CN101423590A - Method for preparing polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch - Google Patents
Method for preparing polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch Download PDFInfo
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- CN101423590A CN101423590A CNA200810243714XA CN200810243714A CN101423590A CN 101423590 A CN101423590 A CN 101423590A CN A200810243714X A CNA200810243714X A CN A200810243714XA CN 200810243714 A CN200810243714 A CN 200810243714A CN 101423590 A CN101423590 A CN 101423590A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a method for preparing a highly-enriched pre-mixed master batch for melting graft of polypropylene and maleic anhydride, which belongs to the technical field of polymer material modification and processing. The method adopts a special mixing method to mix main grafting compositions (grafting monomer, an evocating agent and a degradable inhibitor) and a dispersion resin to produce granular highly-enriched pre-mixed master batch, and the highly-enriched pre-mixed master batch is simply mixed with granular polypropylene resin to perform melting graft on a double screw extruder. The method improves even dispersing property of the grafting compositions, and simultaneously avoids the adhering and falling off of the evocating agent and the grafting monomers on a feed device of the extruder, thereby improving process stability and operating flexibility of the melting graft of the polypropylene and the maleic anhydride, and the quality of grafting products.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the high condensing pre-mixed master batch of polypropylene/maleic anhydride melt grafting.Belong to polymer modification and processing technique field.
Background technology
Polypropylene (PP) is the fastest kind of demand growth in the five big interchangeable heat thermoplastic plastics.Along with updating of polypropylene production technology, polyacrylic performance is greatly improved.But because PP is nonpolar crystalline polymer, lack the polar reaction group on the molecular chain, cause being difficult to carrying out surface printing, application and bonding, also be difficult to fill, brought difficulty for exploitation PP type material with other polymer blending or with filler.In order to enlarge polyacrylic range of application, must carry out modification to polypropylene, give polypropylene with new function.By carrying out grafting with unsaturated polar monomer, on polypropylene molecular chain, introduce polar group or functional side group, can improve the deficiency on its performance, increase new function again simultaneously, be a kind of simple and effective polypropylene modification method.The grafted polar monomer comprises maleic anhydride, vinylformic acid, methacrylic acid, acrylate, methyl propenoic acid glycidyl alcohol ester etc.These monomers with carboxylic acid, acid anhydrides and epoxy-functional except having stronger polarity, also be easy to chemical reactions take place with functional groups such as amidos, carboxyl, hydroxyl.Therefore utilize their grafting on polypropylene molecular chain can improve polyacrylic cohesiveness, dyeability and static resistance effectively.Existing grafting method comprises fusion-grafting, solution graft copolymerization, solid phase grafting, gas phase grafting, radiation grafting, light-initiated grafting etc., wherein the existing industrial applications of solution graft copolymerization and fusion-grafting.
Also exist certain dispute for polypropylene and monomeric grafting mechanism, mainly contain two kinds of viewpoints.The dehydrogenation on the polypropylene molecular chain of the elementary free radical of the first produces the PP macromolecular radical, and dehydrogenation mainly occurs in the tertiary carbon atom position, this macromolecular radical subsequently with monomer addition generation graft reaction.Meanwhile, very unstable because the PP macromolecular radical is the tertiary carbon free radical, the β chain-breaking reaction parallel with graft reaction very easily takes place, cause the graft product molecular weight to descend significantly.Its two be by elementary free radical cause the PP macromolecular radical that produces not with the monomer direct reaction, but the β fracture at first takes place in the PP macromolecular radical, forms 2 PP segments, one of them segment has the end group free radical, another segmental end has pair keys.The segment that has the end group free radical adds with monomer and is shaped as end of the chain grafting.No matter be which kind of viewpoint, all be attended by the β-DeR of PP macromolecular chain in the grafting process, cause the macromolecular chain fracture, molecular weight descends significantly.So polyacrylic graft reaction is accompanied by polyacrylic severely degrade, melt viscosity reduces significantly, the performance of graft product and application is brought have a strong impact on.
