CN111808233A - Halogen-free flame-retardant acrylic resin composition, molding compound product, preparation method and application - Google Patents

Halogen-free flame-retardant acrylic resin composition, molding compound product, preparation method and application Download PDF

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CN111808233A
CN111808233A CN202010918479.2A CN202010918479A CN111808233A CN 111808233 A CN111808233 A CN 111808233A CN 202010918479 A CN202010918479 A CN 202010918479A CN 111808233 A CN111808233 A CN 111808233A
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resin
halogen
acrylic resin
free flame
resin composition
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CN111808233B (en
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刘小青
代金月
腾娜
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • C08J2343/00—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 containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
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Abstract

The invention discloses a halogen-free flame-retardant acrylic resin composition, which comprises bio-based acrylate and phosphorus-containing acrylate with a structure shown in the following formula:
Figure 264187DEST_PATH_IMAGE001
the invention also discloses a preparation method and application of the bio-based halogen-free flame-retardant acrylic resin composition and a cured product thereof. The bio-based halogen-free flame-retardant acrylic resin composition and the condensate thereof have the advantages of simple preparation process, simple and convenient operation method, good controllability, easy implementation and suitability for large-scale industrial production. The bio-based halogen-free flame-retardant acrylic resin composition and the plant oil-based thermosetting resin obtained by curing the same have excellent thermodynamic property and flame retardant property, have the possibility of replacing the same type of petroleum-based products, and have wide application range.

Description

Halogen-free flame-retardant acrylic resin composition, molding compound product, preparation method and application
Technical Field
The invention relates to an acrylic resin composition, in particular to a phosphorus-containing acrylate, a bio-based halogen-free flame-retardant acrylic resin composition, a molding compound product, a preparation method and application thereof, and belongs to the technical field of bio-based thermosetting resin.
Background
The bio-based polymer material is a polymer material taking renewable resources as main raw materials, reduces the consumption of petrochemical products in the plastic industry, reduces the pollution to the environment in the production process of petroleum-based raw materials, has double effects of saving petroleum resources and protecting the environment, is an important development direction of the current polymer material, and has important practical value and wide development space. The vegetable oil has the characteristics of wide sources, large yield and low price, and the main component of the vegetable oil, namely the glycerin fatty acid ester, contains multiple functional groups such as double bonds, ester bonds, allylic hydrogen and the like, so that the vegetable oil is convenient for chemical modification and synthesis, and becomes an important chemical raw material which is widely applied to the synthesis of macromolecules. However, the natural triglyceride has a long soft fat chain segment and a low double bond density, so that the prepared material has a low glass transition temperature and a low mechanical strength. The prior vegetable oil-based high polymer material usually needs to add a large amount of rigid comonomer, such as styrene, divinyl benzene and the like. The introduction of the rigid monomers effectively improves the thermal and mechanical properties of the plant oil-based thermosetting resin, and further expands the application field of the plant oil-based thermosetting resin.
However, like conventional thermosetting resins, such vegetable oil-based polymer materials are easily combustible and cause immeasurable loss of life and property in case of fire during use. However, there is little research on flame retardant modification of vegetable oil-based thermosetting resins at the present stage, which will certainly greatly limit the widespread use of vegetable oil-based thermosetting resins.
Disclosure of Invention
The invention mainly aims to provide a bio-based halogen-free flame-retardant acrylic resin composition, a cured product thereof, a molding compound product and a preparation method thereof, so as to overcome the defects of the prior art.
The invention also aims to provide application of the bio-based halogen-free flame retardant acrylic resin composition.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a halogen-free flame-retardant acrylic resin composition, which comprises the following components in part by weight: resin A, resin B and an initiator; the resin A comprises bio-based acrylate, the resin B comprises phosphorus-containing acrylate, and the phosphorus-containing acrylate has a structure shown in a formula (2):
Figure 51948DEST_PATH_IMAGE001
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Figure 441472DEST_PATH_IMAGE002
Or
Figure 633419DEST_PATH_IMAGE003
(ii) a Y is
Figure 916633DEST_PATH_IMAGE002
Or
Figure 348883DEST_PATH_IMAGE003
；
Z is selected from
Figure 412654DEST_PATH_IMAGE002
、
Figure 345974DEST_PATH_IMAGE003
、
Figure 356131DEST_PATH_IMAGE004
Or
Figure 146233DEST_PATH_IMAGE005
。
The embodiment of the invention also provides a preparation method of the phosphorus-containing acrylate, which comprises the following steps:
in the presence of an acid binding agent, reacting a compound shown as a formula (3) with acryloyl chloride or methacryloyl chloride at-30 ℃ for 6-24 h to obtain phosphorus-containing acrylate;
Figure 634983DEST_PATH_IMAGE006
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2。
In some embodiments, the method of making comprises: carrying out condensation reaction on a mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
Figure 716202DEST_PATH_IMAGE007
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2。
In some embodiments, the biobased acrylate has a structure as shown in formula (1):
Figure 36325DEST_PATH_IMAGE008
（1）
wherein R is selected from
Figure 200590DEST_PATH_IMAGE002
、
Figure 786424DEST_PATH_IMAGE003
、
Figure 858285DEST_PATH_IMAGE009
、
Figure 236177DEST_PATH_IMAGE010
、
Figure 915551DEST_PATH_IMAGE011
Or
Figure 441210DEST_PATH_IMAGE012
。
The embodiment of the invention also provides a preparation method of the bio-based halogen-free flame-retardant acrylic resin cured product, which comprises the following steps: and curing the bio-based halogen-free flame-retardant acrylic resin composition at 60-140 ℃.
The embodiment of the invention also provides the bio-based halogen-free flame-retardant acrylic resin cured product prepared by the method, wherein the glass transition temperature of the cured product is 60-100 ℃, the tensile strength of the cured product is 30-80 MPa, and the flame retardant property of the cured product is above V1 level.
