CN108586734B - Polyester-type polyamide 6 elastomer and its synthetic method - Google Patents
Polyester-type polyamide 6 elastomer and its synthetic method Download PDFInfo
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- CN108586734B CN108586734B CN201810473741.XA CN201810473741A CN108586734B CN 108586734 B CN108586734 B CN 108586734B CN 201810473741 A CN201810473741 A CN 201810473741A CN 108586734 B CN108586734 B CN 108586734B
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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
- C08G69/44—Polyester-amides
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- 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
- C08L77/12—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of polyester-type polyamide 6 elastomer and its synthetic methods.Polyester-type polyamide 6 elastomer of the invention has structure shown in formula I:In formula I, a=3~5, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20.The synthetic method of polyester-type polyamide 6 elastomer of the invention is as follows: being reacted caprolactam with adipic acid to obtain the amide compound of both-end carboxyl first, then the compound and aliphatic lactones, 2,2'- (1,3- phenylene)-bisoxazoline is reacted to obtain polyester-type polyamide 6 elastomer of the present invention, while being blocked the carboxyl end group of polyester-type polyamide 6 elastomer by glycidol based epoxy resin.Polyester-type polyamide 6 elastomer of the invention has excellent impact property and processing performance and chemical resistance.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of polyester-type polyamide 6 elastomer and its synthetic method.
Background technique
Thermoplastic polyamide elastomer (TPAE) belongs to a member in thermoplastic elastomer (TPE) family, relative to extensive use
Thermoplastic polyurethane elastomer (TPU), thermoplastic polyolefin elastomer (TPO), styrenic thermoplastic elastomer (SBC), heat
Thermoplastic polyvinyl chloride elastomer (TPVC) and thermoplastic polyether ester elastomer (TPEE) etc., the preparation of TPAE and application starting compared with
Evening.TPAE was succeeded in developing and was commercialized by German Hughes Electronics in 1979 first, subsequent Upjohn Company, the U.S., French Ah
Support chemical company, The Iams Co., Switzerland, Japanese ink company also succeed in developing in succession and release the respective trade mark.
Thermoplastic polyamide elastomer (TPAE) is mainly the copolymerization being made of polyamide hard section and polyethers or polyester soft segment
Object, wherein the polyamide as hard section mainly has PA6, PA66, PA11, PA12 etc., which essentially dictates polyamide
The characteristics such as density, hardness, fusing point, tensile strength, the resistance to various organic chemicals of thermoplastic elastomer (TPE)；Part as soft segment
Mainly there are polycaprolactone (PCL), polyethylene glycol (PEG), polyoxypropylene (PPG), polytetrahydrofuran (PTMG) etc., the soft segment
Part essentially dictates the low-temperature characteristics of thermoplastic polyamide elastomer, hygroscopicity, antistatic property, dyeability and to certainization
The characteristics such as the stability of product.Meanwhile it can be by adjusting the type and group of hard section in thermoplastic polyamide elastomer and soft segment
The conditions such as proportional, molecular size range and distribution can get the dissimilarities such as hardness, density, heat resistance, hygroscopicity and mechanical property
The TPAE product of energy grade, to meet all kinds of demands in market.
Currently, some researchs have been done to the synthesis of thermoplastic polyamide elastomer in the prior art, and such as: Chinese patent
CN103403065A discloses that a kind of melt-moldability, crystallinity, flexibility be excellent and polyether-polyamide bullet with heat resistance
Property body, diamine structure unit is originated from polyether diamine compound (A-1) and benzene dimethylamine (A-2), dicarboxylic acid structural units and is originated from
The α of carbon number 4~20, ω-straight-chain aliphatic dicarboxylic acids Polyether polyamide elastomer；Chinese patent CN101796099A is disclosed
A kind of transparent polyamide elastomers of general formula structure (1) and its preferred application, wherein R1 is the polyamides being made of following substance
Amine segment: (a) alkyl-substituted bis- (aminocyclohexyl) methane and/or bis- (aminocyclohexyl) propane of 10 to 100 moles of %
With the other alicyclic C6-C36 diamines of 0 to 90 mole of % and/or aliphatic C2-C36 diamines and/or aromatic series C6-C36 diamines,
Wherein concentration data is in terms of the total amount of diamines in polyamide segment, and (b) aliphatic C4-C36 dicarboxylic acids and/or alicyclic C8-
C36 dicarboxylic acids and/or aromatic C 8-C36 dicarboxylic acids and (c) if applicable, lactams and/or amino carboxylic acid C6-C12,
Wherein R2 is selected from residue of divalent: polysiloxanes of the mumber average molar mass within the scope of 200 to 3000g/mol, polyolefin, line style or
Substituted or unsubstituted C2-C36 alkylidene, the C6-C36 cycloalkylidene, C6- of the C2-C5 polyoxyalkylene of branching, line style or branching
C20 aryl, polycaprolactone, the polyester based on aliphatic or alicyclic dicarboxylic acid and glycol, fatty poly-ester carbonate, and these
