CN110527195A - A kind of that resist warping has both the environment-friendly function masterbatch and preparation method of cooperative flame retardant - Google Patents
A kind of that resist warping has both the environment-friendly function masterbatch and preparation method of cooperative flame retardant Download PDFInfo
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- CN110527195A CN110527195A CN201910972405.4A CN201910972405A CN110527195A CN 110527195 A CN110527195 A CN 110527195A CN 201910972405 A CN201910972405 A CN 201910972405A CN 110527195 A CN110527195 A CN 110527195A
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- flame retardant
- environment
- cooperative flame
- resist warping
- friendly function
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 46
- 239000003063 flame retardant Substances 0.000 title claims abstract description 31
- 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 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 150000008301 phosphite esters Chemical class 0.000 claims description 10
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- AYBSOYWZTRUFMW-UHFFFAOYSA-N furan-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AYBSOYWZTRUFMW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920001112 grafted polyolefin Polymers 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
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000428 dust Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 description 20
- 239000003610 charcoal Substances 0.000 description 6
- 239000000805 composite resin Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical group [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses environment-friendly function masterbatch and preparation method feed components weight percentage that a kind of that resist warping has both cooperative flame retardant are as follows: thermoplastic resin 28~48%, hollow glass micropearl 50~70%；Heat stabilizer 0.1~0.3%；Compatilizer 1~3%；Lubricant 0.4~0.8%.Its preparation process are as follows: be uniformly mixed load weighted thermoplastic resin, heat stabilizer, compatilizer, lubricant in batch mixer, the material of preparation is added from the main spout of parallel double-screw extruder, hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and is granulated；When squeezing out processing, extruder barrel temperature control is at 160 DEG C~280 DEG C.The present invention efficiently solves the problems, such as that hollow glass micropearl powder is directly used to easily cause dust pollution, measures inaccurate, layering and be crushed, and prepared masterbatch volatile organic content is low, smell is small, good environmental protection.Raw material sources of the present invention are extensive, cheap, and prepared masterbatch has excellent that resist warping and cooperative flame retardant effect.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of that resist warping has both the environment-friendly function of cooperative flame retardant effect
Masterbatch.The masterbatch can be used for it is thermoplastic resin modified, can also with matrix resin or modified resin compounding after using injection molding, extrusion molding,
The direct machine-shapings of processing methods such as blow molding.
Background technique
Thermoplas tic resin composite is with source is wide, type is more, density is small, the molding spy of cheap and easy processing
Point has very extensive application in national economy every field.Thermoplas tic resin composite generally use injection molding, extrusion molding,
The moulding process such as blow molding, hot pressing are formed under hot melt state in a mold, and then corresponding product is made in cooling and solidifying.But product is certainly
It takes out and is cooled in room temperature and later period placement process in mold, due to being expanded with heat and contract with cold, being orientated the shadows such as difference, uneven thickness
Ring, often generate different directions on difference in shrinkage and buckling deformation.Solve thermoplas tic resin composite's buckling deformation one
It is directly the emphasis studied in the industry, especially in terms of fiber reinforcement analog thermoplastic resin composite materials.Currently, improving thermoplastic
The method of property resin composite materials buckling deformation mainly has: using non-crystalline type anti-shrink polymer, using noncircular cross section
Glass fibre and the spherical isotropic filler of addition, such as glass microballoon, hollow glass micropearl.
Hollow glass micropearl is a kind of rigid pulverulent material of regular spherical structure, low, the dispersed, mobility with density
And the advantages of stability is good, isotropism, apply it in thermoplas tic resin composite can not only reduce density of material,
Thermal coefficient improves material stiffness and thermal stability, and molecular resin chain or threadiness are filled out when can also be effectively improved resin forming
The uneven caused contraction warpage of material orientation is filled, the dimensional stability of product is improved.Such as Publication No. CN101580636A and
The patent of CN107892772A is exactly that the resistance to warping energy of material is improved using hollow glass micropearl.In addition, hollow glass is micro-
Pearl main component is soda lime borosilicate, itself is non-ignitable, and silicon can also promote to burn into charcoal, inhibit burning, plays collaboration resistance
Combustion effect.However, hollow glass micropearl is directly applied as a kind of powder body material, not only technique mistake in above-mentioned patent
Journey is complicated, and measuring difficulties are also easy to the bad stability for causing dust pollution and material layering to make material.
