CN103304948B - 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 claim three large interchangeable heat plastic resins, it is cheap, of many uses; Compared with polyethylene, polyacrylic intensity, hardness, heat-drawn wire are higher; Compared with polyvinyl chloride, owing to not containing chlorine, thus high high-temp stability is better.

For stressed larger Application Areas, polyacrylic intensity, rigidity etc. are still not enough, can not with engineering thermoplastic resin, such as nylon, polycarbonate etc. are compared, but after being strengthened by glass, particle etc., the mechanical property of polypropylene composite material can compare favourably with nylon, polycarbonate etc., and price is lower, these contents are commonly referred to resins for universal use through engineering approaches, and this field has become the focus in 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 short glass fiber, roving glass fiber, continuous glass-fiber, Chopped Strand Mat, natural fiber felt Reinforced Polypropylene respectively, particle reinforce polypropylene aspect comprises mica, talcum powder, calcium carbonate enhancing etc., also has nanometer enhancing etc. in addition.

Polypropylene belongs to nonpolar and hydrophobic material, not polar functionalities, and surface resistivity is high, thus limits its application in wetting ability, static resistance; 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 the research of forefathers, relates to although have everyway, does not have a kind of product can adapt to above-mentioned multiple fields, illustrates respectively below.

In fiber, Mica Reinforced Polypropylene material: adopt MAH-g-PP aqueous dispersion (if desired in conjunction with amino silicane coupling agent) to anticipate fiber, mica, strongthener and MAH-g-PP is made to form good interfacial adhesion, then by treated strongthener and polypropylene composite materials, improve strongthener to disperse at polypropylene matrix, the corresponding raising of composite property.

In polypropylene material wetting ability, static resistance: adopt MAH-g-PP aqueous dispersion (adding carbon black and other additives if desired) to be coated in polypropylene material surface, adopt the mode of heating, pressurization, make that MAH-g-PP aqueous dispersion and polypropylene material surface congruent melting are melted, cocrystallization, thus improve correlated performance.

Improve in its impact resistance at polypropylene material toughening modifying: MAH-g-PP aqueous dispersion fully being dehydrated becomes meal, by this meal and acrylic resin blended, then melt extrude granulation, improve its impact resistance.

Mode and the effect of the certain applications of MAH-g-PP aqueous dispersion are shown in [Zhao Ke.Functionalized polypropylene emulsion and application thereof, the 13 Surface Engineering innovation and practical technique exchanging meeting collection of thesis P128-133, Kaifeng in 2010; 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 Railway Project: (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, containing side branched chain methyl-CH on carbon backbone chain ₃from molecular structure aspect, position residing for methyl, there are four kinds of structures in polypropylene, isotactic → methyl is in side (isotatic polypropylene), a rule → methyl is alternately in both sides (syndiotactic polypropylene), random → methyl is irregular is in both sides (Atactic Polypropelene), in addition, also there is polypropylene molecular chain possessing simultaneously above-mentioned two kinds of structures, as metallocene polypropylene.

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

Isotatic polypropylene be propylene monomer under certain temperature, pressure, be polymerized by Qi Ge-Natta catalyzed; In addition, can form multipolymer between propylene-ethylene, when employing Qi Ge-Natta catalyst, copolymerization is containing a small amount of vinyl monomer, and when forming Co-polypropylene, this multipolymer still has certain crystallizing power; But compare isotatic polypropylene, molecular weight close to time, the strength and stiffness of material decline relatively, but impelling strength increase.

For isotatic polypropylene, because tertiary carbon hydrogen on main chain is comparatively active, easily there is chemical reaction, thus also easily by grafting or atmospheric oxidation; For Co-polypropylene, also easily there is similar chemical reaction.

MAH-g-PP(Maleic Anhydride grafted polypropylene), i.e. maleic anhydride inoculated polypropylene take isotatic polypropylene as the isotatic polypropylene chemical modification thing formed after matrix grafted maleic anhydride.

From molecular weight aspect, only have the molecular weight that isotatic polypropylene, Co-polypropylene can reach higher, they as materials'use, also can be enhanced Material reinforcement; Isotatic polypropylene thermal destruction is isotatic polypropylene wax, and its essence is that n declines, and oxidation by air and be with acidic-group; Co-polypropylene thermal destruction, the Co-polypropylene wax of formation, also oxidation by air and be with acidic-group; And a rule, Atactic Polypropelene molecular weight is not high, is often called syndiotactic polypropylene wax, Atactic Polypropelene wax, they are not containing 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 arranges in side declines, and crystallizing power declines relatively, and not containing acidic-group.

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

(2) polypropylene aqueous dispersion and preparation method thereof:

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

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

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

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

(1) in Atactic Polypropelene wax emulsion, its emulsion particle diameter can reach 0.1-1 μm, its main raw material Atactic Polypropelene wax is a kind of flexibility material of rubber like and uncrystallizable, with this emulsion process strongthener, then because strongthener-polypropylene interface is difficult to crystallization, thus can reduce strongthener-polypropylene Interface adhesive strength, and strongthener-polypropylene interface is the tie that the load born by polypropylene is delivered to strongthener, therefore the reinforced effects of strongthener can decline; In other respects, because Atactic Polypropelene wax is uncrystallizable, its application is also limited.

(2) in metallocene polypropylene wax emulsion (see Chinese patent CN1649954A and CN1798802A), its main raw material metallocene polypropylene wax and isotatic polypropylene, there is some difference in molecular structure for Co-polypropylene, metallocene polypropylene wax and isotatic polypropylene, Co-polypropylene cocrystallization can be had influence on, improve strongthener-polypropylene Interface adhesive strength strong not.

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

(4) metallocene polypropylene wax price is higher, raw material is bought has larger difficulty, and the complicate fabrication process of metallocene polypropylene wax emulsion, cost is higher, thus makes it apply and is restricted.

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

(6) in other respects, due to metallocene polypropylene wax emulsion, relevant application is also limited.

Select the first grafting of Atactic Polypropelene wax, metallocene polypropylene wax or oxidation, improve polarity, wetting ability, reduce the difficulty of emulsification, for the Atactic Polypropelene wax after chemical modification, can directly emulsification at ambient pressure; And for the metallocene polypropylene wax after chemical modification, then due to its molecular structure, need to be dissolved in organic solvent, and then emulsification, finally remove organic solvent again, but such production technique can bring the series of problems of organic solvent; According to the research of contriver, the manufacture craft of metallocene polypropylene wax emulsion can not for the production of MAH-g-PP aqueous dispersion, this is because MAH-g-PP has stronger crystallinity, and polarity is lower, hydrophobicity is stronger, molecular weight is larger.

(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 and polypropylene molecule structure, crystallinity aspect are almost identical or highly similar, when molecular weight is in certain limit, and owing to increasing its polarity containing maleic anhydride, thus make MAH-g-PP can Water-borne modification, for multiple fields, but there is 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 larger, then median size is less, and aqueous dispersion is relatively more stable, and the water-absorbent after MAH-g-PP aqueous dispersion film forming is larger; Depositing in process, MAH-g-PP aqueous dispersion composition granule floats and coalescence gradually, and median size can increase gradually, and the MAH-g-PP aqueous dispersion product needed thus prepared uses within the as far as possible short time; MAH-g-PP aqueous dispersion, in different Application Areass, needs corresponding median size, the following describes.

