CN102627713B - Sulfonated polystyrene flame retardant and low-halogen flame-retardant polypropylene material - Google Patents
Sulfonated polystyrene flame retardant and low-halogen flame-retardant polypropylene material Download PDFInfo
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- CN102627713B CN102627713B CN201210075587.3A CN201210075587A CN102627713B CN 102627713 B CN102627713 B CN 102627713B CN 201210075587 A CN201210075587 A CN 201210075587A CN 102627713 B CN102627713 B CN 102627713B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 polypropylene Polymers 0.000 title claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 32
- 229920001467 poly(styrenesulfonates) Polymers 0.000 title claims abstract description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007336 electrophilic substitution reaction Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 21
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002480 mineral oil Substances 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 235000010446 mineral oil Nutrition 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920005990 polystyrene resin Polymers 0.000 claims description 5
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 claims description 3
- AHJKRLASYNVKDZ-UHFFFAOYSA-N DDD Chemical compound C=1C=C(Cl)C=CC=1C(C(Cl)Cl)C1=CC=C(Cl)C=C1 AHJKRLASYNVKDZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004610 Internal Lubricant Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- SVUJNSGGPUCLQZ-FQQAACOVSA-N tenofovir alafenamide fumarate Chemical compound OC(=O)\C=C\C(O)=O.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1 SVUJNSGGPUCLQZ-FQQAACOVSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 4
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 238000009472 formulation Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 102220470698 BUD13 homolog_V30P_mutation Human genes 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 102220040412 rs587778307 Human genes 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 241001347978 Major minor Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- B29C47/92—
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a sulfonated polystyrene flame retardant and a low-halogen flame-retardant polypropylene material. A preparation method of the sulfonated polystyrene flame retardant comprises the following steps: adding a styrene resin and a sulfonating agent to a nitrogen protection container according to a molar ratio of the styrene resin to the sulfonating agent of 1:1-1:1.1, carrying out an aromatic electrophilic substitution reaction, adding a halogenated salt to the container after ending the aromatic electrophilic substitution reaction to salt out resulting sulfonated products, neutralizing the PH value of reactants in the container to 7-8, and extract-purifying by toluene to obtain the sulfonated polystyrene flame retardant. The low-halogen flame-retardant polypropylene material comprises, by weight, 94-98% of polypropylene, 1-4% of a complex formulation flame retardant, 0.5-1% of a lubricant, 0.2-0.6% of an oxidant and 0.2-0.5% of other assistants. According to the invention, different flame retardation grades of the polypropylene material can be reached by adjusting the application amount of the flame retardant, so a good flame retardation effect can be reached by using a small amount of the flame retardant, and simultaneously the clarity of the polypropylene material is basically not affected.
Description
[technical field]
The present invention relates to polymeric material field, relate in particular to a kind of sulfonated polystyrene fire retardant and low halogen anti-flaming polypropylene material.
[background technology]
Polypropylene flame redardant is with a wide range of applications, and wherein fire retardant used is generally bromide fire retardant, as decabromodiphenyl oxide, TDE, octa-BDE etc.General and the composite use of antimonous oxide of bromide fire retardant, in order to reach UL 94 VO ranks, the adding proportion of this based flame retardant is higher, and total amount reaches 25-30% conventionally.The polypropylene flame redardant cost of being made up of this fire-retardant agent is high, than great (proportion is higher than unmodified resin 37-40%), the mechanical property of material also obviously lowers because of a large amount of adding of fire retardant, in addition, the original transparency of PP resin has been lost in adding of fire retardant, has greatly limited its Application Areas.And sulfonate flame retardant is generally used in the flame-retardant system of polycarbonate on market, poor with the consistency of polyolefin resin.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of sulfonated polystyrene fire retardant, with traditional composite use of bromide fire retardant, better with the consistency of PP resin, under less consumption, can reach good flame retardant effect, and the transparency of PP resin is substantially unaffected.
Another technical problem that will solve of the present invention is to provide a kind of transparency and good flame retardation effect, low halogen anti-flaming polypropylene material that fire retardant addition is few.
