CN115785328A - Partially crosslinked PMMA and preparation method of composite material thereof - Google Patents
Partially crosslinked PMMA and preparation method of composite material thereof Download PDFInfo
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- 238000011417 postcuring Methods 0.000 claims description 17
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 16
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- WRJXGJVVKVFPBH-UHFFFAOYSA-N 2-(propan-2-ylamino)ethyl prop-2-enoate Chemical compound CC(C)NCCOC(=O)C=C WRJXGJVVKVFPBH-UHFFFAOYSA-N 0.000 claims description 2
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- FGSBZZTYGCQZPD-UHFFFAOYSA-N 2-piperidin-1-ylethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1CCCCC1 FGSBZZTYGCQZPD-UHFFFAOYSA-N 0.000 claims description 2
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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 5
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- 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
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- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 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 4
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- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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 1
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Landscapes
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Abstract
The invention belongs to the technical field of synthesis of polymer resin and a composite material thereof, and particularly relates to a preparation method of partially crosslinked PMMA and a composite material thereof. The long chains of the partially crosslinked PMMA are tightly connected through covalent bonds to form a stable three-dimensional netThe strength and toughness of PMMA are enhanced by adjusting the addition amount of diisocyanate, and the tensile strength, impact strength and elongation at break can be respectively improved to 85MPa and 33KJ/m 2 And 10%, and the characteristic of recycling the PMMA resin is reserved; meanwhile, the composite material prepared by the partially crosslinked PMMA and the fiber reinforced material has excellent mechanical properties. The preparation method has the advantages of few additives, simple process, no catalyst, mild and controllable reaction, guarantee of the partially crosslinked PMMA for preparing the composite material under the vacuum infusion molding process, and high application value.
Description
Technical Field
The invention belongs to the technical field of synthesis of polymer resin and a composite material thereof, and particularly relates to a preparation method of partially crosslinked PMMA and a composite material thereof.
Background
Polymethyl methacrylate (PMMA) is an important transparent engineering plastic, and has been widely used in optical materials, construction and packaging industries due to its advantages of light weight, good light transmittance, easy processing, and recyclability. However, the PMMA product often has the defects of low strength and insufficient toughness, so that the wide-range popularization and application thereof are limited.
Aiming at the defects of the PMMA product, the PMMA is toughened and modified by using materials such as nano particles, a core-shell modifier, a rubber elastomer and the like; PMMA is subjected to reinforcing modification by using metal oxide such as alumina, chopped fiber such as glass fiber, cellulose such as lignin and other materials. For example, in patent publication No. CN109735035A, polyolefin macroinitiator containing reactive functional group and Methyl Methacrylate (MMA) monomer are polymerized in situ to prepare toughening agent for modifying PMMA resin, so that the impact strength of PMMA resin is increased to 33KJ/m 2 But the tensile strength is poor and is only about 62 MPa; the patent publication No. CN 109370133A uses extracted lignin to modify a prepolymerized MMA solutionThe tensile strength of the organic glass is improved by 13 percent, but the toughness performance of the organic glass is still not optimized. It can be seen that most of the existing modification methods can only improve one of the properties alone, and it is difficult to achieve the reinforcing modification while toughening modification, and even increase the brittleness of the product while reinforcing modification, so that the toughness property is reduced.
The reinforced and toughened PMMA plate and the manufacturing method thereof are provided by the patent with the patent number of CN114806055A, wherein a polymethyl methacrylate high molecular chain, a polyol polymer and a short-distance connecting unit are adopted as raw material components, the reinforced and toughened PMMA plate is obtained by casting and polymerization, the molecular chains of PMMA are mutually entangled and interlocked under the action of the polyol polymer and the short-distance connecting unit, and the polyol polymers are transversely connected, 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%; the unnotched impact strength of the simply supported beam is improved to 25KJ/m 2 The strength and toughness of the PMMA resin are modified from the perspective of a molecular structure, and the PMMA resin are modified simultaneously, but a catalyst is needed in the modification method to obtain a better reaction effect, and a short-range connecting unit in the modification method cannot directly connect polymethyl methacrylate high molecular chains together, and a polyol polymer is additionally added to realize the connection between the polymethyl methacrylate high molecular chains and the short-range connecting unit, so that more modification additives are added in the PMMA plate, and the modification method is more complicated and is not easy to control.
