CN109467809A - Continuous glass fiber reinforced polypropylene unidirectional prepreg tape and preparation method thereof - Google Patents
Continuous glass fiber reinforced polypropylene unidirectional prepreg tape and preparation method thereof Download PDFInfo
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- CN109467809A CN109467809A CN201811227979.0A CN201811227979A CN109467809A CN 109467809 A CN109467809 A CN 109467809A CN 201811227979 A CN201811227979 A CN 201811227979A CN 109467809 A CN109467809 A CN 109467809A
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- continuous glass
- polypropylene
- fiber reinforced
- glass fibre
- glass fiber
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 124
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 80
- -1 polypropylene Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000007598 dipping method Methods 0.000 claims abstract description 28
- 229920000554 ionomer Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000004804 winding Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000003490 calendering Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 9
- NNAZWLXQGXBKHL-UHFFFAOYSA-N [Zn].O=C1OC(=O)C=C1 Chemical compound [Zn].O=C1OC(=O)C=C1 NNAZWLXQGXBKHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 230000008901 benefit Effects 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 240000002853 Nelumbo nucifera Species 0.000 description 5
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 5
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000009881 electrostatic interaction Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 208000026726 vitreous disease Diseases 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- HJSYJHHRQVHHMQ-ODZAUARKSA-L zinc;(z)-but-2-enedioate Chemical compound [Zn+2].[O-]C(=O)\C=C/C([O-])=O HJSYJHHRQVHHMQ-ODZAUARKSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
Abstract
The invention discloses a kind of preparation methods of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, comprising: 1) is uniformly mixed polypropylene, polypropylene-base ionomer and antioxidant, heating melting obtains melt blend；2) continuous glass fibre is drawn by creel, flattens, subsequently into charger, makes charge opposite with the polymer chain of polypropylene-base ionomer on continuous glass fibre band；3) melt blend, rubbing dipping, calendering dipping, cooling and shaping, winding are coated on the continuous glass fibre handled through step 2).The invention also discloses continuous glass fiber reinforced polypropylene unidirectional prepreg tapes made from the above method.Products of the present invention have the characteristics that polypropylene to continuous glass fibre dipping sufficiently, porosity is low, interface cohesion is good, excellent in mechanical performance and in following process and use process without small molecule volatile matter discharge, can be used for the fields such as continuous fiber reinforced polypropylene sheet material, plate and special-shaped structure piece.
Description
Technical field
The invention belongs to continuous fiber reinforced thermoplastic composite material technical field more particularly to a kind of continuous glass fibres
Reinforced polypropylene unidirectional prepreg tape and preparation method thereof.
Background technique
Continuous fiber reinforced thermoplastic composite material have high comprehensive performance, do not occur in process chemical reaction,
Short molding cycle, preimpregnation material is limited without storage condition, easy to use, wide using temperature, water absorption rate is low, simplifies the molding of component
Process procedure, manufacturing cost are low, the outstanding advantages such as recycling and emission reduction environmental protection can be recycled in waste material, have obtained full generation rapidly
The approval in boundary market.Continuous fiber reinforced thermoplastic composite material can substitute many materials, as die casting, assembled metal part,
Conventional plastic in market, including industrial equipment, automobile, the consumer goods etc..In addition, the advantage continuous fiber reinforcement thermoplastic of cost performance
Property composite material is more attractive in aerospace and national defence, communications and transportation, electric and electronic industry.