In order to solve the problems of the technologies described above; the technical solution used in the present invention is; a kind of sulfonated polystyrene fire retardant; preparation by the following method: polystyrene resin and the sulphonating agent ratio of 1: 1 in molar ratio～1: 1.1 are put into and carried out fragrant electrophilic substitution reaction in the container with nitrogen protection; after fragrance electrophilic substitution reaction finishes; halogeno salt is joined in container; the sulfonated products of reaction is saltoutd out, and the reactant in container obtains described sulfonated polystyrene fire retardant through toluene extracting and purifying after being neutralized to pH value 7～8.
Above-described sulfonated polystyrene fire retardant, described fragrant electrophilic substitution reaction, temperature of reaction is controlled at 50-60 DEG C, and the reaction times is 5-6 hour.
Above-described sulfonated polystyrene fire retardant, described sulphonating agent is the one in the vitriol oil, oleum, sulphur trioxide and chlorsulfonic acid.
Above-described sulfonated polystyrene fire retardant, in the time that sulphonating agent is the vitriol oil, in the vitriol oil, the mass percent of H2SO4 is not less than 98%; In the time that sulphonating agent is oleum, in oleum, the massfraction of sulphur trioxide is not less than 40%; In the time that sulphonating agent is chlorsulfonic acid, the mass percent of HSO3Cl is not less than 97%.
Above-described sulfonated polystyrene fire retardant, sodium hydroxide, sodium carbonate or potassium hydroxide neutralization for reactant in container; Described halogeno salt is Repone K or sodium-chlor, identical with the molar weight of polystyrene to the molar weight of halogeno salt adding in container.
Above-described sulfonated polystyrene fire retardant, the melting index of polystyrene resin, at 220 DEG C, is 20～30g/10min under the test condition of 10 kilograms.
A technical scheme for low halogen anti-flaming polypropylene material, composed of the following components by weight percentage:
Polypropylene 94-98%;
Compound flame retardant 1-4%;
Lubricant 0.5-1%;
Oxidation inhibitor 0.2-0.6%;
Other auxiliary agents 0.2-0.5%;
Described compound flame retardant is the bromide fire retardant of non-biphenyl structural and the compound system of above-mentioned sulfonated polystyrene fire retardant.
Above-described low halogen anti-flaming polypropylene material, the bromide fire retardant of described non-biphenyl structural is one or more in TDE, tetrabromo-bisphenol, brominated Polystyrene, brominated epoxy; The weight proportion of the bromide fire retardant of non-biphenyl structural and sulfonated polystyrene fire retardant is 1: 3 to 3: 1.
Above-described low halogen anti-flaming polypropylene material, described lubricant is interior lubricated and outer lubricated compound system, internal lubricant is N, one in N '-ethylene bis stearamide, TAF, calcium stearate, Zinic stearas, lubricate outward for the one in PE wax, OP wax, E wax, described polypropylene is homopolymerization PP, and other described auxiliary agents are white mineral oil.
Above-described low halogen anti-flaming polypropylene material, by the following method preparation:
1) take raw material by above-mentioned weight percent;
2) polypropylene is first mixed with other auxiliary agents, then mix with compound flame retardant, lubricant, oxidation inhibitor, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material; Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
The present invention select homemade Halogen sulfonate flame retardant and environmental protection bromide fire retardant composite, can make low halogen anti-flaming polypropylene material reach different fire-retardant ranks by the consumption of adjusting fire retardant, under less consumption, can reach good flame retardant effect, the saturating degree of low halogen anti-flaming polypropylene material is substantially unaffected simultaneously.
[embodiment]
Below by embodiment, the present invention is further elaborated:
Sulfonated polystyrene fire retardant Halogen sulfonate flame retardant of the present invention is self-control fire retardant, wherein base-material used is the good polystyrene resin of mobility, melting index is at 220 DEG C, under the test condition of 10 kilograms, be 220 DEG C, under the test condition of 10 kilograms, be 20～30g/10min, preparation process is as follows:
The mol ratio polystyrene of 1: 1～1: 1.1 and sulphonating agent are put into there-necked flask (if the industrial production with nitrogen protection; there-necked flask can replace with reactor) in carry out fragrant electrophilic substitution reaction; controlling temperature of reaction is 50-60 DEG C of left and right; reaction times is 5-6 hour; after reaction finishes; halogeno salt is joined in there-necked flask; sulfonated products is saltoutd out, be neutralized to pH value between 7～8, obtain sulfonated polystyrene through toluene extracting and purifying again through sodium hydroxide, sodium carbonate or potassium hydroxide etc.Wherein sulphonating agent used is the one in the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid.Halogeno salt used is the one in Repone K or sodium-chlor.
