CN112745617A - Heat insulation type acrylic plate - Google Patents
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- CN112745617A CN112745617A CN202011583762.0A CN202011583762A CN112745617A CN 112745617 A CN112745617 A CN 112745617A CN 202011583762 A CN202011583762 A CN 202011583762A CN 112745617 A CN112745617 A CN 112745617A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions 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; Compositions of derivatives of such polymers
- C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a heat insulation type acrylic plate, relates to the technical field of acrylic plates, and aims to solve the problem that the existing acrylic plate is poor in thermal stability. The raw materials comprise the following components in parts by weight: 150 parts of methyl methacrylate 100-one, 2-6 parts of N-single fatty group, 8-15 parts of N-cyclohexyl maleimide, 10-20 parts of styrene, 2-6 parts of fluoro methyl acrylate, 1-1.6 parts of polybutyl acrylate, 10-15 parts of dialkyl vinyl benzene phosphate, 10-15 parts of cross-linking agent, 2-5 parts of toughening agent, 3-12 parts of flame retardant and 1-3 parts of initiator, and step 1, placing the methyl methacrylate in a polymerization kettle, heating and adding the N-single fatty group; step 2, sequentially adding N-cyclohexyl maleimide, styrene, fluoro methyl acrylate, polybutyl acrylate and dialkyl vinyl benzene phosphate; step 3, adding an initiator; step 4, adding the allyl methacrylate, the dibutyltin dimethacrylate and the acrylonitrile into a polymerization kettle; step 5, adding a toughening agent and a flame retardant in sequence; and 6, casting and forming.
Description
Technical Field
The invention relates to the technical field of acrylic plates, in particular to a heat-insulating and heat-preserving type acrylic plate.
Background
The plate body made of acrylic has the characteristics of good light transmission performance, pure color, rich color, attractive appearance, smoothness, long service life, no influence on use and the like. In addition, the acrylic plate can be perfectly combined with aluminum-plastic plate profiles, high-grade screen printing and the like, and is a chemical material. The chemical name is 'PMMA' which belongs to polyacrylate, the acrylic plate has the transparency of common crystal, the light transmittance is more than 92%, the acrylic plate colored by dye has good color developing effect, in addition, the acrylic plate has good processing performance, and the acrylic plate can be divided into a casting type and an extrusion type according to the production process. Either thermoforming (including molding, blow molding and vacuum forming) or machining such as drilling, turning, washing, cutting, etc. may be used.
However, in the use process of the existing acrylic plate, along with the increase of the temperature, the fracture elongation of the acrylic plate in the occurrence of brittle fracture is gradually increased, and researches show that the fracture elongation of the acrylic plate reaches 6.2 when the ambient temperature reaches 60 ℃, organic glass begins to soften when the temperature exceeds a certain temperature, the stretching process shows yield failure, and the acrylic plate is difficult to apply in a specific environment, so that the existing requirements are not met, and a heat insulation type acrylic plate is provided.
Disclosure of Invention
The invention aims to provide a heat insulation type acrylic plate to solve the problem of poor thermal stability of the acrylic plate in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the heat insulation type acrylic plate comprises the following raw materials in parts by weight: 150 parts of methyl methacrylate 100-one, 2-6 parts of N-single fatty group, 8-15 parts of N-cyclohexyl maleimide, 10-20 parts of styrene, 2-6 parts of fluoro methyl acrylate, 1-1.6 parts of polybutyl acrylate, 10-15 parts of dialkyl vinyl benzene phosphate, 10-15 parts of cross-linking agent, 2-5 parts of toughening agent, 3-12 parts of flame retardant and 1-3 parts of initiator.
Preferably, the cross-linking agent is one or a combination of more of allyl methacrylate, dibutyltin dimethacrylate and acrylonitrile, the toughening agent is nano silicon dioxide, and the flame retardant is phosphate.
Preferably, the initiator is one of azobisisobutyronitrile or benzoyl peroxide.