The embodiment of the invention also provides the application of the bio-based halogen-free flame-retardant acrylic resin composition and the cured product thereof in the field of photocuring or thermocuring coating.
The embodiment of the invention also provides a device with a heat-resistant flame-retardant structure, wherein the heat-resistant flame-retardant structure comprises the bio-based halogen-free flame-retardant acrylic resin cured product.
The embodiment of the invention also provides a processing method of the molding compound product, which comprises the following steps: after the bio-based halogen-free flame-retardant acrylic resin composition and a reinforcing material are mixed, the mixture is processed into the shape of a required product by at least any one of the modes of mould pressing, laminating, transfer molding and casting, and then the required product is obtained after solidification.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the bio-based halogen-free flame-retardant acrylic resin composition and the condensate thereof, the high-performance bio-based thermosetting resin with excellent thermodynamic property and flame retardant property is prepared by combining the flame-retardant acrylate with the DOPO structure and the vegetable oil-based thermosetting resin, and particularly, the particularity of the vegetable oil structure can endow the material with good toughness, so that the application field of the vegetable oil-based thermosetting resin is widened, the product has the possibility of replacing petroleum-based products of the same type, and has very good application prospect;
(2) the bio-based halogen-free flame-retardant acrylic resin composition and the condensate thereof provided by the invention have the advantages of simple preparation process, simple and convenient operation method, good controllability, easy implementation and suitability for large-scale industrial production, and the plant oil-based thermosetting resin obtained based on the composition has excellent thermodynamic property and flame retardant property, has the possibility of replacing petroleum-based products of the same type, and has wide application range, thereby expanding the application field of soybean oil-based materials.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a stress-strain graph of the cured product of resin A (i.e., biobased acrylate) in example 1 of the present invention;
FIG. 2 is resin A (i.e., biobased acrylate) of example 1 of the present invention: stress-strain graph of cured product of resin B (i.e., phosphorous acrylate) =80:20 ratio;
FIG. 3 is resin A (i.e., biobased acrylate) of example 2 of the present invention: stress-strain graph of cured product of resin B (i.e., phosphorous acrylate) =60:40 ratio.
Detailed Description
The present inventors have made extensive studies and extensive practices to solve the problem of flame retardancy of vegetable oil-based thermosetting resins, and as a result, the present invention will be described more clearly and completely. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The phosphorus flame retardant has excellent flame retardance, and can promote the polymer to be dehydrated in advance in the combustion process, so that the temperature of the surrounding environment is reduced and is lower than the combustion temperature for flame retardance; in addition, phosphoric acid can form polyphosphoric acid compound at high temperature to cover the surface of the polymer to form a protective layer, and oxygen is prevented from entering the protective layer. The phosphorus-containing compound 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) attracts attention, and the flame-retardant compound based on the structure has very high flame-retardant performance, is easy to chemically modify and can obtain a flame-retardant monomer with good reaction activity.
The main technical scheme of the invention is that the flame-retardant acrylate with the DOPO structure and the plant oil-based thermosetting resin are combined to prepare the high-performance bio-based thermosetting resin with excellent thermodynamic property and flame-retardant property, so that the application field of the plant oil-based thermosetting resin is widened.
One aspect of the embodiments of the present invention provides a class of phosphorus-containing acrylates having a structure as shown in formula (2):
Figure 988866DEST_PATH_IMAGE013
（2）
wherein，R1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Figure 93701DEST_PATH_IMAGE002
Or
Figure 334189DEST_PATH_IMAGE003
(ii) a Y is
Figure 81565DEST_PATH_IMAGE002
Or
Figure 308279DEST_PATH_IMAGE003
；
Z is selected from
Figure 395183DEST_PATH_IMAGE002
、
Figure 134469DEST_PATH_IMAGE003
、
Figure 916611DEST_PATH_IMAGE004
Or
Figure 806070DEST_PATH_IMAGE005
。
Another aspect of an embodiment of the present invention provides a method for preparing a phosphorous acrylate, including:
in the presence of an acid binding agent, reacting a compound shown as a formula (3) with acryloyl chloride or methacryloyl chloride at-30 ℃ for 6-24 h to obtain phosphorus-containing acrylate shown as a formula (2);
Figure 137694DEST_PATH_IMAGE006
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl groups of C1-C6,C1-C6 alkoxy, phenyl, phenoxy or C3-C7 cycloalkyl, R7 is-OH or NH2。
In some embodiments, the molar ratio of the compound represented by formula (3), acryloyl chloride or methacryloyl chloride to the acid scavenger is 1: 6-12: 6 to 12.
In some embodiments, the reaction temperature of the compound of formula (3), acryloyl chloride or methacryloyl chloride, and the acid binding agent is in the range of-30 to 30 ℃.
In some embodiments, the acid scavenger includes an organic base, an inorganic base, and the like, and is not limited thereto.
Further, the organic base may be any one or a combination of two or more of sodium acetate, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, and the like, but is not limited thereto.
Further, the inorganic base includes any one or a combination of two or more of potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and is not limited thereto.
In some embodiments, the method of making comprises: carrying out condensation reaction on a mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
Figure 798614DEST_PATH_IMAGE007
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7; r7 is-OH or NH2。
In some more specific embodiments, the phosphorous containing acrylate is prepared by the steps of:
(1) carrying out condensation reaction on an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5) and a compound shown as a formula (6) under the action of an acid catalyst to obtain a compound shown as a formula (3);
Figure 192686DEST_PATH_IMAGE014
（3）
Figure 10469DEST_PATH_IMAGE007
wherein R is1、R2、R3、R4、R5、R6And R7As previously defined.
