CN115232428B - High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof - Google Patents
High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN115232428B CN115232428B CN202210780518.6A CN202210780518A CN115232428B CN 115232428 B CN115232428 B CN 115232428B CN 202210780518 A CN202210780518 A CN 202210780518A CN 115232428 B CN115232428 B CN 115232428B
- Authority
- CN
- China
- Prior art keywords
- parts
- transparency
- resin composition
- resin
- glue
- 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
- 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 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 229920005990 polystyrene resin Polymers 0.000 title claims abstract description 23
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003292 glue Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002834 transmittance Methods 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- -1 tri (2, 3-dibromopropyl) isocyanuric acid ester Chemical class 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 101100347998 Caenorhabditis elegans nas-21 gene Proteins 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 101100025807 Caenorhabditis elegans nas-30 gene Proteins 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- XDZNMACRGWIRAN-UHFFFAOYSA-N bis(2,4-ditert-butylphenyl) [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphite Chemical compound P(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OCC(CO)(CO)CO XDZNMACRGWIRAN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229920005669 high impact polystyrene Polymers 0.000 abstract description 6
- 239000004797 high-impact polystyrene Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical group BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101710110822 L-histidine 2-aminobutanoyltransferase Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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 provides a high-transparency high-impact flame-retardant polystyrene resin composition and a preparation method thereof, wherein the composition comprises, by weight, 10-20 parts of GPPS resin, 30-50 parts of K glue, 20-50 parts of MS resin, 10-30 parts of PPO resin, 3-10 parts of flame retardant, 0.3-0.5 part of lubricant and 0.1-0.3 part of antioxidant; the high impact polystyrene resin composition obtained by the invention has excellent transparency, toughness, flame retardance, heat resistance and easy processing property, and the resin composition is simple to prepare, low in material cost and high in production efficiency, and fills up the performance defect of transparent GPPS. Meanwhile, the feasibility of replacing transparent ABS with T-HIPS is also provided.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-transparency high-impact flame-retardant polystyrene resin composition and a preparation method thereof.
Background
Polystyrene (Polystyrene, GPPS for short) has the characteristics of excellent transparency, rigidity, electrical insulation, low hygroscopicity and the like, is low in price, easy to process and form, good in product dimensional stability and extremely wide in application, and becomes one of five general plastics in the world. As a transparent material, the light transmittance of the transparent material can reach 90%, and the transparent material can be widely applied to the fields of various instrument shells, lamp covers, optical chemical instrument parts, transparent films, refrigerator drawers, toys and the like. However, the GPPS molecular chain contains a rigid benzene ring structure, so that the product has high brittleness, is extremely easy to crack after being subjected to external stress, and seriously influences the use function of the product, so that the toughening modification of the product is very important.
At present, for toughening of GPPS, two approaches can be mainly divided: (1) toughening method for sacrificing transparency: typical toughening agents include butyl rubber, styrene-butadiene-styrene triblock copolymer (SBS), hydrogenated SBS, ethylene Propylene Diene Monomer (EPDM), metallocene polystyrene elastomer (PSE) and the like, wherein High Impact Polystyrene (HIPS) is a very important class of styrene products derived therefrom. Although these toughening agents can all provide good toughening effects, the transparency of GPPS is sacrificed without exception, thus limiting their application in some fields where transparency is required. (2) toughening method for maintaining transparency: including styrene-butadiene transparent impact resin (K glue) toughening and alloying toughening with transparent substrates (PE, PC, PA, etc.), wherein the alloying toughening involves complex compatibility problems, and the introduction of a proper compatilizer is required to have certain effect, which not only increases the cost but also increases the complexity of the formulation design. From the comprehensive analysis, the GPPS is toughened on the basis of maintaining high transparency, and only K glue is used as a currently available toughening agent. However, as known from the prior literature and patent reports, the GPPS is toughened by the pure K glue, the toughening effect is still limited, and the notch impact of the cantilever beam is difficult to be more than 10KJ/m 2. Meanwhile, the heat resistance of the toughened and modified transparent impact polystyrene (T-HIPS) can be obviously reduced, and the heat deformation temperature is only about 70 ℃ generally, so that the application of the toughened and modified transparent impact polystyrene in the field with heat resistance requirement can be limited to a certain extent. In addition, polystyrene is extremely flammable in air, has a limiting oxygen index of only 18%, and is prone to generate a large amount of black smoke when burned. With the enhancement of people's safety and environmental awareness, most of materials used in household appliances have flame retardant demands in recent years, but a typical flame retardant bromine-antimony compound system of polystyrene can seriously affect the transparency, and as the carbon forming capability of polystyrene is weaker, the flame retardant efficiency of phosphate flame retardant is often limited, the UL 94V 0 grade is difficult to reach with low addition amount, and the heat resistance and/or the transparency of the polystyrene resin can be seriously affected with high addition amount, so the preparation of the polystyrene resin with both transparent high impact and heat resistance and flame retardance is a difficult point.