In order to suppress the degraded in the polypropylene fusion graft process, people have proposed diverse ways.The one, in reaction, suppress PP and generate the tertiary carbon free radical, the circulating reaction of avoiding β-chain rupture to form; The 2nd, introduce other reactions and form competition, to suppress degraded with β-chain-breaking reaction.Because the complicacy of melting graft reaction process and the dependency of various side reactions, to note to influence the carrying out of graft reaction when suppressing DeR as far as possible.The method of the industrial inhibition degradation of polypropylene that has adopted mainly is to add second monomer and adopt composite initiation system in the grafting system at present.Second monomer is generally electron donor such as vinylbenzene, vinyl acetate between to for plastic, acrylamide, acrylate etc.
Patent CN 1182097A discloses the method for polypropylene being carried out the fusion-grafting modification with glycidyl methacrylate (GMA), hydroxyethyl methylacrylate (HEMA) isopolarity monomer.Patent CN 1456430A disclosed " promoting agent for graft copolymerization of polypropylene with maleic anhydride ", it has added the second monomer oleic acid, carries out melting graft reaction in twin screw extruder, the preparation maleic anhydride inoculated polypropylene.Patent CN 1524096A disclosed " maleation polypropylene and its preparation method " adopts scorification to prepare maleic anhydride inoculated polypropylene in special reactor.
Polypropylene/maleic anhydride melt grafting technology that present patent and document are reported is generally: take by weighing components such as polypropylene, maleic anhydride, initiator, degradation inhibitor according to a certain ratio; Join and carry out high-speed stirring in the mixing equipment so that each component uniform mixing; Mixture is added the hopper of screw extrusion press and carry out grafting with melt extrusion in forcing machine; Extrudate is packing after cooling, pelletizing, drying.Though this technological process is fairly simple, obvious deficiency is arranged: the consumption of (1) peroxide initiator is usually in some thousandths of, and accurate measurement is difficulty relatively; (2) between particulate materials, pulverulent material and low levels component, there is the uneven problem of dispersing and mixing; (3) initiator and grafted monomer very easily stick on the hopper and opening for feed of forcing machine, and coming off at random of bur can make the quality of graft reaction and grafts fluctuate.Therefore, need present fusion graft process be improved, with the stability of raising graft process and the quality of grafts.
Summary of the invention
The objective of the invention is in present polypropylene/maleic anhydride melt grafting process since the defective of the inhomogeneous graft process poor stability that brings of graft component blending dispersion and grafts quality fluctuation a kind of stable graft process is provided and improves the grafts method for quality.
The object of the present invention is achieved like this: adopt special blending means that main graft component (grafted monomer, initiator and degradation inhibitor) and dispersion resin are mixed and made into the granulous high condensing pre-mixed master batch, this high condensing pre-mixed master batch can carry out fusion-grafting with granular acrylic resin on twin screw extruder after simply mixing.This method has improved the dispersing uniformity of graft component, avoided simultaneously initiator and grafted monomer on the forcing machine feeding unit adhesion and come off, thereby improve the quality of technology stability, flexibility of operation and the grafted products of polypropylene/maleic anhydride melt grafting.
The invention is characterized in that this method comprises following processing step:
Step 1, polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch preparation
A) under the normal temperature, peroxide initiator is dissolved in formation initiator/degradation inhibitor mixing solutions in second monomer (degradation inhibitor); Maleic anhydride monomer and oxidation inhibitor are mixed in high speed dispersor, form grafted monomer/antioxidant mixture;
B) twin screw extruder is warmed up to certain temperature,, adds from spout with fixed feeding frequency with the feeding machine of vector resin by twin screw extruder;
C) at the inlet that adds of twin screw extruder mixing section leading portion, add grafted monomer/antioxidant mixture continuously by weight-loss type electronics dosing feeder, add initiator/degradation inhibitor mixing solutions continuously by high-pressure metering pump simultaneously, each component is dispersed in the melting carrier resin, and each component is fully wrapped up with the melting carrier resin; In this process, should avoid the decomposition reaction of peroxide initiator;
D) extruded material pelletizing after cooling off is promptly obtained polypropylene/maleic anhydride melt grafting pre-mixed master batch.In order to prevent maleic anhydride volatilization and the moisture absorption in the pre-mixed master batch, aluminium plastic composite packaging is selected in the pre-mixed master batch packing bag for use, and pre-mixed master batch stores under lucifuge, drying conditions.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, described vector resin is that fusing point is lower than 100 ℃ ethylene-octene copolymer (POE), ethylene-butene copolymer (POE) or ethylene-vinyl acetate copolymer (EVA) etc.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, described grafted monomer is a maleic anhydride.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, described initiator is a dicumyl peroxide (DCP), 2,5-dimethyl-2,5 dual-tert-butyl peroxide hexanes (TX101), 3,6,9-triethyl-benzene-3,6,8-trimethylammonium-1,4,7 three peroxide nonanes (TX301) or di-t-butyl peroxide ether etc.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, it is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), vinylbenzene (St), Vinylstyrene (DVB), propylene glycol diacrylate (DPGDA), tri (propylene glycol) diacrylate (TPGDA), trimethylolpropane trimethacrylate (TMPTA), bismaleimides etc. that described degraded suppresses auxiliary agent.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, by weight, the grafted monomer consumption is the 1%-30% of vector resin total amount, is preferably 5%-10%; Initiator amount is the 0.1%-3% of vector resin total amount, is preferably 0.5%-2%; The degradation inhibitor consumption is the 0.1%-15% of vector resin total amount, is preferably 0.5%-5%.
