CN115785328B - Preparation method of partially crosslinked PMMA and composite material thereof - Google Patents
Preparation method of partially crosslinked PMMA and composite material thereof Download PDFInfo
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 125
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 125
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 21
- 238000000465 moulding Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000009755 vacuum infusion Methods 0.000 claims abstract description 3
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- 238000003756 stirring Methods 0.000 claims description 14
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- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000011417 postcuring Methods 0.000 claims description 10
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- 238000001746 injection moulding Methods 0.000 claims description 4
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- LSZFFPVDPBVFRO-UHFFFAOYSA-N 2-(propan-2-ylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(C)NCCOC(=O)C(C)=C LSZFFPVDPBVFRO-UHFFFAOYSA-N 0.000 claims description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 description 6
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- 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 description 4
- GMTJKMKNOIUGPG-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCCCC1 GMTJKMKNOIUGPG-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- FGSBZZTYGCQZPD-UHFFFAOYSA-N 2-piperidin-1-ylethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1CCCCC1 FGSBZZTYGCQZPD-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical group CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the technical field of synthesis of high polymer resin and composite materials thereof, and particularly relates to a preparation method of partially crosslinked PMMA and a preparation method of a composite material thereof. The long chains of the partially cross-linked PMMA are tightly connected through covalent bonds to form a stable three-dimensional network structure, the strength and toughness of the PMMA are enhanced simultaneously by adjusting the addition amount of diisocyanate, and the tensile strength, the impact strength and the elongation at break can be respectively improved to 85MPa and 33KJ/m 2 10 percent of the PMMA resin and the property of recycling and reusing the PMMA resin are maintained; meanwhile, the composite material prepared from the partially crosslinked PMMA and the fiber reinforced material has excellent mechanical properties. The preparation method disclosed by the invention has the advantages of few additives, simple process, no catalyst, mild and controllable reaction, ensures that the obtained partially crosslinked PMMA is used for preparing the composite material under the vacuum infusion molding process, and has higher application value.
Description
Technical Field
The invention belongs to the technical field of synthesis of high polymer resin and composite materials thereof, and particularly relates to a preparation method of partially crosslinked PMMA and a preparation method of a composite material thereof.
Background
Polymethyl methacrylate (Polymethyl methacrylate, PMMA for short) is an important transparent engineering plastic, and has wide application in optical materials, construction and packaging industries due to the advantages of light weight, good light transmittance, easy processing, recycling and the like. However, PMMA products often have the defects of low strength and insufficient toughness, so that the popularization and application of the PMMA products in a large range are limited.
Aiming at the defects of PMMA products, materials such as nano particles, core-shell modifiers, rubber elastomers and the like are commonly used for toughening and modifying PMMA at present; PMMA is reinforcement modified with metal oxides such as alumina, chopped fibers such as fiberglass, cellulose such as lignin, and the like. For example, the patent with publication number CN109735035A adopts a polyolefin macromolecular initiator containing reactive functional groups and methyl methacrylate (Methyl methacrylate, MMA for short) monomer to polymerize in situ to prepare a toughening agent to modify PMMA resin, so that the impact strength of the PMMA resin is improved to 33KJ/m 2 However, the tensile strength is poor and is only about 62 MPa; the patent with publication number CN 109370133A modified the pre-polymerized MMA solution with extracted lignin, resulting in an improvement of 13% in the tensile strength of the plexiglass, but still fails to optimize its toughness properties. It can be seen that the existing modification method can only independently improve the performance on one hand, and is difficult to realize reinforcing modification while toughening modification, and even increase the brittleness of the product while reinforcing modification, so that the toughness performance is reduced.