The copolymer or mixture of unit, and wherein X1 and X2 is amide-(CONH) or ester-(COO) key independently of each other；It is Chinese special
Sharp CN103772643A discloses a kind of preparation method of PA6 system thermoplastic polyamide elastomer material.The polyamide elastomer
It is by heat resistant type modified polyurethane and the low molecular weight PA6 performed polymer of carboxyl end group according to mass fraction, the modified poly- ammonia of heat resistant type
Ester accounts for the 10%~60% of total polymer mass, and the content of carboxyl end group low molecular weight PA6 hard section accounts for total polymer mass
40%~90%；Chinese patent CN104327266A discloses a kind of hydrolysis one-step synthesis method and contains to be made of polyamide 6
Hard section and the soft segment being made of polyethers block co-polymer thermoplastic's elastomer resin preparation method, and obtained by this method
The polyamide 6 thermoplastic elastomer resin arrived；Chinese patent CN105295036A disclose a kind of semi-aromatic polyester amide and
Its synthetic method, the semi-aromatic polyester amide by terephthalic acid (TPA), 11- aminoundecanoic acid, aliphatic lactones and 2,2'- (1,
3- phenylene)-bisoxazoline polycondensation reaction obtains；Chinese patent CN105295035A discloses a kind of semi-aromatic polyester amide
And its synthetic method, the semi-aromatic polyester amide is by 11- aminoundecanoic acid, 6- caprolactone, 2,2'- (1,3- phenylene)-two
Oxazoline polycondensation reaction obtains.
Summary of the invention
Based on this, the purpose of the present invention is to provide one kind to have excellent impact property and processing performance and chemical resistance
Polyester-type polyamide 6 elastomer, can be applied to auto parts and components, mechanical equipment, electric equipment products, sports goods, or make
For the compatilizer of polyester and polyamide and polyamide modified dose etc..
In order to achieve the above-mentioned object of the invention, this invention takes following technical solutions:
A kind of polyester-type polyamide 6 elastomer, with following structure shown in formula I:
In formula I, a=3~5, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20；
The polyester-type polyamide 6 elastomer is by aliphatic lactones, adipic acid, caprolactam, the 2,2'- (Asia 1,3- benzene
Base)-bisoxazoline is copolymerized；The aliphatic lactones, adipic acid, caprolactam, 2,2'- (1,3- phenylene)-dioxazole
The molar ratio of quinoline is 0.1~0.6:0.01~0.1:1:0.01~0.2；
The polyester-type polyamide 6 elastomer is the polyester-type that its carboxyl end group is blocked by glycidol based epoxy resin
Polyamide 6 elastomer.
In wherein some embodiments, the aliphatic lactones, adipic acid, caprolactam, 2,2'- (1,3- phenylene)-
The molar ratio of bisoxazoline is 0.2~0.5:0.01~0.04:1:0.1~0.15.
In wherein some embodiments, the intrinsic viscosity of the polyester-type polyamide 6 elastomer is 0.8~1.8dL/g, glass
Glass temperature Tg>=48 DEG C, melting temperature TmIt is 210~225 DEG C.
In wherein some embodiments, the aliphatic lactones are in gamma-butyrolacton, δ-valerolactone, 6-caprolactone
One or more kinds of mixtures.
In wherein some embodiments, the aliphatic lactones are selected from 6-caprolactone.
In wherein some embodiments, the glycidol based epoxy resin is styrene, methyl methacrylate and first
The copolymer of base glycidyl acrylate.
It is a further object of the present invention to provide a kind of synthetic methods of above-mentioned polyester-type polyamide 6 elastomer.
Specific technical solution is as follows:
A kind of synthetic method of above-mentioned polyester-type polyamide 6 elastomer, comprising the following steps:
(1) by after vacuum drying adipic acid and caprolactam be added in stirring-type polymer reactor, vacuumize 3~
10min, logical 3~10min of inert gas, so recycles 5~10 times, reactant is made to be in the environment under inert gas shielding afterwards
In, controlling system pressure in stirring-type polymer reactor is 0.1~0.5MPa；
(2) by stirring-type polymer reactor airtight heating to 60~100 DEG C, and the stirring of stirring-type polymer reactor is adjusted
After speed is 0~100r/min, to reactant heat-insulation pressure keeping 0.5~4 hour under conditions of pressure itself, it is deflated to normal pressure,
The temperature of stirring-type polymer reactor is down to 25~40 DEG C simultaneously；
(3) aliphatic lactones after vacuum drying are added to step (2) with 2,2'- (1,3- phenylene)-bisoxazoline
In stirring-type polymer reactor in, while glycidol based epoxy resin (EP), titanium compound and suitable water is added；Then
3~10min is vacuumized, 3~10min of inert gas is led to, so recycles 5~10 times, is in reactant under inert gas shielding
Environment in, control stirring-type polymer reactor in system pressure be 0.1~0.5MPa；
(4) by stirring-type polymer reactor airtight heating to 230~255 DEG C, the stirring of stirring-type polymer reactor is adjusted
Speed is 0~100r/min, wherein when the temperature of stirring-type polymer reactor reaches 180 DEG C, is deflated to 1MPa, and maintain
Pressure is deflated to normal pressure after 1MPa, reaction 0.5~4 hour, permanent after the reaction was continued at 230~255 DEG C 0.5~4 hour
Temperature persistently vacuumizes 0.1~2 hour, and reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is one of nitrogen or argon gas；The titanium compound is selected from four fourth of metatitanic acid
The mixture of one or more of ester, isopropyl titanate, n-propyl titanate esters.
