CN103788389B - A kind of long glass fiber reinforced polypropylene and preparation method thereof - Google Patents
A kind of long glass fiber reinforced polypropylene and preparation method thereof Download PDFInfo
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- CN103788389B CN103788389B CN201210426366.6A CN201210426366A CN103788389B CN 103788389 B CN103788389 B CN 103788389B CN 201210426366 A CN201210426366 A CN 201210426366A CN 103788389 B CN103788389 B CN 103788389B
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Abstract
The present invention relates to long glass fiber reinforced polypropylene and preparation method thereof, the method includes blend composition mix homogeneously, melted, contact with the coupling agent treatment long glass fibres through traction after extrusion, by the product solidified molding after contact, pelletizing, described blend composition contains acrylic resin, antioxidant and compatilizer, described acrylic resin is at 230 DEG C, melt mass flow rate under the effect of 2.16kg counterweight is 35 320g/10min, in described blend composition, acrylic resin relative to 100 weight portions, the consumption of described antioxidant is 0.1 0.8 weight portions, the consumption of described compatilizer is 28 weight portions；Described coupling agent treatment long glass fibres is 1:1.3 3.3 with the weight ratio of described blend composition.The rigidity of the long glass fiber reinforced polypropylene that the method that the present invention provides prepares and good fluidity.
Description
Technical field
The present invention relates to a kind of long glass fiber reinforced polypropylene and preparation method thereof.
Background technology
Glass fiber reinforcement pellet extrusion composite technology used by common injection technique manufactures, it
It is to use Bitruder by glass fiber precursor and thermoplastic melt in the barrel of extruder
Melted compound, be extruded into material strip shape by die head, water cooled after be chopped into enhancing pellet, then by this grain
Material is added in injection machine, is expelled in mould be formed the goods of required form after again melting.This technique
The length of fiberglas chopped strand used is generally 3-6mm, glass fibre after Bitruder
Prescinded to 0.75-1.5mm, after injecting through injection machine, glass fibre in final enhancing goods
Length shortens to 0.15-0.33mm further.Owing to glass fibre length shortens dramatically, therefore strengthen effect
Fruit is had a greatly reduced quality.
Long glass fibres pellet refers to the pellet that one-way fiber is arranged, its fibre length and pellet length phase
Deng, generally higher than 5mm.Long-fiber-reinforced thermoplastics is to apply thermoplastic melt equably
Cladding glass fiber single filament, adequately protect glass fibre, infiltrated, draw, cool down, pelletizing forms,
Surrounded by plastics equably due to fiber when injection moulding, decrease strong to fiber of screw in injection molding machine
Dissection, therefore in final goods, fibre length can be up to 0.64-2.9mm, even up to
11.9mm, is 5-20 times of glass fibre length of the preparation of above-mentioned traditional handicraft.This enhancing goods
After burning erosion, remaining glass fibre still can maintain the shape of goods.With traditional pelletize and injection
The glass fibre that technique obtains is compared, the mechanical strength of long fiber reinforcement thermal plastic goods, high-temperature behavior,
Wearing character, lustrous surface and creep-resistant property all improve a lot.
Long-fiber-reinforced thermoplastics (Long Fiber reinforced Thermoplastics is called for short LFT)
It is to realize general-purpose plastics through engineering approaches, the effective means of engineering plastics functionalization, the length one of its glass fibre
As more than 4-5 millimeter, and be positively retained at more than 8mm.In long fiber reinforcement thermoplastic, consumption is
Big for long glass fiber reinforced polypropylene PP Pipe Compound, account for more than the 80% of LFT material.LFT has
Superiority highlighted below: the ratio of (1) intensity/deadweight is the highest.(2) due in injection molding LFT goods
Fiber forms network structure, makes the rigidity of product improve with toughness simultaneously, and injection moulding short glass fiber
Strengthen goods to be then difficult to accomplish this point.(3) in large temperature range, keep the performance of material, indeformable,
And there is low-down creep properties.(4) low-temperature impact toughness of LFT material is even above corresponding virgin resin
And SFT(short glass fiber reinforced thermoplastics) material.(5) shrinkage factor of injection LFT is the lowest,
Can, dimensional requirement accurate goods big with injection moulding size.Typically poly-third containing 40% long glass fibres
The stretch modulus of ene compositions, up to 10000MPa, is 6-8 times of plain polypropylene, has good simultaneously
Good shock resistance.This material is widely used in automobile, household electrical appliances, electromechanical industries, petrochemical industry and leads to
News electronic enterprises.