A reinforced and toughened PMMA plate and its preparing process are disclosed in CN114806055A, which features use of polymethyl methacrylate as high-molecular chain, polyol polymer and short-range connecting unitThe PMMA plate is obtained by casting and polymerizing the raw material components, and the molecular chains of PMMA are mutually entangled and interlocked under the action of the polyol polymer and the short-range connecting unit, so that the toughness and the strength of the PMMA plate are improved, and compared with a comparative example, the tensile strength of PMMA is improved to 75MPa, and is improved by about 15 percent; the notch-free impact strength of the simply supported beam is improved to 25KJ/m 2 The strength and toughness of PMMA resin are improved by about 60%, and the PMMA resin is modified from the molecular structure angle by the method to realize the simultaneous modification of the PMMA resin and the PMMA resin, but a catalyst is needed to obtain a better reaction effect in the modification method, and a short-range connecting unit in the modification method can not directly connect polymethyl methacrylate high polymer chains together, and a polyol polymer is needed to be additionally added to realize the connection of the polymethyl methacrylate high polymer chains and the short-range connecting unit, so that more modified additives are added in the PMMA plate, and the modification method is complicated and difficult to control.
Therefore, the development of the modification method which can simultaneously toughen and strengthen PMMA, has few additives, is simple and convenient to operate, has environment-friendly modification process and does not use a catalyst has important value.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of partially crosslinked PMMA and a composite material thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of the partially crosslinked PMMA comprises the following steps:
(1) Dissolving diisocyanate into MMA, then dripping the diisocyanate into a mixed solution of hindered amine acrylic ester and MMA, stirring and reacting for 1-60min at room temperature to obtain a product 1, and reserving the mixed solution containing the product 1 for later use;
(2) And (3) adding an initiator required by polymerization reaction into the mixed solution containing the product 1 in the step (1), mixing, and carrying out polymerization reaction on the product 1 and MMA under a certain condition to obtain the partially crosslinked PMMA.
Preferably, the ratio of the total mass of MMA to the mass of hindered amine acrylate, diisocyanate is 1 (0.05-0.5): (0.025-0.25), wherein the mass of hindered amine acrylate is 2 times the mass of diisocyanate; the addition amount of the initiator is 0.1-5% of the total mass of MMA and hindered amine acrylate.
Preferably, the diisocyanate is any one of isophorone diisocyanate (isophorone diisocyanate, abbreviated as IPDI), hexamethylene diisocyanate (hexamethylene diisocyanate, abbreviated as HDI), toluene diisocyanate (Toluene diisocyanate, abbreviated as TDI), diphenylmethane-diisocyanate (MDI), and 4,4' -dicyclohexylmethane diisocyanate (HMDI); the hindered amine acrylic ester is any one of tert-butylaminoethyl methacrylate, tert-butylaminoethyl acrylate, isopropylaminoethyl methacrylate, isopropylaminoethyl acrylate, piperidinaminoethyl acrylate and piperidinaminoethyl methacrylate; the initiator is a thermal decomposition initiator and/or a redox initiator; the thermal decomposition initiator is azo compound and/or peroxy compound; the redox initiator is a combination of peroxide and a reducing agent.
More preferably, the azo compound is azobisisobutyronitrile (2, 2'-Azobis (2-methyl propionile), abbreviated as AIBN) or azobisisoheptonitrile (2, 2' -Azobis (2, 4-dimethyl) valerile, abbreviated as ABVN); the peroxy compound is Benzoyl peroxide (BPO for short); the peroxide is BPO or lauroyl peroxide (Dilauroyl peroxide, abbreviated as LPO); the reducing agent is N, N-Dimethyl-p-toluidine (DMT) and/or N, N-Dimethylaniline (DMA).
Preferably, the polymerization reaction condition in the step (2) is that after 0.1-48 hours of reaction at-20-100 ℃, the mixture is post-cured for 0.1-48 hours at 60-120 ℃.
The preparation reaction process of the partially crosslinked PMMA is as follows:
wherein,is the molecular structure of diisocyanate, +.>Molecular structure of hindered amine acrylate +.>Molecular structure of product 1, +.>Is the molecular structure of Methyl Methacrylate (MMA)>Is a partially crosslinked PMMA structure; wherein m is an integer not less than 1, and n is an integer not less than 1; r is R 1 Is hydrogen or methyl, R 2 Is a highly sterically hindered group including tert-butyl, isopropyl or piperidine.
