 ℃ of following melt viscosities, under the temperature that is higher than the Poly Propylene Wax fluxing point, with a spot of tensio-active agent, and a certain amount of water, mix the sufficiently long time, prepare the method for maleinization Poly Propylene Wax aqueous dispersion.This product is mainly used in the floor and covers with paint, lacquer, colour wash, etc. the field, and need Poly Propylene Wax maleinization in advance, this will cause the Poly Propylene Wax of script lower molecular weight further to be degraded, the aqueous dispersion that this method produces has good light transmission, but is difficult to adapt to the requirement of multiple Application Areas of the present invention.

U.S. Patent No. 4240944 and No.4283322 have set forth the preparation method of binder composition that a kind of usefulness deals with the sizing material of glass fibre.This tackiness agent is aqueous dispersion, contain weight-average molecular weight less than 10000 isotactic maleinization Poly Propylene Wax and random maleinization Poly Propylene Wax, alkali and tensio-active agent, add random maleinization Poly Propylene Wax and help the Water-borne modification of isotactic carboxylic acid Poly Propylene Wax, but be difficult to adapt to the requirement of multiple Application Areas of the present invention.

Requiring of Chinese patent CN1133055A and CN1639315A and multiple Application Areas of the present invention is far apart.

Chinese patent CN1649954A and CN1798802A relate to synthetic, the metallocene polypropylene wax solution graft copolymerization modification of metallocene polypropylene wax, the preparation of metallocene polypropylene wax emulsion etc., relevant content illustrates that in front this kind emulsion is difficult to adapt to the requirement of multiple Application Areas of the present invention.

Because it is very big that polypropylene molecule amount, crystallinity, polarity influence its Water-borne modification, adopting aforesaid method is can not Water-borne modification MAH-g-PP.

(2) forefathers' Water-borne modification MAH-g-PP, Chlorinated Polypropylene III

Discover, with an organic solvent make the dissolving of polypropylene and chemical modification thing, with the emulsifying soln method can the Water-borne modification high molecular polypropylene, as French Patent No.2588263, Japanese Patent JP2005036076 etc., but the employing of organic solvent brings a lot of counter productives to its application, is difficult to adapt to application purpose of the present invention.

Direct fusion emulsion process does not with an organic solvent have very big application advantage, and this method is divided into " two-step approach " and " single stage method " two kinds according to the complexity of specific operation process.Whether basis adds low-molecular-weight polypropylene and as emulgate ingredient " single stage method " is divided into two kinds again.

(1) following is " two-step approach " preparation high molecular functional poly propylene aqueous dispersion:

English Patent No.2326164, U.S. Patent No. 6166118, No.5389440 and 5242969 have proposed a kind of " two-step approach " of Water-borne modification functional poly propylene, this technology was divided into for two steps, contents such as the hot water of adding, water vapour, neutralization bases namely need (be arranged under the certain pressure condition) in emulsion process, this method is very high to the requirement of equipment, the functional poly propylene aqueous dispersion average particulate diameter that produces is near 1 μ m, but be difficult to accomplish to control its aqueous dispersion average particulate diameter, be difficult to adapt to application requiring of the present invention.

(2) the adding Poly Propylene Wax prepares high molecular functional poly propylene water-based emulsion as " single stage method " of emulgate ingredient:

U.S. Patent No. 5585192,20040260008, No.6674181,2006/0106151 and No.7691935 in the process of preparation high molecular weight polypropylene water miscible liquid, all added low-molecular-weight polypropylene as i.e. second polyolefine of emulgate ingredient, play and reduce the mixture melt viscosity, thereby reduce the effect of high molecular weight polypropylene emulsification difficulty.And second polyolefine also contain carboxylic acid or anhydride functional group, better with first compatible polyolefin, chemical stability is arranged during high temperature emulsification.The functional poly propylene aqueous dispersion average particulate diameter that produces is near 1 μ m, but is difficult to accomplish to control its aqueous dispersion average particulate diameter, is difficult to adapt to application requiring of the present invention.

(3) " single stage method " preparation high molecular functional poly propylene water-based emulsion:

International monopoly WO2004031246, WO2006/039462, United States Patent (USP) 2006/0069187 have been introduced, and a kind of " a step direct method " prepares the method for high molecular function polypropylene water miscible liquid, the functional poly propylene aqueous dispersion average particulate diameter that produces is near 1 μ m, but be difficult to accomplish to control its aqueous dispersion average particulate diameter, be difficult to adapt to application requiring of the present invention.

Above-mentioned these patents all be the smaller the better with the particle in the emulsion be target, the emulsion particle median size that produces is many about 1 μ m, it is fine to leave standstill stability, relatively be suitable as continuous glass-fiber wire drawing treating compound, but the application of improper other side, these patents can not be satisfied the application background requirement that the inventor mentions.

Summary of the invention

The object of the present invention is to provide a kind of maleic anhydride inoculated polypropylene (MAH-g-PP) aqueous dispersion, it is two other purpose of the present invention that its corresponding preparation method and purposes are provided.

Based on above-mentioned purpose, the present invention has taked following technical scheme:

The maleic anhydride inoculated polypropylene aqueous dispersion, its raw material consists of: weight-average molecular weight is maleic anhydride inoculated polypropylene 5～35wt%, nonionogenic tenside 0.5～20wt%, the carboxylic acid cosurfactant 0.5～20wt% of 20000-60000, according in and maleic anhydride inoculated polypropylene and carboxylic acid cosurfactant acid number summation 0～120% add alkali, all the other are water; The particle median size is 1～50 μ m in the described aqueous dispersion.

The weight-average molecular weight of described maleic anhydride inoculated polypropylene is 30000; The consumption of nonionogenic tenside is 3～10wt% of raw material gross weight; The consumption of carboxylic acid cosurfactant is 3～10wt% of raw material gross weight.

Described nonionogenic tenside is made up of two or more, be selected from the Brij series of surfactants or be selected from the Brij series of surfactants and tween, sapn, OP series of surfactants (that is to say, nonionogenic tenside can all be selected from Brij series, also can from this series of surfactants, choose more than one earlier, from tween, sapn, OP series of surfactants, choose more than one again and be used in combination); Described carboxylic acid cosurfactant is by C ₁₂-C ₂₄Lipid acid and/or alicyclic carboxylic acid form.

Described Brij series of surfactants accounts for more than the 50wt% of nonionogenic tenside gross weight.

Described tween series of surfactants is polysorbas20, tween 21, polysorbate40, polysorbate60, tween 61, polysorbate65, tween 80, sorbimacrogol oleate100 or polysorbate85; Described span series is span 20, span 40, sorbester p18, sorbester p38, sorbester p17 or sorbester p37; Described OP series of surfactants is OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40 or OP-50; Described Brij series of surfactants is Brij-30, Brij-35, Brij-38, Brij-52, Brij-56, Brij-58, Brij-58P, Brij-72, Brij-721, Brij-76, Brij-78, Brij-90, Brij-92, Brij-92V, Brij-93, Brij-93V, Brij-96, Brij-96V, Brij-97, Brij-98, Brij-98V or Brij-99; Described carboxylic acid cosurfactant is selected from two or more in stearic acid, Palmiticacid, oleic acid, linolic acid, linolenic acid, vegetable fatty acid, mixed fatty acid, rosin, staybelite, the sylvic acid.

Described alkali is morpholine, imidazoles, the 1-Methylimidazole, pyrazoles, pyridine, acetyl is for pentanoic, benzene is for dimethylamine, nitrosodimethylamine, triethylamine, phenylethylamine, Uteramin, quadrol, butanediamine, pentamethylene diamine, hexanediamine, aniline, N, accelerine, N, the N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl propylene acid amides, N, the N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, the N-dimethylethanolamine, ammoniacal liquor, NaOH or KOH.

The preparation method of described maleic anhydride inoculated polypropylene aqueous dispersion, step comprises: each raw material is incubated 0.5～2h in 170～200 ℃ of stirrings behind the mixing in proportion, is cooled to room temperature then namely.

Among the described preparation method, adopt following measure effect better: each raw material behind the mixing, is warming up to 150 ℃ earlier in proportion, and the temperature rise rate according to 0.5～3 ℃/min makes temperature be warmed up to 170～200 ℃ from 150 ℃ then; After the insulation again the rate of cooling with 0.5～4 ℃/min make temperature be cooled to 150 ℃ from 170～200 ℃; When temperature was in 150 ℃ to 170～200 ℃, mixing speed was 800～1000rpm, and when temperature was lower than 150 ℃, mixing speed was 200～400rpm.

With the surface treatment agent of described maleic anhydride inoculated polypropylene aqueous dispersion as polypropylene material, with wetting ability, the static resistance of improving the polypropylene material surface; Or with the surface treatment agent of described maleic anhydride inoculated polypropylene aqueous dispersion as polypropylene usefulness strongthener (for example fiber, mica etc.), to improve the interfacial combined function between strongthener and the polypropylene.

With the plasticized modifier of described maleic anhydride inoculated polypropylene aqueous dispersion as polypropylene material, to improve the shock resistance of polypropylene material.

The present invention is main raw material with MAH-g-PP, prepares the MAH-g-PP aqueous dispersion by adopting the fusion emulsifying process, and average diameter of particles is between 1～50 μ m in this aqueous dispersion, and quality better, purposes are wide.

Its corresponding preparation method can once finish in same pressure stirring tank, and its step is simple, and is workable; Grain diameter can be controlled by adjusting prescription and processing parameter in the dispersion thing, and is convenient flexibly.

Elaborate with regard to associated viscera of the present invention below:

At present, the special small pressure stirred autoclave of using for experimental study is arranged on the market, adopt these stills can be engaged in multiple test, what adopt during Water-borne modification MAH-g-PP of the present invention is exactly this small pressure stirred autoclave.In more massive research and engineering application, then need the autoclave pressure according to present test-results design band whipping appts, more to adapt to the requirement of direct Water-borne modification MAH-g-PP.

Adopting the direct Water-borne modification of pressurization emulsifying manner is very difficult technically.Equipment, prescription, technology tie in, can construct the ideal conditions of Water-borne modification MAH-g-PP, wherein the equipment aspect relates generally to feeding device under the form, vacuum system, band press strip spare of type, the stirring rake of pressurization stirring tank, heating unit, refrigerating unit, baffle plate etc.; The prescription aspect relates generally to the type of the type of the type of raw material total amount and proportioning, carboxylic acid cosurfactant and consumption, nonionogenic tenside and consumption, neutralization bases and consumption etc.; Whether process aspect relates generally to temperature rise rate, rate of temperature fall, emulsifying temperature, stirring velocity, churning time, vacuumizes etc.

