CN107955208A - 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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- CN107955208A CN107955208A CN201710982228.9A CN201710982228A CN107955208A CN 107955208 A CN107955208 A CN 107955208A CN 201710982228 A CN201710982228 A CN 201710982228A CN 107955208 A CN107955208 A CN 107955208A
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- Prior art keywords
- inhibiting agent
- flaming smoke
- alkyl
- preparation
- smoke
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- 239000000779 smoke Substances 0.000 title claims abstract description 76
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 alkyl phosphinate Chemical compound 0.000 claims abstract description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 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
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 46
- 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 2
- 239000003063 flame retardant Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000013068 control sample Substances 0.000 description 10
- 239000004800 polyvinyl chloride 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
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 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
- 239000000654 additive Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000004079 fireproofing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000005764 inhibitory process Effects 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
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004425 Makrolon Substances 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
- 230000000996 additive effect Effects 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
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 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
- 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
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development 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
- 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
- 229910000073 phosphorus hydride Inorganic materials 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
- 238000005464 sample preparation method Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of anti-flaming smoke-inhibiting agent and preparation method thereof, including will be if alkyl phosphinate, tributyl tin and the trioctylphosphine shown in formula (I) are in 200 300 DEG C of also contacts the step of；Wherein, in formula (I)：R1For C1 C6 alkyl or phenyls；R2For C1 C6 alkyl or phenyls；M is metallic element, and n is the number 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, its fire resistance in application material can be improved, and fragile materials are not produced, the influence to main material matrix mechanical performance will not be reduced.The preparing raw material of anti-flaming smoke-inhibiting agent is cheap and easy to get so that it has higher application value.
Description
Technical field
The present invention relates to fire retardant, and in particular, to a kind of anti-flaming smoke-inhibiting agent and preparation method thereof.
Background technology
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 the personnel often accommodated in these spaces are very much, 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 halogenated flame retardant that generally uses still use extensively now, the problems such as producing bioxin because burning and after fire
Meeting produce the reason such as poison gas, have been to be concerned by more and more people its harm to human health and environment.At present, secondary phosphine
Hydrochlorate has the advantages that dosage is few, and smoke density is low, no environmental hazard, has been to be concerned by more and more people.But patent document US
Disclosed in 2007/0029532, phosphonate may cause to decompose in process, and can produce in process frangible
Unavailable material, therefore, limit application of the phosphonate as fire retardant.
Patent document CN107207779A, it is entitled：The flame-retardant polymer of phosphorus compound and melam comprising heat treatment
Composition discloses, by will heat the fire retardant of some phosphonates acquisitions at a temperature of 200 DEG C or higher and be used as fire-retardant
The melam or melam derivative of synergist are attached to polymer and can be easily worked under some harsh conditions.But because
Melam or melam derivative are not readily synthesized, and increase the fire retardant application cost of addition melam.
Therefore, on the basis of the advantages that how providing a kind of anti-flaming smoke-inhibiting agent, its smoke density is low in guarantee, no environmental hazard,
The production cost of material is reduced, improves its fire resistance in application material, and do not produce fragile materials, will not be reduced pair
The influence of main material matrix mechanical performance particularly toughness, is a technical problem to be solved urgently.
The content 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 fire resistance 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 these goals, the present invention provides a kind of preparation method of anti-flaming smoke-inhibiting agent, including will be such as formula (I) institute
Alkyl phosphinate, tributyl tin and the trioctylphosphine shown is in the 200-300 DEG C of also contacts the step of；Wherein, formula (I)
In：R1For C1-C6 alkyl or phenyls；R2For C1-C6 alkyl or phenyls；M is metallic element, and n is the number from 1 to 4 so that Mn+It is
Metal cation, is wherein assigned to the electric charge of the cation on n+ representations, and the number that n is 1 to 4.
The present invention also provides the flame-retardant smoke inhibition that a kind of 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 environmental hazard, it is possible to increase its fire resistance in application material, and fragile materials are not produced,
The influence to main material matrix mechanical performance will not be reduced.The preparing raw material of anti-flaming smoke-inhibiting agent is cheap and easy to get so that it is with higher
Application value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of anti-flaming smoke-inhibiting agent, including will as the alkyl phosphinate shown in formula (I),
Tributyl tin and trioctylphosphine 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 phenyls；M is metallic element, and n is the number from 1 to 4 so that Mn+It is metal cation, wherein n+
The electric charge of the cation is assigned on representation, and the number that n is 1 to 4.