In fiber, Mica Reinforced Polypropylene material: improving strongthener-polypropylene interface effective constituent is MAH-g-PP, and tensio-active agent and other additives are then disadvantageous to this; When infiltrating process for glass, require that aqueous dispersion stability is very high, MAH-g-PP aqueous dispersion median size is best close to 1 μm, but the relative quantity such as tensio-active agent, other additives is more; For other application, MAH-g-PP aqueous dispersion median size needs at proper range, but no more than 50 μm, and the relative quantity such as tensio-active agent, other additives is less; In addition, reinforcement form, pretreatment mode and technique, require different to MAH-g-PP aqueous dispersion median size.

In polypropylene material wetting ability, static resistance: MAH-g-PP, tensio-active agent, other additives etc. are all conducive to improving polypropylene material wetting ability, static resistance, but action principle is different, MAH-g-PP can melt with polypropylene congruent melting, cocrystallization, thus caking agent is played, when its content is very few, polypropylene material wetting ability, static resistance are difficult to remain permanent; Tensio-active agent, other additives etc. are very large on polypropylene material wetting ability, static resistance impact; 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 between 1-50 μm, and can control median size, can meet various requirement.

Improve in its impact resistance at polypropylene material toughening modifying: MAH-g-PP, tensio-active agent, other additives etc. have influence on effect polypropylene material toughening modifying being improved to 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 etc. of isotatic polypropylene; In addition, modified technique affects its effect; These contents are all relevant with MAH-g-PP aqueous dispersion median size, and median size between 1-50 μm, and can control median size, can meet various requirement.

If in a set of equipment, by control MAH-g-PP aqueous dispersion median size between 1-50 μm, Average Particle Diameters can be controlled, and not containing organic solvent, to adapt to diversified application, then this method has certain advantage.This just 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 is due to 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 due to its higher crystallization trend 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

For commercial use from the aqueous dispersion of nineteen fifties various functional polyolefin, 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.

At U.S. Patent No. 5290954 discloses a kind of 190 DEG C, melt viscosity is 1000cP-5000cP maleated polypropylene wax, at the temperature higher than Poly Propylene Wax fluxing point, with a small amount of tensio-active agent, and a certain amount of water, mix the sufficiently long time, prepare the method for maleated polypropylene wax aqueous dispersion.This product is mainly used in covering with paint field, floor, and need Poly Propylene Wax maleinization in advance, this will cause the Poly Propylene Wax of lower molecular weight originally to be degraded further, the aqueous dispersion that the method produces has good light transmission, but is difficult to the requirement adapting to multiple Application Areas of the present invention.

U.S. Patent No. 4240944 and No.4283322 set forth a kind of preparation method of binder composition of sizing material with dealing with glass fibre.This tackiness agent is aqueous dispersion, isotactic maleated polypropylene wax and random maleated polypropylene wax, alkali and the tensio-active agent of 10000 is less than containing weight-average molecular weight, add the Water-borne modification that random maleated polypropylene wax contributes to the Carboxylation Poly Propylene Wax of isotactic, but be difficult to the requirement adapting to multiple Application Areas of the present invention.

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

Chinese patent CN1649954A and CN1798802A relates to the preparation etc. of the synthesis of metallocene polypropylene wax, the modification of metallocene polypropylene wax solution graft copolymerization, metallocene polypropylene wax emulsion, relevant content illustrates above, and this kind of emulsion is difficult to the requirement adapting to multiple Application Areas of the present invention.

Because polypropylene molecule amount, crystallinity, polarity affect very large on its Water-borne modification, aforesaid method is adopted to be can not Water-borne modification MAH-g-PP.

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

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

Direct melting emulsion process does not with an organic solvent have very large 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, as emulgate ingredient, " single stage method " is divided into two kinds again.

(1) below for " two-step approach " prepares high molecular functional poly propylene aqueous dispersion:

English Patent No.2326164, U.S. Patent No. 6166118, No.5389440 and 5242969 propose a kind of " two-step approach " of Water-borne modification functional poly propylene, this technique is divided into two steps, namely in emulsion process (under having certain pressure condition) is needed to add the contents such as hot water, water vapour, neutralization bases, the method is very high to the requirement of equipment, the functional poly propylene aqueous dispersion average particulate diameter produced is close to 1 μm, 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) add Poly Propylene Wax and prepare 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 preparing high molecular weight polypropylene water miscible liquid, all add low-molecular-weight polypropylene as emulgate ingredient i.e. the second polyolefine, play and reduce mixture melt viscosity, thus reduce the effect of high molecular weight polypropylene emulsification difficulty.And second polyolefine also containing carboxylic acid or anhydride functional group, better with the first compatible polyolefin, have chemical stability during high temperature emulsification.The functional poly propylene aqueous dispersion average particulate diameter produced close to 1 μm, 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 " prepares high molecular functional poly propylene water-based emulsion:

International monopoly WO2004031246, WO2006/039462, United States Patent (USP) 2006/0069187 describe the method that one " a step direct method " prepares high molecular function polypropylene water miscible liquid, the functional poly propylene aqueous dispersion average particulate diameter produced is close to 1 μm, but be difficult to accomplish to control its aqueous dispersion average particulate diameter, be difficult to adapt to application requiring of the present invention.

These patents above-mentioned are all the smaller the better for target with the particle in emulsion, the emulsion particle median size produced is many at about 1 μm, leave standstill stability fine, relatively be suitable as continuous glass-fiber wire drawing treating compound, but the application of improper other side, these patents can not meet the application background requirement that the present 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, provide its corresponding preparation method and purposes to be two other object of the present invention.

Based on above-mentioned purpose, this invention takes following technical scheme:

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; In described aqueous dispersion, mean particle size is 1 ~ 50 μm.

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 Brij series of surfactants or be selected from Brij series of surfactants and tween, sapn, OP series of surfactants (in other words, nonionogenic tenside can all be selected from Brij series, also first can choose more than one from this series of surfactants, then from tween, sapn, OP series of surfactants, choose more than one combinationally use); Described carboxylic acid cosurfactant is by C ₁₂-C ₂₄lipid acid and/or alicyclic carboxylic acid composition.

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

Described TWEEN Series tensio-active agent is polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, 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; It is two or more that described carboxylic acid cosurfactant is selected from stearic acid, Palmiticacid, oleic acid, linolic acid, linolenic acid, vegetable fatty acid, mixed fatty acid, rosin, staybelite, sylvic acid.

Described alkali is morpholine, imidazoles, 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, N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-dimethylpropionamide, N, N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, N-dimethylethanolamine, ammoniacal liquor, NaOH or KOH.

The preparation method of described maleic anhydride inoculated polypropylene aqueous dispersion, step comprises: stir insulation 0.5 ~ 2h in 170 ~ 200 DEG C after being mixed in proportion by each raw material, be then cooled to room temperature and get final product.

In described preparation method, adopt following measures effect better: after each raw material mixes in proportion, to be first warming up to 150 DEG C, then to make temperature be warmed up to 170 ~ 200 DEG C from 150 DEG C according to the temperature rise rate of 0.5 ~ 3 DEG C/min; Temperature is made to be cooled to 150 DEG C from 170 ~ 200 DEG C with the rate of cooling of 0.5 ~ 4 DEG C/min again after insulation; When temperature is in 150 DEG C to 170 ~ 200 DEG C, mixing speed is 800 ~ 1000rpm, and when temperature is lower than 150 DEG C, mixing speed is 200 ~ 400rpm.

Described maleic anhydride inoculated polypropylene aqueous dispersion is used as the surface treatment agent of polypropylene material, to improve wetting ability, the static resistance on polypropylene material surface; Or described maleic anhydride inoculated polypropylene aqueous dispersion is used as the surface treatment agent of polypropylene strongthener (such as fiber, mica etc.), to improve the interfacial combined function between strongthener and polypropylene.

Described maleic anhydride inoculated polypropylene aqueous dispersion is used as the plasticized modifier of polypropylene material, to improve the shock resistance of polypropylene material.

