CN107955208B - Anti-flaming smoke-inhibiting agent and preparation method thereof - Google Patents
Anti-flaming smoke-inhibiting agent and preparation method thereof Download PDFInfo
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- CN107955208B CN107955208B CN201710982228.9A CN201710982228A CN107955208B CN 107955208 B CN107955208 B CN 107955208B CN 201710982228 A CN201710982228 A CN 201710982228A CN 107955208 B CN107955208 B CN 107955208B
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- inhibiting agent
- flaming smoke
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- smoke
- alkyl
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- 239000000779 smoke Substances 0.000 title claims abstract description 76
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
- 125000001424 substituent group Chemical group 0.000 claims abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims abstract description 12
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 45
- 239000003063 flame retardant Substances 0.000 abstract description 30
- 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 16
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 13
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000013068 control sample Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- -1 phosphorus compound Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- RKXBYSUETPOUCS-UHFFFAOYSA-N C(CCCCCCC)[PH2]=O Chemical compound C(CCCCCCC)[PH2]=O RKXBYSUETPOUCS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 238000005192 partition Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
Abstract
The invention discloses a kind of anti-flaming smoke-inhibiting agents and preparation method thereof, including will have R as shown in formula (I)1And R2Phosphinates, tributyl tin and the trioctylphosphine of substituent group are in the 200-300 DEG C of also contacts the step of；Wherein, in formula (I): R1For C1-C6 alkyl or phenyl；R2For C1-C6 alkyl or phenyl；M is metallic element, the number that n is from 1 to 4.Anti-flaming smoke-inhibiting agent provided by the invention can keep phosphinates smoke density it is low, without the advantages that environmental hazard on the basis of, it can be improved its flame retardant property in application material, and fragile materials are not generated, the influence to main material matrix mechanical performance will not be reduced.Anti-flaming smoke-inhibiting agent to prepare raw material cheap and easy to get so that its application value with higher.
Description
Technical field
The present invention relates to fire retardants, and in particular, to a kind of anti-flaming smoke-inhibiting agent and preparation method thereof.
Background technique
With the development of economy and society, the quickening of life and work rhythm, most of Administrative Areas are no longer fixed reinforcing bars
The house of concrete, is more the working space split in a building, these spaces are rented in the form of lease
To target customer.Since there are many personnel often accommodated in these spaces, fire-retardant fireproof is most important to lease space
It is required that.Common fire retardant has aluminium hydroxide, cerium hydroxide, magnesium hydroxide, halogenated flame retardant, phosphinates and poly cyanamid etc.,
Although the problems such as halogenated flame retardant that generally uses still uses extensively now, can generate dioxin because burning and after fire
Meeting generate the reasons such as poison gas, have been to be concerned by more and more people it to the harm of human health and environment.Currently, and secondary phosphine
The advantages that hydrochlorate has dosage few, and smoke density is low, no environmental hazard, has been to be concerned by more and more people.But patent document US
It is disclosed in 2007/0029532, phosphonate may cause decomposition in process, and can generate in process frangible
Unavailable substance therefore limit application of the phosphonate as fire retardant.
Patent document CN107207779A, title are as follows: the flame-retardant polymer of phosphorus compound and melam comprising heat treatment
Composition discloses, by will heat the fire retardant of certain phosphonates acquisitions under 200 DEG C or higher temperature and as fire-retardant
The melam or melam derivative of synergist are integrated to polymer and can be easily worked under certain harsh conditions.But because
Melam or melam derivative are not readily synthesized, and increase the fire retardant application cost for adding melam.
Therefore, how a kind of anti-flaming smoke-inhibiting agent is provided and is guaranteeing that its smoke density is low, the advantages that no environmental hazard on the basis of,
The production cost for reducing material, improves its flame retardant property in application material, and do not generate fragile materials, will not reduce pair
The influence of main material matrix mechanical performance especially toughness, is a technical problem to be solved urgently.
