CN107857948A - A kind of modified ASA polymeric compositions - Google Patents
A kind of modified ASA polymeric compositions Download PDFInfo
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- CN107857948A CN107857948A CN201711204110.XA CN201711204110A CN107857948A CN 107857948 A CN107857948 A CN 107857948A CN 201711204110 A CN201711204110 A CN 201711204110A CN 107857948 A CN107857948 A CN 107857948A
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- China
- Prior art keywords
- polymeric compositions
- fire retardant
- modified asa
- compositions according
- melamine
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- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 51
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 229920000638 styrene acrylonitrile Polymers 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 9
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229920000578 graft copolymer Polymers 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 7
- 230000003750 conditioning effect Effects 0.000 claims description 7
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003595 mist Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- -1 γ-(methacryloxypropyl) propyl group Chemical group 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- SGPMZDLPUCDQQQ-UHFFFAOYSA-N 1-isocyano-3-(2,2,2-trihydroxyethyl)-7,9-dihydropurine-2,6,8-trione Chemical class OC(CN1C(N(C(C=2NC(NC1=2)=O)=O)[N+]#[C-])=O)(O)O SGPMZDLPUCDQQQ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- TVOKLFHQSPUILS-UHFFFAOYSA-N N1=C(N)N=C(N)N=C1N.P(=O)(O)(O)OCC(C)(CO)C Chemical compound N1=C(N)N=C(N)N=C1N.P(=O)(O)(O)OCC(C)(CO)C TVOKLFHQSPUILS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims 1
- WNZCFUGDYATEOZ-UHFFFAOYSA-N NC(=O)N.P(=O)(O)(O)OCC(CO)(CO)CO Chemical compound NC(=O)N.P(=O)(O)(O)OCC(CO)(CO)CO WNZCFUGDYATEOZ-UHFFFAOYSA-N 0.000 claims 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 10
- 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 group 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 description 9
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical group OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 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
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 210000002700 urine Anatomy 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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 present invention relates to a kind of modified ASA polymeric compositions, including the raw material of following components and parts by weight content：Styrene-acrylonitrile acrylate copolymer 10 50, styrene acrylonitrile copolymer 30 80, acrylic resin 2 15, collaboration auxiliary agent 10 30, collaboration auxiliary agent are the fire retardant being surface-treated through surfactant.Compared with prior art, the composition that the present invention is prepared has excellent glossiness, anti-flammability, the feature of environmental protection and good processability.
Description
Technical field
The present invention relates to field of polymer composite material, more particularly, to a kind of modified ASA polymeric compositions.
Background technology
It is ASA by the three-component grafted EVA of acrylonitrile-styrene-acrylic ester, due to ASA graft copolymer structures
In do not contain remnants double bond, make it have good weatherability and splendid mechanical and physical performance.In recent years, China is to ASA
The demand cumulative year after year of resin, had a very wide range of applications in the field such as automobile, electric, building.
But ASA resin belongs to combustible material, most commonly used domestic market is halogenated flame retardant.In numerous halogen systems
In fire retardant, decabromodiphenyl oxide (DBDPO), tetrabromobisphenol A (TBBPA), octabromodiphenyl ether (OBDPO) etc. or than it is more environmentally friendly
The bromide fire retardants such as brominated triazine fire retardant are best to the flame retardant effect of ASA resin, particularly when they and antimony oxide are matched somebody with somebody
Close in use, ASA resin can be made to reach good fire resistance.But because halide-containing can produce largely in burning
Toxic gas, and because the addition of inorganic matter can decline the surface gloss of product, performance reduces, the grammes per square metre of product increases
Add, do not accomplish real halogen-free flameproof.
Therefore, there is good anti-flammability, and other performances do not produce ill-effect, to health and environment friend to resin
Good effective halogen-free flame-retardant ASA resin is desirable.
