CN114456550A - Polyester composite material and preparation method and application thereof - Google Patents
Polyester composite material and preparation method and application thereof Download PDFInfo
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- CN114456550A CN114456550A CN202111561203.4A CN202111561203A CN114456550A CN 114456550 A CN114456550 A CN 114456550A CN 202111561203 A CN202111561203 A CN 202111561203A CN 114456550 A CN114456550 A CN 114456550A
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- polyester composite
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- glass fiber
- brominated
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- 229920000728 polyester Polymers 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 9
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003365 glass fiber Substances 0.000 claims abstract description 42
- ILOKQJWLMPPMQU-UHFFFAOYSA-N calcium;oxido(oxo)borane Chemical compound [Ca+2].[O-]B=O.[O-]B=O ILOKQJWLMPPMQU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 class 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 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims abstract description 5
- 230000014759 maintenance of location Effects 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 11
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- -1 pentabromobenzyl ester Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 206010027146 Melanoderma Diseases 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 229910021540 colemanite Inorganic materials 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004335 antimony containing inorganic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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)
Abstract
The invention discloses a polyester composite material, which comprises the following components in parts by weight: 100 parts of thermoplastic polyester resin; 15-30 parts of a brominated flame retardant; 20-80 parts of glass fiber; 0.02-0.4 times of calcium borate and/or calcium metaborate in the weight content of the glass fiber. The invention finds that the GWIT of the polyester composite material can be effectively improved under the synergistic effect of the calcium borate and/or the calcium metaborate and the glass fiber, and the black spot in the processing process can also be reduced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyester composite material and a preparation method and application thereof.
Background
The thermoplastic polyester material has the advantages of excellent electrical property, mechanical property, low price and the like, and is widely applied to industries such as electronics and electricity and the like for preparing motors, relays, capacitors and the like. With the gradual improvement of the flame-retardant standard of electric appliances, some materials requiring high hot filament ignition temperature are gradually accepted by the majority of enterprises, but the traditional bromine antimony flame-retardant thermoplastic polyester material has the problems of low hot filament ignition temperature and the like, and the use of the material is influenced.
CN102250450A teaches the use of a char-forming agent to improve the ignition temperature of hot filament thermoplastic polyester hot filaments. CN101928449A points out that the introduction of antimony trioxide, antimony pentoxide, sodium antimonate, zinc borate and the like into thermoplastic polyester improves the hot wire ignition performance of the material. However, the antimony-containing compound has a certain toxicity, so that the antimony-containing compound cannot be applied to the field of frequent contact with human bodies, and meanwhile, zinc borate has a large influence on the mechanical properties of the polyester composite material, so that the zinc borate is difficult to be added in a large amount. In addition, in the prior art, the addition of borate is easy to cause a black spot phenomenon in the production process (see the attached figure 1 in the specification), and the appearance quality of the product, especially the appearance of a white product, is influenced.
Disclosure of Invention
The invention aims to provide a polyester composite material with the advantage of high GWIT and good mechanical property. The invention also aims to provide a preparation method and application of the polyester composite material.
The invention is realized by the following technical scheme:
the polyester composite material comprises the following components in parts by weight:
100 parts of thermoplastic polyester resin;
15-30 parts of brominated flame retardant;
20-80 parts of glass fiber;
calcium borate and/or calcium metaborate with the content of the glass fiber being 0.02 to 0.4 times of the content of the glass fiber.
The content of the calcium borate and/or the calcium metaborate is 0.05 to 0.25 time of the content of the glass fiber.
The calcium borate and calcium metaborate are anhydrous calcium borate and anhydrous calcium metaborate, i.e. do not contain crystal water.
The weight ratio of the calcium borate to the calcium metaborate is 1: 1-3. In order to simultaneously realize the balance of mechanical property and GWIT, the calcium borate and the calcium metaborate are compounded, and the weight ratio can further improve the GWIT, so that the calcium metaborate is suitable for products with higher GWIT values.
The average particle size of the calcium borate, calcium metaborate ranges from 0.3 to 15 microns, preferably from 0.5 to 5 microns.
The chemical formula of calcium borate is: ca3(BO3)2。
The chemical formula of calcium metaborate is: CaB2O4。
The calcium borate and calcium metaborate used for realizing the purpose of the invention can be commercially available products or can be derived from self-made products, and the method comprises the following steps:
polyacrylamide ACUSOL. 445N was purchased from Dow chemistry;
CaCO3acetone and boric acid were purchased from Shanghai Allantin Biotechnology Ltd.
Preparation of calcium borate: dissolving 0.5kg of ACUSOL 445N in 200kg of deionized water, stirring at room temperature, adding 18.6kg of boric acid to the aqueous solution, and adding 12.3kg of CaCO3Gradually adding the calcium borate into the high-speed stirring aqueous solution, obtaining calcium borate suspension when no gas is generated, filtering and drying to obtain calcium borate powder, and screening the powder to obtain calcium borate with different particle sizes.
Preparation of calcium metaborate: dissolving 0.8kg of ACUSOL 445N in 200kg of deionized water, stirring at room temperature, adding 28.6kg of boric acid to the aqueous solution, and adding 11kg of CaCO3Gradually adding into the high-speed stirred aqueous solution to obtain calcium borate when no gas is generatedAnd filtering and drying the suspension to obtain calcium borate powder, and screening the powder to obtain calcium metaborate with different particle sizes.
The purity of the calcium borate and the calcium metaborate obtained by the method is more than 99 percent, and the calcium borate and the calcium metaborate hardly contain other metal ions and crystal water.
The existing commercially available calcium borate and calcium metaborate are mainly obtained by crushing and screening natural minerals. Wherein calcium borate is also called colemanite, has crystal water and also contains a small amount of other impurities such as elements containing silicon, iron, aluminum and the like. The existing commercially available calcium metaborate also has crystal water.
In the resin matrix of the polyester composite, the average retention length of the glass fiber is between 60 and 400 micrometers, preferably the average retention length is between 150 and 350 micrometers, and further preferably the average retention length is between 200 and 300 micrometers. The glass fiber can be long glass fiber or chopped glass fiber, and the retention length of the glass fiber in the resin matrix is mainly controlled by controlling the rotating speed of the screw (the retention length can be slightly changed due to the addition of different glass fibers under the same rotating speed).
The thermoplastic polyester resin is at least one selected from PBT, PET, PETG and PC.
The brominated flame retardant is selected from at least one of decabromodiphenylethane, brominated polystyrene, polybrominated styrene, brominated epoxy resin, polyacrylic acid pentabromobenzyl ester, brominated polycarbonate, brominated bisphenol A, tetrabromophthalimide, brominated triazine and brominated melamine.
Whether 0-2 parts of auxiliary agent is added can be determined according to actual needs, and the auxiliary agent can be an antioxidant and a lubricant.
The preparation method of the polyester composite material comprises the following steps: according to the proportion, the components except the glass fiber are uniformly mixed, the mixture is fed into a double-screw extruder through a main feeding port, the glass fiber is laterally fed, and the polyester composite material is obtained through melting and shearing, wherein the temperature range of a screw cylinder is 210 plus 230 ℃, and the rotating speed is 200 plus 500 rpm.
The polyester composite material is applied to shells of motors and capacitors in electronic and electric appliances.
For being applied to the shells of motors and capacitors in electronic appliances, the GWIT of the polyester composite material is more than 825 ℃, and the notched impact strength of a cantilever beam is more than 5.1kJ/m2And the flexural modulus is more than 4100 MPa.
The invention has the following beneficial effects:
the invention discovers that the anhydrous calcium borate and the calcium metaborate can obviously improve the GWIT of the polyester composite material and keep high flame retardance, has smaller influence on the mechanical property of the polyester composite material compared with other inorganic matters (antimony-containing inorganic compounds, zinc borate and the like), can reduce black spots in the processing process, improves the appearance of the polyester composite material, and has great application value.
Furthermore, the GWIT can be further improved by compounding the calcium borate and the calcium metaborate, and the method is suitable for products with higher GWIT values.
Drawings
FIG. 1: a black spot photograph.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
PBT: 1200-211M, chemical engineering of Changchun (Jiangsu) Ltd;
PET: KH2678C, yingkou Kanghui Shi Limited;
glass fiber: ECS301HP-3, Chongqing International composite Co., Ltd;
decabromodiphenylethane: saytex 8010;
brominated polystyrene: saytex HP-5010 PST.
Calcium borate A: the average grain diameter is 0.32 micron, does not contain crystal water, and is prepared by self;
calcium borate B: the average grain diameter is 0.50 micron, does not contain crystal water, and is prepared by self;
calcium borate C: the average grain diameter is 4.9 microns, and the product does not contain crystal water and is prepared by self;
calcium borate D: the average grain diameter is 14.8 microns, and the product does not contain crystal water and is prepared by self;
calcium metaborate: the average grain diameter is 0.51 micron, does not contain crystal water, and is prepared by self;
colemanite hard: an average particle size of 17.2 microns, containing water of crystallization, turkish ETI;
aqueous calcium metaborate: aladdin, Ca (BO)2)2·2H2O;
Zinc borate: firebrake ZB, Reutou Co;
antimony white: the antimony industry, llc, of the tin mine twinkling stars;
lubricant: stearate esters, commercially available.
Examples and comparative examples preparation methods of polyester composites: according to the proportion, the components except the glass fiber are uniformly mixed, the mixture is fed into a double-screw extruder through a main feeding port, the glass fiber is fed laterally, the polyester composite material is obtained through melting and shearing, the temperature range of a screw cylinder is 210 plus 230 ℃, and the rotating speed is 200 plus 500rpm (the detailed rotating speed is shown in a table).
The test methods are as follows:
(1) GWIT: glow Wire Ignition Temperature (GWIT) test method for IEC 60695-2-13:2014 material.
(2) Notched izod impact strength: the Izod impact strength was measured according to GB/T1843-2008.
(3) Flexural modulus: the flexural properties of the plastics were determined according to ISO 178-2010.
(4) Black spot: 100g of extruded polyester composite particles (each particle having a diameter of 3mm and a length of 5 mm) were placed in a tray, and black spots (different color spots) therein were visually observed and counted for black spots having a diameter of more than 0.5mm (different color spots).
(5) Flame retardancy: and performing flame retardant rating test by using UL 94-2018.
(6) Average retention length of glass fiber: and (3) placing 5 g of particles in a crucible, placing the crucible in a muffle furnace at 650 ℃ for burning for 2 hours, taking out the particles, cooling to normal temperature, placing the rest solid powder on a two-dimensional microscope for observation, distinguishing the length of the particles, continuously reading 200 glass fibers, and finally performing mathematical averaging to obtain the average retention length.
Table 1: EXAMPLES 1-5 polyester composite Material content (parts by weight) and test results
Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
PBT | 100 | 100 | 100 | 100 | |
PET | 100 | ||||
Decabromodiphenylethane | 20 | 20 | 30 | 15 | |
Brominated polystyrene | 20 | ||||
Glass fiber | 50 | 50 | 50 | 20 | 80 |
Calcium borate B | 5 | 5 | 5 | 0.5 | 8 |
Lubricant agent | 0.3 | ||||
Screw speed, rpm | 450 | 450 | 430 | 400 | 400 |
Average glass fiber retention length in microns | 234 | 230 | 243 | 240 | 256 |
GWIT,℃ | 900 | 930 | 825 | 900 | 850 |
Notched Izod impact Strength, kJ/m2 | 7.5 | 6.3 | 6.1 | 6.9 | 8.2 |
Flexural modulus, MPa | 7300 | 8300 | 7500 | 7800 | 7200 |
Black spot | Is free of | Is free of | Is free of | Is free of | Is free of |
Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 |
Table 2: examples 6-12 polyester composite Material content (parts by weight) and test results
Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | |
PBT | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Decabromodiphenylethane | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
Glass fiber | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
Calcium borate B | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
Screw speed, rpm | 600 | 550 | 500 | 450 | 300 | 600 | 200 |
Average glass fiber retention length in microns | 82 | 154 | 200 | 293 | 346 | 60 | 391 |
GWIT,℃ | 930 | 900 | 900 | 900 | 875 | 930 | 850 |
Notched Izod impact Strength, kJ/m2 | 5.2 | 5.8 | 6.3 | 7.9 | 8.2 | 5.1 | 8.7 |
Flexural modulus, MPa | 4600 | 5300 | 6300 | 7200 | 7210 | 4100 | 7800 |
Black spot | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
From examples 1/6-12, it is clear that the retention length of the glass fibers significantly influences the GWIT value and the mechanical properties: most preferably 200-300 microns, wherein the GWIT is 900 ℃ and the mechanical property can also meet the requirements of most products; 150-350 microns is preferred, the GWIT is 900 ℃ and the mechanical property is low when the retention length of the glass fiber is close to 150 microns, but the glass fiber retention length can be applied to a scene with no particularly high requirement on the mechanical property, and the GWIT is 875 ℃ but the mechanical property is high when the retention length of the glass fiber is close to 350 microns, so that the glass fiber retention length is suitable for a scene with a higher requirement on the mechanical property. When the retention length of the glass is close to 60 microns, the GWIT reaches 930 ℃, and the glass has low mechanical property but is suitable for a scene with low requirement on mechanical property and higher requirement on GWIT temperature.