CN101338051A discloses a kind of long glass fiber reinforced polypropylene material and preparation method thereof,
The mass ratio of material component is: polypropylene 35～55 weight %, long glass fibres 35～50 weight %,
Coupling agent 0.3～0.8 weight %, compatilizer 5～10 weight %, flow ability modifying agent 2～4 weight %, anti-
Oxygen agent 0.3～0.6 weight %, lubricant 1～2 weight %.In this invention, polyacrylic melt matter used
Amount flow rate is 10-25g/10min.The method also further describes by double-screw extruding pelletizing,
Using peroxide degradation polypropene composition, to reach polyacrylic high fluidity, but the method exists poly-
The defects such as propylene melt mass flow rate is unstable, abnormal smells from the patient is big.
The commercial car cover plate of storage battery that CN101593817A long glass fiber reinforced polypropylene material produces,
Modified polypropylene material is passed through with heat-resistant aging agent, uvioresistant auxiliary agent, white oil, Masterbatch additive
After stirring mixed melting, and coextrusion after 40% glass fiber yarn of combing mixes, by polypropylene
Resin-coating is at fiberglass outer surface, and is cooled into pellet after being cut off, and can be used for making large-scale
Automobile storage battery cover plate.This patent relates generally to the molding into cover plate of storage battery, to compositions the most in detail
Explanation.In the product prepared, glass fibre can be extruded machine and prescinds, the therefore poor effect of fiberglass reinforced.
CN102127260A relates to a kind of toughening type long glass fiber reinforced polypropylene compositions board-like material
And preparation method thereof, include polypropylene, long glass fibres, toughener, modified polypropene, antioxidant
And color masterbatch.Polyacrylic melt mass flow rate used is 16-40g/10min, its glass fibre from
Adding in the middle part of extruder, glass fibre is impaired to shorten, it is impossible to ensure in long glass fiber reinforced polypropylene
Glass fibre length requirement.
The polypropylene product that foregoing invention provides, owing to the polypropylene mobility provided is low, is unfavorable for glass
The cladding of fiber, it may appear that glass fibre is exposed to the phenomenon of product surface；Additionally, in prior art,
Often glass fibre and polypropylene base resin are mixed together in an extruder uniform, melted, glass fibers
Dimension can be because the mechanicals efforts of extruder be prescinded, it is generally the case that be surrounded by the polypropylene of glass fibre
In goods, the length of glass fibre is 0.01-0.07:1 with the ratio of the length of goods, therefore cannot apply
In the field that some are higher to the mobility of long glass fiber reinforced polypropylene and rigid requirements.
Summary of the invention
The invention aims to overcome the deficiencies in the prior art, it is provided that a kind of can be with higher stream
Long glass fiber reinforced polypropylene of dynamic property and rigidity modulus and preparation method thereof.
The invention provides the preparation method of a kind of long glass fiber reinforced polypropylene, the method includes altogether
Contact with the coupling agent treatment long glass fibres through traction after batch mixing mix homogeneously, melted, extrusion, or
Person by after blend composition mix homogeneously, melted, extrusion with the long glass through coupling agent treatment being in traction state
Glass fiber contacts, by the product solidified molding after contact, described blend composition contains acrylic resin, antioxygen
Agent and compatilizer, described acrylic resin melt matter at 230 DEG C, under the effect of 2.16kg counterweight
Amount flow rate is 35-320g/10min, in described blend composition, relative to poly-the third of 100 weight portions
Olefine resin, the consumption of described antioxidant be 0.1-0.5 weight portion, the consumption of described compatilizer be 2-8 weight
Part；Described coupling agent treatment long glass fibres is 1:1.3-3.3 with the weight ratio of described blend composition.
Present invention also offers the long glass fiber reinforced polypropylene prepared by said method.
Due to the polypropylene used in the preparation method of the long glass fiber reinforced polypropylene that the present invention provides
Mobility is high, can effectively be coated with glass fibre, not have glass fibre and be exposed to product surface
Phenomenon；Additionally, due to mix in an extruder containing the blend composition of polypropylene base resin, melted after just with
Fiberglass particle contact, it is to avoid glass fibre can be because the mechanicals efforts of extruder be prescinded, therefore
High to mobility and the rigidity of long glass fiber reinforced polypropylene.
Detailed description of the invention
The preparation method of the long glass fiber reinforced polypropylene according to the present invention, the method includes blend composition
Contact with the coupling agent treatment long glass fibres through traction after mix homogeneously, melted, extrusion, or by
With the long glass fibers through coupling agent treatment being in traction state after blend composition mix homogeneously, melted, extrusion
Dimension contact, will contact after product solidified molding, described blend composition contain acrylic resin, antioxidant and
Compatilizer, described acrylic resin melt quality stream at 230 DEG C, under the effect of 2.16kg counterweight
Dynamic speed is 35-320g/10min, in described blend composition, relative to the polypropylene tree of 100 weight portions
Fat, the consumption of described antioxidant be 0.1-0.8 weight portion, the consumption of described compatilizer be 2-8 weight portion；
Described coupling agent treatment long glass fibres is 1:1.3-3.3 with the weight ratio of described blend composition.