The present invention take MAH-g-PP as main raw material, and by adopting melting emulsifying process to prepare MAH-g-PP aqueous dispersion, in this aqueous dispersion, average diameter of particles is between 1 ~ 50 μm, and quality better, purposes are wide.

Its corresponding preparation method once can complete in same pressure stirring tank, and its step is simple, workable; In dispersion, grain diameter controls by adjustment composition and engineering parameter, convenient flexibly.

Just associated viscera of the present invention elaborates below:

At present, market has specially for the small pressure stirred autoclave of experimental study, 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 engineer applied, then need the autoclave pressure according to current test-results design band whipping appts, more to adapt to the requirement of direct Water-borne modification MAH-g-PP.

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

A characteristic of the present invention is the size needing particle in control MAH-g-PP aqueous dispersion, to adapt to diversified application.Although aqueous dispersion particle diameter and dosage of surfactant present negative correlation, namely dosage of surfactant is larger, then aqueous dispersion particle diameter is less, but also need combined process parameter could control aqueous dispersion particle diameter, this is because the MAH-g-PP that the present invention relates to has very strong crystallinity, and due to the complicacy of melting Water-borne modification technique and singularity, need the technology being determined granular size in control MAH-g-PP aqueous dispersion by the experimental study of system, describe associated viscera respectively below.

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

With 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: the maleic anhydride employing grafting mode 1, in MAH-g-PP realizes, comprise the techniques such as melting, solution, solid phase, Suspension Graft, different grafting modes, the homogeneity of percentage of grafting and grafting is had a great impact, and isotatic polypropylene wax adopts isotatic polypropylene thermal destruction and manufactures; 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 is mainly because there is very large difference at processing temperature, process aspect in both, isotatic polypropylene thermal destruction needs to carry out more than 300 DEG C, and be interrupted to carry out in batch reactor, cause production cost to increase more, and MAH-g-PP is at about 200 DEG C, adopts single, double screw extrusion press continuous seepage.

Due to molecular weight, the easier Water-borne modification of isotatic polypropylene wax, in the invention of another isotatic polypropylene wax aqueous dispersion of contriver, also the control problem of aqueous dispersion particle diameter is related to, its scope is between 0.1-50 μm, 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, can the method for the low-molecular-weight isotatic polypropylene wax of Water-borne modification, might not be effective to MAH-g-PP Water-borne modification, the formula of Water-borne modification MAH-g-PP needs to specialize 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, composite mode is adopted to form compound emulsifying agent, and in conjunction with carboxylic acid cosurfactant, Water-borne modification isotatic polypropylene wax, its average diameter of particles can be controlled between 0.1-50 μm, but for MAH-g-PP Water-borne modification, then can only obtain larger particle, its diameter is much larger than 50 μm; By the research of contriver, if need the average diameter of particles of control MAH-g-PP aqueous dispersion within 50 μm, especially need to obtain the very little MAH-g-PP water dispersion of median size, the combination of nonionic shape tensio-active agent or the Brij series of preferred Brij series combine with tween, sapn and OP series non-ionic shape tensio-active agent, and the nonionic shape tensio-active agent price of Brij series is higher, describe associated viscera respectively below.

mAH-g-PP material choice:when other conditions are constant, to its aqueous dispersion particle size effect very greatly, weight-average molecular weight is larger, and percentage of grafting is lower, then prepare aqueous dispersion composition granule larger, otherwise then less for the weight-average molecular weight of MAH-g-PP and percentage of grafting; But weight-average molecular weight is larger, MAH-g-PP aqueous dispersion film strength is higher, and relevant effect is better; Thus need to consider many impacts from factor, proper weight-average molecular weight is between 30000-60000, percentage of grafting is between 0.5-1.5wt%, the MAH-g-PP bought by market, its weight-average molecular weight and percentage of grafting provide usually used as the important indicator of product, and the present invention studies weight-average molecular weight to be the MAH-g-PP Water-borne modification process of 30000 and to improve wetting ability, static resistance, the Stainless Steel Cloth surface enhanced polypropylene material on polypropylene material surface; MAH-g-PP weight-average molecular weight and melt viscosity in close relations, the driven terms of mechanics of melt viscosity has influence on aqueous dispersion granular size, percentage of grafting and the interfacial tension of MAH-g-PP are in close relations, its value is larger, interfacial tension then between particle (melt)-water is less, interfacial tension has influence on aqueous dispersion granular size from thermodynamics aspect, kinetics and the impact of thermodynamics on aqueous dispersion granular size described below.

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

If only from can Water-borne modification MAH-g-PP angle consider, negatively charged ion, positively charged ion, nonionogenic tenside and the combination between them all can adopt, 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 carboxylic acid cosurfactant, this tensio-active agent can with nonionogenic tenside compound and form complicated emulsification system, when adding neutralization bases, the carboxylic acid of carboxylic acid cosurfactant is neutralized, become anion surfactant, nonionogenic tenside and anion surfactant compound have emulsifying capacity more better than respective single component usually.

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

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

In invention application background illustrates, MAH-g-PP water-based is turned to different-grain diameter, to adapt to different application purposes, Water-borne modification principle (whipped state): 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 the process, hinder melt coalescence each other, along with the decline of temperature, recrystallizing into molecule form fixes (in our research, pass through microscopic examination, principle can be specified), Water-borne modification technique (whipped state): normal temperature-intensification-insulation-cooling-normal temperature, corresponding MAH-g-PP state is: crystal form (solid)-molten state (melt)-recrystallize state (emulsion particle), and technical difficulty can be analyzed from kinetics and thermodynamics aspect.

kinetic factor:under 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 of melt and corresponding rheological characteristics, only just can produce the aqueous dispersion with certain granules distribution from the angle reducing melt viscosity and increase shearing stress.

thermodynamics:coalescence between MAH-g-PP melt or particle develops to thermodynamics beneficial direction, the effect of tensio-active agent is the minimizing (respective interface is long-pending to be increased) thus contributing to particle diameter by reducing interfacial tension on the one hand, increased the resistance of the coalescence between melt or particle on the other hand by electrostatic and steric repulsion, thermodynamic instability state for extended periods thus can be kept to exist; Differing temps, different states (melt, solid), stirring velocity (at a high speed, middling speed, static), SURFACTANT ADSORPTION and desorb, and oneself state variable effect is to interfacial tension, and then have influence on particle diameter.The action principle of tensio-active agent illustrates, consumption and the particle diameter of tensio-active agent exist negative correlation.

Kinetic factor and Thermodynamics concentrated reflection are in equipment, formula, technique three, and three aspects are coordinated mutually, just can produce the aqueous dispersion meeting application background of the present invention.

Add carboxylic acid cosurfactant, as stearic acid, from kinetic factor, the viscosity adding reduction MAH-g-PP melt of stearic acid, thus the minimizing of particle diameter is contributed to, its prerequisite is that stearic acid and MAH-g-PP are evenly melt blended, and part stearic acid can be adsorbed on bath surface, becomes the one of tensio-active agent; From Thermodynamics, stearic acid due in water solvability lower, the part being adsorbed on bath surface can think nonionogenic tenside, because its molecular structure is more similar with MAH-g-PP, thus can enter MAH-g-PP melt inside and reduce its viscosity, when adding alkali neutralization, then because stearic acid is neutralized by alkali, its water-soluble increase, become anion surfactant, a part is dispersed in water, a part is adsorbed on bath surface, and now, because it is difficult to enter melt inside, the effect reducing MAH-g-PP melt viscosity just declines; The type and consumption etc. of neutralization bases, alkali is added in the different steps of Water-borne modification technique, different on the impact of kinetic factor and Thermodynamics, and then have influence on the particle diameter of MAH-g-PP aqueous dispersion, current correlation theory can only be qualitatively to explanation in this respect, can not the guiding suggestion of quantitative, the relation between type, consumption, neutralization bases etc. and the particle diameter of MAH-g-PP aqueous dispersion adding carboxylic acid cosurfactant can only be determined by experiment out.