The purpose of logical inert gas is the probability for reducing side reaction and occurring before reaction；The purpose vacuumized in reaction process is
The water generated in polycondensation reaction is removed, the progress of polymerization reaction forward direction is conducive to.
In wherein some embodiments, the synthetic method of the polyester-type polyamide 6 elastomer, comprising the following steps:
(1) by after vacuum drying adipic acid and caprolactam be added in stirring-type polymer reactor, vacuumize 4~
6min, logical 4~6min of nitrogen, so recycles 5~7 times, is in reactant in the environment under nitrogen protection afterwards, controls stirring-type
System pressure is 0.2~0.3MPa in polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 70~90 DEG C, and the stirring of stirring-type polymer reactor is adjusted
After speed is 30~50r/min, to reactant heat-insulation pressure keeping 1~2 hour under conditions of pressure itself, it is deflated to normal pressure, together
When the temperature of stirring-type polymer reactor is down to 30~35 DEG C；
(3) aliphatic lactones after vacuum drying are added to step (2) with 2,2'- (1,3- phenylene)-bisoxazoline
In stirring-type polymer reactor in, while glycidol based epoxy resin, titanium compound and suitable water is added；Then it takes out true
4~6min of sky leads to 4~6min of nitrogen, so recycles 5~7 times, is in reactant in the environment under nitrogen protection, control is stirred
Mixing system pressure in formula polymer reactor is 0.2~0.3MPa；
(4) by stirring-type polymer reactor airtight heating to 235~245 DEG C, the stirring of stirring-type polymer reactor is adjusted
Speed is 30~50r/min, wherein when the temperature of stirring-type polymer reactor reaches 180 DEG C, is deflated to 1MPa, and maintain
Pressure is deflated to normal pressure, after the reaction was continued at 235~245 DEG C 1~2 hour, constant temperature is held after 1MPa, reaction 1~2 hour
Continuous to vacuumize 0.3~1 hour, reaction terminates, and supplements nitrogen in discharging；
In above-mentioned steps, the titanium compound is butyl titanate.
In wherein some embodiments, the additional amount of the glycidol based epoxy resin be total monomer weight 0.1~
2%, the additional amount of the titanium compound is the 0.1~2% of total monomer weight；The monomer be aliphatic lactones, adipic acid, oneself
Lactams and 2,2'- (1,3- phenylene)-bisoxazoline.
In wherein some embodiments, the additional amount of the glycidol based epoxy resin be total monomer weight 0.5~
1.5%, the additional amount of titanium compound is the 0.6~1.4% of total monomer weight；The monomer be aliphatic lactones, adipic acid, oneself
Lactams, 2,2'- (1,3- phenylene)-bisoxazoline.
The composition principle of polyester-type polyamide 6 elastomer of the invention is as follows:
In order to improve the reaction rate of esterification and intrinsic viscosity (the i.e. molecule of polyester-type polyamide 6 elastomer
Amount), the present invention is reacted caprolactam with adipic acid to obtain the amide compound of both-end carboxyl first, then the compound
It is reacted to obtain polyester-type polyamide 6 of the present invention with aliphatic lactones, 2,2'- (1,3- phenylene)-bisoxazoline
Elastomer, while being blocked the carboxyl end group of polyester-type polyamide 6 elastomer by glycidol based epoxy resin, it improves poly-
The hydrolytic resistance and thermal stability of ester type polyamide 6 elastomer.
Polyester-type polyamide 6 elastomer provided by the present invention and its synthetic method have the advantage that
(1) polyester-type polyamide 6 elastomer of the invention has excellent impact property and processing performance and chemical resistance,
It can be applied to auto parts and components, mechanical equipment, electric equipment products, sports goods, or the compatilizer as polyester and polyamide
With polyamide modified dose etc..
(2) synthetic method of polyester-type polyamide 6 elastomer of the invention is simple, can be obtained by direct melting copolymerization
It arrives, synthesizing four steps can be carried out continuously, and time and artificial more be saved than batchwise polymerization working system, while total overall reaction is not
It needs to carry out in a solvent, eliminates the subsequent complex process for removing solvent.