According to the present invention, the kind of long glass fibres is not specially required by the present invention, it is preferable that described
Long glass fibres is alkali-free long glass fibres.
According to the present invention, although as long as by above-mentioned containing specific kind and the acrylic resin of content, anti-
After the blend composition mix homogeneously of oxygen agent and compatilizer, melted, extrusion long with the coupling agent treatment through traction
Fiberglass particle contact, just enables to prepare polypropylene by the product solidified molding after contact, pelletizing
Can have high mobility and rigidity concurrently, but in order to make polypropylene preferably flow and make to obtain polyacrylic just
Property strengthen, under preferable case, in described blend composition, relative to the acrylic resin of 100 weight portions,
The consumption of described antioxidant be 0.2-0.4 weight portion, the consumption of described compatilizer be 4-5 weight portion, described
Coupling agent treatment long glass fibres is 1:1.6-2.5 with the weight ratio of described blend composition.
According to the present invention, by the blend composition mix homogeneously containing acrylic resin, antioxidant and compatilizer
Method and condition are known to the skilled person.For example, it is possible to will be containing acrylic resin, antioxidant
Add in high-speed mixer with the blend composition of compatilizer and mix.The condition of described mixing generally includes the most mixed
The rotating speed of conjunction machine, the temperature of mixing and the time of mixing, the rotating speed of described agitator can be such as
100-500 rev/min, the temperature of mixing such as can be 25-65 DEG C, and the time of mixing can be 30-60
Second；Under preferable case, stir the 40-50 second under the rotating speed of 200-400 rev/min, at 25-65 DEG C.
According to the present invention, the method melted by the blend composition containing acrylic resin, antioxidant and compatilizer
It is known to the skilled person with condition.For example, it is possible to by above-mentioned mix homogeneously containing polypropylene tree
The blend composition of fat, antioxidant and compatilizer adds in extruder melted.Described melted method, condition and
Extruder used is known to those skilled in the art.It is for instance possible to use double screw extruder, also
Can use single screw extrusion machine, screw speed is 80-300 rev/min, the feed zone of extruder, pressure
Contracting district, melting zone, the temperature of homogenization zone be respectively 230-280 DEG C, 240-290 DEG C, 240-290 DEG C,
230-280 DEG C, the vacuum of each section is melted under conditions of being 0.02 to 0.09 MPa.
In the present invention, term " acrylic resin " is with propylene as monomer, through catalytic polymerization, refined,
The thermoplastic resin of pelletize, polypropylene therein can be the homopolymer of propylene, it is also possible to be propylene
Copolymer.As it has been described above, the higher acrylic resin of melt mass flow rate can be coated with effectively
Glass fibre.Therefore, although the described acrylic resin in the present invention is at 230 DEG C, at 2.16kg weight
Melt mass flow rate under the effect of code is that 35-320g/10min just can realize goal of the invention, excellent
In the case of choosing, described acrylic resin melt quality at 230 DEG C, under the effect of 2.16kg counterweight
Flow rate is 45-300g/10min, and the mobility of the product so prepared is higher.
According to the present invention, in the preferred case, possibly together with nucleator in described blend composition, relative to 100
The acrylic resin of weight portion, the consumption of described nucleator is 0.02-0.12 weight portion, is preferably
0.05-0.07 weight portion.After adding nucleator, the Chalpy impact that can more effectively improve goods is strong
Degree, hot strength and bending strength.
According to the present invention, various can be used in that described nucleator can be known to the skilled person gathers
The nucleator of allyl resin, as a rule, described nucleator can be dibenzoic acid aluminum, 2,2 '-methylene
In-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphates and aryl phosphate ester aluminium salt one or more；It is preferably virtue
Base phosphate ester aluminium salt.
According to the present invention, various can be used in that described coupling agent can be known to the skilled person is located
The coupling agent of reason glass fibre, as a rule, described coupling agent can be silane coupler, titanate esters idol
One or more in connection agent and aluminate coupling agent.Described silane coupler such as can be selected from γ-(first
Base acryloyl-oxy) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and γ-(2,3-epoxy
Third oxygen) one or more in propyl trimethoxy silicane, the most described coupling agent is γ-(methyl-prop
Alkene acyl-oxygen) propyl trimethoxy silicane (KH570), gamma-aminopropyl-triethoxy-silane (KH550) and
One or more in γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), further
The most described coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570).