(2) Reacting the compound shown in the formula (3) obtained in the step (1) with acryloyl chloride or methacryloyl chloride in the presence of an acid binding agent to obtain phosphorus-containing acrylate shown in the formula (2);
Figure 806387DEST_PATH_IMAGE015
（2）
wherein R is1、R2、R3、R4、R5、R6X, Y and Z are as defined above.
In some embodiments, in step (1), the condensation reaction conditions are: under the protection of nitrogen, the molar mass ratio of the organic phosphorus compound shown in the formula (4), the compound shown in the formula (5) and the compound shown in the formula (6) is 1: 1: 1-6, preferably 1: 1: 3 to 5. Reacting for 12-36 h at 100-130 ℃ under the action of an acid catalyst.
Further, the compound represented by the formula (5) may more specifically be 4,4' -dihydroxybenzophenone, 2-methyl-4, 4' -dihydroxybenzophenone, 2-propyl-4, 4' -dihydroxybenzophenone, 3-hexyl-4, 4' -dihydroxybenzophenone, 4' -dihydroxy-3-methoxybenzophenone, 4' -dihydroxy-3-propoxybenzophenone, 4' -dihydroxy-3-hexyloxybenzophenone, 4' -dihydroxy-3, 3' -dimethoxybenzophenone, 4' -dihydroxy-3, 3' -dipropoxybenzophenone, 4' -dihydroxy-3, 3' -dihexyloxybenzophenone, 4' -dihydroxy-3, 3' -dihexyloxybenzophenone, 4,4 '-dihydroxy-3-phenylbenzophenone, 4' -dihydroxy-3-phenoxybenzophenone, 4 '-dihydroxy-3, 3' -bicycloheptane benzophenone, 4 '-dihydroxy-3, 3' -bicyclopropane benzophenone, and the like, without being limited thereto.
Further, the compound represented by the formula (6) may be more specifically guaiacol, phenol, o-methylphenol, m-oxypropylphenol, m-hexylphenol, aniline, o-methylphenylamine, cyclohexylbenzene, m-ethylaniline, etc., without being limited thereto.
In some embodiments, in the step (1), the mass ratio of the acidic catalyst to the organophosphorus compound represented by the formula (4) is 0.1 to 10: 100. that is, the acidic catalyst for the condensation reaction is used in an amount of 0.1 to 10% by weight based on the content of the organic phosphorus compound represented by formula (4).
In some embodiments, in step (1), the acidic catalyst may be any one or a combination of two or more of organic acid, inorganic acid, lewis acid, and the like, and is not limited thereto.
Further, in the step (1), the organic acid may be acetic acid, trifluoroacetic acid, methanesulfonic acid, aminobenzenesulfonic acid, pyridinesulfonic acid, sulfanilic acid, p-methylbenzenesulfonic acid, or the like; the inorganic acid can be sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; the lewis acid may be aluminum chloride, ferric bromide, ferric chloride, boron trifluoride, etc., without being limited thereto.
In another aspect of the embodiments of the present invention, there is also provided a bio-based halogen-free flame retardant acrylic resin composition, including: resin A, resin B and an initiator; the resin A comprises a biobased acrylate and the resin B comprises the aforementioned phosphorous-containing acrylate.
Further, the bio-based halogen-free flame-retardant acrylic resin composition comprises the following three components:
(1) resin A: a biobased acrylate;
(2) resin B: one or more phosphorus-containing acrylates;
(3) and (3) an initiator.
In some embodiments, the resin a has a structure as shown in formula (1):
Figure 658716DEST_PATH_IMAGE008
（1）
wherein R is selected from
Figure 930297DEST_PATH_IMAGE002
、
Figure 427138DEST_PATH_IMAGE003
、
Figure 156190DEST_PATH_IMAGE009
、
Figure 939339DEST_PATH_IMAGE010
、
Figure 573582DEST_PATH_IMAGE011
Or
Figure 483901DEST_PATH_IMAGE012
。
The resin B has a structure shown in a formula (2):
Figure 254410DEST_PATH_IMAGE015
（2）
in the formula (2), R1、R2、R3、R4、R5、R6Each selected from the group consisting of a hydrogen atom, an alkyl group of C1-C6, an alkoxy group of C1-C6, a phenyl group, a phenoxy group and a cycloalkyl group of C3-C7;
x is
Figure 411722DEST_PATH_IMAGE002
Or
Figure 143049DEST_PATH_IMAGE003
(ii) a Y is
Figure 247271DEST_PATH_IMAGE002
Or
Figure 731342DEST_PATH_IMAGE003
；
Z is selected from
Figure 72937DEST_PATH_IMAGE002
、
Figure 150615DEST_PATH_IMAGE003
、
Figure 183162DEST_PATH_IMAGE004
Or
Figure 662685DEST_PATH_IMAGE005
。
In some embodiments, the mass ratio of resin a (including biobased acrylate), resin B (including phosphorous-containing acrylate) and initiator is 60 to 90: 10-40: 0.03 to 0.06.
In some embodiments, the initiator may be any one or a combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, and the like, without being limited thereto.
In another aspect of the embodiment of the present invention, a preparation method of a bio-based halogen-free flame retardant acrylic resin composition is provided, which includes: the bio-based acrylate is used as the resin A, and the resin B is completely dissolved in the matrix resin according to different proportions at a certain temperature to obtain a uniform mixture.
The embodiment of the invention also provides a preparation method of the bio-based halogen-free flame-retardant acrylic resin cured product, which comprises the following steps: and (3) reacting and curing a mixed reaction system containing the resin A, the resin B and the initiator at the temperature of 60-140 ℃ to finally obtain the flame-retardant plant oil-based resin cured product.
Further, the preparation method comprises the following steps: and curing the matrix resin, the additive resin and the initiator within the temperature range of 60-140 ℃ to finally obtain the flame-retardant plant oil-based resin cured product.