Polypropylene/maleic anhydride melt grafting pre-mixed master batch that the present invention makes, the processing condition of twin screw extruder need control in extruding mixing process.Rising extruder barrel temperature, material viscosity reduces, and helps plasticizing, but causes the distillation of decomposition of initiator and maleic anhydride easily.The increase screw speed can be strengthened the shearing to material, helps material dispersed and mixes, and produces heat but material is subjected to screw rod shearing effect meeting, causes temperature of charge to raise.The temperature in each district of twin screw extruder sees Table 1 in polypropylene of the present invention/maleic anhydride melt grafting pre-mixed master batch manufacturing processed, and screw speed is 50-150r/min.
Twin screw extruder was respectively distinguished the temperature setting when table 1 pre-mixed master batch prepared
| I district temperature/℃ | II district temperature/℃ | III district temperature/℃ | IV district temperature/℃ | V district temperature/℃ | Head temperature/℃ |
| 60-100 | 70-100 | 70-100 | 70-100 | 70-100 | 60-80 |
Step 2, pre-mixed master batch and the grafting of polypropylene mixed melting
A) under the normal temperature, pre-mixed master batch that step 1 is obtained and polypropylene add according to a certain ratio and carry out thorough mixing in the high-speed mixer.Pre-mixed master batch and polyacrylic proportioning are 5～20:95～80, can adjust according to the requirement to percentage of grafting.
B) pre-mixed master batch and polyacrylic uniform mixture are joined twin screw extruder and carry out grafting with melt extrusion.The polypropylene of manufacturing of the present invention/maleic anhydride melt grafting pre-mixed master batch is during with polypropylene mixing extruding graft, the temperature in each district of twin screw extruder sees Table 2, screw speed is 50-200r/min, and material is 1-5min at the mean residence time of twin screw extruder.
Table 2 pre-mixed master batch is respectively distinguished the temperature setting with melt extruding after polypropylene mixes
| I district temperature/℃ | II district temperature/℃ | III district temperature/℃ | IV district temperature/℃ | V district temperature/℃ | Head temperature/℃ |
| 130-160 | 160-180 | 180-220 | 180-230 | 180-230 | 180-230 |
Step 3, the extruded material that step 2 is obtained promptly obtain the polypropylene grafted maleic anhydride product through cooling and dicing.
The present invention adopts preparation pre-mixed master batch earlier, utilize pre-mixed master batch and the grafting of polypropylene mixed melting again, solved the uneven problem of dispersing and mixing between particulate materials, pulverulent material and the low levels component, avoided initiator and grafted monomer on the forcing machine feeding unit adhesion and come off, reached stable graft process, improved the purpose of grafts quality.Simultaneously, also improved the flexibility of operation of polypropylene/maleic anhydride melt grafting technology.
Compared with the prior art, the present invention has the following advantages:
(1) improved dispersing and mixing homogeneity between the graft component;
(2) avoided initiator and grafted monomer on the forcing machine feeding unit adhesion and come off;
(3) graft process stability improves;
(4) have better technological flexibility and operability;
(5) quality of maleic anhydride inoculated polypropylene product obviously improves, and percentage of grafting and melt flow rate (MFR) are stable.
Embodiment
Below with specific embodiment the present invention is further specified, described embodiment is grasped by those skilled in the art easily and verifies.By embodiment the present invention being explained, is not that the present invention is made restriction.