The Chinese patent application number 201010598555.2 discloses a transparent K glue/GPPS alloy material and a preparation method thereof, wherein the material comprises the following raw materials in parts by weight: 69 to 80 parts of K glue, 19 to 30 parts of GPPS, 0.5 to 1 part of lubricant and 0.2 to 0.6 part of antioxidant. In this patent, when the K glue content is as high as 79%, the notched Izod impact strength is only 6KJ/m 2 (ISO standard), the heat distortion temperature is 69 ℃ (ISO standard), and the transmittance is 83%. This suggests that a high transparency, high impact, good heat resistant polystyrene resin cannot be obtained by simply blending the K-glue and GPPS.
Another important application of HIPS modifiers in today's industry of modified plastics is the replacement of ABS to fulfill the market's cost reduction needs. So far, the T-HIPS is used for replacing transparent ABS, and has long way to go, wherein toughness and heat resistance are two key indexes far apart. Up to the present, no T-HIPS product has been available in the market, which has excellent transparent appearance and impact resistance, and also has good flame retardance and heat resistance, so as to achieve the level of replacing transparent ABS with low cost. Therefore, the preparation of the high-transparency high-impact flame-retardant polystyrene resin has great significance.
Disclosure of Invention
In view of the above, the present invention aims to provide a highly transparent, high impact flame retardant polystyrene resin composition and a method for preparing the same.
The aim of the invention is realized by the following technical scheme:
a high-transparency high-impact flame-retardant polystyrene resin composition comprises the following components in percentage by weight:
The GPPS resin is atactic polystyrene resin and is single general-purpose GPPS resin or a mixture of two or more GPPS resins with different mechanical properties.
The K glue is a styrene-butadiene diblock copolymer, the styrene content of the K glue is 70-85%, the transmittance of the K glue is 85-92%, and the K glue can be one or a mixture of K glue with different butadiene contents in SL-803G, SL-838 of mass plastic and KR03 and KR05 of Phillips.
The MS resin is a styrene-acrylic ester block copolymer, wherein the content of acrylic ester components is 10-60%, the transmittance is 87-92%, and the MS resin can be one or more MS resin mixtures with different acrylic ester contents in NAS 21, NAS 30, NAS 90, qimei PM-600 and Japanese electric chemistry TX-100S, TX-100K of the benzene collar;
the PPO resin is a single polyphenyl ether resin or a mixture of two or more polyphenyl ether resins with different mechanical properties, the transmittance is more than 80 percent, and the intrinsic viscosity of the PPO resin measured in toluene at the temperature of 25 ℃ at the concentration of 0.6g/100mL is 30-45 mL/g.
The flame retardant is a halogen-free compound flame retardant system, the halogen component is tris (2, 3-dibromopropyl) isocyanurate (PS-TFR), the halogen-free component is any one phosphate flame retardant of RDP, BDP and solid phosphate (RC 200), and the solid phosphate RC200 is preferable; the addition amount of the flame retardant is related to the proportion of the K glue, and the higher the number of the K glue is, the more the flame retardant is needed.
