CN106700067B - A kind of siliceous reaction-type flame-retarding nylon resin and preparation method thereof - Google Patents
A kind of siliceous reaction-type flame-retarding nylon resin and preparation method thereof Download PDFInfo
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Abstract
A kind of siliceous reaction-type flame-retarding nylon resin and preparation method thereof, preparation method containing the response type phosphonium flame retardant there are two carboxyl end group with amido silicon oil the following steps are included: will mix；Gained mixture and nylon polymerization monomer, catalyst are configured to material by a certain percentage, siliceous reaction-type flame-retarding nylon resin is obtained after the aggregated reaction of the material.Siliceous reaction-type flame-retarding nylon resin produced by the present invention has permanent fire retardant, and flame retardant rating reaches UL94 V-0, oxygen index (OI) 25-45, which has many advantages, such as that good mechanical properties, oxygen index (OI) are high, flame retardant rating is high and better adaptability.
Description
Technical field
The present invention relates to fire-retardant nylon resin and preparation method thereof, in particular to a kind of silicon-contained type fire-retardant nylon resin and its
Preparation method.
Background technique
Nylon is widely used in spinning with its excellent mechanical property, rub resistance, heat resistance, electrical insulating property and weatherability
The fields such as textured fiber, automobile, electronic apparatus, engineering machinery.Relative to general polyolefin, the melt strength of nylon is low, is firing
Drippage is generated in burning, increases the danger of fire-propagation, jeopardizes human production life safety.The fire-retardant advantage of nylon is its point
Containing the hetero atoms such as nitrogen and oxygen in son, combustion heat value and inflammability are lower than polyolefin, and heteroatomic presence, with phosphorus and
The fire retardant reaction of silicon systems can play the performance of silicon class and phosphorus type flame retardant than stronger.
In order to improve the flame retardant property of nylon, industrially mainly realized by the method for physical blending.But due to resistance
The additive amount for firing agent is big, and easy reunion causes stress to be concentrated, the performance decline of material.In addition, additional fire retardant and nylon resin
Compatibility is poor, and fire retardant is easily migrated to material surface, causes Flame Retardancy not lasting.
Copolyreaction type fire-retardant nylon due to fire retardant as copolymerization component participate in polymerization reaction, by chemical bond with polymerize
Object is connected, and can steadily be present in polymeric inner and be lost without migrating, and has permanent fire retardant, and performance is stablized.Example
If No. 201110065541.9 Chinese patents disclose a kind of method for preparing halogen-free reinforced nylon, by phosphonium flame retardant 2- carboxylic
Ethylphenyl phosphinic acids and caprolactam ring opening copolymer form fire-retardant nylon material, the fire-retardant effect of the fire-retardant nylon that this method obtains
Fruit is good, and flame retardant rating reaches UL94V-0.However, at present such patent use be all phosphorus system fire retardant, some is even using single
The fire retardant of functional group causes polymerization to be easy to be blocked in this way, influences its mechanical property.
It is prepared in addition, existing part fire-retardant nylon resin generally passes through extrusion blending and modifying, this fire-retardant nylon
Resin there are flame retardant agent contents it is high, flame retarding efficiency is low the problems such as, cause nylon resin mechanical property relatively low, mobility is poor.Portion
Point reaction-type flame-retarding nylon resin be substantially drippage flame retardant type, when burning, has drip phenomenon, seriously affects answering for material
Use range.There are also the high temperature resistance of the reactive flame retardant of part is poor, and nylon polymerization temperature is high, and response type hinders when polymerization
Agent is fired to be easy to decompose.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind good mechanical properties, oxygen index (OI) are high, flame retardant rating is high and the siliceous reaction-type flame-retarding nylon resin of better adaptability, and corresponding
A kind of preparation method of siliceous reaction-type flame-retarding nylon resin is provided.
In order to solve the above technical problems, technical solution proposed by the present invention is a kind of siliceous reaction-type flame-retarding nylon resin
Preparation method, comprising the following steps:
It will be mixed containing the response type phosphonium flame retardant there are two carboxyl end group with amido silicon oil；
Gained mixture and nylon polymerization monomer, catalyst and other conven-tional adjuvants that addition may be selected are pressed into certain ratio
Example is configured to material, and siliceous reaction-type flame-retarding nylon resin is obtained after the aggregated reaction of the material.
Above-mentioned preparation method, it is preferred that the response type phosphonium flame retardant is with following formula (I) and/or following formula (II)
The compound of shown structure:
The additive amount of the response type phosphonium flame retardant is the 2%-10% of nylon polymerization monomer mass.