A characteristic of the present invention is the size that needs particle in the control MAH-g-PP aqueous dispersion, to adapt to diversified application.Though aqueous dispersion particle diameter and dosage of surfactant present negative correlation, be that dosage of surfactant is more big, then the aqueous dispersion particle diameter is more little, but also need the combined process parameter could control the aqueous dispersion particle diameter, this is because the MAH-g-PP that the present invention relates to has very strong crystallinity, and because complicacy and the singularity of fusion Water-borne modification technology, need determine the technology of granular size in the control MAH-g-PP aqueous dispersion by the experimental study of system, narrate associated viscera below respectively.

There are substantial connection in MAH-g-PP aqueous dispersion granular size and its application, in background technology explanation of the present invention, introduce in Atactic Polypropelene and the metallocene polypropylene wax emulsion, the diameter of its emulsion particle can reach between the 0.1-1 μ m, but the MAH-g-PP molecular weight is bigger, crystallinity is stronger, thereby Water-borne modification is more difficult, research according to the contriver, MAH-g-PP aqueous dispersion average particulate diameter is difficult to reach between the 0.1-1 μ m, can only be near 1 μ m, so the average particulate diameter of MAH-g-PP aqueous dispersion of the present invention is between 1-50 μ m.

With the MAH-g-PP molecular structure closely similar be isotatic polypropylene wax and graft modification thing thereof, the difference performance of both and Water-borne modification thereof is as follows: 1, the maleic anhydride among the MAH-g-PP adopts the grafting mode to realize, comprise technologies such as fusion, solution, solid phase, suspension grafting, different grafting modes, homogeneity to percentage of grafting and grafting has very big influence, and isotatic polypropylene wax adopts the isotatic polypropylene thermal destruction and makes; 2, the weight-average molecular weight of MAH-g-PP is usually more than 20000, and the weight-average molecular weight of isotatic polypropylene wax is below 10000; 3, MAH-g-PP and isotatic polypropylene wax phase ratio, having more advantage in price, this mainly is because there is very big difference in both at processing temperature, process aspect, the isotatic polypropylene thermal destruction need carried out more than 300 ℃, and be in batch reactor, to be interrupted to carry out, it is more to cause production cost to increase, and MAH-g-PP adopts single, double screw extrusion press to produce continuously about 200 ℃.

Because molecular weight is less, the easier Water-borne modification of isotatic polypropylene wax, in the invention of another isotatic polypropylene wax aqueous dispersion of contriver, the control problem that also relates to the aqueous dispersion particle diameter, its scope is between the 0.1-50 μ m, according to relevant theory, can fill a prescription by Water-borne modification isotatic polypropylene wax, also should be able to Water-borne modification MAH-g-PP, but it is true really not so, method that can the low-molecular-weight isotatic polypropylene wax of Water-borne modification might not be effective to the MAH-g-PP Water-borne modification, and the prescription of Water-borne modification MAH-g-PP need be specialized in.

As in the invention of another isotatic polypropylene wax aqueous dispersion of contriver, adopt and select tween, sapn and OP series as nonionogenic tenside, adopt composite mode to form compound emulsifying agent, and in conjunction with the carboxylic acid cosurfactant, Water-borne modification isotatic polypropylene wax, its average diameter of particles can be controlled between the 0.1-50 μ m, but are used for the MAH-g-PP Water-borne modification, then can only obtain bigger particle, its diameter is much larger than 50 μ m; Research by the contriver, control the average diameter of particles of MAH-g-PP aqueous dispersion if desired in 50 μ m, especially need to obtain the very little MAH-g-PP water dispersion of median size, the nonionic shape combinations-of surfactants of preferred Brij series or Brij series and tween, sapn and OP series nonionic shape combinations-of surfactants, and the nonionic shape tensio-active agent price of Brij series is higher, narrates associated viscera below respectively.

The MAH-g-PP material choice:When other conditions were constant, the weight-average molecular weight of MAH-g-PP and percentage of grafting were very big to its aqueous dispersion particle size effect, and weight-average molecular weight is more big, and percentage of grafting is more low, and it is more big then to prepare the aqueous dispersion particle, otherwise then more little; But weight-average molecular weight is more big, and the MAH-g-PP aqueous dispersion becomes film toughness more high, and relevant effect is more good; Thereby need take all factors into consideration many influences from factor, proper weight-average molecular weight is between 30000-60000, percentage of grafting is between 0.5-1.5wt%, MAH-g-PP by the market purchase, its weight-average molecular weight and percentage of grafting provide as the important indicator of product usually, and it is 30000 MAH-g-PP Water-borne modification process and the wetting ability of improving the polypropylene material surface thereof, static resistance, Stainless Steel Wire net surface Reinforced Polypropylene material that the present invention studies weight-average molecular weight; MAH-g-PP weight-average molecular weight and melt viscosity are in close relations, the driven terms of mechanics of melt viscosity has influence on the aqueous dispersion granular size, percentage of grafting and the interfacial tension of MAH-g-PP are in close relations, its value is more big, then the interfacial tension between particle (melt)-water is more little, interfacial tension has influence on the aqueous dispersion granular size from the thermodynamics aspect, and kinetics and thermodynamics illustrate below to the influence of aqueous dispersion granular size.

Tensio-active agent:Tensio-active agent refers to have fixing hydrophilic and oleophilic group, aligns at the surface energy of solution, and has the material that surfactivity can make surface tension significantly descend.The molecular structure of tensio-active agent has amphipathic: an end is hydrophilic radical, and the other end is the hydrophobic group; Hydrophilic radical often is the group of polarity, as carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof, and also hydroxyl, amide group, ehter bond etc.; And the hydrophobic group is nonpolar hydrocarbon chain often, as 8 above hydrocarbon chains of carbon atom.Tensio-active agent is divided into negatively charged ion, positively charged ion, nonionic, both sexes etc.It is disperse phase that the MAH-g-PP Water-borne modification requires exactly with MAH-g-PP, and water is a kind of dispersion system that external phase forms.Tensio-active agent is exactly to form directed adsorption layer in the MAH-g-PP/ water termination, reduces MAH-g-PP/ water termination tension force, makes immiscible MAH-g-PP and water two-phase form the aqueous fraction thing, and this aqueous dispersion has certain stationary phase.

If only from can Water-borne modification MAH-g-PP angle considering, negatively charged ion, positively charged ion, nonionogenic tenside and the combination between them all can be adopted, comprise amphoterics and some special surface promoting agents in addition, MAH-g-PP aqueous dispersion application purpose of the present invention is more, selects nonionogenic tenside to meet the demands.

In MAH-g-PP Water-borne modification process, usually need to add the carboxylic acid cosurfactant, this tensio-active agent can be compound and form complicated emulsification system with nonionogenic tenside, when adding neutralization bases, the carboxylic acid of carboxylic acid cosurfactant is neutralized, become anion surfactant, nonionogenic tenside and anion surfactant be compound to have usually than the better emulsifying capacity of single component separately.

Nonionic surface active agent exists with molecularity in water, so its stability is high, the oleophilic group of this class surfactant molecule generally is chain alkyl or the chain alkyl that has phenyl ring, hydrophilic group mainly be hydroxyl (-OH), ether (-O-), amide group (-CONH ₂), oxyethylene group (-CH ₂CH ₂O-) and many alcohols.No acidic group and basic group in the molecule so the effect of this emulsifying agent is not subject to the influence of solution acid, alkali and inorganic salt, have no adverse reaction with ionogenic surfactant, can mix to use and improve its function, and consistency are good.The wetting ability of nonionogenic tenside be since hydrophilic group on Sauerstoffatom or hydroxyl (-OH) and between the water molecules can form hydrogen bond.Nonionogenic tenside especially is fit to be used with anionic emulsifier, so purposes is very extensive.

The nonionic shape combinations-of surfactants of the preferred Brij series of the present invention or Brij series are used as emulsifying agent with tween, sapn and OP series nonionic shape combinations-of surfactants, and in conjunction with the carboxylic acid cosurfactant, form more complicated emulsification system, test shows, emulsification system plays an important role to the performance of MAH-g-PP aqueous dispersion, directly has influence on the granular size of aqueous dispersion.

In the explanation of invention application background, the MAH-g-PP water-based is turned to different-grain diameter, to adapt to different application purposes, Water-borne modification principle (whipped state): the MAH-g-PP melt is under the effect of shearing stress, ball-type melt generation shear strain and be elongated to cylinder shape, along with the minimizing of diameter and the increase of length, elongated cylinder shape melt fracture becomes several sections, tensio-active agent is wrapped in bath surface in this process, hinder melt and gather also each other, along with decrease of temperature, recrystallize into the molecule form and fix (in our research, by microscopic examination, can clear and definite principle); Water-borne modification technology (whipped state): normal temperature-intensification-insulation-cooling-normal temperature, corresponding MAH-g-PP state is: crystal form (solid)-molten state (melt)-recrystallize attitude (emulsion particle), technical difficulty can be analyzed from kinetics and thermodynamics aspect.

Kinetic factor:Under the MAH-g-PP molten state, can be dispersed into trickle particle be crucial, external factor is shearing stress and corresponding tangential strain, internal factor is the viscosity and corresponding rheological characteristics of melt, has only from the angle that reduces melt viscosity and increase shearing stress just to produce the aqueous dispersion with certain granules distribution.

The thermodynamics factor:Poly-between MAH-g-PP melt or the particle and be to develop to the thermodynamics beneficial direction, the effect of tensio-active agent is by reducing interfacial tension thereby helping the minimizing (respective interface is long-pending to be increased) of particle diameter on the one hand, on the other hand by static and steric repulsion increase poly-between melt or the particle and resistance, thereby can keep the thermodynamic instability state to exist for a long time; Differing temps, different states (melt, solid), stirring velocity (at a high speed, middling speed, static), SURFACTANT ADSORPTION and desorb, and the oneself state variable effect is to interfacial tension, and then have influence on particle diameter.The action principle explanation of tensio-active agent, there are negative correlation in consumption and the particle diameter of tensio-active agent.

Be reflected in equipment, prescription, technology three aspects in kinetic factor and the thermodynamics set of factors, three aspects are coordinated mutually, just can produce the aqueous dispersion that meets application background of the present invention.

