CN104559141B - Preparation method of nylon nucleating agent, prepared nylon nucleating agent and application - Google Patents
Preparation method of nylon nucleating agent, prepared nylon nucleating agent and application Download PDFInfo
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- CN104559141B CN104559141B CN201310503533.7A CN201310503533A CN104559141B CN 104559141 B CN104559141 B CN 104559141B CN 201310503533 A CN201310503533 A CN 201310503533A CN 104559141 B CN104559141 B CN 104559141B
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses a preparation method of a nylon nucleating agent, a prepared nylon nucleating agent and an application. The preparation method comprises the following steps: dissolving a benzoate nucleating agent in water to serve as an aqueous phase, using a light stabilizer as an oil phase, uniformly mixing the aqueous phase and the oil phase with a cosurfactant and a surfactant to form microemulsion. The nylon nucleating agent prepared by the preparation method is applied in modified nylon resin, and counted by 100 parts by weight of nylon resin, the use amount of the nucleating agent is 0.01-10 parts by weight. The nylon nucleating agent has the advantages of small use amount, good effect, low processing cost and simple preparation process, thereby being an ideal nylon resin nucleating agent. Meanwhile, the light stabilizer serving as the oil phase is synchronously added to not only help the nucleating agent to disperse, but also can improve the ageing resistance of the nucleating agent.
Description
Technical field
The present invention relates to nylon field, furtherly, it is to be related to a kind of preparation method of nylon nucleator and by its system
Standby nucleator and application.
Background technology
Nylon（Nylon）, Chinese name polyamide, English name Polyamide（Abbreviation PA）, it is that weight is contained on molecular backbone
Multiple amide group-[NHCO]-thermoplastic resin general name.As most important engineering plastics, its application almost covers every nylon
One field, is most widely used kind in five large-engineering plastics.In order to preferably meet the requirement of the aspects such as application, people are not
The various methods of disconnected research improve to the performance of nylon.Wherein pass through to add nucleator, improve the mechanical property of nylon products
Be realize nylon resin high performance one kind simple, and one of effective method of modifying.
At present, on market, widely used nylon nucleator is divided into organic nucleating agent, inorganic nucleator and macromolecule nucleation
Agent.Organic nucleating agent nucleating effect is obvious, but price is higher, and firm for nylon after its addition reaches certain value
Property is held essentially constant, and that is, mechanical property does not improve further with the raising of addition.Inorganic nucleator is to nylon system
The transparency of product and surface gloss have an impact, and the application in terms of transparent material is restricted.
Sodium benzoate, molecular formula is C6H5CO2Na, is benzoic sodium salt.Sodium benzoate, can used as decentralized nucleator
To improve the crystallization temperature of nylon, shorten crystallization time.Sodium benzoate nucleator, compared with other nucleators, has synthesis technique
Simply, low cost, nontoxic, easily store the advantages of.
Chinese patent CN1935899A discloses a kind of environmental-protection fire-resistant nylon composition and preparation method thereof, wherein added
Nucleator is amide-type organic nucleating agent, such as Long carbon chain carboxylic acid calcium salt or Long carbon chain carboxylic acid sodium salt one kind therein, or makes
With nylon 22 as high molecular nucleating agent；United States Patent (USP) US3080345A and US4866115A use sodium phenyl phosphinate, tertiary fourth
Base sodium hypophosphite, Acetates and phenol etc. as the nucleator of PA, to improve its crystallization rate and optics, mechanical property.
How on the basis of consumption is few, the excellent nylon nucleator of processability is a direction of research.
Content of the invention
For solving produced problem in prior art, the invention provides a kind of preparation method of nylon nucleator and by it
The nylon nucleator of preparation and application.The nucleator of the present invention is easily scattered microemulsion, can promote nucleator further in Buddhist nun
Disperse in imperial resin, introduce the light stabilizer with ultraviolet resistance degraded simultaneously in microemulsion, on the one hand improve the resistance to of material
Ageing properties, on the other hand help nucleator dispersion.
An object of the present invention is to provide a kind of preparation method of nylon nucleator.