Foregoing shows, kinetic factor and Thermodynamics joint effect are to the particle diameter of MAH-g-PP aqueous dispersion, if but need to accomplish MAH-g-PP aqueous dispersion average particle size control techniques, then mainly through controlling 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 raw material aspect, process aspect, stirring aspect remains unchanged, as long as this three aspect changes to some extent, capital has influence on MAH-g-PP aqueous dispersion average particle size.

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

For the small pressure stirred autoclave determined, stirring velocity is higher, often the particle diameter of aqueous dispersion is less, stability is better, but general small pressure stirred autoclave, there is the limit in its stirring velocity, close to the stirring velocity of the limit, the accessories such as the bearing in easy damage equipment, and easily produce more serious vibrations, long-time operation, pressurized vessel etc. is easily caused to occur fatigure failure and occur potential safety hazard, therefore stirring velocity needs to control in suitable scope, and in intensification, insulation emulsification, in temperature-fall period, stirring velocity is change, stirring velocity is very large to the grain diameter influence of aqueous dispersion, the form of stirring arm is also the important factor affecting aqueous dispersion particle diameter, although have relevant theory to explain to the form of stirring arm, test shows, these theories are not effective, the form joint effect aqueous dispersion grain diameter of stirring velocity, stirring arm.

More satisfactory agitation condition is: between 150 DEG C to 170 ~ 200 DEG C, rotating speed is 800-1000rpm, when temperature is lower than 150 DEG C, rotating speed is 200-400rpm, this is because at about 150 DEG C, MAH-g-PP blend generation melting transition, namely by solid to melt (intensification), melt recrystallization (cooling), between 150 DEG C to 170 ~ 200 DEG C, it is the interval key of melting Water-borne modification, stirring velocity is now in the tolerance band of equipment, be the bigger the better, stirring velocity is limited between 800-1000rpm by the present invention, aspects of contents can be taken into account, when temperature is lower than 150 DEG C, also need certain stirring velocity, rotating speed is that 200-400rpm can meet the demands.

Under heat-retaining condition, the Water-borne modification time is between 0.5-2 hour, and lower than 0.5 hour, be then difficult to form stable aqueous dispersion, higher than 2 hours, lose time, energy consumption is high, the more satisfactory time is 1-1.5 hour.

Water-borne modification temperature must higher than the 20-50 degree of MAH-g-PP blend fusing point, namely between 170 ~ 200 DEG C of degree, temperature is low, then the particle diameter of aqueous dispersion is bigger than normal, and temperature is high, then easily there is oxidative degradation even variable color in MAH-g-PP, causes molecular weight to decline further, more satisfactory temperature is between 180-190 DEG C, and according to MAH-g-PP molecular-weight adjusting.

It has been generally acknowledged that heat-up rate and cooling rate affect very little on Water-borne modification, but the present invention's research shows, heat-up rate and the quality of cooling rate on aqueous dispersion have suitable impact, particularly with 150 DEG C for boundary, its reason is not clear at present, 170 ~ 200 DEG C are warmed up to from 150 DEG C, heat-up rate 0.5 ~ 3 DEG C/min, desirably 1.7 ~ 1.9 DEG C/min, 150 DEG C are cooled to from 170 ~ 200 DEG C, rate of cooling is 0.5 ~ 4 DEG C/min, desirably 2.5 ~ 3.0 DEG C/min, when temperature is lower than 150 DEG C, can heat up at faster speed or lower the temperature.

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

The MAH-g-PP content range of aqueous dispersion changes between 5 ~ 35wt%, and 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 the amount required for 0 ~ 120% of MAH-g-PP and carboxylic acid cosurfactant total acidity.

This test adopts and put into pressure stirring tank, according to certain explained hereafter MAH-g-PP aqueous dispersion after blended for the additives such as MAH-g-PP, nonionogenic tenside, carboxylic acid cosurfactant, neutralization bases.

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, it is relatively more effective for vacuumizing before adopting test according to principle, but the systematic testing of contriver shows, vacuumizes MAH-g-PP aqueous dispersion coloured effect little, perhaps be that Cucumber high temperature is with regard to variable color, perhaps be always there is a small amount of oxygen to be difficult to drain completely only, in the present invention, whether vacuumize not as necessary content.

Although MAH-g-PP Water-borne modification is a kind of technique behavior based on physical process, but certain possible chemical reaction can be there is in this process, fully contact with MAH-g-PP as remnant oxygen in pressurized vessel and be oxidized MAH-g-PP further, nonionogenic tenside and carboxylic acid cosurfactant may be oxidized, the 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, formula, technique three aspect, MAH-g-PP aqueous dispersion is made up of following material: MAH-g-PP particle, the carboxylic acid cosurfactant of Water-borne modification, water-soluble additive, tensio-active agent in aqueous phase, water, neutralization bases etc., the carboxylic acid cosurfactant of Water-borne modification is present in water with the form of fine particle (between 0.1-1 μm), more stable, and MAH-g-PP particle (it comprises MAH-g-PP, carboxylic acid cosurfactant, tensio-active agent, neutralization bases) unstable, its ascent rate and particle diameter, aqueous dispersion viscosity is relevant.

Part carboxylic acid cosurfactant can be emulsified by a surfactant and be present in liquid phase, and the carboxylic acid cosurfactant in aqueous phase, tensio-active agent is invalid to dispersion and minimizing MAH-g-PP particle diameter, only be adsorbed on MAH-g-PP particle surface or enter into the carboxylic acid cosurfactant of its inside, tensio-active agent, the diameter of neutralization bases to minimizing MAH-g-PP particle is effective, therefore can not simply by increase carboxylic acid cosurfactant, tensio-active agent, the amount of neutralization bases reduces or the diameter of control MAH-g-PP particle, and need synthetic study equipment, formula, technique tripartite is in the face of the impact of granular size, for the present invention, the control of MAH-g-PP granular size is mainly realized by the change of formula, the following describes content in this respect, emphasis is various composition roles, the foundation etc. selected.

Carboxylic acid cosurfactant is by C ₁₂-C ₂₄lipid acid and/or alicyclic carboxylic acid composition, its effect: 1, because molecular chain structure is similar to MAH-g-PP, thus under melting condition, carboxylic acid cosurfactant can with MAH-g-PP mixing, reduce melt viscosity, thus contribute to MAH-g-PP Water-borne modification; 2, due to molecular chain structure band carboxylic acid, partial radical of hydroxy, thus has certain emulsification function; 3, when adding neutralization bases, because the carboxylic acid of molecular chain structure is neutralized, thus emulsifying property changes, become anion surfactant, in introduction above, comparatively describe the composite emulsifying system be made up of nonionogenic tenside and anion surfactant in detail and there is emulsifying capacity more better than single emulsifier; 4, saturated or unsaturated fatty acids: liquid or solid-state, line style or band branched structure, containing the modified fat mixture of acid, acid anhydrides, ester, the purposes of lipid acid is can under prerequisite of not degrading, except reducing the melt viscosity of MAH-g-PP, the effect of lubricant can also be played in glass process; 5, lipid acid provides one and is similar to polyacrylic structure, improve glass fibre dispersiveness in the composite, and fiber and the consistency of resin matrix in process of cooling, emulsion is made to bear the acidity of change and the different HLB value needed for emulsifying system because lipid acid can provide, simultaneously can also as a kind of emulgate ingredient, so lipid acid can be used alone as emulsifying agent or with other combination of components, be applied to multiple emulsifying system.