Summary of the invention
The object of the present invention is to provide a kind of anti-flaming smoke-inhibiting agent and preparation method thereof, which is keeping phosphinic acids
On the basis of the advantages that smoke density of salt is low, no environmental hazard, its flame retardant property in application material can be improved, and do not produce
Raw fragile materials, will not reduce the influence to main material matrix mechanical performance, also, adjuvant used more economical.
To achieve the goals above, the present invention provides a kind of preparation methods of anti-flaming smoke-inhibiting agent, including will be such as formula (I) institute
That shows has R1And R2Phosphinates, tributyl tin and the trioctylphosphine of substituent group are in the step of 200-300 DEG C of also contacts
Suddenly；Wherein, in formula (I): R1For C1-C6 alkyl or phenyl；R2For C1-C6 alkyl or phenyl；M is metallic element, and n is from 1 to 4
Number so that Mn+It is metal cation, the charge of the cation is wherein assigned on n+ representation, and n is 1 to 4
Number.
The present invention also provides a kind of flame-retardant smoke inhibitions that the preparation method according to previously described anti-flaming smoke-inhibiting agent is prepared
Agent.
Through the above technical solutions, anti-flaming smoke-inhibiting agent provided by the invention can keep phosphinates smoke density it is low,
On the basis of the advantages that without environmental hazard, its flame retardant property in application material can be improved, and do not generate fragile materials,
The influence to main material matrix mechanical performance will not be reduced.Anti-flaming smoke-inhibiting agent to prepare raw material cheap and easy to get so that its have it is higher
Application value.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation methods of anti-flaming smoke-inhibiting agent, including will have R as shown in formula (I)1And R2Replace
Phosphinates, tributyl tin and the trioctylphosphine of base are in the 200-300 DEG C of also contacts the step of；Wherein, in formula (I): R1
For C1-C6 alkyl or phenyl；R2For C1-C6 alkyl or phenyl；M is metallic element, the number that n is from 1 to 4, so that Mn+It is metal
Cation is wherein assigned to the charge of the cation, and the number that n is 1 to 4 on n+ representation.
Raw material type and preparation process, the available fire-retardant suppression of those skilled in the art are selected according to above-mentioned technical proposal
Fumicants.Anti-flaming smoke-inhibiting agent provided by the invention can keep phosphinates smoke density it is low, without environmental hazard the advantages that base
On plinth, its flame retardant property in application material can be improved, and do not generate fragile materials, will not reduce to main material matrix machine
The influence of tool performance.Anti-flaming smoke-inhibiting agent to prepare raw material cheap and easy to get so that it is with higher application value.
In the above-mentioned technical solutions, there is R shown in formula (I)1And R2The phosphinates of substituent group, there is comparative maturity at present
Synthetic method, such as grignard reagent method, aluminum chloride-catalyzed reaction, free radical addition method, metal coordination catalysis addition process etc.,
Commercially available product.There is R in following embodiment in the present invention1And R2The phosphinates of substituent group is purchased from Deqing four seas
Work Co., Ltd.
Anti-flaming smoke-inhibiting agent of the invention may be added to that it is a variety of prepare in the high molecular raw material such as plastics or rubber, to obtain
Target material is obtained, to improve the anti-flammability of material, for example, being added to polyolefin homopolymer and copolymer, rubber, polyester, epoxy
Resin, polyurethane, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene oxide, styrene polymer and copolymer gather
Carbonic ester, acrylate copolymer, polyamide, polyacetals, epoxy resin is in the materials of main base.It can also use different poly-
The mixture of object, such as polyphenylene ether/styrene resin resin blends are closed, polyvinyl chloride/ABS contains methacrylonitrile and Alpha-Methyl benzene
The ABS and polyester/ABS or polycarbonate/ABS of ethylene.Above-mentioned polymer can cooperate other additives to be used together.In
It prepares in target material, other additives can be added, for example, plasticizer, lubricant, emulsifier, pigment, dyestuff, optical brightening
Agent, fire-proofing chemical, antistatic agent, foaming agent, filler, toughener, stabilizer, toughness modifier etc., it is different to enumerate.
