CN104231262B - A kind of preparation method of organophosphor copolymerization fire-retardant polyamide material - Google Patents
A kind of preparation method of organophosphor copolymerization fire-retardant polyamide material Download PDFInfo
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- CN104231262B CN104231262B CN201410489935.0A CN201410489935A CN104231262B CN 104231262 B CN104231262 B CN 104231262B CN 201410489935 A CN201410489935 A CN 201410489935A CN 104231262 B CN104231262 B CN 104231262B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 43
- 239000004952 Polyamide Substances 0.000 title claims abstract description 40
- 229920002647 polyamide Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 150000004985 diamines Chemical class 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 150000001721 carbon Chemical group 0.000 claims description 42
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 41
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 38
- 125000001118 alkylidene group Chemical group 0.000 claims description 31
- -1 alicyclic diamine Chemical class 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 150000003951 lactams Chemical class 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 241001597008 Nomeidae Species 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 10
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims description 4
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- VJHDPVWEDUCKRQ-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O.NCCCCCCCCCCCC(O)=O VJHDPVWEDUCKRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 3
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 claims description 3
- WULPUQZASCZTPO-UHFFFAOYSA-N azacycloundecan-2-one Chemical compound O=C1CCCCCCCCCN1 WULPUQZASCZTPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 1
- 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 14
- 238000000034 method Methods 0.000 abstract description 7
- 239000010409 thin film Substances 0.000 abstract description 7
- 238000009941 weaving Methods 0.000 abstract description 7
- 229920006351 engineering plastic Polymers 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000004079 fireproofing Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 0 CC(*(C1CC1)C(*C(*)P(Oc(cccc1)c1-c1c(C)cccc1)=O)=O)I Chemical compound CC(*(C1CC1)C(*C(*)P(Oc(cccc1)c1-c1c(C)cccc1)=O)=O)I 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000021003 saturated fats Nutrition 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- CIZDDCNPJDBQMU-UHFFFAOYSA-N Cc1c(C(C=CC=C2)/C2=[O]\OC)cccc1 Chemical compound Cc1c(C(C=CC=C2)/C2=[O]\OC)cccc1 CIZDDCNPJDBQMU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to fire proofing field, be specifically related to a kind of for weaving, the preparation method of the organophosphor copolymerization fire-retardant polyamide material of engineering plastics, thin film.The preparation method of this organophosphor copolymerization fire-retardant polyamide material, specifically includes following steps: fire retardant is reacted by (1) in advance with diamines monomer, prepares performed polymer；(2) monomer, catalyst and described performed polymer will be polymerized and add reactor, prepare organophosphor copolymerization fire-retardant polyamide material.This organophosphor copolymerization fire-retardant polyamide material that the present invention provides, the addition of reactive flame retardant is little, it is not necessary to adding synergistic flame retardant, in preparation process, viscosity is controlled, the serviceability of the polymer that end reaction obtains is good, may be used for the every field such as weaving, engineering plastics, thin film.Meanwhile, raw material usage amount is few, and technique is simple, low cost, and exploitativeness is high, and the fire resistance of the product made is high.
Description
Technical field
The present invention relates to fire proofing field, be specifically related to a kind of for weaving, the organophosphor copolymerization of engineering plastics, thin film
The preparation method of fire-retardant polyamide material.
Background technology
Polyamide (such as PA6, PA66) has many excellent performances, is widely used in the necks such as weaving, thin film, engineering plastics
Territory.But polyamide itself does not has anti-flammability, fire may be caused.Therefore Flameproof polyamide always polyamide industry is ground
The problem studied carefully.
Polyamide is fire-retardant at present is generally divided into two kinds of ways from technological angle, and one is after polymerizing polyamide, adds resistance
Combustion agent and relevant synergistic flame retardant, be blended processing；Another kind is to introduce fire-retardant component in polyamide polymerization process, and copolymerization adds
Work.
Processing mode is blended, adds fire retardant ratio greatly, reduce mechanics and the electric property of polyamide self；And can not use
In textile industry and thin film industry.
