CN113881178A - Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof - Google Patents
Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof Download PDFInfo
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- CN113881178A CN113881178A CN202111146673.4A CN202111146673A CN113881178A CN 113881178 A CN113881178 A CN 113881178A CN 202111146673 A CN202111146673 A CN 202111146673A CN 113881178 A CN113881178 A CN 113881178A
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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
- 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
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The invention discloses a weather-resistant flame-retardant polymethyl methacrylate composite material, a preparation method and application thereof, wherein the weather-resistant flame-retardant polymethyl methacrylate composite material comprises the following components: polymethyl methacrylate, flame retardant containing phosphorus cations, flexibilizer, light stabilizer, ultraviolet absorbent and other auxiliary agents; the flame retardant containing the phosphorus cations consists of phosphorus cations and anions; according to the invention, the flame retardant containing phosphorus cations with a specific structure is selected to be matched with the light stabilizer and the ultraviolet absorber, so that the problem of mechanical property attenuation of the flame-retardant polymethyl methacrylate composite material after photo-aging is solved, a good flame-retardant effect is achieved, and the excellent weather resistance and optical transmission property of matrix resin are retained; the prepared weather-resistant flame-retardant composite material has high transparency, light aging resistance and excellent flame retardant property, and can be widely applied to the fields of architectural decoration, lighting lamps or electronic appliances.
Description
Technical Field
The invention relates to the technical field of flame-retardant plastic materials, in particular to a weather-resistant flame-retardant polymethyl methacrylate composite material and a preparation method and application thereof.
Background
Polymethyl methacrylate (PMMA), commonly known as plexiglass, has a light transmittance of up to 92% and a transparency similar to that of quartz glass. The PMMA has the characteristics of excellent weather resistance, higher surface hardness, surface glossiness and the like, and the characteristics enable the PMMA to be suitable for application fields with higher requirements on appearance and weather resistance in industries such as aviation, automobiles, electronics, medical treatment, chemical industry, building materials, bathrooms, advertising signs and the like.
When PMMA is applied to lighting equipment and advertisement decorative materials, the traditional requirement only needs to consider transparency and weather resistance. However, as the safety standard of the current home appliances is gradually improved, manufacturers gradually convert the requirements into the requirements on the flame retardant property, the electrical property and the like of the material during material selection, and the requirement on the flame retardant property of the PMMA material is also gradually improved. Pure PMMA is flammable, the oxygen index is only 17.3, a large amount of methyl methacrylate monomer can be generated by decomposition in the combustion process, and the monomer is very high in flammability; the decomposition mechanism also determines that the PMMA is difficult to perform flame retardant modification, and the transparency and the weather resistance of the PMMA must be considered while the PMMA is subjected to flame retardant modification, otherwise, the prepared flame retardant PMMA is not suitable for the most conventional application field.
Therefore, the development of the flame-retardant polymethyl methacrylate composite material with excellent weather resistance has great research significance and application value.
Disclosure of Invention
In order to overcome the defect that the polymethyl methacrylate composite material in the prior art cannot simultaneously realize high weather resistance, halogen-free high-efficiency flame retardant property and high transparency, the invention aims to provide the weather-resistant flame-retardant polymethyl methacrylate composite material, which overcomes the defect that the weather resistance is sharply reduced after the transparent flame retardant modification of polymethyl methacrylate, and has excellent weather resistance while maintaining excellent transparency and halogen-free flame retardant property.
The invention also aims to provide a preparation method of the weather-resistant flame-retardant polymethyl methacrylate composite material.
The invention also aims to provide application of the weather-resistant flame-retardant polymethyl methacrylate composite material in the fields of architectural decoration, lighting lamps or electronic and electric appliances.