In the process, there is R in anti-flaming smoke-inhibiting agent of the invention1And R2The phosphinates of substituent group will not be in high temperature
Flame retardant property is lost in process, in applied material, does not also find the generation of brittle substance.Below, with this
Application of the anti-flaming smoke-inhibiting agent of invention in the material based on polyvinyl chloride is illustrated.
In the present invention, have flame retardant property excellent in order to obtain, fragile materials are few in the material after processing, the material after processing
Expect the anti-flaming smoke-inhibiting agent of good mechanical property, it is preferable that the temperature of the also contacts is 240-280 DEG C.
Have flame retardant property excellent in order to obtain, fragile materials are few in the material after processing, the mechanical property of materials after processing
Good anti-flaming smoke-inhibiting agent, it is highly preferred that the condition of the also contacts includes: will have R shown in formula (I)1And R2Substituent group
Then phosphinates, tributyl tin and trioctylphosphine are kept the temperature in 240-250 DEG C of mixing 20-30min in 260-280 DEG C
1.5-2.5h。
In the present invention, R in formula (I)1And/or R2It can be alkyl or benzene replaced one of a variety of substituent groups
One of base, such as nitro, halogen, hydroxyl, amino are a variety of.
In the present invention, it is preferred to which the alkyl is unsubstituted or by one of halogen, hydroxyl, amino or a variety of
Replaced alkyl.
In the above-mentioned technical solutions, the type of alkyl can be able to be straight chained alkyl, or branch there are many selection
Alkyl.Alkyl, which is substituted position replaced base, can be 1 substitution there are many selection, be also possible to 2-6 and take
Generation.Also, quantity replaced substituent group can also there are many selections, for example, can be monosubstituted, it can also be polysubstituted,
Realize the present invention.
Phenyl be substituted base replaced position can there are many selection, it is o-, m-, pair substitution can be achieved the present invention.
Also, quantity replaced substituent group can also there are many selections, for example, can be monosubstituted, it can also be polysubstituted, it can be achieved
The present invention.
In order to reduce the halogen production for being known as poisonous gas of high-temp combustion, it is highly preferred that halogenic substituent is not contained in alkyl,
The alkyl is unsubstituted or by one of hydroxyl, amino or a variety of replaced alkyl.
In the present invention, it is preferred to which the phenyl is unsubstituted or by one of halogen, hydroxyl, amino or a variety of
Replaced phenyl.
In order to reduce the halogen production for being known as poisonous gas of high-temp combustion, it is highly preferred that halogenic substituent is not contained in alkyl,
The phenyl is unsubstituted or by one of hydroxyl, amino or a variety of replaced alkyl.
Formula (I) M can be common metal element, it is preferable that in order to have R in formula (I)1And R2The secondary phosphine of substituent group
Hydrochlorate is cheap and easy to get, it is preferable that M is Li, K, Na, Mg, Ca, Ba, Zn, Zr, B, Al, Si, Ti, Sn or Sb in formula (I).
In the present invention, it is highly preferred that in order to which there is R in formula (I)1And R2The phosphinates of substituent group is cheap and easy to get,
M is Ca or Al.
In the present invention, there is R1And R2The weight ratio of the phosphinates of substituent group, tributyl tin and trioctylphosphine can
It is adjusted in a wider range, the anti-flaming smoke-inhibiting agent in the application can be obtained.Have flame retardant property excellent in order to obtain, processing
Fragile materials are few in material afterwards, the good anti-flaming smoke-inhibiting agent of the mechanical property of materials after processing, have R shown in formula (I)1And R2
The weight ratio of the phosphinates of substituent group, tributyl tin and trioctylphosphine is 10:1-3:6-10.
It is highly preferred that having flame retardant property more excellent in order to obtain, fragile materials are less in the material after processing, after processing
The mechanical property of materials good anti-flaming smoke-inhibiting agent has R shown in formula (I)1And R2Phosphinates, the tributyl tin and three of substituent group
The weight ratio of n-octyl phosphine oxide is 10:1-3:8-10.
The present invention also provides a kind of anti-flaming smoke-inhibiting agents prepared according to the preparation method of previously described anti-flaming smoke-inhibiting agent.