Chinese patent CN101397391A discloses a kind of flame-retardant ASA material and preparation method thereof.Flame-retardant ASA material is by weight
Amount percentage is prepared from the following components:The ternary graft copolymer 72 that acrylonitrile, styrene, acrylate form~
82%；Toughener 2~7%；Tetrabromobisphenol A 12~18%；Antimony oxide 3.0~7.0%；Ultra-violet absorber 0.3~
0.5%；Antioxidant 0.1~1.0%；Lubricant 0.3~0.7%.But the patent is using tetrabromobisphenol A and antimony oxide
Compound flame retardant, tetrabromobisphenol A as common fire retardant, its contamination hazard be it will be apparent that its pollution capacity have it is very high
Persistence, and be very easy to be accumulated in human body, main harm has：First, Long Term Contact brominated flame retardant can hinder greatly
The development of brain and bone；Secondly, it can discharge bromination bioxin and furans when being incinerated processing, and both materials are all
It is easily carcinogen.Tetrabromobisphenol A is expressly stated limitation in the POHS instructions of Norway.Antimony oxide is a kind of nothing
Machine compound, and it is harmful, when it is added in material as fire retardant, the mechanicalness of material can be significantly affected
Can, can increase the proportion of material.
The content of the invention
There is splendid resistance it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
The modified ASA polymeric compositions of combustion property and processing characteristics.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of modified ASA polymeric compositions, including the raw material of following components and parts by weight content：Styrene-acrylonitrile-the third
Olefin(e) acid ester copolymer 10-50, SAN 30-80, acrylic resin 2-15, collaboration auxiliary agent 10-30,
Described collaboration auxiliary agent is the fire retardant being surface-treated through surfactant.
Preferably, fire retardant is selected from pentaerythritol phosphate, starch phosphate melamine salt, pentaerythritol phosphate urine
Plain salt, neopentyl glycol phosphate melamine salt, hypo-aluminum orthophosphate, trihydroxyethyl isocyanuric salt, the contracting glyceride of isocyanuric acid three,
Two kinds or more in melamine cyanurate or melamine polyphosphate.
It is further preferred that fire retardant is two in hypo-aluminum orthophosphate, melamine cyanurate or melamine polyphosphate
Kind or more.
Preferably, surfactant includes melamine, titanate coupling agent, silicone, silicone oil or silane coupler, the table of use
Face inorganic agent, screened by substantial amounts of Experimental comparison, the principle of condensed phase fire retardant mechanism, choosing are coordinated based on gas phase fire retardant mechanism
With the melamine class compound and the isocyanide good into charcoal containing nitrogen, oxygen element simultaneously of main performance gas phase fire retardant mechanism
For uric acid ester type compound as auxiliary flame retardant, the composite flame retardant system has high flame retarding efficiency and limited oxygen index, fire-retardant
The addition of agent is low, the good mechanical performance of material, and the compatibility of surface treated fire retardant and ASA resin and scattered
Property is obtained for further raising.
It is further preferred that the preferred gamma-aminopropyl-triethoxy-silane of surfactant, γ-glycidyl ether oxygen propyl three
Methoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane or one kind in the different titanium acyl titanate esters of isopropyl three or
Two kinds.Surface treated fire retardant can solve fire retardant labile problem in process, can be preferably in resin
In be uniformly dispersed, while improving flame retarding efficiency, also significantly increase the erosion-resisting characteristics of polymer.
Preferably, fire retardant is stirred into 5-20 minutes in high-speed mixer, keeps fire retardant in 1000-2000rpm
High-speed stirred state under fraction time be slowly added to or surface conditioning agent sprayed into mist, continue to stir 5-20 minutes, i.e.,
The processing to fire retardant is completed, the surface conditioning agent of addition and the weight ratio of fire retardant are 0.05-3:100.Above-mentioned technological parameter
Be advantageous to being uniformly dispersed for surfactant, speed easily causes very much the caking of fire retardant slowly, and addition will also result in very much resistance soon
Fire the surfactant processing skewness on agent surface.It can so cause the flame retarding efficiency of material unstable.
Preferably, the number-average molecular weight of styrene-acrylonitrile-acrylic ester ternary graft copolymer is 20000-
900000, particle diameter is 0.5-4.0 μm.
Preferably, the number-average molecular weight of SAN is 100000-600000.