Raw material type and preparation process, those skilled in the art are selected to obtain fire-retardant suppression 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, it is possible to increase its fire resistance in application material, and fragile materials are not produced, it will not reduce to main material matrix machine
The influence of tool performance.The preparing raw material of anti-flaming smoke-inhibiting agent is cheap and easy to get so that its application value with higher.
In the above-mentioned technical solutions, the alkyl phosphinate shown in formula (I), there is the synthetic method of comparative maturity, example at present
Such as grignard reagent method, aluminum chloride-catalyzed reaction, free radical addition method, metal coordination catalysis addition process etc., are commercially available product.This
Alkyl phosphinate in invention in following embodiment is purchased from Deqing four seas Chemical Co., Ltd..
The present invention anti-flaming smoke-inhibiting agent may be added to that it is a variety of prepare in the high molecular raw material such as plastics or rubber, so as 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 compound, such as polyphenylene ether/styrene resin resin blends, polyvinyl chloride/ABS, containing methacrylonitrile and Alpha-Methyl benzene
The ABS of ethene, and polyester/ABS or makrolon/ABS.Above-mentioned polymer can coordinate other additives to be used together.
Prepare in target material, other additives can be added, for example, plasticizer, lubricant, emulsifying agent, pigment, dyestuff, optical brightening
Agent, fire-proofing chemical, antistatic additive, foaming agent, filler, toughener, stabilizer, toughness modifier etc., differ and enumerate.
In the process, the alkyl phosphinate in anti-flaming smoke-inhibiting agent of the invention will not lose in high temperature working processes
Fire resistance, in the material applied, does not find the generation of brittle material yet.Below, with the flame-retardant smoke inhibition of the present invention
Agent is illustrated in polyvinyl chloride for the application in the material of main body.
In the present invention, excellent with fire resistance 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.
Excellent with fire resistance 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：By the alkyl phosphinate shown in formula (I), three fourths
Ji Xi and trioctylphosphine mix 20-30min in 240-250 DEG C, then keep the temperature 1.5-2.5h in 260-280 DEG C.
In the present invention, R in formula (I)1And/or R2Can be by a kind of alkyl or benzene substituted in a variety of substituents
One or more in base, such as nitro, halogen, hydroxyl, amino.
In the present invention, it is preferred to the alkyl is unsubstituted or by the one or more in halogen, hydroxyl, amino
The alkyl substituted.
In the above-mentioned technical solutions, the type of alkyl can have multiple choices, can be straight chained alkyl, or side chain
Alkyl.Alkyl is substituted the position that base is substituted can multiple choices, can be 1 substitution or 2-6 take
Generation.Also, the quantity that substituent is substituted can also have multiple choices, for example, can be monosubstituted, can also be polysubstituted,
Realize the present invention.
Phenyl, which is substituted the position that base is substituted, can a multiple choices, it is o-, m-, to substitution the present invention can be achieved.
Also, the quantity that substituent is substituted can also have multiple choices, for example, can be monosubstituted, can also be polysubstituted, it can be achieved
The present invention.
High-temp combustion is halogen to be known as the production of poisonous gas in order to reduce, it is highly preferred that halogenic substituent is not contained in alkyl,
The alkyl is by alkyl that is unsubstituted or being substituted by the one or more in hydroxyl, amino.
In the present invention, it is preferred to the phenyl is unsubstituted or by the one or more in halogen, hydroxyl, amino
The phenyl substituted.
High-temp combustion is halogen to be known as the production of poisonous gas in order to reduce, it is highly preferred that halogenic substituent is not contained in alkyl,
The phenyl is by alkyl that is unsubstituted or being substituted by the one or more in hydroxyl, amino.
Formula (I) M can be common metal element, it is preferable that in order to which the alkyl phosphinate in formula (I) is cheap and easy to get,
Preferably, 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 the alkyl phosphinate in formula (I) is cheap and easy to get, M is Ca or Al.
