CN107446129A - A kind of preparation method of anti-aging semi-aromatic nylon resin - Google Patents
A kind of preparation method of anti-aging semi-aromatic nylon resin Download PDFInfo
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- CN107446129A CN107446129A CN201710702386.4A CN201710702386A CN107446129A CN 107446129 A CN107446129 A CN 107446129A CN 201710702386 A CN201710702386 A CN 201710702386A CN 107446129 A CN107446129 A CN 107446129A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic 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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Abstract
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：Under nitrogen protection; polyimides complex salt, semi-aromatic nylon complex salt, polyhydroxy-alcohol, auxiliary agent are added in polymerization reaction kettle together; and amorphous nylon salt is added with one or two kinds of in lactams, anti-aging semi-aromatic nylon resin is prepared in temperature and the pressure of telo merization kettle；Wherein, the auxiliary agent includes organic stabilizer, and the organic stabilizer is one kind in phenolic group, amido, phosphorus base and thioether based stabilizer.Preparation method of the present invention is simple, is suitable for mass producing, and also has excellent ageing resistace while the semi-aromatic nylon resin excellent in mechanical performance being prepared.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of preparation method of nylon resin.
Background technology
Semi-aromatic nylon is to be obtained by aromatic diacid or diamines with aliphatic diamine or diacid polycondensation, in nylon molecules master
Aromatic rings is introduced in chain, the heat resistance and mechanical performance of material is improved, reduces water absorption rate, improve dimensional stability, fill out
The sky between general engineering plastic (such as amorphous nylon and polyester) and very-high performance material (such as PEEK, polysulfones and LCP) is mended
In vain.
Semi-aromatic nylon has excellent chemical proofing, processing characteristics and heat endurance so that is particularly suitable for applying
In automobile and electric field.Semi-aromatic nylon is often used on the high-temperature-resistant structure part of automobile, generally 150 DEG C, very
Persistently used to 200 DEG C, but because heat ageing, mechanical property tends to reduce.Improve the heat aging performance of semi-aromatic nylon,
Show high mechanical property conservation rate under aging condition, be more beneficial for it and applied in hot oxygen environment.Chinese patent
CN102112549B, CN102597114B disclose polyamide and are first pre-mixed with modified additive, then by physical modification method, change
The heat aging performance of kind nylon material, but it only accounts for the stretching performance retentivity of composite, lacks comprehensive evaluation.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided a kind of
The preparation method of anti-aging semi-aromatic nylon resin with high mechanical property conservation rate.In order to solve the above technical problems, this
Inventing the technical scheme proposed is：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：Under nitrogen protection, it is polyamides is sub-
Amine complex salt, semi-aromatic nylon complex salt, polyhydroxy-alcohol, auxiliary agent are added in polymerization reaction kettle together, and add aliphatic Buddhist nun
For imperial salt with one or two kinds of in lactams, anti-aging semi-aromatic nylon tree is prepared in temperature and the pressure of telo merization kettle
Fat；
Wherein, the auxiliary agent includes organic stabilizer, and the organic stabilizer is that phenolic group, amido, phosphorus base and thioether group are steady
Determine one kind in agent.
In above-mentioned preparation method, it is preferred that reaction system needs to be constantly in nitrogen protection, and otherwise material gathers in the later stage
It is oxidized easily after conjunction.
In above-mentioned preparation method, it is preferred that the polyimides complex salt by amino-terminated polyimide prepolymer with
Binary acid reaction with same mole is prepared, and the semi-aromatic nylon complex salt is reacted by aromatic acid and aliphatic diamine
It is prepared, the amorphous nylon salt is prepared by aliphatic dibasic acid and aliphatic diamine reaction.
When prepared by the polyimides complex salt, the preparation method of the amino-terminated polyimide prepolymer is as follows：
First under nitrogen protection, by diamines dissolving in organic solvent, under conditions of ice-water bath, add in three times into organic solvent
Entering dianhydride, stirring reaction obtains the organic solvent solution of polyamic acid, then in the organic solvent solution of polyamic acid between addition
The mixed solvent of dimethylbenzene and pyridine, 12~20h of back flow reaction at 60 ± 5 DEG C, precipitated successively by absolute ethyl alcohol after cooling,
Suction filtration, 18~24h of acetone extraction, deionized water wash 3~5 times, 100~120 DEG C of 16~24h of vacuum drying, obtain powdered
Amino-terminated polyimide prepolymer.
