CN117069974A - Methyl methacrylate resin system and method for forming fiber reinforced material by room-temperature in-situ dip transfer molding - Google Patents
Methyl methacrylate resin system and method for forming fiber reinforced material by room-temperature in-situ dip transfer molding Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 46
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000001721 transfer moulding Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000000805 composite resin Substances 0.000 claims abstract description 28
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 24
- 239000007924 injection Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- -1 nitrogen-nitrogen dimethyl-p-toluidine Chemical compound 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 17
- 238000005470 impregnation Methods 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 239000004925 Acrylic resin Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 229920000178 Acrylic resin Polymers 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The application discloses a methyl methacrylate resin system and a method for forming a fiber reinforced material by room-temperature in-situ dip transfer molding, and belongs to the technical field of preparation of resin-based composite materials. Firstly, PMMA is dissolved in MMA, and filler is added to obtain a PMMA-MMA system with certain viscosity; then adding an initiator, an accelerator, a dispersing agent and a release agent, and uniformly mixing to obtain a PMMA-MMA resin system for in-situ dip transfer molding at room temperature; finally, the fiber is impregnated by a molding device, and in-situ polymerization molding is completed, so that the fiber reinforced thermoplastic composite material is obtained. The PMMA-MMA resin system provided by the application can realize efficient fiber impregnation, and can realize in-situ polymerization reaction at room temperature to prepare the fiber reinforced material. Solves the difficult problems of uncontrolled prepolymerization, large shrinkage and complex molding process of the thermoplastic composite material in the preparation of the existing thermoplastic acrylic resin system.
Description
Technical Field
The application belongs to the technical field of resin matrix composite material preparation, and particularly relates to a methyl methacrylate resin system and a method for forming a fiber reinforced material by room-temperature in-situ dip transfer molding.
Background
The thermoplastic acrylic resin has low viscosity, and the in-situ polymerization can be used for preparing the fiber reinforced thermoplastic composite material with high impregnation degree, high fiber content and high performance, so that the problems of large equipment investment and high production cost of the thermoplastic composite material are solved. However, when the methacrylate resin for in-situ polymerization molding is prepared, the high heat release amount leads to the high temperature in the mold cavity to cause the polymerization to be out of control, the production efficiency is low, and the low-temperature storage and transportation are required, so that the fiber-reinforced methacrylate resin-based composite material cannot be popularized and applied on a large scale.
Chinese patent CN102181115A proposes a polymethacrylate product and its preparation method, but in the practical course, PMMA and MMA are mixed uniformly, then initiator is added, PMMA is dissolved by reaction heat, the dissolution effect is poor, the viscosity of the system is up to 10000 Pa.S to 200 ten thousand Pa.S, the system can not be applied to in-situ polymerization molding of fiber reinforced thermoplastic composite materials, and MMA is exploded by the reaction heat, meanwhile, because of the existence of initiator in PMMA-MMA system, PMMA-MMA system needs to be stored and transported at low temperature, in addition, the molding method of fiber reinforced methacrylate resin matrix composite materials needs to be carried out at high temperature, energy consumption is reduced, and development of a system and method capable of molding fiber reinforced materials at room temperature is particularly important.
Disclosure of Invention
The application provides a methyl methacrylate resin system and a method for forming a fiber reinforced material by room-temperature in-situ dip-molding thereof, aiming at the defects in the prior art.
The technical scheme of the application is as follows:
the application aims to provide a method for molding a fiber reinforced material by room-temperature in-situ dip-molding of a methyl methacrylate resin system, which comprises the steps of injecting a PMMA-MMA resin system into a glue injection tank, connecting the glue injection tank with a glue injection port of a mold by using a tetrafluoro tube, vacuumizing the inside of a cavity of the mold from a glue outlet of the mold, opening a valve of the glue injection port, sucking the PMMA-MMA resin system into a mold cavity to dip fibers by using vacuum, and completing room-temperature in-situ dip-molding to obtain the fiber reinforced material.