Including：
Benzoate nucleator is dissolved in water as aqueous phase, light stabilizer as oil phase and cosurfactant, surface activity
Agent mix homogeneously forms microemulsion；
Described liquid light stabilizer is double（1,2,2,6,6- pentamethyl -4- piperidyl）SA ester (Tinuvin765),
Two-(N- methyl -2,2,6,6- tetramethyl -4- arsenic piperidinyl) last of the ten Heavenly stems diester and methyl-(N- methyl -2,2,6,6- tetramethyl -4- arsenic pyridine
Base last of the ten Heavenly stems diester (292), double (1,2,2,6, the 6- pentamethyl -4- piperidines) ester of diacid and 1- (methyl) -8- (1,2,2,6,6- five first
Base -4- piperidines) one of the mixture (GW-508) of sebacate or combination；It is preferably GW-508；
Cosurfactant is alcohols, preferably ethanol；
Surfactant is described surfactant is polyoxyethylene -20- sorbitan monooleate, polyoxyethylene -
20- sorbitan monostearate, polyoxyethylene -20- anhydrous sorbitol list myristinate, polyoxyethylene -20- dehydration mountain
One of pears alcohol monolaurate or combination.
It is preferably polyoxyethylene -20- sorbitan monooleate（Tween 80）；
Described benzoate is preferably sodium benzoate；Molecular formula is C6H5CO2Na, is benzoic sodium salt.Sodium benzoate is made
For decentralized nucleator, the crystallization temperature of nylon can be improved, shorten crystallization time.Sodium benzoate nucleator and other nucleators
Compare, have the advantages that synthesis technique is simple, low cost, nontoxic, easily store.
Wherein, in microemulsion,
The content of aqueous phase is 20～80wt%；
The content of liquid light stabilizer is 5～20wt%；
The content of surfactant is 10～40wt%；
The content of cosurfactant is 5～20wt%.
In aqueous phase, the concentration of benzoate is completely dissolved with the organic nucleating agent adding and is advisable, generally 5～30wt%.
Mix and blend equipment in preparation method is the mixing apparatus generally adopting in manufacture field, such as：Magnetic stirring apparatuss,
High shear dispersion machine etc..
The second object of the present invention is to provide a kind of nylon nucleator prepared by methods described.
Described organic nucleating agent benzoate, can dissolve in water.Using the water having dissolved benzoate nucleator as
Aqueous phase, using liquid light stabilizer as oil phase, will be common to above-mentioned aqueous phase, oil phase and surfactant, cosurfactant activating agent
Mixed, obtain the microemulsion of stable uniform, i.e. nucleator microemulsion
The third object of the present invention is to provide a kind of nylon nucleator prepared by methods described in modification of nylon resin
Application.
Counted with nylon resin for 100 weight portions, the consumption of described benzoate nucleator is 0.01～10 weight portion, excellent
Select 0.01～1 weight portion.
Specifically can employ the following technical solutions：
Microemulsion containing nucleator is added in nylon with antioxidant, stirs mix homogeneously with height, after being dried in an oven,
Nucleator composite nylon is obtained using double screw extruder extrusion.
Benzoate nucleator is dissolved in the aqueous phase of microemulsion by the present invention using micro-emulsion process, and due to microemulsion
Oil phase can make it disperse preferably in nylon matrix, thus effectively expanding the contact area of nucleator and nylon matrix.
In the case of nucleation agent content identical, the nucleator using micro-emulsion process preparation has more preferable nucleating effect and mechanical property
Energy.Therefore, micro-emulsion process preparation benzoate nucleator be applied in nylon as nucleator, have consumption few, effect
Really good, processing cost is low, the advantages of preparation process is simple, is a kind of nucleator of preferable nylon resin.Light stabilizer simultaneously
Synchronously add as oil phase, not only assist in nucleator and disperse moreover it is possible to improve its ageing-resistant performance, improve the mechanical property of material
Energy.
Specific embodiment
With reference to embodiment, further illustrate the present invention.
Embodiment 1
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 20wt%.Adopt
With magnetic stirrer, sequentially add dehydrated alcohol, GW-508, Tween 80, dissolved the aqueous phase of sodium benzoate, said components
Quality proportioning is 20/20/40/20, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）,
Mixing time 5 minutes.The microemulsion mixing is 1# nucleator microemulsion.