According to the present invention, the present invention concentration special restriction useless to described coupling agent, it is possible to use
Described pure coupling agent, is preferably used the aqueous solution of coupling agent.The aqueous solution of coupling agent is preferably used.This
Invent the concentration to coupling agent aqueous solution not specially require, under preferable case, described coupling agent solution
Concentration can be 0.05-1.5 weight %, more preferably 0.05-1 weight %.
Method and the condition of the long glass fibres of coupling agent treatment are not particularly limited by the present invention, can adopt
Carry out by the method for coupling agent treatment long glass fibres of the prior art.For example, it is possible to by long glass fibers
Dimension impregnates 30-60 minute in the silane coupler aqueous solution that concentration is 0.05-0.15 weight %, then exists
It is dried 3-5 hour under conditions of 80-90 DEG C.
According to the present invention, the long glass fibers that described long glass fibres can be known to the skilled person
Dimension, it is preferable that the tensile yield strength of described long glass fibres is 40-80 MPa, and stretch modulus is 5-10
Ji Pa, the length of monfil > 10 meters, fiber number is 0.5-1.0 denier, and fusing point is > 250 DEG C.
In the present invention, described antioxidant can be various antioxidant commonly used in the art, is not particularly limited.
Usually, described antioxidant can be the combination of primary antioxidant and auxiliary antioxidant, and wherein, described master resists
Oxygen agent has the function of capture polymer peroxy radical, can be hindered phenol system antioxidant；Described auxiliary
Antioxidant can effective hydroperoxides in decomposing copolymer, prevent its homolysis produce new free radical,
Cause the carrying out of Auto-oxidation reaction, such as, can be to resist selected from phosphite ester system antioxidant and monothioester system
One or more in oxygen agent.In the present invention, the example of described antioxidant can include but not limited to: 2,6-
Di-tert-butyl-4-methy phenol, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester,
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (that is, antioxidant 1010), sulfur
For diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethyl-2,4,6-three (3,5-
Di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine
-2,4,6 (1H, 3H, 5H)-triketones, three (2-methyl-4-hydroxyl-5-tert-butyl benzene) butane and 2,2 '-di-2-ethylhexylphosphine oxides
(4-methyl-6-tert-butylphenol).Specifically, the example of described auxiliary antioxidant can be but be not limited to:
Three [2,4-di-tert-butyl-phenyl] phosphite ester (that is, irgasfos 168), four (2,4-di-tert-butylphenol)-4,4 '-
Xenyl diphosphites, three nonylated phenyl phosphite esters, double (2,4-DI-tert-butylphenol compounds) Ji Wusi
The double octadecyl of alcohol diphosphites, thio-2 acid and dilauryl thiodipropionate.From further
The angle improving antioxygenic property is set out, and described antioxidant is preferably using described phenol system antioxidant as main anti-
Oxygen agent, using phosphite ester and/or monothioester as auxiliary antioxidant.Described primary antioxidant resists with described auxiliary
The ratio of oxygen agent can be the conventional selection of this area.Usually, described primary antioxidant resists with described auxiliary
The weight ratio of oxygen agent can be 1:0.5-2.The consumption of described antioxidant can be the conventional selection of this area,
Such as: relative to acrylic polymers described in 100 weight portions, the content of described antioxidant can be 0.01-0.8
Weight portion, preferably 0.2-0.4 weight portion.
According to the present invention, various can be used in that described antioxidant can be known to the skilled person gathers
The antioxidant of allyl resin, described antioxidant can be Hinered phenols antioxidant, phosphite ester kind antioxidant
With one or more in suffocated amine antioxidant；It is preferably Hinered phenols antioxidant and phosphorous acid esters resist
Oxygen agent.When described antioxidant is Hinered phenols antioxidant and phosphite ester kind antioxidant, although the present invention
The weight ratio of described Hinered phenols antioxidant and phosphite ester kind antioxidant is not specially required, preferably feelings
Under condition, the weight ratio of described Hinered phenols antioxidant and phosphite ester kind antioxidant is 0.25-1:1, enters one
Step is preferably 1:1-2.
According to the present invention, various can be used in that the described compatibility can be known to the skilled person gathers
The compatibility of allyl resin, as a rule, the described compatibility can be maleic anhydride inoculated polypropylene, horse
One or more in maleic anhydride grafted polyethylene and acrylic acid-grafted polypropylene, preferably maleic anhydride connect
Branch polypropylene.