The patent of invention of publication number CN108276670A disclose a kind of polypropylene injection molding low-gravity filling master batch and its
Preparation method comprising the component of following parts by weight: 35-50 parts of polypropylene, 20-40 parts of hollow glass micropearl, talcum powder 20-
25 parts, 3-5 parts of compatilizer, 0.5-1 parts of antioxidant and 1-2 parts of carbon black, wherein hollow glass micropearl partial size is 15~20 μm.The hair
Bright patent not only simplifies the operation that powdery hollow glass micropearl is added when polypropylene injection molding, avoids generating fugitive dust when addition, also
The hollow glass micropearl for solving powdery disperses difficult, easy lamination problem in polypropylene, but since talcum powder will lead to fire retardant
It fails, talcum powder is introduced in formula reduces the cooperative flame retardant effect for even losing hollow glass micropearl, and hollow glass is micro-
Pearl Particle size requirements are too small, narrow limits, and that resist warping effect is unobvious, and raw material sources are difficult, and price is also expensive, is unfavorable for big model
Enclose popularization and application.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, and provide a kind of easy to use, feature of environmental protection
Good and that resist warping at low cost has both the environment-friendly function masterbatch of cooperative flame retardant.
It is a further object to provide the preparation sides that above-mentioned that resist warping has both the environment-friendly function masterbatch of cooperative flame retardant
Method.
Above-mentioned purpose to realize the present invention, the technical solution adopted by the present invention are as follows:
A kind of that resist warping of the present invention has both the environment-friendly function masterbatch of cooperative flame retardant, according to weight percent, feed components
Percentage composition are as follows:
Wherein: thermoplastic resin is polyethylene, polypropylene, polyamide, ethylene-vinyl acetate copolymer, acrylic nitrile-butadiene two
Alkene-styrol copolymer, polyolefin elastomer, any one or two kinds and the above mixture in ethylene propylene diene rubber.
Feed components weight percentage is preferred are as follows:
The hollow glass micropearl partial size is 20~60 μm, and density is 0.8~1.8g/cm3, and pass through Modifiers Surface
Modification, modifying agent are silane coupling agent, titanate coupling agent, any one in aluminate coupling agent.
The heat stabilizer is Hinered phenols antioxidant, phosphite ester antioxidant, amine antioxidants, thioesters are anti-
Any one in oxygen agent or two kinds and the above mixture.
The compatilizer is maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafted polyolefin
Olefin elastomer, glycidyl methacrylate graft polyolefin elastomer, styrene-acrylonitrile-maleic anhydride tercopolymer copolymerization
Any one or two kinds or more in object, styrene-acrylonitrile-glycidyl methacrylate terpolymer mix
Object.
The lubricant is the mixture of one of silicone powder, ethylene bis stearamide or both arbitrary proportion.
A kind of that resist warping of the present invention has both the preparation method of the environment-friendly function masterbatch of cooperative flame retardant, it is characterised in that use with
Lower technique:
(1) various components are weighed by raw material proportioning；
(2) load weighted thermoplastic resin, heat stabilizer, compatilizer, lubricant are uniformly mixed in batch mixer；
(3) by step (2) preparation material from the main spout of parallel double-screw extruder be added, hollow glass micropearl from
Side spout is added, and after melting mixing homogenizing, squeezes out and is granulated；When squeezing out processing, extruder barrel temperature control is at 160 DEG C~280 DEG C.
The extruder barrel temperature control of extruder is preferred in 210 DEG C~245 DEG C ranges in step (3).
