CN113881178B - 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
- Publication number
- CN113881178B CN113881178B CN202111146673.4A CN202111146673A CN113881178B CN 113881178 B CN113881178 B CN 113881178B CN 202111146673 A CN202111146673 A CN 202111146673A CN 113881178 B CN113881178 B CN 113881178B
- Authority
- CN
- China
- Prior art keywords
- polymethyl methacrylate
- retardant
- flame
- composite material
- weather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 67
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- -1 phosphorus cations Chemical class 0.000 claims abstract description 20
- 239000004611 light stabiliser Substances 0.000 claims abstract description 18
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 238000005034 decoration Methods 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000004580 weight loss Effects 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 206010051246 Photodermatosis Diseases 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000008845 photoaging Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229940030980 inova Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical group [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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, a flame retardant containing phosphorus cations, a toughening agent, a light stabilizer, an ultraviolet absorber and other auxiliary agents; the flame retardant containing 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 excellent weather resistance and optical transmission characteristics of matrix resin are reserved; the prepared weather-resistant flame-retardant composite material has high transparency, light aging resistance and excellent flame retardance, and can be widely applied to the fields of building decoration, lighting fixtures 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, a preparation method and application thereof.
Background
Polymethyl methacrylate (PMMA), commonly known as organic glass, has a light transmittance of up to 92% and has transparency similar to that of quartz glass. PMMA has excellent weather resistance, higher surface hardness, higher surface glossiness and other characteristics, 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, bathroom, advertising signs and the like.
When PMMA is applied to lighting equipment and advertisement decorative materials, the traditional requirement only needs to be compatible with transparency and weather resistance. However, with the gradual improvement of the safety standard of the existing household electrical appliances, manufacturers gradually convert the requirements into requirements on the flame retardant property, the electrical property and the like of materials when selecting materials, and the requirements on the flame retardant property of PMMA materials are also gradually improved. Pure PMMA is inflammable, the oxygen index is only 17.3, and a large amount of methyl methacrylate monomer is generated by decomposition in the combustion process, so that the monomer has very high inflammability; the decomposition mechanism also determines that flame-retardant modification of PMMA is very difficult, and transparency and weather resistance of PMMA are required to be simultaneously considered when 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 realize high weather resistance, halogen-free high-efficiency flame retardant performance and high transparency at the same time, the invention aims to provide the weather-resistant flame retardant polymethyl methacrylate composite material, which overcomes the defect that the weather resistance of the polymethyl methacrylate is rapidly reduced after transparent flame retardant modification, and has excellent weather resistance while maintaining excellent transparency and halogen-free flame retardant characteristics.
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 building decoration, lighting fixtures or electronic appliances.
In order to achieve the aim of the invention, 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 flexibilizer, 0.1-5 parts of light stabilizer, 0.1-5 parts of ultraviolet absorber and 0-5 parts of other auxiliary agents;
the flame retardant containing phosphorus cations consists of phosphorus cations and anions; wherein the structure of the phosphorus-containing cation is as follows:
wherein,,R 1 、R 2 、R 3 、R 4 independently selected from C 1-6 Unsubstituted saturated alkyl or substituted saturated alkyl.
In the invention, the phosphorus cation-containing flame retardant with a specific structure is selected, and contains short-chain saturated alkane, so that the light aging resistance is poor, short-chain alkane free radicals are easily generated by decomposition under the action of ultraviolet light, the free radicals have high activity and are easily attacked to PMMA resin matrix, the resin matrix is rapidly degraded under the irradiation of ultraviolet light, and the mechanical property of the material is rapidly reduced, and even the surface of the material is cracked.
According to the invention, the phosphorus cation-containing flame retardant 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 phosphorus cation-containing flame retardant on PMMA is relieved and eliminated, and the flame retardant effect of the flame retardant under the combustion condition is not influenced.
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 flexibilizer, 0.3-3 parts of light stabilizer, 0.3-3 parts of ultraviolet absorber and 0.3-3 parts of other auxiliary agents.