(3) in the synthetic method of polyester-type polyamide 6 elastomer of the invention, when caprolactam and aliphatic lactones polymerize
The low molecule extractable matter of generation can be taken away in the 4th step esterification process by high vacuum, and remaining low molecule extractable matter is not
It will affect the performance of thermoplastic elastomer (TPE), therefore do not need both may be used using additional extraction equipment come separate low molecular extractable matter
It can also be energy saving to save the time.
Detailed description of the invention
Fig. 1 is the synthesis process flow diagram of polyester-type polyamide 6 elastomer of the present invention；
Fig. 2 is the nonisothermal crystallization melting curve figure of polyester-type polyamide 6 elastomer prepared by the embodiment of the present invention 5.
Specific embodiment
In order to further appreciate that feature of the invention, technological means and specific purposes achieved, function, parsing is originally
The advantages of invention and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism is as follows (synthesis process flow diagram is see Fig. 1) for polyester-type polyamide 6 elastomer of the present invention:
Wherein, a=3~5, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20.
Reaction mechanism
By above-mentioned reaction equation (1) and (2) it is found that adipic acid and caprolactam carry out ring-opening reaction, after caprolactam open loop
Amino End Group react to obtain the amide compound of both-end carboxyl with the carboxyl end group of adipic acid, the then amide compound of both-end carboxyl
Carboxyl end group, the terminal hydroxy group after aliphatic lactones open loop and carboxyl end group, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline
Group, these three groups can react to each other to obtain polyester-type polyamide 6 elastomer of the present invention.By above-mentioned reaction equation
(3) it is found that the carboxyl end group of polyester-type polyamide 6 elastomer can with the epoxy reaction of glycidol based epoxy resin (EP),
To achieve the purpose that polyester-type polyamide 6 elastomer blocks.
Raw material used in the embodiment of the present invention is as follows:
Gamma-butyrolacton contains chemical limited liability company purchased from Zhejiang connection.
δ-valerolactone is purchased from Suzhou Fu Lu Biotechnology Co., Ltd.
6-caprolactone contains chemical limited liability company purchased from Zhejiang connection.
Adipic acid is purchased from Zibo Shuan Ou Chemical Co., Ltd..
Caprolactam is purchased from Hubei Sanning Chemical Industry Co., Ltd..
2,2'- (1,3- phenylene)-bisoxazolines, purchased from uncommon love (Shanghai) the chemical conversion industry Development Co., Ltd of ladder.
The copolymer of styrene, methyl methacrylate and glycidyl methacrylate (belongs to glycidol class ring
Oxygen resin), it is purchased from Shanxi-Prov Inst of Chemical Industry.
Butyl titanate is purchased from Sinopharm Chemical Reagent Co., Ltd..
Embodiment 1:
A kind of synthetic method of polyester-type polyamide 6 elastomer of the present embodiment, comprising the following steps:
(1) 1.5g (0.01mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.1MPa；
(2) by stirring-type polymer reactor airtight heating to 60 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 10r/min, to reactant heat-insulation pressure keeping 4 hours under conditions of pressure itself, it is deflated to normal pressure, while temperature is down to 25
℃；
(3) by 8.6g (0.1mol) gamma-butyrolacton, 2.2g (0.01mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 0.1% benzene of total monomer weight is added
The copolymer (0.1g) of ethylene, methyl methacrylate and glycidyl methacrylate is total as end-capping reagent, addition monomer
Medium of 0.1% butyl titanate (0.1g) of weight as catalyst, addition 100mL water as mass-and heat-transfer；Then it takes out
Vacuum 5min leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, and control stirring-type is poly-
Closing system pressure in reactor is 0.1MPa；
(4) by stirring-type polymer reactor airtight heating to 230 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
10r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, be deflated to 1MPa, and maintain pressure in 1MPa, instead
After answering 4 hours, it is deflated to normal pressure, after the reaction was continued at 230 DEG C 4 hours, constant temperature is persistently vacuumized 0.1 hour, and reaction terminates,
Nitrogen is supplemented in discharging.
Reaction equation is as follows:
Wherein, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20.
Embodiment 2:
A kind of synthetic method of polyester-type polyamide 6 elastomer of the present embodiment, comprising the following steps:
(1) 14.6g (0.1mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.5MPa；
(2) by stirring-type polymer reactor airtight heating to 100 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 100r/min, to reactant heat-insulation pressure keeping 0.5 hour under conditions of pressure itself, it is deflated to normal pressure, while temperature drops
To 40 DEG C；
(3) by 60.1g (0.6mol) δ-valerolactone, 43.2g (0.2mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 2% benzene second of total monomer weight is added
The copolymer (4.6g) of alkene, methyl methacrylate and glycidyl methacrylate is as end-capping reagent, addition total weight of monomer
Medium of 2% butyl titanate (4.6g) of amount as catalyst, addition 150mL water as mass-and heat-transfer；Then it vacuumizes
5min leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, and control stirring-type polymerization is anti-
Answering system pressure in device is 0.5MPa；
(4) by stirring-type polymer reactor airtight heating to 255 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
100r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, it is deflated to 1MPa, and maintains pressure in 1MPa,
After reaction 0.5 hour, it is deflated to normal pressure, after the reaction was continued at 255 DEG C 0.5 hour, constant temperature is persistently vacuumized 2 hours, reaction
Terminate, supplements nitrogen in discharging.