A kind of that resist warping of the present invention has both the preparation method of the environment-friendly function masterbatch of cooperative flame retardant, comprehensively considers the comprehensive of product
Performance is closed, is excellent in the case where feed components weight percentage is according to following proportion:
The thermoplastic polyamide resin, the heat stabilizer be amine antioxidants and phosphite ester antioxidant it
Than the mixture for 2:1, the compatilizer be maleic anhydride stem grafting polyolefin elastomer, the lubricant be silicone powder,
The ratio between ethylene bis stearamide is the mixture of 4:3.
Compared with prior art, a kind of that resist warping of the present invention has both the environment-friendly function masterbatch of cooperative flame retardant and preparation method is adopted
With being had the positive effect that after above technical scheme:
(1) present invention efficiently solves directly easily causes dust pollution, metering to be not allowed, divide using hollow glass micropearl powder
Layer and broken problem, prepared masterbatch hollow glass micropearl content is high, easy to use, can be not only used for thermoplastic resin and changes
Property, using direct machine-shapings of processing methods such as injection molding, extrusion molding, blow moldings after can also being compounded with matrix resin or modified resin；
(2) present invention strictly screens and controls the use of small molecule auxiliary agent, prepared masterbatch volatile organic content is low,
Smell is small, good environmental protection；
(3) hollow glass micropearl of the present invention is from a wealth of sources, cheap, prepared masterbatch have excellent that resist warping and
Cooperative flame retardant effect.
Specific embodiment
To further describe the present invention, below with reference to embodiment, the ring of cooperative flame retardant is had both to a kind of that resist warping of the present invention
It protects functional master batch and preparation method is further elaborated.Described embodiment is only that present invention a part is implemented
Example, instead of all the embodiments.It should be pointed out that those skilled in the art, not departing from the present invention
Under the premise of design, various modifications and improvements can be made.This belongs to protection scope of the present invention.
Embodiment 1
By 45.7kg homopolypropylene, 0.2kg Hinered phenols antioxidant, 0.1kg phosphite ester antioxidant, 1.5kg horse
Maleic anhydride grafted polypropylene, 0.5kg ethylene bis stearamide are in batch mixer after mixing from parallel double-screw extruder master
Spout is added, and 52kg hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and is granulated, extruder machine
Cylinder temperature control is at 175 DEG C~220 DEG C.
Embodiment 2
By 37.2kg homopolypropylene, 0.1kg Hinered phenols antioxidant, 0.1kg phosphite ester antioxidant, the Malaysia 2kg
Anhydride-grafted polypropylene, 0.6kg ethylene bis stearamide are fed from parallel double-screw extruder master after mixing in batch mixer
Material mouth is added, and 60kg hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and is granulated, extruder barrel
Temperature is controlled at 175 DEG C~220 DEG C.
Embodiment 3
By 31.5kg homopolypropylene, 0.1kg Hinered phenols antioxidant, 0.1kg phosphite ester antioxidant, 2.5kg horse
Maleic anhydride grafted polypropylene, 0.8kg ethylene bis stearamide are in batch mixer after mixing from parallel double-screw extruder master
Spout is added, and 65kg hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and is granulated, extruder machine
Cylinder temperature control is at 175 DEG C~220 DEG C.
Embodiment 4
42kg polyamide 6,0.2kg amine antioxidants, 0.1kg phosphite ester antioxidant, the grafting of 2kg maleic anhydride is poly-
Olefin elastomer, 0.4kg ethylene bis stearamide, 0.3kg silicone powder are squeezed from parallel double-screw after mixing in batch mixer
Owner's spout is added out, and 55kg hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and is granulated, squeezes
Machine extruder barrel temperature control is at 210 DEG C~245 DEG C out.
Embodiment 5
31.5kg polyamide 6,0.2kg amine antioxidants, 0.1kg phosphite ester antioxidant, 2.4kg maleic anhydride are connect
Branch polyolefin elastomer, 0.5kg ethylene bis stearamide, 0.3kg silicone powder are in batch mixer after mixing from parallel double spiral shells
Bar squeezes out owner's spout and is added, and 65kg hollow glass micropearl is added from side spout, after melting mixing homogenizing, squeezes out and makes
Grain, extruder barrel temperature are controlled at 210 DEG C~245 DEG C.