Thermoplasticity unidirectional prepreg tape is to impregnate the one-way tape that unidirectional continuous fiber is formed with thermoplastic resin, these are unidirectional pre-
Leaching band forms again at high temperature, may finally prepare the thermoplastic composite product of continuous fiber reinforcement.Prepreg tape preparation
In the process, the thermoplastic resin of high melt viscosity is most important to the performance of final products to the pre-preg of continuous fiber.Application
Number for 200810201216.9 patent application by extruder fusion plastification thermoplastic resin, then by the thermoplasticity of molten state
Resin completes pre-preg of the resins to continuous fiber by staggeredly double extrusion dies of special designing, then again by dip roll into
The scheme of continuous fiber reinforced thermoplastic composite material prepreg is obtained after one step dipping, chill roll are cooling.However, special designing
Die head it is complicated, wherein being easy to exist to be easy to cause melt to thermally decompose at dead angle, and continued access is relatively more tired after fibrous fracture
Difficulty causes the fluctuation of continuous fiber thermoplastic prepreg fiber content larger, to influence properties of product, reduces the general of equipment
Property.To avoid the above problem, application No. is 201710120299.8 patent application meters to be smeared by level-one application device, second level
Device, three-level application device and the multistage parallel interaction application device of level Four application device composition, realize macromolecule melt die head
Outer direct application process implements molten state thermoplastic resin to continuous fiber and dipping.But this multistage parallel interaction applies
It is complicated to smear device composed structure, increases the difficulty of composite material prepreg manufacture craft.Application No. is 201610806836.X
Patent application thermoplastic resin is extruded by semi-vitreous strand using melt spinning method, and vertically drop down onto pretreated
Continuous fiber surface, then strand is evenly arranged between continuous fiber in parallel by bonding roller effect, it infiltrates, completes by hot pressing
The infiltration that thermoplastic resin continuously infiltrates fiber.But spinning technique is more complicated compared to direct melting extrusion technique, in addition,
How control accurate semi-molten state strand is evenly arranged between reinforcing fiber in parallel, and is difficult the technical issues of solving.For from
Thermoplastic melt viscosity height is fundamentally solved, resin is sufficiently impregnated the problem of fiber difficulty, application No. is
201711316721.3 patent application also proposed powdery resin elder generation pre-preg continuous fiber, then remelted, roll-in is multiple
The technology of conjunction.But the range of choice of the thermoplastic resin for being applicable in the technology is restricted, and is such as only applicable to polyaryl ether
Ketone, polyaryletherketone ketone, aromatic polyetherimide；Polyarylsufone, polyarylene sulfide, aromatic polyamide, e pioic acid methyl ester, fluorination
Polymer.This is because most of common thermoplastic resin be all exist in the form of a particle, and particle toughness it is higher, from granular
It is machined to powdered, process is complicated, and cost is very high, therefore the technology is also difficult becomes general technology.In addition, application No. is
201410198628.7 patent application, which is disclosed, carries out pre-preg to continuous fiber using the suspension of thermoplastic resin, however
Material after dipping needs further to remove moisture therein, and technique is more complicated, if moisture removal is not thorough, remaining water
Divide and vaporized during the later period, hot pressing was compound, stomata easy to form deteriorates the performance of composite material.
Corona charging is that the corona discharge of air partial breakdown is caused to generate ion beam bombardment sample using a uniform electric field
Product, and make charge deposition in sample.The electrode of corona charging is usually that pin electrode charging or needle end are located at same level
The multistylus electrode of interior array distribution charges.The principle of corona charging is as shown in Figure 2.Add usually between ordinary electrode and needle electrode
Number kilovoltage, is allowed to that corona discharge occurs, this corona field is to the particle excitated generation charge of air gap, and charge deposition is in the table of sample
Face or near surface, to make surface charge and volume charge certain on sample band.Because corona charging apparatus is simple, operation side
Just, the features such as charge efficiency is high and distribution of charges is uniform, is widely used in production and processing.
Summary of the invention
Goal of the invention: providing that a kind of porosity is low, and the continuous glass fiber reinforced polypropylene of better mechanical property is unidirectionally pre-
Soak band.
Simple and easy above-mentioned continuous glass fiber reinforced polypropylene list is prepared it is a further object of the present invention to provide a kind of
To the method for prepreg tape.
Technical solution: the present invention provides a kind of preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, packet
Include following steps:
1) polypropylene, polypropylene-base ionomer and antioxidant are uniformly mixed, heating melting obtains melt blend；
2) continuous glass fibre is drawn by creel, flattens, subsequently into charger, makes continuous glass fibre band
The upper charge opposite with the polymer chain of the polypropylene-base ionomer；
3) coating step 1 on the continuous glass fibre handled through step 2)) made from the melt blend, rubbing leaching
Stain, calendering dipping, cooling and shaping, winding obtain the continuous glass fiber reinforced polypropylene unidirectional prepreg tape.
In step 1), polyacrylic 20~80g/10min of melt index；Polypropylene-base ionomer is polypropylene grafted Malaysia
(preparation of polypropylene grafted maleic anhydride zinc is referring to Master's thesis: Yuan Xianpei, polypropylene grafted MALEIC ACID, ZINC SALT ionomer for acid anhydrides zinc
Preparation and the research of modified polypropene/nylon-6 co-mixing system, master thesis, Dalian Polytechnic University, 2010, the 23rd
Page)；Antioxidant is antioxidant 1010；The mass ratio of polypropylene, polypropylene-base ionomer and antioxidant is 20~30: 1~5:
0.03~0.07.