According to the present invention, it is each that described maleic anhydride inoculated polypropylene can be known to the skilled person
Plant the maleic anhydride inoculated polypropylene of the compatilizer that can be used in acrylic resin, as a rule, described horse
The percent grafting of the maleic anhydride in maleic anhydride grafted polypropylene can be 1-5%, maleic anhydride grafting poly-third
Alkene is 2-15g/10min, preferably 6-10 at the melt mass flow rate of 230 DEG C, 2.16kg counterweight
g/10min。
According to the present invention, it is each that described maleic anhydride grafted polyethylene can be known to the skilled person
Plant the maleic anhydride grafted polyethylene of the compatilizer that can be used in polyvinyl resin, as a rule, described horse
The percent grafting of the maleic anhydride in maleic anhydride grafted polyethylene can be 1-5%, and maleic anhydride is grafted poly-second
Alkene is 2-15g/10min, preferably 6-10 at the melt mass flow rate of 230 DEG C, 2.16kg counterweight
g/10min。
According to the present invention, it is various that described acrylic acid-grafted polypropylene can be known to the skilled person
Can be used in the acrylic acid-grafted polypropylene of the compatilizer of acrylic resin, as a rule, described acrylic acid
Acrylic acid percent grafting in graft polypropylene can be 1-5%, acrylic acid-grafted polypropylene 230 DEG C,
The melt mass flow rate of 2.16kg counterweight is 2-15g/10min, preferably 6-10g/10min.
According to the present invention, blend composition after the extrusion connects with the coupling agent treatment long glass fibres through traction
After touch, obtain infiltrating the long glass fibres of blend composition.Well known to those skilled in the art, can be right
The long glass fibres of infiltration blend composition, by the product solidified molding after contact, pelletizing, makes long glass fibres
RPP.
According to the present invention, method and condition that the long glass fibres infiltrating blend composition carries out pelletizing are also this
Known in skilled person, it is for instance possible to use the long glass fibres of infiltration blend composition is carried out by pelleter
Pelletize.
Present invention also offers the long glass fiber reinforced polypropylene prepared by said method.
Hereinafter will be described the present invention by embodiment.
The method of testing related in following example and comparative example is as follows:
1, melt mass flow rate (MFR): carry out according to standard ASTM D1238-04；
2, content of glass fiber (glass fiber content): carry out according to standard ASTM D2584-02；
3, hot strength, elongation at break: carry out according to standard ASTM D638-08；
4, bending strength, bending modulus: carry out according to standard ASTM D790-07；
5, spiral arm beam impact strength (IZOD notch impact strength): according to standard ASTM D256-06
Carry out；
6, Rockwell hardness: carry out according to standard ASTM D785-08；
7, heat distortion temperature (1.82MPa): carry out according to standard ASTM D648-07；
8, molding shrinkage: carry out according to standard ASTM D955-08, test is being parallel and perpendicular to
Molding shrinkage on melt flows direction, is designated as M respectivelyParallelAnd MVertically。
9, the length testing of long glass fiber reinforced polypropylene composition article: by standard GB/T
9345.1-2008 is carried out, and the length of the long glass fibres of coupling agent treatment is complete with the ratio of the length of goods
The length of roving glass fiber and former composition article length ratio after burning.
10, percent grafting: use determination of acid-basetitration, the method for test is particularly as follows: precise purifies
After graft polymers sample about 0.5g, be dissolved in appropriate dimethylbenzene, backflow 15min after be cooled to
70 DEG C, the potassium hydroxide-ethanol being subsequently adding 0.1mol/L carries out saponification backflow, after 1h, then with phenolphthalein-
Thymolphthalein mixed indicator, while hot with the acetic acid-xylene solution back titration of 0.1mol/L to terminal.Connect
The computing formula of branch rate is:
Wherein, M is maleic anhydride molecule quality (98.06)；NHACDense for acetic acid-xylene solution
Degree (mol/L)；V0Volume (mL) by acetic acid-xylene solution consumed during blank titration；V is for containing
The volume (mL) of consumed acetic acid-xylene solution is titrated during product；W is the weight (g) of sample.
Embodiment 1
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof.
By the propylene homopolymer resins (melt mass flow rate is 45g/10min) of 100 weight portions, 4
(percent grafting is 2% to the polypropylene grafted maleic anhydride of weight portion, and melt mass flow rate is
8g/10min), the aryl phosphate ester aluminium salt of 0.06 weight portion, [β-(3, the 5-bis-tertiary fourths of 0.1 weight portion
Base-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, 0.2 weight portion three (2,4-di-tert-butyl-phenyl) sub-
Phosphate ester addition high-speed mixer is sufficiently mixed, obtains blend composition；Then toward the master of double screw extruder
Feeding device adds aforementioned blend composition, melts blend composition, and the temperature in each district of extruder is followed successively by
250 DEG C, 260 DEG C, 260 DEG C, 250 DEG C, obtain melt polypropylene impregnation liquid.
By long glass fibres, (tensile yield strength is 60 MPas, and stretch modulus is 8 lucky handkerchiefs, monfil
Length > 10 meters, fiber number is 0.8 denier, and fusing point is > 250 DEG C) 150g is at the silane coupled agent concentration of KH570
It is the aqueous solution of 0.8 weight % to impregnate 30 minutes, is then dried 4 hours in the baking oven of 80 DEG C, obtains
The long glass fibres of coupling agent treatment.