Preferably, the polymethyl methacrylate has a melt index of 3-16g/10min under the condition of 230 ℃/3.8kg according to ISO 1133-1-2011 test standard, the residual monomer content (weight percent of residual monomer) is 0-0.1 wt.%, and the light transmittance is 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 polarity of the anionic group of the flame retardant containing phosphorus cations is strong, and the flame retardant is easy to absorb water and dissociate, so that the flame retardant effect of the flame retardant is affected; in addition, when the moisture 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 melt blending modification and the subsequent injection molding process with polymethyl methacrylate, so that the optical characteristics of the final product are affected.
Preferably, said R 1 、R 2 、R 3 Independently preferably from C 2-6 Saturated alkyl groups of (a); r is R 4 Selected from C 2-4 Saturated alkyl groups of (a); the R is 1 、R 2 、R 3 、R 4 The substituent is-OH or-NH 2 。
Preferably, the structure of the anion in the flame retardant containing phosphorus cations is one of the following structures:
wherein R is 5 、R 6 Independently selected from C 1-6 Unsubstituted saturated alkyl or substituted saturated alkyl of (a); r is R 7 Is C 6-8 Is a hydrocarbon group.
Further preferably, the R 5 、R 6 Independently selected from C 2-4 Saturated alkyl groups of (a); the R is 5 、R 6 The substituent is-OH or-NH 2 ；R 7 Contains an aromatic ring and a non-aromatic five-membered or six-membered ring.
The phosphorus cation-containing flame retardant can be a single ionic liquid compound or more than one composition.
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 benzophenone or benzotriazole.
According to the invention, the ultraviolet absorber and the light stabilizer are adopted at the same time, and the ultraviolet absorber can absorb most of ultraviolet energy irradiated to the surface and the inside of the transparent material, so that the damage of ultraviolet to the flame retardant is reduced, and the generation of destructive active free radicals is reduced; the light stabilizer has a good function of capturing free radicals, can effectively capture the generated destructive free radicals, and prevents the destructive free radicals from attacking a polymer molecular chain to degrade materials and reduce performance.
Preferably, the other auxiliary agent is at least one of an antioxidant, a lubricant or a colorant.
Further preferably, the antioxidant is at least one of hindered phenols or phosphites.
Further preferably, the lubricant is at least one of amides, stearates or esters.
Further preferably, the colorant is a dye-based or other colorant having a special 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 phosphorus cation-containing flame retardant, a toughening agent, a light stabilizer, an ultraviolet absorber and other auxiliary agents, carrying out melt blending, and 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 180-240 ℃, and the screw rotating speed is 200-800 rpm.
The application of the weather-resistant flame-retardant polymethyl methacrylate composite material in the fields of building decoration, lighting fixtures or electronic appliances is also in 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 absorbent and the light stabilizer, so that the defects of the 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, meanwhile, 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 is not affected, and the transparent flame retardant glass can be applied to parts with light transmission display and flame retardant requirements.
(2) The preparation method of the weather-resistant flame-retardant polymethyl methacrylate composite material is simple and convenient to implement, has the advantage of cost, and has high design freedom.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The reagents selected for each example and comparative example of the present invention are described below:
polymethyl methacrylate resin:
1. the melt index is 3g/10min (230 ℃/3.8 kg), the residual monomer content is 0.09 wt%, and the light transmittance is 92%
Model: PMMA CM-205 manufacturer: qimei;
2. the melt index is 8g/10min (230 ℃/3.8 kg), the residual monomer content is 0.09 wt%, and the light transmittance is 92%
Model: PMMA CM-207 manufacturer: qimei;
3. the melt index is 16g/10min (230 ℃/3.8 kg), the residual monomer content is 0.09 wt%, and the light transmittance is 92%
Model: PMMA CM-211 manufacturer: qimei;
flame retardant containing phosphorus cations:
1. model: AR-S11 (weight loss rate after drying treatment at 105+ -2deg.C: 0.03%) manufacturer: inova; the specific structural formula is shown in the formula (1):
2. model: DR-S15 (weight loss rate after drying treatment at 105+ -2deg.C is 0.08%) manufacturer: inova; the specific structural formula is shown in the formula (2):
3. model: BR-S13 (weight loss rate after drying treatment at 105+ -2deg.C: 0.06%) manufacturer: inova; the specific structural formula is shown in the formula (3):
conventional flame retardants: phosphonic acid tris (2-chloropropyl) ester
Model: TCPP manufacturer: qingdao Mei Ling;
toughening agent: butadiene grafted acrylate styrene copolymer
Model: m-210 manufacturer: a brillouin state;
light stabilizers: hindered amines
Model: CHISORB 770 manufacturer: taiwan double bond;
ultraviolet absorber: benzotriazole compounds
Model: CHISORB 234 manufacturer: taiwan double bond;
an antioxidant:
1. hindered phenol type number: the CHINOX 1010 manufacturer: taiwan double bond;
2. phosphite type number: the CHINOX 168 manufacturer: taiwan double bond.