In step 1), after mixing by polypropylene, polypropylene-base ionomer and antioxidant, heated by extruder molten
Melt, squeeze out, obtains melt blend；Extruder is double screw extruder, draw ratio 44, and extruder heating melting squeezes out
Temperature is 170 DEG C~190 DEG C, engine speed 500r/min~800r/min of the extruder, the vacuum of extruder exhaust section
Degree >=0.05MP.
In step 2), enter charger before, further include the continuous glass fibre is preheated to 180 DEG C~
200 DEG C of the step of；To 2~8m/min of hauling speed of continuous glass fibre；To guarantee that it is more that continuous glass fibre can take
Charge applies charger to improve melt blend to the impregnating speed and wetting capacity of continuous glass fibre
Voltage be 15kV~100kV, and make continuous glass fibre 1~2cm at a distance from the pin electrode of charger, continuously
The time that glass fibre charges in charger is 0.5~2min；It is opposite with polypropylene-base ionomer polymer chain
Charge is positive charge.
In step 3), to 8~12m/min of hauling speed of continuous glass fibre；In the continuous glass handled through step 2)
Coating step 1 on fiber) made from melt blend method particularly includes: step 1) is obtained into melt blend and is applied to applicator roll
Surface, draw the continuous glass fibre that handle through step 2) across the gap of applicator roll and pressing roller, impregnate compound；It applies
The temperature for covering roller and pressing roller is respectively 170 DEG C~190 DEG C, and the pressure of pressing roller is 2~5MPa (between applicator roll and pressing roller
Gap setting be continuous glass fibre can be made to pass through, and be applied to pressing roller on continuous glass fibre pressure 2~
5MPa)；Rubbing dipping is implemented by crumpling roller, and the temperature for crumpling roller is 170 DEG C~190 DEG C；Calendering dipping is to pass through pressure
Prolong roller implementation, the temperature of stack is 170 DEG C~190 DEG C, and the surface of 2~5MPa of pressure, stack are contacted with ground line, with
Eliminate continuous glass fibre electrostatic remained on surface；Cooling and shaping is implemented by chill roll, the temperature 20 of chill roll
DEG C~50 DEG C, 1~2MPa of pressure；Winding is implemented by wind-up roll.
Another aspect of the present invention provides a kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, wraps by weight
Include following components: 20~30 parts of polypropylene, 70~80 parts of glass fibre, 1~5 part of polypropylene grafted maleic anhydride zinc, antioxidant
0.03~0.07 part, which is made by above-mentioned preparation method.
It is a feature of the present invention that being filled before coating melt blend to continuous glass fibre surface by corona charging
It sets and deposits positive charge on the surface of continuous glass fibre monofilament.When the continuous glass fibre that surface is deposited with positive charge enters coating
The gap of roller and pressing roller, with pre-preg, compound tense in melt blend, molecular backbone is negatively charged in melt blend
From aggressiveness under the action of electrostatic attraction, penetrate between the monofilament of continuous glass fibre.Due to the molecular backbone structure of ionomer
It is fully compatible for the acrylic resin in polypropylene, with mixture, under the action of polypropylene-base ionomer, substantially increase poly-
Allyl resin is to the impregnating speed and wetting capacity of continuous glass fibre, and final realization melt polypropylene is to continuous glass fibre
It is sufficiently impregnated.