In the present invention, the weight ratio of alkyl phosphinate, tributyl tin and trioctylphosphine can be in relative broad range
It is adjusted, can obtain the anti-flaming smoke-inhibiting agent in the application.It is excellent with fire resistance in order to obtain, in the material after processing easily
The matter that minces is few, the good anti-flaming smoke-inhibiting agent of the mechanical property of materials after processing, alkyl phosphinate, tributyl tin shown in formula (I)
Weight ratio with trioctylphosphine is 10：1-3：6-10.
It is highly preferred that having in order to obtain, fire resistance is more excellent, and fragile materials are less in the material after processing, after processing
The good anti-flaming smoke-inhibiting agent of the mechanical property of materials, the weight of alkyl phosphinate, tributyl tin and trioctylphosphine shown in formula (I)
Amount is than being 10：1-3：8-10.
The present invention also provides a kind of anti-flaming smoke-inhibiting agent 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 environmental hazard, it is possible to increase its fire resistance in application material, and fragile materials are not produced,
The influence to main material matrix mechanical performance will not be reduced.The preparing raw material of anti-flaming smoke-inhibiting agent is cheap and easy to get so that it is with higher
Application value.
The present invention anti-flaming smoke-inhibiting agent may be added to that it is a variety of prepare in the high molecular raw material such as plastics or rubber, so as 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 compound, such as polyphenylene ether/styrene resin resin blends, polyvinyl chloride/ABS, containing methacrylonitrile and Alpha-Methyl benzene
The ABS of ethene, and polyester/ABS or makrolon/ABS.Above-mentioned polymer can coordinate other additives to be used together.
Prepare in target material, other additives can be added, for example, plasticizer, lubricant, emulsifying agent, pigment, dyestuff, optical brightening
Agent, fire-proofing chemical, antistatic additive, foaming agent, filler, toughener, stabilizer, toughness modifier etc., differ and enumerate.
In the process, the alkyl phosphinate in anti-flaming smoke-inhibiting agent of the invention will not lose in high temperature working processes
Fire resistance, in the material applied, does not find the generation of brittle material yet.Below, with the flame-retardant smoke inhibition of the present invention
Agent is illustrated in polyvinyl chloride for the application in the material of main body.Anti-flaming smoke-inhibiting agent provided by the invention is particularly suitable for application as
Fire retardant is added in the raw material of fire proofing, so that good mechanical property is obtained, fire-retardant, environmentally friendly fire proofing.
For present situation, current most of office spaces are no longer the houses of fixed armored concrete, are more one
The working space split in building, anti-flaming smoke-inhibiting agent prepared by the present invention are highly suitable as preparing 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 that lease space is to fire-retardant, environmentally friendly, durable requirement at present significantly.And the present invention's
Anti-flaming smoke-inhibiting agent cost is relatively low, can reduce the cost of manufacture in lease space indirectly, therefore, have very high popularization and application valency
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 the 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 keep the temperature 1.5h in 260 DEG C, wherein, R1For methyl；R2For phenyl, M Al, n 3, obtains fire-retardant
Smoke suppressant A1.
Embodiment 2
Prepare anti-flaming smoke-inhibiting agent：
In parts by weight, by the 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 keep the temperature 2h in 270 DEG C, wherein, R1For n-propyl；R2For the isopropyl being optionally substituted by a hydroxyl group on 1, M
For Al, n 3, obtains anti-flaming smoke-inhibiting agent A2.
Embodiment 3
Prepare anti-flaming smoke-inhibiting agent：
In parts by weight, by the alkyl phosphinic acid shown in 10 parts of formulas (I), 3 parts of tributyl tins and 10 parts of trioctylphosphines
30min is mixed in 250 DEG C, then keeps the temperature 2.5h in 280 DEG C, wherein, R1For the n-hexyl substituted by chlorine on 6；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 the 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 keep the temperature 2h in 200 DEG C, wherein, R1For n-propyl；R2For the isopropyl being optionally substituted by a hydroxyl group on 1, M
For Al, n 3, obtains anti-flaming smoke-inhibiting agent A4.
Embodiment 5
Prepare anti-flaming smoke-inhibiting agent：
In parts by weight, by the 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 keep the temperature 2h in 300 DEG C, 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
Method according to embodiment 4 prepares anti-flaming smoke-inhibiting agent, the difference is that mixing temperature and holding temperature are 150 DEG C,
Obtain anti-flaming smoke-inhibiting agent B1.