The preparation principle of the partially crosslinked PMMA is as follows: the monomer hindered amine acrylic ester and diisocyanate firstly undergo polyurea reaction to prepare a product 1 containing large steric hindrance ureido in a molecular structure, unsaturated double bonds are contained at two ends of the product 1, free radical copolymerization reaction is carried out between the unsaturated double bonds in the product 1 and MMA monomers under the action of an initiator, and two ends of the product 1 are grafted with PMMA molecular chains, namely, at the moment, PMMA molecular long chains form cross-linking with each other due to the product 1, so that partially cross-linked PMMA is formed. Under a certain degree of crosslinking, acting force among PMMA molecular chains is enhanced, so that the tensile strength is improved, the addition amount of diisocyanate is regulated, and the strength and toughness of the partially crosslinked PMMA can be improved.
The invention also includes partially crosslinked PMMA prepared by the above method.
The invention also includes a partially crosslinked PMMA composite material comprising the partially crosslinked PMMA described above and a fiber reinforcement.
Preferably, the fibrous reinforcement is chopped or continuous; the chopped fibers are one or more of chopped carbon fibers, chopped glass fibers, chopped aramid fibers and chopped high-density polyethylene fibers; the continuous fibers are one or more of carbon fibers, glass fibers, basalt fibers and aramid fibers; the continuous fibers are continuous fiber yarns or fiber cloths.
The preparation method of the partially crosslinked PMMA composite material is any one of injection molding, vacuum assisted infusion molding, compression molding, winding molding and pultrusion.
Preferably, the method for preparing the partially crosslinked PMMA composite material by the vacuum assisted infusion molding method comprises the following specific steps of:
step a: dissolving diisocyanate into MMA, then dropwise adding the mixture of hindered amine acrylate and MMA, stirring and reacting for 1-60min at room temperature to obtain a product 1, wherein the ratio of the total amount of MMA substances to the amounts of hindered amine acrylate and diisocyanate is 1 (0.05-0.5) (0.025-0.25), the amount of the hindered amine acrylate substances is 2 times that of the diisocyanate substances, and the mixture containing the product 1 is reserved for standby;
step b: adding an initiator required by polymerization reaction into the mixed solution containing the product 1 in the step a, wherein the addition amount of the initiator is 0.1-5% of the total mass of MMA and hindered amine acrylate, and uniformly stirring to obtain a mixed solution;
step c: and c, defoaming the mixed solution in the step b, adopting a vacuum assisted pouring molding method, pouring vacuum (vacuum negative pressure is- (0.08-0.1) MPa) into a prefabricated body paved by a fiber reinforced material, reacting (i.e. curing) the prefabricated body poured with the mixed solution at the temperature of 0-100 ℃ for 0.1-48h, then post-curing at the temperature of 60-120 ℃ for 0.1-48h, and demolding and post-treating to obtain the composite material of the partially crosslinked PMMA.
The invention has the beneficial effects that:
1. the invention provides a preparation method of partially crosslinked PMMA, which comprises the steps of firstly enabling diisocyanate and hindered amine acrylic ester to react to generate an intermediate product (namely a product 1) containing hindered ureido groups, wherein both ends of a molecular structure of the product 1 contain unsaturated double bonds, then, the unsaturated double bonds and MMA monomers are subjected to free radical polymerization reaction through initiation of an initiator, and finally, the partially crosslinked PMMA is obtained, long chains of the PMMA polymer are connected with each other through the product 1, so that the long chains are connected through covalent bonds, namely, the crosslinking connection mode is tighter, a stable three-dimensional network structure is formed, and the improvement of mechanical properties of the partially crosslinked PMMA is facilitated.