Therefore, the development of a modification method which can simultaneously toughen and strengthen PMMA, has few additives, is simple and convenient to operate, has an 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 purpose, the technical scheme of the invention is realized as follows:
a process for the preparation of partially crosslinked PMMA comprising the steps of:
(1) Dissolving diisocyanate into MMA, then dropwise adding the diisocyanate into the mixed solution of hindered amine acrylate 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), mixing, and carrying out polymerization reaction on the product 1 and MMA under certain conditions 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) to (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 the MMA and the hindered amine acrylate.
Preferably, the diisocyanate is any one of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and 4,4' -dicyclohexylmethane diisocyanate (HMDI); the hindered amine acrylate is any one of tert-butylaminoethyl methacrylate, tert-butylaminoethyl acrylate, isopropylaminoethyl methacrylate, isopropylaminoethyl acrylate, piperidinoethyl acrylate and piperidinoethyl methacrylate; the initiator is a thermal decomposition type initiator and/or a redox initiator; the thermal decomposition initiator is an azo compound and/or a peroxide compound; the redox initiator is a combination of a peroxide and a reducing agent.
More preferably, the azo compound is azobisisobutyronitrile (2,2 '-Azobis (2-methyl propionitril), AIBN for short) or azobisisoheptonitrile (2,2' -Azobis (2,4-dimethyl) valonitrile, ABVN for short); the peroxy compound is Benzoyl Peroxide (BPO); the peroxide is BPO or lauroyl peroxide (LPO for short); the reducing agent is N, N-Dimethyl-p-toluidine (DMT for short) and/or N, N-dimethylaniline (DMA for short).
Preferably, the polymerization reaction in the step (2) is carried out under the conditions of reaction at-20-100 ℃ for 0.1-48h and post-curing at 60-120 ℃ for 0.1-48h.
The reaction process for preparing the partially crosslinked PMMA is as follows:
wherein the content of the first and second substances,
is the molecular structure of diisocyanate and has the following structure,
is the molecular structure of the hindered amine acrylate,
is the molecular structure of the product 1,
is the molecular structure of Methyl Methacrylate (MMA),
is a structure of partially cross-linked PMMA; wherein m is an integer not less than 1, and n is an integer not less than 1; r 1 Is hydrogen or methyl, R 2 Hindered groups that are highly hindered include t-butyl, isopropyl, or piperidine.
The preparation principle of the partially crosslinked PMMA: the method comprises the following steps of firstly carrying out polyurea reaction on monomer hindered amine acrylate and diisocyanate to prepare a product 1 containing large steric hindrance carbamido in a molecular structure, wherein two ends of the product 1 contain unsaturated double bonds, under the action of an initiator, free radical copolymerization reaction is carried out between the unsaturated double bonds in the product 1 and an MMA monomer, two ends of the product 1 are grafted with PMMA molecular chains, namely, the PMMA molecular long chains are mutually crosslinked due to the product 1, and thus the partially crosslinked PMMA is formed. Under a certain crosslinking degree, the acting force among PMMA molecular chains is enhanced, so that the tensile strength is improved, and meanwhile, the strength and the toughness of the partially crosslinked PMMA can be simultaneously improved by adjusting the addition amount of diisocyanate.
The present invention also includes partially crosslinked PMMA prepared using the above method.
The invention also comprises a partially crosslinked PMMA composite material, which contains the partially crosslinked PMMA and a fiber reinforced material.
Preferably, the fibrous reinforcement is chopped or continuous fibers; 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 fiber is one or more of carbon fiber, glass fiber, basalt fiber and aramid fiber; the continuous fiber is continuous fiber yarn or fiber cloth.
The preparation method of the partially crosslinked PMMA composite material is any one of injection molding method, vacuum-assisted infusion molding method, compression molding method, winding molding method and pultrusion method.