Add the carboxylic acid cosurfactant, as hard ester acid, from kinetic factor, the adding of hard ester acid reduces the viscosity of MAH-g-PP melt, thereby help the minimizing of particle diameter, its prerequisite is that hard ester acid is melt blended evenly with MAH-g-PP, and the hard ester acid of part can be adsorbed on bath surface, becomes a kind of of tensio-active agent; From the thermodynamics factor, hard ester acid is owing to solvability in water is lower, the part that is adsorbed on bath surface can be thought nonionogenic tenside, because its molecular structure is more similar to MAH-g-PP, thereby it is inner and reduce its viscosity to enter the MAH-g-PP melt, when adding the alkali neutralization, then owing to hard ester acid is neutralized by alkali, its water-soluble increase becomes anion surfactant, and a part is dispersed in the water, a part is adsorbed on bath surface, and this moment, because it is difficult to enter melt inside, the effect that reduces the MAH-g-PP melt viscosity just descends; Add the type of neutralization bases, alkali and consumption etc. in the different steps of Water-borne modification technology, influence to kinetic factor and thermodynamics factor is different, and then have influence on the particle diameter of MAH-g-PP aqueous dispersion, present correlation theory can only be qualitatively to explanation in this respect, quantitative guiding suggestion can not be provided, the relation between the particle diameter of the type, consumption, neutralization bases etc. of adding carboxylic acid cosurfactant and MAH-g-PP aqueous dispersion can only be determined by experiment out.

Foregoing shows, kinetic factor and thermodynamics factors are to the particle diameter of MAH-g-PP aqueous dispersion, but accomplish MAH-g-PP aqueous dispersion average grain particle diameter control techniques if desired, then main by control carboxylic acid cosurfactant kind and consumption, nonionogenic tenside kind and consumption, carboxylic acid cosurfactant consumption/nonionogenic tenside consumption, (carboxylic acid cosurfactant+nonionogenic tenside) total amount/MAH-g-PP realizes, this prerequisite is the raw material aspect, process aspect, the stirring aspect remains unchanged, this three aspect is as long as change to some extent all can have influence on MAH-g-PP aqueous dispersion average grain particle diameter.

The following explanation overwhelming majority is based on the conclusion of test, can provide explanation qualitatively from kinetic factor and thermodynamics factor, but be difficult to quantitative forecast and guidance.

For the small pressure stirred autoclave of determining, stirring velocity is more high, often the particle diameter of aqueous dispersion is more little, stability is more good, but general small pressure stirred autoclave, there is the limit in its stirring velocity, near the stirring velocity of the limit, the accessories such as bearing in the damage equipment, and the more serious vibrations of production easily easily, long-time operation, cause pressurized vessel etc. fatigure failure to occur easily and potential safety hazard occurs, so stirring velocity need control in suitable scope, and heat up, insulation emulsification, in the temperature-fall period, stirring velocity changes, and stirring velocity is very big to the grain diameter influence of aqueous dispersion; The form of stirring arm also is the important factor that influences the aqueous dispersion particle diameter, though have relevant theory to explain to the form of stirring arm, test shows that these theories are not resultful; The form of stirring velocity, stirring arm influences the aqueous dispersion grain diameter jointly.

More satisfactory agitation condition is: between 150 ℃ to 170～200 ℃, rotating speed is 800-1000rpm, when temperature is lower than 150 ℃, rotating speed is 200-400rpm, this is because about 150 ℃, MAH-g-PP blend generation melting transition, namely by solid to melt (intensification), melt recrystallize (cooling), between 150 ℃ to 170～200 ℃, be the interval key of fusion Water-borne modification, the stirring velocity of this moment is the bigger the better in the tolerance band of equipment, the present invention is limited to stirring velocity between the 800-1000rpm, can take into account many-sided content; When temperature is lower than 150 ℃, also need certain stirring velocity, rotating speed is that 200-400rpm can meet the demands.

The Water-borne modification time was lower than 0.5 hour under the heat-retaining condition between 0.5-2 hour, then was difficult to form stabilized aqueous and disperseed thing, was higher than 2 hours, lost time, the energy consumption height, and the more satisfactory time is 1-1.5 hour.

The Water-borne modification temperature must be higher than the 20-50 degree of MAH-g-PP blend fusing point, namely between 170～200 ℃ of degree, temperature is low, then the particle diameter of aqueous dispersion is bigger than normal, and the temperature height, then oxidative degradation even variable color take place in MAH-g-PP easily, cause molecular weight further to descend, more satisfactory temperature is between 180-190 ℃, and according to the MAH-g-PP molecular-weight adjusting.

It has been generally acknowledged that heat-up rate and cooling rate are very little to the Water-borne modification influence, but the present invention studies show that, heat-up rate and cooling rate are that suitable influence is arranged to the quality of aqueous dispersion, be boundary with 150 ℃ particularly, its reason is not clear at present, be warmed up to 170～200 ℃ from 150 ℃, 0.5～3 ℃/min of heat-up rate, that more satisfactory is 1.7～1.9 ℃/min, cool to 150 ℃ from 170～200 ℃, rate of cooling is 0.5～4 ℃/min, and that more satisfactory is 2.5 ~ 3.0 ℃/min, when temperature is lower than 150 ℃, can heat up at faster speed or lower the temperature.

The material total amount should for the autoclave pressure volume 1/2～3/4 between, low excessively material causes Water-borne modification not carry out, and too high material also causes Water-borne modification incomplete, more satisfactory is about 2/3.

The MAH-g-PP content range of aqueous dispersion changes between 5～35wt%, and the non-ionic surfactant concentration scope changes between 0.5～20wt%, and more satisfactory is between 3～10wt%; Carboxylic acid cosurfactant content range changes between 0.5～20wt%, and more satisfactory is between 3～10wt%; The consumption of neutralization bases is in being enough to and 0～120% needed amount of MAH-g-PP and carboxylic acid cosurfactant total acidity.

This test is adopted with putting into the pressure stirring tank after the additive blend such as MAH-g-PP, nonionogenic tenside, carboxylic acid cosurfactant, neutralization bases, according to certain explained hereafter MAH-g-PP aqueous dispersion.

In MAH-g-PP Water-borne modification process, more content relates to MAH-g-PP aqueous dispersion problem of oxidation, in order to solve problem in this respect, adopt according to principle that to vacuumize before the test be more effective, but contriver's systematic testing shows, vacuumize MAH-g-PP aqueous dispersion variable color influence little, perhaps be that some material high temperature is with regard to variable color, perhaps be always to exist a spot of oxygen to be difficult to drain fully only, in the present invention, whether vacuumize not as necessary content.

Though the MAH-g-PP Water-borne modification is a kind of technology behavior based on physical process, but certain possible chemical reaction can take place in this process, fully contact with MAH-g-PP and further oxidation MAH-g-PP as remnant oxygen in the pressurized vessel, oxidation may take place in nonionogenic tenside and carboxylic acid cosurfactant, complex chemical reactions such as the pyrolytic decomposition that neutralization bases is possible or oxidation, make the granular size of MAH-g-PP Water-borne modification rely on equipment, prescription, technology three aspects, the MAH-g-PP aqueous dispersion is made up of following material: the MAH-g-PP particle, the carboxylic acid cosurfactant of Water-borne modification, water-soluble additive, the tensio-active agent of aqueous phase, water, neutralization bases etc., the carboxylic acid cosurfactant of Water-borne modification is present in the water with the form (between the 0.1-1 μ m) of fine particle, more stable, and the MAH-g-PP particle (it comprises MAH-g-PP, the carboxylic acid cosurfactant, tensio-active agent, neutralization bases) instability, its ascent rate and particle diameter, aqueous dispersion viscosity is relevant.

Part carboxylic acid cosurfactant can be present in the liquid phase by tensio-active agent emulsification, and the carboxylic acid cosurfactant of aqueous phase, tensio-active agent is invalid to disperseing and reducing the MAH-g-PP particle diameter, only be adsorbed on the MAH-g-PP particle surface or enter into its inner carboxylic acid cosurfactant, tensio-active agent, neutralization bases is effective to the diameter that reduces the MAH-g-PP particle, therefore can not be simply by increasing the carboxylic acid cosurfactant, tensio-active agent, the amount of neutralization bases reduces or controls the diameter of MAH-g-PP particle, and need synthetic study equipment, prescription, the tripartite influence in the face of granular size of technology, for the present invention, mainly be the control that realizes the MAH-g-PP granular size by the variation of prescription, the following describes content in this respect, emphasis is various composition roles, the foundation of selection etc.

The carboxylic acid cosurfactant is by C ₁₂-C ₂₄Lipid acid and/or alicyclic carboxylic acid form, its effect: 1, because molecular chain structure is similar to MAH-g-PP, thereby under melting condition, the carboxylic acid cosurfactant can with the MAH-g-PP mixing, reduce melt viscosity, thereby help the MAH-g-PP Water-borne modification; 2, owing to molecular chain structure band carboxylic acid, partial radical of hydroxy, thereby have certain emulsification function; 3, when adding neutralization bases, because the carboxylic acid of molecular chain structure is neutralized, thereby emulsifying property changes, become anion surfactant, in the introduction in front, describe the composite emulsifying system of being formed by nonionogenic tenside and anion surfactant in detail and have than the better emulsifying capacity of single emulsifying agent; 4, saturated or unsaturated fatty acids: liquid or solid-state, line style or band branched structure contain the modified fat mixture of acid, acid anhydrides, ester, and the purposes of lipid acid is for can be under the prerequisite of not degrading, except reducing the melt viscosity of MAH-g-PP, can also in handling, play glass the effect of lubricant; 5, lipid acid provides a kind of polyacrylic structure that is similar to, improved the dispersiveness of glass fibre in matrix material, and fiber and the consistency of resin matrix in process of cooling, because can providing, lipid acid make emulsion bear acidity and the required different HLB value of emulsifying system of variation, simultaneously can also be as a kind of emulgate ingredient, so lipid acid can use separately as emulsifying agent or with other combination of components, be applied to multiple emulsifying system.

The carboxylic acid cosurfactant is made up of stearic acid, Palmiticacid, oleic acid, linolic acid, linolenic acid, vegetable fatty acid, mixed fatty acid, rosin, staybelite, sylvic acid, preferred multiple carboxylic acid cosurfactant combination, its consumption is the 0.5-20wt% of aqueous dispersion quality, and preferable amount is 3-10wt%.

Vegetable fatty acid, mixed fatty acid are by different types of C ₁₂-C ₂₄Saturated and unsaturated fatty acids and alicyclic carboxylic acid form, and sell with commodity basis, thereby can buy in market.

Rosin is a kind of resinous substance that is come by the pine tree collection, as raw material, can further be processed into staybelite, sylvic acid, color also shoals thereupon, namely by yellow or brown rosin, become staybelite, the sylvic acid of white, rosin, staybelite, sylvic acid can use as the carboxylic acid cosurfactant, when needs light color aqueous dispersion, intend adopting staybelite, sylvic acid.Rosin, staybelite, sylvic acid can buy in market.