A preparation method of a heat insulation type acrylic plate comprises the following steps:
step 1: putting a certain amount of methyl methacrylate into a polymerization kettle, heating and stirring to 48-58 ℃, adding N-single fat group, and continuously stirring for 20min at the temperature to form prepolymerization treatment on the methyl methacrylate;
step 2: polymerizing with N-single fatty group, keeping the temperature, adding N-cyclohexyl maleimide, styrene, fluoro methyl acrylate, poly butyl acrylate and dialkyl vinyl benzene phosphate in turn, raising the temperature of the polymerization kettle to 80-95 ℃, and stirring the inside of the polymerization kettle for 30-50 min;
and step 3: after stirring, adding an initiator when the temperature of the polymerization kettle is reduced to 45-68 ℃, and continuously stirring for 30min at the temperature;
and 4, step 4: after the promotion with the initiator is finished, quantitatively adding the allyl methacrylate, the dibutyltin dimethacrylate and the acrylonitrile into a polymerization kettle, and stirring for 30-50min at 80-95 ℃ to finish the promotion of the thermal stability and the impact strength of the polymer;
and 5: after polymerization with the cross-linking agent is completed, sequentially and quantitatively adding the toughening agent and the flame retardant, stirring at 90 ℃ for 20min, and cooling to room temperature at the speed of 6-10 ℃/h after stirring is completed, so as to complete improvement of the strength and the flame retardant property of the polymer;
step 6: and after polymerization is finished, casting and molding through a casting machine, and cooling to obtain the acrylic plate blank.
Preferably, the stirring speed of the polymerization kettle in the steps 1-5 is 2000 r/min.
Preferably, vinyl acetate is used as a solvent in the step 5, so that the toughening agent is well dispersed in the homopolymer.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the poly-copolymerized methyl methacrylate polymerization, the homopolymer takes methyl methacrylate as a main body, N-cyclohexyl maleimide, styrene, fluoro methyl acrylate, poly butyl acrylate and dialkyl vinyl benzene phosphate are involved in the polymerization, the addition of the styrene can reduce the yellow color difference of the plate surface of the acrylic plate, the heat resistance of the homopolymer can be improved and the mechanical property thereof can be improved by adding the styrene, the softening point of the fluoro methyl acrylate is involved in the copolymerization, the fluoro methyl acrylate can reach 146 ℃, the fluoro methyl acrylate has good thermal stability, the poly butyl acrylate is copolymerized with the methyl methacrylate, the softening temperature of the homopolymer can be improved along with the increase of the content of the internal fluorine monomer, the impact strength and the tensile strength are correspondingly improved, the poly butyl acrylate has excellent toughening effect on the acrylic plate along with the increase of the using amount of the poly butyl acrylate, the tensile strength of the acrylic plate is gradually reduced, the characteristic of obvious transition from brittle fracture to ductile fracture is shown, and the impact strength is obviously improved.
2. According to the invention, the allyl methacrylate, the dibutyltin dimethacrylate and the acrylonitrile are used as cross-linking agents, the homopolymer formed by the allyl methacrylate and the methyl methacrylate has higher surface hardness and better wear resistance, the thermal stability of the homopolymer is further improved along with the increase of the addition amount of the allyl methacrylate, the softening point of the homopolymer of the dibutyltin dimethacrylate and the methyl methacrylate can reach 178 ℃ at most, tin atoms contained in the homopolymer have a certain protection effect on high-energy rays, and the thermal stability of the homopolymer is further improved.
3. According to the invention, the phosphate ester is used as a flame retardant, the phosphate ester is mixed with dialkyl vinyl benzene phosphate and acrylonitrile in the homopolymer to improve the carbon residual amount, the carbon residual amount is improved along with the improvement of the phosphorus content in the phosphate ester, the flame retardant effect is better, the dialkyl phosphonate eliminates small molecular alkyl through intramolecular reaction to form nucleophilic phosphate, and the homopolymer is promoted to form a high-thermal-stability annular structure.