Preferably, the vacuum assisted infusion molding method is used for preparing the partially crosslinked PMMA composite material by the following specific steps:
step a: dissolving diisocyanate into MMA, then dropwise adding the diisocyanate into a mixed solution 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 substance amount of MMA to the substance amounts of hindered amine acrylate and diisocyanate is 1 (0.05-0.5) to (0.025-0.25), and the substance amount of hindered amine acrylate is 2 times of that of diisocyanate, and the mixed solution containing the product 1 is reserved for later use;
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 obtained in the step (b), and performing vacuum assisted infusion molding by using a vacuum assisted infusion molding method, wherein the vacuum negative pressure is- (0.08-0.1) MPa, the preform which is infused with the mixed solution is subjected to reaction (i.e. curing) for 0.1-48h at the temperature of 0-100 ℃, and then is subjected to post-curing for 0.1-48h at the temperature of 60-120 ℃, and the composite material of the partially crosslinked PMMA is obtained after demolding and post-treatment.
The invention has the beneficial effects that:
1. the invention provides a preparation method of partially crosslinked PMMA, firstly, diisocyanate and hindered amine acrylate are subjected to polyurea reaction to generate an intermediate product (namely a product 1) containing hindered ureido groups, both ends of the 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 under the initiation of an initiator to finally obtain the partially crosslinked PMMA, and long chains of the PMMA polymer are mutually connected through the product 1, so that the long chains are connected through covalent bonds, namely, the crosslinking among the long chains is formed.
2. The preparation method of the partially crosslinked PMMA provided by the invention has the advantages that the whole steps are clear and simple, the reaction process is controllable, the polyurea reaction among small molecules can be ensured to be complete, no by-product is generated, meanwhile, the subsequent free radical polymerization reaction is not influenced by the polyurea reaction, and the structure of the final product, namely the partially crosslinked PMMA, is ensured; 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 when the polyurea reaction is finished, the next polymerization reaction can be directly carried out, and the reaction steps are effectively simplified.
3. According to the preparation method of the partially crosslinked PMMA, a large amount of MMA is contained in the whole reaction system and is not reacted during polymerization reaction, the viscosity of the reaction system is low, and the polymerization reaction can be initiated by an initiator, so that the polymerization reaction has a certain induction period, a vacuum-assisted infusion molding process can be directly implemented, namely, a mixed solution containing the partially crosslinked PMMA is defoamed and then is impregnated into a fiber reinforced preform in a vacuum infusion mode, and finally, the fiber reinforced resin matrix composite material, namely the partially crosslinked PMMA composite material, is prepared.
4. The partially crosslinked PMMA prepared by the method has certain crosslinking degree and more excellent mechanical property than pure PMMA resin because the molecules are crosslinked through the product 1, the strength and the toughness can be simultaneously enhanced 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 And 10%; meanwhile, the hindered urea bond in the network of the partially crosslinked PMMA molecule is a dynamic valence-supplying chemical bond which can be dissociated at high temperature, and molecular healing, recycling and shape memory can be carried out through a dissociation exchange mechanism, so that the characteristic of the PMMA resin that can be recycled is reserved. Meanwhile, the composite material prepared by the partially crosslinked PMMA and the fiber reinforced material has excellent mechanical property, and PMMA can be recycled, so the composite material is an environment-friendly composite material.
5. The preparation method of the partially crosslinked PMMA provided by the invention has the advantages of few additives, simple process, environmental protection, no catalyst, mild and controllable reaction, guarantees that the partially crosslinked PMMA can be suitable for preparing the composite material under the vacuum infusion molding process, and expands the wide application of the partially crosslinked PMMA resin in the fields of wind power blades, ships, yachts and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: 4.2182g HDI is dissolved in 20g MMA, and then is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, and the mixture is stirred and reacted for 10min at room temperature to prepare a product 1; wherein the ratio of the total molar amount of MMA to the molar amount of t-butylaminoethyl methacrylate and HDI is 1;
step 2: adding 1.0925g LPO required by polymerization reaction and 0.4435g DMT required by polymerization reaction into the mixed solution containing the product 1 in the step 1, stirring the mixture until the mixture is in a transparent and particle-free state, then carrying out polymerization reaction on the product 1 and MMA at the temperature of 25 ℃ for 8 hours, and carrying out post-curing at the temperature of 80 ℃ for 3 hours to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA produced in this example were tested: adopting the existing sample strip preparation method, preparing a standard test sample strip by pouring the mixed solution containing the partially crosslinked PMMA in the step 2, and characterizing the tensile strength, the elongation at break and the unnotched impact strength of the simply supported beam according to the ISO international standard to obtain the mechanical properties: the tensile strength is 79MPa, and the impact strength is 31KJ/m 2 The elongation at break was 9%.
