CN106243638A - Halogen-free flame-retardant PBT (polybutylene terephthalate) material - Google Patents
Halogen-free flame-retardant PBT (polybutylene terephthalate) material Download PDFInfo
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- CN106243638A CN106243638A CN201610602000.8A CN201610602000A CN106243638A CN 106243638 A CN106243638 A CN 106243638A CN 201610602000 A CN201610602000 A CN 201610602000A CN 106243638 A CN106243638 A CN 106243638A
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- halogen
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- retardant
- fire retardant
- pbt
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 28
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 25
- 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 abstract description 18
- 229920001707 polybutylene terephthalate Polymers 0.000 title description 42
- 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
- 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
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 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
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 239000001177 diphosphate Substances 0.000 claims description 10
- 235000011180 diphosphates Nutrition 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 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
- PYLQXBCYFPDGBI-UHFFFAOYSA-N Nc1nc(N)nc(N)n1.OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O Chemical compound Nc1nc(N)nc(N)n1.OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O PYLQXBCYFPDGBI-UHFFFAOYSA-N 0.000 abstract 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 abstract 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 57
- 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
- 238000002156 mixing Methods 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 description 1
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 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
- 230000001276 controlling effect Effects 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
- 238000004519 manufacturing process 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 229910000077 silane Inorganic materials 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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a halogen-free flame-retardant PBT material which is prepared from the following components in parts by weight: 100 parts of PBT resin, 15-25 parts of halogen-free composite flame retardant, 0.5-5 parts of processing aid and 0.05-0.10 part of composite antioxidant; the halogen-free composite flame retardant consists of pentaerythritol diphosphate melamine salt, melamine cyanurate, aluminum hypophosphite and triphenyl phosphate according to the weight ratio of (4-6) to (1-4) to (13-21) to (1-4); the processing aid is polysiloxane; the composite antioxidant is composed of an antioxidant 1076 and an antioxidant 168 according to the weight ratio of (0.02-0.03) to (0.04-0.06). The halogen-free flame-retardant PBT material disclosed by the invention has the advantages of less dosage of a halogen-free composite flame-retardant system, good flame-retardant effect, no influence on the comprehensive mechanical property of the halogen-free flame-retardant PBT material, and particularly higher heat resistance.
Description
The application is Application No. 201510309013.1, filing date on June 8th, 2015, and invention and created name is " nothing
Halogen flame-retardant PBT material and preparation method thereof " the divisional application of application for a patent for invention.
Technical field
The present invention relates to a kind of macromolecular material and preparation method thereof, be specifically related to a kind of fire retardant PBT with no halogen material and
Preparation method.
Background technology
Polybutylene terephthalate (PBT) (polybutylene terephthalate is called for short PBT) is by Isosorbide-5-Nitrae-fourth two
The thermoplastic polyester that alcohol obtains with p-phthalic acid or terephthalate polycondensation.Owing to PBT has thermostability, weather-proof
Property, the advantage such as resistance to chemical reagents, electrical characteristic are good, water absorption is little, gloss is good, be widely used in electronic apparatus, auto parts,
The fields such as machinery, household wares, are one of five big general engineering plastics.Currently used flame-retardant PBT includes the flame-retardant PBT of halogen/antimony
And fire retardant PBT with no halogen.Substantial amounts of corrosivity toxic gas and flue dust is produced, easily when previous class flame-retardant PBT is due to hot tearing and burning
Produce secondary disaster.Therefore according to the international market application development trend to flame retarded polymeric material, advocate and use halogen-free flameproof
PBT material, particularly electronic apparatus, auto parts industry.It addition, thin-walled, lightweight small-sized now with many part requirement and system
Making quickly, this newest fire retardant PBT with no halogen provides opportunity.
The greatest problem that existing fire retardant PBT with no halogen material exists is: need the fire retardant of bigger consumption to obtain
Preferably flame retardant effect, so will be substantially reduced the mechanical property of PBT material, in particular so that fragility increases, thus limits
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, this Halogenless composite fire retardant is made up of following component: the aluminum phenylphosphinate of 20-80% weight ratio, 10-60%
The melamine cyanurate of weight ratio, the Firebrake ZB of 1-20% weight ratio, the triphenyl phosphate of 1-10% weight ratio, 1-5% weight
Tetramethylolmethane stearic acid four ester of ratio.
Chinese patent literature CN103205017A discloses a kind of halogen-free flame retardants and halogen-free anti-flaming PBT composite
Preparation method, this halogen-free flame retardants includes phosphinates 45～65 parts, melamine polyphosphate 15～30 parts, and resorcinol is double
(diphenyl phosphoester) 10～25 parts, silane coupler 0.3 part, pentaerythritol stearate 0.2 part.
There is identical problem in above two Halogenless composite fire retardant: (1) flame-retardant system cooperative effect is the best, and fire retardant is used
Measuring less then flame retardant effect the best, amount of flame-retardant agent then can reduce mechanical property relatively greatly；(2) thermostability is the best, needs to add glass
Glass fiber improves thermostability, and production equipment then producing and can be caused serious mill by the addition of glass fibre in forming process
Damage.
Summary of the invention
An object of the present invention is to solve the problems referred to above, it is provided that a kind of fire resistance, mechanical strength and thermostability
All preferably 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.
The technical scheme realizing 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: PBT resin 100 parts, Halogenless composite fire retardant 15～35 parts, processing aid 0.5～5 parts and composite antioxidant
0.05～0.10 part.
Described Halogenless composite fire retardant is by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, hypophosphorous acid
Aluminum, triphenyl phosphate are according to (2～10): (1～8): (10～30): the weight ratio composition of (1～5).
Halogenless composite fire retardant weight portion preferably 15～25 parts in terms of PBT resin 100 parts.
Described Halogenless composite fire retardant is preferably by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, secondary
Aluminum phosphate, triphenyl phosphate are according to (4～6): (1～4): (13～21): the weight ratio composition of (1～4).
Described processing aid is polysiloxanes.
Described composite antioxidant by antioxidant 1076 and irgasfos 168 according to (0.02～0.03): (0.04～0.06)
Weight ratio composition.
The technical scheme realizing 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 weighed according to formula, Halogenless composite fire retardant, processing aid and composite antioxidant are poured into the most mixed
Mixing in conjunction machine, until the produced frictional heat of mixing makes temperature of charge be increased to 80 DEG C～90 DEG C, discharging cools down.
2. being sent in double screw extruder melt extrude by the mixed material after cooling, the billot extruded is cold through tank
But, it is pulled into pelleter pelletize, obtains fire retardant PBT with no halogen material.
Above-mentioned steps 2. in, the temperature in each district 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, use this Halogen to be combined
Flame-retardant system only needs less consumption can obtain preferable flame retardant effect (oxygen index (OI) is more than 32%, vertical combustion V-0 level), simultaneously
Do not interfere with the comprehensive mechanical property of fire retardant PBT with no halogen material, the most also there is higher thermostability, without glass yet
In the case of fiber, its vicat softening temperature is more than 180 DEG C.
Detailed description of the invention
(embodiment 1)
The fire retardant PBT with no halogen material of the present embodiment is made up 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's is secondary
Aluminum phosphate, the triphenyl phosphate of 2kg, the polysiloxanes of 1.5kg, the antioxidant 1076 of 0.02kg and the antioxidant of 0.04kg
168。
The preparation method of above-mentioned fire retardant PBT with no halogen material has steps of:
1. pouring in high-speed mixer by above-mentioned each component according to formula, start motor, controlling agitator speed is 900 revs/min
Clock mixes, until the produced frictional heat of mixing makes temperature of charge be increased to 80 DEG C～90 DEG C, discharging cools down.
2. being sent in double screw extruder melt extrude by the mixed material after cooling, the billot extruded is cold through tank
But, it is pulled into pelleter pelletize, obtains fire retardant PBT with no halogen material.
The temperature in each district 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.
(embodiment 2～embodiment 6)
The preparation method of each embodiment is same as in 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)
The fire retardant PBT with no halogen material that embodiment 1～embodiment 6 prepare is used injection moulding machine injection standard specimen, and by state
Family's standard carries out mechanical property and fire resistance test to this standard specimen, and test result is shown in Table 2.
Table 2
| Test performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hot strength/MPa | 39.03 | 38.17 | 37.58 | 36.53 | 37.68 | 38.32 |
| The anti-notch impact strength of cantilever beam/KJ m-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 |
(comparative example 1～comparative example 4)
Each comparative example is substantially the same manner as Example 1, and difference is fire retardant kind and the consumption thereof used, and is specifically shown in Table 3.
Wherein:
The fire retardant that comparative example 1 and comparative example 2 use is that the Halogen that Chinese patent literature CN102002218A embodiment 1 prepares is multiple
Closing fire retardant (being referred to as fire retardant A in table 3), consumption is respectively 20g and 45g.
The fire retardant that comparative example 3 and comparative example 4 use is the nothing that Chinese patent literature CN103205017A embodiment 1 prepares
Halogen composite flame-retardant agent (is referred to as fire retardant B) in table 3, consumption 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 retardant A | 45g fire retardant A | 20g fire retardant B | 45g fire retardant 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 |
(comparative example 5～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 |
(comparative example 8～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 |
(comparative example 11～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 |
(comparative example 15～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)
The fire retardant PBT with no halogen material that comparative example 1～comparative example 18 prepare is used injection moulding machine injection standard specimen, and by state
Family's standard carries out mechanical property and fire resistance test to this standard specimen, and 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 |
| Hot strength/MPa | 39.03 | 37.58 | 34.58 | 36.58 | 35.58 |
| The anti-notch impact strength of cantilever beam/kJ m-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 |
| Hot strength/MPa | 39.82 | 40.15 | 39.78 | 40.65 | 40.33 | 40.31 |
| The anti-notch impact strength of cantilever beam/kJ m-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 |
| Hot strength/MPa | 39.65 | 40.72 | 39.88 | 39.62 |
| The anti-notch impact strength of cantilever beam/kJ m-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 |
| Hot strength/MPa | 40.62 | 41.61 | 39.48 | 41.93 |
| The anti-notch impact strength of cantilever beam/kJ m-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)
1. a fire retardant PBT with no halogen material, it is characterised in that: it is made up of following components in parts by weight: PBT resin 100
Part, Halogenless composite fire retardant 15～25 parts, processing aid 0.5～5 parts and composite antioxidant 0.05～0.10 part；
Described Halogenless composite fire retardant is by pentaerythrite diphosphate ester melamine salt, melamine cyanurate, hypo-aluminum orthophosphate, phosphorus
Triphenyl phosphate ester is according to (4～6): (1～4): (13～21): the weight ratio composition of (1～4)；
Described processing aid is polysiloxanes；
Described composite antioxidant by antioxidant 1076 and irgasfos 168 according to (0.02～0.03): the weight of (0.04～0.06)
Amount is than composition.
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| CN106189221B (en) * | 2016-08-05 | 2018-10-02 | 江苏晋伦塑料科技有限公司 | A kind of halogen-free flame-retardant glass fiber enhancing nylon and its preparation method and application |
| 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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| CN1268686C (en) * | 2003-07-27 | 2006-08-09 | 横店集团得邦工程塑料有限公司 | Heat and humidity resistant ,enhanced flame-retardant poly-butylene terephthalate composite materials and preparation method thereof |
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| CN101928448B (en) * | 2010-08-16 | 2013-03-13 | 中国科学技术大学 | Nano composite flame-retardant reinforced polyester engineering plastic and preparation method thereof |
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