Lipid acid is divided into saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid, in MAH-g-PP Water-borne modification process, because the existence of high temperature and oxygen, oxidizing reaction may take place in lipid acid, cause its emulsification function to descend, and color burn, in order to obtain the MAH-g-PP aqueous dispersion than light colour, preferred saturated fatty acid is as the carboxylic acid cosurfactant.

In contriver's research, the kind of carboxylic acid cosurfactant and consumption have very big influence to the size of MAH-g-PP aqueous fraction composition granule, the combination of preferred two or more carboxylic acid cosurfactants, single carboxylic acid cosurfactant effect is not as two or more combinations.

The nonionic surfactants type plays a key effect for the MAH-g-PP Water-borne modification, nonionogenic tenside among the present invention is by polysorbas20, tween 21, polysorbate40, polysorbate60, tween 61, polysorbate65, tween 80, sorbimacrogol oleate100, polysorbate85, span 20, span 40, sorbester p18, sorbester p38, sorbester p17, sorbester p37, OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40, OP-50, Brij-30, Brij-35, Brij-38, Brij-52, Brij-56, Brij-58, Brij-58P, Brij-72, Brij-721, Brij-76, Brij-78, Brij-90, Brij-92, Brij-92V, Brij-93, Brij-93V, Brij-96, Brij-96V, Brij-97, Brij-98, Brij-98V, compositions such as Brij-99, these homologue nonionogenic tensides, structure is very close, identical hydrophilic group is arranged, the structure of hydrophobic group is also identical, the difference that chain length is only arranged, same series non-ionic surfactants, from hydrophobic to hydrophilic, corresponding HLB value variation range is very big, in contriver's research, studied with nonionic surfactant combinations between a series of and the different series the influence of MAH-g-PP aqueous dispersion granular size, the result shows that the combined effect of Brij series non-ionic surfactants is best, but because Brij series price is higher, angle is considered from reducing cost, can adopt other serial non-ionic surfactants and Brij series compound, Brij series nonionic shape tensio-active agent need account for more than the 50wt% of nonionic shape tensio-active agent total amount, nonionic shape dosage of surfactant is the 0.5-20wt% of aqueous dispersion quality, preferred 3-10wt%; The employing of Brij series and consumption are the characteristics of MAH-g-PP Water-borne modification, do not use Brij series in contriver's the isotatic polypropylene wax Water-borne modification content.

Be the distinctive designated value of surfactant molecule based on the HLB value, so the HLB value of mixed surfactant has additivity, can be calculated by the massfraction of each tensio-active agent of its composition:

HLB _A,B=HLB _A·A%+HLB _B·B%

As HLB value=9.5 of Brij-30, HLB value=4.9 of Brij-72 account for 60%, Brij-72 as Brij-30 in the mixing nonionogenic tenside and account for 40%, and can try to achieve mixed surfactant HLB value is 7.7.In the present invention, the required HLB value scope of MAH-g-PP Water-borne modification is between 5.5～9.3, between preferred 7～8.

The calculating of above-mentioned HLB value does not reflect the influence of carboxylic acid cosurfactant, neutralization bases, in fact different types of carboxylic acid cosurfactant and consumption, different types of neutralization bases and consumption are influential to the HLB value, but do not have correlation theory to calculate.

Nonionogenic tenside and carboxylic acid cosurfactant all play the effect of emulsification MAH-g-PP in MAH-g-PP Water-borne modification process, and to the quality of MAH-g-PP aqueous dispersion, the particle size effect of aqueous dispersion is very big.

At the MAH-g-PP raw material, technology, under the prerequisite that stirring remains unchanged, accomplish MAH-g-PP aqueous dispersion average grain particle diameter control techniques if desired, then main by control carboxylic acid cosurfactant kind and consumption, nonionogenic tenside kind and consumption, carboxylic acid cosurfactant consumption/nonionogenic tenside consumption, (carboxylic acid cosurfactant+nonionogenic tenside) total amount/MAH-g-PP realizes, nonionogenic tenside kind and consumption can determine that carboxylic acid cosurfactant kind and consumption then need by testing definite by the calculating of HLB value.

In preparation aqueous dispersion process, the effect of neutralization bases is not limited only to neutralizing agent, is used for regulating the pH value of aqueous dispersion.Neutralization bases and lipid acid can be at the soap of water-oil interface generation as tensio-active agent, and the interface composite membrane that this layer is firm is conducive to improve the stability of aqueous dispersion.In addition, the adding of neutralization bases also has bigger influence to the viscosity of aqueous dispersion sometimes, and the viscosity of aqueous dispersion also is to influence the stable important factor of aqueous dispersion; But the contriver studies show that, can not add neutralization bases sometimes, can obtain high-quality aqueous dispersion equally.

Neutralization commonly used has morpholine with alkali, imidazoles, the 1-Methylimidazole, pyrazoles, pyridine, acetyl is for pentanoic, benzene is for dimethylamine, nitrosodimethylamine, triethylamine, phenylethylamine, Uteramin, quadrol, butanediamine, pentamethylene diamine, hexanediamine, aniline, N, accelerine, N, the N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl propylene acid amides, N, the N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, the N-dimethylethanolamine, ammoniacal liquor, sometimes can use NaOH and KOH etc., the add-on of neutralization bases is enough to neutralized aqueous and disperses 0～120% of each composition acid number summation of thing.

The adding mode of neutralization bases (be with adding after pressing adding, emulsification to finish before the emulsification in adding, the emulsion process, do not add) all can have influence on the performance of aqueous dispersion, and the preceding mode that adds neutralization bases of emulsification is adopted in this test.

In contriver's systematic study, the color of the type of neutralization bases and MAH-g-PP aqueous dispersion has certain relation, and for the MAH-g-PP aqueous dispersion that is used for the glass wire drawing, color is very important factor, need conscientiously select neutralization bases.

In preparation MAH-g-PP aqueous dispersion process, oxidizing reaction may take place in the MAH-g-PP fusion Water-borne modification process, other additive, as nonionogenic tenside, the carboxylic acid cosurfactant, oxidizing reaction also can take place in neutralization bases etc., this reaction produces bad consequence to the color of MAH-g-PP aqueous dispersion sometimes, and bring problem for the application of this product, sometimes also can have influence on the size of aqueous dispersion particle, in order to reduce the MAH-g-PP high-temperature discoloration, sometimes need to add antioxidant, comprise water-soluble, oil-soluble inhibitor, usually the oil soluble oxidation inhibitor that is applied to PP can adopt, and for the various strongthener of the present invention and various application, antioxidant is not the composition that test must be added.

Similar with antioxidant, the color adaptation agent also is a MAH-g-PP aqueous dispersion that only is used for the glass wire drawing, as Sodium Pyrosulfite etc., be for the color that makes aqueous dispersion can be better.But result by experiment, the adding of additive whether and what of add-on, not obvious to the influence of aqueous dispersion color, it is agnogenio.

The effect of defoamer is the foam that produces in the MAH-g-PP aqueous dispersion production process in order to reduce, be exactly the defoamer that often adopts as octanol etc., this foam is influential to the stability of producing, the equipment cleaning of producing after finishing, but result by experiment, whether and what of add-on the adding of defoamer, influence to the aqueous dispersion foam is not obvious, and it is agnogenio, so defoamer is not the composition that necessarily needs interpolation.

The effect of anticorrosive agent is in order to prolong the duration of service of MAH-g-PP aqueous dispersion, reducing airborne microorganism is dissolved in the MAH-g-PP aqueous dispersion, and cause the corrosion of aqueous dispersion rotten, Sodium Benzoate commonly used etc. can adopt, but the product of producing owing to the present invention is used soon, thereby anticorrosive agent is not necessary added ingredients.

The effect of thickening material is in order to improve the viscosity of MAH-g-PP aqueous dispersion, reduce the ascent rate of MAH-g-PP, make that aqueous dispersion stability is better, as Walocel MT 20.000PV etc., but the product of producing owing to the present invention is used soon, thereby thickening material is not necessary added ingredients.

For MAH-g-PPW that can not Water-borne modification, they stick on stirring arm and the still wall usually, can adopt usual method to make it to break away from, adopt common equipment, these materials are pulverized and homogenized as colloidal mill, mulser etc., make its median size below 50 μ m, be used for glass Nomex (glass surface felt), natural fiber acupuncture (surface of natural fibers felt) etc.; Relatively directly pulverize MAH-g-PP, under this condition can not Water-borne modification MAH-g-PP, easier pulverizing, this is because it is during through recrystallize, tensio-active agents etc. and MAH-g-PP form the cause of blend, and its intensity, hardness, particle diameter all have largely and descend.

MAH-g-PP aqueous dispersion performance need by test analysis to estimate, performance test comprises: directly perceived and the observation of aqueous dispersion particle form, color, leave standstill changes in hardness before and after stability, yield, level of residue, apparent viscosity, transparence, particle diameter and distribution, the MAH-g-PP Water-borne modification, always quality etc.

Directly perceived and aqueous dispersion particle form observation: treat that Water-borne modification finishes, after from autoclave pressure, pouring out material, adopt its aqueous dispersion form of appearance method gross examination of skeletal muscle, be preferably the milk shape aqueous dispersion of MAH-g-PP true qualities homogeneous, relatively poor is that only there is most of solid particulate in some by Water-borne modification; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is more near ball-type, and then stability is more good.

Color:After the mixed system process pressurizing melting emulsion process of MAH-g-PP and the complexity of compositions such as other various nonionogenic tensides, carboxylic acid cosurfactant, alkali, the color outward appearance may change, and color might be brought influence to follow-up aqueous dispersion application, adopts appearance method to observe the aqueous dispersion color.

Leave standstill stability:As one of aqueous dispersion important performance perameter, the testing method that leaves standstill stability of aqueous dispersion is at room temperature vertically placed for the 6ml-8ml aqueous dispersion is poured in the 15ml test tube, observes its stratification state.Leave standstill stability in aqueous dispersion under the room temperature can stablize the placement time (with the sky) characterize.

Yield:The yield of aqueous dispersion deducts level of residue with the material total amount that adds autoclave pressure, obtains divided by the material total amount again, represents with percentage ratio.The aqueous dispersion yield has reflected the degree that the Water-borne modification process is carried out, and numerical value is more high, and the MAH-g-PP amount that then enters aqueous dispersion is more many.

Level of residue:Behind the Water-borne modification end of processing, solid matter remaining in the autoclave pressure is carried out weighing, add up the not amount of Water-borne modification.