Embodiment 1:
With acrylic resin (PP, melt flow rate (MFR) is 3.5g/10min), maleic anhydride (MAH), initiator 2,5-dimethyl-2,5 dual-tert-butyl peroxide hexanes (TX101), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and Vinylstyrene (DVB) mix in high speed dispersor, and its prescription is as follows: 100 parts of PP, 1.2 part MAH, 0.15 part TX101,0.3 part of antioxidant 1010,0.5 part of DVB.
Preparation process is as follows: with 100 parts of PP, 1.2 part MAH, 0.15 part initiator TX101,0.3 part antioxidant 1010,0.5 part DVB is according to the proportioning weighing, add in the high speed dispersor and mix, the hopper that adds twin screw extruder then carries out grafting with melt extrusion, and every section temperature of twin screw extruder is respectively: 150 ℃ of I district temperature, 180 ℃ of II district temperature, 200 ℃ of III district temperature, 210 ℃ of IV district temperature, 210 ℃ of V district temperature, 210 ℃ of head temperatures, the feed screw rotating speed is 30r/min, and the main-machine screw rotating speed is 150r/min.The residence time of material in twin screw extruder is 1.2min.Then the graft product cooling and dicing is promptly obtained polypropylene grafted maleic anhydride product (PP-g-MAH).
Embodiment 2:
Initiator TX101 and Vinylstyrene (DVB) are dissolved mixing by a certain percentage, maleic anhydride and antioxidant 1010 are mixed in high speed dispersor by a certain percentage.With ethylene/octene (POE, 70 ℃ of fusing points, melt flow rate (MFR) 10g/10min) the main opening for feed from twin screw extruder adds, use weight-loss type electronics dosing feeder that the side loading mouth of maleic anhydride/antioxidant 1010 mixture from the twin screw extruder mixing section added continuously, by high-pressure metering pump the following opening for feed of initiator/Vinylstyrene mixing solutions from the twin screw extruder mixing section injected continuously, each component is forced to dispersing and mixing in forcing machine, and the POE that is melted parcel.Extrudate obtains pre-mixed master batch through cooling and dicing.Pre-mixed master batch consists of: 100 parts of POE, 12 parts of MAH, 1.5 parts of TX101,5.0 parts of DVB, 3.0 parts of antioxidant 1010s.
Preparation process is as follows: accurate 12 parts of MAH of weighing and 3.0 parts of antioxidant 1010s will mix in the above-mentioned material adding high speed dispersor.Accurately take by weighing 1.5 parts of initiator TX101 and 5.0 parts of DVB, and TX101 is dissolved in forms mixing solutions among the DVB.100 parts of POE are added twin screw extruder master charging opening melt extrude, the control feeding rate is 2kg/min; Use weight-loss type electronics dosing feeder that the side loading mouth of maleic anhydride/antioxidant 1010 mixture from the twin screw extruder mixing section added continuously, the control feeding rate is 0.30kg/min; Adopt high-pressure metering pump that the following opening for feed of initiator/Vinylstyrene mixing solutions from the twin screw extruder mixing section injected continuously, the control feeding rate is 0.14L/min (density of mixing solutions in the time of 25 ℃ is 0.932g/mL); Material is extruded continuously.In this process, should avoid the decomposition reaction of peroxide initiator, 60 ℃ of I district temperature, 80 ℃ of II district temperature, 80 ℃ of III district temperature, 80 ℃ of IV district temperature, 70 ℃ of V district temperature, 70 ℃ of head temperatures.Twin screw extruder screw speed 100r/min.At last the extrudate cooling and dicing is promptly obtained highly enriched polypropylene/maleic anhydride melt grafting pre-mixed master batch.
Embodiment 3:
Pre-mixed master batch and polypropylene homo resin (PP with embodiment 2 preparations, melt flow rate (MFR) 3.5g/10min) in high speed dispersor, mixes according to a certain ratio, on twin screw extruder, carry out fusion-grafting then, preparation maleic anhydride inoculated polypropylene product.Preparation process is as follows: will 90 parts of PP and 10 parts of pre-mixed master batch add in the high speed dispersors and mix because that two kinds of materials are is granular, so be easy to mix.The material that mixes is added twin screw extruder carry out grafting with melt extrusion, every section temperature of twin screw extruder is respectively: 150 ℃ of I district temperature, 180 ℃ of II district temperature, 200 ℃ of III district temperature, 210 ℃ of IV district temperature, 210 ℃ of V district temperature, 210 ℃ of head temperatures; The feed screw rotating speed is 30r/min, and the main-machine screw rotating speed is 150r/min.The residence time of material in twin screw extruder is 1.2min.Then the graft product cooling and dicing is promptly obtained polypropylene grafted maleic anhydride product (PP-g-MAH).