Through the above technical solutions, anti-flaming smoke-inhibiting agent provided by the invention can keep phosphinates smoke density it is low,
On the basis of the advantages that without environmental hazard, its flame retardant property in application material can be improved, and do not generate fragile materials,
The influence to main material matrix mechanical performance will not be reduced.Anti-flaming smoke-inhibiting agent to prepare raw material cheap and easy to get so that its have it is higher
Application value.
Anti-flaming smoke-inhibiting agent of the invention may be added to that it is a variety of prepare in the high molecular raw material such as plastics or rubber, to obtain
Target material is obtained, to improve the anti-flammability of material, for example, being added to polyolefin homopolymer and copolymer, rubber, polyester, epoxy
Resin, polyurethane, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene oxide, styrene polymer and copolymer gather
Carbonic ester, acrylate copolymer, polyamide, polyacetals, epoxy resin is in the materials of main base.It can also use different poly-
The mixture of object, such as polyphenylene ether/styrene resin resin blends are closed, polyvinyl chloride/ABS contains methacrylonitrile and Alpha-Methyl benzene
The ABS and polyester/ABS or polycarbonate/ABS of ethylene.Above-mentioned polymer can cooperate other additives to be used together.In
It prepares in target material, other additives can be added, for example, plasticizer, lubricant, emulsifier, pigment, dyestuff, optical brightening
Agent, fire-proofing chemical, antistatic agent, foaming agent, filler, toughener, stabilizer, toughness modifier etc., it is different to enumerate.
In the process, there is R in anti-flaming smoke-inhibiting agent of the invention1And R2The phosphinates of substituent group will not be in high temperature
Flame retardant property is lost in process, in applied material, does not also find the generation of brittle substance.Below, with this
Application of the anti-flaming smoke-inhibiting agent of invention in the material based on polyvinyl chloride is illustrated.Anti-flaming smoke-inhibiting agent provided by the invention
It is particularly suitable for application as fire retardant to be added in the raw material of fire proofing, to obtain good mechanical property, fire-retardant, environmentally friendly is fire-retardant
Material.
For status, it is more one that current most of office spaces, which are no longer the houses of fixed armored concrete,
The working space split in building, anti-flaming smoke-inhibiting agent prepared by the present invention are highly suitable as preparation lease space material
Fire retardant use.
Further, if preparing flame-proof sheet material in this, as fire retardant, this flame-proof sheet material is then used for partition space,
The working space of lease is made, will meet significantly and lease space at present to fire-retardant, environmentally friendly, durable requirement.And it is of the invention
Cost is relatively low for anti-flaming smoke-inhibiting agent, can reduce the cost of manufacture in lease space indirectly, therefore, has very high popularization and application valence
Value.
The present invention will be described in detail by way of examples below.
Embodiment 1
Prepare anti-flaming smoke-inhibiting agent:
In parts by weight, by alkyl phosphinic acid shown in 10 parts of formulas (I), 1 part of tributyl tin and 6 parts of trioctylphosphines in
240 DEG C of mixing 20min, then in 260 DEG C of heat preservation 1.5h, wherein R1For methyl；R2For phenyl, M Al, n 3 is obtained fire-retardant
Smoke suppressant A1.
Embodiment 2
Prepare anti-flaming smoke-inhibiting agent:
In parts by weight, by alkyl phosphinic acid shown in 10 parts of formulas (I), 2 parts of tributyl tins and 8 parts of trioctylphosphines in
245 DEG C of mixing 25min, then in 270 DEG C of heat preservation 2h, wherein R1For n-propyl；R2For the isopropyl being optionally substituted by a hydroxyl group on 1, M
Anti-flaming smoke-inhibiting agent A2 is obtained for Al, n 3.
Embodiment 3
Prepare anti-flaming smoke-inhibiting agent:
In parts by weight, by alkyl phosphinic acid shown in 10 parts of formulas (I), 3 parts of tributyl tins and 10 parts of trioctylphosphines
In 250 DEG C of mixing 30min, then in 280 DEG C of heat preservation 2.5h, wherein R1For the n-hexyl replaced on 6 by chlorine；R2For by amino
Substituted methyl, M Al, n 3, obtains anti-flaming smoke-inhibiting agent A3.