The second object of the application is to provide a methyl methacrylate resin system in the method for molding the fiber reinforced material by room temperature in-situ dip-molding, wherein the resin system comprises PMMA-MMA composite resin, an initiator, an accelerator, a release agent and a dispersing agent; wherein the viscosity of the PMMA-MMA composite resin is 500-3000 mPa.S, and the PMMA-MMA composite resin consists of PMMA, MMA and filler.
Further defined, the resin system comprises 100 parts by mass of PMMA-MMA composite resin, 0.5-3 parts by mass of initiator, 0.5-3 parts by mass of accelerator, 0.5-3 parts by mass of release agent and 0.5-2 parts by mass of dispersing agent.
Further defined, the PMMA-MMA composite resin comprises, by mass, 30-70 parts of PMMA, 10-70 parts of MMA and 0.5-40 parts of filler.
Further defined, the preparation of the PMMA-MMA composite resin: and mixing PMMA, MMA and filler, and dissolving at 60-220 ℃ to obtain the PMMA-MMA composite resin.
Further defined, the initiator is one or more of tert-butyl perbenzoate, dibenzoyl peroxide and azobisisobutyronitrile.
Further defined, the promoter is one or both of dimethylaniline and nitrogen-nitrogen dimethyl-p-toluidine.
Further defined, the dispersant is a modified polyurethane solution.
Still further defined, the dispersant is BYK-W974.
Further defined, the release agent is an organic fatty acid, or a mixed solution of lipid and amine.
Further defined, the filler is one or more of aluminum hydroxide, precipitated silica, light calcium carbonate, heavy calcium carbonate, clay, organoclay and mica powder.
The third object of the application is to provide a preparation method of the methyl methacrylate resin system, which comprises the steps of dissolving PMMA in MMA at 60-220 ℃, adding filler to obtain PMMA-MMA composite resin with the viscosity of 500-3000 mPa.S, cooling to 20-30 ℃, adding initiator, accelerator, release agent and dispersing agent, and stirring uniformly to obtain PMMA-MMA resin system for room temperature in-situ dip transfer molding.
Compared with the prior art, the application has the following beneficial effects:
(1) According to the application, PMMA is used as a main raw material, and through melting in MMA and adjusting the mass ratio of PMMA, filler and MMA, the specific regulation and control of the viscosity of the PMMA-MMA composite resin are realized, the heat release amount and the solidification shrinkage rate in the subsequent product forming process are reduced, and the problem of uncontrolled MMA prepolymerization in the preparation of methacrylate resin for in-situ dip transfer molding is solved.
(2) The application can separate and preserve PMMA-MMA resin system and other components (initiator, filler and dispersing agent) for in-situ injection pultrusion of fiber reinforced thermoplastic composite material, and solves the problems of low-temperature storage and transportation of the resin system.
(3) The initiator and the accelerator form a redox system, so that the initiation and polymerization rates are improved, the polymerization temperature is reduced, the higher molecular weight of the polymer can be obtained at room temperature, and the process time is reduced. The application uses the system to avoid the polymerization of resin with high heat release, which causes the polymerization of resin caused by overhigh temperature in the die cavity, and avoid the chain termination reaction generated by the transfer of free radical to solvent, monomer and polymer chain due to higher reaction temperature, thereby reducing the molecular weight of polymer.
(4) The application adopts the organic fatty acid as the release agent, has high compatibility with PMMA-MMA resin system for in-situ dip transfer molding, has wetting and coupling effects on fillers, fibers and the like, improves the mechanical properties of products, and migrates to the surfaces of the products to form chemical reaction films in the curing process, keeps the isolation between the products and the mold, and ensures the smoothness of the surfaces of the products.
(5) The thermoplastic acrylic resin system provided by the application can be applied to the preparation of fiber reinforced materials in room temperature in-situ impregnation transfer molding, and the product has good mechanical property and durability, has extremely broad application prospect in the fields of aerospace, automobile industry, construction, energy sources, energy storage and the like, and can obviously improve economic benefit.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.
The indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Reference to "one embodiment" or "an embodiment" of the present application means that a particular feature, structure, or characteristic may be included in at least one implementation of the present application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The endpoints of the ranges and any values disclosed in the application are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the following examples, all materials are commercially available in parts by mass, BYK-W974 as a dispersant and NODA-1968 as a release agent.