2. The preparation method of the partially crosslinked PMMA provided by the invention has clear and simple overall steps and controllable reaction process, ensures that the polyurea reaction between small molecules can be ensured to be complete, does not generate byproducts, does not influence the subsequent free radical polymerization reaction, and ensures the structure of a final product, namely the partially crosslinked PMMA; in addition, MMA is used as a solvent for the polyurea reaction in the whole reaction process, and other organic solvents are not used, so that the solvent is not required to be removed at the end of the polyurea reaction, the next polymerization reaction can be directly carried out, and the reaction steps are effectively simplified.
3. The preparation method of the partially crosslinked PMMA comprises the steps that a large amount of MMA is not reacted in a whole reaction system during polymerization reaction, the viscosity of the reaction system is low, and the polymerization reaction can be carried out only by initiating an initiator, so that the preparation method has a certain period of induction period, and the preparation method can directly implement a vacuum assisted pouring molding process, namely, the mixed solution containing the partially crosslinked PMMA is defoamed and then is immersed into a fiber reinforced preform in a vacuum pouring mode, so that the fiber reinforced resin matrix composite material, namely the partially crosslinked PMMA composite material, is finally prepared.
4. The partially crosslinked PMMA prepared by the method has certain crosslinking degree due to the crosslinking between molecules through the product 1, has more excellent mechanical properties than the pure PMMA resin, can be simultaneously enhanced in strength and toughness by adjusting the addition amount of diisocyanate, and can be respectively improved to 85MPa, 33KJ/m in tensile strength, impact strength and elongation at break 2 And 10%; at the same timeThe hindered urea bond in the network of the partially crosslinked PMMA molecules is a dynamic valence-supplying chemical bond, and can be dissociated at high temperature, and molecular healing, recycling and shape memory can be performed through a dissociation exchange mechanism, so that the characteristic of recycling and reusing the PMMA resin is maintained. Meanwhile, the composite material prepared from the partially crosslinked PMMA and the fiber reinforced material has excellent mechanical properties, and PMMA can be recycled, so that the composite material is environment-friendly.
5. The preparation method of the partially crosslinked PMMA has the advantages of few additives, simple process, environment friendliness, no use of catalysts, mild and controllable reaction, ensures that the partially crosslinked PMMA can be suitable for preparing composite materials under a vacuum infusion molding process, and expands the wide application of the partially crosslinked PMMA resin in the fields of wind power blades, ships and yachts and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The experimental methods used in the examples of the present invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 4.2182g of HDI is dissolved in 20g of MMA, and then added dropwise to a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and stirred at room temperature for reaction for 10min to obtain a product 1; wherein the ratio of the total molar quantity of MMA to the molar quantity of tert-butylaminoethyl methacrylate and HDI is 1:0.05:0.025, and the mixed solution containing the product 1 is reserved for standby;
step 2: 1.0925g of LPO and 0.4435g of DMT which are peroxides required by polymerization reaction are added into the mixed solution containing the product 1 in the step 1, the mixed solution is stirred to be transparent and particle-free, then the product 1 and MMA are polymerized under the environment of 25 ℃ for 8 hours, and the mixed solution is post-cured for 3 hours at 80 ℃ to obtain a product containing the partially cross-linked PMMA.
The mechanical properties of the partially crosslinked PMMA prepared in this example were tested: adopting the existing spline preparation method, preparing a standard test spline by pouring the mixed solution containing the partially crosslinked PMMA in the step 2, characterizing the tensile strength, the elongation at break and the notch-free impact strength of the standard spline according to the ISO international standard, and measuring the mechanical properties: tensile strength of 79MPa and impact strength of 31KJ/m 2 The elongation at break was 9%.
Example 2
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 8.6976g of MDI was dissolved in 30g of MMA and then slowly added dropwise to a mixture of 21.3064g of isopropylaminoethyl methacrylate and 70g of MMA, and reacted at room temperature with stirring for 20 minutes to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to the isopropyl amino ethyl methacrylate to the molar ratio of MDI are 1:0.1:0.05, and the mixed solution containing the product 1 is reserved for standby;
step 2: 1.7776g of LPO and 1.7412g of DMA as peroxide required by polymerization reaction are added into the mixed solution containing the product 1 in the step 1, the product 1 and MMA are subjected to polymerization reaction at 40 ℃ under the anaerobic condition for 5 hours, and the mixed solution is post-cured for 3 hours at 90 ℃ to obtain a product containing partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 80MPa and the impact strength was 32KJ/m 2 The elongation at break was 9%.