The utility model has the advantages that the present invention uses polypropylene-base ionomer blended and modified polypropylene, the melt mixed made first
Contain the polyacrylic polymer chain with certain negative electrical charge in object, is dipping object with the melt blend, is dipped through corona and fills
Electricity has the continuous glass fibre of electrostatic charge opposite with polypropylene-base ionomer polymer chain, is polymerize using polypropylene-base ionomer
Strong electrostatic interaction between object chain and continuous glass fibre realizes abundant leaching of the melt polypropylene to continuous glass fibre
Stain prepares high-performance continuous glass fiber reinforced polypropylene unidirectional prepreg tape.In terms of existing technologies, the present invention is based on molten
Melt impregnation technology and prepare polypropylene unidirectional prepreg tape, the more existing powder infusion of technique, suspension dipping are more simple.It is melted with existing
Melt dipping technique to compare, has the advantage that (1) in melt polypropylene and continuous glass fibre pre-preg compound tense, the present invention
Without special extrusion die or coating mechanism, simple applicator roll is used only, so that it may complete melt polypropylene and continuous glass
The pre-preg of glass fiber, impregnation technology and production operation are more simple；(2) present invention utilizes the polymer of polypropylene-base ionomer
Electrostatic interaction between chain and continuous glass fibre surface improves melt polypropylene to the dipping energy of continuous glass fibre
Power, with by fiberglass surfacing coat small molecule coupling agent improve resin compared with the prior art of fiber impregnation ability,
During the preparation process, the problem of decomposing there is no the small molecule coupling agent because of the excessively high generation of temperature, influence dipping effect, in addition,
The problem of small molecule coupling agent pyrolytic is not present because of prepreg tape product of the invention, so in post-production and use process
It is middle to be generated without toxic volatile matter, it is more environmentally-friendly.(3) the present invention is based on the polymer chain of polypropylene-base ionomer and oppositely chargeds
Continuous glass fibre between electrostatic interaction, realize the abundant good leaching that increases to continuous glass fibre of melt polypropylene
Van der Waals force improves polymer melt pair between stain, with coupling agent and polymer melt of the prior art based on fiberglass surfacing
The impregnability of glass fibre is compared, and electrostatic interactions are stronger, and effect is rapider, therefore, compared with prior art, this hair
Bright polypropylene is more abundant to the dipping of continuous glass fibre, pickling efficiency is high, and the production efficiency of prepreg tape product is higher.(4)
Continuous glass fiber reinforced polypropylene unidirectional prepreg tape prepared by the present invention have polypropylene to continuous glass fibre dipping sufficiently,
Porosity is low, interface cohesion is good, excellent in mechanical performance and in following process and use process without small molecule volatile matter discharge
The features such as, the continuous glass fiber reinforced polypropylene unidirectional prepreg tape can be used for continuous fiber reinforced polypropylene sheet material, plate with
And the fields such as special-shaped structure piece.
Detailed description of the invention
Fig. 1 is the preparation system schematic diagram of continuous glass fiber reinforced polypropylene unidirectional prepreg tape；
Fig. 2 is the schematic illustration of corona charging.
Specific embodiment
As shown in Figure 1, the preparation system of continuous glass fiber reinforced polypropylene unidirectional prepreg tape includes creel 1, exhibition yarn dress
Set 2, baking oven 3, charger 4, double screw extruder 5, applicator roll 6, pressing roller 7, rubbing roller group 8, stack 9, cooling
Roller 10 and wind-up roll 11, wherein creel 1, exhibition yarn feeding device 2, baking oven 3, charger 4, applicator roll 6, pressing roller 7, rubbing
Roller group 8, stack 9, chill roll 10 and wind-up roll 11 are successively disposed adjacent, double screw extruder 5 be arranged in applicator roll 6 it is oblique on
Side, applicator roll 6 are vertically arranged with pressing roller 7, and wherein pressing roller 7 is located at the lower section of applicator roll 6.
In Fig. 2, each appended drawing reference is respectively pin electrode 12, positive charge 13, sample 14 and grounding electrode 15.
Embodiment 1
A kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, is prepared as follows completion:
(1) polypropylene, the 5 parts by weight of polypropylene grafted maleic anhydride zinc for being 80g/10min by 20 parts by weight melt index
Uniform with 0.03 parts by weight antioxidant 1010 mixed at high speed, it is 44,170 DEG C of extrusion temperature, engine speed that draw ratio in Fig. 1, which is added,
Uniformly, obtained polypropylene-base melt blend is squeezed out to constant temperature 170 for mixing plasticizing in the double screw extruder 5 of 500r/min
DEG C applicator roll 6 surface；
(2) by the continuous glass fibre of 80 parts by weight by creel 1 with the speed drawing of 6m/min, will by exhibition yarn feeding device 2
Continuous glass fibre flatten to after planar, continue traction plane shape continuous glass fibre pass through constant temperature to 180 DEG C baking oven 3 it is pre-
Heat is to 180 DEG C, then the charger 4 that traction plane shape continuous glass fibre is 100KV through overvoltage, fills in corona charging
In setting, the distance of the pin electrode (anode) of continuous glass fibre plan range charger is 2cm, on continuous glass fibre
Point by charger 4 charging time be 2min, become positively charged lotus；
(3) the planar continuous glass fibre after charging is drawn across temperature is 170 DEG C of applicator rolls 6 and pressing roller 7
Interface, the pressure 4MPa of pressing roller 7 make continuous glass fibre impregnate with polypropylene-base melt blend, is compound, using temperature
For the further dipping, compound of 180 DEG C of rubbing roller groups 8, continue to draw to the stack 9 that temperature is 180 DEG C, pressure is 4MPa into
One step roll-in dipping after eliminating electrostatic, continues the chill roll 10 drawn to temperature is 30 DEG C, pressure is 1.5MPa, final molding,
Winding, prepared continuous glass fiber reinforced polypropylene unidirectional prepreg tape porosity 0.058%.