The long glass fibres impregnating through silane coupler KH570 and being dried is drawn, to hang down by up-coiler
Directly in cross-head direction by being arranged on the immersion slot of the head of extruder, make melted for 5000g third
Alkene melt impregnation liquid with traction after 150g long glass fibres contact in immersion slot 0.05 minute after cooling,
Pelletizing, makes glass fiber reinforced polypropylene goods.
Composition and the character of the glass fiber reinforced polypropylene of preparation illustrate in Table 1.
Comparative example 1
The method using embodiment 1 prepares long glass fiber reinforced polypropylene, except for the difference that, and polypropylene tree
The melt mass flow rate of fat is 30g/10min.Preparation glass fiber reinforced polypropylene composition and
Character illustrates in Table 1.
Comparative example 2
The method using embodiment 1 prepares long glass fiber reinforced polypropylene, except for the difference that, even through silane
Connection agent KH570 impregnate and the long glass fibres that is dried and blend composition add the master of double screw extruder in the lump
Feeding device melts.Composition and the character of the glass fiber reinforced polypropylene of preparation illustrate in Table 1.
Embodiment 2
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof
By the propylene homopolymer resins (melt mass flow rate is 100g/10min) of 100 weight portions, 5
(percent grafting is 2% to the polypropylene grafted maleic anhydride of weight portion, and melt mass flow rate is
8g/10min), [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane of 0.1 weight portion
Ester, three (2,4-di-tert-butyl-phenyl) phosphite ester of 0.2 weight portion, 0.2 weight portion thio-2 acid
Dilauryl addition high-speed mixer is sufficiently mixed, obtains blend composition；Then toward double screw extruder
Main feeding device adds aforementioned blend composition, melts blend composition, and the temperature in each district of extruder is followed successively by
250 DEG C, 260 DEG C, 260 DEG C, 250 DEG C, obtain glass impregnation liquid.
By the long glass fibres of 40 weight portions, (tensile yield strength is 60 MPas, and stretch modulus is 8 Jis
Handkerchief, the length of monfil > 10 meters, fiber number is 0.8 denier, and fusing point is > 250 DEG C) at KH570 silane
Coupling agent concentrations be 0.08 weight % aqueous solution in impregnate 30 minutes, then dry in the baking oven of 80 DEG C
Dry 4 hours.
The long glass fibres that traction impregnates through silane coupler KH570 and is dried, by melted blend composition
Contact in immersion slot 0.05 minute with the long glass fibres after traction, rear cooling, pelletizing, make glass
TRPP.Composition and the character of the glass fiber reinforced polypropylene of preparation illustrate in Table 1.
Embodiment 3
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof
By the propylene homopolymer resins (melt mass flow rate is 100g/10min) of 100 weight portions, 5
(percent grafting is 1.5% to the polypropylene grafted maleic anhydride of weight portion, and melt mass flow rate is
8g/10min), the aryl phosphate ester aluminium salt of 0.06 weight portion, [β-(3, the 5-bis-tertiary fourths of 0.1 weight portion
Base-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, 0.2 weight portion three (2,4-di-tert-butyl-phenyl) sub-
Phosphate ester and 0.2 weight portion dilauryl thiodipropionate addition high-speed mixer are sufficiently mixed, obtain
Blend composition；Then the main feeding device toward double screw extruder adds aforementioned blend composition, carries out blend composition
Melted, the temperature in each district of extruder is followed successively by 250 DEG C, 260 DEG C, 260 DEG C, 250 DEG C, obtains glass leaching
Stain liquid.
By the long glass fibres of 40 weight portions, (tensile yield strength is 60 MPas, and stretch modulus is 8 Jis
Handkerchief, the length of monfil > 10 meters, fiber number is 0.8 denier, and fusing point is > 250 DEG C) at KH570 silane
Coupling agent concentrations be 0.08 weight % aqueous solution in impregnate 30 minutes, then dry in the baking oven of 80 DEG C
Dry 4 hours.