4. According to the invention, the nano silicon dioxide is used as a toughening agent, the mechanical property and the thermal property of the acrylic plate can be changed by adding the nano silicon dioxide, the impact strength and the tensile strength of the acrylic plate modified by the nano silicon dioxide are in a descending trend along with the increase of the content of the nano silicon dioxide, the softening point temperature is in an ascending trend, and the softening point temperature can be increased under the condition of ensuring the balance point of the impact strength and the tensile strength by adding the nano silicon dioxide in a quantitative manner to participate in the polymerization process.
Drawings
FIG. 1 is a diagram showing the steps of preparing the heat insulating acrylic plate of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments,
example 1:
a heat insulation type acrylic plate takes the following substances in parts by weight: 100 parts of methyl methacrylate, 2 parts of N-single fat base, 8 parts of N-cyclohexyl maleimide, 10 parts of styrene, 2 parts of fluoro methyl acrylate, 1 part of polybutyl acrylate, 10 parts of dialkyl vinyl benzene phosphate, 10 parts of cross-linking agent, 2 parts of toughening agent, 3 parts of flame retardant and 1 part of initiator.
Further, the cross-linking agent is one or a combination of more of methacrylic acid allyl ester, dibutyltin dimethacrylate and acrylonitrile, the toughening agent is nano silicon dioxide, and the flame retardant is phosphate ester.
Further, the initiator is one of azodiisobutyronitrile or benzoyl peroxide.
The preparation method of the heat insulation type acrylic plate comprises the following steps:
step 1: placing 100 parts of methyl methacrylate in a polymerization kettle, heating and stirring to 48 ℃, adding 2 parts of N-single fatty group, and continuously stirring for 20min at the temperature to form prepolymerization treatment on the methyl methacrylate;
step 2: after polymerizing with N-single fatty group, maintaining the temperature, adding 8 parts of N-cyclohexyl maleimide, 10 parts of styrene, 2 parts of methyl fluoroacrylate, 1 part of polybutyl acrylate and 10 parts of dialkyl vinyl benzene phosphate in sequence, raising the temperature of a polymerization kettle to 80 ℃, and stirring the inside of the polymerization kettle for 30 min;
and step 3: after stirring, 1 part of azobisisobutyronitrile is added when the temperature of the polymerization kettle is reduced to 45 ℃, and stirring is continued for 30min at the temperature;
and 4, step 4: after the promotion with azodiisobutyronitrile is finished, adding 2 parts of allyl methacrylate, 2 parts of dibutyltin dimethacrylate and 6 parts of acrylonitrile into a polymerization kettle, and stirring at 80 ℃ for 30min to finish the improvement of the thermal stability and the impact strength of the polymer;
and 5: after polymerization with a cross-linking agent is completed, sequentially adding 2 parts of nano silicon dioxide and 3 parts of phosphate ester, stirring at 90 ℃ for 20min, and cooling to room temperature at the speed of 6 ℃/h after stirring is completed, so as to complete improvement of polymer strength and flame retardant property;
step 6: and after polymerization is finished, casting and molding through a casting machine, and cooling to obtain the acrylic plate blank.
Further, in the steps 1-5, the stirring speed of the polymerization kettle is 2000 r/min.
Further, vinyl acetate is used as a solvent in the step 5, so that the toughening agent is well dispersed in the polymer.
In the step, the heat insulation and preservation type acrylic plate with the softening point of 146.7 ℃, the tensile strength of 74.6MPa and the impact strength of the plate which can be effectively improved by 34.2 percent can be obtained.
Example 2:
a heat insulation type acrylic plate takes the following substances in parts by weight: 120 parts of methyl methacrylate, 4 parts of N-single aliphatic group, 15 parts of N-cyclohexyl maleimide, 20 parts of styrene, 5 parts of fluoro methyl acrylate, 1.5 parts of polybutyl acrylate, 12 parts of dialkyl vinyl benzene phosphate, 12 parts of cross-linking agent, 4 parts of toughening agent, 8 parts of flame retardant and 2 parts of initiator.
Further, the cross-linking agent is one or a combination of more of methacrylic acid allyl ester, dibutyltin dimethacrylate and acrylonitrile, the toughening agent is nano silicon dioxide, and the flame retardant is phosphate ester.
Further, the initiator is one of azodiisobutyronitrile or benzoyl peroxide.
