CN103772612A - Preparation method for maleic anhydride-grafted polypropylene - Google Patents
Preparation method for maleic anhydride-grafted polypropylene Download PDFInfo
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- CN103772612A CN103772612A CN201210413278.2A CN201210413278A CN103772612A CN 103772612 A CN103772612 A CN 103772612A CN 201210413278 A CN201210413278 A CN 201210413278A CN 103772612 A CN103772612 A CN 103772612A
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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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
-
- 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
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
-
- 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
-
- 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
-
- 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 preparation method for maleic anhydride-grafted polypropylene. The preparation method comprises the following steps: (1) uniformly mixing 0.4 to 2 parts of an initiator and 0.6 to 2 parts of styrene by weight; (2) adding 110 parts of polypropylene and 0.6 to 2 parts of maleic anhydride by weight into a high-speed mixing machine and mixing for 1 to 3 minutes, and meanwhile dropwise adding the product obtained by the step (1); (3) adding the product obtained by the step (2) into a double-screw extruder, blending, extruding, melting and grafting to prepare the maleic anhydride-grafted polypropylene. Compared with the prior art, the preparation method has short reaction time, simple preparation and low production cost, and is suitable for industrialization; an anti-oxidant is not required to be added; the effective reaction time can be prolonged by controlling the factors, such as the rotating speed of a main machine, the feeding rotating speed, the temperature and the like; meanwhile, the maleic anhydride-grafted polypropylene with high grafting rate can be obtained by adding the styrene, so that the grafting efficiency of maleic anhydride is improved; the preparation method does not have special requirements on the double-screw extruder, a liquid feeding device is not required, and the length-diameter selection range is large.
Description
Technical field
The invention belongs to processing of high molecular material technical field, especially relate to a kind of preparation method of maleic anhydride inoculated polypropylene.
Background technology
Maleic anhydride inoculated polypropylene (being called for short PP-g-MAH) is a kind of common and effective compatilizer, be widely used in modified plastics, can prepare by several different methods, comparatively speaking, melt grafting is that one is simple to operate, cost is low, is suitable for industrialized preparation method.
Percentage of grafting is the important parameter that judges maleic anhydride inoculated polypropylene quality quality.All the time, adopt melt grafting to prepare maleic anhydride inoculated polypropylene, gained maleic anhydride inoculated polypropylene percentage of grafting is all lower, adds vinylbenzene in formula, can increase substantially percentage of grafting, obtains the maleic anhydride inoculated polypropylene of high-quality.
Chinese patent CN101724148B discloses a kind of maleic anhydride inoculated polypropylene that can obtain higher molecular weight and melt strength, but is only applicable to polypropylene powder, is not suitable for polypropylene granules; This method need to add oxidation inhibitor, and preparation process complexity, causes maleic anhydride inoculated polypropylene cost higher.
Chinese patent CN101492517B discloses the preparation method that maleic anhydride inoculated polypropylene is prepared in a kind of phase Free Radicals graft polymerization, and this method long reaction time, has improved industrialized difficulty and cost greatly.
Adopt twin screw extruder, utilize melt grafting to prepare maleic anhydride inoculated polypropylene, can improve percentage of grafting by " effective reaction time " that extend between polypropylene and maleic anhydride.And this " effective reaction time " is relevant with factors such as forcing machine length-to-diameter ratio, engine speed, feeding rotating speed, temperature.
Summary of the invention
Object of the present invention is exactly the preparation method who provides in order to overcome the defect that above-mentioned prior art exists that a kind of preparation process is simple, production cost is low, is suitable for industrialized maleic anhydride inoculated polypropylene.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for maleic anhydride inoculated polypropylene, the method comprises the following steps:
(1) by weight, 0.4-2 part initiator and 0.6-2 part vinylbenzene are mixed;
(2) by weight, in high-speed mixer, add 100 parts of polypropylene and 0.6-2 part maleic anhydride, mix 1-3min, dropwise add step (1) gains simultaneously;
(3) step (2) gains are joined in twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene.