Example 1:
the embodiment adopts a vacuum auxiliary fiber reinforced thermoplastic methacrylate resin matrix composite resin in-situ impregnation transfer molding mode for molding. The method comprises the following specific steps:
firstly, raw material treatment before molding:
and calculating the number of required fiber layers according to the target plate size and the carbon fiber volume fraction, and cutting the fiber cloth to the required size.
In the second step, a thermoplastic acrylate resin is prepared.
Weighing 60 parts of PMMA, 20 parts of filler nano aluminum hydroxide and 40 parts of MMA, completely dissolving PMMA particles in the MMA at 180 ℃, and then adding the filler nano aluminum hydroxide to obtain PMMA-MMA composite resin with the viscosity of 1300 mPa.S; and cooling the PMMA-MMA composite resin to 25 ℃, and then adding 1 part of dibenzoyl peroxide, 1 part of nitrogen-nitrogen dimethyl para-toluidine, 0.5 part of dispersing agent and 2 parts of release agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, resin in-situ impregnation transfer molding:
transferring the PMMA-MMA resin system into a glue injection tank, and connecting the glue injection tank with a glue injection port of a mould by using a tetrafluoro tube.
Vacuumizing from a glue outlet of a die, controlling the vacuum degree to be 0.02MPa, vacuumizing for 40min, discharging gas in a die cavity, opening a glue injection port valve, sucking resin in a glue injection tank into the die cavity to impregnate fibers by utilizing vacuum, controlling the film filling time to be 30min, closing the glue outlet valve after the die filling and the impregnation are completed, and forming the fiber reinforced composite material plate in 1 h according to a preset time program.
According to standard GBT3365-2008, the degree of fiber impregnation of the product is 95%, the fiber volume fraction is 60%, the tensile strength of the product is 1980MPa according to ASTMD3039, the bending strength of the product is 2100MPa according to ASTMD7264, and the volume shrinkage of the product is 0.2% according to ASTMD 955.
Comparative example 1:
the specific preparation process of the comparative example is as follows:
firstly, raw material treatment before molding:
and calculating the number of required fiber layers according to the target plate size and the carbon fiber volume fraction, and cutting the fiber cloth to the required size.
In the second step, a thermoplastic acrylate resin is prepared.
Weighing 60 parts of PMMA and 40 parts of MMA, and uniformly mixing to obtain a PMMA-MMA resin system; 1 part of dibenzoyl peroxide, 1 part of nitrogen-nitrogen dimethyl para-toluidine, 20 parts of filler nano aluminum hydroxide, 0.5 part of dispersing agent and 2 parts of release agent are added into the PMMA-MMA resin system, so that PMMA particles have poor solubility and burst aggregation phenomenon, and the method can not be applied to forming the fiber reinforced thermoplastic methyl methacrylate resin matrix composite material in an in-situ dip transfer molding mode.
Comparative example 2:
the specific preparation process of the comparative example is as follows:
firstly, raw material treatment before molding:
and calculating the number of required fiber layers according to the target plate size and the carbon fiber volume fraction, and cutting the fiber cloth to the required size.
In the second step, a thermoplastic acrylate resin is prepared.
Weighing 60 parts of PMMA, 20 parts of filler nano aluminum hydroxide and 40 parts of MMA, completely dissolving PMMA particles in the MMA at 180 ℃, and then adding the filler nano aluminum hydroxide to obtain PMMA-MMA composite resin with the viscosity of 1300 mPa.S; and cooling the PMMA-MMA composite resin to 25 ℃, and adding 1 part of dibenzoyl peroxide, 1 part of nitrogen-nitrogen dimethyl para-toluidine and 0.5 part of dispersing agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, resin in-situ impregnation transfer molding:
transferring the PMMA-MMA resin system into a glue injection tank, and connecting the glue injection tank with a glue injection port of a mould by using a tetrafluoro tube.
Vacuumizing from a glue outlet of a die, controlling the vacuum degree to be 0.02MPa, vacuumizing for 40min, discharging gas in a die cavity, opening a glue injection port valve, sucking resin in a glue injection tank into the die cavity to impregnate fibers by utilizing vacuum, controlling the film filling time to be 30min, closing the glue outlet valve after the die filling and the impregnation are completed, and controlling the time according to a preset time program, wherein the time is 1 hour in the comparative example, so as to form the fiber reinforced composite material plate.