Sulfonated polystyrene fire retardant embodiment 1:
The polystyrene that is 1: 1 by mol ratio and oleum join in the there-necked flask with nitrogen protection, wherein the melting index of polystyrene is 20g/10min, in oleum, the massfraction of sulphur trioxide is 40%, control temperature of reaction at 60 DEG C, reaction times is 6 hours, after reaction finishes, by reaction system cool to room temperature, in reaction vessel, add and the sodium-chlor of polystyrene with molar weight, sulfonated products is saltoutd out, be neutralized to pH value to 7～8 with sodium hydroxide, filter, after oven dry, obtain sulfonated polystyrene fire retardant through toluene extracting and purifying.
Sulfonated polystyrene fire retardant embodiment 2:
The polystyrene that is 1: 1.02 by mol ratio and the vitriol oil join in the there-necked flask with nitrogen protection; wherein the melting index of polystyrene is 25g/10min; in the vitriol oil, the massfraction of H2SO4 is 98%; control temperature of reaction at 60 DEG C; reaction times is 5 hours; after reaction finishes; by reaction system cool to room temperature; in reaction vessel, add and the Repone K of polystyrene with molar weight; sulfonated products is saltoutd out; be neutralized to pH value to 7～8 with potassium hydroxide, filter, after oven dry, obtain sulfonated polystyrene fire retardant through toluene extracting and purifying.
Sulfonated polystyrene fire retardant embodiment 3:
The polystyrene that is 1: 1.05 by mol ratio and chlorsulfonic acid join in the there-necked flask with nitrogen protection; wherein the melting index of polystyrene is 30g/10min; the massfraction of chlorsulfonic acid is 97%; control temperature of reaction at 50 DEG C; reaction times is 5 hours; after reaction finishes; by reaction system cool to room temperature; in reaction vessel, add and the sodium-chlor of polystyrene with molar weight; sulfonated products is saltoutd out; be neutralized to pH value to 7～8 with sodium hydroxide, filter, after oven dry, obtain sulfonated polystyrene fire retardant through toluene extracting and purifying.
The composition of the low halogen anti-flaming polypropylene material of the present invention is (%) by weight percentage: polypropylene PP 94-98%; Compound flame retardant 1-4%; Lubricant 0.5-1%; Oxidation inhibitor 0.2-0.6%.Other auxiliary agents 0.2-0.5%.
Wherein PP is homopolymerization PP resin, as: V30G, Z30S, T30S, HJ730 etc.; Fire retardant is the compound system of above-mentioned homemade sulfonated polystyrene fire retardant and environmental protection bromide fire retardant, and the environmental protection fire retarding agent that wherein bromide fire retardant is non-biphenyl structural, as TDE, tetrabromo-bisphenol, brominated Polystyrene, brominated epoxy etc.
Lubricant is interior lubricated and outer lubricated compound system, and internal lubricant is N, N '-ethylene bis stearamide (EBS), TAF, calcium stearate, Zinic stearas etc., outer lubricating for PE wax, OP wax, E wax etc.
Oxidation inhibitor is the compound system of major-minor oxidation inhibitor, primary antioxidant be Hinered phenols as 1010,1076, auxiliary antioxidant is that phosphorous acid esters are as TPP, ODPP, 168; Other auxiliary agents are mainly white mineral oils.