The long glass fibres that traction impregnates through silane coupler KH570 and is dried, by melted blend composition
Contact in immersion slot 0.05 minute with the long glass fibres after traction, rear cooling, pelletizing, make glass
TRPP.Composition and the character of the glass fiber reinforced polypropylene of preparation illustrate in Table 1.
Embodiment 4
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof
By the Noblen (melt mass flow rate is 200g/10min) of 100 weight portions, 5 weights
(percent grafting is 1.5% to the polypropylene grafted maleic anhydride of amount part, and melt mass flow rate is
10g/10min), [β-(the tertiary fourth of 3,5-bis-of the aryl phosphate ester aluminium salt of 0.05 weight portion, 0.1 weight portion
Base-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, 0.2 weight portion three (2,4-di-tert-butyl-phenyl) sub-
Phosphate ester addition high-speed mixer is sufficiently mixed, obtains blend composition；Then the master of double screw extruder
Feeding device adds aforementioned blend composition, extruder feed zone, compressional zone, melting zone, the temperature of homogenization zone
It is followed successively by 250 DEG C, 260 DEG C, 260 DEG C, 250 DEG C, obtains the blend composition melted.Traction is through silane coupled
The long glass fibres that agent KH560 impregnates and is dried, by the long glass fibers after melted blend composition and traction
Dimension cools down after contacting 0.05 minute in immersion slot, pelletizing, makes glass fiber reinforced polypropylene.Preparation
Glass fiber reinforced polypropylene composition and character illustrate in Table 1.
Embodiment 5
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof
By the propylene homopolymer resins (melt mass flow rate is 200g/10min) of 100 weight portions, 5
(percent grafting is 2% to the polypropylene grafted maleic anhydride of weight portion, and melt mass flow rate is
8g/10min), [β-(the 3,5-di-t-butyl of the aryl phosphate ester aluminium salt of 0.06 weight portion, 0.1 weight portion
-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphorous of 0.2 weight portion
Being sufficiently mixed in acid esters addition high-speed mixer, obtain blend composition, wherein the weight of acrylic resin is
5000g；Then the main feeding device toward double screw extruder adds aforementioned blend composition, carries out blend composition
Melted, the temperature in each district of extruder is followed successively by 250 DEG C, 260 DEG C, 260 DEG C, 250 DEG C, obtains glass leaching
Stain liquid.
By the long glass fibres of 50 weight portions, (tensile yield strength is 60 MPas, and stretch modulus is 8 Jis
Handkerchief, the length of monfil > 10 meters, fiber number is 0.8 denier, and fusing point is > 250 DEG C) at KH550 silane
Coupling agent concentrations be 0.08 weight % aqueous solution in impregnate 30 minutes, then dry in the baking oven of 80 DEG C
Dry 4 hours.
The long glass fibres that traction impregnates through Silane coupling agent KH550 and is dried, by melted blend composition
Contact in immersion slot 0.05 minute with the long glass fibres after traction, rear cooling, pelletizing, make glass
TRPP.Composition and the character of the glass fiber reinforced polypropylene of preparation illustrate in Table 1.
Embodiment 6
Long glass fiber reinforced polypropylene that this embodiment provides for the present invention is described and preparation method thereof
By the Noblen (melt mass flow rate is 300g/10min) of 100 weight portions, 5 weights
Amount part polypropylene grafted maleic anhydride (percent grafting is 2%, and melt mass flow rate is 8g/10min),
The aryl phosphate ester aluminium salt of 0.06 weight portion, [β-(the 3,5-di-tert-butyl-hydroxy phenyl) of 0.1 weight portion
Propanoic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphite ester of 0.2 weight portion add at a high speed
Mixer is sufficiently mixed, obtains blend composition；Then before the main feeding device at double screw extruder adds
State blend composition, extruder feed zone, compressional zone, melting zone, the temperature of homogenization zone be followed successively by 250 DEG C,
260 DEG C, 260 DEG C, 250 DEG C, obtain the blend composition melted.Draw and impregnate through Silane coupling agent KH550
And be dried long glass fibres, by melted blend composition with draw after long glass fibres connect in immersion slot
Touch 0.05 minute, rear cooling, pelletizing, make glass fiber reinforced polypropylene.The glass fibre of preparation increases
Strong polyacrylic composition and character illustrate in Table 1.
Embodiment 7
The method using embodiment 1 identical prepares long glass fiber reinforced polypropylene, except for the difference that, is blended
Material is added without nucleator.
Embodiment 8
The identical method of embodiment 1 is used to prepare long glass fiber reinforced polypropylene compositions, except for the difference that,
Coupling agent in blend composition is KH560.