The antioxidant is hindered phenol antioxidant and phosphite antioxidant, the hindered phenol antioxidant comprises pentaerythritol tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate ], and the phosphite antioxidant comprises triphenyl phosphate, tri (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol bis (2, 4-di-tert-butylphenyl) phosphite.
Further, the antioxidant is preferably a hindered phenol antioxidant and a phosphite antioxidant according to the mass ratio of 1: (1-2) mixing and adding.
The lubricant comprises one or more of fatty acid amide lubricants, stearate lubricants, fatty acid ester lubricants and silicone lubricants.
A preparation method of a high-transparency high-impact flame-retardant polystyrene resin composition specifically comprises the following steps:
(1) The components are prepared according to the following weight portions:
(2) Adding the components in the step (1) into a high-speed mixer according to the parts by weight, fully mixing, then placing into a screw machine, carrying out melt extrusion at the extrusion temperature of 200-250 ℃ and the screw rotating speed of 200-500 rpm, cooling and granulating to obtain the high-transparency high-impact flame-retardant polystyrene resin composition.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention selects four components with similar refractive indexes and good compatibility: GPPS, K glue, MS resin and PPO resin are blended to obtain a transparent matrix, the light transmittance of the product is kept above 85%, and the haze is lower than 15%;
(2) On the basis of toughening GPPS by using K glue, the invention adopts MS resin which is not commonly used in industry as a compatilizer, further enhances the interfacial adhesion between GPPS and K glue, is beneficial to exerting the toughening effect of K glue to a greater extent, and solves the problem that the notch impact strength of GPPS/K glue cannot be greatly improved by the synergistic effect of MS resin and K glue, and the highest impact can be more than 20kJ/m 2;
(3) The PPO resin with excellent compatibility is added, so that the toughness of the toughening system can be further stabilized, the heat resistance of the toughening system can be obviously improved, the heat deformation temperature can reach more than 80 ℃ (ISO standard), the toughness and the heat resistance are balanced, and the improvement of the flame retardant property of the system is facilitated;
(4) The halogen-free compound flame-retardant system is selected, the transparency and the heat resistance of the system are not affected by the tri (2, 3-dibromopropyl) isocyanic acid ester (PS-TFR) and the solid phosphate (RC 200) under the proper addition, and the tri (2, 3-dibromopropyl) isocyanic acid ester and the solid phosphate can synergistically flame-retardant, and simultaneously, the flame-retardant effect is exerted in a gas phase and a condensed phase, so that the flame-retardant performance of the system can be stabilized to be 1.6mm V0 flame retardant;
(5) The high impact polystyrene resin composition obtained by the invention has excellent transparency, toughness, flame retardance, heat resistance and easy processing property, and the resin composition is simple to prepare, low in material cost and high in production efficiency, and fills up the performance defect of transparent GPPS. Meanwhile, the feasibility of replacing transparent ABS with T-HIPS is also provided.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Examples 1 to 7
Examples 1-7 provide a method for preparing a highly transparent, high impact flame retardant polystyrene resin composition, the components and amounts of which are shown in Table 1.
The preparation methods of examples 1 to 7 are as follows:
according to the weight portions of the formula components in the table 1, the raw materials are added into a high-speed mixer for fully mixing, then are placed into a double-screw extruder for melt extrusion at the extrusion temperature of 200-250 ℃ and the screw rotating speed of 200-500 rpm, and are cooled and granulated to obtain the product.