Described initiator is preferably 0.6-1 part, and described vinylbenzene is preferably 0.8-1.2 part, and described maleic anhydride is preferably 0.8-1.2 part.
Described polypropylene is homo-polypropylene or Co-polypropylene, and described polyacrylic form is powdery or granular.
Described initiator is dicumyl peroxide (DCP) or di-t-butyl peroxide (DTBP).
Described initiator is preferably di-t-butyl peroxide.
The diameter of described twin screw extruder is 30-92mm, and length-to-diameter ratio is 35-52.
The diameter of described twin screw extruder is preferably 72mm, and length-to-diameter ratio is preferably 40.
When the middle blending extrusion of step (3), twin screw extruder temperature is; Feeding section 100-160 ℃, melt zone 160-190 ℃, homogenizing zone 190-210 ℃, head 190-210 ℃; The engine speed of twin screw extruder is 200-360r/min, and feeding rotating speed is 40-60r/min.
When the middle blending extrusion of step (3), the engine speed of twin screw extruder is preferably 5: 1 with the ratio of feeding rotating speed.
When the middle blending extrusion of step (3), the engine speed of twin screw extruder is preferably 300r/min, and feeding rotating speed is preferably 60r/min.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention utilizes twin screw extruder, adopts melt grafting to prepare maleic anhydride inoculated polypropylene, and the reaction times is short, and preparation is simple, and production cost is low, is applicable to industrialization;
(2) the present invention does not need to add oxidation inhibitor;
(3) the present invention, by factors such as main control system rotating speeds, feeding rotating speed, temperature, can extend " effective reaction time ", adds vinylbenzene can obtain the maleic anhydride inoculated polypropylene of high percentage of grafting simultaneously, improves " grafting efficiency " of maleic anhydride;
(4) present stage, the special twin screw extruder of industrial general employing length-to-diameter ratio 52 is prepared maleic anhydride inoculated polypropylene, sometimes also need liquid drawing-in device, the present invention does not have special requirement to twin screw extruder, do not need liquid charging device, and be applicable to the twin screw extruder of length-to-diameter ratio 35-52.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
In embodiment, the percentage of grafting test procedure of maleic anhydride inoculated polypropylene used is as follows:
(1) take 2g maleic anhydride inoculated polypropylene (PP-g-MAH) and be placed in 500ml Florence flask, add 150ml dimethylbenzene, 130 ℃ of reflux 2h, after cooling 1h, add 150ml acetone, leave standstill 30min, filter, with acetone cleaning three times, obtain white, powdery product, product is taken out for subsequent use after 80 ℃ of vacuum drying ovens dry 12h.
(2) take 0.6g step (1) products therefrom, the namely PP-g-MAH after purifying, be dissolved in 100ml dimethylbenzene, 130 ℃ of reflux 30min, cooling 5min, accurately pipette 0.05mol/LKOH-ethanol standardized solution 25mL with transfer pipet, 130 ℃ of reflux 2h, add 2 phenolphthalein indicators, use while hot the titration of 0.5mol/LHCL standardized solution, solution is become colorless by redness, after cooling 30min, solution becomes redness again, again mend and drip with KOH-ethanol standardized solution, the KOH-ethanol standardized solution volume V2 that record consumes, with following formula calculating percentage of grafting: G
mAH=9.806* (V
1c
1-C
2v
2)/2000m*100%
G
mAHfor the percentage of grafting of maleic anhydride inoculated polypropylene; C
1for KOH-ethanol concentration of standard solution, V
1for adding the volume of excessive KOH-ethanol standardized solution; C
2for the concentration of HCL standardized solution, V
2for back titration neutralizes the volume that consumes HCL standardized solution more than alkali; M is the quality of purifying PP-g-MAH.
Wherein, the preparation method of 0.05mol/L KOH-ethanol standardized solution is as follows:
Take 2gKOH, be placed in 500ml volumetric flask, add 2ml distilled water to dissolve, be settled to 500ml with 95% ethanol, be transferred in polythene container airtight placement 24h.