The polymethyl methacrylate composite material of each embodiment and the comparative example is prepared by the following steps:
and respectively weighing polymethyl methacrylate, a phosphorus cation-containing flame retardant, a toughening agent, a light stabilizer, an ultraviolet absorber and other auxiliary agents according to the proportion, putting the materials into a mixer, mixing the materials at a rotating speed of 1000 revolutions per minute for 5 minutes, taking out the materials, adding the mixed materials into a double-screw extruder (the temperature setting range of each section of the extruder is 200 ℃, and the screw rotating speed setting range is 400 revolutions per minute) for melt blending, and then carrying out water-cooling bracing granulation 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 example and comparative example of the invention are as follows:
(1) Flame retardant performance test (vertical burn): preparing a material into a spline with the diameter of 125mm and 13mm and the diameter of 0.8mm according to a test standard ANSI/UL-94-2013 for testing;
(2) Notched impact strength test: injection molding into a bar-shaped spline (notch Type A) meeting the requirements of ISO 180-2000 cantilever beam notch impact strength test, and performing notch impact strength test at 23+/-2 ℃;
(3) Weather resistance test (notched impact strength after aging): injection molding into a bar-shaped spline meeting the requirements of ISO 180-2000 cantilever beam notch impact strength test, aging for 500 hours under the condition of ISO 4892-2-2013 interior decoration, taking out, adjusting for more than 40 hours at normal temperature, testing the notch impact strength at 23+/-2 ℃, recording the strength data of the spline when the spline is broken, and calculating and keeping the data before aging;
wherein retention (%) = (notched impact strength after aging/notched impact strength before aging) ×100;
(4) Light transmittance test: the sample is molded into a 80mm 50mm 2mm template, and the transmittance of the template is tested by a transmittance tester according to the test standard GB/T2410-2008.
Examples 1 to 9
This example provides a series of weatherable flame retardant polymethyl methacrylate composites formulated as 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 polymethyl methacrylate composites with the formulations shown in table 2.
Table 2 formulations (parts) of comparative examples 1 to 4
| Comparative example | 1 | 2 | 3 | 4 |
| Polymethyl methacrylate 1 | 79.5 | 79.5 | 79.5 | 79.5 |
| Flame retardant 1 containing phosphorus cations | 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 examples and comparative examples
As shown by the performance test results in Table 3, the flame-retardant PMMA materials prepared according to examples 1 to 9 can achieve flame retardance of UL 94V-0 level or more, and the light transmittance of the materials is 88% or more; after the xenon lamp of the material is aged for 500 hours, the material is little damaged, and the notch impact strength retention rate is over 90 percent.
In the 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 relatively low, which 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 PMMA system has no flame retardant effect at all, and the impact on the notch impact strength and the light transmittance of the material is larger; comparative example 3 does not contain any light stabilizer or ultraviolet light absorber, the xenon lamp of the material is damaged to a greater extent in the aging process, and the notch impact strength retention rate after aging is extremely low; the comparative example 4, which was added with a light stabilizer alone, also failed to effectively shield the damage of ultraviolet rays to the material, and the notched impact strength retention after aging was also relatively low.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the 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 the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
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 flexibilizer, 0.1-5 parts of light stabilizer, 0.1-5 parts of ultraviolet absorber and 0-5 parts of other auxiliary agents;
the flame retardant containing phosphorus cations consists of phosphorus cations and anions; wherein the structure of the phosphorus-containing cation is as follows:
wherein R is 1 、R 2 、R 3 、R 4 Independently selected from C 1-6 Unsubstituted saturated alkyl or substituted saturated alkyl of (a);
the light stabilizer is hindered amine; the ultraviolet absorbent is at least one of diphenyl ketone and benzotriazole.