The materials of table 1 are as follows:
GPPS: GPPS-525, zhongxin Guoan;
k glue-1: SL803G, 75% styrene, 25% butadiene, 89% transmittance, guangdong and plastic stock;
k glue-2: SL838, which has a styrene content of 70%, a butadiene content of 30% and a light transmittance of 90%, by Guangdong and plastic stock;
PPO: PPE/ZM035, intrinsic viscosity 35mL/g, mesochemistry;
MS-1: NAS 21, which has a styrene content of about 80%, a methyl methacrylate content of about 20%, a light transmittance of 90%, and an intel benzene collar;
PS-TFR: tris (2, 3-dibromopropyl) isocyanurate, dongguan city long flame retardant materials limited;
RC200: solid phosphate flame retardant, zhejiang Wansheng Co., ltd;
An antioxidant: irganox 1010, irganox 168, CIBA refining Co;
and (3) a lubricant: EBS, korea SIN WOUN.
The performance evaluation mode and the implementation standard thereof are as follows:
1. characterization of transparency:
transmittance: 2mm thick plaques, tested according to ISO13468-1 standard
Haze: 2mm thick plates, tested according to ISO 14782 standard
2. Characterization of mechanical properties:
Notched Izod impact Strength: the impact energy was 5.5J, the test temperature was 23℃according to ISO 179-1:2010 (E) standard;
Tensile strength: testing according to ISO 527-1:2019 standard, wherein the testing condition is 50mm/min;
heat distortion temperature: testing according to ISO 75-1:2020 standard, wherein the testing condition is 120 ℃/h,1.80MPa;
3. characterization of flame retardant properties:
vertical combustion: 1.6mm flame retardant bars, tested according to UL94 standard.
Table 1 example formulation, parts by weight and Properties
Comparative examples 1 to 7
Comparative examples 1-7 provide a method for preparing a high transparent, high impact flame retardant polystyrene resin composition comprising the steps of:
According to the weight portions of the formula components in the table 2, the raw materials are added into a high-speed mixer for fully mixing, then are placed into a double-screw extruder for melt extrusion at the extrusion temperature of 200-250 ℃ and the screw rotating speed of 200-500 rpm, and are cooled and granulated to obtain the product.
Wherein the materials of table 2 are as follows:
MS-2: PM-600 with styrene content of 40%, methyl methacrylate content of 60%, light transmittance of 90%, taiwan Qimei;
SMA: SMA700, a styrene-maleic anhydride copolymer, shanghai Hua New electronic Material Co., ltd.
Table 2 comparative example formulation parts by weight
Comparative example 1, compared with example 1, eliminates MS and PPO, and the equivalent amount of the MS and PPO is replaced by K glue, and the toughness of the system is poor, which shows that the toughening effect of single K glue on GPPS is very limited;
Comparative example 2, compared to example 1, removes MS and replaces it with K glue equally, since there is a lack of strong interfacial adhesion between GPPS and K glue, the toughness of the system is significantly lower than example 1, indicating that MS plays a key role in the toughness of GPPS/K glue system;
Comparative example 3, compared to example 2, with PPO removed, has significantly lower heat resistance than example 2, and the resulting system has reduced char formation and reduced flame retardant properties;
Comparative example 4, in which K glue-2 was changed to K glue-1 having a lower butadiene content than in example 1, the toughness improvement of the material was very limited due to the too low amount of K glue;
Comparative example 5, in which MS-1 was replaced with MS-2, has significantly lower light transmittance and toughness than example 1, and has far less effect than that of example 1, because the methacrylate component content is too high and the interaction between the components is weakened due to the difference in polarity;
In comparative example 6, compared with the compound system of the simple K glue and the MS resin in example 1, the compatibility of the compound system and the compound system is very good, the toughness can be greatly improved, but the heat resistance and the mechanical strength are too low, and the flame retardance is more difficult to reach V0;
Comparative example 7, compared with example 6, the flame retardant changed to a single RC200, the light transmittance was significantly reduced, and the synergistic flame retardant effect was lost, resulting in flame retardance failing to reach V0 at the same addition amount;
Comparative example 8, in which the ms was replaced with SMA, has significantly lower toughness and light transmittance than example 1.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (6)
1. The high-transparency high-impact flame-retardant polystyrene resin composition is characterized by comprising the following components in parts by weight:
10-20 parts of GPPS resin
30-50 Parts of K glue
MS resin 20-50 parts
10-30 Parts of PPO resin
3-10 Parts of flame retardant
0.3-0.5 Part of lubricant
0.1-0.3 Part of antioxidant;
The K glue is a styrene-butadiene diblock copolymer, the styrene content of the K glue is 70%, and the light transmittance of the K glue is 90%;
The MS resin is one or more of an Infinil benzene collar NAS 21, an NAS 30 and an NAS 90;
The flame retardant is a halogen-free compound flame retardant system, the halogen component is tri (2, 3-dibromopropyl) isocyanuric acid ester, and the halogen-free component comprises any one of RDP, BDP and solid phosphate.