Table 1
Continued 1
From the data of table 1, long glass fiber reinforced polypropylene compositions system prepared by the inventive method
The length of coupling agent treatment long glass fibres in product and the length of goods birds of the same feather flock together third than prior art same
The length of the glass fibre in alkene goods and the length of goods are than big, and good combination property.
Claims (17)
1. the preparation method of a long glass fiber reinforced polypropylene, it is characterised in that the method includes
Long glass fibres with the coupling agent treatment through traction after blend composition mix homogeneously, melted, extrusion is connect
Touch, or by after blend composition mix homogeneously, melted, extrusion be in traction state through coupling agent treatment
Long glass fibres contact, will contact after product solidified molding, described blend composition contain acrylic resin,
Antioxidant and compatilizer, described acrylic resin melting at 230 DEG C, under the effect of 2.16kg counterweight
Weight flow rate is 35-320g/10min, in described blend composition, relative to 100 weight portions
Acrylic resin, the consumption of described antioxidant be 0.1-0.8 weight portion, the consumption of described compatilizer be 2-8
Weight portion；The long glass fibres of described coupling agent treatment is 1:1.3-3.3 with the weight ratio of described blend composition.
Method the most according to claim 1, wherein, in described blend composition, relative to 100
The acrylic resin of weight portion, the consumption of described antioxidant is 0.2-0.4 weight portion, described compatilizer
Consumption is 4-5 weight portion；Described coupling agent treatment long glass fibres is 1 with the weight ratio of described blend composition:
1.6-2.5。
Method the most according to claim 1, wherein, described melting is carried out in an extruder, institute
State the feed zone of extruder, compressional zone, melting zone, the temperature of homogenization zone be respectively 230-280 DEG C,
240-290 DEG C, 240-290 DEG C, 230-280 DEG C, the vacuum of each section is 0.02 to 0.09 MPa.
Method the most according to claim 1, wherein, described acrylic resin at 230 DEG C,
The melt mass flow rate of the melt mass flow rate under the effect of 2.16kg counterweight is
45-300g/10min。
Method the most according to claim 1 and 2, wherein, possibly together with nucleation in described blend composition
Agent, relative to the acrylic resin of 100 weight portions, the consumption of described nucleator is 0.02-1.2 weight portion；
Described nucleator selected from dibenzoic acid aluminum, 2,2 '-methylene-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphate and
In aryl phosphate ester aluminium salt one or more.
Method the most according to claim 5, wherein, possibly together with nucleator in described blend composition,
Relative to the acrylic resin of 100 weight portions, the consumption of described nucleator is 0.05-0.07 weight portion；
Described nucleator is aryl phosphate ester aluminium salt.
Method the most according to claim 1, wherein, the long glass fibres of described coupling agent treatment
By long glass fibres is impregnated in the silane coupler aqueous solution that concentration is 0.05-1.5 weight %
30-60 minute, then it is dried under conditions of 80-90 DEG C and obtains for 3-5 hour.
8. according to the method described in claim 1 or 7, wherein, described coupling agent be silane coupler,
One or more in titanate coupling agent and aluminate coupling agent.
Method the most according to claim 8, wherein, described coupling agent is γ-(methacryl
Oxygen) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and γ-(2,3-epoxy the third oxygen) propyl group
One or more in trimethoxy silane.
Method the most according to claim 1, wherein, described coupling agent is with concentration range as 0.05-1.5
The coupling agent solution of weight % uses.
11. methods according to claim 10, wherein, described coupling agent is with concentration range as 0.05-1
The coupling agent solution of weight % uses.
12. methods according to claim 1 and 2, wherein, described antioxidant is selected from Hinered phenols
One or more in antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant.
13. methods according to claim 12, wherein, described antioxidant is Hinered phenols antioxygen
Agent and phosphite ester kind antioxidant.
14. according to the method described in claim 1,2 or 7, wherein, drawing of described long glass fibres
Stretching yield strength and be 40-80 MPa, stretch modulus is 5-10 Ji handkerchief, the length of monfil > 10 meters,
Fiber number is 0.5-1.0 denier, and fusing point is > 250 DEG C.
15. methods according to claim 1 and 2, wherein, described compatilizer is selected from maleic anhydride
One or more in graft polypropylene, maleic anhydride grafted polyethylene and acrylic acid-grafted polypropylene.
16. methods according to claim 15, wherein, described compatilizer is maleic anhydride grafting
Polypropylene.
The long glass fibres that 17. are prepared by method described in any one in claim 1-16 strengthens poly-third
Alkene.
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Effective date of registration: 20170222 Address after: 100029 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum Chemical Co Patentee after: Beijing Yanshan Petrochemical High-Tech Technology Co., Ltd Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petroleum Chemical Co |