Table 3: EXAMPLES 13-19 polyester composite Material content (parts by weight) and test results
Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 | Example 19 | |
PBT | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Decabromodiphenylethane | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
Glass fiber | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
Calcium borate B | 1 | 2.5 | 12.5 | 20 | |||
Calcium borate A | 5 | ||||||
Calcium borate C | 5 | ||||||
Calcium borate D | 5 | ||||||
Screw speed, rpm | 400 | 400 | 400 | 400 | 400 | 400 | 400 |
Average glass fiber retention length in microns | 231 | 245 | 239 | 233 | 243 | 250 | 249 |
GWIT,℃ | 850 | 900 | 900 | 930 | 850 | 875 | 850 |
Notched Izod impact Strength, kJ/m2 | 8.1 | 7.5 | 5.6 | 5.3 | 5.8 | 6.3 | 5.2 |
Flexural modulus, MPa | 7300 | 7300 | 7700 | 7900 | 7300 | 7150 | 7000 |
Black spot | 3 | Is free of | Is free of | Is free of | Is composed of | Is free of | Is free of |
Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
From examples 1/13-16, it is clear that the preferred formulation of calcium borate with glass fibers has no black spots, and that GWIT reaches 900 ℃ and that notched Izod impact strength and flexural modulus are sufficiently maintained at high levels.
From examples 1/17 to 19, it is clear that the particle size of calcium borate significantly affects GWIT and mechanical properties, and that within the preferred particle size range GWIT, higher notched impact strength and better flame retardancy are obtained.
Table 4: examples 20-25 polyester composite Material content (parts by weight) and test results
Example 20 | Example 21 | Example 22 | Example 23 | Example 24 | Example 25 | |
PBT | 100 | 100 | 100 | 100 | 100 | 100 |
Decabromodiphenylethane | 20 | 20 | 20 | 20 | 20 | 20 |
Glass fiber | 50 | 50 | 50 | 50 | 50 | 50 |
Calcium borate B | 3.33 | 2.5 | 1.67 | 1.25 | 1 | |
Calcium metaborate | 5 | 1.67 | 2.5 | 3.33 | 3.75 | 4 |
Screw speed, rpm | 400 | 400 | 400 | 400 | 400 | 400 |
Average glass fiber retention length in microns | 237 | 246 | 236 | 240 | 244 | 241 |
GWIT,℃ | 875 | 900 | 930 | 930 | 930 | 900 |
Notched Izod impact Strength, kJ/m2 | 7.1 | 6.9 | 7.2 | 7.5 | 7.9 | 7.8 |
Flexural modulus, MPa | 7300 | 7900 | 7300 | 7250 | 7200 | 7100 |
Black spot | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of |
Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
From examples 1/20-25, it can be seen that the ratio of calcium borate: higher GWIT when calcium metaborate =1:1-3 range.
Table 5: comparative example polyester composite Material Each component content (parts by weight) and test results
Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
PBT | 100 | 100 | 100 | 100 | 100 | 100 |
Decabromodiphenylethane | 20 | 20 | 20 | 20 | 20 | 20 |
Glass fiber | 50 | 50 | 50 | 50 | 50 | 50 |
Calcium borate B | 0.5 | 25 | ||||
Colemanite borate | 5 | |||||
Hydrous calcium metaborate | 5 | |||||
Zinc borate | 5 | |||||
Antimony white | 5 | |||||
Screw speed, rpm | 450 | 450 | 450 | 450 | 450 | 450 |
Average glass fiber retention length in microns | 232 | 244 | 239 | 233 | 248 | 242 |
GWIT,℃ | 825 | 850 | 800 | 775 | 825 | 750 |
Notched Izod impact Strength, kJ/m2 | 9.1 | 3.1 | 5.3 | 4.5 | 2.1 | 7.3 |
Flexural modulus, MPa | 7300 | 8200 | 7700 | 7900 | 7300 | 7150 |
Black spot | 8 | Is free of | 11 | Is free of | 9 | 10 |
Flame retardancy | V-1 | V-0 | V-1 | V-0 | V-0 | V-0 |
As is clear from comparative example 1/2, when the amount of calcium borate added is too low, not only the flame retardance is not reached at V-0, but also the number of black spots is large; when the amount of calcium borate added is too large, the izod notched impact strength is too low.
As can be seen from comparative example 3, the colemanite obtained from a commercially available natural mineral did not achieve the technical effect of reducing black spots, and was inferior in flame retardancy and GWIT.