Reaction equation is as follows:
Wherein, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20.
Embodiment 3:
A kind of synthetic method of polyester-type polyamide 6 elastomer of the present embodiment, comprising the following steps:
(1) 1.5g (0.01mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.2MPa；
(2) by stirring-type polymer reactor airtight heating to 70 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 30r/min, to reactant heat-insulation pressure keeping 2 hours under conditions of pressure itself, it is deflated to normal pressure, while temperature is down to 30
℃；
(3) by 22.8g (0.2mol) 6-caprolactone, 21.6g (0.1mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 0.5% benzene of total monomer weight is added
The copolymer (0.8g) of ethylene, methyl methacrylate and glycidyl methacrylate is total as end-capping reagent, addition monomer
Medium of 0.6% butyl titanate (1g) of weight as catalyst, addition 130mL water as mass-and heat-transfer；Then it takes out true
Empty 5min leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, control stirring-type polymerization
System pressure is 0.2MPa in reactor；
(4) by stirring-type polymer reactor airtight heating to 235 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
30r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, be deflated to 1MPa, and maintain pressure in 1MPa, instead
After answering 2 hours, it is deflated to normal pressure, after the reaction was continued at 235 DEG C 2 hours, constant temperature is persistently vacuumized 0.3 hour, and reaction terminates,
Nitrogen is supplemented in discharging.
Reaction equation is as follows:
Wherein, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20.
Embodiment 4:
A kind of synthetic method of polyester-type polyamide 6 elastomer of the present embodiment, comprising the following steps:
(1) 5.8g (0.04mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) by stirring-type polymer reactor airtight heating to 90 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 50r/min, to reactant heat-insulation pressure keeping 1 hour under conditions of pressure itself, it is deflated to normal pressure, while temperature is down to 35
℃；
(3) by 57.1g (0.5mol) 6-caprolactone, 32.4g (0.15mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 1.5% benzene of total monomer weight is added
The copolymer (3.1g) of ethylene, methyl methacrylate and glycidyl methacrylate is total as end-capping reagent, addition monomer
Medium of 1.4% butyl titanate (2.9g) of weight as catalyst, addition 140mL water as mass-and heat-transfer；Then it takes out
Vacuum 5min leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, and control stirring-type is poly-
Closing system pressure in reactor is 0.3MPa；
(4) by stirring-type polymer reactor airtight heating to 245 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
50r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, be deflated to 1MPa, and maintain pressure in 1MPa, instead
After answering 1 hour, it is deflated to normal pressure, after the reaction was continued at 245 DEG C 1 hour, constant temperature is persistently vacuumized 1 hour, and reaction terminates,
Nitrogen is supplemented when discharging.
Reaction equation is the same as embodiment 3.
Embodiment 5:
A kind of synthetic method of polyester-type polyamide 6 elastomer of the present embodiment, comprising the following steps:
(1) 2.9g (0.02mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) by stirring-type polymer reactor airtight heating to 80 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 40r/min, to reactant heat-insulation pressure keeping 1.5 hours under conditions of pressure itself, it is deflated to normal pressure, while temperature is down to
33℃；
(3) by 34.2g (0.3mol) 6-caprolactone, 30.3g (0.14mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 1% benzene second of total monomer weight is added
The copolymer (1.8g) of alkene, methyl methacrylate and glycidyl methacrylate is as end-capping reagent, addition total weight of monomer
Medium of 1% butyl titanate (1.8g) of amount as catalyst, addition 120mL water as mass-and heat-transfer；Then it vacuumizes
5min leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, and control stirring-type polymerization is anti-
Answering system pressure in device is 0.3MPa；
(4) by stirring-type polymer reactor airtight heating to 240 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
40r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, be deflated to 1MPa, and maintain pressure in 1MPa, instead
After answering 1.5 hours, it is deflated to normal pressure, after the reaction was continued at 240 DEG C 1.5 hours, constant temperature is persistently vacuumized 0.5 hour, reaction
Terminate, supplements nitrogen in discharging.
Reaction equation is the same as embodiment 3.
The nonisothermal crystallization melting curve figure of the polyester-type polyamide 6 elastomer that the present embodiment is prepared as shown in Fig. 2,
The peak temperature (i.e. melting temperature) that the melting peak of the polyester-type polyamide 6 elastomer is shown in figure is 217.35 DEG C.