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 amount, and preferable amount is 3-10wt%.

Vegetable fatty acid, mixed fatty acid are by different types of C ₁₂-C ₂₄saturatedly to form with unsaturated fatty acids and alicyclic carboxylic acid, and to sell with commodity basis, thus can commercially buy.

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

Lipid acid is divided into saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid, in MAH-g-PP Water-borne modification process, due to the existence of high temperature and oxygen, may oxidizing reaction be there is in lipid acid, its emulsification function is caused to decline, and color burn, in order to obtain the MAH-g-PP aqueous dispersion compared with light colour, preferred saturated fatty acid is as carboxylic acid cosurfactant.

In the research of contriver, the kind of carboxylic acid cosurfactant and the size of consumption to MAH-g-PP aqueous fraction composition granule have a great impact, the combination of preferred two or more carboxylic acid cosurfactant, single carboxylic acid cosurfactant effect is not as two or more combinations.

Non-ionic surfactant-type plays a key effect for MAH-g-PP Water-borne modification, and the nonionogenic tenside in the present invention is by polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, 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, the compositions such as Brij-99, these homologue nonionogenic tensides, structure is very close, there is identical hydrophilic group, the structure of hydrophobic group is also identical, only there is the difference of chain length, same series non-ionic surfactants, from hydrophobic to hydrophilic, corresponding HLB value variation range is very large, in the research of contriver, studied with nonionic surfactant combinations between a series of and different series the impact of MAH-g-PP aqueous dispersion granular size, result shows that the combined effect of Brij series non-ionic surfactants is best, but because Brij series price is higher, consider from reducing costs angle, non-ionic surfactant and the Brij series compound of other series can be adopted, Brij series non-ionic shape tensio-active agent needs more than the 50wt% accounting for nonionic shape tensio-active agent total amount, nonionic shape dosage of surfactant is the 0.5-20wt% of aqueous dispersion amount, preferred 3-10wt%, the employing of Brij series and consumption are the features of MAH-g-PP Water-borne modification, do not use Brij series in the isotatic polypropylene wax Water-borne modification content of contriver.

Be the distinctive designated value of surfactant molecule based on HLB value, therefore 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 40% as Brij-30 in mixing nonionogenic tenside accounts for 60%, Brij-72, can try to achieve mixed surfactant HLB value is 7.7.In the present invention, the HLB value scope needed for MAH-g-PP Water-borne modification between 5.5 ~ 9.3, preferably between 7 ~ 8.

The calculating of above-mentioned HLB value does not reflect the impact 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 HLB value, but do not have correlation theory to calculate.

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

At MAH-g-PP raw material, technique, under stirring the prerequisite remained unchanged, if need to accomplish MAH-g-PP aqueous dispersion average particle size control techniques, then mainly through controlling 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 be determined by the calculating of HLB value, carboxylic acid cosurfactant kind and consumption then need to be determined by test.

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 generate the soap as tensio-active agent on water-oil interface, and this layer firmly Interface composites film is conducive to the stability improving aqueous dispersion.In addition, adding of neutralization bases also has larger impact to the viscosity of aqueous dispersion sometimes, and the viscosity of aqueous dispersion is also affect the stable important factor of aqueous dispersion; But the research of contriver shows, sometimes can not add neutralization bases, high-quality aqueous dispersion can be obtained equally.

Conventional neutralization alkali has morpholine, imidazoles, 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, N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-dimethylpropionamide, N, N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, N-dimethylethanolamine, ammoniacal liquor, sometimes NaOH and KOH etc. can be used, the add-on of neutralization bases is enough to 0 ~ 120% of neutralized aqueous dispersion each composition acid number summation.

The feed postition of neutralization bases (add before emulsification, with pressurely in emulsion process to add, emulsification add after terminating, do not add) all can have influence on the performance of aqueous dispersion, and this test adds the mode of neutralization bases before adopting emulsification.

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

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

Similar with antioxidant, color adaptation agent is also only for the MAH-g-PP aqueous dispersion of glass fiber wire drawing, as Sodium Pyrosulfite etc., is to enable the color of aqueous dispersion better.But result by experiment, whether adding and the number of add-on of additive, not obvious on the impact of aqueous dispersion color, it is agnogenio.

The effect of defoamer is to reduce the foam produced in MAH-g-PP aqueous dispersion production process, if octanol etc. is exactly the defoamer often adopted, this foam on produce stability, produce terminate after equipment cleaning have impact, but result by experiment, whether adding and the number of add-on of defoamer, not obvious on the impact of aqueous dispersion foam, it is agnogenio, and therefore defoamer is not certain composition needing to add.

The effect of anticorrosive agent is the duration of service in order to extend MAH-g-PP aqueous dispersion, biosolubilization in minimizing air is in MAH-g-PP aqueous dispersion, and cause the septic yeast of aqueous dispersion, conventional Sodium Benzoate etc. can adopt, but the product produced due to the present invention is used soon, thus anticorrosive agent is not necessary added ingredients.

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

For can not the MAH-g-PPW of Water-borne modification, they stick on stirring arm and still wall usually, usual method can be adopted to make it to depart from, adopt common equipment, as colloidal mill, mulser etc. by these materials pulverize and homogenize, make its median size below 50 μm, 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 the MAH-g-PP of Water-borne modification, more easily pulverize, this is because it is through recrystallize, tensio-active agents etc. form the cause of blend with MAH-g-PP, and its intensity, hardness, particle diameter all have and decline largely.

MAH-g-PP aqueous dispersion performance need by test analysis with evaluate, performance test comprises: changes in hardness before and after directly perceived and aqueous dispersion particle form observation, color, standing stability, yield, level of residue, apparent viscosity, transparence, size and distribution, MAH-g-PP Water-borne modification, total quality etc.

Directly perceived and aqueous dispersion particle form is observed: treat that Water-borne modification completes, pour out material from autoclave pressure after, adopt its aqueous dispersion form of appearance method gross examination of skeletal muscle, be preferably the milk shape aqueous dispersion that MAH-g-PP true qualities are homogeneous, poor is that only some, by Water-borne modification, exists most of solid particulate; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is more close to ball-type, then stability is better.

color:at the mixed system of the complexity of the compositions such as MAH-g-PP and other various nonionogenic tenside, carboxylic acid cosurfactant, alkali after pressurizing melting emulsion process, color appearance may change, and color likely brings impact to the application of follow-up aqueous dispersion, appearance method is adopted to observe aqueous dispersion color.

leave standstill stability:as one of aqueous dispersion important performance perameter, the testing method of the standing stability of aqueous dispersion, for pour in 15ml test tube by 6ml-8ml aqueous dispersion, is at room temperature vertically placed, and observes its stratification state.The time (with sky) that standing stability can stablize placement in aqueous dispersion under room temperature characterizes.

yield:the yield of aqueous dispersion deducts level of residue with the material total amount adding autoclave pressure, then obtains divided by material total amount, is expressed as a percentage.Aqueous dispersion yield reflects the degree that Water-borne modification process is carried out, and numerical value is higher, then the MAH-g-PP amount entering aqueous dispersion is more.

level of residue:after Water-borne modification end of processing, solid matter remaining in autoclave pressure is weighed, add up the amount of non-Water-borne modification.