In the preparation method of above-mentioned polyimides complex salt, it is preferred that the organic solvent be DMF,
One or several kinds of mixing in DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE.
The structural formula of the dianhydride is as follows：
Wherein, X is：Singly-bound, O, S, C=O, Any of or it is several；
The structural formula of the diamines is as follows：
Wherein, Y is：Singly-bound, O, Any of or it is several
Kind.
The diamines can also be 1,4- butanediamine, 1,6- hexamethylene diamines, 1,7- heptamethylene diamines, 1,8- octamethylenediamines, 1,9- nonyls two
Amine, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecamethylene diamines, 1,13- tridecane diamines, 2- methyl isophthalic acids, 5- penta
Diamines, 2,2,4- trimethyl -1,6- hexamethylene diamines and 2- methyl isophthalic acids, the one or more in 8- octamethylenediamines.
In the preparation method of above-mentioned polyimides complex salt, the binary acid preferred aliphat dicarboxylic acids or alicyclic dicarboxyl
Acid, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dimethyl malonic acid, 3,
3- diethyl succinic acids, 2- methyl adipic acid, 2,2- dimethylated pentanedioic acids, 1,3- cyclopentane dicarboxylic acids and 1,4- hexamethylene dicarboxyls
One or more in acid.The binary acid can also select aromatic acid, such as terephthalic acid (TPA), M-phthalic acid, 2-
Methylterephthalic acid, 2,5- dichloroterephthalicacid acids, 2,6- naphthalenes diacid, 2,7- naphthalenes diacid, 1,4- naphthalenes diacid, 4,4 '-biphenyl
One or more in dioctyl phthalate, diphenyl methane -4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxylic acids.
Concrete operation step prepared by the semi-aromatic nylon complex salt is：Aromatic acid is filled in deionized water
Divide and be well mixed, be heated to 50~80 DEG C, binary aliphatic amine aqueous solution is added under the conditions of strong stirring, regulation pH value is
7.0~8.0, continue stirring 0.5~2 hour, filtered after sufficiently cool, it is compound that vacuum drying obtains white powder semi-aromatic nylon
Salt.
In prepared by above-mentioned semi-aromatic nylon complex salt, it is preferred that the aromatic acid is terephthalic acid (TPA), isophthalic two
Formic acid, 2- methylterephthalic acids, 2,5- dichloroterephthalicacid acids, 2,6- naphthalenes diacid, 2,7- naphthalenes diacid, 1,4- naphthalenes diacid, 4,
One kind in 4 '-biphenyl dicarboxylic acid, diphenyl methane -4,4 '-dicarboxylic acids, phthalic acid, diphenyl sulfone -4,4 '-dicarboxylic acids
Or it is several, it is furthermore preferred that the aromatic acid be terephthalic acid (TPA), M-phthalic acid and phthalic acid in one kind or
It is several.
In prepared by above-mentioned semi-aromatic nylon complex salt, it is preferred that described aliphatic diamine is Putriscine, 1,6-
Hexamethylene diamine, 1,7- heptamethylene diamines, 1,8- octamethylenediamines, 1,9-nonamethylene diamine, 1,10- decamethylene diamine 1,11- hendecanes diamines, 1,12- 12
Alkane diamines, 1,13- tridecane diamines, 2- methyl isophthalic acids, 5- pentanediamines, 2,2,4- trimethyl -1,6- hexamethylene diamines and 2- methyl isophthalic acids, 8-
One or more in octamethylenediamine, it is furthermore preferred that described aliphatic diamine is 1,6- hexamethylene diamines, decamethylene diamine, 1,12- 12
One or more in alkane diamines, 1,13- tridecane diamines, it is further preferred that described aliphatic diamine be 1,6- oneself
Diamines.
When prepared by the amorphous nylon salt, it is preferred that the aliphatic dibasic acid be malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dimethyl malonic acid, 3,3- diethyl succinic acids, 2- methyl adipic acids
With the one or more in 2,2- dimethylated pentanedioic acids；The aliphatic diamine is 1,4- butanediamine, 1,6- hexamethylene diamines, 1,7-
Heptamethylene diamine, 1,8- octamethylenediamines, 1,9-nonamethylene diamine, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecamethylene diamines, 1,
13- tridecane diamines, 2- methyl isophthalic acids, 5- pentanediamines, 2,2,4- trimethyl -1,6- hexamethylene diamines and 2- methyl isophthalic acids, in 8- octamethylenediamines
One or more.