Comparative example 1:
A kind of synthetic method of polyester-type polyamide 6 elastomer of this comparative example, comprising the following steps:
(1) 2.9g (0.02mol) adipic acid, 113.2g (1mol) caprolactam after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so circulation 6 times, reactant is made to be present in the ring under nitrogen protection
In border, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) by stirring-type polymer reactor airtight heating to 80 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 40r/min, to reactant heat-insulation pressure keeping 1.5 hours under conditions of pressure itself, it is deflated to normal pressure, while temperature is down to
33℃；
(3) by 34.2g (0.3mol) 6-caprolactone, 30.3g (0.14mol) 2,2'- (Asia the 1,3- benzene after vacuum drying
Base)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while 1% metatitanic acid of total monomer weight is added
Medium of four butyl esters (1.8g) as catalyst, addition 120mL water as mass-and heat-transfer；Then 5min is vacuumized, nitrogen is led to
5min, so circulation 6 times, are present in reactant in the environment under nitrogen protection, control system in stirring-type polymer reactor
Pressure is 0.3MPa；
(4) by stirring-type polymer reactor airtight heating to 240 DEG C, the mixing speed for adjusting stirring-type polymer reactor is
40r/min, wherein when stirring-type polymer reactor temperature reaches 180 DEG C, be deflated to 1MPa, and maintain pressure in 1MPa, instead
After answering 1.5 hours, it is deflated to normal pressure, after the reaction was continued at 240 DEG C 1.5 hours, constant temperature is persistently vacuumized 0.5 hour, reaction
Terminate, supplements nitrogen in discharging.
The following are embodiment 1-5 and the raw material of comparative example 1 to form list.
1 embodiment 1-5 of table and the raw material of comparative example 1 form list
The polyester-type polyamide 6 elastomer that above-described embodiment is prepared carries out following performance test:
Tensile property: GB/T 1040-2006 standard testing, rate of extension 50mm/min are pressed.
Impact property: GB/T 1843-2008 standard testing is pressed, batten is with a thickness of 4mm.
Melt index: pressing GB/T 3682-2000 standard testing, and test temperature is 250 DEG C, loads as 2.16kg.
Chemical resistance: GB/T 11547-2008 standard testing is pressed, the injection molding batten of polyester-type polyamide 6 elastomer is set
In dimethylbenzene, the testing time is 1 day, the tensile strength of test injection molding batten.The calculation formula of performance change percentage are as follows:
Y is performance change percentage, X in formula1To impregnate preceding performance number, X accordingly2For a certain performance number after immersion.
Intrinsic viscosity: GB/T 1632-2008 standard testing is pressed, solvent is the concentrated sulfuric acid.
Glass transition temperature: GB/T 19466.2-2004 standard testing is pressed.
Melting temperature: GB/T 19466.3-2004 standard testing is pressed.
Hydrolytic resistance: the injection molding batten of polyester-type polyamide 6 elastomer being placed in boiling water (>=99 DEG C), boiling 1 hour,
The tensile strength of test injection molding batten.The calculation formula of performance change percentage are as follows:
Y is performance change percentage, X in formula1For performance number before corresponding boiling, X2For a certain performance number after boiling.
It thermally decomposes initial temperature: pressing GB/T 13464-2008 standard testing.
The performance test results are as shown in table 2.
The performance list of 2 embodiment 1-5 of table and the polyester-type polyamide 6 elastomer of comparative example 1
Compared with Example 5, the aliphatic lactones of embodiment 1 are gamma-butyrolacton to embodiment 1, and the aliphatic of embodiment 5
Lactone is 6-caprolactone, so the carbochain of the structural unit of embodiment 1 wants short compared to embodiment 5, amido bond density
Want high compared with embodiment 5, and aliphatic lactones, 2,2'- (1,3- phenylene)-bisoxazoline, catalyst metatitanic acid four that it is added
Butyl ester will lack compared with embodiment 5, from Table 2, it can be seen that the tensile strength of the polyester-type polyamide 6 elastomer of embodiment 1, molten
Melt index and chemical resistance and is higher than embodiment 5, and notch impact strength, intrinsic viscosity, glass transition temperature, melting temperature
Degree, hydrolytic resistance and thermal decomposition initial temperature will be lower than embodiments 5.
Compared with Example 5, the aliphatic lactones of embodiment 2 are δ-valerolactone to embodiment 2, and the aliphatic of embodiment 5
Lactone is 6-caprolactone, so the carbochain of the structural unit of embodiment 2 wants short compared to embodiment 5, amido bond density
Want high compared with embodiment 5, while the aliphatic lactones of its addition, 2,2'- (1,3- phenylene)-bisoxazoline, catalyst metatitanic acid
Four butyl esters are more compared with embodiment 5, from Table 2, it can be seen that the notch shock of the polyester-type polyamide 6 elastomer of embodiment 2
Intensity, intrinsic viscosity, glass transition temperature, melting temperature and hydrolytic resistance are higher than embodiment 5, and tensile strength, melting
Index, chemical resistance and thermal decomposition initial temperature will be lower than embodiments 5.
Compared with Example 5, comparative example 1 is not added with end-capping reagent glycidol based epoxy resin to comparative example 1, obtained poly-
The end group of ester type polyamide 6 elastomer is active carboxyl end group, and embodiment 5 is added to end-capping reagent glycidol based epoxy resin.
From Table 2, it can be seen that comparative example 1 adds end-capping reagent glycidol based epoxy resin due to not having, polyester-type obtained is poly-
The performance of 6 elastomer of amide is all lower than embodiment 5.
Embodiment 3~5 is to adjust aliphatic lactones, adipic acid, 2,2'- (1,3- phenylene)-bisoxazoline, styrene,
The copolymer of methyl methacrylate and glycidyl methacrylate, the additive amount of butyl titanate can from table 2
Out, with aliphatic lactones, adipic acid, 2,2'- (1,3- phenylene)-bisoxazoline, styrene, methyl methacrylate and first
The additive amount of the copolymer of base glycidyl acrylate, butyl titanate increases, the notch punching of polyester-type polyamide 6 elastomer
Hit intensity, intrinsic viscosity, glass transition temperature, melting temperature, hydrolytic resistance and thermal decomposition initial temperature gradually increase, and draw
Intensity, melt index and chemical resistance is stretched then to gradually decrease.Wherein, the polyester-type polyamide 6 elastomer of embodiment 5 is comprehensive
It can be best.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of polyester-type polyamide 6 elastomer, it is characterised in that its, there is following structure shown in formula I:
In formula I, a=3~5, m=2~20, n=2~20, x=10~100, y=10~100, z=1~20；
The polyester-type polyamide 6 elastomer is by aliphatic lactones, adipic acid, caprolactam, 2,2'- (1,3- phenylene)-two
Oxazoline is copolymerized；The aliphatic lactones, adipic acid, caprolactam, 2,2'- (1,3- phenylene)-bisoxazoline rub
You are than being 0.1~0.6:0.01~0.1:1:0.01~0.2；The polyester-type polyamide 6 elastomer is that its carboxyl end group is shunk
The polyester-type polyamide 6 elastomer that glycerol based epoxy resin is blocked；
The synthetic method of the polyester-type polyamide 6 elastomer the following steps are included:
(1) adipic acid after vacuum drying is added in stirring-type polymer reactor with caprolactam, vacuumizes 3~10min,
Lead to 3~10min of inert gas afterwards, so recycle 5~10 times, be in reactant in the environment under inert gas shielding, controls
System pressure is 0.1~0.5MPa in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 60~100 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 0~100r/min, to reactant heat-insulation pressure keeping 0.5~4 hour under conditions of pressure itself, it is deflated to normal pressure, simultaneously
The temperature of stirring-type polymer reactor is down to 25~40 DEG C；
(3) aliphatic lactones after vacuum drying are added in step (2) with 2,2'- (1,3- phenylene)-bisoxazoline
In stirring-type polymer reactor, while glycidol based epoxy resin, titanium compound and suitable water is added；Then 3 are vacuumized
~10min leads to 3~10min of inert gas, so recycles 5~10 times, reactant is made to be in the environment under inert gas shielding
In, controlling system pressure in stirring-type polymer reactor is 0.1~0.5MPa；
(4) by stirring-type polymer reactor airtight heating to 230~255 DEG C, the mixing speed of stirring-type polymer reactor is adjusted
For 0~100r/min, wherein when the temperature of stirring-type polymer reactor reaches 180 DEG C, be deflated to 1MPa, and maintain pressure
After 1MPa, reaction 0.5~4 hour, it is deflated to normal pressure, after the reaction was continued at 230~255 DEG C 0.5~4 hour, constant temperature is held
Continuous to vacuumize 0.1~2 hour, reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is one of nitrogen or argon gas；The titanium compound is selected from butyl titanate, titanium
The mixture of one or more of isopropyl propionate, n-propyl titanate esters.
2. polyester-type polyamide 6 elastomer according to claim 1, which is characterized in that the aliphatic lactones, oneself two
Acid, caprolactam, 2,2'- (1,3- phenylene)-bisoxazoline molar ratio be 0.2~0.5:0.01~0.04:1:0.1~
0.15。
3. polyester-type polyamide 6 elastomer according to claim 1, which is characterized in that the polyester-type polyamide 6 elasticity
The intrinsic viscosity of body is 0.8~1.8dL/g, glass transition temperature Tg>=48 DEG C, melting temperature TmIt is 210~225 DEG C.
4. polyester-type polyamide 6 elastomer according to claim 1-3, which is characterized in that in the aliphatic
Ester is selected from the mixture of one or more of gamma-butyrolacton, δ-valerolactone, 6-caprolactone.
5. polyester-type polyamide 6 elastomer according to claim 4, which is characterized in that the aliphatic lactones are selected from ε-
Caprolactone.