Preferably, acrylic resin is polymethyl methacrylate,
It is further preferred that superelevation light polymethyl methacrylate can be used.
Preferably, antioxidant, anti-UV auxiliary agents, lubricant or coloring agent can also be added in raw material.
It is further preferred that one or more of the antioxidant in antioxidant 1010, antioxidant 1076 or irgasfos 168,
Can individually or compounding use.Anti- UV auxiliary agents are a kind of function additives, and its effect is to prevent and delay resin in use
Light aging, increase the service life；One kind in magnesium stearate, Tissuemat E or silicone oil can be selected in lubricant；Coloring agent includes
Pigment or dyestuff, it is the color for changing resin material, meets requirement in actual applications.
Extrusion molding is carried out using single screw extrusion machine, double screw extruder, mixer, kneader or moulding machine, preferably
Parallel dual-screw extruding machine, each area's extrusion temperature control is at 190 DEG C -240 DEG C.In addition, using 40-80 DEG C of cooling water to extrusion
Thing is cooled down.It can be that a quarter inch is long or smaller to cut material grain prepared during extrudate.
Compared with prior art, the composition that is prepared of the present invention have excellent glossiness, anti-flammability, the feature of environmental protection and
Good processability.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
Fire retardant is surface-treated：15wt% hypo-aluminum orthophosphate is stirred 5 minutes in high-speed mixer, is keeping fire retardant
High-speed stirred state under fraction time be slowly added to or sprayed into mist 0.3wt% gamma-aminopropyl-triethoxy-silane,
Continue stirring 10 minutes, i.e., add 6wt% melamine cyanurate and 0.3wt%168 again, continue stirring 10 minutes i.e.
It can discharge.
It is 600000/15wt% styrene-acrylonitriles-acrylic ester ternary graft copolymer by number-average molecular weight, number is equal
Molecular weight be 300000/41.4wt% SAN, 7wt% polymethyl methacrylates, at through surface
After the fire retardant of reason is well mixed in high-speed mixer together, melt blending in parallel dual-screw extruding machine is added to, by it
Discharge carries out water cooling and pelletizing to form a kind of extrudate, to the extrudate.Prepared material grain can be with when cutting extrudate
It is that a quarter inch is long or smaller.The temperature of parallel dual-screw extruding machine is set as 200-240 DEG C, the water temperature setting of cooling water
For 60 DEG C.Limited oxygen index is 28.5, and the UL94 burning testers test through standard, thickness is that 3.2mm flammability ratings are V-0
Level.
Embodiment 2
Fire retardant is surface-treated：18wt% hypo-aluminum orthophosphate is stirred 5 minutes in high-speed mixer, is keeping fire retardant
High-speed stirred state under fraction time be slowly added to or sprayed into mist 0.3wt% γ-glycidyl ether oxygen propyl three
Methoxy silane, continue stirring 10 minutes, i.e., add 6wt% melamine polyphosphate and 0.5wt%168 again, continue
Stirring can discharge for 10 minutes.
It is 600000/20wt% styrene-acrylonitriles-acrylic ester ternary graft copolymer by number-average molecular weight, number is equal
Molecular weight be 300000/40.2wt% SAN, 5wt% polymethyl methacrylates, at through surface
After the fire retardant of reason is well mixed in high-speed mixer together, melt blending in parallel dual-screw extruding machine is added to, by it
Discharge carries out water cooling and pelletizing to form a kind of extrudate, to the extrudate.Prepared material grain can be with when cutting extrudate
It is that a quarter inch is long or smaller.The temperature of parallel dual-screw extruding machine is set as 200-240 DEG C, the water temperature setting of cooling water
For 60 DEG C.Limited oxygen index is 29.6, and the UL94 burning testers test through standard, thickness is that 3.2mm flammability ratings are V-0
Level.
Embodiment 3
Fire retardant is surface-treated：15wt% hypo-aluminum orthophosphate is stirred 5 minutes in high-speed mixer, is keeping fire retardant
High-speed stirred state under fraction time be slowly added to or sprayed into mist 0.3wt% gamma-aminopropyl-triethoxy-silane,
Continue stirring 10 minutes, i.e., add 6wt% trihydroxyethyl isocyanuric salt and 0.3wt%168 again, continue stirring 10 minutes
It can discharge.