In order to achieve the purpose, the invention adopts the following technical scheme:
45-94.8 parts of polymethyl methacrylate, 5-20 parts of flame retardant containing phosphorus cations, 0-20 parts of toughening agent, 0.1-5 parts of light stabilizer, 0.1-5 parts of ultraviolet absorbent and 0-5 parts of other auxiliary agents;
the flame retardant containing the phosphorus cations consists of phosphorus cations and anions; wherein the structure of the phosphorus-containing cation is shown as follows:
wherein R is1、R2、R3、R4Independently selected from C1-6Or a substituted saturated alkyl group.
According to the invention, the flame retardant containing the phosphorus cations with a specific structure is selected, and contains short-chain saturated alkane, so that the flame retardant is poor in light aging resistance and is easy to decompose under the action of ultraviolet light to generate short alkane free radicals, and the free radicals are high in activity and easy to attack a PMMA resin matrix, so that the resin matrix is quickly degraded under the irradiation of the ultraviolet light, the mechanical property of the material is quickly reduced, and even the surface is cracked.
According to the invention, the flame retardant containing the phosphorus cations with a specific structure is selected to be matched with the light stabilizer and the ultraviolet absorber, so that the problem of mechanical property attenuation of the flame-retardant polymethyl methacrylate composite material after photo-aging is solved, the strong catalytic degradation effect of the flame retardant containing the phosphorus cations on PMMA is relieved and eliminated, and the flame retardant can exert the flame-retardant effect under the combustion condition.
Preferably, the weather-resistant flame-retardant polymethyl methacrylate composite material comprises the following components in parts by weight: 66-86.1 parts of polymethyl methacrylate, 8-15 parts of flame retardant containing phosphorus cations, 5-10 parts of toughening agent, 0.3-3 parts of light stabilizer, 0.3-3 parts of ultraviolet absorbent and 0.3-3 parts of other auxiliary agents.
Preferably, the polymethyl methacrylate has a melt index of 3-16g/10min at 230 ℃/3.8kg according to ISO 1133-1-2011 test standard, a residual monomer content (weight percentage of residual monomers) of 0-0.1 wt%, and a light transmittance of 90-92%.
Preferably, the phosphorus cation-containing flame retardant has a weight loss rate of 0-0.1% after drying treatment in a vacuum oven at a temperature of 105 +/-2 ℃ according to GB/T6284-2006 test standard.
The anionic group of the flame retardant containing the phosphorus cation has stronger polarity and is easy to absorb water and dissociate, so that the flame retardant effect of the flame retardant is influenced; in addition, when the moisture content exceeds the standard, the thermal stability of the flame retardant containing the phosphorus cations is also poor, and the flame retardant is easy to decompose and yellow in the processes of melt blending modification and subsequent injection molding with polymethyl methacrylate, so that the optical characteristics of the final product are influenced.
Preferably, said R is1、R2、R3Independently preferably from C2-6Saturated alkyl groups of (a); r4Is selected from C2-4Saturated alkyl groups of (a); the R is1、R2、R3、R4Wherein the substituent is-OH or-NH2。
Preferably, the structure of the anion in the phosphorus cation containing flame retardant is one of the following structures:
wherein R is5、R6Independently selected from C1-6Unsubstituted saturated alkyl or substituted saturated alkyl of (a); r7Is C6-8Alkyl group of (1).
Further preferably, said R5、R6Independently selected from C2-4Saturated alkyl groups of (a); the R is5、R6Wherein the substituent is-OH or-NH2；R7Contains an aromatic ring, non-aromatic five-membered ring or six-membered ring.
The flame retardant containing the phosphorus cation can be a single ionic liquid compound or a composition of more than one.
Preferably, the toughening agent is a butadiene grafted acrylate styrene copolymer.
Preferably, the light stabilizer is a hindered amine.
Preferably, the ultraviolet absorber is at least one of benzophenones or benzotriazoles.
The invention adopts the ultraviolet absorbent and the light stabilizer at the same time, the ultraviolet absorbent can absorb most of the ultraviolet energy irradiated on the surface and the interior of the transparent material, the damage of ultraviolet rays to the flame retardant is reduced, and the generation of destructive active free radicals is reduced; the light stabilizer has good effect of capturing free radicals, can effectively capture generated destructive free radicals, and prevents the destructive free radicals from attacking polymer molecular chains to cause material degradation and performance attenuation.