Further, another aspect of the embodiment of the present invention provides the bio-based halogen-free flame retardant cured acrylic resin prepared by the method, wherein the glass transition temperature of the cured acrylic resin is 60 to 100 ℃, the tensile strength of the cured acrylic resin is 30 to 80MPa, and the flame retardant property of the cured acrylic resin is above grade V1.
The invention also provides the application of the bio-based halogen-free flame retardant acrylic resin composition and the cured product thereof in the fields of photo-curing or thermosetting coatings and the like.
In another aspect of the embodiments of the present invention, there is also provided a device having a heat-resistant flame-retardant structure, where the heat-resistant flame-retardant structure includes the aforementioned bio-based halogen-free flame-retardant cured acrylic resin.
Another aspect of an embodiment of the present invention further provides a method for processing a molding compound product, including: the bio-based halogen-free flame-retardant acrylic resin composition is mixed with a reinforcing material, then is processed into the shape of a required product by at least any one of mould pressing, laminating, transfer molding and casting, and is solidified to obtain the required product.
Further, the reinforcing material includes mineral powder, glass fiber, etc. and is not limited thereto, and the addition amount thereof may be a common addition amount well known in the art.
Furthermore, the processes of mould pressing, laminating, transfer molding and casting are accompanied by heating, and the heating temperature is 180-250 ℃.
For example, the processing method of the molding compound product provided by the embodiment of the invention comprises the following steps:
soaking glass fiber in the halogen-free flame-retardant acrylic resin composition, taking out the soaked glass fiber, and air-drying to prepare a glass fiber prepreg;
laminating a plurality of glass fiber prepregs and heating to laminate at the heating temperature of 220 to 220~At 240 ℃ under a pressure of 30kg/cm3~60kg/cm3The time is more than 30 min.
For example, an embodiment of the present invention provides a method for preparing a transfer molded workpiece, including:
placing the section into a die cavity of a die, and preheating the die to 60-100 ℃;
and (3) pouring the halogen-free flame-retardant acrylic resin composition into a mold cavity of the mold by using a transfer molding machine, pressurizing after the gel point of the adhesive is reached, and performing gradient curing at 60-140 ℃.
For example, the embodiment of the present invention provides a flame retardant laminated structure, which includes a plurality of structural layers stacked together, where the structural layers are film-like materials or sheet-like materials, where at least one structural layer includes a fully cured product of the halogen-free flame retardant acrylic resin composition, or where at least two adjacent structural layers are fixedly connected by the fully cured product of the halogen-free flame retardant acrylic resin composition. Wherein each structural layer can also be composed of metal, plastic, non-metal inorganic material or composite thereof. The flame-retardant laminated structure can be applied to flame-retardant protective materials of buildings, vehicles, aerospace equipment and electronic products.
In a word, in the bio-based halogen-free flame-retardant acrylic resin composition provided by the invention, the matrix resin AESO is a bio-based monomer derived from a large amount of bio-based raw materials, so that the consumption of petrochemical products in the plastic industry can be reduced, the pollution to the environment in the production process of petroleum-based raw materials is also reduced, and the bio-based halogen-free flame-retardant acrylic resin composition has double effects of saving petroleum resources and protecting the environment; the introduction of the phosphorus-containing additive resin does not cause negative influence on the performance of the matrix resin, but improves the flame retardant performance of the material; secondly, the preparation method and the application of the bio-based halogen-free flame-retardant acrylic resin composition and the cured product thereof have the advantages of simple and convenient process, small pollution, low toxicity and simple post-treatment, and the obtained resin not only has good processability, but also has good flame retardant property and mechanical property of the prepared casting body and coating.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
In the following examples, the flame retardancy of cured bio-based halogen-free flame-retardant acrylic resin was measured using a vertical burning tester, in which V0 was the highest grade in the vertical burning test.
In the following examples, the resin A was obtained from commercially available epoxy soybean oil acrylate, and the others were obtained mainly according to the methods described in the literature (Polymer, 2005, 46(1): 71-80; Journal of Applied Polymer science, 2001, 82(3): 703-.
Example 1
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst methanesulfonic acid (0.1 wt% of the DOPO content) in 4 parts of guaiacol at 120 ℃, and reacting at the temperature for 36 hours to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 6 parts of triethylamine were dissolved in an appropriate amount of DMSO. After cooling the system to 0 ℃, slowly dripping 6 parts of acryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring and reacting for 12 hours after finishing the dripping, so as to obtain the resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol).
Figure 178111DEST_PATH_IMAGE016
Resin B
Figure 867718DEST_PATH_IMAGE017
Resin A
Resin A (the stress-strain diagram of the cured product thereof is shown in FIG. 1) and resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol) were mixed in accordance with a ratio of 80:20 at 50 c, and 0.03 part of benzoyl peroxide as an initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 66 ℃, the tensile strength is 33MPa (a stress-strain curve is shown in figure 2), and the flame retardant property is V1 grade.
From a comparison of FIGS. 1 and 2, it can be seen that the mechanical strength of the cured product of the pure resin A is very low and is not satisfactory for various applications. And the addition of the resin B can obviously improve the mechanical strength of the vegetable oil-based thermosetting resin.
Example 2
Synthesis of additive resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst acetic acid (1 wt% of the DOPO content) in 5 parts of phenol at 130 ℃ and reacting at the temperature for 24 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 10 parts of potassium carbonate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and after the reaction is finished, the stirring reaction is continued for 15 hours, so as to obtain the addition resin (4, 4' -dihydroxy benzophenone/DOPO/phenol).