The scaling method of 0.05mol/L KOH-ethanol standardized solution is as follows:
Take the working standard reagent Potassium Hydrogen Phthalate that 0.75g is dried to constant weight in 105-110 ℃ of electric oven, be dissolved in the water of 50ml without carbonic acid gas, add 2 instructions phenolphthalein solutions (10g/L), be titrated to solution pinkiness with the potassium hydroxide-ethanol solution preparing, do blank test simultaneously.Demarcate before use.
The concentration of potassium hydroxide-ethanol standardized solution, numerical value represents with mole every liter, calculation formula is as follows:
C(KOH)＝m*1000/(V
1-V
2)M
In formula: the quality of m-Potassium Hydrogen Phthalate, unit is gram (g).V
1the volume of-potassium hydroxide-ethanol solution, unit is milliliter (ml).The volume of V2-blank assay potassium hydroxide-ethanol solution, unit is milliliter (ml).The molar mass of M-Potassium Hydrogen Phthalate, unit is gram every mole (g/mol), numerical value is 204.22.
The preparation method of 0.5mol/L hydrochloric acid standard solution is as follows:
Take 22ml hydrochloric acid, be settled in 500ml water, shake up.
The scaling method of 0.5mol/L hydrochloric acid standard solution is as follows:
Take 0.95g in 270 ℃ of-300 ℃ of High Temperature Furnaces Heating Apparatuss calcination to the working standard reagent anhydrous sodium carbonate of constant weight, be dissolved in 50ml water, add 10 tetrabromo-mcresolsulfonphthalein-methyl red indicating liquids, be titrated to solution with the hydrochloric acid soln preparing and become garnet from green, boil 2min, after cooling, continue to be titrated to solution and be again garnet, do blank assay simultaneously.The concentration of joining hydrochloric acid standard solution is C
hCL=1000m/ (V
1-V
2) M, in formula, M is 52.994, is the half of sodium carbonate molecular weight; V
1by in calibration process the volume of consumption hydrochloric acid soln, unit is ml; V
2for the volume of hydrochloric acid soln that blank assay consumes, unit is ml.
In embodiment, select the twin-screw extrusion of three kinds of diameters that the present invention is described.Diameter 30mm forcing machine, 1st, 2 district belongs to feeding section, and 3rd, 4 district belong to melt zone, and 5th, 6 district belong to homogenizing zone; Diameter 75mm forcing machine, 1,2,3 districts belong to feeding section, and 4,5,6 districts belong to melt zone, and 7,8,9 districts belong to homogenizing zone; Diameter 92mm forcing machine, 1,2,3,4 districts belong to feeding section, and 5,6,7,8 districts belong to melt zone, and 9,10,11,12 districts belong to homogenizing zone.
Embodiment 1
A. count by weight, take initiator DTBP0.4 part, 0.6 part of vinylbenzene, mixes;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene T30S and 0.6 part of maleic anhydride, mix 1min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 0.51%.。
Twin screw extruder diameter is 30mm, and length-to-diameter ratio is 35, engine speed 200r/min, and feeding rotating speed 40r/min, temperature setting is set to: 1 100 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 190 ℃, districts, 5 190 ℃, districts, 6 190 ℃, districts, 190 ℃ of heads.
Embodiment 2
A. count by weight, take initiator DTBP2 part, 2 parts of vinylbenzene, mix;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene 1215C and 2 parts of maleic anhydrides, mix 3min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 1.41%.
Twin screw extruder diameter is 92mm, and length-to-diameter ratio is 52, engine speed 360r/min, feeding rotating speed 60r/min, temperature setting is set to: 1 100 ℃, district, 2 130 ℃, districts, 3 160 ℃, districts, 4 175 ℃, districts, 5 190 ℃, districts, 6 200 ℃, districts, 7 200 ℃, districts, 8 200 ℃, districts, 9 200 ℃, districts, 10 200 ℃, districts, 11st district, 200 ℃, 12 200 ℃, districts, 210 ℃ of heads.