Embodiment 4
Prepare anti-flaming smoke-inhibiting agent:
In parts by weight, by alkyl phosphinic acid shown in 10 parts of formulas (I), 2 parts of tributyl tins and 8 parts of trioctylphosphines in
200 DEG C of mixing 25min, then in 200 DEG C of heat preservation 2h, wherein R1For n-propyl；R2For the isopropyl being optionally substituted by a hydroxyl group on 1, M
Anti-flaming smoke-inhibiting agent A4 is obtained for Al, n 3.
Embodiment 5
Prepare anti-flaming smoke-inhibiting agent:
In parts by weight, by alkyl phosphinic acid shown in 10 parts of formulas (I), 2 parts of tributyl tins and 8 parts of trioctylphosphines in
300 DEG C of mixing 25min, then in 300 DEG C of heat preservation 2h, wherein R1 is n-propyl；R2 is the isopropyl being optionally substituted by a hydroxyl group on 1,
M is Al, and n 3 obtains anti-flaming smoke-inhibiting agent A5.
Comparative example 1
Anti-flaming smoke-inhibiting agent is prepared according to the method for embodiment 4, the difference is that mixing temperature and holding temperature are 150 DEG C,
Obtain anti-flaming smoke-inhibiting agent B1.
Comparative example 2
Anti-flaming smoke-inhibiting agent is prepared according to the method for embodiment 4, the difference is that mixing temperature and holding temperature are 350 DEG C,
Obtain anti-flaming smoke-inhibiting agent B2.
Comparative example 3
10 parts of alkyl phosphinic acids in embodiment 2 obtain anti-flaming smoke-inhibiting agent B3 in 270 DEG C of heat preservation 2.4h.
Comparative example 4
10 parts of alkyl phosphinic acids in embodiment 2, number are anti-flaming smoke-inhibiting agent B4.
Application examples 1
Anti-flaming smoke-inhibiting agent A1-A5 and B1-B4 are applied to respectively to prepare the plate of flame-proof polyvinyl chloride, preparation method is such as
Under:
In parts by weight, by 100 parts of PVC-SG5 type polyvinyl chloride, 125 parts of nanometer grade calcium carbonate, dimethyl tin oxide PVC
4.5 parts of stabilizer, 0.8 part of stearic acid, 20 parts of 2.8 parts of ACR K-123 modifying agent and corresponding anti-flaming smoke-inhibiting agent, prior to 130 DEG C
The mixed 1.2h of heat, then at 70 DEG C of cold mixed 30min, then in 180 DEG C of extrusion moldings.
Anti-flaming smoke-inhibiting agent therein is each independently A1-A5 and B1-B4, respectively corresponds to obtain the fire-retardant polychlorostyrene that number is
Ethylene plate a1-a5 and b1-b4.In addition, not adding the polyvinyl chloride of any anti-flaming smoke-inhibiting agent according further to above method preparation
Plate, as blank control.
Detect example 1
Analyze a1-a5 and b1-b4 flame-proof polyvinyl chloride plate and blank control polyvinyl-chloride plate material tensile strength and
Impact flexibility, examination criteria are as follows: according to GB/T1040.3-2006 sample preparation and detect tensile strength, examined with GB/T1043.1-2008
Survey impact flexibility.
It is found through detection, the tensile strength and impact flexibility of each plate obviously do not become relative to the trend of other plates
Change, i.e., tensile strength is high, and impact flexibility is also high.Wherein, there is apparent brittle fracture in b3 and b4, cause tensile strength and
Impact flexibility is poor, wherein b4 is worst, only the 20% of blank control sample；Tensile strength and impact in b1 and b2 is tough
Property be superior to b3, there is not apparent brittle fracture, still, tensile strength and impact flexibility are differed compared with blank control sample
It is larger, only 50% or so of blank control sample.