2. The weather-resistant flame-retardant polymethyl methacrylate composite material of claim 1, wherein the polymethyl methacrylate has a melt index of 3-16 2210min at 230 ℃ 23.822, a residual monomer content of 0-0.1 wt.% and a light transmittance of 90-92% according to ISO 1133-1-2011 test standard.
3. The weather-resistant flame-retardant polymethyl methacrylate composite material of claim 1, wherein the phosphorus cation-containing flame retardant has a weight loss rate of 0-0.1% after drying treatment at a temperature of 105+/-2 ℃ according to the GB2T 6284-2006 test standard.
4. The weatherable flame retardant polymethyl methacrylate composite of claim 1, wherein R 1 、R 2 、R 3 Independently preferably from C 2-6 Saturated alkyl groups of (a); r is R 4 Selected from C 2-4 Saturated alkyl groups of (a); the R is 1 、R 2 、R 3 、R 4 The substituent is-OH or-NH 2 。
5. The weather-resistant flame-retardant polymethyl methacrylate composite material of claim 1, wherein the structure of anions in the flame retardant containing phosphorus cations is one of the following structures:
wherein R is 5 、R 6 Independently selected from C 1-6 Unsubstituted saturated alkyl or substituted saturated alkyl of (a); r is R 7 Is C 6-8 Is a hydrocarbon group.
6. The weatherable flame retardant polymethyl methacrylate composite of claim 5 wherein R 5 、R 6 Independently selected from C 2-4 Saturated alkyl groups of (a); the R is 5 、R 6 The substituent is-OH or-NH 2 ；R 7 Contains an aromatic ring and a non-aromatic five-membered or six-membered ring.
7. The weatherable flame retardant polymethyl methacrylate composite of claim 1, wherein the toughening agent is a butadiene grafted acrylate styrene copolymer; the other auxiliary agent is at least one of an antioxidant, a lubricant or a colorant.
8. The method for preparing the weather-resistant flame-retardant polymethyl methacrylate composite material according to any one of claims 1 to 7, which is characterized by comprising the following steps:
uniformly mixing polymethyl methacrylate, a phosphorus cation-containing flame retardant, a toughening agent, a light stabilizer, an ultraviolet absorber and other auxiliary agents, carrying out melt blending, and carrying out water-cooling bracing and granulating to obtain the weather-resistant flame-retardant polymethyl methacrylate composite material.