It is 600000/15wt% styrene-acrylonitriles-acrylic ester ternary graft copolymer by number-average molecular weight, number is equal
Molecular weight be 300000/41.4wt% SAN, 7wt% polymethyl methacrylates, at through surface
After the fire retardant of reason is well mixed in high-speed mixer together, melt blending in parallel dual-screw extruding machine is added to, by it
Discharge carries out water cooling and pelletizing to form a kind of extrudate, to the extrudate.Prepared material grain can be with when cutting extrudate
It is that a quarter inch is long or smaller.The temperature of parallel dual-screw extruding machine is set as 200-240 DEG C, the water temperature setting of cooling water
For 60 DEG C.Limited oxygen index is 29.5, and the UL94 burning testers test through standard, thickness is that 3.2mm flammability ratings are V-0
Level.
Embodiment 4
A kind of modified ASA polymeric compositions, including the raw material of following components and parts by weight content：Styrene-acrylonitrile-the third
Olefin(e) acid ester copolymer 10, SAN 80, acrylic resin 2, collaboration auxiliary agent 10.
The number-average molecular weight of the styrene-acrylonitrile used-acrylic ester ternary graft copolymer is 20000, and particle diameter is
0.5 μm, the number-average molecular weight of SAN is 100000, and acrylic resin is polymethyl methacrylate,
Collaboration auxiliary agent is that hypo-aluminum orthophosphate, melamine cyanurate, the melamine being surface-treated through surfactant silicone gather
Phosphate.When being surface-treated, fire retardant is stirred 5 minutes in high-speed mixer, is keeping fire retardant in 1000rpm
High-speed stirred state under fraction time be slowly added to or surface conditioning agent sprayed into mist, continue stirring 5 minutes, that is, complete
Processing to fire retardant, the surface conditioning agent of addition and the weight ratio of fire retardant are 0.05:100.
In addition, antioxidant, anti-UV auxiliary agents, lubricant or coloring agent can also be added in raw material.Antioxidant is selected from anti-
One or more in oxygen agent 1010, antioxidant 1076 or irgasfos 168, can individually or compounding use.Anti- UV auxiliary agents are one
Class function additive, its effect is to prevent and delay the light aging of resin in use, is increased the service life；Lubricant is optional
With one kind in magnesium stearate, Tissuemat E or silicone oil；Coloring agent includes pigment or dyestuff, is the color for changing resin material,
Meet requirement in actual applications.
The present invention is when producing preparation, using single screw extrusion machine, double screw extruder, mixer, kneader or molding
Machine carries out extrusion molding, and each area's extrusion temperature control is at 190 DEG C -240 DEG C.In addition, using 40-80 DEG C of cooling water to extrudate
Cooled down.It can be that a quarter inch is long or smaller to cut material grain prepared during extrudate.
Embodiment 5
A kind of modified ASA polymeric compositions, including the raw material of following components and parts by weight content：Styrene-acrylonitrile-the third
Olefin(e) acid ester copolymer 50, SAN 30, acrylic resin 15, collaboration auxiliary agent 30.
The number-average molecular weight of the styrene-acrylonitrile used-acrylic ester ternary graft copolymer is 900000, and particle diameter is
4.0 μm, the number-average molecular weight of SAN is 600000, and acrylic resin is superelevation light polymethyl
Sour methyl esters, collaboration auxiliary agent are through surfactant γ-(methacryloxypropyl) propyl trimethoxy silicane, the different titanium acyl of isopropyl three
The contracting glyceride of isocyanuric acid three, the melamine cyanurate that titanate esters are surface-treated.When being surface-treated, will hinder
Combustion agent is stirred 20 minutes in high-speed mixer, and in the case where keeping high-speed stirred state of the fire retardant in 2000rpm, fraction time is slow
Add or surface conditioning agent is sprayed into mist, continue stirring 20 minutes, that is, complete the processing to fire retardant, the surface of addition
The weight of inorganic agent and fire retardant ratio is 3:100.