Embodiment 2
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 5wt%；Using
Magnetic stirrer, sequentially adds dehydrated alcohol, GW-508, Tween 80, has dissolved the aqueous phase of sodium benzoate, said components matter
Amount proportioning is 5/5/10/80, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）, stirring
5 minutes time.The microemulsion mixing is 2# nucleator microemulsion.
Embodiment 3
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 10wt%.Adopt
With magnetic stirrer, sequentially add dehydrated alcohol n-butyl alcohol, GW-508, polysorbate60, disperseed the aqueous phase of sodium benzoate, on
Stating constituent mass proportioning is 20/20/40/20, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Turn every
Minute）, mixing time 5 minutes.The microemulsion mixing is 3# nucleator microemulsion.
Embodiment 4
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 30wt%.Adopt
With magnetic stirrer, sequentially add dehydrated alcohol, GW-508, Tween 80, disperseed the aqueous phase of sodium benzoate, said components
Quality proportioning is 5/5/10/80, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）, stir
Mix the time 5 minutes.The microemulsion mixing is 4# nucleator microemulsion.
Embodiment 5
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 25wt%.Adopt
With magnetic stirrer, sequentially add dehydrated alcohol, GW-508, Tween 80, disperseed the aqueous phase of sodium benzoate, said components
Quality proportioning is 20/20/40/20, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）,
Mixing time 5 minutes.The microemulsion mixing is 5# nucleator microemulsion.
Embodiment 6
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 15wt%.Adopt
With magnetic stirrer, sequentially add dehydrated alcohol, 292, polysorbate60, disperseed the aqueous phase of sodium benzoate, said components matter
Amount proportioning is 5/5/10/80, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）, stirring
5 minutes time.The microemulsion mixing is 6# nucleator microemulsion.
Embodiment 7
By sodium benzoate（Fine chemistry industry institute is recovered in Tianjin）Dissolved in deionized water with the concentration of 10wt%.Adopt
With magnetic stirrer, sequentially add n-butyl alcohol, Tinuvin765, Tween 80, disperseed the aqueous phase of sodium benzoate, above-mentioned group
Quality proportioning is divided to be 5/5/10/80, using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Rpm）,
Mixing time 5 minutes.The microemulsion mixing is 7# nucleator microemulsion.
Comparative example 1
Using magnetic stirring apparatuss（Model）Stirring, sequentially adds dehydrated alcohol, GW-508, Tween 80, deionized water, above-mentioned
Constituent mass proportioning is 20/20/40/20, and using magnetic stirrer, the rotating speed of magnetic stirring apparatuss is 200rpm（Turn every point
Clock）, mixing time 5 minutes.The microemulsion mixing is blank microemulsion 0#.
The formula of embodiment and comparative example is shown in Table 1.
Table 1. microemulsion formula table
Embodiment 8
By the 1# nucleator microemulsion of preparation in embodiment 1 and nylon 6（Sinopec Ba Ling branch company）, antioxidant 1098
With 168 (Switzerland vapour Ba Jiaji produces, the two is used in mixed way with 1/1 ratio) mix, its concrete composition：Nylon 6 is 100
Part, 1.25 parts of 1# nucleator microemulsion, 0.4 part of antioxidant 1098/168 mixture（Wherein each constituent content is all with parts by weight
Meter）, in high speed agitator（Beijing's English spy's plastics machinery head factory, model GH-10DY）Middle mixing one minute, dries in 80oC air blast
After drying in case, with the ZSK-25 twin-screw extrusion system of German Wernerand Pleiderer company（Draw ratio 30：1st, straight
Footpath 25mm）Blending pelletize, each section of temperature of extruder is respectively 230 DEG C, 235 DEG C, 235 DEG C, 235 DEG C, 235 DEG C, 220 DEG C of (heads
Temperature), after gained pellet is dried, through injector (ningbo of china Hai Tian company produces, model HTF110X/1J) injection, make examination
Sample standard batten.