In above-mentioned preparation method, it is preferred that the polyhydroxy-alcohol is ethylene-vinyl alcohol copolymer, polyvinyl alcohol and double seasons
One or more in penta tetrol.
In above-mentioned preparation method, it is preferred that the lactams is in caprolactam, 11 lactams and lauric lactam
It is one or more of.
In above-mentioned preparation method, it is preferred that the auxiliary agent also includes catalyst, the catalyst be auxiliary agent include phosphoric acid,
One kind in phosphorous acid, hypophosphorous acid and the derivative of its salt and ester, the mass ratio of the catalyst and organic stabilizer is 1:
0.5~1:2, it is furthermore preferred that the mass ratio of the catalyst and organic stabilizer is 1:1.
In above-mentioned preparation method, it is preferred that the polyimides complex salt, semi-aromatic nylon complex salt, polyhydroxy-alcohol, fat
The parts by weight that fat race nylon salt, lactams and auxiliary agent add are：0.01~8 part of polyimides complex salt, semi-aromatic nylon is compound
30~70 parts of salt, 0.01~10 part of polyhydroxy-alcohol, 30~70 parts of amorphous nylon salt, 30~70 parts of lactams, auxiliary agent 0.05~2
Part.It is furthermore preferred that the parts by weight that the polyimides complex salt, polyhydroxy-alcohol and auxiliary agent add are：Polyimides complex salt 0.1
~4 parts, 0.5~6 part of polyhydroxy-alcohol, 0.1~0.5 part of auxiliary agent.It is further preferred that the polyimides complex salt and polyhydroxy
Alcohol add parts by weight be：0.5~3 part of polyimides complex salt, 1~4 part of polyhydroxy-alcohol.The parts by weight of each material of the above are not
Including the water contained in the material.The property for the anti-aging semi-aromatic nylon resin that above-mentioned preparation method obtains and its each composition
Parts by weight have direct contact, and inventor is based on substantial amounts of experimental exploring, and it is anti-ageing to show prepared by the component using above-mentioned parts by weight
Change the most outstanding of semi-aromatic nylon resin.
In above-mentioned preparation method, it is preferred that the temperature of the telo merization kettle is to make temperature in the kettle first with pressure
With pressure in 210~220 DEG C and 1~4h of pressurize under 1.8~2.0MPa, then being vented makes pressure in kettle be gradually decrease to normal pressure, and
Temperature in the kettle is gradually risen to 300~350 DEG C, finally in kettle pressure be -0.1~-0.04MPa, temperature be 300~350
Continue 10~30min of reaction under the conditions of DEG C.
The main chemical reactions formula of the inventive method sees below formula (1), formula (2), formula (3), formula (4), formula (5) and formula (6),
Wherein, formula (1) represents the synthesis equation of polyimide preformed polymer, and formula (2) represents the synthesis equation of polyimides complex salt,
Formula (3) represents the synthesis equation of semi-aromatic nylon complex salt, the synthesis equation (fat of formula (4) polyimide modified nylon dragon
Race's nylon salt), formula (5) represents the synthesis equation (lactams) of polyimide modified nylon dragon, and formula (6) represents copolymer nylon
Synthesis equation.
H2N-PI-NH2+HOOC-R1-COOH→H3N-PI-NH3 OOC-R1-COO
Formula (2)
Compared with prior art, the advantage of the invention is that：
1. the present invention introduces polyamide-imide structure in semi-aromatic nylon strand, polyimides contains heteroaromatic, its
It is randomly distributed in semi-aromatic nylon main chain, the rigidity and heat resistance of material can be improved, the semi-aromatic nylon tree being prepared
Also there is excellent ageing resistace while fat excellent in mechanical performance.
2. the present invention adds polyhydroxy-alcohol in the course of the polymerization process, the anti-aging efficiency of organic stabilizer, polyhydroxy can be improved
Alcohol can produce synergistic effect with organic stabilizer at high temperature, and both can rapidly capture produced in polymer decomposable process at high temperature
Raw free radical, carries out terminating reaction, effectively suppresses the aging of polymer at high temperature, the semi-aromatic nylon resin being prepared
Ageing resistace it is very excellent.
3. the preparation method of the present invention is simple, it is suitable for mass producing.
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
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 1：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：
Step 1：
(1) under the protection of nitrogen, 4,4 '-diaminodiphenyl ether is dissolved in DMF solvent, so
Afterwards under conditions of ice-water bath, the double phthalic anhydrides of 4,4 '-oxygen are added in three times and are stirred and are reacted, obtain polyamic acid
DMF solution, wherein 4,4 '-diaminodiphenyl ether and 3,3 ', 4,4 '-oxydiphthalic mol ratio
For 1.5:Isosorbide-5-Nitrae, 4 '-diaminodiphenyl ether and 3,3 ', 4,4 '-oxydiphthalic total amount accounts for system (diamines, dianhydride and molten
Agent) mass fraction be 15%；
(2) meta-xylene/pyridine is added in the N,N-dimethylformamide solution of polyamic acid prepared by step (1) to mix
(volume ratio 2 in bonding solvent:1), then flow back 18h at 60 ± 5 DEG C, obtains the N of TPI, N- dimethyl methyls
Amide solvent, precipitated, filtered with absolute ethyl alcohol after cooling, acetone extraction 20h, deionized water wash 3 times, 100 DEG C of vacuum drying
20h, finally give powdered amino-terminated TPI performed polymer；
(3) under nitrogen protection, polyimide prepolymer and dimethylformamide are well mixed, open and stir and heat
To 120 DEG C, the dimethyl formamide solution of polyimide prepolymer is obtained；By adipic acid (with polyimide prepolymer equimolar
Number) and dimethylformamide be well mixed, open be stirred and heated to 100 DEG C, obtain the dimethyl formamide solution of adipic acid；
The dimethyl formamide solution of the dimethyl formamide solution of polyimide prepolymer and adipic acid is well mixed, and fills it
Divide reaction, centrifuge washing, polyimides complex salt is obtained after vacuum drying；
Step 2：
Phthalic acid and appropriate deionized water are well mixed, are heated to 70 DEG C, opens stirring, adds 1,6- hexamethylene diamines
The aqueous solution, pH most 7.5~7.7 is adjusted, continue stirring 1 hour, be cooled to room temperature, filtration drying obtains white powder PA6T salt
(semi-aromatic nylon complex salt)；
Step 3：
By 80g polyimides complex salt, 1918g PA6T salt, 1918g PA66 salt, 80g ethylene-vinyl alcohol copolymers, 4g
Sodium hypophosphite, 4g(organic stabilizer), 1000g water are added in 10L HTHP polymeric kettles, replace nitrogen three times
Stirring is opened after gas, temperature in the kettle is heated to 215 DEG C, pressure is risen to as 1.9MPa, pressurize 2h in kettle；Being vented again makes kettle internal pressure
Power is gradually decrease to normal pressure, temperature in the kettle is gradually risen to 320 DEG C；Finally pressure is -0.06MPa in kettle, temperature 320
Continue to react 15min under the conditions of DEG C, then open bottom valve, tie rod pelletizing, be dried in vacuo 10h, that is, obtain being modified semi-aromatic nylon
Resin, its fusing point is 300 DEG C, inherent viscosity 1.35dl/g, and carries out ageing properties test.
Comparative example 1：
The operating procedure of this comparative example is same as Example 1, does not add polyimides complex salt and second in step 3 simply
Alkene-ethenol copolymer.
Embodiment 2：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：
Step 1 is the same as embodiment 1；
Step 2 is the same as embodiment 1；
Step 3：
By 80g polyimides complex salt, 2877g PA6T salt, 959g caprolactams, 80g ethylene-vinyl alcohol copolymers, 4g
Sodium hypophosphite, 4g(organic stabilizer), 1000g water are added in 10L HTHP polymeric kettles, replace nitrogen three times
Stirring is opened after gas, temperature in the kettle is heated to 215 DEG C, pressure is risen to as 1.9MPa, pressurize 4h in kettle；Being vented again makes kettle internal pressure
Power is gradually decrease to normal pressure, temperature in the kettle is gradually risen to 320 DEG C；Finally pressure is -0.06MPa in kettle, temperature 320
Continue to react 15min under the conditions of DEG C, then open bottom valve, tie rod pelletizing, be dried in vacuo 10h, that is, obtain being modified semi-aromatic nylon
Resin, its fusing point are 300 DEG C, inherent viscosity 1.25dl/g.
Comparative example 2：
The operating procedure of this comparative example is same as Example 2, does not add polyimides complex salt and second in step 3 simply
Alkene-ethenol copolymer.
Embodiment 3：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：
Step 1 is the same as embodiment 1；
Step 2 is the same as embodiment 1；
Step 3：
By 80g polyimides complex salt, 2302g PA6T salt, 1150g PA66 salt, 384g caprolactams, 80g ethene-second
Enol copolymer, 4g sodium hypophosphites, 4g(organic stabilizer), 1000g water add 10L HTHP polymeric kettles
In, stirring is opened after replacing nitrogen three times, temperature in the kettle is heated to 215 DEG C, pressure is risen to as 1.9MPa, pressurize 4h in kettle；
Being vented again makes pressure in kettle be gradually decrease to normal pressure, temperature in the kettle is gradually risen to 320 DEG C；Finally in kettle pressure for-
0.06MPa, temperature continue to react 15min under the conditions of being 320 DEG C, then open bottom valve, tie rod pelletizing, be dried in vacuo 10h, produce
To modified semi-aromatic nylon resin, its fusing point is 302 DEG C, inherent viscosity 1.3dl/g.
Comparative example 3：
The operating procedure of this comparative example is same as Example 3, does not add polyimides complex salt and second in step 3 simply
Alkene-ethenol copolymer.
Embodiment 4：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：
Step 1 is the same as embodiment 1；
Step 2 is the same as embodiment 1；
Substitute the ethylene/vinyl alcohol copolymer in embodiment 1 with polyvinyl alcohol in step 3, remaining step is the same as embodiment 1.
Comparative example 4：
The operating procedure of this comparative example is same as Example 4, does not add polyimides complex salt in step 3 simply and gathers
Vinyl alcohol.
Embodiment 5：
A kind of preparation method of anti-aging semi-aromatic nylon resin, comprises the following steps：
Step 1 is the same as embodiment 1；
Step 2 is the same as embodiment 1；
Substitute the ethylene/vinyl alcohol copolymer in embodiment 1, the same embodiment of remaining step with bipentaerythrite in step 3
1。
Comparative example 5-1：
The operating procedure of this comparative example is same as Example 5, does not add polyimides complex salt and double in step 3 simply
Pentaerythrite.
Comparative example 5-2：
The operating procedure of this comparative example is same as Example 5, does not simply add organic stabilizer in step 3
Comparative example 5-3：
The operating procedure of this comparative example is same as Example 5, does not simply add bipentaerythrite in step 3.
Comparative example 5-4：
The operating procedure of this comparative example is same as Example 5, does not add polyimides complex salt in step 3 simply.
Performance test is carried out to the resin obtained in embodiment 1~5 and comparative example 1~5, as a result as shown in table 1, table 2.
Table 1：The performance test data of embodiment 1~5
Table 2：The performance test data of comparative example 1~5
As seen from the above table, the aging 800h either at 150 DEG C, or the aging 800h at 180 DEG C, obtain in embodiment
The property retention rate of resin be all substantially better than comparative example, polyimides complex salt, organic stabilizer, polyhydroxy-alcohol lack arbitrarily
A kind of component, its property retention rate can decline, and show that polyimides complex salt, organic stabilizer, polyhydroxy-alcohol can improve
The anti-aging efficiency of resin.The method of testing of above-mentioned experimental result is as follows：
1. inherent viscosity [η]
The semiaromatic copolymer nylon of test is dissolved in the concentrated sulfuric acid, obtain concentration be respectively 1g/dl, 0.8g/dl,
0.6g/dl, 0.4g/dl, 0.2g/dl, the logarithmic specific concentration viscosity η of solution is measured at 25 DEG Cinh：
ηinh=[ln (t1/t0)]/C
Wherein t0Represent the time (s) of solvent outflow, t1The time (s) of sample solution outflow is represented, C represents sample solution
Concentration (g/dl), ηinhRepresent logarithmic specific concentration viscosity (dl/g)；
By ηinhData Extrapolation to concentration be 0, obtain the inherent viscosity [η] of sample.