It is similar to copolymerization processing mode at present, as (201180022888.3) such as BASF AG introduce fire-retardant group of copolymerization
Part polymerization efficiency is low, complex process, and cost is high.
Patent (201410056761.9) also discloses that a kind of scheme of fire-retardant nylon, but this scheme is in the preparation,
All raw materials are simultaneously introduced reactor react, can not get the material that viscosity is controlled, also need to add at polymerization process simultaneously
Entering the synergistic flame retardant of vast scale, cost of material is higher, and PA6 viscosity is difficult to control, and fire-retardant effective ingredient ratio is done the highest,
Material is caused to be difficult to apply to weaving and film applications.
Summary of the invention
It is an object of the invention to provide a kind of organophosphor copolymerization fire-retardant polyamide material, the addition of reactive flame retardant
Little, it is not necessary to adding synergistic flame retardant, in preparation process, viscosity is controlled, the serviceability of the polymer that end reaction obtains
Good, may be used for the every field such as weaving, engineering plastics, thin film.Meanwhile, raw material usage amount is few, and technique is simple, and low cost can
Implementation is high, and the fire resistance of the product made is high.
The present invention is achieved in that the preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material, specifically include as
Lower step:
(1) in advance fire retardant is prepared performed polymer with diamines monomer or aminoacid carboxylic class monomer reaction；
(2) monomer, catalyst and performed polymer will be polymerized and add reactor, prepare organophosphor copolymerization Flameproof polyamide material
Material.
In the present invention, in advance fire retardant and diamines monomer or aminoacid carboxylic class monomer reaction, obtaining performed polymer, this is pre-
With Amino End Group on aggressiveness, then performed polymer is added in polymerization monomer with the form of fire retardant, participate in poly-under catalyst action
Close reaction, so add with the form of performed polymer that fire retardant reaction process can realize reacting controlled, viscosity is controlled, generation point
Son amount is the most controlled, obtains the polyamide polymer that effective fire-retardant unit content is controlled, and this polyamide polymer can be well
For thin film and field of textiles, its excellent flame retardancy simultaneously.
In prior art, be to be simultaneously introduced all of raw material in reactor to react, and if will polymerization monomer and
When fire retardant is simultaneously introduced, the amido in polymerization monomer and the carboxyl in fire retardant can react, and lose activity, and contain
The compound of carboxyl is inherently used as the envelope of polymerization process and breaks, and as reaction terminating agent, polyreaction cannot continue, and can not get gluing
Spend controlled material；From the point of view of course of reaction, and each strand to may participate in the effective fire-retardant unit of polymerization limited, can not get
The more fire proofing of high fire-retardance demand.
As a example by caprolactam, caprolactam polycondensation reaction mechanism is as follows:
1, polyamide belongs to step-reaction polymerization:
(1) first caprolactam hydrolysis generates glycine
(2) glycine Step Condensation
(3) nitrogen-atoms on amino is to the electrophilic attack of caprolactam, makes strand increase
The speed ratio amino of caprolactam ring-opening polymerisation and carboxyl are faster from the speed of polycondensation, and mainly hydrolysis gathers
Close, therefore at the Amino End Group of progressively polymerization process significant proportion to be retained, if Amino End Group and carboxyl react in advance, polycondensation process
By extreme influence, even stop, can not get the polymer of higher molecular weight, be therefore difficult to produce the variety classes that viscosity is controlled
Polycaprolactam.From the point of view of course of reaction, and each strand to may participate in the effective fire-retardant unit of polymerization limited, can not get
The more fire proofing of high fire-retardance demand.
Further, in step (1),
Described fire retardant isOr withDerivant for matrix；
Wherein said R1 and R2 is the alkylidene of 1-10 carbon atom, or any one in R1 and R2 is H；X1, X2 are
H or 1-4 may replace the halogen of H on phenyl ring；
Described diamines monomer is hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamidogen, dodecamethylene diamine, aliphatic series C6
Any one in C20 Alkylenediamine, aromatic diamine or alicyclic diamine.
Further, in step (1), in production, the mol ratio controlling fire retardant and diamines monomer is 1:(1-10)；
Product is the mixture of performed polymer and amine salt, and wherein performed polymer and amine salt all contain Amino End Group.