The resulting masterbatch of embodiment 1-5 is tested, the results are shown in Table 1.
Table 1
It can be seen that from the above experimental data, masterbatch of the present invention has the good feature of environmental protection.
To further illustrate masterbatch practical application effect of the present invention, using embodiment 2 and 4 gained masterbatch of embodiment respectively into
Composite usage experiment is gone.
Comparative example 1
50% long glass fiber-reinforced polypropylene of 600g mass ratio, 90g high are melted into copolymer polypropylene, 300g flame-retardant master batch, 10g charcoal
Black masterbatch after mixing, the injection molding in injection molding machine.
Application example 1
50% long glass fiber-reinforced polypropylene of 600g mass ratio, 90g high are melted into copolymer polypropylene, 300g flame-retardant master batch, 10g charcoal
Black masterbatch, 2 gained masterbatch of 100g embodiment after mixing, the injection molding in injection molding machine.
Application example 2
50% long glass fiber-reinforced polypropylene of 600g mass ratio, 90g high are melted into copolymer polypropylene, 300g flame-retardant master batch, 10g charcoal
Black masterbatch, 2 gained masterbatch of 150g embodiment after mixing, the injection molding in injection molding machine.
Application example 3
50% long glass fiber-reinforced polypropylene of 550g mass ratio, 90g high are melted into copolymer polypropylene, 250g flame-retardant master batch, 10g charcoal
Black masterbatch, 2 gained masterbatch of 100g embodiment after mixing, the injection molding in injection molding machine.
Comparative example 2
By 45kg polyamide 66,0.2kg amine antioxidants, 0.1kg phosphite ester antioxidant, 0.5kg silicone powder,
0.2kg flow ability modifying agent, 5kg antimony oxide, 18kg brominated Polystyrene, the dedicated black masterbatch of 1kg nylon mix in batch mixer
It is added after closing uniformly from the main spout of parallel double-screw extruder, 30kg glass fiber yarn is added from glass fiber opening, and melting mixing is equal
After change, squeeze out and be granulated, extruder barrel temperature control at 220 DEG C~265 DEG C, and by gained particle drying after in injection molding machine
Injection molding.
Application example 4
2 gained particle of 850g comparative example and 4 gained masterbatch of 150g embodiment are dried after mixing, and in injection molding machine
Injection molding.
The above comparative example and application example respectively in injection molding machine injection molding growth 150mm × wide 100mm × thickness 3mm plate,
Long 150mm × wide 10mm × thickness 4mm standard dumb-bell shape test bars, long 80mm × wide 10mm × thickness 4mm standard bar shaped test specimens
Item and long 125mm × wide 13mm × thickness 3mm standard flame retardant test batten, and its performance is tested by relevant criterion, as a result such as 2 institute of table
Show.
Table 2
Note: angularity test is referring to GB/T 4677.5-1984 method, using the long 150mm × wide 100mm × thickness 3mm of molding
The plate of size is bending edge lengths, angularity (%)=plate depth of camber/bending edge lengths with length 150mm
(150mm) × 100%.
It can be seen that by the test result of upper table, environment-friendly function masterbatch obtained will not drop in application process through the invention
The physical mechanical property of low original material, and there is excellent resistance to warping energy and cooperative flame retardant effect.
The hollow glass micropearl that the present invention uses is a kind of rigid pulverulent material of regular spherical structure, isotropism, In
It can play the role of skeletal support in thermoplastic resin, due to shrinking caused by melt flows orientation when being effectively improved resin forming
Warpage；Hollow glass micropearl can also promote to burn into charcoal, starvation and heat transfer when resin burns, and inhibit burning, reach
To cooperative flame retardant effect.In addition, functional master batch prepared by the present invention avoids directly using caused by hollow glass micropearl powder
Dust pollution, metering be inaccurate, layering and Crushing Problem, and the feature of environmental protection is good, easy to use, can be used for it is thermoplastic resin modified,
Using direct machine-shapings of processing methods such as injection molding, extrusion molding, blow moldings after being compounded with matrix resin or modified resin.