The surface of the fiber reinforced thermoplastic acrylic composite material has a gully and has the phenomena of broken filaments and fibers.
The degree of fiber impregnation of the product was 95% and the fiber volume fraction was 58% according to the standard GBT3365-2008, and the tensile strength of the product was 1540MPa and the flexural strength was 1460MPa according to the standard GBT 13096-2008.
Comparative example 3:
the specific preparation process of the comparative example is as follows:
firstly, raw material treatment before molding:
and calculating the number of required fiber layers according to the target plate size and the carbon fiber volume fraction, and cutting the fiber cloth to the required size.
In the second step, a thermoplastic methacrylate resin is prepared.
Weighing 60 parts of PMMA and 40 parts of MMA, and completely dissolving PMMA particles in the MMA at 180 ℃ to obtain PMMA-MMA composite resin with the viscosity of 1000 mPa.S; and cooling the PMMA-MMA composite resin to 25 ℃, and then adding 1 part of dibenzoyl peroxide, 1 part of nitrogen-nitrogen dimethyl para-toluidine, 20 parts of filler nano aluminum hydroxide, 0.5 part of dispersing agent and 2 parts of release agent, and fully and uniformly mixing to obtain the PMMA-MMA resin system.
Thirdly, resin in-situ impregnation transfer molding:
transferring the PMMA-MMA resin system into a glue injection tank, and connecting the glue injection tank with a glue injection port of a mould by using a tetrafluoro tube.
Vacuumizing from a glue outlet of a die, controlling the vacuum degree to be 0.02MPa, vacuumizing for 40min, discharging gas in a die cavity, opening a glue injection port valve, sucking resin in a glue injection tank into the die cavity to impregnate fibers by utilizing vacuum, controlling the film filling time to be 30min, closing the glue outlet valve after the die filling and the impregnation are completed, and controlling the time according to a preset time program, wherein the time is 1 hour in the comparative example, so as to form the fiber reinforced composite material plate.
Voids appear on the surface of the fiber reinforced thermoplastic methyl methacrylate composite material.
According to the standard GBT3365-2008, the degree of fiber impregnation of the product is 90%, the fiber volume fraction is 60%, and according to the standard GBT13096-2008, the tensile strength of the product is 1020MPa, and the bending strength of the product is 1010MPa.
The inventive embodiments disclosed above are merely intended to help illustrate the inventive embodiments. The examples are not intended to be exhaustive or to limit the application to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, to thereby enable others skilled in the art to best understand and utilize the application.
The inventive embodiments disclosed above are merely intended to help illustrate the inventive embodiments. The examples are not intended to be exhaustive or to limit the application to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, to thereby enable others skilled in the art to best understand and utilize the application.
Claims (10)
1. A method for molding a fiber reinforced material by in-situ dip-molding at room temperature of a methyl methacrylate resin system is characterized in that a PMMA-MMA resin system is injected into a glue injection tank, the glue injection tank is connected with a glue injection port of a mold by a tetrafluoro tube, the inside of a cavity of the mold is vacuumized from a glue outlet of the mold, a valve of the glue injection port is opened, and the PMMA-MMA resin system is sucked into the cavity to impregnate the fiber by vacuum, so that the fiber reinforced material is obtained.
2. Methyl methacrylate resin system according to claim 1, characterized in that it comprises a PMMA-MMA composite resin, an initiator, an accelerator, a release agent and a dispersing agent; wherein the viscosity of the PMMA-MMA composite resin is 500-3000 mPa.S, and the PMMA-MMA composite resin consists of PMMA, MMA and filler.
3. The resin system according to claim 2, wherein the resin system comprises 100 parts by mass of PMMA-MMA composite resin, 0.5-3 parts by mass of initiator, 0.5-3 parts by mass of accelerator, 0.5-3 parts by mass of release agent and 0.5-2 parts by mass of dispersant.
4. The resin system according to claim 2, wherein the PMMA-MMA composite resin comprises, by mass, 30-70 parts of PMMA, 10-70 parts of MMA and 0.5-40 parts of filler.