Embodiment 2
A kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, is prepared as follows completion:
It (1) is the polypropylene of 20g/10min, 1 part of polypropylene grafted maleic anhydride zinc and 0.07 part by 30 parts of melt index
Antioxidant 1010 mixed at high speed is uniform, and pair that draw ratio in Fig. 1 is 44,190 DEG C of extrusion temperature, engine speed 800r/min is added
Uniformly, obtained polypropylene-base melt blend is squeezed out to 190 DEG C of constant temperature of applicator roll 6 for mixing plasticizing in screw extruder 5
Surface；
(2) by 70 parts of continuous glass fibre by creel 1 with the speed drawing of 8m/min, will be continuous by exhibition yarn feeding device 2
Glass fibre is flattened to the baking oven 3 for after planar, continuing traction plane shape continuous glass fibre and passing through constant temperature to 200 DEG C and is preheated to
200 DEG C, then the charger 4 that traction plane shape continuous glass fibre is 15KV through overvoltage, in charger,
The distance of the pin electrode (anode) of continuous glass fibre plan range charger is 1cm, the point on continuous glass fibre
Time by the charging of charger 4 is 1min, and become positively charged lotus；
(3) the planar continuous glass fibre after charging is drawn across temperature is 190 DEG C of applicator rolls 6 and pressing roller 7
Interface, the pressure 3MPa of pressing roller 7 make continuous glass fibre impregnate with polypropylene-base melt blend, is compound, using temperature
For the further dipping, compound of 190 DEG C of rubbing roller groups 8, continue to draw to the stack 9 that temperature is 190 DEG C, pressure is 5MPa into
One step roll-in dipping after eliminating electrostatic, continues the chill roll 10 drawn to temperature is 20 DEG C, pressure is 2MPa, final molding, receipts
Volume, prepared continuous glass fiber reinforced polypropylene unidirectional prepreg tape porosity 0.04%.
Embodiment 3
A kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, is prepared as follows completion:
It (1) is the polypropylene of 50g/10min, 3 parts of polypropylene grafted maleic anhydride zinc and 0.05 part by 25 parts of melt index
Antioxidant 1010 mixed at high speed is uniform, and pair that draw ratio in Fig. 1 is 44,180 DEG C of extrusion temperature, engine speed 650r/min is added
Uniformly, obtained polypropylene-base melt blend is squeezed out to 185 DEG C of constant temperature of applicator roll 6 for mixing plasticizing in screw extruder 5
Surface；
(2) by 60 parts of continuous glass fibre by creel 1 with the speed drawing of 4m/min, will be continuous by exhibition yarn feeding device 2
Glass fibre is flattened to the baking oven 3 for after planar, continuing traction plane shape continuous glass fibre and passing through constant temperature to 190 DEG C and is preheated to
190 DEG C, then the charger 4 that traction plane shape continuous glass fibre is 57.5KV through overvoltage, in charger
In, the distance of the pin electrode (anode) of continuous glass fibre plan range charger is 1.5cm, on continuous glass fibre
Point by charger 4 charging time be 2min, become positively charged lotus；
(3) the planar continuous glass fibre after charging is drawn across temperature is 185 DEG C of applicator rolls 6 and pressing roller 7
Interface, the pressure of pressing roller 7 are 5MPa, so that continuous glass fibre is impregnated with polypropylene-base melt blend, is compound, using temperature
The rubbing roller group 8 that degree is 185 DEG C further impregnates, is compound, continues the calendering drawn to temperature is 180 DEG C, pressure is 3.5MPa
The further roll-in of roller 9 dipping after eliminating electrostatic, continues the chill roll 10 drawn to temperature is 35 DEG C, pressure is 1.5MPa, finally
Molding, winding, prepared continuous glass fiber reinforced polypropylene unidirectional prepreg tape porosity 0.05%.