In the preparation process of halogen anti-flaming polypropylene material of the present invention, first PP, white mineral oil are fully mixed, make uniform liquid be distributed to PP pellet surface, and then add compound flame retardant, lubricant, oxidation inhibitor to mix.The raw material mixing is put into the loading hopper of twin screw extruder, through melt extruding, and granulation; Complete processing is as follows: twin screw extruder one district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
For ease of the present invention is further understood, now in conjunction with specific embodiments the preparation process of the low halogen anti-flaming polypropylene material of the present invention is described in detail:
Low halogen anti-flaming polypropylene material embodiment 1:
Take by weight percentage PP (trade mark is V30G) 94%, fire retardant 4% (wherein making fire retardant by oneself is 2.8%, and environmental protection bromide fire retardant is TDE, and consumption is 1.2%), lubricant 1%, oxidation inhibitor 0.5%, white mineral oil 0.5%, fully mixes PP, white mineral oil, add again compound flame retardant, lubricant, oxidation inhibitor to mix, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material.Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
Low halogen anti-flaming polypropylene material embodiment 2:
Take by weight percentage PP (trade mark is Z30S) 95%, fire retardant 3% (wherein making fire retardant by oneself is 2%, and environmental protection bromide fire retardant is TDE, and consumption is 1%), lubricant 1%, oxidation inhibitor 0.6%, white mineral oil 0.4%, fully mixes PP, white mineral oil, add again compound flame retardant, lubricant, oxidation inhibitor to mix, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material.Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
Low halogen anti-flaming polypropylene material embodiment 3:
Take by weight percentage PP (trade mark is HJ730) 96%, (wherein make fire retardant by oneself is 1.25% to fire retardant 2.5%, environmental protection bromide fire retardant is tetrabromo-bisphenol, consumption is 1.25%), lubricant 0.7%, oxidation inhibitor 0.3%, white mineral oil 0.5%, PP, white mineral oil are fully mixed, add again compound flame retardant, lubricant, oxidation inhibitor to mix, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material.Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
Low halogen anti-flaming polypropylene material embodiment 4:
Take by weight percentage PP (trade mark is T30S) 97%, fire retardant 2% (wherein making fire retardant by oneself is 0.8%, and environmental protection bromide fire retardant is brominated epoxy, and consumption is 1.2%), lubricant 0.4%, oxidation inhibitor 0.3%, white mineral oil 0.3%, fully mixes PP, white mineral oil, add again compound flame retardant, lubricant, oxidation inhibitor to mix, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material.Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
Low halogen anti-flaming polypropylene material embodiment 5:
Take by weight percentage PP (trade mark is V 30G) 98%, (wherein make fire retardant by oneself is 0.3% to fire retardant 1%, environmental protection bromide fire retardant is brominated Polystyrene, consumption is 0.7%), lubricant 0.4%, oxidation inhibitor 0.4%, white mineral oil 0.2%, PP, white mineral oil are fully mixed, add again compound flame retardant, lubricant, oxidation inhibitor to mix, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material.Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20Mpa.
Performance test:
Tensile strength is tested by ASTM D-638 standard.Specimen types is I type, batten size (mm): (176 ± 2) (length) × (12.6 ± 0.2) (end width) × (3.05 ± 0.2) (thickness), draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by ASTM D-790 standard.Specimen types is specimen size (mm): (128 ± 2) × (12.67 ± 0.2) × (3.11 ± 0.2), and rate of bending is 20mm/min;
Socle girder notched Izod impact strength is tested by ASTM D-256 standard.Specimen types is I type, specimen size (mm): (63 ± 2) × (12.45 ± 0.2) × (3.1 ± 0.2); Breach type is category-A, and breach residual thickness is 1.9mm;
Melting index is tested by ASTM D-1238, and probe temperature is 200 DEG C, and load is 10 kilograms, and be 5min warm up time;
Heat-drawn wire is tested by ASTM D-648, specimen size (mm): (128 ± 2) × (12.45 ± 0.2) × (3.1 ± 0.2), and load is 1.82Mpa;
Flame retardant properties is tested by UL94, test size (mm): (128 ± 2) × (12.67 ± 0.2) × (3.11 ± 0.2), flame height 20mm.
ASTM D1003 standard for transparence, print thickness 2mm.
Embodiment 1-5 formula and material property are in table 1:
Table 1
As can be seen from the above table, the flame retardant effect of compound flame retardant is very high, and addition is far below the consumption of conventional P P fire retardant.Along with the increase of amount of flame-retardant agent, fire-retardant rank also increases thereupon, in the time that the consumption of compound flame retardant reaches 3%, can reach fire-retardant V0.Due to adding of lower aq fire retardant, PP material proportion is low, and transparency is up to 80%.Can meet office appliance, household electrical appliance, automobile etc. requires in anti-flaming transparent field.
Above technical scheme can find out, the present invention has following beneficial effect:
1: the transparent flame-retarding PP that the present invention makes, its characteristic is that fire retardant used is for self-control Halogen sulfonate flame retardant and the composite use of environmental protection bromide fire retardant, addition is low, good flame retardation effect.