Figure 313743DEST_PATH_IMAGE018
Resin B
Figure 523138DEST_PATH_IMAGE017
Resin A
Resin a and resin B (4, 4' -dihydroxybenzophenone/DOPO/phenol) were mixed in the following 60:40 is stirred and mixed at 55 c and 0.06 part of initiator t-butyl hydroperoxide is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 83 ℃, the tensile strength is 58MPa (a stress-strain curve is shown in figure 3), and the flame retardant property is V0 grade.
From a comparison of FIGS. 1 and 3, it can be seen that the mechanical strength of the cured product of the pure resin A is very low and is not satisfactory for various applications. And the addition of the resin B can obviously improve the mechanical strength of the vegetable oil-based thermosetting resin.
Example 3
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-2-methylbenzophenone, 1 part of DOPO and a catalyst sulfuric acid (0.5 wt% of the DOPO content) in 5 parts of aniline at 130 ℃, reacting for 12 hours at the temperature, filtering while hot, and cleaning to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of pyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 20 hours after the reaction is finished, and finally the solvent is removed to obtain the additive resin B (4, 4' -dihydroxy-2-methylbenzophenone/DOPO/aniline).
Figure 458733DEST_PATH_IMAGE019
Resin B
Figure 776582DEST_PATH_IMAGE020
Resin A
Resin a and resin B (4, 4' -dihydroxy-2-methylbenzophenone/DOPO/aniline) were mixed in a 70: 30 ℃ and 0.05 part of di-tert-butyl peroxide as an initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 91 ℃, the tensile strength is 69MPa, and the flame retardant property is V0 grade.
Example 4
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-methoxybenzophenone, 1 part of DOPO and a catalyst aminobenzenesulfonic acid (1.5 wt% of the DOPO content) in 5 parts of m-ethylaniline at 120 ℃ and reacting at the temperature for 12 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer and 10 parts of triethanolamine were dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 18 hours after the completion, and finally the solvent is removed to obtain an additive resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-ethylaniline).
Figure 370506DEST_PATH_IMAGE021
Resin B
Figure 152517DEST_PATH_IMAGE020
Resin A
Resin a and resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-ethylaniline) were mixed in the following 70: 30 at 55 c, and 0.03 part of an initiator of methyl ethyl ketone peroxide was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 65 ℃, the tensile strength is 54MPa, and the flame retardant property is V0 grade.
Example 5
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst of ferric chloride (4.5 wt% of the DOPO content) in 2 parts of phenol at 130 ℃ and reacting for 12 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of potassium bicarbonate were dissolved and dispersed in an appropriate amount of DMSO. After cooling the system to 0 ℃, slowly dripping 12 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, continuing to stir for reaction for 10 hours after the reaction is finished, and finally removing the solvent to obtain an additive resin B (4, 4' -dihydroxy benzophenone/DOPO/phenol).
Figure 931117DEST_PATH_IMAGE022
Resin B
Figure 608699DEST_PATH_IMAGE023
Resin A
Resin a and resin B (4, 4' -dihydroxybenzophenone/DOPO/phenol) were mixed in the following 50: 50 at 50 c, and 0.06 part of azobisisobutyronitrile as an initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 68 ℃, the tensile strength is 71MPa, and the flame retardant property is V0 grade.
Example 6
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-methoxybenzophenone, 1 part of DOPO and a catalyst pyridine sulfonic acid (2.5 wt% of DOPO content) in 5 parts of guaiacol at 100 ℃, and reacting at the temperature for 36 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 8 parts of N, N-diisopropylethylamine were dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 8 hours after the completion, and the stirring reaction is continued for 24 hours after the completion, so that the additive resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/guaiacol) is obtained.
Figure 130947DEST_PATH_IMAGE024
Resin B
Figure 767465DEST_PATH_IMAGE025
Resin A
The resin A and the resin B ((4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/guaiacol) are stirred and mixed at a mass ratio of 90: 10 at 60 ℃, and a mixture of 0.05 part of an initiator dicumyl peroxide is added to the mixture, and finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the procedures are that the resin solution is pre-cured at 60 ℃ for 2-4h, then is heated to 80 ℃ for curing for 2-4h, and finally is cured at 140 ℃ for 2-4 h.
The glass transition temperature of the obtained casting is 42 ℃, the tensile strength is 37MPa, and the flame retardant property is V1 grade.
Example 7
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dimethoxybenzophenone, 1 part of DOPO and a catalyst phosphoric acid (10 wt% of the DOPO content) in 6 parts of guaiacol at 100 ℃, and reacting for 34 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 8 parts of sodium bicarbonate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 20 hours after the completion, and the stirring reaction is continued for 24 hours after the completion, so that the additive resin B (4, 4 '-dihydroxy-3, 3' -dimethoxy benzophenone/DOPO/guaiacol) is obtained.
Figure 592332DEST_PATH_IMAGE026
Resin B
Figure 619194DEST_PATH_IMAGE023
Resin A
The resin A and the resin B ((4, 4 '-dihydroxy-3, 3' -dimethoxybenzophenone/DOPO/guaiacol) are stirred and mixed at the temperature of 60 ℃ according to the mass ratio of 90: 10, and a mixture of 0.04 part of initiator tert-butyl peroxybenzoate is added into the mixture, finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the program is that the resin solution is pre-cured at the temperature of 60 ℃ for 2 to 4 hours, then is heated to 80 ℃ for curing for 2 to 4 hours, and finally is cured at the temperature of 140 ℃ for 2 to 4 hours.
The glass transition temperature of the obtained casting is 42 ℃, the tensile strength is 23MPa, and the flame retardant property is V1 grade.
Example 8
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dipropoxybenzophenone, 1 part of DOPO and a catalyst aluminum chloride (7.5 wt% of the DOPO content) in 1 part of aniline at 120 ℃, and reacting for 14 hours at the temperature to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 8 parts of 4-dimethylaminopyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to-30 ℃, 12 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 24 hours after the completion of the dripping reaction, so that an additive resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/aniline) is obtained.