Apparent viscosity: the NDJ-79 type rotary viscosity design determining that adopts Shanghai Tongji University to produce in the test, it is applicable to the mensuration of the apparent viscosity of the absolute viscosity of various Newtonian liquids and quasi-viscous liquid.During measurement, at first should select proper container and supporting rotor according to the approximate range of the viscosity of sample, make the reading pointer as far as possible between the 20%-85% of scale card, guarantee the accuracy of reading.Be under 25 ℃ in temperature, 1 minute stable total indicator reading of record rotor rotation can be measured aqueous dispersion viscosity.

Transparence:The transparence of aqueous dispersion is an index of aqueous dispersion performance.Be 1% aqueous dispersion with 1g aqueous dispersion and 99g deionized water mixed diluting, it is 600nm that the UV-2102 PSC type ultraviolet-visible pectrophotometer of producing with UNICO(Shanghai) Instruments Co., Ltd. is set wavelength, tests its transparence.

Particle diameter and distribution:Aqueous dispersion grain diameter size and size distribution thereof have decisive influence to the stability of aqueous dispersion, and grain diameter is more little, particle size distribution range is more narrow more stable.Water is diluted to finite concentration with aqueous dispersion, uses the LS-POP(VI) the type laser particle analyzer measures its particle diameter and size distribution.

The hardness of water dispersion:The MAH-g-PP raw material is heated to 180 degree left and right sides fusion film forming, the shore hardness instrument tested for hardness that adopts Shanghai Yanrun Ray Machine Technology Co., Ltd. to produce; With corresponding MAH-g-PP aqueous dispersion, first low temperature removes moisture, in 180 degree left and right sides fusion film forming, adopts shore hardness instrument tested for hardness then, with this hardness and the contrast of raw material hardness.

Total quality:The total quality of aqueous dispersion according to aqueous dispersion yield, level of residue, leave standstill stability, particle diameter and take all factors into consideration an index of weighing the aqueous dispersion overall performance that draws, aqueous dispersion is divided into four classes from high to low: good, in, general, poor.

Description of drawings

Fig. 1 is the size distribution figure of embodiment 1 gained aqueous dispersion;

Fig. 2 is the size distribution figure of embodiment 2 gained aqueous dispersion;

Fig. 3 is the size distribution figure of embodiment 3 gained aqueous dispersion;

Fig. 4 is the size distribution figure of the comparative example 1 gained aqueous dispersion of embodiment 1;

Fig. 5 is the size distribution figure of the comparative example 2 gained aqueous dispersion of embodiment 1;

Fig. 6 is the size distribution figure of embodiment 4 gained aqueous dispersion;

Fig. 7 is the size distribution figure of the repetition example gained aqueous dispersion of embodiment 4;

Fig. 8 is the size distribution figure of embodiment 5 gained aqueous dispersion;

Fig. 9 is the size distribution figure of embodiment 6 gained aqueous dispersion;

Figure 10 is the size distribution figure of embodiment 7 gained aqueous dispersion;

Figure 11 is the size distribution figure of the comparative example 1 gained aqueous dispersion of embodiment 4;

Figure 12 is the size distribution figure of the comparative example 2 gained aqueous dispersion of embodiment 4;

Figure 13 is the size distribution figure of the comparative example 3 gained aqueous dispersion of embodiment 4;

Figure 14 is the size distribution figure of the comparative example 4 gained aqueous dispersion of embodiment 4;

Figure 15 is the infrared spectrograms of embodiment 5 gained aqueous dispersion after 80 ℃ of dehydrations;

Figure 16 is the infrared spectrogram that embodiment 5 gained aqueous dispersion are done behind 175 ℃ of following drying and forming-films;

Figure 17 be embodiment 5 gained aqueous dispersion with the infrared spectrogram of KH-550 mixture;

Figure 18 is TGA, the DTA curve of embodiment 4 gained aqueous dispersion;

Figure 19 is TGA, the DTA curve of certain commercialization metallocene polypropylene wax emulsion;

Figure 20 is that the PP plate is through the change curve of the mixture process front and rear surfaces resistance ρ of MAH-g-PP2 aqueous dispersion or MAH-g-PP2 aqueous dispersion and epoxy grafts s, a-f represents among the figure: the untreated PP plate of a-, the PP plate that b-MAH-g-PP2 aqueous dispersion is handled, c-MAH-g-PP2 aqueous dispersion and epoxy grafts are pressed the PP plate of mass ratio 1:0.5 combination treatment, d-MAH-g-PP2 aqueous dispersion and epoxy grafts are pressed the PP plate of mass ratio 1:1 combination treatment, e-MAH-g-PP2 aqueous dispersion and epoxy grafts are the PP plate of 1:1.5 combination treatment by mass ratio, and f-MAH-g-PP2 aqueous dispersion and epoxy grafts are pressed the PP plate of mass ratio 1:2 mixture process;

Figure 21 is that the PP plate is through the change curve of the mixture process front and rear surfaces resistance ρ of MAH-g-PP2 aqueous dispersion or MAH-g-PP2 aqueous dispersion and carbon black s, a-g represents among the figure: the untreated PP plate of a-, b-MAH-g-PP2 aqueous dispersion is handled the PP plate, c-MAH-g-PP2 aqueous dispersion+1% carbon black is handled the PP plate, d-MAH-g-PP2 aqueous dispersion+2% carbon black is handled the PP plate, e-MAH-g-PP2 aqueous dispersion+3% carbon black is handled the PP plate, f-MAH-g-PP2 aqueous dispersion+4% carbon black is handled the PP plate, and g-MAH-g-PP2 aqueous dispersion+5% carbon black is handled the PP plate;

Figure 22 is the surface resistivity ρ s variation diagrams of different PP plates behind solvent wiping, a-f represents among the figure: a-MAH-g-PP2 aqueous dispersion is handled the PP plate, b-MAH-g-PP2 aqueous dispersion+1% carbon black is handled the PP plate, c-MAH-g-PP2 aqueous dispersion+2% carbon black is handled the PP plate, d-MAH-g-PP2 aqueous dispersion+3% carbon black is handled the PP plate, e-MAH-g-PP2 aqueous dispersion+4% carbon black is handled the PP plate, and f-MAH-g-PP2 aqueous dispersion+5% carbon black is handled the PP plate;

Figure 23 is that different PP plates are to the contact angle variation diagram of water, a-g represents among the figure: the untreated PP plate of a-, b-MAH-g-PP2 aqueous dispersion is handled the PP plate, c-MAH-g-PP2 aqueous dispersion+1% carbon black is handled the PP plate, d-MAH-g-PP2 aqueous dispersion+2% carbon black is handled the PP plate, e-MAH-g-PP2 aqueous dispersion+3% carbon black is handled the PP plate, and f-MAH-g-PP2 aqueous dispersion+4% carbon black is handled the PP plate, and g-MAH-g-PP2 aqueous dispersion+5% carbon black is handled the PP plate.

Embodiment

Below the invention will be further described by preferred embodiment, but protection scope of the present invention is not limited thereto.

Raw material:MAH-g-PP1, percentage of grafting are 0.8wt%, melting index (2.16kg/230 ℃)＞50g/10min, weight-average molecular weight 60000; MAH-g-PP2, percentage of grafting are 0.8-1.0wt%, melting index (2.16kg/190 ℃) 40-60g/10min, weight-average molecular weight 30000; MAH-g-PP1 and MAH-g-PP2 all are Nanjing moral bar chemical industry company limited products.

Equipment:1 liter of pressurization stirring tank.

The preparation method that following each embodiment adopts: with MAH-g-PP, water, carboxylic acid cosurfactant, tensio-active agent, neutralization bases is disposable joins in the pressure stirring tank, behind the seal-off pressure stirring tank, be warmed up to 150 ℃ from normal temperature, temperature rise rate be 5 ℃/more than the min; From 150 ℃ to 180 ℃, temperature rise rate is 1.8 ℃/min; Behind 180 ℃ of emulsifying temperatures, be incubated 1.5 hours; According to the cooling of the speed of 2.8 ℃/min, be down to back below 150 ℃ with the speed cooling of 5 ℃/min then, to 40 ℃ with bottom discharge.

Be warmed up to 150 ℃ from normal temperature, stirring velocity is 300rpm; Between 150 ℃-180 ℃, stirring velocity is 1000rpm; 180 ℃ of insulation emulsifications, stirring velocity is 1000rpm; Cool to normal temperature from 150 ℃, stirring velocity is 300rpm.

When stirring velocity remains unchanged, when processing condition are constant, MAH-g-PP aqueous dispersion average grain particle diameter control techniques: carboxylic acid cosurfactant kind and consumption, nonionogenic tenside kind and consumption, carboxylic acid cosurfactant consumption/nonionogenic tenside consumption, (carboxylic acid cosurfactant+nonionogenic tenside) total amount/MAH-g-PP.

The I class: raw material is the MAH-g-PP1 aqueous dispersion

Embodiment 1: the MAH-g-PP1 of 120g, water 413ml, oleic acid 27g, Brij-30:18.4g, Brij-72:8.6g, HLB value: 8, N, N-dimethylethanolamine: 13g.The index of gained aqueous dispersion: yield: 85%; Level of residue: 90g; Color: milky white; Transmittance: 13.8%; Leave standstill stability: 1 day; Apparent viscosity 16.4mPa.s; Median size: 44.3 μ m; Best result cloth particle diameter 56.6 μ m; The total quality of aqueous dispersion: in; Hardness after the aqueous dispersion drying/raw material hardness=85%; Size distribution as shown in Figure 1.

Embodiment 2: change the oleic acid among the embodiment 1 stearic acid of equal in quality into, all the other are constant.The index of gained aqueous dispersion: yield: 88%; Level of residue: 72g; Color: milky white; Transmittance: 12.9%; Leave standstill stability: 1 day; Apparent viscosity 22.3mPa.s; Median size: 35.1 μ m; Best result cloth particle diameter 45.3 μ m; The total quality of aqueous dispersion: in; Hardness after the aqueous dispersion drying/raw material hardness=75%; Size distribution as shown in Figure 2.

Embodiment 3: change the oleic acid among the embodiment 1 into oleic acid 7.2g and sylvic acid 10.8g, all the other are constant.The index of gained aqueous dispersion: yield: 95%; Level of residue: 30g; Color: milky white; Transmittance: 10.9%; Leave standstill stability: 2 days; Apparent viscosity 20.4mPa.s; Median size: 25.7 μ m; Best result cloth particle diameter 34.6 μ m; The total quality of aqueous dispersion: in; Hardness after the aqueous dispersion drying/raw material hardness=80%; Size distribution is seen Fig. 3.