Example 2
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: dissolving 8.6976g MDI in 30g MMA, slowly dropwise adding the solution into a mixed solution of 21.3064g isopropyl aminoethyl methacrylate and 70g MMA, stirring and reacting at room temperature for 20min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to isopropyl aminoethyl methacrylate and MDI is 1;
step 2: adding 1.7776g LPO required by polymerization reaction and 1.7412g DMA required by the reduction agent 1.7412g DMA into the mixed solution containing the product 1 in the step 1, carrying out polymerization reaction on the product 1 and MMA at 40 ℃ and under an oxygen-free condition for 5h, and carrying out post-curing at 90 ℃ for 3h to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were measured with reference to the method for measuring mechanical properties in example 1, and the tensile strength was 80MPa, and the impact strength was 32KJ/m 2 The elongation at break was 9%.
Example 3
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: dissolving 11.1008g IPDI in 25g MMA, then dropwise adding the solution into a mixed solution of 18.3028g piperidine aminoethyl acrylate and 75g MMA, stirring and reacting at room temperature for 30min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to the piperidine aminoethyl acrylate and the IPDI is 1;
step 2: adding 0.2839g BPO and 0.1183g DMT required by polymerization reaction into the mixed solution containing the product 1 in the step 1, carrying out polymerization reaction on the product 1 and MMA at-20 ℃ under an oxygen-free condition for 48h, and carrying out post-curing at 120 ℃ for 1.5h to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were measured with reference to the method for measuring mechanical properties in example 1, and it was found that the tensile strength was 78MPa and the impact strength was 30KJ/m 2 The elongation at break was 8%.
Example 4
This example provides a process for the preparation of partially crosslinked PMMA by the following steps:
step 1: 22.2053g IPDI is dissolved in 35g MMA, then is dripped into a mixed solution of 39.6020g piperidine aminoethyl methacrylate and 65g MMA, the stirring reaction is carried out for 50min at room temperature, so as to prepare a product 1, wherein the molar ratio of the total molar amount of MMA to piperidine aminoethyl methacrylate and IPDI is 1;
step 2: and (2) adding 0.3282g of BPO and 0.137g of DMT which are required by the polymerization reaction into the mixed solution containing the product 1 in the step (1), carrying out the polymerization reaction on the product 1 and MMA at 100 ℃ under the oxygen-free condition for 1h, and carrying out post-curing at 110 ℃ for 2h to obtain the product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were measured with reference to the method for measuring mechanical properties 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
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: dissolving 22.2053g IPDI in 35g MMA, then dropwise adding the solution into a mixed solution of 39.6020g piperidine aminoethyl methacrylate and 65g MMA, stirring and reacting at room temperature for 50min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to piperidine aminoethyl methacrylate and IPDI is 1;
step 2: adding an initiator AIBN 6.9801g required by the polymerization reaction into the mixed liquid containing the product 1 in the step 1, carrying out the polymerization reaction on the product 1 and MMA at the temperature of 50 ℃ for 12 hours, and carrying out post-curing at the temperature of 110 ℃ for 2 hours to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were measured with reference to the method for measuring mechanical properties 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
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: dissolving 43.4965g TDI in 60g MMA, then dropwise adding the solution into a mixed solution of 84.5455g tert-butylaminoethyl acrylate and 40g MMA, stirring and reacting at room temperature for 1min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to the tert-butylaminoethyl acrylate and TDI is 1;
step 2: adding ABVN 0.1845g of initiator required for polymerization into the mixed liquid containing the product 1 in the step 1, carrying out polymerization reaction on the product 1 and MMA at the temperature of 30 ℃ for 48h, and carrying out post-curing at the temperature of 120 ℃ for 0.3h to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were measured with reference to the method for measuring mechanical properties 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
This example provides a method for preparing partially crosslinked PMMA, comprising the following steps:
step 1: dissolving 26.2088g HMDI in 55g MMA, then dropwise adding the solution into a mixed solution of 39.424g isopropyl amino ethyl acrylate and 45g MMA, stirring and reacting at room temperature for 60min to obtain a product 1, wherein the molar ratio of the total molar amount of MMA to isopropyl amino ethyl acrylate and HMDI is 1;
step 2: adding an initiator BPO 6.9712g required by the polymerization reaction into the mixed solution containing the product 1 in the step 1, carrying out the polymerization reaction on the product 1 and MMA at the temperature of 100 ℃ for 0.1h, and carrying out post-curing at the temperature of 80 ℃ for 48h to obtain a product containing the partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA obtained in this example were tested by referring to the method for testing mechanical properties of example 1, and it was found that the tensile strength was 78MPa, and the impact strength was 31KJ/m 2 The elongation at break was 9%.