Embodiment 3
A. count by weight, take initiator DTBP1 part, 1 part of vinylbenzene, mixes;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene 425 powder and 1 part of maleic anhydride, mix 2min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 0.81%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 40, engine speed 300r/min, and feeding rotating speed 60r/min, temperature setting is set to: 1 160 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 210 ℃, districts, 5 210 ℃, districts, 6 210 ℃, districts, 7 210 ℃, districts, 8 210 ℃, districts, 9 210 ℃, districts, 210 ℃ of heads.
Embodiment 4
A. count by weight, take initiator DTBP0.8 part, 1.2 parts of vinylbenzene, mix;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene T30S and 1.2 parts of maleic anhydrides, mix 1min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 0.88%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 42, engine speed 360r/min, and feeding rotating speed 50r/min, temperature setting is set to: 1 100 ℃, district, 2 160 ℃, districts, 3 170 ℃, districts, 4 180 ℃, districts, 5 190 ℃, districts, 6 200 ℃, districts, 7 200 ℃, districts, 8 200 ℃, districts, 9 200 ℃, districts, 200 ℃ of heads.
Embodiment 5
A. count by weight, take initiator DTBP0.8 part, 0.8 part of vinylbenzene, mixes;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene 1215C and 0.8 part of maleic anhydride, mix 2min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 0.71%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 40, engine speed 280r/min, and feeding rotating speed 56r/min, temperature setting is set to: 1 140 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 190 ℃, districts, 5 190 ℃, districts, 6 190 ℃, districts, 7 190 ℃, districts, 8 190 ℃, districts, 9 190 ℃, districts, 190 ℃ of heads.
Embodiment 6
A. count by weight, take 0.8 part of initiator DCP, 1 part of vinylbenzene, mixes;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene 425 powder and 1 part of maleic anhydride, mix 3min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 0.80%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 40, engine speed 280r/min, and feeding rotating speed 56r/min, temperature setting is set to: 1 140 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 190 ℃, districts, 5 190 ℃, districts, 6 190 ℃, districts, 7 190 ℃, districts, 8 190 ℃, districts, 9 190 ℃, districts, 190 ℃ of heads.
Embodiment 7
A. count by weight, take 0.8 part of initiator DCP, 1.5 parts of vinylbenzene, mix;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene T30S and 1.5 parts of maleic anhydrides, mix 2min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 1.18%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 40, engine speed 280r/min, and feeding rotating speed 56r/min, temperature setting is set to: 1 140 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 190 ℃, districts, 5 190 ℃, districts, 6 190 ℃, districts, 7 190 ℃, districts, 8 190 ℃, districts, 9 190 ℃, districts, 190 ℃ of heads.
Embodiment 8
A. count by weight, take 1 part of initiator DCP, 1 part of vinylbenzene, mixes;
B. count by weight, in high-speed mixer, add 100 parts of polypropylene 1215C and 1.5 parts of maleic anhydrides, mix 3min, dropwise add the mixture of a step gained simultaneously;
C. b step gained mixture is joined to twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene, and surveying percentage of grafting is 1.15%.
Twin screw extruder diameter is 75mm, and length-to-diameter ratio is 40, engine speed 280r/min, and feeding rotating speed 56r/min, temperature setting is set to: 1 140 ℃, district, 2 160 ℃, districts, 3 180 ℃, districts, 4 190 ℃, districts, 5 190 ℃, districts, 6 190 ℃, districts, 7 190 ℃, districts, 8 190 ℃, districts, 9 190 ℃, districts, 190 ℃ of heads.
In embodiment 1～embodiment 8, the relation of reaction times and percentage of grafting and grafting efficiency is as shown in table 1:
Table 1PP-g-MAH reaction times and percentage of grafting
Reaction times in table 1 refers to the screw rod residence time of reactant at twin screw extruder.The ratio of the maleic anhydride content adding during grafting efficiency refers to maleic anhydride content that polypropylene connects and reacts, the maleic anhydride content namely making full use of ratio.
Embodiment 9
A preparation method for maleic anhydride inoculated polypropylene, the method comprises the following steps:
(1) by weight, 0.6 part of initiator DCP and 1 part of vinylbenzene are mixed;
(2) by weight, in high-speed mixer, add 100 parts of homo-polypropylene and 1 part of maleic anhydride, mix 2min, dropwise add step (1) gains simultaneously;
(3) step (2) gains are joined in twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene.