Example 3
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 11.1008g of IPDI was dissolved in 25g of MMA and then added dropwise to a mixture of 18.3028g of piperidinoethyl acrylate and 75g of MMA, and reacted at room temperature with stirring for 30 minutes to obtain a product 1, wherein the molar ratio of the total molar quantity of MMA to the piperidyl amino ethyl acrylate to the molar ratio of the IPDI are 1:0.1:0.05, and the mixed solution containing the product 1 is reserved for standby;
step 2: 0.2839g of BPO and 0.1183g of DMT which are peroxides required by polymerization reaction are added into the mixed solution containing the product 1 in the step 1, the product 1 and MMA are polymerized under the condition of minus 20 ℃ and no oxygen, the reaction time is 48 hours, and the product is cured for 1.5 hours at 120 ℃ to obtain the product containing the partially cross-linked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 78MPa and the impact strength was 30KJ/m 2 The elongation at break was 8%.
Example 4
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 22.2053g of IPDI was dissolved in 35g of MMA and then added dropwise to a mixture of 39.6020g of piperidinoethyl methacrylate and 65g of MMA, and reacted at room temperature with stirring for 50 minutes to obtain a product 1, wherein the molar ratio of the total molar quantity of MMA to the piperidinoethyl methacrylate to the molar ratio of IPDI are 1:0.2:0.1, and the mixed solution containing the product 1 is reserved for standby;
step 2: 0.3282g of BPO and 0.137g of DMT which are peroxides required by polymerization reaction are added into the mixed solution containing the product 1 in the step 1, the product 1 and MMA are polymerized under the condition of 100 ℃ and no oxygen, the reaction time is 1h, and the product is cured for 2h at 110 ℃ to obtain the product containing the partially cross-linked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 81MPa and the impact strength was 32KJ/m 2 The elongation at break was 10%.
Example 5
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 22.2053g of IPDI was dissolved in 35g of MMA and then added dropwise to a mixture of 39.6020g of piperidinoethyl methacrylate and 65g of MMA, and reacted at room temperature with stirring for 50 minutes to obtain a product 1, wherein the molar ratio of the total molar quantity of MMA to the piperidinoethyl methacrylate to the molar ratio of IPDI are 1:0.2:0.1, and the mixed solution containing the product 1 is reserved for standby;
step 2: 6.9801g of AIBN, an initiator required for polymerization, was added to the mixture containing the product 1 in the step 1, and the product 1 was polymerized with MMA at 50℃for 12 hours and post-cured at 110℃for 2 hours to give a product containing partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 80MPa and the impact strength was 33KJ/m 2 The elongation at break was 9%.
Example 6
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 43.4965g of TDI is dissolved in 60g of MMA, then is dripped into 84.5455g of mixed solution of tert-butylaminoethyl acrylate and 40g of MMA, and is stirred at room temperature for reaction for 1min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to the tert-butylaminoethyl acrylate to the molar ratio of TDI are 1:0.5:0.25, and the mixed solution containing the product 1 is reserved for standby;
step 2: to the mixture containing the product 1 of step 1, 0.1845g of an initiator ABVN required for polymerization was added, and the product 1 was polymerized with MMA at 30℃for 48 hours and post-cured at 120℃for 0.3 hours to give a product containing partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 85MPa and the impact strength was 33KJ/m 2 The elongation at break was 10%.