Embodiment 9
1.25 parts of 1# nucleator microemulsion in embodiment 8 is changed to 2.5 parts, remaining each component ratio is all constant, altogether
It is mixed even, remaining operation and extrusion, injecting condition are all with embodiment 8.
Embodiment 10
1.25 parts of 1# nucleator microemulsion in embodiment 8 is changed to 5 parts, remaining each component ratio is all constant, blending
Uniformly, remaining operation and extrusion, injecting condition are all with embodiment 8.
Embodiment 11
1# nucleator microemulsion in embodiment 8 is changed to 2# nucleator microemulsion, remaining each component ratio is all constant, blending
Uniformly, remaining operation and extrusion, injecting condition are all with embodiment 8.
Embodiment 12
1# nucleator microemulsion 1.25 in embodiment 8 is changed to 2.5 parts of 2# nucleator microemulsion, remaining each component ratio
Example is all constant, and uniformly, remaining operation and extrusion, injecting condition are all with embodiment 8 for blending.
Embodiment 13
1.25 parts of 1# nucleator microemulsion in embodiment 8 is changed to 5 parts of 2# nucleator microemulsion, remaining each component ratio
Example is all constant, and uniformly, remaining operation and extrusion, injecting condition are all with embodiment 8 for blending.
Comparative example 2
By 100 parts of PA6 and the direct mix of 0.4 part of antioxidant, remaining operates and extrusion, all same embodiment of injecting condition
8.
Comparative example 3
By 100 parts of PA6, sodium benzoate nucleator 500ppm (parts per million), 0.4 part of mix of antioxidant, its
Remaining operation and extrusion, injecting condition are all with embodiment 8.
Comparative example 4
By 100 parts of PA6, sodium benzoate nucleator 1000ppm, 0.4 part of mix of antioxidant, remaining operation and extrusion,
Injecting condition is all with embodiment 8.
Comparative example 5
By 100 parts of PA6, sodium benzoate nucleator 2000ppm, 0.4 part of mix of antioxidant, remaining operation and extrusion,
Injecting condition is all with embodiment 8.
Comparative example 6
By 100 parts of PA6, sodium benzoate nucleator 4000ppm, 0.4 part of mix of antioxidant, remaining operation and extrusion,
Injecting condition is all with embodiment 8.
Test：
The standard batten obtaining embodiment 8～13 and comparative example 2～6 injection respectively is carried out curved by ISO178 testing standard
Bent performance test, by ISO75-2:2004 testing standards carry out heat distortion temperature test, and the result obtaining is listed in table 2.Aging examination
Test by GB/T16422.2-1999 standard testing.Condition：1. periodicity of illumination：Irradiance 0.51W/m2 (340nm)；Black mark temperature 65
℃；38 DEG C of spin manifold temperature；Relative humidity 50%；Time 102min；2. illumination+spray cycle：Irradiance 0.51W/m2 (340nm)；
Black 65 DEG C of temperature of mark；38 DEG C of spin manifold temperature；Relative humidity 50%；Time 18min.Totally 500 hours.
Test result is shown in Table 2
Table 2 test recipe and performance table
As shown in table 2, it is dissolved in, using by nucleator, the method being redispersed in microemulsion in PA6, ratio has been directly added into
PA6 mechanical property after machine nucleator improves more.Add the embodiment of the SB nucleator of 2000ppm for example with microemulsion method
10, its bending modulus improves 11% than the comparative example 5 being directly added into 2000ppmSB.
Test several sample aging before and after bending property as shown in table 3.
Table 3
As shown in table 3, test several samples aging before and after bending property.Result shows, pure nylon resin, curved
Bent modulus drops to 1.71GPa from 1.99GPa, and the range of decrease is 11%；After with the addition of the sodium benzoate of 500ppm, its bending modulus exists
12% is have dropped from 2.12GPa, to 1.87GPa before and after aging.And adopt light stabilizer to add nylon tree as the microemulsion of oil phase
After fat, the bending moduluses of embodiment 8 slightly drop to 2.09GPa from 2.21GPa, and fall is 5%.The bending of embodiment 11
Modulus declines and reduces, and is reduced to 2.10GPa from 2.18GPa, the range of decrease is only 3.7%, illustrates that the addition of light stabilizer substantially reduces
The palliating degradation degree of nylon resin, after degradation, remains to maintain its higher bending property.