Figure 148396DEST_PATH_IMAGE027
Resin B
Figure 452469DEST_PATH_IMAGE020
Resin A
Resin a and resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/aniline) were mixed in the following 60:40 mass ratio was stirred and mixed at 60 c, and 0.05 part of an initiator of diisopropyl peroxydicarbonate was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 56 ℃, the tensile strength is 45MPa, and the flame retardant property is V0 grade.
Example 9
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dihexobenzophenone, 1 part of DOPO and a catalyst boron trifluoride (3.5 wt% of DOPO content) in 6 parts of o-toluidine at 100 ℃, and reacting at the temperature for 20 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of N, N-diisopropylethylamine were dissolved in an appropriate amount of DMSO. After the system is cooled to 30 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 24 hours after the reaction is finished, so that the additive resin B (4, 4 '-dihydroxy-3, 3' -dihexobenzophenone/DOPO/o-methylbenzylamine) is obtained.
Figure 900768DEST_PATH_IMAGE028
Resin B
Figure 680505DEST_PATH_IMAGE029
Resin A
Resin a and resin B (4, 4 '-dihydroxy-3, 3' -dihexylobenzophenone/DOPO/o-methylbenzylamine) were mixed in the following ratio of 80:20 at 60 c, and 0.03 parts of t-butylperoxypivalate as an initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 41 ℃, the tensile strength is 35MPa, and the flame retardant property is V1 grade.
Example 10
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst p-methylbenzenesulfonic acid (0.5 wt% of the DOPO content) in 4 parts of o-methylphenol at 120 ℃, and reacting for 16 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 8 parts of potassium bicarbonate were dissolved and dispersed in an appropriate amount of DMSO. After cooling the system to 0 ℃, slowly dripping 6 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring for reacting for 6 hours to obtain the resin B (4, 4' -dihydroxybenzophenone/DOPO/o-methyl phenol).
Figure 416992DEST_PATH_IMAGE030
Resin B
Figure 762523DEST_PATH_IMAGE017
Resin A
Resin a and resin B (4, 4' -dihydroxybenzophenone/DOPO/o-methylphenol) were mixed according to a 60:40 mass ratio was stirred and mixed at 50 c, and 0.04 part of initiator dicyclohexyl peroxydicarbonate was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body was 71 ℃ and the tensile strength was 58 MPa.
Example 11
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-methoxybenzophenone, 1 part of DOPO and a catalyst nitric acid (6.5 wt% of the DOPO content) in 5 parts of m-hexylphenol at 130 ℃ and reacting at the temperature for 12 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 8 parts of a mixture of pyridine and triethylamine are dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 24 hours after the completion of the dripping reaction, so that an additive resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-hexylphenol) is obtained.
Figure 319406DEST_PATH_IMAGE031
Resin B
Figure 196227DEST_PATH_IMAGE025
Resin A
The resin A and the resin B ((4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-hexylphenol) are stirred and mixed at a mass ratio of 70: 30 at 60 ℃, and 0.03 part of dicumyl peroxide as an initiator is added to the mixture, and finally, the obtained resin solution is subjected to gradient heating curing in a vacuum oven, wherein the procedures are that the resin solution is pre-cured at 60 ℃ for 2-4h, then heated to 80 ℃ for curing for 2-4h, and finally cured at 140 ℃ for 2-4 h.
The glass transition temperature of the obtained casting is 50 ℃, the tensile strength is 41MPa, and the flame retardant property is V0 grade.
Example 12
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dipropoxybenzophenone, 1 part of DOPO and a catalyst p-aminobenzenesulfonic acid (10 wt% of the DOPO content) in 6 parts of m-oxypropylphenol at 125 ℃, and reacting for 10 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of this phosphorus-containing monomer, 8 parts of sodium carbonate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to-20 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 24 hours after the completion of the dripping reaction, so that an additive resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/m-oxypropylphenol) is obtained.
Figure 191864DEST_PATH_IMAGE032
Resin B
Figure 329585DEST_PATH_IMAGE029
Resin A
Resin a and resin B (4, 4' -dihydroxy-3-dipropoxybenzophenone/DOPO/m-oxopropylphenol) were mixed in the following 60:40 at 60 c, and 0.03 part of an initiator of diisopropyl peroxydicarbonate is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 60 ℃, the tensile strength is 49MPa, and the flame retardant property is V0 grade.
Example 13
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-phenylbenzophenone, 1 part of DOPO and a catalyst trifluoroacetic acid (0.5 wt% of the DOPO content) in 4 parts of phenol at 120 ℃, and reacting for 16 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 8 parts of sodium acetate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 6 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 6 hours after the completion of the dripping reaction, so that the resin B (4, 4' -dihydroxy-3-phenylbenzophenone/DOPO/phenol) is obtained.
Figure 932736DEST_PATH_IMAGE033
Resin B
Figure 483803DEST_PATH_IMAGE034
Resin A
Resin a and resin B (4, 4' -dihydroxy-3-phenylbenzophenone/DOPO/phenol) were mixed in the following 60:40 mass ratio was stirred and mixed at 50 c, and 0.04 part of initiator lauroyl peroxide was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body was 79 ℃ and the tensile strength was 62 MPa.
Example 14
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-phenoxybenzophenone, 1 part of DOPO and a catalyst hydrochloric acid (10 wt% of the DOPO content) in 6 parts of m-oxypropylphenol at 125 ℃, and reacting for 10 hours at the temperature to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 8 parts of 4-dimethylaminopyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to-20 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 24 hours after the completion of the dripping reaction, so that an additive resin B (4, 4' -dihydroxy-3-phenoxybenzophenone/DOPO/m-oxypropylphenol) is obtained.