Wherein, twin screw extruder diameter is 30mm, and length-to-diameter ratio is 35, engine speed 200r/min, and feeding rotating speed 56r/min, temperature setting is set to: feeding section 100-160 ℃, melt zone 160-190 ℃, homogenizing zone 190-210 ℃, head 190-210 ℃, 190 ℃ of heads.
Chinese patent CN101724148B is carrying out before the reaction of melting free radical grafting, first by polypropylene powder and oxidation inhibitor melt blending, afterwards again by melt blending the acrylic resin of oxidation inhibitor carry out the reaction of melting free radical grafting.Compared with high speed blend of the present invention, fusion-grafting, this method needs melt blending, fusion-grafting two-step reaction, and preparation is complicated, has improved production cost.With reference to the data in this patent, can find that " grafting efficiency " of this method maleic anhydride is no more than 75%, the embodiment in associative list 1, in the present invention, " grafting efficiency " of maleic anhydride is minimum 71%, is up to 89%.This method preparation method is only applicable to polypropylene powder, and preparation method of the present invention is not only applicable to polypropylene powder, is also applicable to polypropylene granules.
Chinese patent CN101492517B discloses a kind of preparation method who prepares maleic anhydride inoculated polypropylene, and this method need to experience closed reactor mixing, 50-120 ℃ reaction obtains maleic anhydride inoculated polypropylene for 1-10 hour." grafting efficiency " of this method reaches as high as 96%, but need in airtight reactor, react, and the reaction times reach 1-10 hour, compared with the present invention, production cost is high, long reaction time, is unsuitable for industrialization.
In sum, the invention provides the preparation method that a kind of reaction times is short, percentage of grafting is high, " grafting efficiency " height is suitable for the maleic anhydride inoculated polypropylene of suitability for industrialized production, and conversion unit (twin screw extruder) is not had to special requirement.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a preparation method for maleic anhydride inoculated polypropylene, is characterized in that, the method comprises the following steps:
(1) by weight, 0.4-2 part initiator and 0.6-2 part vinylbenzene are mixed;
(2) by weight, in high-speed mixer, add 100 parts of polypropylene and 0.6-2 part maleic anhydride, mix 1-3min, dropwise add step (1) gains simultaneously;
(3) step (2) gains are joined in twin screw extruder, blending extrusion, fusion-grafting is prepared maleic anhydride inoculated polypropylene.
2. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 1, is characterized in that, described initiator is preferably 0.6-1 part, and described vinylbenzene is preferably 0.8-1.2 part, and described maleic anhydride is preferably 0.8-1.2 part.
3. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 1, is characterized in that, described polypropylene is homo-polypropylene or Co-polypropylene, and described polyacrylic form is powdery or granular.
4. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 1, is characterized in that, described initiator is dicumyl peroxide or di-t-butyl peroxide.
5. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 4, is characterized in that, described initiator is preferably di-t-butyl peroxide.
6. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 1, is characterized in that, the diameter of described twin screw extruder is 30-92mm, and length-to-diameter ratio is 35-52.
7. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 6, is characterized in that, the diameter of described twin screw extruder is preferably 72mm, and length-to-diameter ratio is preferably 40.
8. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 1, is characterized in that, when the middle blending extrusion of step (3), twin screw extruder temperature is: feeding section 100-160 ℃, melt zone 160-190 ℃, homogenizing zone 190-210 ℃, head 190-210 ℃; The engine speed of twin screw extruder is 200-360r/min, and feeding rotating speed is 40-60r/min.
9. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 8, is characterized in that, when the middle blending extrusion of step (3), the engine speed of twin screw extruder is preferably 5: 1 with the ratio of feeding rotating speed.
10. the preparation method of a kind of maleic anhydride inoculated polypropylene according to claim 9, is characterized in that, when the middle blending extrusion of step (3), the engine speed of twin screw extruder is preferably 300r/min, and feeding rotating speed is preferably 60r/min.
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