Apparent viscosity: the NDJ-79 type rotary viscosity design determining adopting Shanghai Tongji University to produce in test, it is applicable to the mensuration of the absolute viscosity of various Newtonian liquid and the apparent viscosity of quasi-viscous liquid.During measurement, first should select suitable container and supporting rotor according to the approximate range of the viscosity of sample, make reading pointer as far as possible between the 20%-85% of scale card, guarantee the accuracy of reading.At temperature is 25 DEG C, record rotor rotates 1 minute stable total indicator reading, can measure aqueous dispersion viscosity.

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

size and distribution:aqueous dispersion grain diameter size and the stability of size distribution on aqueous dispersion thereof have conclusive impact, and grain diameter is less, particle size distribution range is more narrow more stable.With water, aqueous dispersion being diluted to finite concentration, with LS-POP(VI) type laser particle analyzer measures its particle diameter and size distribution.

the hardness of water dispersion:by MAH-g-PP heating raw materials to about 180 degree melting film forming, adopt the shore hardness instrument tested for hardness that Shanghai Yanrun Ray Machine Technology Co., Ltd. produces; By corresponding MAH-g-PP aqueous dispersion, first low temperature removes moisture, then about 180 degree melting film forming, adopts shore hardness instrument tested for hardness, by this hardness and raw material hardness balance.

total quality:the total quality of aqueous dispersion according to aqueous dispersion yield, level of residue, leave standstill stability, particle diameter and consider the index that of drawing weighs aqueous dispersion overall performance, aqueous dispersion is divided into four classes from high to low: good, in, general, poor.

Accompanying drawing explanation

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Figure 15 is the infrared spectrogram of embodiment 5 gained aqueous dispersion after 80 DEG C of dehydrations;

Figure 16 is the infrared spectrogram that embodiment 5 gained aqueous dispersion is done after drying and forming-film at 175 DEG C;

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

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

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

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

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

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

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

Embodiment

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

raw material:mAH-g-PP1, percentage of grafting is 0.8wt%, melting index (2.16kg/230 DEG C) > 50g/10min, weight-average molecular weight 60000; MAH-g-PP2, percentage of grafting is 0.8-1.0wt%, melting index (2.16kg/190 DEG C) 40-60g/10min, weight-average molecular weight 30000; MAH-g-PP1 and MAH-g-PP2 is all Nanjing De Ba Chemical Co., Ltd. products.

equipment:1 liter of stirred under pressure still.

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

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

When stirring velocity remains unchanged, when processing condition are constant, MAH-g-PP aqueous dispersion average particle size 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.

ith class: raw material is 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 μm; Best result cloth particle diameter 56.6 μm; The total quality of aqueous dispersion: in; Hardness after aqueous dispersion drying/raw material hardness=85%; Size distribution as shown in Figure 1.

embodiment 2: the stearic acid oleic acid in embodiment 1 being changed into equal in quality, 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 μm; Best result cloth particle diameter 45.3 μm; The total quality of aqueous dispersion: in; Hardness after aqueous dispersion drying/raw material hardness=75%; Size distribution as shown in Figure 2.

embodiment 3: the oleic acid in embodiment 1 is changed 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 μm; Best result cloth particle diameter 34.6 μm; The total quality of aqueous dispersion: in; Hardness after aqueous dispersion drying/raw material hardness=80%; Size distribution is shown in Fig. 3.

the comparative example 1 of embodiment 1:mAH-g-PP1 in 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 μm; Best result cloth particle diameter 6.6 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=70%; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is close to ball-type, and size distribution is shown in Fig. 4.

the comparative example 2 of embodiment 1:mAH-g-PP1 in 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 μm; Best result cloth particle diameter 20.6 μm; The total quality of aqueous dispersion: medium; Hardness after aqueous dispersion drying/raw material hardness=80%; Size distribution as shown in Figure 5.

iIth class: raw material is 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 μm; Best result cloth particle diameter 5.2 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=73%; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is close to ball-type, and size distribution as shown in Figure 6.

the repetition example of embodiment 4:formula, technique 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 μm; Best result cloth particle diameter 6.5 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=72%; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is close to ball-type, and size distribution is shown in Fig. 7.

embodiment 5: the stearic acid oleic acid in embodiment 4 being changed into equal in quality, 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 μm; Best result cloth particle diameter 23.4 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=89%; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is close to ball-type, and size distribution as shown in Figure 8.

embodiment 6: the oleic acid in embodiment 4 is changed 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 μm; Best result cloth particle diameter 35.4 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=81%; Size distribution is shown in Fig. 9.

embodiment 7: the oleic acid in embodiment 4 is changed 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 μm; Best result cloth particle diameter 42.4 μm; The total quality of aqueous dispersion: in; Hardness after aqueous dispersion drying/raw material hardness=82%; Size distribution as shown in Figure 10.

the comparative example 1 of embodiment 4:mAH-g-PP2 in 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 μm; Best result cloth particle diameter 1.7 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=65%; Adopt the form of particle in observation by light microscope aqueous dispersion, the shape of particle is close to ball-type, and size distribution as shown in figure 11.

the comparative example 2 of embodiment 4:mAH-g-PP2 in 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 μm; Best result cloth particle diameter 16.7 μm; The total quality of aqueous dispersion: good; Hardness after aqueous dispersion drying/raw material hardness=72%; Size distribution is shown in Figure 12.

the comparative example 3 of embodiment 4:mAH-g-PP2 in 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 μm; Best result cloth particle diameter 29.0 μm; The total quality of aqueous dispersion: medium; Hardness after aqueous dispersion drying/raw material hardness=85%; Size distribution as shown in figure 13.

the comparative example 4 of embodiment 4:mAH-g-PP2 in 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 μm; Best result cloth particle diameter 58.0 μm; The total quality of aqueous dispersion: medium; Hardness after 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

By embodiment 5 mAH-g-PP2aqueous dispersion is after 80 DEG C of dryings are fully dewatered for 2 hours, mix with certain proportion with Potassium Bromide, 0.5h is dried in about 70 DEG C after abundant grinding, two parallel sample compressing tablets are produced with tabletting machine, measure with WQF-510 type Fourier infrared spectrograph (Beijing Rayleigh Analytical Instrument Co., Ltd), during mensuration with pure Potassium Bromide as a setting, scanning times is 20 times, resolving power 1cm ^-1, sweep limit 4000cm ^-1~ 400cm ^-1, gained infrared spectra as shown in figure 15.

? mAH-g-PP2carboxylic-acid emulsifying agent is adopted, the neutralization bases salify of nonionogenic tenside and amine in aqueous dispersion preparation process.Wherein 3443.32cm ^-1for N-H stretching vibration, 1630.05cm ^-1for the formation vibration of C=O in acid amides, 1094.16cm ^-1c-N stretching vibration, 3000cm ^-1~ 2800cm ^-1between the 2957.12cm that occurs ^-1, 2921.72cm ^-1for the C-H stretching vibration peak of methyl and methylene radical, 1459.46cm ^-1and 1381.71cm ^-1for the formation vibration peak of C-H.

The MAH-g-PP2 aqueous dispersion of Example 5, do Infrared spectroscopy after 175 DEG C of drying and forming-films, result as shown in figure 16.

Contrast Figure 16 and Figure 15 can find out, has occurred 1732.12cm-in Figure 16 ¹the carboxyl C=O peak at place, illustrate also to have occurred in aqueous dispersion high temperature film forming a small amount of in and the phenomenon of salt pyrolysis.

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

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

Figure 17 and Figure 16 is contrasted, 1732cm ^-1carboxylic acid absorption peak disappears, at 1632cm ^-1the shape of neighbouring absorption peak changes, this is because form the absorption peak of acid amides, Figure 17 and Figure 16 exists very large difference, especially at 1100cm ^-1-400cm ^-1scope in, illustrate that the amido in KH-550 and the carboxyl in aqueous dispersion there occurs chemical reaction, form stronger Chemical bond, both combinations have influence on its infrared spectrogram.