Claims (9)
1. the environment-friendly function masterbatch that a kind of that resist warping has both cooperative flame retardant, it is characterised in that feed components weight percentage
Are as follows:
The thermoplastic resin is polyethylene, polypropylene, polyamide, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-
Styrol copolymer, polyolefin elastomer, any one or two kinds and the above mixture in ethylene propylene diene rubber.
2. the environment-friendly function masterbatch that a kind of that resist warping as described in claim 1 has both cooperative flame retardant, it is characterised in that raw material is each
Composition weight percentage composition are as follows:
3. the environment-friendly function masterbatch that a kind of that resist warping as claimed in claim 1 or 2 has both cooperative flame retardant, it is characterised in that: institute
The hollow glass micropearl partial size stated is 20~60 μm, and density is 0.8~1.8g/cm3, and pass through modifier surface modified processing,
Modifying agent is silane coupling agent, titanate coupling agent, any one in aluminate coupling agent.
4. the environment-friendly function masterbatch that a kind of that resist warping as claimed in claim 3 has both cooperative flame retardant, it is characterised in that: described
Heat stabilizer is Hinered phenols antioxidant, phosphite ester antioxidant, amine antioxidants, any one in thioester antioxidant
Kind or two kinds and the above mixture.
5. the environment-friendly function masterbatch that a kind of that resist warping as claimed in claim 4 has both cooperative flame retardant, it is characterised in that: described
Compatilizer is maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, methyl-prop
Olefin(e) acid ethylene oxidic ester grafted polyolefin olefin elastomer, styrene-acrylonitrile-maleic anhydride terpolymer, styrene-propene
Any one in nitrile-glycidyl methacrylate terpolymer or two kinds and the above mixture.
6. the environment-friendly function masterbatch that a kind of that resist warping as claimed in claim 5 has both cooperative flame retardant, it is characterised in that: described
Lubricant is the mixture of one of silicone powder, ethylene bis stearamide or both arbitrary proportion.
7. a kind of that resist warping as claimed in claim 6 has both the preparation method of the environment-friendly function masterbatch of cooperative flame retardant, feature
It is using following technique:
(1) various components are weighed by raw material proportioning；
(2) load weighted thermoplastic resin, heat stabilizer, compatilizer, lubricant are uniformly mixed in batch mixer；
(3) material by step (2) preparation is added from the main spout of parallel double-screw extruder, and hollow glass micropearl is from side feed
Material mouth is added, and after melting mixing homogenizing, squeezes out and is granulated；When squeezing out processing, extruder barrel temperature control is at 160 DEG C~280 DEG C.
8. a kind of that resist warping as claimed in claim 7 has both the preparation method of the environment-friendly function masterbatch of cooperative flame retardant, feature
Be: the extruder barrel temperature control of extruder is at 210 DEG C~245 DEG C.
9. a kind of that resist warping as claimed in claim 8 has both the preparation method of the environment-friendly function masterbatch of cooperative flame retardant, feature
It is feed components weight percentage are as follows:
The thermoplastic polyamide resin, the heat stabilizer are that the ratio between amine antioxidants and phosphite ester antioxidant are
The mixture of 2:1, the compatilizer are maleic anhydride stem grafting polyolefin elastomer, and the lubricant is silicone powder, ethylene
The ratio between bis-stearamides are the mixture of 4:3.
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| CN114517010A (en) * | 2020-11-19 | 2022-05-20 | 安特普工程塑料（苏州）有限公司 | Low-density nylon composite material and preparation method thereof |
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| CN113512257A (en) * | 2021-05-18 | 2021-10-19 | 中钢集团马鞍山矿山研究总院股份有限公司 | Low-density functional master batch for extrusion and injection molding process and preparation method thereof |
| CN115181366A (en) * | 2022-07-15 | 2022-10-14 | 智筑汇创(上海)新材料科技有限公司 | Halogen-free flame-retardant EPDM foam composite material and preparation method thereof |
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Application publication date: 20191203 |