Embodiment 4:
Change the polypropylene homo resin among the embodiment 3 into polypropylene copolymer resins (cPP, melt flow rate (MFR) 2.0g/10min), all the other are with embodiment 3.Use the pre-mixed master batch and the acrylic resin of embodiment 2 preparations on twin screw extruder, to prepare polypropylene grafted maleic anhydride product (cPP-g-MAH).
Embodiment 1 and embodiment 3-4 make the comparison of product:
Table 3. embodiment 1 and embodiment 3-4 make the comparison of graft product
By the graft effect of grafts behind the comparison forcing machine running different time, use the pre-mixed master batch grafting as can be seen than the percentage of grafting height that makes the direct mixed grafting of used additives, technology stability is good.
Embodiment 5:
With polypropylene/maleic anhydride melt grafting pre-mixed master batch of preparation among the embodiment 2 common polythene film packaging bag hermetic package, in lucifuge exsiccant warehouse, store 3 months, then with acrylic resin (the PP melt flow rate (MFR) is 3.5g/10min) mixed melting grafting, all the other conditions such as embodiment 3.
Embodiment 6:
Polypropylene/maleic anhydride melt grafting the pre-mixed master batch of preparation among the embodiment 2 is packed with the packing bag of polyethylene/nylon multilayer copolymerized compound membrane, in lucifuge exsiccant warehouse, store 3 months, then with acrylic resin (the PP melt flow rate (MFR) is 3.5g/10min) mixed melting grafting, all the other conditions such as embodiment 3.
Embodiment 7:
Polypropylene/maleic anhydride melt grafting the pre-mixed master batch of preparation among the embodiment 2 is packed with plastic-aluminum combined film package bag, in lucifuge exsiccant warehouse, store 3 months, then with acrylic resin (the PP melt flow rate (MFR) is 3.5g/10min) mixed melting grafting, all the other conditions such as embodiment 3.
Embodiment 3 and embodiment 5-7 make the comparison of product:
Table 4. embodiment 3 and embodiment 5-7 make the comparison of graft product
| Sample | Pre-mixed master batch is stored packing material | Graft product | Melt flow rate (MFR) (g/10min) | MAH percentage of grafting (%) |
| Embodiment 3 | Do not store | PP-g-MAH | 7.5 | 0.52 |
| Embodiment 5 | The common polythene film | PP-g-MAH | 5.8 | 0.45 |
| Embodiment 6 | The polyethylene coextrusion nylon film | PP-g-MAH | 7.7 | 0.51 |
| Embodiment 7 | Aluminum-plastic composite membrane | PP-g-MAH | 7.6 | 0.52 |
Can find to use the seal-packed pre-mixed master batch of common polythene film packaging bag relatively, the obvious variation of result of use, and use polyethylene/nylon multilayer copolymerized compound membrane or the seal-packed pre-mixed master batch of plastic-aluminum combined film package bag, result of use is suitable with the pre-mixed master batch of not depositing.
Embodiment 8:
Polypropylene/maleic anhydride melt grafting the pre-mixed master batch of preparation among the embodiment 2 is packed with plastic-aluminum combined film package bag, in lucifuge exsiccant warehouse, store 6 months, then with acrylic resin (the PP melt flow rate (MFR) is 3.5g/10min) mixed melting grafting, all the other conditions such as embodiment 3.
Embodiment 9:
Polypropylene/maleic anhydride melt grafting the pre-mixed master batch of preparation among the embodiment 2 is packed with plastic-aluminum combined film package bag, in lucifuge exsiccant warehouse, store 9 months, then with acrylic resin (the PP melt flow rate (MFR) is 3.5g/10min) mixed melting grafting, all the other conditions such as embodiment 3.