Above-mentioned preparation method, it is preferred that the amido silicon oil be Amino End Group polysiloxanes, side group include methyl,
Ethyl, propyl or phenyl.It is furthermore preferred that the amido silicon oil be Amino End Group methylsiloxane, number-average molecular weight be 300~
10000。
Above-mentioned preparation method, it is preferred that the nylon polymerization monomer is mainly lactams or amino acid, preferably is selected from following formula
(I) and/or the compound of structure shown in following formula (II):
Formula (I): H2N(CH2)xCOOH；
Formula (II):
X, y are the natural number of 2-12 in above formula.It is furthermore preferred that the lactams is caprolactam, oenantholcatam, 12
Lactams；The amino acid is aminocaproic acid or aminoundecanoic acid.It is furthermore preferred that in order to preferably regulate and control the mechanical property of product
Can, the nylon polymerization monomer is preferably the composition of caprolactam, lauric lactam, or is aminocaproic acid, amino 11
The composition of acid.
Above-mentioned preparation method, it is preferred that the catalyst is water or inorganic acid, and the inorganic acid includes phosphoric acid, phosphorous
One or more of acid, metaphosphoric acid；The additive amount of the catalyst is the 1%~5% of nylon polymerization monomer mass.
Above-mentioned preparation method, it is preferred that the polymerization reaction is carried out in two steps: the reaction temperature of the first step is 200 DEG C
~280 DEG C, 2-8h is kept, pressure control is 0.2~2.0MPa；Second step, after polymerization reaction kettle pressure release to normal pressure, negative reaction
3-16h, pressure control are -0.05~-0.1Mpa.
Above-mentioned preparation method, it is preferred that the response type phosphonium flame retardant and amido silicon oil are with the ratio of equimolar ratio
Example mixing.
As a general technical idea, the present invention also provides a kind of siliceous reaction-type flame-retardings that above-mentioned preparation method obtains
Nylon resin, the siliceous reaction-type flame-retarding nylon resin have permanent fire retardant, and flame retardant rating reaches UL94V-0, oxygen index (OI)
For 25-45.
The technical solution of aforementioned present invention by after the fire retardant with reaction structure is mixed with amido silicon oil and
Nylon monomer copolymerization, so that fire retardant is copolymerized in nylon molecules chain, while implanting silicon atom in the molecular structure, has
The cooperative flame retardant of silicon, gained nylon resin flame retardant effect is more preferable, and the siliceous reaction-type flame-retarding nylon resin that this method obtains has
Permanent fire retardant.
Compared with the prior art, the advantages of the present invention are as follows:
1. amido silicon oil is added using the response type phosphonium flame retardant with reaction structure in the present invention, make itself and Buddhist nun
Imperial monomer copolymerization, is steadily present in polymeric inner and is lost without migrating；Due to joined silicon atom in the molecular structure,
Cooperative flame retardant effect is formd with phosphorus flame retardant, because of the carboxyl and ammonia of response type phosphonium flame retardant specifically preferred according to the invention
The reaction of base silicone oil, it is faster at carbon speed in burning, higher at carbon efficiencies than blending, the problems such as dispersing is not present, solves
Nylon is easy the problem of burning drippage, and has permanent fire retardant.
2. amido silicon oil proposed by the present invention and response type phosphonium flame retardant compounded technology, solve flame retarding efficiency first
Low, fire retardant is precipitated and resin mechanical properties decrease problem, high-efficient using fire-retardant nylon resins fire retardant prepared by the present invention, resistance
Fuel efficiency fruit is good (UL94-V0), and good mechanical properties；
3. the general blending type amount of flame-retardant agent of amount ratio will lack, and not under conditions of reaching identical flame retardant effect
It can be because process causes migration to be lost.
Siliceous reaction-type flame-retarding nylon resin of the invention can be widely applied in textile fabric, military project, aerospace, rail
The fields such as road traffic, automobile, engineering machinery, electronic apparatus, building, furniture, daily necessities have preferable industrial applications
Prospect.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment:
A kind of preparation method of siliceous reaction-type flame-retarding nylon resin of the invention, comprising the following steps:
(1) the response type phosphonium flame retardant and amido silicon oil of carboxyl end group are mixed according to 1: 1 molar ratio there are two containing
It closes；
(2) the response type phosphonium flame retardant and amido silicon oil that mix are added in autoclave, while nylon is added
Polymerized monomer and catalyst (dosage of catalyst is the 4% of nylon polymerization monomer mass), fasten feeding cover, use nitrogen repeatedly for three times
Air in gas displacement autoclave；
(3) heated to equipped with the autoclave of material, temperature made to reach 200 DEG C~280 DEG C, kettle press 0.2Mpa~
Under 2.0Mpa, 2~6h is reacted；
(4) pressure-relief valve is opened, autoclave is slowly made to be down to normal pressure, 3~15h of vacuumize process after parked 30min, very
Reciprocal of duty cycle is controlled in -0.05~-0.09MPa；
(5) for pressure to normal pressure, after standing balance a period of time, nitrogen extrudes material discharging, draws in last inflated with nitrogen to kettle
Siliceous reaction-type flame-retarding nylon resin product of the invention can be obtained in silk pelletizing, boiling, vacuum drying.