The comparative example 1 of embodiment 1:MAH-g-PP1 among the embodiment 1 is reduced to 30g.The index of gained aqueous dispersion: yield: 98%; Level of residue: 10g; Color: milky white; Transmittance: 23.8%; Leave standstill stability:＞200 days; Apparent viscosity 6.4mPa.s; Median size: 4.8 μ m; Best result cloth particle diameter 6.6 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=70%; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is near ball-type, and size distribution is seen Fig. 4.

The comparative example 2 of embodiment 1:MAH-g-PP1 among the embodiment 1 is reduced to 60g.The index of gained aqueous dispersion: yield: 90%; Level of residue: 54g; Color: milky white; Transmittance: 28.8%; Leave standstill stability: 7 days; Apparent viscosity 12.4mPa.s; Median size: 16.3 μ m; Best result cloth particle diameter 20.6 μ m; The total quality of aqueous dispersion: medium; Hardness after the aqueous dispersion drying/raw material hardness=80%; Size distribution as shown in Figure 5.

The II class: raw material is the MAH-g-PP2 aqueous dispersion

Embodiment 4: the MAH-g-PP2 of 80g, water 440ml, oleic acid 27g, Brij-30:18.4g, Brij-72:8.6g, HLB value: 8, N, N-dimethylethanolamine: 13g.Gained aqueous dispersion index: yield: 98%; Level of residue: 10g; Color: milky white; Transmittance: 18.8%; Leave standstill stability:＞200 days; Apparent viscosity 14.4mPa.s; Median size: 4.2 μ m; Best result cloth particle diameter 5.2 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=73%; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is near ball-type, and size distribution as shown in Figure 6.

The repetition example of embodiment 4:Prescription, technology etc. are identical with example 4, and the index of gained aqueous dispersion is as follows: yield: 98%; Level of residue: 12g; Color: milky white; Transmittance: 20.8%; Leave standstill stability:＞200 days; Apparent viscosity 18.4mPa.s; Median size: 5.3 μ m; Best result cloth particle diameter 6.5 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=72%; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is near ball-type, and size distribution is seen Fig. 7.

Embodiment 5: change the oleic acid among the embodiment 4 stearic acid of equal in quality into, all the other are constant.The index of gained aqueous dispersion is as follows: yield: 97%; Level of residue: 15g; Color: milky white; Transmittance: 22.8%; Leave standstill stability: 7 days; Apparent viscosity 26.4mPa.s; Median size: 17.9 μ m; Best result cloth particle diameter 23.4 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=89%; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is near ball-type, and size distribution as shown in Figure 8.

Embodiment 6: change the oleic acid among the embodiment 4 into oleic acid 7.2g and sylvic acid 10.8g, all the other are constant.The index of gained aqueous dispersion: yield: 97%; Level of residue: 20g; Color: milky white; Transmittance: 25.8%; Leave standstill stability: 5 days; Apparent viscosity 22.4mPa.s; Median size: 26.7 μ m; Best result cloth particle diameter 35.4 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=81%; Size distribution is seen Fig. 9.

Embodiment 7: change the oleic acid among the embodiment 4 into stearic acid 7.2g and sylvic acid 10.8g, all the other are constant.The index of gained aqueous dispersion: yield: 96%; Level of residue: 25g; Color: milky white; Transmittance: 28.8%; Leave standstill stability: 2 days; Apparent viscosity 30.4mPa.s; Median size: 34.8 μ m; Best result cloth particle diameter 42.4 μ m; The total quality of aqueous dispersion: in; Hardness after the aqueous dispersion drying/raw material hardness=82%; Size distribution as shown in figure 10.

The comparative example 1 of embodiment 4:MAH-g-PP2 among the embodiment 4 is reduced to 40g, other parameter constants.The index of gained aqueous dispersion: yield: 99%; Level of residue: 5g; Color: milky white; Transmittance: 18.8%; Leave standstill stability:＞200 days; Apparent viscosity 14.4mPa.s; Median size: 1.3 μ m; Best result cloth particle diameter 1.7 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=65%; Adopt the form of particle in the observation by light microscope aqueous dispersion, coating of particles is near ball-type, and size distribution as shown in figure 11.

The comparative example 2 of embodiment 4:MAH-g-PP2 among the embodiment 4 is increased to 120g.The index of gained aqueous dispersion: yield: 99%; Level of residue: 5g; Color: milky white; Transmittance: 18.8%; Leave standstill stability: 7 days; Apparent viscosity 22.4mPa.s; Median size: 12.2 μ m; Best result cloth particle diameter 16.7 μ m; The total quality of aqueous dispersion: good; Hardness after the aqueous dispersion drying/raw material hardness=72%; Size distribution is seen Figure 12.

The comparative example 3 of embodiment 4:MAH-g-PP2 among the embodiment 4 is increased to 180g, other parameter constants.The index of gained aqueous dispersion is as follows: yield: 85%; Level of residue: 103g; Color: milky white; Transmittance: 20.1%; Leave standstill stability: 4 days; Apparent viscosity 34.4mPa.s; Median size: 21.5 μ m; Best result cloth particle diameter 29.0 μ m; The total quality of aqueous dispersion: medium; Hardness after the aqueous dispersion drying/raw material hardness=85%; Size distribution as shown in figure 13.

The comparative example 4 of embodiment 4:MAH-g-PP2 among the embodiment 4 is increased to 260g, other parameter constants.The index of gained aqueous dispersion is as follows: yield: 80%; Level of residue: 153g; Color: milky white; Transmittance: 28.8%; Leave standstill stability: 1 day; Apparent viscosity 54.4mPa.s; Median size: 44.1 μ m; Best result cloth particle diameter 58.0 μ m; The total quality of aqueous dispersion: medium; Hardness after the aqueous dispersion drying/raw material hardness=90%; Size distribution as shown in figure 14.

(1) raw material is the aqueous dispersion basic physical properties of MAH-g-PP2

(1) MAH-g-PP2 aqueous dispersion Infrared spectroscopy

With embodiment's 5 MAH-g-PP2Aqueous dispersion is after 80 ℃ of dryings were fully dewatered in 2 hours, mix with certain proportion with Potassium Bromide, fully grind the back and in about 70 ℃, dry 0.5h, produce two parallel sample compressing tablets with tabletting machine, measure with WQF-510 type Fourier infrared spectrograph (Beijing Rayleigh Analytical Instrument Co.,Ltd), with pure Potassium Bromide as a setting, scanning times is 20 times, resolving power 1cm during mensuration ^-1, sweep limit 4000cm ^-1~ 400cm ^-1, the gained infrared spectra as shown in figure 15.

MAH-g-PP2Adopt carboxylic-acid emulsifying agent, the neutralization bases salify of nonionogenic tenside and amine in the aqueous dispersion preparation process.3443.32cm wherein ^-1Be N-H stretching vibration, 1630.05cm ^-1Be the formation vibration of C=O in the acid amides, 1094.16cm ^-1The C-N stretching vibration, 3000cm ^-1~ 2800cm ^-1Between the 2957.12cm that occurs ^-1, 2921.72cm ^-1Be the C-H stretching vibration peak of methyl and methylene radical, 1459.46cm ^-1And 1381.71cm ^-1Formation vibration peak for C-H.

Get the MAH-g-PP2 aqueous dispersion of embodiment 5, do Infrared spectroscopy behind 175 ℃ of drying and forming-films, the result as shown in figure 16.

Contrast Figure 16 and Figure 15 1732.12cm-occurred as can be seen among Figure 16 ¹The carboxyl C=O peak at place illustrates the phenomenon that has also occurred a small amount of neutralized salt pyrolysis in aqueous dispersion high temperature film forming.

(2) the mixed Infrared spectroscopy of MAH-g-PP2 aqueous dispersion and KH-550

R-aminopropyl triethoxysilane coupling agent (KH-550): density (25 ℃), 946g/ml, boiling point 217oC, Nanjing is chemical company forward.Coupling agent (KH-550), dehydrated alcohol, distilled water are made into 10% homogeneous solution in the 10:82:8 ratio, in the time of in embodiment 5 aqueous dispersion being added drop-wise to 10% KH-550 solution, have tangible gelatin phenomenon to occur.Do infrared analysis after 175 ℃ of film forming of mixture of embodiment 5 aqueous dispersion and KH-550 reaction, the gained spectrogram as shown in figure 17.

With Figure 17 and Figure 16 contrast, 1732cm ^-1The carboxylic acid absorption peak disappears, at 1632cm ^-1Near the shape of absorption peak changes, and this is that there are very big difference in Figure 17 and Figure 16, especially at 1100cm because form the absorption peak of acid amides ^-1-400cm ^-1Scope in, illustrate that chemical reaction has taken place for amido among the KH-550 and the carboxyl in the aqueous dispersion, form more intense Chemical bond, both combinations have influence on its infrared spectrogram.

(3) MAH-g-PP2 aqueous dispersion thermogravimetric analysis

In fully dehydration of 80 ℃ of dryings 2 hours, the MAH-g-PP2 aqueous dispersion is carried out thermogravimetric (TGA) to the differential thermal-thermogravimetric analyzer (DTG-60) that utilizes Japanese Shimadzu company to make in nitrogen atmosphere and differential thermal (DTA) is analyzed with embodiment 4 aqueous dispersion.Temperature rise rate is 10 ℃/min, and the intensification scope is room temperature-300 ℃.Gained TGA and DTA curve are seen Figure 18.

As seen from Figure 18, for the TGA curve, tangible thermal weight loss does not appear in MAH-g-PP2 aqueous dispersion total system before 200 ℃, has only the moisture evaporation of small amount of residual, shows that the system of aqueous dispersion is heat-staple before this; When temperature is higher than 200 ℃, because the thermolysis of MAH-g-PP2 volatilization causes weight loss rate obviously to increase; For the DTA curve, between 145 ℃ ~ 160 ℃, there is endotherm(ic)peak, this is due to the MAH-g-PP2 particle fusion, because MAH-g-PP2 is crystal material, therefore the film-forming temperature of its aqueous dispersion should be not less than its melt temperature, when the film formation time of test aqueous dispersion, the setting of film-forming temperature should be not less than 145 ℃.

(4) metallocene polypropylene wax emulsion thermogravimetric analysis

The commercial metallocene polypropylene wax emulsion of selecting certain company to produce is done thermogravimetric analysis, this emulsion applications is used as the treating compound composition in the glass wire drawing, its mean diameter is between 0.1-1 μ m, 80 ℃ down made it fully dehydration in dry 2 hours after, it is carried out thermogravimetric (TGA) to the differential thermal-thermogravimetric analyzer (DTG-60) that utilizes Japanese Shimadzu company to make then in air atmosphere and differential thermal (DTA) is analyzed.Temperature rise rate is 10 ℃/min, and the intensification scope is room temperature-300 ℃.Gained TGA and DTA curve are as shown in figure 19.