Example 7
The embodiment provides a preparation method of partially crosslinked PMMA, which comprises the following steps:
step 1: 26.2088g of HMDI is dissolved in 55g of MMA, then is dripped into 39.424g of mixed solution of isopropyl amino ethyl acrylate and 45g of MMA, and is stirred at room temperature for reaction for 60min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to isopropyl amino ethyl acrylate to the molar ratio of HMDI to the molar ratio of the total molar amount of HMDI to the molar ratio of isopropyl amino ethyl acrylate to the molar ratio of HMDI to the molar ratio of the total molar amount of HMI to the molar ratio of isopropyl amino ethyl acrylate to the molar ratio of HMDI to the molar ratio of the total molar ratio of isopropyl amino ethyl acrylate to the molar ratio of HMi to the molar ratio of 1 is 1:0.2:0.1, and the molar ratio of the total MMA is kept for standby;
step 2: 6.9712g of BPO, which is an initiator required for polymerization, is added to the mixed solution containing the product 1 in the step 1, the product 1 and MMA are polymerized at 100 ℃ for 0.1h, and the mixture is post-cured at 80 ℃ for 48h, so that a product containing partially crosslinked PMMA is obtained.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by the mechanical property test method of example 1, and the tensile strength was 78MPa and the impact strength was 31KJ/m 2 The elongation at break was 9%.
Comparative example
A partially crosslinked PMMA was prepared as described in example 1, except that HDI was not added to the reaction mixture (i.e., no diisocyanate was added), 9.2521g of t-butylaminoethyl methacrylate was blended with 100g of MMA, 1.0925g of LPO, and 0.4435g of DMT as reducing agent were added, and after stirring to be particle-free, polymerization was carried out at 25℃for 8 hours and post-curing at 80℃for 3 hours to give a product containing partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA was measured by the mechanical property test method of example 1, and the tensile strength was 68MPa and the impact strength was 23KJ/m 2 The elongation at break was 5% and the values of the three parameters were all smaller than the partially crosslinked PMMA prepared in example 1. It has thus been shown that the addition of diisocyanate in the present invention is indeed effective in improving the tensile strength and impact strength, i.e. strength and toughness, of the partially crosslinked PMMA.
Meanwhile, the partially crosslinked PMMA bars prepared in examples 1 to 7 above were crushed into small pieces, and then put into a molding machine to be melted at 140℃and hot-pressed into standard test bars. The mechanical properties of the hot pressed standard bars were kept unchanged compared to the properties before breaking and melting according to ISO international standards.
Example 8
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: 1.0925g of peroxide needed by polymerization reaction, 0.4435g of reducing agent DMT and the mixture containing the product 1 in the step a are added and stirred to a transparent particle-free state;
step c: b, defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum assisted pouring molding method, pouring the mixed solution into a preform paved by unidirectional high-alkali glass fiber cloth under the vacuum of-0.08 MPa, curing the preform infused with the mixed solution at 25 ℃ for 8 hours, then post-curing at 80 ℃ for 3 hours, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the surface density of the unidirectional high-alkali glass fiber cloth is 1250g/m 2 Wherein the volume fraction of the fibrous reinforcement is 60%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 1442.3MPa in the 0 ° direction and a tensile modulus of 46.5GPa.
Example 9
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: 1.0925g of peroxide needed by polymerization reaction, 0.4435g of reducing agent DMT and the mixture containing the product 1 in the step a are added and stirred to a transparent particle-free state;
step c: b, after defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum auxiliary pouring molding method, pouring the mixed solution into a preform which is formed by laying unidirectional carbon fiber cloth (specification: T700 SC) under the vacuum negative pressure of-0.09 MPa, curing the preform filled with the mixed solution at the temperature of 0 ℃ for 45 hours, then post-curing at the temperature of 120 ℃ for 2 hours, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 1988.1MPa in the 0 ° direction and a tensile modulus of 127.5GPa.
Example 10
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: adding 0.6639g of BPO and 0.4435g of DMT serving as a reducing agent required by polymerization reaction into the mixed solution containing the product 1 in the step a, and stirring to a transparent particle-free state;
step c: b, after defoaming the mixed solution obtained in the step b, adopting a vacuum auxiliary pouring molding method, vacuumizing, pouring the mixed solution into a prefabricated body paved by unidirectional basalt fiber cloth (specification: 12 k-200G) under the vacuum negative pressure of minus 0.08MPa, curing the prefabricated body filled with the mixed solution at the temperature of 40 ℃ for 6 hours, then post-curing at the temperature of 80 ℃ for 6 hours, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 1250.5MPa in the 0 ° direction and a tensile modulus of 92.8GPa.