Further, in step (1), in advance described fire retardant and diamines monomer are reacted when preparing described performed polymer,
Also can add aminocarboxylic acrylic monomer；
When preparing described performed polymer, described aminocarboxylic acrylic monomer and described diamines monomer are simultaneously introduced and described resistance
Combustion agent reaction, or be individually added into described fire retardant and react with described diamines monomer；
Described aminocarboxylic acrylic monomer is the compound omega-amino carboxylic acid that lactams open loop obtains, or, omega-amino carboxylic
Acid.
Further, described aminocarboxylic acrylic monomer is the ω position straight chain saturated fat by amino substituted carbon number 4-18
Aliphatic carboxylic acid, 6-aminocaprolc acid, 11-amino undecanoic acid, 12 amino dodecanoic acid or PAMBA.
Further, in step (2), specifically include following steps:
A. polymerization monomer and catalyst are added reactor, evacuation, be filled with nitrogen, be malleation shape in keeping reactor
State；
B. reacting by heating still, controls reactor temperature and is 240-290 DEG C, after pressure is 0.01-1.0MPa, starts stirring
Continuously stirred 6-14 hour of device；
C. reducing mixing speed, it is-0.01 to-0.1MPa that reactor is evacuated to vacuum, then inflated with nitrogen is to normal pressure
The described performed polymer of the 1.5%-20% of material total amount in rear interpolation reactor；
The most again being evacuated to vacuum is-0.01 to-0.1MPa, and reactor temperature is continually maintained in 240-290 DEG C,
Copolyreaction 15-150 minute；
The most finally being filled with nitrogen, control reacting kettle inner pressure is 0.02-0.3MPa, discharges material, cooling, pelletizing, extraction,
It is dried to obtain end product.
Further, in step a, the addition of described polymerization monomer is 5-65 times of described fire retardant weight, described in urge
The addition of agent is the 1% of described polymerization monomer weight.
Further, in step a, described polymerization monomer is caprolactam, caprinolactam, 11 lactams, acyl in 12
Amine and possess the various lactam monomers of lactams feature, or its any one derivant；
Or, it is possible to the binary acid of participation copolymerization or binary amine compound: hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane
Diamidogen, dodecamethylene diamine, adipic acid, decanedioic acid, Azelaic Acid, heneicosanedioic acid, dodecanedioic acid, p-phthalic acid, isophthalic two
Formic acid or their derivant, and other aliphatic series and aromatic dicarboxylic acids, and aliphatic series C6 C20 Alkylenediamine, aromatic diamine
Or one or more in alicyclic diamine；
Or, with caprolactam as principal monomer, with binary acid or the binary amine compound that can participate in copolymerization above
In any one or a few copolymerization combining form.
Further, in step b, described temperature is 260-280 DEG C, pressure is 0.05-0.8MPa, and mixing time is 8-9
Hour；
In step c, described vacuum is-0.01 to-0.06MPa.
Further, in step d, described vacuum is-0.01 to-0.06MPa, and reactor temperature is 260-270 DEG C,
The time of copolyreaction is 20-90 minute；
In step e, controlling described reacting kettle inner pressure is 0.04-0.0.15MPa.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material, specifically includes following steps:
(1) in advance fire retardant is reacted with diamines monomer, prepare performed polymer.
Preferably, described fire retardant isOr withFor matrix
Derivant；
Wherein said R1And R2It is the alkylidene of 1-10 carbon atom；
Or one of them in R1 and R2 is H；X1、X2The halogen of H on phenyl ring is may replace, such as Br etc. for H or 1-4.