Comparative example
Partially crosslinked PMMA was prepared as described in example 1, except that no HDI was 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 were added, stirred until no particles were present and then polymerized at 25 ℃ for 8h, and post-cured at 80 ℃ for 3h to produce a product containing partially crosslinked PMMA.
The mechanical properties of the partially crosslinked PMMA were measured by the method of measuring mechanical properties in reference to example 1, and it was found that the tensile strength was 68MPa, and the impact strength was 23KJ/m 2 Elongation at break of 5% and three parameter values are smaller than for the partially crosslinked PMMA prepared in example 1. Thus, it shows that the inventionIt is clear that the addition of diisocyanate does effectively increase the tensile strength and impact strength of the partially crosslinked PMMA, i.e., increases the strength and toughness.
Meanwhile, the partially crosslinked PMMA specimens prepared in examples 1-7 above were broken into small pieces, and then placed in a molding press to be melted at a temperature of 140 ℃ and hot-pressed into standard test specimens. The mechanical properties of the hot-pressed standard sample strip are kept unchanged compared with the properties before crushing and melting when the hot-pressed standard sample strip is tested 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 HDI is dissolved in 20g MMA, then the solution is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature 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 LPO required by polymerization reaction and 0.4435g DMT 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, defoaming the mixed solution obtained in the step b, adopting a vacuum-assisted pouring forming method, vacuumizing, pouring into a prefabricated body which is paved by unidirectional high-alkali glass fiber cloth under the vacuum negative pressure of-0.08 MPa, curing the prefabricated body which is poured with the mixed solution at the temperature of 25 ℃ for 8 hours, then post-curing at the temperature of 80 ℃ for 3 hours, and demoulding for post-treatment to obtain the partially crosslinked PMMA composite material, wherein the surface density of the unidirectional glass fiber cloth is 1250g/m 2 Wherein the volume fraction of the fibrous reinforcement is 60%.