5. The resin system according to claim 2, wherein the PMMA, MMA and filler are mixed and then dissolved at 60-220 ℃ to obtain the PMMA-MMA composite resin.
6. The resin system according to claim 2, wherein the initiator is one or more of tert-butyl perbenzoate, dibenzoyl peroxide and azobisisobutyronitrile, the accelerator is one or two of dimethylaniline and nitrogen-nitrogen dimethyl-p-toluidine, and the release agent is an organic fatty acid or a mixed solution of lipid and amine.
7. The resin system of claim 2 wherein the dispersant is a modified polyurethane solution.
8. The resin system of claim 7, wherein the dispersant is BYK-W974.
9. The resin system according to claim 2, wherein the filler is one or more of aluminum hydroxide, precipitated silica, light calcium carbonate, heavy calcium carbonate, clay, organoclay, mica powder.
10. The method for preparing the methyl methacrylate resin system according to any one of claims 2 to 9, which is characterized in that PMMA is dissolved in MMA at 60 to 220 ℃, filler is added to obtain PMMA-MMA composite resin with the viscosity of 500 to 3000 mPa.S, the PMMA-MMA composite resin is cooled to 20 to 30 ℃, and initiator, accelerator, release agent and dispersing agent are added to the PMMA-MMA composite resin, and the PMMA-MMA composite resin is uniformly stirred to obtain the PMMA-MMA resin system for room temperature in-situ dip transfer molding.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181115A (en) * | 2011-02-12 | 2011-09-14 | 台州艾斐建材有限公司 | Polymethyl methacrylate product and preparation method thereof |
| CN111040353A (en) * | 2019-12-03 | 2020-04-21 | 江苏华昇新材料科技有限公司 | Bulk molding compound prepared from polymethyl methacrylate powder and free of styrene component |
| US20210054137A1 (en) * | 2018-03-09 | 2021-02-25 | Nippon Steel Chemical & Material Co., Ltd. | Resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material using same |
| CN113549178A (en) * | 2021-07-14 | 2021-10-26 | 江苏华昇新材料科技有限公司 | High-strength BMC bulk molding compound prepared from PMMA powder and MMA monomer and preparation method thereof |
| US20220250335A1 (en) * | 2021-02-11 | 2022-08-11 | Johns Manville | Lightweight thermoplastic composite products and methods of making same |
| CN115850895A (en) * | 2023-01-05 | 2023-03-28 | 郑州中科新兴产业技术研究院 | Continuous fiber reinforced PMMA composite material and preparation method and application thereof |
| CN116120600A (en) * | 2023-01-17 | 2023-05-16 | 哈尔滨工业大学 | In-situ impregnation forming method for fiber reinforced thermoplastic composite material |
-
2023
- 2023-07-18 CN CN202310879035.6A patent/CN117069974B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181115A (en) * | 2011-02-12 | 2011-09-14 | 台州艾斐建材有限公司 | Polymethyl methacrylate product and preparation method thereof |
| US20210054137A1 (en) * | 2018-03-09 | 2021-02-25 | Nippon Steel Chemical & Material Co., Ltd. | Resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material using same |
| CN111040353A (en) * | 2019-12-03 | 2020-04-21 | 江苏华昇新材料科技有限公司 | Bulk molding compound prepared from polymethyl methacrylate powder and free of styrene component |
| US20220250335A1 (en) * | 2021-02-11 | 2022-08-11 | Johns Manville | Lightweight thermoplastic composite products and methods of making same |
| CN113549178A (en) * | 2021-07-14 | 2021-10-26 | 江苏华昇新材料科技有限公司 | High-strength BMC bulk molding compound prepared from PMMA powder and MMA monomer and preparation method thereof |
| CN115850895A (en) * | 2023-01-05 | 2023-03-28 | 郑州中科新兴产业技术研究院 | Continuous fiber reinforced PMMA composite material and preparation method and application thereof |
| CN116120600A (en) * | 2023-01-17 | 2023-05-16 | 哈尔滨工业大学 | In-situ impregnation forming method for fiber reinforced thermoplastic composite material |
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