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

by embodiment 4 aqueous dispersion in 80 DEG C of dryings fully dehydration in 2 hours, the differential thermal-thermogravimetric analyzer (DTG-60) utilizing Shimadzu, Japan to manufacture in nitrogen atmosphere, carries out thermogravimetric (TGA) to MAH-g-PP2 aqueous dispersion and differential thermal (DTA) is analyzed.Temperature rise rate is 10 DEG C/min, and temperature elevating range is room temperature-300 DEG C.Gained TGA and DTA curve are shown in Figure 18.

As seen from Figure 18, for TGA curve, there is not obvious thermal weight loss in MAH-g-PP2 aqueous dispersion whole system before 200 DEG C, only has a small amount of residual moisture evaporation, show that the system of aqueous dispersion is before this heat-staple; When temperature is higher than 200 DEG C, because the thermolysis of MAH-g-PP2 is volatilized, weight loss rate is caused obviously to increase; For DTA curve, endotherm(ic)peak is there is between 145 DEG C ~ 160 DEG C, this is caused by 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 testing the film formation time of aqueous dispersion, the setting of film-forming temperature should be not less than 145 DEG C.

(4) metallocene polypropylene wax emulsion thermogravimetric analysis

The commercial metallocene polypropylene wax emulsion selecting certain company to produce does thermogravimetric analysis, this emulsion applications uses in glass fiber wire drawing as treating compound composition, its mean diameter is between 0.1-1 μm, after at 80 DEG C, drying makes it fully dehydration for 2 hours, the differential thermal-thermogravimetric analyzer (DTG-60) then utilizing Shimadzu, Japan to manufacture in air atmosphere, carries out thermogravimetric (TGA) to it and differential thermal (DTA) is analyzed.Temperature rise rate is 10 DEG C/min, and temperature elevating range is room temperature-300 DEG C.Gained TGA and DTA curve are as shown in figure 19.

As can be seen from Figure 19 when this emulsion is below 200 DEG C, thermostability is good, and when temperature is more than 200 DEG C, emulsion system starts there is a small amount of thermal weight loss, but final rate of weight loss is significantly less than Figure 18; Can find out that from DTA curve this emulsion is compared with Figure 18, has more two absorption peaks when 45-100 DEG C; The characteristic of metallocene polypropylene wax molecular structure makes its pyro-oxidation resistance be better than MAH-g-PP2, thus shows that, in thermogravimetric analysis figure, thermal weight loss rate obviously reduces, and endotherm(ic)peak showed increased.

(2) MAH-g-PP2 aqueous dispersion improves polyacrylic wetting ability, static resistance

Polypropylene PP belongs to nonpolar and hydrophobic material, not polar functionalities, and surface resistivity is high, thus limits its application in wetting ability, static resistance, the following describes MAH-g-PP2 aqueous dispersion and improves polyacrylic wetting ability, static resistance content.

(1) experimental raw and instrument

PP plate (2mm is thick, commercially available); MAH-g-PP2 aqueous dispersion (embodiment 4, median size 4.2 μm, solid content 20%); The graft block thing (the graft block thing of epoxy resin and Macrogol 4000, self-control) of epoxy resin; 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

PP plate is cut into the square block that size is 15 × 15cm, then puts it in acetone soln and clean, to remove the dirt on PP plate surface, then the acetone on PP plate surface is washed away with deionized water, then soak 10min with ethanol purge, finally clean with deionized water rinsing, room temperature dries for subsequent use.

3) surface treatment of PP plate

(1) MAH-g-PP2 aqueous dispersion is coated on pretreated PP plate equably, puts into vacuum drying oven 110 DEG C oven dry, then applies certain pressure on its surface and place 1h under 190 DEG C of conditions, finally cool to room temperature again.

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

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

(4) the resistance to wiping of the rear PP plate of process

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

(5) chart surface resistanceρ s

The surface resistivity s through the PP plate of different surface treatment is measured with ZC46A type megger.

(6) PP plate surface contact angle is measured

Take deionized water as test liquid, the static contact angle of the rear PP plate surface of process and Air Interface is measured with JJC-1 type wetting angle determining instrument, 6 points (spacing between adjacent measuring point is no less than 1cm) surveyed by each sample, get the value of arithmetical av as experiment gained contact angle of 6 points.

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

Different mixtures is measured to the sticking power of PP plate according to the cross-hatching in GB/T 9286-98.

(8) result and discussion

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

The mixture of MAH-g-PP2 aqueous dispersion or MAH-g-PP2 aqueous dispersion and epoxy grafts is utilized to carry out surface treatment to PP plate, measure the resistance on PP plate surface before and after process, the agent of research different surface treatment is on the impact of PP plate surface resistivity, and measurement result is shown in Figure 20.

As can be seen from Figure 20, the surface resistivity of untreated PP plate is 10 ¹⁴Ω, after 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 containing emulsifying agent in MAH-g-PP2 aqueous dispersion, the hydroaropic substances such as tensio-active agent, MAH-g-PP2 aqueous dispersion is coated in 110 DEG C, PP plate surface and dries removing moisture wherein, and MAH-g-PP2 particle and PP plate all reach fusing point and start melting time under 190 DEG C of high temperature, due to the consistency between MAH-g-PP2 and PP, make 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 again moisture existing in air, thus PP plate surface forms one deck conductive layer, and then the surface resistivity of PP plate declines after making process.Add the epoxy grafts of different mass in MAH-g-PP2 aqueous dispersion after, PP plate surface resistivity drops to 10 ¹⁰about Ω, and along with the increase of epoxy grafts amount, modified PP plate surface resistivity change is little.

(8.2) MAH-g-PP2 aqueous dispersion and carbon black composite use surface treatment 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 on the impact of PP plate surface resistivity.As can be seen from Figure 21, the surface resistivity of untreated PP plate is 10 ¹⁴Ω, after 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 are used process PP plate, found that originally along with the increase of carbon black mass mark, the surface resistivity of modified PP plate slowly drops to 10 ^8.7Ω.But when the massfraction of carbon black reaches 4%, the surface resistivity of modified PP plate sharply declines and reaches 10 ⁶Ω, and continue the massfraction increasing carbon black, the surface resistivity change of PP plate is not obvious.The reason of this phenomenon may be when the massfraction of carbon black is lower, and after process, the carbon black particle distribution on PP plate surface comparatively disperses, the carbon black particle distance effect of still thus conducting electricity comparatively greatly bad each other.Along with the increase of carbon black mass mark, the distance between adjacent carbon black particle slowly reduces, and finally makes the surface of the PP plate after process define the path of conduction, surface resistivity is sharply declined.Because the path that can conduct electricity defines, even if so the surface resistivity change increasing the modified PP of massfraction of carbon black further neither be clearly.

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

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

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

Finish materials type	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, be used alone MAH-g-PP2 aqueous dispersion process PP plate, the sticking power of aqueous dispersion to PP plate is fine.The major cause of this phenomenon is: MAH-g-PP2 particle and PP melting simultaneously in aqueous dispersion when 190 DEG C, exists the process of a cocrystallization between the two in the process of melting cooling, and after this process makes to cool, both cohesive forces are fine.When carbon black and the blended use of MAH-g-PP2 aqueous dispersion and the content of carbon black is less time, 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 also process after PP plate surfaceness also obviously increase.