Preferably, described fire retardant and derivant thereof are following several:
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkyl of H or 1-10 carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkylidene of 1-10 carbon atom；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is 1-10 carbon atom
Alkyl；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, and R2 is H or 1-10
The alkyl of carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is H or 1-10 carbon atom
Alkyl；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the Asia of 1-10 carbon atom
Alkyl；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is that 1-10 carbon is former
The alkyl of son；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, R2 be H or
The alkyl of 1-10 carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkane of H or 1-10 carbon atom
Base；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the Asia of 1-10 carbon atom
Alkyl；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is 1-10 carbon
The alkyl of atom；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, and R2 is H or 1-10
The alkyl of individual carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is H or 1-10 carbon atom
Alkyl；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the Asia of 1-10 carbon atom
Alkyl；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is 1-10
The alkyl of carbon atom；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, R2 be H or
The alkyl of 1-10 carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is H or 1-10 carbon atom
Alkyl；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkylene of 1-10 carbon atom
Base；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is that 1-10 carbon is former
The alkyl of son；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, and R2 is H or 1-
The alkyl of 10 carbon atoms；
R1 is the alkylidene of 1-10 carbon atom, and R2 is H or 1-10 carbon atom
Alkyl；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkylene of 1-10 carbon atom
Base；
R1 and R2 is respectively the alkylidene of 1-10 carbon atom, and R3 is 1-10 carbon
The alkyl of atom；
R1 and R3 is respectively the alkylidene of 1-10 carbon atom, and R2 is H or 1-10
The alkyl of individual carbon atom；
R1 is the alkylidene of 1-10 carbon atom, and R2 is the alkylidene of 1-10 carbon atom.
In the present invention, fire retardant is most preferably DDP,
Preferably, described diamines monomer is hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamidogen, dodecamethylene diamine, fat
Race C6—C20Any one in Alkylenediamine, aromatic diamine or alicyclic diamine and derivant thereof；
It is highly preferred that diamines monomer is:Wherein n is 1-20, can select one of which or
Several.This programme is most preferably
In step (1), in production, the mol ratio controlling fire retardant and diamines monomer is 1:(1-10)；
Product is the mixture of performed polymer and amine salt, and wherein performed polymer and amine salt all contain Amino End Group, fire retardant and
The one-tenth salt product of diamines monomer can also follow-up be polymerized monomer and react, when reaction, become salt product and be polymerized monomer
Provide the Amino End Group of standby activity in follow-up polymerization process pre-ionization, Amino End Group again with remaining lactams electrophilic reaction.So, in system
The amine salt simultaneously produced in the product of standby performed polymer has no adverse effect for whole course of reaction, and it also can participate in reaction transfer
Turn to final purpose product.
In advance described fire retardant and diamines monomer are reacted when preparing described performed polymer, also include adding aminocarboxylic acids
Monomer；
Preferably, when preparing performed polymer, described aminocarboxylic acrylic monomer and described diamines monomer are simultaneously introduced and institute
State fire retardant reaction, or be individually added into described fire retardant and react with described diamines monomer；
Described aminocarboxylic acrylic monomer is the compound omega-amino carboxylic acid that lactams open loop obtains, or, omega-amino carboxylic
Acid.
Preferably, described aminocarboxylic acrylic monomer is the ω position straight chain saturated fat by amino substituted carbon number 4-18
Race's carboxylic acid, 6-aminocaprolc acid, 11-amino undecanoic acid, 12 amino dodecanoic acid or PAMBA.
The fire retardant of all above type and diamines monomer reaction, the polyreaction being between carboxyl and amino, with
As a example by fire retardant (DDP) and hexamethylene diamine, its reaction is as follows:
Prepolymerization becomes performed polymer overall reaction as follows:
Reaction terminates, and its product is performed polymer and DDP hexamethylene diamine salt mixture, preferably controls DDP and hexamethylene diamine in reaction
Mol ratio is 1:(1-10), either performed polymer still becomes salt product, all contains Amino End Group.
(2) monomer, catalyst and described performed polymer will be polymerized and add reactor, prepare organophosphor copolymerization Flameproof polyamide
Material.
Specifically include following steps:
A. polymerization monomer and catalyst are added reactor, evacuation, be filled with nitrogen, be malleation shape in keeping reactor
State；
Wherein, in being polymerized monomer preferably caprolactam, caprinolactam, 11 lactams, lauric lactam and possessing
The various lactam monomers of amide feature, or its any one derivant；
Or, it is possible to the binary acid of participation copolymerization or binary amine compound: hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane
Diamidogen, dodecamethylene diamine, adipic acid, decanedioic acid, Azelaic Acid, heneicosanedioic acid, dodecanedioic acid, p-phthalic acid, isophthalic two
Formic acid or their derivant, and other aliphatic series and aromatic dicarboxylic acids, and aliphatic series C6—C20Alkylenediamine, aromatic diamine
Or one or more in alicyclic diamine；
Or, with arbitrary lactams as principal monomer, with various lactams, binary acid or two that can participate in copolymerization above
Any one or a few copolymerization combining form in unit's aminated compounds.
In the present invention, fire retardant is most preferably caprolactam.
The addition of catalyst is the 1% of polymerization monomer weight, and the addition of performed polymer is the 1.5-of polymerization monomer weight
20%, preferably 5-15%.
Preferably, the addition of described polymerization monomer, catalyst and performed polymer is than for 94:1:5.
B. reacting by heating still, controls reactor temperature and is 240-290 DEG C, after pressure is 0.01-1.0MPa, starts stirring
Continuously stirred 6-14 hour of device；
Preferably, described temperature be 260-280 DEG C, pressure be 0.05-0.8MPa.
Wherein, the size of the reaction molecular amount obtained as required, the continuously stirred time is according to different pressure and temperature
The size of degree determines, under the conditions of equal temperature and pressure, its mixing time of bigger molecular weight is longer, less molecular weight
Mixing time is less；During churning, the temperature and pressure in reactor is definite value.
C. reduce mixing speed, reactor is evacuated to vacuum for-0.01 to-0.1MPa again inflated with nitrogen to after normal pressure
The described performed polymer of the 1.5%-20% of material total amount in interpolation reactor；
Preferably, vacuum is-0.01 to-0.06MPa.
The most again being evacuated to vacuum is-0.01 to-0.1MPa, and reactor temperature is continually maintained in 240-290 DEG C,
Copolyreaction 15-150 minute；
Preferably, described vacuum is-0.01 to-0.06MPa, and reactor temperature is 260-270 DEG C, copolyreaction
Time is 20-90 minute.
The most finally being filled with nitrogen, control reacting kettle inner pressure is 0.02-0.3MPa, discharges material, cooling, pelletizing, extraction,
It is dried to obtain end product.
Preferably, controlling described reacting kettle inner pressure is 0.04-0.0.15MPa.
In this technique, it is also possible to by performed polymer be polymerized monomer, catalyst is simultaneously introduced reactor, use b workshop section, d work
Section and e workshop section are polymerized, and polymerizate is the molecular structure product of fire-retardant unit and the random copolymerization structure being polymerized monomer, but
Its response time is longer, when the polymer molecular weight that can obtain as required controls to react corresponding to reactor pressure and temperature
Between.
Compared to the prior art, the present invention by improve technique, control reaction atmosphere, it is not necessary to add synergistic flame retardant and
Other additive, the organophosphor copolymerization fire-retardant polyamide material serviceability made is good, may be used for weaving, engineering plastics, thin
The every field such as film.Meanwhile, raw material usage amount is few, and technique is simple, low cost, and exploitativeness is high, the anti-flammability of the product made
Can be high.Contrast is not added with flame retardant resin, and flame retardant rating reaches UL94 V-0 level, and limited oxygen index increases substantially, and minimum reaches
To 32, peak can reach 45.
A kind of organophosphor copolymerization Flameproof polyamide that the present invention provide is discussed in detail below by several specifically embodiments
The preparation method of material.
Embodiment 1:
Fire retardant and hexamethylene diamine react that to obtain the mixture of No. 1 performed polymer and DDP hexamethylene diamine salt standby, wherein fire retardant with
The mol ratio of hexamethylene diamine is 1:1.