2. fusing point
Using the fusing point of plum Teller-support benefit DSC1 Instrument measuring samples, under nitrogen atmosphere, risen from room temperature with 10 DEG C/minute
Temperature keeps 5min to 330 DEG C, room temperature when then being cooled down with 10 DEG C/minute of speed, then is warming up to 330 with 10 DEG C/minute of speed
DEG C, endotherm peak temperature now is melting point polymer.
3. mechanical property
The semiaromatic copolymer nylon injection test bars of preparation, according to GB/T1040.2 standard testing tensile strengths, according to
GB/T9341-2008 standard testings bending strength and bending modulus, according to GB/T1043.1 standard testing simple beam impact strengths.
4. ageing resistace
The nylon injection-molding test bars of preparation, according to GB/T7141-2008 in air heat aging test chamber (model GT-
7017-EMU) carry out thermal aging test to batten, the condition of degradation is respectively 150 DEG C, 800h, 180 DEG C, 800h.To entering
Sample after row degradation, further according to GB/T1040.2 standard testing tensile strengths, according to GB/T9341-2008 standard testings
Bending strength and bending modulus, according to GB/T1043.1 standard testing simple beam impact strengths；Pass through sample after degradation
Mechanical property conservation rate carrys out the ageing resistace of evaluate sample.
Claims (10)
1. a kind of preparation method of anti-aging semi-aromatic nylon resin, it is characterised in that comprise the following steps：Protected in nitrogen
Under, polyimides complex salt, semi-aromatic nylon complex salt, polyhydroxy-alcohol, auxiliary agent are added in polymerization reaction kettle together, and is added
Enter amorphous nylon salt with one or two kinds of in lactams, temperature and the pressure of telo merization kettle are prepared anti-aging half
Aramid fiber resin；
Wherein, the auxiliary agent includes organic stabilizer, and the organic stabilizer is phenolic group, amido, phosphorus base and thioether based stabilizer
In one kind.
2. the preparation method of anti-aging semi-aromatic nylon resin according to claim 1, it is characterised in that the polyamides is sub-
Amine complex salt is prepared by amino-terminated polyimide prepolymer and binary acid reaction with same mole, and the semi-aromatic nylon is answered
Salt is closed to be prepared by aromatic acid and aliphatic diamine reaction, the amorphous nylon salt by aliphatic dibasic acid and
Aliphatic diamine reaction is prepared.
3. the preparation method of anti-aging semi-aromatic nylon resin according to claim 2, it is characterised in that the aromatic series
Binary acid is the one or more in terephthalic acid (TPA), M-phthalic acid, phthalic acid；
The aliphatic dibasic acid is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the last of the ten Heavenly stems two
Acid, dimethyl malonic acid, 3,3- diethyl succinic acids, 2- methyl adipic acid and one kind or several in 2,2- dimethylated pentanedioic acids
Kind；
The aliphatic diamine be 1,4- butanediamine, 1,6- hexamethylene diamines, 1,7- heptamethylene diamines, 1,8- octamethylenediamines, 1,9-nonamethylene diamine,
1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecamethylene diamines, 1,13- tridecane diamines, 2- methyl isophthalic acids, 5- penta 2
Amine, 2,2,4- trimethyl -1,6- hexamethylene diamines and 2- methyl isophthalic acids, the one or more in 8- octamethylenediamines.
4. the preparation method of anti-aging semi-aromatic nylon resin according to claim 1, it is characterised in that the polyhydroxy
Alcohol is the one or more in ethylene-vinyl alcohol copolymer, polyvinyl alcohol and bipentaerythrite.
5. the preparation method of anti-aging semi-aromatic nylon resin according to claim 1, it is characterised in that the lactams
For the one or more in caprolactam, 11 lactams and lauric lactam.
6. the preparation method of anti-aging semi-aromatic nylon resin according to claim 1, it is characterised in that the auxiliary agent is also
Including catalyst, the catalyst is one kind in phosphoric acid, phosphorous acid, hypophosphorous acid and the derivative of its salt and ester, described to urge
The mass ratio of agent and organic stabilizer is 1:0.5~1:2.