The preparation method of the heat insulation type acrylic plate comprises the following steps:
step 1: placing 120 parts of methyl methacrylate into a polymerization kettle, heating and stirring to 55 ℃, adding 4 parts of N-single fatty group, and continuously stirring for 20min at the temperature to form prepolymerization treatment on the methyl methacrylate;
step 2: after polymerizing with N-single fatty group, keeping the temperature, adding 15 parts of N-cyclohexyl maleimide, 20 parts of styrene, 5 parts of methyl fluoroacrylate, 1.5 parts of polybutyl acrylate and 12 parts of dialkyl vinyl benzene phosphate in sequence, raising the temperature of a polymerization kettle to 93 ℃, and stirring the inside of the polymerization kettle for 45 min;
and step 3: after stirring, 2 parts of benzoyl peroxide are added when the temperature of the polymerization kettle is reduced to 62 ℃, and stirring is continued for 30min at the temperature;
and 4, step 4: after the promotion with the initiator is finished, adding 3 parts of allyl methacrylate, 3 parts of dibutyltin dimethacrylate and 6 parts of acrylonitrile into a polymerization kettle, and stirring at 93 ℃ for 45min to finish the improvement of the thermal stability and the impact strength of the polymer;
and 5: after polymerization with a cross-linking agent is completed, sequentially adding 4 parts of nano silicon dioxide and 8 parts of phosphate ester, stirring at 90 ℃ for 20min, and cooling to room temperature at a speed of 8 ℃/h after stirring is completed to complete improvement of polymer strength and flame retardant property;
step 6: and after polymerization is finished, casting and molding through a casting machine, and cooling to obtain the acrylic plate blank.
Further, in the steps 1-5, the stirring speed of the polymerization kettle is 2000 r/min.
Further, vinyl acetate is used as a solvent in the step 5, so that the toughening agent is well dispersed in the polymer.
In the step, the heat insulation and preservation type acrylic plate with the softening point of 162.8 ℃, the tensile strength of 70.4MPa and the impact strength of the plate which can be effectively improved by 30.2 percent can be obtained.
Example 3:
a heat insulation type acrylic plate takes the following substances in parts by weight: 150 parts of methyl methacrylate, 6 parts of N-single fat base, 10 parts of N-cyclohexyl maleimide, 15 parts of styrene, 3 parts of fluoro methyl acrylate, 1.2 parts of polybutyl acrylate, 15 parts of dialkyl vinyl benzene phosphate, 15 parts of cross-linking agent, 2 parts of flexibilizer, 12 parts of flame retardant and 1.5 parts of initiator.
Further, the cross-linking agent is one or a combination of more of methacrylic acid allyl ester, dibutyltin dimethacrylate and acrylonitrile, the toughening agent is nano silicon dioxide, and the flame retardant is phosphate ester.
Further, the initiator is one of azodiisobutyronitrile or benzoyl peroxide.
The preparation method of the heat insulation type acrylic plate comprises the following steps:
step 1: placing 150 parts of methyl methacrylate in a polymerization kettle, heating and stirring to 58 ℃, adding 6 parts of N-single fatty group, and continuously stirring for 20min at the temperature to form prepolymerization treatment on the methyl methacrylate;
step 2: after polymerizing with N-single fatty group, keeping the temperature, sequentially adding 10 parts of N-cyclohexyl maleimide, 15 parts of styrene, 3 parts of methyl fluoroacrylate, 1.2 parts of polybutyl acrylate and 15 parts of dialkyl vinyl benzene phosphate, finishing the addition, raising the temperature of a polymerization kettle to 80-95 ℃, and simultaneously stirring the inside of the polymerization kettle for 30-50 min;
and step 3: after the stirring is completed, 1.5 parts of azobisisobutyronitrile is added when the temperature of the polymerization kettle is reduced to 68 ℃, and the stirring is continued for 30min at the temperature;
and 4, step 4: after the promotion with the initiator is finished, adding 5 parts of allyl methacrylate, 3 parts of dibutyltin dimethacrylate and 7 parts of acrylonitrile into a polymerization kettle, and stirring at 88 ℃ for 43min to finish the improvement of the thermal stability and the impact strength of the polymer;
and 5: after polymerization with a cross-linking agent is completed, stirring 2 parts of nano silicon dioxide and 12 parts of phosphate ester at 90 ℃ for 20min, and cooling to room temperature at a speed of 8 ℃/h after stirring is completed to complete improvement of polymer strength and flame retardant property;
step 6: and after polymerization is finished, casting and molding through a casting machine, and cooling to obtain the acrylic plate blank.