By caprolactam with account for the catalyst of caprolactam weight 1% and add reactor, evacuation, it is filled with nitrogen, keeps
It is malleation in reactor；Reacting by heating still, controls reactor temperature and is 240 DEG C, after pressure is 0.3MPa, starts agitating device
Continuously stirred 8 hours；Reduce mixing speed, reactor be evacuated to vacuum for-0.05MPa, then inflated with nitrogen is to after normal pressure,
The performed polymer of the 1.5% of interpolation caprolactam weight；
Again being evacuated to-0.05MPa, reactor temperature is continually maintained in 240 DEG C, copolyreaction 15 minutes；Finally
Being filled with nitrogen, control reacting kettle inner pressure is 0.02MPa, discharges material, cooling, pelletizing, extracts, is dried to obtain end product,
Its relative viscosity is 2.4, and limited oxygen index is 32, and flame retardant rating reaches V-0.
Wherein said fire retardant isDescribed prepare performed polymer diamine be
Fire retardant is 1:1 with the mol ratio of diamine.
Embodiment 2:
Fire retardant and nonamethylene diamine react that to obtain the mixture of No. 2 performed polymers and fire retardant nonamethylene diamine salt standby, the most fire-retardant
Agent is 1:3 with the mol ratio of nonamethylene diamine.
By mass ratio be the caprolactam of 1:1:1 ratio, 11 lactams, hexamethylene diamine and caprolactam, 11 lactams,
The catalyst of hexamethylene diamine gross weight 1% adds reactor, evacuation, is filled with nitrogen, is malleation in keeping reactor；
Reacting by heating still, controls reactor temperature and is 250 DEG C, after pressure is 0.5MPa, starts agitating device and persistently stir
Mix 7 hours；Reduce mixing speed, reactor is evacuated to vacuum for adding quite after-0.04MPa inflated with nitrogen again to normal pressure
In lactams and the performed polymer prepared by the fire retardant of the 2% of diamidogen weight summation；Again be evacuated to vacuum for-
0.01MPa, temperature in the kettle is continually maintained in 250 DEG C, copolyreaction 30 minutes；
Finally being filled with nitrogen, control reacting kettle inner pressure is 0.02MPa, discharges material, cooling, pelletizing, extract, be dried
To end product, its relative viscosity is 1.8, and limited oxygen index is 33, and flame retardant rating reaches V-0.
Wherein fire retardant isWith,
Described diamine isWithFire retardant
WithAndWithMol ratio be 1:1:1:1.
Embodiment 3:
Fire retardant and decamethylene diamine react that to obtain the mixture of No. 3 performed polymers and fire retardant decamethylene diamine salt standby, the most fire-retardant
Agent is 1:4 with the mol ratio of decamethylene diamine.
It is that the caprolactam of 1:1:1 ratio, adipic acid, hexamethylene diamine and caprolactam, adipic acid, hexamethylene diamine are total by mass ratio
The catalyst of weight 1% adds reactor, evacuation, is filled with nitrogen, is malleation in keeping reactor；
Reacting by heating still, controls reactor temperature and is 280 DEG C, after pressure is 0.7MPa, starts agitating device and persistently stir
Mix 9 hours；Reduce mixing speed, reactor is evacuated to vacuum for adding quite after-0.06MPa inflated with nitrogen again to normal pressure
In the performed polymer of the 2% of all polymerization monomer weights；Again being evacuated to vacuum is-0.06MPa, and temperature in the kettle continues to keep
At 280 DEG C, copolyreaction 50 minutes；
Finally being filled with nitrogen, control reacting kettle inner pressure is 0.05MPa, discharges material, cooling, pelletizing, extract, be dried
To end product, its relative viscosity is 2.8, and limited oxygen index is 39, and flame retardant rating reaches V-0.
Wherein fire retardant isOr
Described diamine isFire retardant is 1:1:8 with the mol ratio of diamine.
Embodiment 4:
Fire retardant and hexamethylene diamine react that to obtain the mixture of No. 4 performed polymers and fire retardant hexamethylene diamine salt standby, the most fire-retardant
Agent is 1:8 with the mol ratio of hexamethylene diamine.