A standard composite material strip is prepared according to ISO international standards, and the strength of the composite material is tested, wherein the tensile strength of the partially crosslinked PMMA composite material prepared in the above way in the 0 DEG direction is 1442.3MPa, and the tensile modulus is 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 HDI is dissolved in 20g MMA, then the solution is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature 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 LPO required by polymerization reaction and 0.4435g DMT 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, defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum assisted infusion molding method, infusing the mixed solution into a prefabricated body paved by unidirectional carbon fiber cloth (specification: T700 SC) under the vacuum negative pressure of-0.09 MPa, curing the prefabricated body infused with the mixed solution at 0 ℃ for 45h, then post-curing at 120 ℃ for 2h, and demolding to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
A standard composite material strip is prepared according to ISO international standards, and the strength of the composite material is tested, wherein the tensile strength of the partially crosslinked PMMA composite material prepared in the above way in the 0 DEG direction is 1988.1MPa, and the tensile modulus is 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 HDI is dissolved in 20g MMA, then the solution is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature 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 BPO and 0.4435g DMT 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, defoaming the mixed liquid obtained in the step b, vacuumizing by adopting a vacuum-assisted pouring forming method, pouring the mixed liquid into a prefabricated body which is horizontally paved by unidirectional basalt fiber cloth (the specification is 12 k-200G) under the vacuum negative pressure of-0.08 MPa, curing the prefabricated body which is poured with the mixed liquid at 40 ℃ for 6h, post-curing at 80 ℃ for 6h, and demoulding and post-treating to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
According to ISO international standard, a standard composite material strip is prepared and tested for strength, and the tensile strength of the partially crosslinked PMMA composite material prepared in the above way in the 0-degree direction is 1250.5MPa, and the tensile modulus is 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 HDI is dissolved in 20g MMA, then the solution is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature 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 peroxydodecanyl and 0.4435g of DMT 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 c, defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum-assisted pouring forming method, pouring the mixed solution into a prefabricated body which is laid by unidirectional aramid fiber cloth under the vacuum negative pressure of-0.098 MPa, curing the prefabricated body which is poured with the mixed solution at 100 ℃ for 2 hours, then post-curing at 120 ℃ for 1 hour, and demoulding and post-treating to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 60%.
A standard composite bar was prepared according to ISO international standard and tested for strength, and the partially crosslinked PMMA composite material prepared above had a tensile strength of 506.3MPa in the 0 ℃ direction 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 HDI is dissolved in 20g MMA, then is dripped into the mixed liquid of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature for 10min to prepare a product 1, and the mixed liquid containing the product 1 is reserved for standby;
step b: adding 1.0925g of peroxydodecanyl and 0.4435g of DMT 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 (c) defoaming the mixed solution obtained in the step (b), vacuumizing by adopting a vacuum-assisted infusion molding method, infusing into a preform paved by chopped glass fibers (the specification is that the diameter of a fiber monofilament is 10 mu m, and the length of the fiber is 4 mm) under the vacuum negative pressure of-0.098 MPa, curing the preform infused with the mixed solution at 100 ℃ for 2h, then post-curing at 120 ℃ for 1h, and demolding and post-treating to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 40%.
A standard composite material strip is prepared according to ISO international standard and tested for strength, and the prepared partially-crosslinked PMMA composite material has the tensile strength of 98.8MPa and the tensile modulus of 3.4GPa.
Example 13
This example provides a method for preparing a partially crosslinked PMMA composite, comprising the following steps:
step a: 4.2182g HDI is dissolved in 20g MMA, then the solution is dripped into a mixed solution of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature 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 peroxydodecanyl and 0.4435g of DMT 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 (b) defoaming the mixed solution obtained in the step (b), vacuumizing by adopting a vacuum-assisted infusion molding method, infusing into a prefabricated body paved by glass fiber bidirectional cloth (specification: EWR600-1000, fiber monofilament diameter of 10 mu m) under the vacuum negative pressure of-0.098 MPa, curing the prefabricated body infused with the mixed solution at 100 ℃ for 2h, post-curing at 120 ℃ for 1h, and demolding to obtain the partially crosslinked PMMA composite material, wherein the volume fraction of the fiber reinforced material is 55%.
A standard composite material strip is prepared according to ISO international standards, and the strength of the composite material is tested, wherein the tensile strength of the partially crosslinked PMMA composite material prepared in the above way in the 0 DEG direction is 261.2MPa, and the tensile modulus is 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 HDI is dissolved in 20g MMA, then is dripped into the mixed liquid of 9.2521g tert-butylaminoethyl methacrylate and 80g MMA, the reaction is stirred at room temperature for 10min to prepare a product 1, and the mixed liquid containing the product 1 is reserved for standby;
step b: adding 1.0925g of peroxydodecanyl and 0.4435g of DMT 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 c, defoaming the mixed solution obtained in the step b, vacuumizing by adopting a vacuum-assisted infusion molding method, infusing the mixed solution into a prefabricated body paved by continuous glass fiber yarns under the vacuum negative pressure of-0.098 MPa, curing the prefabricated body infused with the mixed solution at 100 ℃ for 2 hours, post-curing at 120 ℃ for 1 hour, and demolding and post-treating 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, the partially crosslinked PMMA composite prepared above had a tensile strength of 705.2MPa and a tensile modulus of 26.7GPa.