The response type phosphonium flame retardant that the present embodiment is selected is following formula (I), in the compound of structure shown in following formula (II)
At least one, the additive amount of response type phosphonium flame retardant are the 2%-20% of nylon polymerization monomer mass, each specific embodiment
The specific response type phosphonium flame retardant and its dosage selected can be found in the following table 1.
The amido silicon oil that the present embodiment is selected is Amino End Group methylsiloxane, and number-average molecular weight Mn is 1000.
The nylon polymerization monomer that the present embodiment is selected is caprolactam, in lauric lactam, aminocaproic acid, aminoundecanoic acid
One or two, the specific nylon polymerization monomer and its dosage that each specific embodiment is selected can be found in the following table 1.
The catalyst that the present embodiment is selected is water；The additive amount of catalyst is the 4% of nylon polymerization monomer mass.
The siliceous reaction-type flame-retarding nylon resin that the above-mentioned preparation method of the present embodiment obtains has permanent fire retardant, fire-retardant etc.
Grade reaches UL94V-0, and limit oxygen index is in 38-43, and mechanical performance index is referring to the following table 2.
Comparative example 1:
A kind of preparation method of fire-retardant nylon resin, comprising the following steps:
(1) by response type phosphonium flame retardant (above formula (I)) be added autoclave in, while be added nylon polymerization monomer oneself
Lactams and catalyst water (dosage of catalyst is the 4% of gross weight), fasten feeding cover, anti-with nitrogen displacement high pressure repeatedly for three times
Answer air in kettle；Each reaction raw materials and its dosage can be found in the following table 1；
(2) heated to equipped with the autoclave of material, temperature made to reach 200 DEG C~280 DEG C, kettle press 0.2Mpa~
Under 2.0Mpa, 2~12h is reacted；
(3) pressure-relief valve is opened, autoclave is slowly made to be down to normal pressure, 2~8h of vacuumize process after parked 30min, very
Reciprocal of duty cycle is controlled in -0.05~0.9MPa；
(4) for pressure to normal pressure, after standing balance a period of time, nitrogen extrudes material discharging, draws in last inflated with nitrogen to kettle
Fire-retardant nylon naval stores can be obtained in silk pelletizing, boiling, vacuum drying.
The flame retardant rating of the fire-retardant nylon resin of this comparative example reaches UL94V-2, and 38, mechanical property refers to limit oxygen index
Mark is referring to the following table 2.
Comparative example 2:
A kind of preparation method of fire-retardant nylon resin, comprising the following steps:
(1) into autoclave, (dosage of catalyst is total for addition nylon polymerization monomer caprolactam and catalyst water
The 4% of weight), feeding cover is fastened, repeatedly for three times with air in nitrogen displacement autoclave；Each reaction raw materials and its dosage can join
It see the table below 1；
(2) heated to equipped with the autoclave of material, temperature made to reach 200 DEG C~280 DEG C, kettle press 0.2Mpa~
Under 2.0Mpa, 2~12h is reacted；
(3) pressure-relief valve is opened, autoclave is slowly made to be down to normal pressure, 2~8h of vacuumize process after parked 30min, very
Reciprocal of duty cycle is controlled in -0.05~0.9MPa；
(4) for pressure to normal pressure, after standing balance a period of time, nitrogen extrudes material discharging, draws in last inflated with nitrogen to kettle
Fire-retardant nylon naval stores can be obtained in silk pelletizing, boiling, vacuum drying.
The flame retardant rating of the fire-retardant nylon resin of this comparative example reaches UL94V-2, and 22, mechanical property refers to limit oxygen index
Mark is referring to the following table 2.
Table 1: embodiment and comparative example material formula table (unit: g)
Table 2: each embodiment and comparative example the performance test results
Comprehensive Tables 1 and 2 as it can be seen that compared with comparative example 1,2, the oxygen index (OI) of product of the embodiment of the present invention improve it is obvious that
But under conditions of no addition amido silicon oil, combustion zone fire drippage, flame retardant rating is still UL94V2 grades；And this hair
The all samples of bright embodiment have all reached UL94V0 grades, thus illustrate, the response type phosphonium flame retardant in the present invention can improve
The oxygen index (OI) of material, but after amido silicon oil is added, its flame retardant rating can be improved.Contain pasc reaction in section Example of the present invention
Type fire-retardant nylon resin has a little reduction than pure nylon resin mechanical property, but is receiving in range.