9. Use of the weather-resistant flame-retardant polymethyl methacrylate composite material according to any one of claims 1 to 7 in the field of building decoration, lighting fixtures or electronic appliances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111146673.4A CN113881178B (en) | 2021-09-28 | 2021-09-28 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111146673.4A CN113881178B (en) | 2021-09-28 | 2021-09-28 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113881178A CN113881178A (en) | 2022-01-04 |
| CN113881178B true CN113881178B (en) | 2023-05-09 |
Family
ID=79007607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111146673.4A Active CN113881178B (en) | 2021-09-28 | 2021-09-28 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113881178B (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654369A (en) * | 1995-07-25 | 1997-08-05 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Antistatic thermoplastic resin composition |
| CN101906234A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polymethylmethacrylate composition and preparation method thereof |
| CN106336606A (en) * | 2016-09-28 | 2017-01-18 | 芜湖创科新材料科技有限公司 | Extra weather-resistant antiflaming ASA/PMMA color coextrusion material for plastic building material and preparation method of extra weather-resistant antiflaming ASA/PMMA color coextrusion material |
| CN107325329B (en) * | 2017-06-22 | 2019-02-15 | 中国科学院宁波材料技术与工程研究所 | A kind of halogen-free flame retardants and the high molecular material containing the fire retardant |
| CN107540996A (en) * | 2017-09-06 | 2018-01-05 | 张永霞 | A kind of preparation method of flame-retarded resin dispersion liquid |
| CN108102022A (en) * | 2017-11-20 | 2018-06-01 | 南通诺为新材料科技有限公司 | A kind of polypropylene flame redardant acids plastics and preparation method and application |
| CN108659438A (en) * | 2018-05-10 | 2018-10-16 | 苏州双象光学材料有限公司 | A kind of preparation method of flame retardant type poly methyl methacrylate polymer |
| CN109181193A (en) * | 2018-09-25 | 2019-01-11 | 苏州优利金新材料有限公司 | One kind is exempted to spray PMMA/ASA material and preparation method thereof |
| CN113354867A (en) * | 2020-03-06 | 2021-09-07 | 南通诺为新材料科技有限公司 | Flame-retardant thermoplastic polyamide, flame retardant and application |
| CN113214319B (en) * | 2021-04-30 | 2022-06-14 | 上海交通大学 | Quaternary phosphonium salt flame retardant and synthetic method and application thereof |
-
2021
- 2021-09-28 CN CN202111146673.4A patent/CN113881178B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 韩新宇 ; 杨丽 ; 毕成良 ; 王晓英 ; 张宝贵 ; .烷基次膦酸盐作为阻燃剂的应用研究.天津化工.2009,(02),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113881178A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108148391B (en) | Ultraviolet-resistant halogen-free flame-retardant PC/ABS alloy and preparation method thereof | |
| CN112538252B (en) | Transparent hydrolysis-resistant weather-resistant halogen-free flame-retardant polycarbonate composite material | |
| CN103788615B (en) | Low volatilization flame retardant polycarbonate composition of a kind of high light and its preparation method and application | |
| CN105111659A (en) | Infrared-permeable transparent flame-retardant composite material and method for preparing same | |
| CN103509326B (en) | A kind of Halogen-free flame-retardant cold-resistant polycarbonate alloy and preparation method thereof | |
| CN101469096A (en) | Flame-retardant polypropylene film material | |
| CN110643165A (en) | High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof | |
| CN111793338B (en) | Compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and preparation method thereof | |
| CN103113720B (en) | Flame-retardant PET resin combination with anti-yellowing function and preparation method thereof | |
| CN107254085B (en) | Polyolefin auxiliary agent composition with high oxidation resistance | |
| CN108129820B (en) | High-weather-resistance PC/ABS alloy material and preparation method thereof | |
| CN113881178B (en) | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof | |
| CN101768340A (en) | PET resin composition with anti-yellowing function and preparation method thereof | |
| CN111117046B (en) | Low-addition high-flame-retardance flame-retardant master batch and preparation method thereof | |
| CN109535563B (en) | Environment-friendly composite material and preparation method and application thereof | |
| CN104725760A (en) | Halogen-free flame-retardant ABS material and preparation method thereof | |
| CN105199305B (en) | A kind of flame-retardant ABS compound material and preparation method thereof | |
| CN112251019B (en) | Polyamide halogen-free flame retardant composition and application thereof | |
| CN115433429A (en) | Halogen-free flame-retardant PET/ASA alloy material and preparation method thereof | |
| CN110698831A (en) | High-filling high-impact high-weather-resistance environment-friendly flame-retardant PC/ABS composite material | |
| CN113072789A (en) | PMMA/MBS/AS polymer composite material AMS and preparation method thereof | |
| CN110698835A (en) | PC/PBT composite flame-retardant material for vehicle interior trim and preparation method thereof | |
| CN113105734B (en) | Preparation method of weather-resistant, high-toughness, wear-resistant and flame-retardant alloy plastic material | |
| CN114933792B (en) | Polycarbonate alloy material and preparation method and application thereof | |
| CN114410096B (en) | Cobalt-containing organic montmorillonite modified heat aging resistant flame retardant PC optical film material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |