CN106243638B - A kind of fire retardant PBT with no halogen material - Google Patents
A kind of fire retardant PBT with no halogen material Download PDFInfo
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- CN106243638B CN106243638B CN201610602000.8A CN201610602000A CN106243638B CN 106243638 B CN106243638 B CN 106243638B CN 201610602000 A CN201610602000 A CN 201610602000A CN 106243638 B CN106243638 B CN 106243638B
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- fire retardant
- pbt
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 59
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 29
- 150000002367 halogens Chemical class 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 28
- -1 pentaerythrite diphosphate ester melamine salt Chemical class 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000001177 diphosphate Substances 0.000 claims abstract description 11
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 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 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 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 abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 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 abstract description 12
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 57
- 229920001707 polybutylene terephthalate Polymers 0.000 description 40
- 238000005452 bending Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012757 flame retardant agent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- DBKFYOISCCPYTQ-UHFFFAOYSA-K C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O Chemical compound C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O DBKFYOISCCPYTQ-UHFFFAOYSA-K 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 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 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of fire retardant PBT with no halogen material, it is made of following components in parts by weight：0.05~0.10 part of 100 parts of PBT resins, 15~25 parts of Halogenless composite fire retardant, 0.5~5 part of processing aid and composite antioxidant；The Halogenless composite fire retardant by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, hypo-aluminum orthophosphate, triphenyl phosphate according to（4~6）∶（1~4）∶（13~21）:（1~4）Weight ratio composition；The processing aid is polysiloxanes；The composite antioxidant by antioxidant 1076 and irgasfos 168 according to（0.02~0.03）:（0.04~0.06）Weight ratio composition.The fire retardant PBT with no halogen material Halogen composite flame retardant system dosage of the present invention is less and flame retardant effect is preferable, while will not influence the comprehensive mechanical property of fire retardant PBT with no halogen material, especially also has higher heat resistance.
Description
The application is Application No. 201510309013.1, and the applying date is on June 8th, 2015, and invention and created name is " nothing
The divisional application of the application for a patent for invention of halogen flame-retardant PBT material and preparation method thereof ".
Technical field
The present invention relates to a kind of high molecular material and preparation method thereof, and in particular to a kind of fire retardant PBT with no halogen material and its
Preparation method.
Background technology
Polybutylene terephthalate (PBT)（Polybutylene terephthalate, abbreviation PBT）It is by 1,4- fourths two
The thermoplastic polyester that alcohol is obtained with terephthalic acid (TPA) or terephthalate polycondensation.Since PBT has heat resistance, weather-proof
Property, resistance to chemical reagents, the advantages that electrical characteristic is good, water imbibition is small, gloss is good, be widely used in electronic apparatus, auto parts,
The fields such as machinery, household wares, are five big general one of engineering plastics.The flame-retardant PBT used at present includes the flame-retardant PBT of halogen/antimony
And fire retardant PBT with no halogen.Preceding one kind flame-retardant PBT is due to producing substantial amounts of corrosivity toxic gas and flue dust when hot tearing and burning, easily
Produce secondary disaster.Therefore the application development trend according to international market to flame retarded polymeric material, promotion use halogen-free flameproof
PBT material, particularly electronic apparatus, auto parts industry.In addition, now with many part requirements are small-sized, thin-walled, lightweight and system
Make quickly, this more new fire retardant PBT with no halogen provides opportunity.
Greatest problem existing for existing fire retardant PBT with no halogen material is：Needing the fire retardant of larger dosage could obtain
Preferable flame retardant effect, will so substantially reduce the mechanical property of PBT material, in particular so that brittleness increases, so as to limit
Its application in engineering field.
Chinese patent literature CN102002218A discloses a kind of Halogenless composite fire retardant for fiber glass reinforced PBT material
And preparation method thereof, which is made of following component：The aluminum phenylphosphinate of 20-80% weight ratios, 10-60%
The melamine cyanurate of weight ratio, the zinc borate of 1-20% weight ratios, the triphenyl phosphate of 1-10% weight ratios, 1-5% weight
Four ester of pentaerythrite stearic acid of ratio.
Chinese patent literature CN103205017A discloses a kind of halogen-free flame retardants and halogen-free anti-flaming PBT composite
Preparation method, the halogen-free flame retardants include 45~65 parts of phosphinates, 15~30 parts of melamine polyphosphate, resorcinol pair
（Diphenyl phosphoester）10~25 parts, 0.3 part of silane coupling agent, 0.2 part of pentaerythritol stearate.
Above two Halogenless composite fire retardant there are it is identical the problem of：（1）Flame-retardant system cooperative effect is bad, and fire retardant is used
The smaller then flame retardant effect of amount is bad, and amount of flame-retardant agent is larger, can reduce mechanical property；（2）Heat resistance is bad, it is necessary to add glass
Glass fiber improves heat resistance, and the addition of glass fibre can then cause production equipment in production and forming process seriously to grind
Damage.
The content of the invention
It is an object of the present invention to solve the above problems, there is provided a kind of fire resistance, mechanical strength and heat resistance
Preferable fire retardant PBT with no halogen material.
Another object of the present invention is to provide the preparation method of above-mentioned fire retardant PBT with no halogen material.
Realizing the technical solution of one of the object of the invention is：A kind of fire retardant PBT with no halogen material, it is by following weight parts
Component is made：100 parts of PBT resins, 15~35 parts of Halogenless composite fire retardant, 0.5~5 part of processing aid and composite antioxidant
0.05~0.10 part.
The Halogenless composite fire retardant is by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, hypophosphorous acid
Aluminium, triphenyl phosphate according to（2~10）∶（1~8）∶（10~30）:（1~5）Weight ratio composition.
Halogenless composite fire retardant parts by weight are by preferably 15~25 parts in terms of 100 parts of PBT resins.
The Halogenless composite fire retardant is preferably by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, secondary
Aluminum phosphate, triphenyl phosphate according to（4~6）∶（1~4）∶（13~21）:（1~4）Weight ratio composition.
The processing aid is polysiloxanes.
The composite antioxidant by antioxidant 1076 and irgasfos 168 according to（0.02~0.03）:（0.04~0.06）
Weight ratio composition.
Realizing the technical solution of another object of the present invention is：The preparation method of above-mentioned fire retardant PBT with no halogen material, has following
Step：
1. the PBT resin, Halogenless composite fire retardant, processing aid and the composite antioxidant that are weighed according to formula are poured into height
Mixed in fast mixer, until frictional heat caused by mixing causes temperature of charge to be increased to 80 DEG C~90 DEG C, discharging cooling.
2. mixed material after cooling is sent to melting extrusion in double screw extruder, the billot extruded is cold through sink
But pelleter granulation, is pulled into, up to fire retardant PBT with no halogen material.
Above-mentioned steps 2. in, the temperature in each area of double screw extruder is：T1=190~200 DEG C, T2=195~205 DEG C, T3=
200~210 DEG C, T4=205~215 DEG C, T5=210~220 DEG C, T6=215~225 DEG C, T7=220~230 DEG C, T8=225~235
DEG C, T9=230~240 DEG C, TMould=220~230 DEG C.
The good effect that the present invention has：The fire retardant PBT with no halogen material of the present invention uses pentaerythrite diphosphate ester melamine
Salt, melamine cyanurate, hypo-aluminum orthophosphate and triphenyl phosphate composition Halogen composite flame retardant system, it is compound using the Halogen
Flame-retardant system only needs less dosage to obtain preferable flame retardant effect（Oxygen index (OI) is more than 32%, V-0 grades of vertical combustion）, at the same time
The comprehensive mechanical property of fire retardant PBT with no halogen material will not be influenced, especially also there is higher heat resistance, do not adding glass
Its vicat softening temperature is more than 180 DEG C in the case of fiber.
Embodiment
（Embodiment 1）
The fire retardant PBT with no halogen material of the present embodiment is made of the component of following weight：
The PBT resin of 100kg, the pentaerythrite diphosphate ester melamine salt of 4kg, the melamine cyanurate of 1kg, 13kg
Hypo-aluminum orthophosphate, the triphenyl phosphate of 2kg, the polysiloxanes of 1.5kg, the antioxidant 1076 of 0.02kg and the antioxygen of 0.04kg
Agent 168.
The preparation method of above-mentioned fire retardant PBT with no halogen material has steps of：
1. above-mentioned each component is poured into high-speed mixer according to formula, start motor, it is 900 to control agitator speed
Rev/min mixed, until frictional heat caused by mixing causes temperature of charge to be increased to 80 DEG C~90 DEG C, discharging cooling.
2. mixed material after cooling is sent to melting extrusion in double screw extruder, the billot extruded is cold through sink
But pelleter granulation, is pulled into, up to fire retardant PBT with no halogen material.
The temperature in each area of double screw extruder is：T1=190~200 DEG C, T2=195~205 DEG C, T3=200~210 DEG C, T4=
205~215 DEG C, T5=210~220 DEG C, T6=215~225 DEG C, T7=220~230 DEG C, T8=225~235 DEG C, T9=230~240
DEG C, TMould=220~230 DEG C.
（2~embodiment of embodiment 6）
The preparation method of each embodiment is same as Example 1, and difference is the weight proportion of each component, is specifically shown in Table
1。
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg | 100kg | 100kg |
| Pentaerythrite diphosphate ester melamine salt | 4kg | 4kg | 5kg | 5kg | 6kg | 6kg |
| Melamine cyanurate | 1kg | 1.5kg | 2kg | 3kg | 3kg | 4kg |
| Hypo-aluminum orthophosphate | 13kg | 16kg | 20kg | 21kg | 20kg | 18kg |
| Triphenyl phosphate | 2kg | 1.5kg | 3kg | 4kg | 2kg | 1kg |
| Polysiloxanes | 1.5kg | 2kg | 2kg | 2.5kg | 3kg | 3kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.03kg | 0.03kg | 0.03kg |
| Irgasfos 168 | 0.04kg | 0.05kg | 0.06kg | 0.04kg | 0.05kg | 0.06kg |
（Application examples）
By fire retardant PBT with no halogen material made from 1~embodiment of embodiment 6 using injection moulding machine injection standard specimen, and
Mechanical property is carried out to the standard specimen by national standard and fire resistance is tested, test result is shown in Table 2.
Table 2
| Test performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Tensile strength/MPa | 39.03 | 38.17 | 37.58 | 36.53 | 37.68 | 38.32 |
| Anti- notch impact strength/the KJm of cantilever beam-2 | 3.68 | 3.91 | 3.32 | 3.67 | 3.15 | 3.44 |
| Bending strength/MPa | 64.12 | 63.89 | 62.15 | 61.38 | 60.54 | 63.56 |
| Bending modulus/MPa | 2200 | 2130 | 2080 | 2090 | 1890 | 1960 |
| Oxygen index (OI)/% | 33.2 | 34.6 | 35.0 | 36.4 | 34.9 | 33.8 |
| Vertical combustion | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Microcaloire softening temperature/DEG C | 182 | 183 | 184 | 182 | 184 | 182 |
（1~comparative example of comparative example 4）
Each comparative example is substantially the same manner as Example 1, and difference is the fire retardant species and its dosage used, is specifically shown in
Table 3.
Wherein：
The fire retardant that comparative example 1 and comparative example 2 use is nothing made from Chinese patent literature CN102002218A embodiments 1
Halogen composite flame-retardant agent（It is known as fire retardant A in table 3）, dosage is respectively 20g and 45g.
The fire retardant that comparative example 3 and comparative example 4 use is nothing made from Chinese patent literature CN103205017A embodiments 1
Halogen composite flame-retardant agent（It is known as fire retardant B in table 3）, dosage is respectively 20g and 45g.
Table 3
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg |
| Fire retardant | 20g fire retardants A | 45g fire retardants A | 20g fire retardants B | 45g fire retardants B |
| Polysiloxanes | 1.5kg | 1.5kg | 1.5kg | 1.5kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.02kg |
| Irgasfos 168 | 0.04kg | 0.04kg | 0.04kg | 0.04kg |
（5~comparative example of comparative example 7）
Each comparative example is substantially the same manner as Example 1, and difference is to be shown in Table 4.
Table 4
| Embodiment 1 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg |
| Pentaerythrite diphosphate ester melamine salt | 4kg | 4kg | - | - |
| Melamine cyanurate | 1kg | - | 1kg | - |
| Hypo-aluminum orthophosphate | 13kg | 13kg | 13kg | 13kg |
| Triphenyl phosphate | 2kg | - | - | 2kg |
| Polysiloxanes | 1.5kg | 1.5kg | 1.5kg | 1.5kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.02kg |
| Irgasfos 168 | 0.04kg | 0.04kg | 0.04kg | 0.04kg |
（8~comparative example of comparative example 10）
Each comparative example is substantially the same manner as Example 1, and difference is to be shown in Table 5.
Table 5
| Embodiment 1 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg |
| Pentaerythrite diphosphate ester melamine salt | 4kg | 4kg | 4kg | - |
| Melamine cyanurate | 1kg | 1kg | - | 1kg |
| Hypo-aluminum orthophosphate | 13kg | - | - | - |
| Triphenyl phosphate | 2kg | - | 2kg | 2kg |
| Polysiloxanes | 1.5kg | 1.5kg | 1.5kg | 1.5kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.02kg |
| Irgasfos 168 | 0.04kg | 0.04kg | 0.04kg | 0.04kg |
（11~comparative example of comparative example 14）
Each comparative example is substantially the same manner as Example 1, and difference is to be shown in Table 6.
Table 6
| Embodiment 1 | Comparative example 11 | Comparative example 12 | Comparative example 13 | Comparative example 14 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg | 100kg |
| Pentaerythrite diphosphate ester melamine salt | 4kg | 4kg | 4kg | 4kg | - |
| Melamine cyanurate | 1kg | 1kg | 1kg | - | 1kg |
| Hypo-aluminum orthophosphate | 13kg | 13kg | - | 13kg | 13kg |
| Triphenyl phosphate | 2kg | - | 2kg | 2kg | 2kg |
| Polysiloxanes | 1.5kg | 1.5kg | 1.5kg | 1.5kg | 1.5kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.02kg | 0.02kg |
| Irgasfos 168 | 0.04kg | 0.04kg | 0.04kg | 0.04kg | 0.04kg |
（15~comparative example of comparative example 18）
Each comparative example is substantially the same manner as Example 1, and difference is to be shown in Table 7.
Table 7
| Embodiment 1 | Comparative example 15 | Comparative example 16 | Comparative example 17 | Comparative example 18 | |
| PBT resin | 100kg | 100kg | 100kg | 100kg | 100kg |
| Pentaerythrite diphosphate ester melamine salt | 4kg | 4kg | - | - | - |
| Melamine cyanurate | 1kg | - | 1kg | - | - |
| Hypo-aluminum orthophosphate | 13kg | - | - | 13kg | - |
| Triphenyl phosphate | 2kg | - | - | - | 2kg |
| Polysiloxanes | 1.5kg | 1.5kg | 1.5kg | 1.5kg | 1.5kg |
| Antioxidant 1076 | 0.02kg | 0.02kg | 0.02kg | 0.02kg | 0.02kg |
| Irgasfos 168 | 0.04kg | 0.04kg | 0.04kg | 0.04kg | 0.04kg |
（Contrast application examples）
By fire retardant PBT with no halogen material made from 1~comparative example of comparative example 18 using injection moulding machine injection standard specimen, and
Mechanical property is carried out to the standard specimen by national standard and fire resistance is tested, test result is shown in Table 8~table 11.
Table 8
| Test performance | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile strength/MPa | 39.03 | 37.58 | 34.58 | 36.58 | 35.58 |
| Anti- notch impact strength/the kJm of cantilever beam-2 | 3.68 | 3.92 | 2.72 | 3.72 | 2.32 |
| Bending strength/MPa | 64.12 | 61.15 | 60.35 | 63.18 | 62.54 |
| Bending modulus/MPa | 2200 | 2180 | 1986 | 2140 | 2030 |
| Oxygen index (OI)/% | 33.2 | 27.3 | 32.0 | 27.2 | 33.1 |
| Vertical combustion | V-0 | V-2 | V-0 | V-2 | V-0 |
| Microcaloire softening temperature/DEG C | 182 | 170 | 178 | 173 | 175 |
Table 9
| Test performance | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Tensile strength/MPa | 39.82 | 40.15 | 39.78 | 40.65 | 40.33 | 40.31 |
| Anti- notch impact strength/the kJm of cantilever beam-2 | 4.11 | 4.15 | 4.07 | 4.25 | 4.05 | 4.45 |
| Bending strength/MPa | 64.15 | 64.48 | 63.58 | 65.08 | 64.83 | 65.16 |
| Bending modulus/MPa | 2198 | 2210 | 2243 | 2190 | 2210 | 2240 |
| Oxygen index (OI)/% | 22.1 | 22.0 | 22.4 | 18.0 | 18.0 | 18.0 |
| Vertical combustion | - | - | - | - | - | - |
| Microcaloire softening temperature/DEG C | 183 | 184 | 183 | 182 | 182 | 182 |
Table 10
| Test performance | Comparative example 11 | Comparative example 12 | Comparative example 13 | Comparative example 14 |
| Tensile strength/MPa | 39.65 | 40.72 | 39.88 | 39.62 |
| Anti- notch impact strength/the kJm of cantilever beam-2 | 3.25 | 3.91 | 3.43 | 3.46 |
| Bending strength/MPa | 63.08 | 64.47 | 62.08 | 62.38 |
| Bending modulus/MPa | 2090 | 2180 | 1990 | 1980 |
| Oxygen index (OI)/% | 31.8 | 18.0 | 29.8 | 29.3 |
| Vertical combustion | V-0 | - | V-1 | V-1 |
| Microcaloire softening temperature/DEG C | 179 | 180 | 178 | 178 |
Table 11
| Test performance | Comparative example 15 | Comparative example 16 | Comparative example 17 | Comparative example 18 |
| Tensile strength/MPa | 40.62 | 41.61 | 39.48 | 41.93 |
| Anti- notch impact strength/the kJm of cantilever beam-2 | 4.21 | 4.45 | 3.36 | 4.32 |
| Bending strength/MPa | 65.36 | 64.95 | 63.15 | 63.43 |
| Bending modulus/MPa | 2245 | 2283 | 2128 | 2260 |
| Oxygen index (OI)/% | 18.0 | 18.0 | 28.5 | 18.0 |
| Vertical combustion | - | - | V-2 | - |
| Microcaloire softening temperature/DEG C | 180 | 180 | 178 | 180 |
Claims (1)
- A kind of 1. fire retardant PBT with no halogen material, it is characterised in that：It is made of following components in parts by weight：PBT resins 100 0.05~0.10 part of part, 15~25 parts of Halogenless composite fire retardant, 0.5~5 part of processing aid and composite antioxidant；The Halogenless composite fire retardant is by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, hypo-aluminum orthophosphate, phosphorus Triphenyl phosphate ester according to（4~6）∶（1~4）∶（13~21）:（1~4）Weight ratio composition；The processing aid is polysiloxanes；The composite antioxidant by antioxidant 1076 and irgasfos 168 according to（0.02~0.03）:（0.04~0.06）Weight Amount is than composition.
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| CN106700440B (en) * | 2016-12-16 | 2019-02-19 | 佛山市三水金戈新型材料有限公司 | A kind of heat conductive flame-retarding polyester composite and preparation method thereof |
| CN108203526A (en) * | 2016-12-20 | 2018-06-26 | 上海杰事杰新材料(集团)股份有限公司 | A kind of halogen-free flameproof TPO elastomeric materials and preparation method thereof |
| CN106832419B (en) * | 2017-01-05 | 2019-04-12 | 东莞市宏泰基阻燃材料有限公司 | A kind of fire retardant and its preparation method and application |
| CN107266786B (en) * | 2017-07-11 | 2020-03-17 | 江苏理工学院 | Polypropylene halogen-free flame-retardant master batch and preparation method thereof |
| CN111234312B (en) * | 2020-03-27 | 2020-11-10 | 北京理工大学 | Aluminum hypophosphite composite halogen-free flame retardant, preparation and application thereof |
| CN113502035A (en) * | 2021-07-26 | 2021-10-15 | 洪湖市一泰科技有限公司 | Halogen-free flame-retardant polyester composite material and preparation method thereof |
| CN115197551B (en) * | 2022-08-10 | 2023-08-22 | 金发科技股份有限公司 | Low-modulus halogen-free flame-retardant PBT composite material, and preparation method and application thereof |
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| ES2307988T3 (en) * | 2003-11-07 | 2008-12-01 | Italmatch Chemicals S.P.A. | HALOGEN FREE FLAME RETARDING POLYCARBONATE COMPOSITIONS. |
| CN101575351B (en) * | 2009-05-30 | 2012-02-01 | 山东天一化学股份有限公司 | Method for preparing phosphorus-nitrogen expanding fire retardant |
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| CN102002218B (en) * | 2010-11-24 | 2013-01-09 | 广东省石油化工研究院 | Halogen-free compound flame retardant for glass fiber reinforced PBT (Polybutylene Terephthalate) material and preparation method thereof |
| CN103122120B (en) * | 2013-03-08 | 2015-07-29 | 上海安凸塑料添加剂有限公司 | A kind of halogen-free flameproof acrylonitrile-butadiene-styrene copolymer composition |
| CN103342880B (en) * | 2013-07-29 | 2016-02-03 | 广东顺德顺炎新材料有限公司 | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof |
| CN103483670A (en) * | 2013-10-10 | 2014-01-01 | 长园集团股份有限公司 | 150 DEG C high-flame-retardant halogen-free red phosphorus-free modified material |
| CN104327467B (en) * | 2014-11-21 | 2016-06-08 | 古道尔工程塑胶（深圳）有限公司 | A kind of intumescent high glow-wire ignition temperature PBT composite and preparation method thereof |
| CN104479353B (en) * | 2014-12-19 | 2017-09-22 | 西华大学 | A kind of novel halogen-free flame-retardant composition, fire retardant PBT with no halogen engineering plastic composite material and preparation method thereof |
| CN104650441B (en) * | 2015-03-16 | 2017-10-17 | 四川大学 | One kind can ceramic flame-retardant high-molecular composite and application |
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|---|---|---|---|---|
| CN103756269A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof |
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