The tensile strength of other samples and the sequence from excellent to bad of impact flexibility are as follows: blank control sample, a2, a1, a3,
A4, a5, wherein a2 and blank control are close, and tensile strength and impact flexibility are 98% or more of blank control sample；A1 and
The tensile strength and impact flexibility of a3 is 95% or so of blank control sample；The tensile strength and impact flexibility of a4 and a5 is sky
88% or more of white control sample；Wherein the tensile strength of blank control sample is 62MPa.
Detect example 2
Oxygen index (OI), the cigarette for analyzing a1-a5 and b1-b4 flame-proof polyvinyl chloride plate and blank control polyvinyl-chloride plate material are close
Degree, wherein the standard of oxygen index (OI) test is GB/T2406.2-2009；The testing standard of smoke density is GB/T8627-2007.
The results show that the oxygen index (OI) of a1-a5 is all larger than 27%, belong to firing-difficult matter.Specifically, wherein oxygen index (OI) from height to
Low is successively a3, a2, a4, a5, a1, and the oxygen index (OI) difference that the oxygen index (OI) of oxygen index (OI) up to 42%, the a1 of a3 are 35%, b1-b4 is not
Greatly, 29% or so, wherein the oxygen index (OI) of blank control sample is 18%.
The results show that the smoke density of a1-a5 is not much different, in 45SDR hereinafter, the smoke density of b1-b4 is in 49-58SDR
Between, the smoke density of blank control sample is 67SDR.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of anti-flaming smoke-inhibiting agent, which is characterized in that including that will have R as shown in formula (I)1And R2Substituent group
Phosphinates, tributyl tin and trioctylphosphine in the 200-300 DEG C of also contacts the step of；
Wherein, in formula (I): R1For C1-C6 alkyl or phenyl；R2For C1-C6 alkyl or phenyl；M is metallic element, and n is from 1 to 4
Number so that Mn+It is metal cation, the charge of the cation is wherein assigned on n+ representation, and n is 1 to 4
Number.
2. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1, wherein the temperature of the also contacts is 240-
280℃。
3. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein the condition of the also contacts includes:
To there is R shown in formula (I)1And R2Phosphinates, tributyl tin and the trioctylphosphine of substituent group are mixed in 240-250 DEG C
20-30min, then in 260-280 DEG C of heat preservation 1.5-2.5h.
4. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein the alkyl be it is unsubstituted or by
One of halogen, hydroxyl, amino or a variety of replaced alkyl.
5. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein the phenyl be it is unsubstituted or by
One of halogen, hydroxyl, amino or a variety of replaced phenyl.
6. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein in formula (I) M be Li, K, Na, Mg,
Ca, Ba, Zn, Zr, B, Al, Si, Ti, Sn or Sb.
7. the preparation method of anti-flaming smoke-inhibiting agent according to claim 6, wherein M is Ca or Al.
8. the preparation method of anti-flaming smoke-inhibiting agent according to claim 7, wherein have R shown in formula (I)1And R2Substituent group
Phosphinates, tributyl tin and trioctylphosphine weight ratio be 10:1-3:6-10.
9. the preparation method of anti-flaming smoke-inhibiting agent according to claim 8, wherein have R shown in formula (I)1And R2Substituent group
Phosphinates, tributyl tin and trioctylphosphine weight ratio be 10:1-3:8-10.
10. a kind of anti-flaming smoke-inhibiting agent of the preparation method preparation of -9 described in any item anti-flaming smoke-inhibiting agents according to claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104736549A (en) * | 2013-07-24 | 2015-06-24 | 科聚亚公司 | Phosphorus containing flame retardants |
| CN105085984A (en) * | 2015-08-14 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant and flame-retardant high polymer material comprising same |
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- 2017-10-20 CN CN201710982228.9A patent/CN107955208B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104736549A (en) * | 2013-07-24 | 2015-06-24 | 科聚亚公司 | Phosphorus containing flame retardants |
| CN105085984A (en) * | 2015-08-14 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Halogen-free flame retardant and flame-retardant high polymer material comprising same |
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