Figure 955235DEST_PATH_IMAGE035
Resin B
Figure 822828DEST_PATH_IMAGE029
Resin A
Resin a and resin B (4, 4' -dihydroxy-3-phenoxybenzophenone/DOPO/m-oxopropylphenol) were mixed in the following 60:40 at 60 c, and 0.03 part of cumene hydroperoxide as an initiator is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 65 ℃, the tensile strength is 54MPa, and the flame retardant property is V0 grade.
Example 15
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -bicycloheptane benzophenone, 1 part of DOPO and a catalyst of ferric bromide (10 wt% of DOPO content) in 6 parts of guaiacol at 100 ℃, and reacting for 34 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer and 8 parts of sodium carbonate are dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 20 hours after the completion, and the stirring reaction is continued for 24 hours after the completion, so that the additive resin B (4, 4 '-dihydroxy-3, 3' -bicycloheptane benzophenone/DOPO/guaiacol) is obtained.
Figure 49410DEST_PATH_IMAGE036
Resin B
Figure 494298DEST_PATH_IMAGE025
Resin A
Resin a and resin B (4, 4 '-dihydroxy-3, 3' -bicycloheptane benzophenone/DOPO/guaiacol) were mixed according to a 90: 10 at 60 c, and 0.04 part of initiator cyclohexanone peroxide is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 52 ℃, the tensile strength is 36MPa, and the flame retardant property is V1 grade.
Example 16
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dicyclopropane benzophenone, 1 part of DOPO and a catalyst of p-toluenesulfonic acid (10 wt% of the DOPO content) in 6 parts of guaiacol at 100 ℃, and reacting for 34 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 10 parts of sodium bicarbonate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 20 hours after the completion, and the stirring reaction is continued for 24 hours after the completion, so that the additive resin B (4, 4 '-dihydroxy-3, 3' -dicyclopropane benzophenone/DOPO/guaiacol) is obtained.
Figure 641858DEST_PATH_IMAGE037
Resin B
Figure 82067DEST_PATH_IMAGE038
Resin A
Resin a and resin B (4, 4 '-dihydroxy-3, 3' -dicyclopropane benzophenone/DOPO/guaiacol) were mixed according to a 70: 30 mass ratio was stirred and mixed at 60 ℃, and 0.04 part of azobisisoheptonitrile as an initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 68 ℃, the tensile strength is 53MPa, and the flame retardant property is V0 grade.
Comparative example 1
This comparative example differs from example 1 in that:
adding resin B: unsaturated resin TAIC
Figure 151654DEST_PATH_IMAGE039
Resin B
Figure 224783DEST_PATH_IMAGE017
Resin A
Resin a (aeso) and resin b (taic) were mixed according to 80:20 mass ratio at 50 c and an appropriate amount of the initiator benzoyl peroxide was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 35 ℃, the tensile strength is 9MPa, and the flame retardant property is V1 grade.
Comparative example 2
This comparative example differs from example 1 in that:
adding resin B: unsaturated resin GACA
Figure 100335DEST_PATH_IMAGE040
Resin B
Figure 332734DEST_PATH_IMAGE034
Resin A
Resin a (aeso) and resin b (taic) were mixed according to a 60:40 was stirred and mixed at 55 c and the appropriate amount of initiator t-butyl hydroperoxide was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 60 deg.C for 2-4h, heating to 80 deg.C, curing for 2-4h, and finally curing at 140 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 63 ℃, the tensile strength is 22MPa, and the flame retardant grade is zero.
Example 21: referring to example 1, resin A and resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol) were uniformly mixed and heated to 50 deg.C, and then an initiator, benzoyl peroxide and carbon fiber, were added to form a bio-based halogen-free flame-retardant acrylic resin composition (in which the carbon fiber content was about 3 wt%)Then adding the bio-based halogen-free flame retardant acrylic resin composition at the ratio of 40kg/cm2The pressure of the pressure injection is injected into a die cavity of a metal die heated to about 60 ℃ for precuring, then the pressure is maintained, and the temperature of the die cavity is heated to 60-140 ℃ for gradient curing to obtain a sample. The sample has excellent tensile resistance and flame retardance.
Example 22: drying the silicon micropowder at about 100 ℃ for 4-6 h, and adding the silicon micropowder, resin A, resin B (4, 4' -dihydroxy benzophenone/DOPO/guaiacol) in example 1 (the mass ratio of the two is 80: 20), an initiator benzoyl peroxide (accounting for 0.03 percent of the total material mass) and the silicon micropowder (accounting for 1-5 percent of the total material mass) into a mixing tank preheated to about 60 ℃; preheating a vacuum casting tank to about 60 ℃, keeping the vacuum casting tank for 1h, then starting to vacuumize, keeping the vacuum degree for 3-5h when the vacuum degree reaches above 5mbar, then casting the epoxy resin mixture in the mixing tank into a mold, and then carrying out gradient curing at 60-140 ℃ to obtain the sample. The sample has excellent tensile resistance and flame retardance.
Example 23: referring to example 1, resin a and resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol) were uniformly mixed and heated to 60 ℃, and then an initiator, benzoyl peroxide, was added to form an epoxy resin composition;
impregnating the epoxy resin composition with glass fiber (China megastone, Inc.) and then drying the impregnated composition with hot air to prepare a prepreg, wherein the epoxy resin content is 45 wt%;
laminating 6 glass fiber prepregs, heating the laminated film at 220-240 deg.C and 40kg/cm3Extruding for 80min to obtain pressed product.
The pressed piece can be used as a flame-retardant laminated structure in a plurality of fields, for example, the pressed piece can be used as a building interior wall decoration material or can be prepared into a fireproof door and the like, and the pressed piece has excellent high-temperature resistance, flame retardance and other properties.