Example 11
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: adding 1.0925g of lauroyl peroxide and 0.4435g of DMT serving as reducing agents required by polymerization reaction into the mixed solution containing the product 1 in the step a, and stirring until the mixed solution is transparent and has no particles;
step c: b, after defoaming the mixed solution obtained in the step b, adopting a vacuum auxiliary pouring molding method, vacuumizing, pouring the mixed solution into a preform paved by unidirectional aramid fiber cloth under the vacuum negative pressure of-0.098 MPa, curing the preform infused with the mixed solution at the temperature of 100 ℃ for 2 hours, then post-curing at the temperature of 120 ℃ for 1 hour, and performing demolding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength in the 0 ° direction of 506.3MPa and a tensile modulus of 29.4GPa.
Example 12
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: adding 1.0925g of lauroyl peroxide and 0.4435g of DMT serving as reducing agents required by polymerization reaction into the mixed solution containing the product 1 in the step a, and stirring until the mixed solution is transparent and has no particles;
step c: and d, after defoaming the mixed solution obtained in the step b, adopting a vacuum auxiliary pouring molding method, vacuumizing, pouring the mixed solution into a preform paved by chopped glass fibers (specification: fiber monofilament diameter 10 mu m, fiber length 4 mm) under the vacuum negative pressure of-0.098 MPa, curing the preform infused with the mixed solution at the temperature of 100 ℃ for 2 hours, then post-curing at the temperature of 120 ℃ for 1 hour, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 40%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 98.8MPa and a tensile modulus of 3.4GPa.
Example 13
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: adding 1.0925g of lauroyl peroxide and 0.4435g of DMT serving as reducing agents required by polymerization reaction into the mixed solution containing the product 1 in the step a, and stirring until the mixed solution is transparent and has no particles;
step c: and d, after defoaming the mixed solution obtained in the step b, adopting a vacuum auxiliary pouring molding method, vacuumizing, pouring the mixed solution into a preform paved by glass fiber bidirectional cloth (with the specification of EWR600-1000 and the fiber monofilament diameter of 10 mu m) under the vacuum negative pressure of minus 0.098MPa, curing the preform infused with the mixed solution at the temperature of 100 ℃ for 2 hours, then curing the mixed solution at the temperature of 120 ℃ for 1 hour, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 55%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 261.2MPa in the 0 ° direction and a tensile modulus of 9.7GPa.
Example 14
The embodiment provides a preparation method of a partially crosslinked PMMA composite material, which comprises the following steps:
step a: 4.2182g of HDI is dissolved in 20g of MMA, then is dripped into a mixed solution of 9.2521g of tert-butylaminoethyl methacrylate and 80g of MMA, and is stirred at room temperature for reaction for 10min to prepare a product 1, and the mixed solution containing the product 1 is reserved for later use;
step b: adding 1.0925g of lauroyl peroxide and 0.4435g of DMT serving as reducing agents required by polymerization reaction into the mixed solution containing the product 1 in the step a, and stirring until the mixed solution is transparent and has no particles;
step c: and d, after defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum auxiliary pouring molding method, pouring the mixed solution into a preform paved by continuous glass fiber yarns under the vacuum negative pressure of-0.098 MPa, curing the preform infused with the mixed solution at the temperature of 100 ℃ for 2 hours, then post-curing at the temperature of 120 ℃ for 1 hour, and performing demoulding post-treatment to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 70%.
Standard composite bars were prepared according to ISO international standards and tested for strength, and the partially cross-linked PMMA composites prepared above had a tensile strength of 705.2MPa and a tensile modulus of 26.7GPa.