Preferably, the other auxiliary agent is at least one of an antioxidant, a lubricant or a colorant.
More preferably, the antioxidant is at least one of hindered phenols and phosphites.
Further preferably, the lubricant is at least one of amides, stearates or esters.
Further preferably, the colorant is of the dye type or other colorant having a particular aesthetic effect.
The invention also provides a preparation method of the weather-resistant flame-retardant polymethyl methacrylate composite material, which comprises the following steps:
uniformly mixing polymethyl methacrylate, a flame retardant containing phosphorus cations, a toughening agent, a light stabilizer, an ultraviolet absorbent and other auxiliaries, carrying out melt blending, carrying out water-cooling bracing and granulating to obtain the weather-resistant flame-retardant polymethyl methacrylate composite material.
Preferably, the melt extrusion conditions are: the melt extrusion temperature is 180-.
The application of the weather-resistant flame-retardant polymethyl methacrylate composite material in the fields of building decoration, lighting lamps or electronic and electric appliances is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the flame retardant containing the phosphorus cations with a specific structure is compounded with the ultraviolet absorber and the light stabilizer, so that the defects of a traditional flame retardant system, such as shading and negative influence on impact strength, can be avoided while a better flame retardant effect is achieved; the influence of the flame retardant on the weather resistance of the polymethyl methacrylate can be counteracted, the ultraviolet blocking weather resistance of the polymethyl methacrylate is improved, the strong catalytic degradation effect of the flame retardant containing phosphorus cations on the polymethyl methacrylate is relieved and eliminated, and the problem of mechanical property attenuation of the ionic liquid flame-retardant polymethyl methacrylate composite material after photo-aging is solved; meanwhile, the visible light transmission effect of the material is not influenced, and the material can be applied to parts with requirements on light transmission display and flame retardance.
(2) The preparation method of the weather-resistant flame-retardant polymethyl methacrylate composite material prepared by the invention is simple and convenient to implement, has the cost advantage and has high design freedom.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The reagents selected for the examples and comparative examples of the present invention are illustrated below:
polymethyl methacrylate resin:
1. the melt index is 3g/10min (230 ℃/3.8kg), the residual monomer content is 0.09 wt.%, and the light transmittance is 92%
The model is as follows: PMMA CM-205 manufacturer: the beauty is high;
2. the melt index is 8g/10min (230 ℃/3.8kg), the residual monomer content is 0.09 wt.%, and the light transmittance is 92%
The model is as follows: PMMA CM-207 manufacturer: the beauty is high;
3. the melt index is 16g/10min (230 ℃/3.8kg), the residual monomer content is 0.09 wt.%, and the light transmittance is 92%
The model is as follows: PMMA CM-211 manufacturer: the beauty is high;
flame retardant containing phosphorus cation:
1. the model is as follows: AR-S11 (weight loss rate of 0.03% after drying treatment at 105 + -2 deg.C) manufacturer: inovia; the specific structural formula is shown as formula (1):
2. the model is as follows: DR-S15 (weight loss rate of 0.08% after drying treatment at 105 + -2 deg.C) manufacturer: inovia; the specific structural formula is shown as formula (2):
3. the model is as follows: BR-S13 (weight loss rate of 0.06% after drying treatment at 105 + -2 deg.C) manufacturer: inovia; the specific structural formula is shown as formula (3):
conventional flame retardants: phosphonic acid tris (2-chloropropyl) ester
The model is as follows: TCPP manufacturer: american Union of Qingdao;
a toughening agent: butadiene grafted acrylate styrene copolymer
The model is as follows: manufacturer M-210: a bell jar;
light stabilizer: hindered amines
The model is as follows: CHISORB 770 manufacturer: taiwan double bond;
ultraviolet absorber: benzotriazoles
The model is as follows: CHISORB 234 manufacturer: taiwan double bond;
antioxidant:
1. hindered phenol type: CHINOX 1010 manufacturer: taiwan double bond;
2. phosphite type: CHINOX 168 manufacturer: taiwan double bond.