As can be seen from Figure 19 this emulsion thermostability below 200 ℃ the time is preferably, and when temperature surpassed 200 ℃, emulsion system began to have small amount of thermal weightlessness, but final rate of weight loss is significantly less than Figure 18; This emulsion is compared with Figure 18 as can be seen from the DTA curve, has more two absorption peaks in the time of 45-100 ℃; The characteristic of metallocene polypropylene wax molecular structure makes its pyro-oxidation resistance be better than MAH-g-PP2, thereby shows that among the thermogravimetric analysis figure, the thermal weight loss rate obviously reduces, and the endotherm(ic)peak showed increased.

(2) the MAH-g-PP2 aqueous dispersion is improved polyacrylic wetting ability, static resistance

Polypropylene PP belongs to nonpolar and hydrophobic material, polar functionalities not, and the surface resistivity height, thus limit it in the application of wetting ability, static resistance, the following describes the MAH-g-PP2 aqueous dispersion and improve polyacrylic wetting ability, static resistance content.

(1) experimental raw and instrument

PP plate (2mm is thick, and is commercially available); MAH-g-PP2 aqueous dispersion (embodiment 4, median size 4.2 μ m, solid content 20%); The grafting block thing of Resins, epoxy (the grafting block thing of Resins, epoxy and Macrogol 4000, self-control); ZC46A type megger (Shanghai Precision Scientific Apparatus Co., Ltd); JJC-1 type wetting angle contact angle instrument (Changchun opticinstrument head factory).

(2) pre-treatment of PP plate

The PP plate is cut into the square block that size is 15 * 15cm, puts it in the acetone soln then and clean, to remove the dirt on PP plate surface, then use the acetone on deionized water flush away PP plate surface, clean with ethanol then and immersion 10min, rinse well with deionized water at last, room temperature is dried standby.

3) surface treatment of PP plate

(1) the MAH-g-PP2 aqueous dispersion is coated on the pretreated PP plate equably, puts into 110 ℃ of oven dry of vacuum drying oven, applies certain pressure on its surface then and place 1h under 190 ℃ of conditions, cools to room temperature more at last.

(2) the MAH-g-PP2 aqueous dispersion is mixed with mass ratio 1:0.5,1:1,1:1.5,1:2 respectively with the grafting block thing of Resins, epoxy, then according to step (1) with this mixture process PP plate.

(3) add a certain amount of carbon black in the MAH-g-PP2 aqueous dispersion, the massfraction of carbon black is respectively 1%, 2%, 3%, 4%, 5%, comes to handle polypropylene board according to step (1) with mixed material.

(4) the anti-wiping of processing back PP plate

Respectively in deionized water, ethanol, three kinds of solvents of acetone with absorbent cotton wiping through surface-treated PP plate surface 300 times, measure the resistance (relative humidity 50%, 25 ℃ of temperature) on PP plate surface then.

(5) measure surface resistivityρ s

With the surface resistivity s of ZC46A type megger mensuration through the PP of different surface treatment plate.

(6) measure PP plate surface contact angle

Be test liquid with the deionized water, measure the static contact angle of handling PP plate surface, back and air interface with JJC-1 type measurement and determination of humidifying angle instrument, each sample is surveyed 6 points (spacing between the adjacent measuring point is no less than 1cm), gets the arithmetical av of 6 points as the value of experiment gained contact angle.

(7) the MAH-g-PP2 aqueous dispersion is to the sticking power of PP plate

Measure different mixtures to the sticking power of PP plate according to the cross-hatching among the GB/T 9286-98.

(8) result and discussion

(8.1) MAH-g-PP2 aqueous dispersion and the composite use surface modification of epoxy grafts polypropylene

Utilize the mixture of MAH-g-PP2 aqueous dispersion or MAH-g-PP2 aqueous dispersion and epoxy grafts that the PP plate is carried out surface treatment, measure the resistance on PP plate surface before and after handling, the agent of research different surface treatment is to the influence of PP plate surface resistivity, and measurement result is seen Figure 20.

As can be seen from Figure 20, the be untreated surface resistivity of PP plate is 10 ¹⁴Ω, behind MAH-g-PP2 aqueous dispersion individual curing PP plate, the surface resistivity of PP plate drops to 10 ¹²Ω.The major cause of this phenomenon is to contain emulsifying agent in the MAH-g-PP2 aqueous dispersion, hydroaropic substances such as tensio-active agent, the MAH-g-PP2 aqueous dispersion is coated in the 110 ℃ of oven dry in PP plate surface removes wherein moisture, begin fusion and all reach fusing point at 190 ℃ of high temperature MAH-g-PP2 of following time particles and PP plate, because the consistency between MAH-g-PP2 and the PP, make the MAH-g-PP2 particle to PP plate surface transport and the small molecules of tensio-active agent and emulsifying agent moves to air interface, the water-wet side of tensio-active agent can absorb existing moisture in the air again, thereby PP plate surface forms one deck conductive layer, and then the surface resistivity of handling back PP plate is descended.After adding the epoxy grafts of different mass in the MAH-g-PP2 aqueous dispersion, PP plate surface resistivity drops to 10 ¹⁰About Ω, and along with the increase of epoxy grafts amount, PP plate surface resistivity changes little after the modification.

(8.2) the composite use surface treatment of MAH-g-PP2 aqueous dispersion and carbon black polypropylene

What Figure 21 studied is that the composite front and back of carbon black of MAH-g-PP2 aqueous dispersion and different amounts are to the influence of PP plate surface resistivity.As can be seen from Figure 21, the surface resistivity of untreated PP plate is 10 ¹⁴Ω, behind MAH-g-PP2 aqueous dispersion individual curing PP plate, the surface resistivity of PP plate drops to 10 ¹²Ω.MAH-g-PP2 aqueous dispersion and carbon black used handle the PP plate, found that originally along with the increase of carbon black mass mark, the surface resistivity of PP plate slowly drops to 10 after the modification ^8.7Ω.But when the massfraction of carbon black reached 4%, the rapid decline of the surface resistivity of PP plate reached 10 after the modification ⁶Ω, and continuation increases the massfraction of carbon black, the surface resistivity of PP plate changes not obvious.The reason of this phenomenon may be when the massfraction of carbon black is low, and the carbon black particle of handling PP plate surface, back distributes and comparatively disperses, and carbon black particle is the distance effect of big thereby conduction and bad still each other.Along with the increase of carbon black mass mark, the distance between adjacent carbon black particle slowly reduces, and finally makes PP plate surface after the processing form the path of conduction, makes surface resistivity sharply descend.Because the path that can conduct electricity has formed, so even increasing further after the massfraction modification of carbon black that the surface resistivity of PP changes neither be clearly.

(8.3) the different surface treatment material is to the sticking power of PP plate

Adopt cross-hatching measure the MAH-g-PP2 aqueous dispersion and with the sticking power of carbon black stock to the PP plate, measurement result sees Table 1.

Table 1 different surface treatment material is to the sticking power of PP plate

The finish materials type	The MAH-g-PP2 aqueous dispersion	MAH-g-PP2 aqueous dispersion+1% carbon black	MAH-g-PP2 aqueous dispersion+2% carbon black	MAH-g-PP2 aqueous dispersion+3% carbon black	MAH-g-PP2 aqueous dispersion+4% carbon black	MAH-g-PP2 aqueous dispersion+5% carbon black
							Sticking power/level	0	0	0	1	2	2

As can be seen from Table 1, use the MAH-g-PP2 aqueous dispersion to handle the PP plate separately, aqueous dispersion is fine to the sticking power of PP plate.The major cause of this phenomenon is: MAH-g-PP2 particle and PP fusion simultaneously in the aqueous dispersion in the time of 190 ℃, in the process of fusion cooling, there is the process of a cocrystallization between the two, and this process makes that both cohesive forces of cooling back are fine.When the content of carbon black and the blend use of MAH-g-PP2 aqueous dispersion and carbon black more after a little while, blend better can reach 0 grade to the sticking power of PP plate, drops to 1 grade when the content of carbon black reaches 3% postadhesion power.After the massfraction of carbon black reaches 4%, loss of adhesion to 2 grades and the also obviously increase of processing back PP plate surfaceness.

(8.4) the different surface treatment material is to the influence of the anti-wiping in PP plate surface

Utilize differing materials that the PP plate is carried out surface treatment, in different solvents, the PP plate is carried out surperficial wiping then, the surface resistivity of PP plate after the mensuration wiping, measurement result is seen Figure 22.：

As can be seen from Figure 22, the PP plate that adopts the MAH-g-PP2 aqueous dispersion to handle does not change through different solvents wiping rear surface resistance, shows with the anti-wiping properties of MAH-g-PP2 aqueous dispersion processing back PP plate fine.The major cause of this phenomenon is that the cocrystallization between MAH-g-PP2 aqueous dispersion and the PP plate makes cohesive force between the two strong, thereby is subjected to the influence of solvent wiping less.And the anti-wiping properties of the PP plate of handling through aqueous dispersion and carbon black stock along with the increase of content of carbon black variation.When content of carbon black smaller or equal to 3% the time, solvent wiping front and rear surfaces resistance change is little, the anti-wiping properties of handling back PP plate this moment still can.And when the massfraction of carbon black reaches 4%, obviously increase with the surface resistivity of PP plate behind 3 kinds of solvent wipings, anti-wiping properties descends.The reason that produces this phenomenon may be that the surface-coated thing is loss of adhesion to the PP plate when content of carbon black reaches 4%, and roughness increases, and cohesive strength between the two descends, and after the solvent wiping experiment, the antistatic surface component incurs loss, and surface resistivity increases.

(8.5) the PP plate after the differing materials surface treatment to the contact angle of water

Measure the PP plate that is untreated, MAH-g-PP2 aqueous dispersion processing PP plate, MAH-g-PP2 aqueous dispersion and carbon black stock respectively and handle PP plate surface to the contact angle of water, measurement result is seen Figure 23.

As can be seen from Figure 23, undressed PP plate surface contact angle is 87o; Through the PP plate that MAH-g-PP2 aqueous dispersion individual curing is crossed, its contact angle to water has dropped to 77o.The MAH-g-PP2 aqueous dispersion is handled PP plate surface hydrophilicity is strengthened, its major cause is to contain hydrophilic small molecules such as tensio-active agent, emulsifying agent in the MAH-g-PP2 aqueous dispersion, the fusion simultaneously of 190 ℃ of following PP plates and MAH-g-PP2 particle, hydrophilic small molecules makes the PP plate surface after handling descend to the contact angle of water to the air interface migration.Utilize aqueous dispersion and carbon black stock that the PP plate is carried out surface treatment, the increase with carbon black reduces the PP plate after the processing to the contact angle of water, and minimum is about 45o; But after the carbon black mass mark reached 4%, it was the increase of PP plate surfaceness that contact angle continues main reasons for decrease.