Embodiment 3 and embodiment 7-9 make the comparison of product:
Table 5. embodiment 3 and embodiment 7-9 make the comparison of graft product
| Sample | The pre-mixed master batch period of storage | Graft product | Melt flow rate (MFR) (g/10min) | MAH percentage of grafting (%) |
| Embodiment 3 | Do not store | PP-g-MAH | 7.5 | 0.52 |
| Embodiment 7 | 3 months | PP-g-MAH | 7.6 | 0.52 |
| Embodiment 8 | 6 months | PP-g-MAH | 7.3 | 0.51 |
| Embodiment 9 | 9 months | PP-g-MAH | 7.2 | 0.50 |
Claims (3)
1. the preparation method of polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch is characterized in that may further comprise the steps:
Step 1, polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch preparation
A) under the normal temperature, initiator is dissolved in forms initiator/degradation inhibitor mixing solutions in the degradation inhibitor; Grafted monomer and oxidation inhibitor are mixed in high speed dispersor, form grafted monomer/antioxidant mixture;
B) twin screw extruder is warmed up to certain temperature,, adds from spout with fixed feeding frequency with the feeding machine of vector resin by twin screw extruder;
C) at the inlet that adds of twin screw extruder mixing section leading portion, add grafted monomer/antioxidant mixture continuously by weight-loss type electronics dosing feeder, add initiator/degradation inhibitor mixing solutions continuously by high-pressure metering pump simultaneously, each component is dispersed in the melting carrier resin, and each component is fully wrapped up with the melting carrier resin;
D) extruded material pelletizing after cooling off is promptly obtained polypropylene/maleic anhydride melt grafting pre-mixed master batch;
Wherein said vector resin is that fusing point is lower than 100 ℃ ethylene-octene copolymer, ethylene-butene copolymer or ethylene-vinyl acetate copolymer; Described grafted monomer is a maleic anhydride; Described initiator is a dicumyl peroxide, 2,5-dimethyl-2,5 dual-tert-butyl peroxide hexane, 3,6,9-triethyl-benzene-3,6,8-trimethylammonium-1,4,7 three peroxide nonanes or di-t-butyl peroxide ether; It is vinylbenzene, Vinylstyrene, propylene glycol diacrylate, tri (propylene glycol) diacrylate, trimethylolpropane trimethacrylate or bismaleimides that described degraded suppresses auxiliary agent; Described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, 2,6 ditertiary butyl p cresol.
Described polypropylene/maleic anhydride melt grafting pre-mixed master batch by weight, the grafted monomer consumption is the 1%-30% of vector resin total amount; Initiator amount is the 0.1%-3% of vector resin total amount; The degradation inhibitor consumption is the 0.1%-15% of vector resin total amount;
Twin screw extruder was respectively distinguished the temperature setting when pre-mixed master batch prepared: I district degree 60-100 ℃, and 70-100 ℃ in II district, 70-100 ℃ in III district, 70-100 ℃ in IV district, 70-100 ℃ in V district, head 60-80 ℃; Screw speed is 50-150r/min;
Step 2, pre-mixed master batch and the grafting of polypropylene mixed melting
A) under the normal temperature, pre-mixed master batch that step 1 is obtained and polypropylene add according to a certain ratio and carry out thorough mixing in the high-speed mixer; Pre-mixed master batch and polyacrylic proportioning are 5～20:95～80;
B) pre-mixed master batch and polyacrylic uniform mixture are joined twin screw extruder and carry out grafting with melt extrusion; Twin screw extruder was respectively distinguished the temperature setting when pre-mixed master batch prepared: I district degree 130-160 ℃, and 160-180 ℃ in II district, 180-220 ℃ in III district, 180-230 ℃ in IV district, 180-230 ℃ in V district, head 180-230 ℃; Screw speed is 50-200r/min, and material is 1-5min at the mean residence time of twin screw extruder;
Step 3, the extruded material that step 2 is obtained promptly obtain the polypropylene grafted maleic anhydride product through cooling and dicing.
2. the preparation method of polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch according to claim 1, it is characterized in that: described polypropylene/maleic anhydride melt grafting pre-mixed master batch by weight, the grafted monomer consumption is the 5%-10% of vector resin total amount; Initiator amount is the 0.5%-2% of vector resin total amount; The degradation inhibitor consumption is the 0.5%-5% of vector resin total amount.
3. the preparation method of polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch according to claim 1, it is characterized in that: aluminium plastic composite packaging is selected in the pre-mixed master batch packing bag for use.
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