The polymethyl methacrylate composite materials of the examples and the comparative examples of the present invention were prepared by the following processes:
weighing polymethyl methacrylate, a phosphorus cation-containing flame retardant, a toughening agent, a light stabilizer, an ultraviolet absorbent and other auxiliaries according to the proportion, putting the materials into a mixer, mixing the materials at the rotating speed of 1000 r/min for 5min, taking the materials out, adding the mixed materials into a double-screw extruder (the temperature of each section of the extruder is set to be 200 ℃, and the rotating speed of the screw is set to be 400 r/min), carrying out melt blending, carrying out water cooling, drawing strips and granulating to obtain the weather-resistant flame-retardant polymethyl methacrylate composite material.
The performance test method and standard of the polymethyl methacrylate composite material of each embodiment and comparative example of the invention are as follows:
(1) flame retardant performance test (vertical burn): the material was prepared into 125mm by 13mm by 0.8mm bars for testing according to test standard ANSI/UL-94-2013;
(2) notched impact strength test: molding into a bar-shaped sample strip (notch Type A) meeting the requirements of the ISO 180-plus 2000 cantilever beam notch impact strength test, and carrying out the notch impact strength test at the temperature of 23 +/-2 ℃;
(3) weathering performance test (notched impact strength after aging): performing injection molding to obtain a rod-shaped sample strip meeting the requirements of ISO 180-2000 Izod notched impact strength test, aging for 500 hours under the conditions of ISO 4892-2-2013, taking out the sample strip, adjusting the sample strip at normal temperature for more than 40 hours, testing the notched impact strength at the temperature of 23 +/-2 ℃, recording the strength data of the sample strip when the sample strip is punched out, and calculating the retention rate of the data before aging;
wherein the retention (%) (notched impact strength after aging/notched impact strength before aging) × 100;
(4) and (3) testing light transmittance: the sample was injection molded into a sample plate of 80mm x 50mm x 2mm, and the light transmittance of the sample plate was measured using a light transmittance tester according to test standard GB/T2410-.
Examples 1 to 9
This example provides a series of weatherable flame retardant polymethylmethacrylate composite materials with the formulation shown in Table 1.
TABLE 1 formulations (parts) of examples 1 to 9
Comparative examples 1 to 4
This comparative example provides a series of polymethylmethacrylate composite materials having the formulation given in table 2.
TABLE 2 formulations of comparative examples 1 to 4 (parts)
| Comparative example | 1 | 2 | 3 | 4 |
| Polymethyl methacrylate 1 | 79.5 | 79.5 | 79.5 | 79.5 |
| Flame retardant containing phosphorus cation 1 | 30 | / | 10 | 10 |
| Conventional flame retardants | / | 10 | / | / |
| Toughening agent | 8 | 8 | 8 | 8 |
| Light stabilizers | 1 | 1 | / | 1 |
| Ultraviolet absorber | 1 | 1 | / | / |
| Antioxidant 1 | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant 2 | 0.4 | 0.4 | 0.4 | 0.4 |
The flame retardant properties, mechanical properties and optical properties of each of the examples and comparative examples were measured according to the above-mentioned methods, and the results are shown in Table 3.
TABLE 3 results of Performance test of each example and comparative example
As can be seen from the performance test results in Table 3, the flame-retardant PMMA material prepared according to the embodiments 1-9 can achieve flame retardance above UL 94V-0 level, and the light transmittance of the material is above 88%; after the material xenon lamp is aged for 500 hours, the material is slightly damaged, and the retention rate of the notch impact strength is over 90 percent.