(8.4) different surface treatment material is on the impact of PP plate surface wiping-resistance

Utilize differing materials to carry out surface treatment to PP plate, then in different solvents, carry out surface wipes to PP plate, the surface resistivity of PP plate after mensuration wiping, measurement result is shown in Figure 22.：

As can be seen from Figure 22, adopt the PP plate of MAH-g-PP2 aqueous dispersion process not change through different solvents wiping rear surface resistance, show with the resistance to wiping properties of PP plate after the process of MAH-g-PP2 aqueous dispersion fine.The major cause of this phenomenon is that the cocrystallization between MAH-g-PP2 aqueous dispersion and PP plate makes cohesive force between the two strong, and the impact thus by solvent wiping is less.And be deteriorated along with the increase of content of carbon black through the resistance to wiping properties of the PP plate of aqueous dispersion and carbon black stock process.When content of carbon black is less than or equal to 3%, solvent wiping front and rear surfaces resistance change is little, and now after process, the resistance to wiping properties of PP plate still can.And when the massfraction of carbon black reaches 4%, obviously increase by the surface resistivity of PP plate after 3 kinds of solvent wipings, resistance to wiping degradation.The reason producing this phenomenon may be that surface-coated thing is loss of adhesion to PP plate when content of carbon black reaches 4%, and roughness increases, and cohesive strength between the two declines, and after solvent wiping experiment, antistatic surface component incurs loss, and surface resistivity increases.

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

Measure the contact angle of untreated PP plate, MAH-g-PP2 aqueous dispersion process PP plate, MAH-g-PP2 aqueous dispersion and carbon black stock process PP plate surface to water respectively, measurement result is shown in 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, it have decreased to 77o to the contact angle of water.The process of MAH-g-PP2 aqueous dispersion can make PP plate surface hydrophilicity strengthen, its major cause is containing the hydrophilic small molecules such as tensio-active agent, emulsifying agent in MAH-g-PP2 aqueous dispersion, PP plate and the melting simultaneously of MAH-g-PP2 particle at 190 DEG C, hydrophilic small molecules makes the PP plate surface after processing decline to the contact angle of water to Air Interface migration.Utilize aqueous dispersion and carbon black stock to carry out surface treatment to PP plate, the contact angle of PP plate to water after process reduces with the increase of carbon black, and minimum is about 45o; But after carbon black mass mark reaches 4%, the major cause that contact angle continues to decline is the increase of PP plate surfaceness.

conclusion:

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

(3) MAH-g-PP2 aqueous dispersion improves Stainless Steel Cloth surface enhanced polypropylene material

Adopt MAH-g-PP2 aqueous dispersion, and in conjunction with epoxy grafts, carbon black etc., significantly can reduce by PP plate surface resistivity, with water contact angle, but this mode is subject to a definite limitation, as carbon black color problem, for making final goods close to the primary colors of PP plate, and reduce PP plate surface resistivity, increase PP plate surface hydrophilicity, adopt Stainless Steel Cloth surface enhanced.

(1) experimental raw and instrument

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

(2) pre-treatment of PP plate

PP plate is cut into the square block that size is 15 × 15cm, then puts it in acetone soln and clean, to remove the dirt on PP plate surface, then the acetone on PP plate surface is washed away with deionized water, then soak 10min with ethanol purge, finally clean with deionized water rinsing, room temperature dries for subsequent use.

(3) preparation of PP composite panel

a.stainless Steel Cloth (being cut to the square of 15 × 15cm) is sprawled at PP thin sheet surface, then be placed in and be warming up to 190 DEG C of moulding presss (the FM-11 type that Beijing Fu Ma Science and Technology Ltd. produces) in advance, during compressing tablet, after first preheating 3min, mold pressure 3MPa is cooled to 40 DEG C of dischargings after suppressing 5min.

B. on Stainless Steel Cloth (being cut to the square of 15 × 15cm), smear MAH-g-PP2 aqueous dispersion, normal temperature prepares matrix material according to the method for A after placing and removing moisture.

(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 bending speed is 2mm/min.

(5) result and discussion

Untreated Stainless Steel Cloth can not with PP compound; Smear the Stainless Steel Cloth after process and PP compound through MAH-g-PP2 aqueous dispersion good, call PP/ Stainless Steel Cloth composition board in the following text.

(5.1) tensile property

Carry out Elongation test to PP plate and PP/ Stainless Steel Cloth composition board, test result is in table 2.

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

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

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

(5.2) bending property

Carry out bending property test to PP plate and PP/ Stainless Steel Cloth composition board, test result is in 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
			PP plate	19.9	1285.4
PP plate/Stainless Steel Cloth compound	20.0	1600.0

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

(5.3) outward appearance, wetting ability, surface resistivity

Outward appearance: the color of PP/ Stainless Steel Cloth composition board is more shallow, obviously can find out that from surface Stainless Steel Cloth is embedded in PP plate, and better, when mechanically processing test bars, both can not be separated for Stainless Steel Cloth and PP plate binding ability.

Wetting ability: the good hydrophilic property of PP/ Stainless Steel Cloth composition board in the PP plate adopting the process of MAH-g-PP2 aqueous dispersion, this is because Stainless Steel Wire is inherently hydrophilic.

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

Conclusion: untreated Stainless Steel Cloth can not with PP compound, and through MAH-g-PP2 aqueous dispersion smear the Stainless Steel Cloth after process can with PP compound, this is because MAH-g-PP2 aqueous dispersion can with PP cocrystallization, stretching after both compounds, bending property increase, and wetting ability is better, surface resistivity is almost 0.

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

MAH-g-PP2 aqueous dispersion film forming characteristics is shown in [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].MAH-g-PP2 aqueous dispersion process glass, induction glass-polypropylene interface occur that scorching content is shown in [Tao Yingying, Zhao Ke .PP-g-MAH emulsion is on the impact [J] at PP/GF interface. prints during chemical industry, 2012,26(4): 11-15], the application of fiber, mica process see [Zhao Ke. functionalized polypropylene emulsion and application thereof, 13 Surface Engineering innovation and practical technique exchanging meeting collection of thesis P128-133, Kaifeng in 2010; 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; In described aqueous dispersion, mean particle size is 1 ~ 50 μm.

2. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 1, it 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 Brij series of surfactants, or 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 composition.

4. maleic anhydride inoculated polypropylene aqueous dispersion as claimed in claim 3, it 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, it is characterized in that, described TWEEN Series tensio-active agent is polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, 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; It is two or more that described carboxylic acid cosurfactant is selected from stearic acid, Palmiticacid, oleic acid, linolic acid, linolenic acid, vegetable fatty acid, mixed fatty acid, rosin, staybelite, sylvic acid.

6. the maleic anhydride inoculated polypropylene aqueous dispersion as described in claim 1 or 2 or 4 or 5, it is characterized in that, described alkali is morpholine, imidazoles, 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, N-Diethyl Aniline, benzylamine, methane amide, acrylamide, first is for ethanamide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-dimethylpropionamide, N, N-diethylformamide, hexanolactam, thanomin, diethanolamine, trolamine, methyl-nitramine, 2-amino-2-methyl propyl alcohol, N, N-dimethylethanolamine, ammoniacal liquor, NaOH or KOH.

7. the preparation method of maleic anhydride inoculated polypropylene aqueous dispersion described in claim 1 or 2 or 4 or 5, is characterized in that, stirs insulation 0.5 ~ 2h, be then cooled to room temperature and get final product after being mixed in proportion by each raw material in 170 ~ 200 DEG C.

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

9. the maleic anhydride inoculated polypropylene aqueous dispersion described in claim 1 or 2 is used as the surface treatment agent of polypropylene material or polypropylene strongthener.

10. the maleic anhydride inoculated polypropylene aqueous dispersion described in claim 1 or 2 is used as the plasticized modifier of polypropylene material.