Comparative example 2
Method according to embodiment 4 prepares anti-flaming smoke-inhibiting agent, 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 keep the temperature 2.4h in 270 DEG C, obtain anti-flaming smoke-inhibiting agent B3.
Comparative example 4
10 parts of alkyl phosphinic acids in embodiment 2, numbering are anti-flaming smoke-inhibiting agent B4.
Application examples 1
Anti-flaming smoke-inhibiting agent A1-A5 and B1-B4 are applied to the plate for preparing flame-proof polyvinyl chloride respectively, preparation method is such as
Under：
In parts by weight, by 100 parts of PVC-SG5 types polyvinyl chloride, 125 parts of nanometer grade calcium carbonate, dimethyl tin oxide PVC
4.5 parts of stabilizer, 0.8 part of stearic acid, 2.8 parts of ACR K-123 modifying agent and corresponding 20 parts of 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 the corresponding fire-retardant polychlorostyrene for obtaining numbering and being
Ethylene plate a1-a5 and b1-b4.In addition, the polyvinyl chloride for not adding any anti-flaming smoke-inhibiting agent is prepared according further to the above method
Plate, as blank control.
Detect example 1
Analyze a1-a5 and b1-b4 flame-proof polyvinyl chlorides plate and blank control polyvinyl-chloride plate material tensile strength and
Impact flexibility, examination criteria are：According to GB/T1040.3-2006 sample preparations and tensile strength is detected, is examined with GB/T1043.1-2008
Survey impact flexibility.
Find after testing, the tensile strength and impact flexibility of each plate substantially 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 obvious brittle fracture in b3 and b4, cause tensile strength and
Impact flexibility is poor, wherein, b4 is worst, is 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 obvious brittle fracture, still, tensile strength and impact flexibility are differed compared with blank control sample
It is larger, it is only 50% or so of blank control sample.
The tensile strength of other samples and the order from excellent to bad of impact flexibility are：Blank control sample, a2, a1, a3,
A4, a5, wherein, a2 is approached with blank control, and tensile strength and impact flexibility are more than the 98% 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
More than the 88% 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 chlorides 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 higher than 27%, belong to firing-difficult matter.Specifically, wherein, oxygen index (OI) from height to
Low is a3, a2, a4, a5, a1 successively, and the oxygen index (OI) that the oxygen index (OI) of oxygen index (OI) up to 42%, the a1 of a3 are 35%, b1-b4 differs 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 below 45SDR, 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 described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of anti-flaming smoke-inhibiting agent, it is characterised in that including will be such as the alkyl phosphinate shown in formula (I), three
Butyl tin and trioctylphosphine are in the 200-300 DEG C of also contacts the step of；
Wherein, in formula (I)：R1For C1-C6 alkyl or phenyls；R2For C1-C6 alkyl or phenyls；M is metallic element, and n is from 1 to 4
Number so that Mn+It is metal cation, the electric charge of the cation is wherein assigned on n+ representations, 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：
Alkyl phosphinate, tributyl tin and trioctylphosphine shown in formula (I) is mixed into 20-30min in 240-250 DEG C, then
1.5-2.5h is kept the temperature in 260-280 DEG C.
4. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein, the alkyl for it is unsubstituted or by
The alkyl that one or more in halogen, hydroxyl, amino are substituted.
5. the preparation method of anti-flaming smoke-inhibiting agent according to claim 1 or 2, wherein, the phenyl for it is unsubstituted or by
The phenyl that one or more in halogen, hydroxyl, amino are substituted.
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, alkyl phosphinate shown in formula (I), three
Butyl tin and the weight ratio of trioctylphosphine are 10：1-3：6-10.
9. the preparation method of anti-flaming smoke-inhibiting agent according to claim 8, wherein, alkyl phosphinate shown in formula (I), three
Butyl tin and the weight ratio of trioctylphosphine are 10：1-3：8-10.
A kind of 10. anti-flaming smoke-inhibiting agent prepared according to the preparation method of claim 1-9 any one of them anti-flaming smoke-inhibiting agents.
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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
- 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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