From the results of the measurements of mechanical properties of the partially crosslinked PMMA composite materials obtained in examples 8 to 14, it can be seen that the fiber-reinforced partially crosslinked PMMA composite material prepared by the vacuum assisted infusion molding method has excellent mechanical properties; meanwhile, the PMMA resin in the composite material can be recycled by a solvent dissolving method, and the fiber reinforced material can also be recycled, such as being used for preparing the composite material again.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the partially crosslinked PMMA 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 acrylate and MMA, stirring and reacting at room temperature for 1-60min to obtain a product 1, and reserving the mixed solution containing the product 1 for later use;
(2) And (2) adding an initiator required by the 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.
2. Process for the preparation of partially crosslinked PMMA according to claim 1, wherein: the ratio of the total mass of the MMA to the mass of the hindered amine acrylate and the diisocyanate is 1 (0.05-0.5) to (0.025-0.25), wherein the mass of the hindered amine acrylate is 2 times of that of the diisocyanate; the addition amount of the initiator is 0.1-5% of the total mass of the MMA and the hindered amine acrylate.
3. Process for the preparation of partially crosslinked PMMA according to claim 1, wherein: the diisocyanate is any one of IPDI, HDI, TDI, MDI and HMDI; the hindered amine acrylate is any one of tert-butylaminoethyl methacrylate, tert-butylaminoethyl acrylate, isopropylaminoethyl methacrylate, isopropylaminoethyl acrylate, piperidinoethyl acrylate and piperidinoethyl methacrylate; the initiator is a thermal decomposition type initiator and/or a redox initiator; the thermal decomposition initiator is an azo compound and/or a peroxide compound; the redox initiator is a combination of a peroxide and a reducing agent.
4. The method for preparing partially crosslinked PMMA according to claim 1, wherein the polymerization conditions in the step (2) are: reacting at-20 to 100 ℃ for 0.1 to 48h, and curing at 60 to 120 ℃ for 0.1 to 48h.
5. Partially crosslinked PMMA prepared by a process according to any of claims 1 to 4.
6. A partially crosslinked PMMA composite, characterized in that: the partially crosslinked PMMA composite material comprises the partially crosslinked PMMA of claim 5 and a fiber reinforcement material.
7. A partially crosslinked PMMA composite according to claim 6, characterized in that: the fiber reinforced 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.
8. A method of preparing a partially crosslinked PMMA composite material as claimed in claim 6, characterized in that: the preparation method is any one of injection molding, vacuum-assisted infusion molding, compression molding, winding molding and pultrusion molding.
9. The method for preparing a partially crosslinked PMMA composite according to claim 8, wherein the vacuum assisted infusion molding method comprises the steps of: defoaming the mixed solution of the product 1 with the initiator added in the step (2) of claim 1, vacuum-filling the mixed solution into a prefabricated body paved by fiber reinforced materials by a vacuum-assisted filling molding method, and then carrying out curing reaction, demolding and post-treatment to obtain the partially crosslinked PMMA composite material.
10. A method of preparing a partially cross-linked PMMA composite according to claim 9, wherein: the vacuum negative pressure of the vacuum infusion is (0.08 to 0.1) MPa; the curing reaction condition is that the curing is firstly carried out for 0.1 to 48h at the temperature of 0 to 100 ℃, and then the post-curing is carried out for 0.1 to 48h at the temperature of 60 to 120 ℃.
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| CN103998211A (en) * | 2011-10-21 | 2014-08-20 | 阿肯马法国公司 | Composite material via in-situ polymerization of thermoplastic (meth)acrylic resins and its use |
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| CN103998211A (en) * | 2011-10-21 | 2014-08-20 | 阿肯马法国公司 | Composite material via in-situ polymerization of thermoplastic (meth)acrylic resins and its use |
| CN113583211A (en) * | 2021-07-30 | 2021-11-02 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| 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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