By mass ratio be the caprolactam of 1:2:1:1, lauric lactam, hexamethylene diamine, adipic acid and caprolactam, in 12
Amide, hexamethylene diamine, the catalyst of adipic acid gross weight 1% add reactor, evacuation, are filled with nitrogen, in keeping reactor are
Malleation；
Reacting by heating still, controls reactor temperature and is 280 DEG C, after pressure is 0.7MPa, starts agitating device and persistently stir
Mix 6 hours；Reduce mixing speed, reactor is evacuated to vacuum for adding in oneself after-0.08MPa inflated with nitrogen again to normal pressure
The fire retardant of the 20% of amide weight；Again being evacuated to vacuum is-0.08MPa, and temperature in the kettle is continually maintained in 280 DEG C,
Copolyreaction 90 minutes；
Finally being filled with nitrogen, control reacting kettle inner pressure is 0.07MPa, discharges material, cooling, pelletizing, extract, be dried
To end product, its relative viscosity is 1.6, and limited oxygen index is 45, and flame retardant rating reaches V-0.
Wherein fire retardant isDescribed diamine isFire retardant with
The mol ratio of diamine is 1:8.
Embodiment 5:
The mixture that fire retardant and hendecane diamine reactant obtain No. 5 performed polymers and fire retardant hendecane diamine salts is standby,
Wherein fire retardant is 1:6 with the mol ratio of hendecane diamidogen.
By No. 5 pre-polymerizations of lauric lactam, the catalyst of lauric lactam weight 1%, and lauric lactam weight 15%
Body is simultaneously introduced reactor, evacuation, is filled with nitrogen, is malleation in keeping reactor；
Reacting by heating still, controls reactor temperature and is 290 DEG C, after pressure is 1.0MPa, starts agitating device and persistently stir
Mix 10 hours；Reduce mixing speed, reactor is evacuated to vacuum for adding oneself after-0.05MPa inflated with nitrogen again to normal pressure
The fire retardant of the 2% of lactams weight；Again being evacuated to vacuum is-0.05MPa, and temperature in the kettle is continually maintained in 290 DEG C,
Copolyreaction 150 minutes；
Finally being filled with nitrogen, control reacting kettle inner pressure is 0.07MPa, discharges material, cooling, pelletizing, extract, be dried
To end product, its relative viscosity is 2.4, and limited oxygen index is 42, and flame retardant rating reaches V-0.
Wherein fire retardant isWith
Described diamine isFire retardant is 1:6 with the mol ratio of both diamines.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (13)
1. the preparation method of an organophosphor copolymerization fire-retardant polyamide material, it is characterised in that specifically include following steps:
(1) in advance fire retardant is reacted with diamines monomer, prepare performed polymer；
(2) monomer, catalyst and described performed polymer will be polymerized and add reactor, prepare organophosphor copolymerization Flameproof polyamide material
Material；
Wherein, described in step (1), fire retardant isOr withFor base
The derivant of body；
Wherein said R1And R2It is the alkylidene of 1-10 carbon atom；
X1、X2The halogen of H on phenyl ring is may replace for H or 1-4；
Described diamines monomer is aliphatic series C6—C20Any one in Alkylenediamine, aromatic diamine or alicyclic diamine.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 1, it is characterised in that institute
Stating diamines monomer is hexamethylene diamine, any one in decamethylene diamine, nonamethylene diamine, hendecane diamidogen, dodecamethylene diamine.