Further, in the steps 1-5, the stirring speed of the polymerization kettle is 2000 r/min.
Further, vinyl acetate is used as a solvent in the step 5, so that the toughening agent is well dispersed in the polymer.
In the step, the heat insulation and preservation type acrylic plate with the softening point of 158.7 ℃, the tensile strength of 77.4MPa and the plate impact strength capable of being effectively improved by 36.1 percent can be obtained.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that the present embodiments be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. The heat insulation type acrylic plate is characterized by comprising the following raw materials in parts by weight: 150 parts of methyl methacrylate 100-one, 2-6 parts of N-single fatty group, 8-15 parts of N-cyclohexyl maleimide, 10-20 parts of styrene, 2-6 parts of fluoro methyl acrylate, 1-1.6 parts of polybutyl acrylate, 10-15 parts of dialkyl vinyl benzene phosphate, 10-15 parts of cross-linking agent, 2-5 parts of toughening agent, 3-12 parts of flame retardant and 1-3 parts of initiator.
2. The insulating acrylic sheet according to claim 1, wherein: the cross-linking agent is one or a combination of more of allyl methacrylate, dibutyltin dimethacrylate and acrylonitrile, the toughening agent is nano silicon dioxide, and the flame retardant is phosphate.
3. The insulating acrylic sheet according to claim 1, wherein: the initiator is one of azodiisobutyronitrile or benzoyl peroxide.
4. The method for preparing the heat insulation type acrylic plate according to any one of claims 1 to 3, wherein: the method comprises the following steps:
step 1: putting a certain amount of methyl methacrylate into a polymerization kettle, heating and stirring to 48-58 ℃, adding N-single fat group, and continuously stirring for 20min at the temperature to form prepolymerization treatment on the methyl methacrylate;
step 2: polymerizing with N-single fatty group, keeping the temperature, adding N-cyclohexyl maleimide, styrene, fluoro methyl acrylate, poly butyl acrylate and dialkyl vinyl benzene phosphate in turn, raising the temperature of the polymerization kettle to 80-95 ℃, and stirring the inside of the polymerization kettle for 30-50 min;
and step 3: after stirring, adding an initiator when the temperature of the polymerization kettle is reduced to 45-68 ℃, and continuously stirring for 30min at the temperature;
and 4, step 4: after the promotion with the initiator is finished, quantitatively adding the allyl methacrylate, the dibutyltin dimethacrylate and the acrylonitrile into a polymerization kettle, and stirring for 30-50min at 80-95 ℃ to finish the promotion of the thermal stability and the impact strength of the homopolymer;
and 5: after polymerization with the cross-linking agent is completed, sequentially and quantitatively adding the toughening agent and the flame retardant, stirring at 90 ℃ for 20min, and cooling to room temperature at the speed of 6-10 ℃/h after stirring is completed, so as to complete improvement of the strength and the flame retardant property of the homopolymer;
step 6: and after polymerization is finished, casting and molding through a casting machine, and cooling to obtain the acrylic plate blank.
5. The insulating acrylic plate of claim 4, wherein: in the steps 1-5, the stirring speed of the polymerization kettle is 2000 r/min.
6. The insulating acrylic plate of claim 4, wherein: in the step 5, vinyl acetate is used as a solvent, so that the toughening agent is well dispersed in the homopolymer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011583762.0A CN112745617A (en) | 2020-12-28 | 2020-12-28 | Heat insulation type acrylic plate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011583762.0A CN112745617A (en) | 2020-12-28 | 2020-12-28 | Heat insulation type acrylic plate |
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