From the measurement results of the mechanical property parameters of the partially crosslinked PMMA composites obtained in examples 8 to 14, it was found that the fiber reinforced partially crosslinked PMMA composites prepared by the vacuum assisted injection molding method had excellent mechanical properties; meanwhile, PMMA resin in the composite material can be recycled through a solvent dissolution method, and the fiber reinforced material can be reused at the moment, for example, the PMMA resin can be reused for preparing the composite material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A method for preparing partially crosslinked PMMA, which is characterized by comprising the following preparation steps:
(1) Dissolving diisocyanate into MMA, then dropwise adding the diisocyanate into a mixed solution of hindered amine acrylic ester and MMA, stirring and reacting for 1-60min at room temperature to obtain a product 1, and reserving the mixed solution containing the product 1 for later use;
(2) Adding an initiator required by polymerization reaction into the mixed solution containing the product 1 in the step (1) and mixing, and carrying out polymerization reaction on the product 1 and MMA under a certain condition to obtain the partially crosslinked PMMA;
the ratio of the total mass of MMA to the mass of hindered amine acrylate to the mass of diisocyanate is 1 (0.05-0.5) (0.025-0.25), wherein the mass of the hindered amine acrylate is 2 times the mass of the diisocyanate; the addition amount of the initiator is 0.1-5% of the total mass of MMA and hindered amine acrylate.
2. The method for preparing partially crosslinked PMMA according to claim 1, wherein: the diisocyanate is any one of IPDI, HDI, TDI, MDI and HMDI; the hindered amine acrylic ester is any one of tert-butylaminoethyl methacrylate, tert-butylaminoethyl acrylate, isopropylaminoethyl methacrylate, isopropylaminoethyl acrylate, piperidinaminoethyl acrylate and piperidinaminoethyl methacrylate; the initiator is a thermal decomposition initiator and/or a redox initiator; the thermal decomposition initiator is azo compound and/or peroxy compound; redox initiators are combinations of peroxides and reducing agents.
3. The method for preparing partially crosslinked PMMA according to claim 1, wherein the polymerization conditions in the step (2) are: after reacting for 0.1-48 hours at-20-100 ℃, post-curing for 0.1-48 hours at 60-120 ℃.
4. Partially crosslinked PMMA prepared by the process of any one of claims 1 to 3.
5. A partially crosslinked PMMA composite, characterized by: the partially crosslinked PMMA composite material comprises the partially crosslinked PMMA according to claim 4 and a fiber reinforced material.
6. The partially crosslinked PMMA composite of claim 5, wherein: the fiber reinforcement material is chopped fiber or continuous fiber; the chopped fiber is one or more of chopped carbon fiber, chopped glass fiber, chopped aramid fiber and chopped high-density polyethylene fiber; the continuous fiber is one or more of carbon fiber, glass fiber, basalt fiber and aramid fiber.
7. The method for preparing the partially crosslinked PMMA composite material according to claim 5, wherein the method comprises the following steps: the preparation method is any one of injection molding, vacuum assisted infusion molding, compression molding, winding molding and pultrusion.
8. The method of preparing a partially crosslinked PMMA composite of claim 7 wherein the vacuum assisted injection molding method comprises the steps of: defoaming the mixed solution of the product 1 added with the initiator in the step (2) of claim 1, adopting a vacuum-assisted pouring molding method, pouring the mixed solution into a prefabricated body paved by fiber reinforced materials in vacuum, and obtaining the partially cross-linked PMMA composite material through curing reaction, demolding and post-treatment.
9. The method of preparing a partially crosslinked PMMA composite of claim 8, wherein: the vacuum negative pressure of the vacuum infusion is- (0.08-0.1) MPa; the curing reaction conditions are that the curing is carried out for 0.1 to 48 hours at the temperature of 0 to 100 ℃ and then the post-curing is carried out for 0.1 to 48 hours at the temperature of 60 to 120 ℃.
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| CN114806055A (en) * | 2022-05-19 | 2022-07-29 | 浙江华帅特新材料科技有限公司 | Reinforced and toughened PMMA plate and manufacturing method thereof |
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