7. the preparation method of anti-aging semi-aromatic nylon resin according to claim 1, it is characterised in that the polyamides is sub-
Amine complex salt, semi-aromatic nylon complex salt, polyhydroxy-alcohol, amorphous nylon salt, lactams and the parts by weight of auxiliary agent addition are：It is poly-
0.01~8 part of acid imide complex salt, 30~70 parts of semi-aromatic nylon complex salt, 0.01~10 part of polyhydroxy-alcohol, amorphous nylon
30~70 parts of salt, 30~70 parts of lactams, 0.05~2 part of auxiliary agent.
8. the preparation method of anti-aging semi-aromatic nylon resin according to claim 7, it is characterised in that the polyamides is sub-
The parts by weight that amine complex salt, polyhydroxy-alcohol and auxiliary agent add are：0.1~4 part of polyimides complex salt, polyhydroxy-alcohol 0.5~6
Part, 0.1~0.5 part of auxiliary agent.
9. the preparation method of anti-aging semi-aromatic nylon resin according to claim 8, it is characterised in that the polyamides is sub-
Amine complex salt and the parts by weight of polyhydroxy-alcohol addition are：0.5~3 part of polyimides complex salt, 1~4 part of polyhydroxy-alcohol.
10. according to the preparation method of anti-aging semi-aromatic nylon resin according to any one of claims 1 to 9, its feature exists
In, the telo merization kettle temperature and pressure for make first temperature in the kettle and pressure 210~220 DEG C with 1.8~
1~4h of pressurize under 2.0MPa, then being vented makes pressure in kettle be gradually decrease to normal pressure, and make temperature in the kettle gradually rise to 300~
350 DEG C, finally in kettle pressure be -0.1~-0.04MPa, temperature continue 10~30min of reaction under the conditions of being 300~350 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285532A (en) * | 2018-01-16 | 2018-07-17 | 郑州大学 | A kind of preparation method of 65 salt of nylon |
| CN110498918A (en) * | 2019-08-13 | 2019-11-26 | 江门市凯生工程塑料有限公司 | A kind of preparation method of high-strength wearable damage property nylon resin |
| CN114736369A (en) * | 2022-05-25 | 2022-07-12 | 北京化工大学 | Modified nylon and preparation method thereof |
| CN115449071A (en) * | 2022-09-29 | 2022-12-09 | 株洲时代新材料科技股份有限公司 | Copolyamide resin containing imide structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012107217A (en) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | Polyamide resin composition and film composed of the same |
| CN103923313A (en) * | 2014-04-30 | 2014-07-16 | 株洲时代新材料科技股份有限公司 | Method for preparing semi aromatic copolymer nylon |
| CN106336512A (en) * | 2016-08-11 | 2017-01-18 | 株洲时代新材料科技股份有限公司 | Preparation method of polyimide modified nylon resin |
-
2017
- 2017-08-16 CN CN201710702386.4A patent/CN107446129B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012107217A (en) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | Polyamide resin composition and film composed of the same |
| CN103923313A (en) * | 2014-04-30 | 2014-07-16 | 株洲时代新材料科技股份有限公司 | Method for preparing semi aromatic copolymer nylon |
| CN106336512A (en) * | 2016-08-11 | 2017-01-18 | 株洲时代新材料科技股份有限公司 | Preparation method of polyimide modified nylon resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285532A (en) * | 2018-01-16 | 2018-07-17 | 郑州大学 | A kind of preparation method of 65 salt of nylon |
| CN108285532B (en) * | 2018-01-16 | 2020-04-03 | 郑州大学 | Preparation method of nylon 65 salt |
| CN110498918A (en) * | 2019-08-13 | 2019-11-26 | 江门市凯生工程塑料有限公司 | A kind of preparation method of high-strength wearable damage property nylon resin |
| CN114736369A (en) * | 2022-05-25 | 2022-07-12 | 北京化工大学 | Modified nylon and preparation method thereof |
| CN115449071A (en) * | 2022-09-29 | 2022-12-09 | 株洲时代新材料科技股份有限公司 | Copolyamide resin containing imide structure and preparation method thereof |
| CN115449071B (en) * | 2022-09-29 | 2024-04-09 | 株洲时代新材料科技股份有限公司 | Copolyamide resin containing imide structure and preparation method thereof |
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