As can be seen from comparative example 4, commercially available hydrated calcium metaborate does not increase GWIT as much as anhydrous calcium metaborate.
From comparative example 5, it is understood that the zinc borate has a large influence on the mechanical properties and is not able to suppress black spots.
As can be seen from comparative example 6, the GWIT of antimony white as a flame retardant synergist was low and black spots could not be suppressed.
Claims (10)
1. The polyester composite material is characterized by comprising the following components in parts by weight:
100 parts of thermoplastic polyester resin;
15-30 parts of brominated flame retardant;
20-80 parts of glass fiber;
0.02-0.4 times of calcium borate and/or calcium metaborate in the weight content of the glass fiber.
2. The polyester composite according to claim 1, wherein the content of calcium borate and/or calcium metaborate is 0.05-0.25 times the content of glass fibers.
3. The polyester composite of claim 1 or 2, wherein the calcium borate and calcium metaborate are anhydrous calcium borate, anhydrous calcium metaborate.
4. The polyester composite according to claim 1 or 2, characterized in that the weight ratio of calcium borate to calcium metaborate is 1 (1-3).
5. A polyester composite according to claim 1 or 2, characterized in that the average particle size of the calcium borate and calcium metaborate is in the range of 0.3-15 microns, preferably 0.5-5 microns.
6. The polyester composite according to claim 1 or 2, wherein the average retention length of the glass fibers in the resin matrix of the polyester composite is between 60 and 400 microns, preferably between 150 and 350 microns, further preferably between 200 and 300 microns.
7. The polyester composite according to claim 1 or 2, wherein the thermoplastic polyester resin is at least one selected from the group consisting of PBT, PET, PETG, PC; the brominated flame retardant is selected from at least one of decabromodiphenylethane, brominated polystyrene, polybrominated styrene, brominated epoxy resin, polyacrylic acid pentabromobenzyl ester, brominated polycarbonate, brominated bisphenol A, tetrabromophthalimide, brominated triazine and brominated melamine.
8. The polyester composite material according to claim 1 or 2, further comprising 0 to 2 parts by weight of an auxiliary agent, wherein the auxiliary agent is at least one selected from an antioxidant and a lubricant.
9. A process for the preparation of a polyester composite according to any one of claims 1 to 8, characterized in that it comprises the following steps: according to the proportion, the components except the glass fiber are uniformly mixed, the mixture is fed into a double-screw extruder through a main feeding port, the glass fiber is laterally fed, and the polyester composite material is obtained through melting and shearing, wherein the temperature range of a screw cylinder is 210-230 ℃, and the rotating speed of a screw is 200-500 rpm.
10. Use of the polyester composite according to any of claims 1 to 8 for the housing of motors, capacitors in electronic appliances.
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WO2003020826A1 (en) * | 2001-08-29 | 2003-03-13 | Albemarle Corporation | Flame retardant compositions |
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JP4209164B2 (en) * | 2002-09-26 | 2009-01-14 | 旭化成ケミカルズ株式会社 | Flame retardant polyamide resin composition |
JP5499686B2 (en) * | 2009-12-21 | 2014-05-21 | 三菱エンジニアリングプラスチックス株式会社 | Flame retardant polybutylene terephthalate resin composition |
JP5091367B1 (en) * | 2011-10-24 | 2012-12-05 | パナソニック株式会社 | Thermoplastic resin composition for insulating parts and insulating parts |
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JP7071236B2 (en) * | 2018-07-03 | 2022-05-18 | ポリプラスチックス株式会社 | Flame-retardant polybutylene terephthalate resin composition for electrically insulating parts |
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WO2003020826A1 (en) * | 2001-08-29 | 2003-03-13 | Albemarle Corporation | Flame retardant compositions |
JP2011148917A (en) * | 2010-01-22 | 2011-08-04 | Mitsubishi Engineering Plastics Corp | Thermally conductive polyalkylene terephthalate resin composition and resin molded body |
WO2013085789A1 (en) * | 2011-12-09 | 2013-06-13 | Icl-Ip America Inc. | Low antimony or antimony trioxide-free flame retarded thermoplastic composition |
WO2015037592A1 (en) * | 2013-09-10 | 2015-03-19 | ウィンテックポリマー株式会社 | Flame-retardant polybutylene terephthalate resin composition |
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WO2023116334A1 (en) * | 2021-12-20 | 2023-06-29 | 金发科技股份有限公司 | Polyester composite material, preparation method therefor and application thereof |
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