Conclusion:

PP plate surface resistivity is 10 ¹⁴Ω is with water contact angle 87o; Adopt the MAH-g-PP2 aqueous dispersion, and in conjunction with epoxy grafts, carbon black etc., PP plate surface resistivity can be reduced to 10 significantly ⁶About Ω, be reduced to about 45o significantly with water contact angle, and surface modification has weather resistance, scrub performance, this be because the MAH-g-PP2 aqueous dispersion can with the cause of PP cocrystallization.

(3) the MAH-g-PP2 aqueous dispersion is improved Stainless Steel Wire net surface Reinforced Polypropylene material

Adopt the MAH-g-PP2 aqueous dispersion, and in conjunction with epoxy grafts, carbon black etc., can reduce significantly with PP plate surface resistivity, with water contact angle, but this mode is subjected to certain limitation, as the carbon black color problem, for making resultant articles near the primary colors of PP plate, and reduce PP plate surface resistivity, increase PP plate surface hydrophilicity, adopt the Stainless Steel Wire net surface to strengthen.

(1) experimental raw and instrument

PP plate (2mm is thick, and is commercially available); MAH-g-PP2 aqueous dispersion (embodiment 4, median size 4.2 μ m, solid content 20%); Stainless Steel Cloth (diameter is 0.24mm, and mesh 2 * 2mm is commercially available).

(2) pre-treatment of PP plate

The PP plate is cut into the square block that size is 15 * 15cm, puts it in the acetone soln then and clean, to remove the dirt on PP plate surface, then use the acetone on deionized water flush away PP plate surface, clean with ethanol then and immersion 10min, rinse well with deionized water at last, room temperature is dried standby.

(3) preparation of PP composite panel

A.Stainless Steel Cloth (being cut to the square of 15 * 15cm) is sprawled at the PP thin sheet surface, place then and be warming up to 190 ℃ of moulding presss (the FM-11 type that the rich equine skill in Beijing company limited produces) in advance, during compressing tablet, behind the preheating 3min of elder generation, behind the mold pressure 3MPa compacting 5min, be cooled to 40 ℃ of dischargings.

B. smear the MAH-g-PP2 aqueous dispersion at Stainless Steel Cloth (being cut to the square of 15 * 15cm), after normal temperature is placed and to be removed moisture, prepare matrix material according to the method for A.

(4) PP composite panel Mechanics Performance Testing

Instrument: electronic universal tester CMT6104, Shenzhen City Xinsansi Metering Technology Co., Ltd.

According to GB/T1040-92, tension specimen is 135 * 10 * 2mm, and gauge length is 50mm, and draw speed is 50mm/min; According to GB9341-88, bend specimen is 120 * 10 * 2mm, and gauge length is 64mm, and crooked speed is 2mm/min.

(5) result and discussion

Untreated Stainless Steel Cloth can not be compound with PP; Stainless Steel Cloth after the MAH-g-PP2 aqueous dispersion is smeared processing and PP are compound good, call PP/ Stainless Steel Cloth composition board in the following text.

(5.1) tensile property

PP plate and PP/ Stainless Steel Cloth composition board are carried out Elongation test, and test result sees Table 2.

The tensile property of table 2:PP plate, PP/ Stainless Steel Cloth composition board

Specimen types	Tensile strength/MPa	Tensile modulus/MPa
			The PP plate	34.0	1810.7
The PP/ Stainless Steel Cloth is compound	39.4	1864.9

As shown in Table 2, compound back draft intensity has by a small margin to be increased, and tensile modulus is constant substantially.

(5.2) bending property

PP plate and PP/ Stainless Steel Cloth composition board are carried out the bending property test, and test result sees Table 3.

The bending property of table 3:PP plate, PP plate/Stainless Steel Cloth composition board

Specimen types	Flexural strength/MPa	Modulus in flexure/MPa
			The PP plate	19.9	1285.4
PP plate/Stainless Steel Cloth is compound	20.0	1600.0

As shown in Table 3, the modulus in flexure of composition board increases, and flexural strength is constant substantially.

(5.3) outward appearance, wetting ability, surface resistivity

Outward appearance: the color of PP/ Stainless Steel Cloth composition board is more shallow, can find out obviously that from the surface Stainless Steel Cloth is embedded on the PP plate, and Stainless Steel Cloth and the PP ability of closing that hardens is better, and during with mechanical system processing test bars, both can not separate.

Wetting ability: the good hydrophilic property of PP/ Stainless Steel Cloth composition board is in the PP plate that adopts the MAH-g-PP2 aqueous dispersion to handle, and this is because Stainless Steel Wire itself is exactly hydrophilic.

Surface resistivity: because Stainless Steel Cloth has good electrical conductivity, when adopting the ohmmeter test, composite surface resistance is almost 0.

Conclusion: untreated Stainless Steel Cloth can not be compound with PP, and the Stainless Steel Cloth after the MAH-g-PP2 aqueous dispersion is smeared processing can be compound with PP, this be because the MAH-g-PP2 aqueous dispersion can with the cause of PP cocrystallization, stretching, bending property after both are compound increase, and wetting ability is better, and surface resistivity is almost 0.

(4) other performances of MAH-g-PP2 aqueous dispersion and application

MAH-g-PP2 aqueous dispersion film forming characteristics see [Liu Fan, Zhao Ke. the research [J] of maleic anhydride inoculated polypropylene emulsion optimum filming condition. modern application and coating, 2013,16(1): 15-18; Tao Yingying, Dang Jingchuan, Zhao Ke. the film forming characteristics research [J] of maleic anhydride inoculated polypropylene emulsion. Light Engineering Institutes Of Zhengzhou's journal, 2012,27(5): 30-33].The MAH-g-PP2 aqueous dispersion handles glass, induce glass-polypropylene interface the scorching content to occur sees [Tao Yingying, Zhao Ke .PP-g-MAH emulsion is to the influence [J] at PP/GF interface. prints during chemical industry, 2012,26(4): 11-15], see in the application that fiber, mica are handled [Zhao Ke. functionalized polypropylene emulsion and application thereof, the 13 Surface Engineering innovated and practical technique exchanging meeting collection of thesis P128-133,2010 years Kaifeng; Http:// www.cnfrp.net/news/echo.php id=40119].

Claims (10)

1. maleic anhydride inoculated polypropylene aqueous dispersion, it is characterized in that, raw material consists of: weight-average molecular weight is maleic anhydride inoculated polypropylene 5～35wt%, nonionogenic tenside 0.5～20wt%, the carboxylic acid cosurfactant 0.5～20wt% of 20000-60000, according in and maleic anhydride inoculated polypropylene and carboxylic acid cosurfactant acid number summation 0～120% add alkali, all the other are water; The particle median size is 1～50 μ m in the described aqueous dispersion.

2. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 1 is characterized in that, the weight-average molecular weight of described maleic anhydride inoculated polypropylene is 30000; The consumption of nonionogenic tenside is 3～10wt% of raw material gross weight; The consumption of carboxylic acid cosurfactant is 3～10wt% of raw material gross weight.

3. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 1 or 2, it is characterized in that, described nonionogenic tenside is made up of two or more, is selected from the Brij series of surfactants, perhaps is selected from Brij series of surfactants and tween, sapn, OP series of surfactants; Described carboxylic acid cosurfactant is by C ₁₂-C ₂₄Lipid acid and/or alicyclic carboxylic acid form.

4. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 3 is characterized in that, described Brij series of surfactants accounts for more than the 50wt% of nonionogenic tenside gross weight.

5. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 3 is characterized in that, described tween series of surfactants is polysorbas20, tween 21, polysorbate40, polysorbate60, tween 61, polysorbate65, tween 80, sorbimacrogol oleate100 or polysorbate85; Described span series is span 20, span 40, sorbester p18, sorbester p38, sorbester p17 or sorbester p37; Described OP series of surfactants is OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40 or OP-50; Described Brij series of surfactants is Brij-30, Brij-35, Brij-38, Brij-52, Brij-56, Brij-58, Brij-58P, Brij-72, Brij-721, Brij-76, Brij-78, Brij-90, Brij-92, Brij-92V, Brij-93, Brij-93V, Brij-96, Brij-96V, Brij-97, Brij-98, Brij-98V or Brij-99; Described carboxylic acid cosurfactant is selected from two or more in stearic acid, Palmiticacid, oleic acid, linolic acid, linolenic acid, vegetable fatty acid, mixed fatty acid, rosin, staybelite, the sylvic acid.

6. as claim 1 or 2 or 4 or 5 described maleic anhydride inoculated polypropylene aqueous dispersion, it is characterized in that, described alkali is morpholine, imidazoles, the 1-Methylimidazole, pyrazoles, pyridine, acetyl is for pentanoic, benzene is for dimethylamine, nitrosodimethylamine, triethylamine, phenylethylamine, Uteramin, quadrol, butanediamine, pentamethylene diamine, hexanediamine, aniline, N, accelerine, N, the N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl propylene acid amides, N, the N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, the N-dimethylethanolamine, ammoniacal liquor, NaOH or KOH.

7. claim 1 or 2 or the preparation method of 4 or 5 described maleic anhydride inoculated polypropylene aqueous dispersion is characterized in that, each raw material is stirred insulation 0.5～2h in 170～200 ℃ behind the mixing in proportion, is cooled to room temperature then namely.

8. as the preparation method of maleic anhydride inoculated polypropylene aqueous dispersion as described in the claim 7, it is characterized in that, each raw material behind the mixing, is warming up to 150 ℃ earlier in proportion, and the temperature rise rate according to 0.5～3 ℃/min makes temperature be warmed up to 170～200 ℃ from 150 ℃ then; After the insulation again the rate of cooling with 0.5～4 ℃/min make temperature be cooled to 150 ℃ from 170～200 ℃; When temperature was in 150 ℃ to 170～200 ℃, mixing speed was 800～1000rpm, and when temperature was lower than 150 ℃, mixing speed was 200～400rpm.

With claim 1 or 2 described maleic anhydride inoculated polypropylene aqueous dispersion as polypropylene material or the polypropylene surface treatment agent with strongthener.

10. with claim 1 or the 2 described maleic anhydride inoculated polypropylene aqueous dispersion plasticized modifier as polypropylene material.

Images