2. The high transparency, high impact flame retardant polystyrene resin composition of claim 1, wherein the GPPS resin is an atactic polystyrene resin.
3. The high-transparency high-impact flame-retardant polystyrene resin composition according to claim 1, wherein the PPO resin is a single polyphenylene ether resin or a mixture of two or more polyphenylene ether resins having different mechanical properties, and has a transmittance of 80% or more and an intrinsic viscosity of 30 to 45 mL/g measured in toluene at a concentration of 0.6 g/100 mL at 25 ℃.
4. The high transparency, high impact flame retardant polystyrene resin composition according to claim 1, wherein said antioxidants comprise hindered phenolic antioxidants and/or phosphite antioxidants;
The hindered phenol antioxidant comprises pentaerythritol tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate ];
The phosphite antioxidant comprises one or more of triphenyl phosphate, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol bis (2, 4-di-tert-butylphenyl) phosphite.
5. The high-transparency, high-impact flame-retardant polystyrene resin composition according to claim 1, wherein the lubricant comprises one or more of fatty acid amide-based lubricants, stearate-based lubricants, fatty acid ester-based lubricants and silicone-based lubricants.
6. A method for preparing the high-transparency, high-impact flame-retardant polystyrene resin composition according to any one of claims 1 to 5, comprising the steps of:
(1) The components are prepared according to the following weight portions:
10-20 parts of GPPS resin,
30-50 Parts of K glue,
20-50 Parts of MS resin,
10-30 Parts of PPO resin,
3-10 Parts of a flame retardant,
0.3 To 0.5 part of lubricant,
0.1-0.3 Part of antioxidant;
(2) And (2) adding the components in the step (1) into a high-speed mixer according to the parts by weight, fully mixing, then placing into a screw machine, carrying out melt extrusion at the extrusion temperature of 200-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the high-transparency high-impact flame-retardant polystyrene resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210780518.6A CN115232428B (en) | 2022-07-04 | 2022-07-04 | High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210780518.6A CN115232428B (en) | 2022-07-04 | 2022-07-04 | High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115232428A CN115232428A (en) | 2022-10-25 |
| CN115232428B true CN115232428B (en) | 2024-05-24 |
Family
ID=83671125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210780518.6A Active CN115232428B (en) | 2022-07-04 | 2022-07-04 | High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115232428B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975305B (en) * | 2022-12-28 | 2024-08-23 | 上海金发科技发展有限公司 | Transparent polystyrene composition and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006249446A (en) * | 2006-06-26 | 2006-09-21 | Dainippon Ink & Chem Inc | Method for producing transparent, impact-resistant styrene-based resin composition |
| CN104086911A (en) * | 2014-07-14 | 2014-10-08 | 东莞市德诚塑化科技有限公司 | Transparent impact-resistance polystyrene and preparation method thereof |
| CN110092960A (en) * | 2019-03-29 | 2019-08-06 | 金发科技股份有限公司 | A kind of thermoplastic polymer composition and preparation method thereof |
| CN112745592A (en) * | 2020-12-29 | 2021-05-04 | 成都金发科技新材料有限公司 | Styrene composition and application and preparation method thereof |
| CN114410099A (en) * | 2022-01-10 | 2022-04-29 | 上海金山锦湖日丽塑料有限公司 | Transparent flame-retardant MPPO resin composition and preparation method thereof |
| CN114479297A (en) * | 2021-12-29 | 2022-05-13 | 上海金发科技发展有限公司 | High-impact-resistance wear-resistant transparent polystyrene composition and preparation method and application thereof |