In addition, antioxidant, anti-UV auxiliary agents, lubricant or coloring agent can also be added in raw material.Antioxidant is selected from anti-
One or more in oxygen agent 1010, antioxidant 1076 or irgasfos 168, can individually or compounding use.Anti- UV auxiliary agents are one
Class function additive, its effect is to prevent and delay the light aging of resin in use, is increased the service life；Lubricant is optional
With one kind in magnesium stearate, Tissuemat E or silicone oil；Coloring agent includes pigment or dyestuff, is the color for changing resin material,
Meet requirement in actual applications.
The present invention is when producing preparation, using single screw extrusion machine, double screw extruder, mixer, kneader or molding
Machine carries out extrusion molding, and each area's extrusion temperature control is at 190 DEG C -240 DEG C.In addition, using 40-80 DEG C of cooling water to extrudate
Cooled down.It can be that a quarter inch is long or smaller to cut material grain prepared during extrudate.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
- A kind of 1. modified ASA polymeric compositions, it is characterised in that the raw material including following components and parts by weight content：Styrene- AN-AE 10-50, SAN 30-80, acrylic resin 2-15, collaboration auxiliary agent 10-30,Described collaboration auxiliary agent is the fire retardant being surface-treated through surfactant.
- 2. a kind of modified ASA polymeric compositions according to claim 1, it is characterised in that described fire retardant is selected from season Penta tetrol phosphate, starch phosphate melamine salt, pentaerythritol phosphate urea salt, neopentyl glycol phosphate melamine Salt, hypo-aluminum orthophosphate, trihydroxyethyl isocyanuric salt, the contracting glyceride of isocyanuric acid three, melamine cyanurate or melamine Two kinds or more in Quadrafos.
- 3. a kind of modified ASA polymeric compositions according to claim 1, it is characterised in that described fire retardant is preferably secondary Two kinds or more in aluminum phosphate, melamine cyanurate or melamine polyphosphate.
- A kind of 4. modified ASA polymeric compositions according to claim 1, it is characterised in that described surfactant bag Include melamine, titanate coupling agent, silicone, silicone oil or silane coupler.
- 5. a kind of modified ASA polymeric compositions according to claim 1, it is characterised in that described surfactant is excellent Select gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl group One or both of trimethoxy silane or the different titanium acyl titanate esters of isopropyl three.
- 6. a kind of modified ASA polymeric compositions according to claim 1, it is characterised in that by fire retardant in mixed at high speed 5-20 minutes are stirred in machine, are slowly added to or with mist keeping fire retardant fraction under 1000-2000rpm rotating speed stirrings Shape form sprays into surface conditioning agent, continues to stir 5-20 minutes, that is, completes the processing to fire retardant, the surface conditioning agent of addition with The weight ratio of fire retardant is 0.05-3:100.
- A kind of 7. modified ASA polymeric compositions according to claim 1, it is characterised in that described styrene-propene The number-average molecular weight of nitrile-acrylic ester ternary graft copolymer is 20000-900000, and particle diameter is 0.5-4.0 μm.
- A kind of 8. modified ASA polymeric compositions according to claim 1, it is characterised in that described styrene-acrylonitrile The number-average molecular weight of copolymer is 100000-600000.
- A kind of 9. modified ASA polymeric compositions according to claim 1, it is characterised in that described acrylic resin For polymethyl methacrylate, preferably superelevation light polymethyl methacrylate.
- 10. a kind of modified ASA polymeric compositions according to claim 1, it is characterised in that can also be added in raw material anti- Oxygen agent, anti-UV auxiliary agents, lubricant or coloring agent.
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| CN112608564A (en) * | 2020-11-30 | 2021-04-06 | 金发科技股份有限公司 | High-weather-resistance ASA material and preparation method and application thereof |
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| CN105504569A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | Wear-resistant ASA/PMMA (acrylonitrile-styrene-acrylate/polymethylmethacrylate) blend material with high weather resistance and high gloss and preparation method thereof |
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