In comparative example 1, the addition amount of the flame retardant is too high, the initial notch impact strength of the material is greatly influenced, and meanwhile, the notch impact strength retention rate after aging is also low and is only less than 50%; in the comparative example 2, the conventional phosphate flame retardant is adopted, and under the condition of the same addition amount, the flame retardant effect is completely absent in a PMMA system, and the impact on the notch impact strength and the light transmittance of the material is relatively large; comparative example 3 does not contain any light stabilizer and ultraviolet absorber, the material xenon lamp is damaged to a greater extent in the aging process, and the retention rate of the notch impact strength after aging is extremely low; comparative example 4, which only contains a light stabilizer, can not effectively shield the material from the damage of ultraviolet rays, and the retention rate of the notch impact strength after aging is also low.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The weather-resistant flame-retardant polymethyl methacrylate composite material is characterized by comprising the following components in parts by weight: 45-94.8 parts of polymethyl methacrylate, 5-20 parts of flame retardant containing phosphorus cations, 0-20 parts of toughening agent, 0.1-5 parts of light stabilizer, 0.1-5 parts of ultraviolet absorbent and 0-5 parts of other auxiliary agents;
the flame retardant containing the phosphorus cations consists of phosphorus cations and anions; wherein the structure of the phosphorus-containing cation is shown as follows:
wherein R is1、R2、R3、R4Independently selected from C1-6Or a substituted saturated alkyl group.
2. The weather-resistant flame-retardant polymethyl methacrylate composite material as claimed in claim 1, wherein the polymethyl methacrylate has a melt index of 3-16g/10min at 230 ℃/3.8kg according to ISO 1133-1-2011 test standard, a residual monomer content of 0-0.1 wt.%, and a light transmittance of 90-92%.
3. The weather-resistant flame-retardant polymethyl methacrylate composite material as claimed in claim 1, wherein the phosphorus cation-containing flame retardant has a weight loss rate of 0-0.1% after drying treatment at 105 ± 2 ℃ according to the test standard of GB/T6284-.
4. The weather-resistant flame-retardant polymethylmethacrylate composite material according to claim 1, wherein R is1、R2、R3Independent of each otherPreferably from C2-6Saturated alkyl groups of (a); r4Is selected from C2-4Saturated alkyl groups of (a); the R is1、R2、R3、R4Wherein the substituent is-OH or-NH2。
5. The weather-resistant flame-retardant polymethyl methacrylate composite material according to claim 1, wherein the structure of the anion in the phosphorus cation-containing flame retardant is one of the following structures:
wherein R is5、R6Independently selected from C1-6Unsubstituted saturated alkyl or substituted saturated alkyl of (a); r7Is C6-8Alkyl group of (1).
6. The weather-resistant flame-retardant polymethylmethacrylate composite material according to claim 5, wherein R is5、R6Independently selected from C2-4Saturated alkyl groups of (a); the R is5、R6Wherein the substituent is-OH or-NH2；R7Contains an aromatic ring, non-aromatic five-membered ring or six-membered ring.
7. The weather-resistant flame-retardant polymethylmethacrylate composite material according to claim 1, wherein the light stabilizer is a hindered amine; the ultraviolet absorbent is at least one of benzophenone or benzotriazole.
8. The weather-resistant flame retardant polymethylmethacrylate composite material according to claim 1, wherein the toughening agent is butadiene grafted acrylate styrene copolymer; the other auxiliary agent is at least one of an antioxidant, a lubricant or a coloring agent.
9. The preparation method of the weather-resistant flame-retardant polymethyl methacrylate composite material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
uniformly mixing polymethyl methacrylate, a flame retardant containing phosphorus cations, a toughening agent, a light stabilizer, an ultraviolet absorbent and other auxiliaries, carrying out melt blending, carrying out water-cooling bracing and granulating to obtain the weather-resistant flame-retardant polymethyl methacrylate composite material.
10. The use of the weather-resistant flame-retardant polymethyl methacrylate composite material according to any one of claims 1 to 8 in the fields of architectural decoration, lighting lamps or electronic and electric appliances.
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