In addition, it was also found that being stretched strong when using the nylon polymerization monomer of single kind in product of the invention
When spending and bending strength performance is relatively preferable, and using two kinds of compound monomers, then impact strength performance is preferable, this makes this hair
Bright preparation method can adapt to the performance requirement of different product by adjusting recipe ingredient.
Therefore the siliceous reaction-type flame-retarding nylon resin good mechanical properties that the present invention synthesizes, and oxygen index (OI) is high, resistance
It fires grade and reaches UL 94V-0 grades.Textile fabric, military project, aerospace, rail traffic, automobile, engineering machinery, electronic apparatus,
The fields such as building, furniture, daily necessities have broad application prospects.
Claims (9)
1. a kind of preparation method of siliceous reaction-type flame-retarding nylon resin, comprising the following steps:
It will be mixed containing the response type phosphonium flame retardant there are two carboxyl end group with amido silicon oil；
Gained mixture and nylon polymerization monomer, catalyst are configured to material by a certain percentage, after the aggregated reaction of the material
Obtain siliceous reaction-type flame-retarding nylon resin；And silicon atom is present in nylon resin strand, the response type phosphor-containing flame-proof
Agent and amido silicon oil are mixed with the ratio of equimolar ratio, and the additive amount of response type phosphonium flame retardant is nylon polymerization monomer mass
2%-10%.
2. preparation method according to claim 1, which is characterized in that the response type phosphonium flame retardant is with following formula
(I) and/or the compound of structure shown in following formula (II):
。
3. preparation method according to claim 1, which is characterized in that the amido silicon oil is the polysiloxanes of Amino End Group,
Its side group includes methyl, ethyl, propyl or phenyl.
4. preparation method according to claim 3, which is characterized in that the amido silicon oil is Amino End Group methylsiloxane,
Its number-average molecular weight is 300~10000.
5. preparation method according to any one of claims 1 to 4, which is characterized in that the nylon polymerization monomer is selected from
The compound of structure shown in following formula (I) and/or following formula (II):
Formula (I): H2N(CH2)xCOOH；
Formula (II):；
X, y are the natural number of 2-12 in above formula.
6. preparation method according to claim 5, which is characterized in that the nylon polymerization monomer is caprolactam, 12
The composition of lactams, or be aminocaproic acid, the composition of aminoundecanoic acid.
7. preparation method according to any one of claims 1 to 4, which is characterized in that the catalyst is water or inorganic
Acid, the inorganic acid include one or more of phosphoric acid, phosphorous acid, metaphosphoric acid；The additive amount of the catalyst is poly- for nylon
Close the 1%~5% of monomer mass.
8. preparation method according to any one of claims 1 to 4, which is characterized in that the polymerization reaction in two steps into
Row: the reaction temperature of the first step is 200 DEG C~280 DEG C, keeps 2-8h, and pressure control is 0.2~2.0 MPa；Second step, polymerization
After reaction kettle pressure release to normal pressure, negative reaction 3-16h, pressure control is -0.05~-0.1Mpa.
9. the siliceous reaction-type flame-retarding nylon resin that a kind of preparation method as described in any one of claim 1~8 obtains, special
Sign is that the siliceous reaction-type flame-retarding nylon resin has permanent fire retardant, and flame retardant rating reaches UL94 V-0, and oxygen index (OI) is
25-45。
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| CN112480688A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Silicon rubber composition and preparation method and application thereof |
| CN112920410B (en) * | 2021-01-29 | 2022-05-27 | 浙江恒逸石化研究院有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
| CN118126522A (en) * | 2024-05-07 | 2024-06-04 | 江苏新视界先进功能纤维创新中心有限公司 | Copolymerization modified nylon 66 with low gel content and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1974721A (en) * | 2006-11-16 | 2007-06-06 | 上海交通大学 | Silicious expanding fire retardant and its prepn process |
| CN103694468A (en) * | 2014-01-14 | 2014-04-02 | 株洲时代新材料科技股份有限公司 | Nylon resin and preparation method thereof |
| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
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| JP2011079944A (en) * | 2009-10-06 | 2011-04-21 | Dow Corning Toray Co Ltd | Manufacturing method for aramid silicone polymer |
| CN103642048B (en) * | 2013-12-02 | 2016-04-13 | 浙江科技学院 | Polyamide organic silicon thermoplastic elastomer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1974721A (en) * | 2006-11-16 | 2007-06-06 | 上海交通大学 | Silicious expanding fire retardant and its prepn process |
| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
| CN103694468A (en) * | 2014-01-14 | 2014-04-02 | 株洲时代新材料科技股份有限公司 | Nylon resin and preparation method thereof |
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