Embodiment 4
A kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, is prepared as follows completion:
It (1) is the polypropylene of 70g/10min, 4 parts of polypropylene grafted maleic anhydride zinc and 0.06 part by 28 parts of melt index
Antioxidant 1010 mixed at high speed is uniform, and pair that draw ratio in Fig. 1 is 44,185 DEG C of extrusion temperature, engine speed 700r/min is added
Uniformly, obtained polypropylene-base melt blend is squeezed out to 190 DEG C of constant temperature of applicator roll 6 for mixing plasticizing in screw extruder 5
Surface；
(2) by 78 parts of continuous glass fibre by creel 1 with the speed drawing of 6m/min, will be continuous by exhibition yarn feeding device 2
Glass fibre is flattened to the baking oven 3 for after planar, continuing traction plane shape continuous glass fibre and passing through constant temperature to 195 DEG C and is preheated to
195 DEG C, then the charger 4 that traction plane shape continuous glass fibre is 80KV through overvoltage, in charger,
The distance of the pin electrode (anode) of continuous glass fibre plan range charger is 1.8cm, on continuous glass fibre
Time of the point by the charging of charger 4 is 1.5min, and become positively charged lotus；
(3) the planar continuous glass fibre after charging is drawn across temperature is 190 DEG C of applicator rolls 6 and pressing roller 7
Interface, the pressure of pressing roller 7 are 4MPa, with polypropylene-base melt blend dipping, compound, the stranding for being 185 DEG C using temperature
It rubs roller group 8 further impregnate, is compound, continues the further roll-in of stack 9 leaching drawn to temperature is 185 DEG C, pressure is 4MPa
Stain after eliminating electrostatic, continues the chill roll 10 drawn to temperature is 40 DEG C, pressure is 2MPa, final molding, winding are prepared
Continuous glass fiber reinforced polypropylene unidirectional prepreg tape porosity 0.055%.
Embodiment 5
A kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, is prepared as follows completion:
It (1) is the polypropylene of 30g/10min, 4 parts of polypropylene grafted maleic anhydride zinc and 0.04 part by 23 parts of melt index
Antioxidant 1010 mixed at high speed is uniform, and pair that draw ratio in Fig. 1 is 44,175 DEG C of extrusion temperature, engine speed 600r/min is added
Uniformly, obtained polypropylene-base melt blend is squeezed out to 175 DEG C of constant temperature of applicator roll 6 for mixing plasticizing in screw extruder 5
Surface；
(2) by 73 parts of continuous glass fibre by creel 1 with the speed drawing of 8m/min, will be continuous by exhibition yarn feeding device 2
Glass fibre is flattened to the baking oven 3 for after planar, continuing traction plane shape continuous glass fibre and passing through constant temperature to 185 DEG C and is preheated to
185 DEG C, then the charger 4 that traction plane shape continuous glass fibre is 30KV through overvoltage, in charger,
The distance of the pin electrode (anode) of continuous glass fibre plan range charger is 1.2cm, on continuous glass fibre
Time of the point by the charging of charger 4 is 2min, and become positively charged lotus；
(3) the planar continuous glass fibre after charging is drawn across temperature is 175 DEG C of applicator rolls 6 and pressing roller 7
Interface, the pressure of pressing roller 7 are 5MPa, with polypropylene-base melt blend dipping, compound, the stranding for being 175 DEG C using temperature
It rubs roller group 8 further impregnate, is compound, continues the further roll-in of stack 9 drawn to temperature is 175 DEG C, pressure is 2.5MPa
Dipping after eliminating electrostatic, continues the chill roll 10 drawn to temperature is 25 DEG C, pressure is 1.2MPa, final molding, winding, institute
The porosity 0.057% of the continuous glass fiber reinforced polypropylene unidirectional prepreg tape of preparation.
Continuous glass fiber reinforced polypropylene unidirectional prepreg tape in the various embodiments described above is reduced into obtain standard batten, is carried out
Tensile strength test, the standard of test are ASTM-D638, and every group is at least tested 10 battens, are averaged, test result such as table
Shown in 1.