-
2022
- 2022-07-04 CN CN202210780518.6A patent/CN115232428B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006249446A (en) * | 2006-06-26 | 2006-09-21 | Dainippon Ink & Chem Inc | Method for producing transparent, impact-resistant styrene-based resin composition |
| CN104086911A (en) * | 2014-07-14 | 2014-10-08 | 东莞市德诚塑化科技有限公司 | Transparent impact-resistance polystyrene and preparation method thereof |
| CN110092960A (en) * | 2019-03-29 | 2019-08-06 | 金发科技股份有限公司 | A kind of thermoplastic polymer composition and preparation method thereof |
| CN112745592A (en) * | 2020-12-29 | 2021-05-04 | 成都金发科技新材料有限公司 | Styrene composition and application and preparation method thereof |
| CN114479297A (en) * | 2021-12-29 | 2022-05-13 | 上海金发科技发展有限公司 | High-impact-resistance wear-resistant transparent polystyrene composition and preparation method and application thereof |
| CN114410099A (en) * | 2022-01-10 | 2022-04-29 | 上海金山锦湖日丽塑料有限公司 | Transparent flame-retardant MPPO resin composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115232428A (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI242582B (en) | Improved flow carbonate polymer blends | |
| CN101812202B (en) | Halogen-free low-smoke flame-retardant polypropylene/polyamide composite material and preparation method | |
| CN112322014B (en) | Low-temperature-resistant PC alloy material and preparation method thereof | |
| CN103013088A (en) | High-rigidity polycarbonate composite material and preparation method thereof | |
| CN115232428B (en) | High-transparency high-impact flame-retardant polystyrene resin composition and preparation method thereof | |
| CN108117732B (en) | Halogen-free flame-retardant polycarbonate alloy and preparation method thereof | |
| CN103788615A (en) | High-gloss and low-volatility flame retardant polycarbonate composition as well as preparation method and application thereof | |
| US6376606B1 (en) | Semi-transparent blends of polyphenylene ether and styrenic copolymers | |
| CN104448666A (en) | High-toughness PPE/HIPS/PP (Polypheylene Ether/High Impact Polystyrene/Propene Polymer) ternary alloy and preparation as well as application | |
| CN102936402A (en) | Low-smoke heat-resistant halogen-free flame-retardant polycarbonate/acrylonitrile-butadiene-styrene resin composition and preparation method thereof | |
| WO2001090207A1 (en) | Block copolymer and composition thereof | |
| EP0930341B1 (en) | Process for preparing semi-transparent blends of polyphenylene ether and styrenic radial block copolymers | |
| CN113105733A (en) | Flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN112322020A (en) | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof | |
| WO2024082522A1 (en) | Flame-retardant polycarbonate composite material, preparation method therefor, and application thereof | |
| CN115584114B (en) | Polycarbonate alloy composition and preparation method and application thereof | |
| CN114410099B (en) | Transparent flame-retardant MPPO resin composition and preparation method thereof | |
| EP2052031A1 (en) | Poly (arylene ether) composition, method, and article | |
| CN112724627A (en) | PC/ABS alloy material and application thereof | |
| CA2382071C (en) | Improved flow carbonate polymer blends | |
| CN115651383A (en) | Polycarbonate alloy material and preparation method and application thereof | |
| CN111393742A (en) | Environment-friendly flame-retardant polypropylene-nylon alloy material and preparation method thereof | |
| CN111285976A (en) | Preparation method of maleic anhydride grafted PA6 compatilizer for PA6/PPO alloy material | |
| CN110527269B (en) | Modified polycarbonate material and preparation method thereof | |
| CN110894331B (en) | Environment-friendly low-smoke flame-retardant HIPS 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 |