6. polyester-type polyamide 6 elastomer according to claim 1-3, which is characterized in that the glycidol
Based epoxy resin is the copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
7. a kind of synthetic method of any one of claim 1-6 polyester-type polyamide 6 elastomer, which is characterized in that including
Following steps:
(1) adipic acid after vacuum drying is added in stirring-type polymer reactor with caprolactam, vacuumizes 3~10min,
Lead to 3~10min of inert gas afterwards, so recycle 5~10 times, be in reactant in the environment under inert gas shielding, controls
System pressure is 0.1~0.5MPa in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 60~100 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 0~100r/min, to reactant heat-insulation pressure keeping 0.5~4 hour under conditions of pressure itself, it is deflated to normal pressure, simultaneously
The temperature of stirring-type polymer reactor is down to 25~40 DEG C；
(3) aliphatic lactones after vacuum drying are added in step (2) with 2,2'- (1,3- phenylene)-bisoxazoline
In stirring-type polymer reactor, while glycidol based epoxy resin, titanium compound and suitable water is added；Then 3 are vacuumized
~10min leads to 3~10min of inert gas, so recycles 5~10 times, reactant is made to be in the environment under inert gas shielding
In, controlling system pressure in stirring-type polymer reactor is 0.1~0.5MPa；
(4) by stirring-type polymer reactor airtight heating to 230~255 DEG C, the mixing speed of stirring-type polymer reactor is adjusted
For 0~100r/min, wherein when the temperature of stirring-type polymer reactor reaches 180 DEG C, be deflated to 1MPa, and maintain pressure
After 1MPa, reaction 0.5~4 hour, it is deflated to normal pressure, after the reaction was continued at 230~255 DEG C 0.5~4 hour, constant temperature is held
Continuous to vacuumize 0.1~2 hour, reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is one of nitrogen or argon gas；The titanium compound is selected from butyl titanate, titanium
The mixture of one or more of isopropyl propionate, n-propyl titanate esters.
8. the synthetic method of polyester-type polyamide 6 elastomer according to claim 7, which is characterized in that including following step
It is rapid:
(1) adipic acid after vacuum drying is added in stirring-type polymer reactor with caprolactam, vacuumizes 4~6min,
Lead to 4~6min of nitrogen afterwards, so recycles 5~7 times, be in reactant in the environment under nitrogen protection, control stirring-type polymerization
System pressure is 0.2~0.3MPa in reactor；
(2) by stirring-type polymer reactor airtight heating to 70~90 DEG C, and the mixing speed of stirring-type polymer reactor is adjusted
After 30~50r/min, to reactant heat-insulation pressure keeping 1~2 hour under conditions of pressure itself, it is deflated to normal pressure, simultaneously will
The temperature of stirring-type polymer reactor is down to 30~35 DEG C；
(3) aliphatic lactones after vacuum drying are added in step (2) with 2,2'- (1,3- phenylene)-bisoxazoline
In stirring-type polymer reactor, while glycidol based epoxy resin, titanium compound and suitable water is added；Then 4 are vacuumized
~6min leads to 4~6min of nitrogen, so recycles 5~7 times, is in reactant in the environment under nitrogen protection, controls stirring-type
System pressure is 0.2~0.3MPa in polymer reactor；
(4) by stirring-type polymer reactor airtight heating to 235~245 DEG C, the mixing speed of stirring-type polymer reactor is adjusted
For 30~50r/min, wherein when the temperature of stirring-type polymer reactor reaches 180 DEG C, be deflated to 1MPa, and maintain pressure
After 1MPa, reaction 1~2 hour, it is deflated to normal pressure, after the reaction was continued at 235~245 DEG C 1~2 hour, constant temperature is persistently taken out
Vacuum 0.3~1 hour, reaction terminated, and supplemented nitrogen in discharging；
In above-mentioned steps, the titanium compound is butyl titanate.
9. the synthetic method of polyester-type polyamide 6 elastomer according to claim 7 or 8, which is characterized in that the shrink
The additional amount of glycerol based epoxy resin is the 0.1~2% of total monomer weight, and the additional amount of the titanium compound is total monomer weight
0.1~2%；The monomer is aliphatic lactones, adipic acid, caprolactam and 2,2'- (1,3- phenylene)-bisoxazoline.
10. the synthetic method of polyester-type polyamide 6 elastomer according to claim 9, which is characterized in that the shrink is sweet
The additional amount of type epoxy resins is the 0.5~1.5% of total monomer weight, and the additional amount of the titanium compound is total monomer weight
0.6~1.4%；The monomer is aliphatic lactones, adipic acid, caprolactam and 2,2'- (1,3- phenylene)-dioxazole
Quinoline.
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| CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
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| CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
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| 环氧类扩链剂制备高黏度尼龙6及其性能表征;宗胜男等;《工程塑料应用》;20140731;第42卷(第7期);30-33 |
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