3. the preparation method of an organophosphor copolymerization fire-retardant polyamide material, it is characterised in that specifically include following steps:
(1) in advance fire retardant is reacted with diamines monomer, prepare performed polymer；
(2) monomer, catalyst and described performed polymer will be polymerized and add reactor, prepare organophosphor copolymerization Flameproof polyamide material
Material；
It is characterized in that, described in step (1), fire retardant is:
Wherein, R1 and R3 is respectively the alkylidene of 1-10 carbon atom, and R2 is the alkyl of H or 1-10 carbon atom；Further
, described diamines monomer is hexamethylene diamine, any one in decamethylene diamine, nonamethylene diamine, hendecane diamidogen, dodecamethylene diamine.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to any one of claim 1 to 3, its
Being characterised by, in step (1), in production, the mol ratio controlling fire retardant and diamines monomer is 1:(1-10)；
Product is the mixture of performed polymer and amine salt, and wherein performed polymer and amine salt all contain Amino End Group.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to any one of claim 1 to 3, its
It is characterised by, in step (1), in advance described fire retardant and diamines monomer is reacted when preparing described performed polymer, also include adding
Enter aminocarboxylic acrylic monomer；
When preparing described performed polymer, described diamines monomer and described aminocarboxylic acrylic monomer are simultaneously introduced and described fire retardant
Reaction；
Described aminocarboxylic acrylic monomer is the compound omega-amino carboxylic acid that lactams open loop obtains, or, omega-amino carboxylic acid.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 5, it is characterised in that institute
Stating aminocarboxylic acrylic monomer is the ω position straight chain representative examples of saturated aliphatic carboxylic by amino substituted carbon number 4-18, and 6-amino is own
Any one or several of acid, 11-amino undecanoic acid, 12 amino dodecanoic acid or PAMBA.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 4, it is characterised in that step
Suddenly, in (2), following steps are specifically included:
A. polymerization monomer and catalyst are added reactor, evacuation, be filled with nitrogen, be barotropic state in keeping reactor；
B. reacting by heating still, controls reactor temperature and is 240-290 DEG C, after pressure is 0.01-1.0MPa, starts stirring dress
Put continuously stirred 6-14 hour；
C. reducing mixing speed, it is-0.01 to-0.1MPa that reactor is evacuated to vacuum, then inflated with nitrogen is to after normal pressure
Add described performed polymer and the mixture of amine salt of the 1.5%-20% of material total amount in reactor；
The most again being evacuated to vacuum is-0.01 to-0.1MPa, and reactor temperature is continually maintained in 240-290 DEG C,
Copolyreaction 15-150 minute；
The most finally being filled with nitrogen, control reacting kettle inner pressure is 0.02-0.3MPa, discharges material, cooling, pelletizing, extract, dry
Dry obtain end product.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 7, it is characterised in that step
In rapid a, the addition of described polymerization monomer is 5-65 times of described fire retardant weight, and the addition of described catalyst is described
The 1% of polymerization monomer weight.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 7, it is characterised in that step
In rapid a, described polymerization monomer is the various lactam monomers possessing lactams feature, or its any one derivant；
Or, it is possible to the binary acid of participation copolymerization or binary amine compound: adipic acid, decanedioic acid, Azelaic Acid, hendecane two
Acid, dodecanedioic acid, p-phthalic acid, M-phthalic acid or their derivant, and other aliphatic series and aromatic dicarboxylic acids, and
Aliphatic series C6—C20One or more in Alkylenediamine, aromatic diamine or alicyclic diamine；
Or, with arbitrary lactams as principal monomer, with any one lactams, binary acid or the binary that can participate in copolymerization above
Any one or a few copolymerization combining form in aminated compounds.
The preparation method of a kind of organophosphor copolymerization fire-retardant polyamide material the most according to claim 9, it is characterised in that
Described polymerization monomer is caprolactam, caprinolactam, 11 lactams, lauric lactam or its any one derivant.
The preparation method of 11. a kind of organophosphor copolymerization fire-retardant polyamide material according to claim 9, it is characterised in that
Described can participate in copolymerization binary amine compound be: hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane diamidogen, dodecamethylene diamine
Or their derivant.
The preparation method of 12. a kind of organophosphor copolymerization fire-retardant polyamide material according to claim 7, it is characterised in that
In step b, described temperature is 260-280 DEG C, pressure is 0.01-1.0MPa, and mixing time is 6-14 hour；In step c,
Described vacuum is-0.01 to-0.1MPa.
The preparation method of 13. a kind of organophosphor copolymerization fire-retardant polyamide material according to claim 7, it is characterised in that
In step d, described vacuum is-0.01 to-0.1MPa, and reactor temperature is 260-270 DEG C, the time of copolyreaction
For 15-90 minute；In step e, controlling described reacting kettle inner pressure is 0.02-0.3MPa.
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of an organic phosphorus copolymer flame retardant polyamide material Effective date of registration: 20231221 Granted publication date: 20160824 Pledgee: Zhenjiang Yitongda Cross border Trade Service Co.,Ltd. Pledgor: JIANGSU RUIMEIFU INDUSTRY Co.,Ltd. Registration number: Y2023980073231 |