The mechanical property of continuous glass fiber reinforced polypropylene unidirectional prepreg tape prepared by each embodiment of table 1
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, which is characterized in that the preparation method packet
Include following steps:
1) polypropylene, polypropylene-base ionomer and antioxidant are uniformly mixed, heating melting obtains melt blend；
2) continuous glass fibre is drawn by creel, flatten, subsequently into charger, make on continuous glass fibre band with
The opposite charge of the polymer chain of the polypropylene-base ionomer；
3) coating step 1 on the continuous glass fibre handled through step 2)) made from the melt blend, rubbing dipping,
Calendering dipping, cooling and shaping, winding obtain the continuous glass fiber reinforced polypropylene unidirectional prepreg tape.
2. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In, in step 1), the polyacrylic 20~80g/10min of melt index；The polypropylene-base ionomer is polypropylene grafted
Maleic anhydride zinc；The antioxidant is antioxidant 1010；The mass ratio of the polypropylene, polypropylene-base ionomer and antioxidant is
20~30: 1~5: 0.03~0.07.
3. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In, in step 1), after mixing by polypropylene, polypropylene-base ionomer and antioxidant, by extruder heating melting, squeeze
Out, the melt blend is obtained；The extruder is double screw extruder, the extruder heating melting, the temperature of extrusion
It is 170 DEG C~190 DEG C, engine speed 500r/min~800r/min of the extruder.
4. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In, in step 2), enter charger before, further include that the continuous glass fibre is preheated to 180 DEG C~200 DEG C
Step.
5. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In in step 2) and step 3), to 2~8m/min of hauling speed of the continuous glass fibre.
6. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In in step 2), the voltage of the charger is 15kV~100kV, and the continuous glass fibre is filled with the corona
The distance of the pin electrode of electric installation is 1~2cm, and the time charged in the charger is 0.5~2min, and described
The opposite charge of polypropylene-base ionomer polymer chain is positive charge.
7. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In in step 3), the coating step 1 on the continuous glass fibre handled through step 2)) made from the melt blend
Method particularly includes: step 1) is obtained into the surface that melt blend is applied to applicator roll, draws the continuous glass handled through step 2)
Glass fiber passes through the gap of applicator roll and pressing roller, impregnate compound.
8. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 7, feature exist
In the temperature of the applicator roll and pressing roller is respectively 170 DEG C~190 DEG C, and the pressure of pressing roller is 2~5MPa.
9. the preparation method of continuous glass fiber reinforced polypropylene unidirectional prepreg tape according to claim 1, feature exist
In in step 3), the rubbing dipping is implemented by crumpling roller, and the temperature of the rubbing roller is 170 DEG C~190 DEG C；Institute
Stating calendering dipping is implemented by stack, and the temperature of the stack is 170 DEG C~190 DEG C, pressure 2~5MPa, described
The surface of stack is contacted with ground line；The cooling and shaping is implemented by chill roll, the temperature 20 DEG C~50 of chill roll
DEG C, 1~2MPa of pressure；The winding is implemented by wind-up roll.
10. a kind of continuous glass fiber reinforced polypropylene unidirectional prepreg tape, the continuous glass fiber reinforced polypropylene are unidirectionally pre-
Soak band includes following components by weight: 20~30 parts of polypropylene, 70~80 parts of glass fibre, and polypropylene grafted maleic anhydride
1~5 part of zinc, 0.03~0.07 part of antioxidant, which is characterized in that the continuous glass fiber reinforced polypropylene unidirectional prepreg tape is by weighing
Benefit require any one of 1~9 described in preparation method be made.
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| CN115612205A (en) * | 2022-10-11 | 2023-01-17 | 安徽泓诺新材料有限公司 | Cross-linked polypropylene foam material with good cohesiveness and preparation method thereof |
| EP4116081A4 (en) * | 2020-03-02 | 2024-03-27 | Mitsui Chemicals Inc | Unidirectional fiber-reinforced thermoplastic resin sheet and method for manufacturing same |
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Denomination of invention: Continuous glass fiber reinforced polypropylene unidirectional pre impregnated tape and its preparation method Granted publication date: 20210803 Pledgee: Bank of China Limited Zhenjiang Runzhou Branch Pledgor: JIANGSU SUNENG NEW MATERIALS TECHNOLOGY CO.,LTD. Registration number: Y2024980003657 |