Example 24: a method of making a transfer molded workpiece comprising:
(1) and (4) coating a release agent on the inner surface of the mold, and drying. Putting the fiber felt section, the three-dimensional braided fabric, the metal framework and other sections into a mold, and closing the mold;
(2) resin A and resin B from example 1 (4, 4' -dihydroxybenzophenone/DOPO/guaiacol) (both in the proportions referred to in example 1) were placed in respective transfer molding machine A, B pots; weighing initiator benzoyl peroxide (the dosage is referred to example 1), and placing the initiator benzoyl peroxide in a tank B; starting the A, B tank to stir, heating to about 60 ℃, vacuumizing and removing bubbles;
(3) preheating a die workpiece with the section at 60 ℃;
(4) the materials in the A, B tank are fully mixed through a transfer molding machine head and poured into the whole mold from an opening above the workpiece;
(5) when the gel point of the adhesive is reached, pressurizing;
(6) and carrying out gradient curing at the temperature of 60-140 ℃ to obtain the required workpiece.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. A halogen-free flame-retardant acrylic resin composition is characterized by comprising: resin A, resin B and an initiator; the resin A comprises bio-based acrylate, the resin B comprises phosphorus-containing acrylate, and the phosphorus-containing acrylate has a structure shown in a formula (2):
Figure 438754DEST_PATH_IMAGE001
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Figure 42821DEST_PATH_IMAGE002
Or
Figure 528029DEST_PATH_IMAGE003
(ii) a Y is
Figure 462618DEST_PATH_IMAGE002
Or
Figure 301261DEST_PATH_IMAGE003
；
Z is selected from
Figure 254173DEST_PATH_IMAGE002
、
Figure 661015DEST_PATH_IMAGE003
、
Figure 66588DEST_PATH_IMAGE004
Or
Figure 974502DEST_PATH_IMAGE005
。
2. The halogen-free flame retardant acrylic resin composition according to claim 1, wherein the phosphorus-containing acrylate is prepared by a method comprising:
in the presence of an acid binding agent, reacting a compound shown as a formula (3) with acryloyl chloride or methacryloyl chloride at-30 ℃ for 6-24 h to obtain phosphorus-containing acrylate;
Figure 532653DEST_PATH_IMAGE006
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2。
3. The halogen-free flame retardant acrylic resin composition according to claim 2, wherein: the mol ratio of the compound shown in the formula (3), acryloyl chloride or methacryloyl chloride to the acid binding agent is 1: 6-12: 6-12;
and/or the acid-binding agent comprises an organic base and/or an inorganic base, wherein the organic base comprises any one or a combination of more than two of sodium acetate, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine and triethanolamine, and the inorganic base comprises any one or a combination of more than two of potassium carbonate, sodium bicarbonate and potassium bicarbonate;
and/or, the preparation method comprises the following steps: carrying out condensation reaction on a mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
Figure 359664DEST_PATH_IMAGE007
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2；
The molar ratio of the organophosphorus compound represented by the formula (4), the compound represented by the formula (5) to the compound represented by the formula (6) is 1: 1: 1-6;
the mass ratio of the acidic catalyst to the organic phosphorus compound represented by the formula (4) is 0.1-10: 100, respectively;
the acidic catalyst comprises any one or the combination of more than two of organic acid, inorganic acid and Lewis acid.
4. The halogen-free flame-retardant acrylic resin composition according to claim 1, wherein the bio-based acrylate has a structure represented by formula (1):
Figure 336DEST_PATH_IMAGE008
（1）
wherein R is selected from
Figure 180782DEST_PATH_IMAGE002
、
Figure 108286DEST_PATH_IMAGE003
、
Figure 591351DEST_PATH_IMAGE009
、
Figure 909200DEST_PATH_IMAGE010
、
Figure 955654DEST_PATH_IMAGE011
Or
Figure 285135DEST_PATH_IMAGE012
。
5. The halogen-free flame retardant acrylic resin composition according to claim 1, wherein: the mass ratio of the resin A to the resin B to the initiator is 90-60: 10-40: 0.03 to 0.06;
and/or the initiator comprises any one or the combination of more than two of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
6. A preparation method of a bio-based halogen-free flame-retardant acrylic resin cured product is characterized by comprising the following steps: curing the halogen-free flame-retardant acrylic resin composition according to any one of claims 1 to 5 at 60 to 140 ℃.
7. The cured bio-based halogen-free flame-retardant acrylic resin prepared by the method according to claim 6, wherein the cured bio-based halogen-free flame-retardant acrylic resin has a glass transition temperature of 60 to 100 ℃, a tensile strength of 30 to 80MPa, and a flame retardant property of V1 grade or higher.
8. A method for processing a molding compound product is characterized by comprising the following steps: the halogen-free flame retardant acrylic resin composition according to any one of claims 1 to 5, after being mixed with a reinforcing material, is processed into the shape of a desired product by at least any one of molding, laminating, transfer molding and casting, and is then cured to obtain the desired product.
9. A method for processing a molding compound product is characterized by comprising the following steps:
providing the halogen-free flame retardant acrylic resin composition according to any one of claims 1 to 5;
soaking glass fiber in the halogen-free flame-retardant acrylic resin composition, taking out the soaked glass fiber, and air-drying to prepare a glass fiber prepreg;
laminating a plurality of glass fiber prepregs, and heating to laminate at 220-240 ℃ under 30kg/cm3~60kg/cm3The time is more than 30 min.
10. A flame-retardant laminated structure comprising a plurality of structural layers which are laminated, wherein the structural layers are film-like materials or sheet-like materials, wherein at least one structural layer comprises a fully cured product of the halogen-free flame-retardant acrylic resin composition according to any one of claims 1 to 5, or wherein at least two adjacent structural layers are fixedly connected by a fully cured product of the halogen-free flame-retardant acrylic resin composition according to any one of claims 1 to 5.
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