2: a kind of transparent flame-retarding PP that the present invention proposes, because the addition of fire retardant is less, substantially do not affect original transparency of PP, expand its Application Areas.
Above a kind of anti-flaming transparent PP material provided by the present invention and preparation method thereof is described in detail, applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; , for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, to sum up, this description should not be construed as limitation of the present invention meanwhile.
Claims (9)
1. a low halogen anti-flaming polypropylene material, is characterized in that, composed of the following components by weight percentage:
Described compound flame retardant is the bromide fire retardant of non-biphenyl structural and the compound system of sulfonated polystyrene fire retardant; Wherein sulfonated polystyrene fire retardant; preparation by the following method: by polystyrene resin and sulphonating agent in molar ratio the ratio of 1:1～1:1.1 put into and in the container with nitrogen protection, carry out fragrant electrophilic substitution reaction; after fragrance electrophilic substitution reaction finishes; halogeno salt is joined in container; the sulfonated products of reaction is saltoutd out, and the reactant in container obtains described sulfonated polystyrene fire retardant through toluene extracting and purifying after being neutralized to pH value 7～8.
2. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, described fragrant electrophilic substitution reaction, temperature of reaction is controlled at 50-60 DEG C, and the reaction times is 5-6 hour.
3. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, described sulphonating agent is the one in the vitriol oil, oleum, sulphur trioxide and chlorsulfonic acid.
4. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, in the time that sulphonating agent is the vitriol oil, and H in the vitriol oil
2sO
4mass percent be not less than 98%; In the time that sulphonating agent is oleum, in oleum, the massfraction of sulphur trioxide is not less than 40%; In the time that sulphonating agent is chlorsulfonic acid, HSO
3the mass percent of Cl is not less than 97%.
5. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, sodium hydroxide, sodium carbonate or potassium hydroxide neutralization for reactant in container; Described halogeno salt is Repone K or sodium-chlor, identical with the molar weight of polystyrene to the molar weight of halogeno salt adding in container.
6. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, the melting index of polystyrene resin, at 220 DEG C, is 20～30g/10min under the test condition of 10 kilograms.
7. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, the bromide fire retardant of described non-biphenyl structural is one or more in TDE, tetrabromo-bisphenol, brominated Polystyrene, brominated epoxy; The weight proportion of the bromide fire retardant of non-biphenyl structural and sulfonated polystyrene fire retardant is 1:3 to 3:1.
8. low halogen anti-flaming polypropylene material according to claim 1, it is characterized in that, described lubricant is interior lubricated and outer lubricated compound system, internal lubricant is N, one in N '-ethylene bis stearamide, TAF, calcium stearate, Zinic stearas, lubricate outward for the one in PE wax, OP wax, E wax, described polypropylene is homopolymerization PP, and other described auxiliary agents are white mineral oil.
9. low halogen anti-flaming polypropylene material according to claim 1, is characterized in that, by the following method preparation:
1) take raw material by weight percent claimed in claim 1;
2) polypropylene is first mixed with other auxiliary agents, then mix with compound flame retardant, lubricant, oxidation inhibitor, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes alloy material; Wherein, the temperature setting of the each district of screw rod is respectively: a district temperature 240-245 DEG C, and two district temperature 245-250 DEG C, three district temperature 245-250 DEG C, four district temperature 245-250 DEG C, head 240-245 DEG C, the residence time 1～3min, pressure is 10-20MPa.
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|---|---|---|---|---|
| CN1957037A (en) * | 2004-03-23 | 2007-05-02 | 索尼株式会社 | Flame retardant, flame-retardant resin composition and method for producing flame retardant |
| CN101899125A (en) * | 2010-07-16 | 2010-12-01 | 深圳市科聚新材料有限公司 | Transparent flame-retardant PMMA and preparation method thereof and method for preparing flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1957037A (en) * | 2004-03-23 | 2007-05-02 | 索尼株式会社 | Flame retardant, flame-retardant resin composition and method for producing flame retardant |
| CN101899125A (en) * | 2010-07-16 | 2010-12-01 | 深圳市科聚新材料有限公司 | Transparent flame-retardant PMMA and preparation method thereof and method for preparing flame retardant |
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