Therefore, nucleator SB adds PA6 by the method for microemulsion, on the one hand because the oil phase of microemulsion can improve and Buddhist nun
The compatibility of imperial matrix, help nucleator preferably disperse, in the case that content is low, just play good nucleation thus
Improve material property, and using inorganic nucleator can cost-effective, on the other hand due in microemulsion oil phase be light stabilizer,
The ageing-resistant performance of material can be improved.Therefore, the method that microemulsion method of the present invention prepares nucleator is a kind of preferable
Nucleator preparation method.
Claims (6)
1. a kind of preparation method of nylon nucleator is it is characterised in that methods described includes：
Benzoate nucleator is dissolved in water as aqueous phase, liquid light stabilizer as oil phase and cosurfactant, surface activity
Agent mix homogeneously forms microemulsion；
Described liquid light stabilizer is double (1,2,2,6,6- pentamethyl -4- piperidyl) sebacate, double (1,2,2,6,6- five first
Base -4- piperidines) sebacate and 1- methyl -8- (1,2,2,6,6- pentamethyl -4- piperidines) sebacate mixture in one
Plant or combine；
Cosurfactant is alcohols；
Described surfactant is polyoxyethylene -20- sorbitan monooleate, and polyoxyethylene -20- anhydrous sorbitol list is hard
Fat acid ester, polyoxyethylene -20- anhydrous sorbitol list myristinate, in polyoxyethylene -20- sorbitan mono-laurate
One kind or combination；
Wherein, in microemulsion,
The content of aqueous phase is 20～80wt%；
The content of liquid light stabilizer is 5～20wt%；
The content of surfactant is 10～40wt%；
The content of cosurfactant is 5～20wt%.
2. nylon nucleator as claimed in claim 1 preparation method it is characterised in that：
Described benzoate is sodium benzoate；
Described liquid light stabilizer is GW-508；
Described cosurfactant is ethanol；
Described surfactant is polyoxyethylene -20- sorbitan monooleate.
3. nylon nucleator as claimed in claim 1 preparation method it is characterised in that：
In aqueous phase, the concentration of benzoate is 5～30wt%.
4. a kind of nylon nucleator of the preparation method preparation as described in one of claims 1 to 3.
5. a kind of nylon nucleator of the preparation method preparation as described in one of claims 1 to 3 is in modification of nylon resin
Application it is characterised in that：
Counted with nylon resin for 100 weight portions, the consumption of described benzoate nucleator is 0.01～10 weight portion.
6. application in modification of nylon resin for the nylon nucleator as claimed in claim 5 it is characterised in that：
Counted with nylon resin for 100 weight portions, the consumption of described benzoate nucleator is 0.01～1 weight portion.
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| CN201310503533.7A CN104559141B (en) | 2013-10-23 | 2013-10-23 | Preparation method of nylon nucleating agent, prepared nylon nucleating agent and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3080345A (en) * | 1958-02-06 | 1963-03-05 | Du Pont | Process for fabrication of shaped articles from linear superpolycarbonamides to provide improved products |
| CN101421341A (en) * | 2006-02-27 | 2009-04-29 | 耶路撒冷希伯来大学伊森姆研究发展公司 | Method for nucleating polymers |
| CN102020842A (en) * | 2010-12-22 | 2011-04-20 | 东莞市意普万工程塑料有限公司 | Nylon composite material special for electric wire and cable jacket and preparation method thereof |
-
2013
- 2013-10-23 CN CN201310503533.7A patent/CN104559141B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3080345A (en) * | 1958-02-06 | 1963-03-05 | Du Pont | Process for fabrication of shaped articles from linear superpolycarbonamides to provide improved products |
| CN101421341A (en) * | 2006-02-27 | 2009-04-29 | 耶路撒冷希伯来大学伊森姆研究发展公司 | Method for nucleating polymers |
| CN102020842A (en) * | 2010-12-22 | 2011-04-20 | 东莞市意普万工程塑料有限公司 | Nylon composite material special for electric wire and cable jacket and preparation method thereof |
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