CN108715635A - Polyether-type nylon66 fiber thermoplastic elastomer (TPE) and its synthetic method - Google Patents
Polyether-type nylon66 fiber thermoplastic elastomer (TPE) and its synthetic method Download PDFInfo
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- CN108715635A CN108715635A CN201810501026.2A CN201810501026A CN108715635A CN 108715635 A CN108715635 A CN 108715635A CN 201810501026 A CN201810501026 A CN 201810501026A CN 108715635 A CN108715635 A CN 108715635A
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- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract
The invention discloses a kind of polyether-type nylon66 fiber thermoplastic elastomer (TPE) and its synthetic methods.The polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention has structure shown in formula I：In formula I, a=2~4, m=5~100, n=2~20, x=3~50, y=10~100, z=1~20.The synthetic method of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention is as follows：Hexamethylene diamine and adipic acid are subjected to the amide compound that both-end carboxyl is obtained by the reaction first, then the compound and polyether Glycols, 2,2'- (1,3- phenylenes)-bisoxazoline carries out that polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention is obtained by the reaction, while being blocked the terminal hydroxy group of polyether-type nylon66 fiber thermoplastic elastomer (TPE) and end carboxyl by glycidol based epoxy resin.The polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present 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 polyether-type nylon66 fiber thermoplastic elastomer (TPE) and its synthesis side
Method.
Background technology
Nylon thermoplastic's elastomer (TPAE) belongs to a member in thermoplastic elastomer (TPE) family, relative to widely applied
Thermoplastic polyurethane elastomer (TPU), thermoplastic polyolefin elastomer (TPO), styrenic thermoplastic elastomer (SBC), thermoplastic
Property polyvinyl chloride elastomer (TPVC) and thermoplastic polyether ester elastomer (TPEE) etc., the preparation and application starting of TPAE compared with
Evening.TPAE was succeeded in developing and was commercialized by German Hughes Electronics in 1979 first, subsequent Upjohn Company of the U.S., French Ah
Support chemical company, The Iams Co. of Switzerland, Japanese ink company also succeed in developing and release the respective trade mark in succession.
Nylon thermoplastic's elastomer (TPAE) is mainly the copolymer being made of nylon hard section and polyethers or polyester soft segment,
The middle nylon as hard section mainly has PA6, PA66, PA11, PA12 etc., which essentially dictates nylon thermoplastic's elasticity
The characteristics such as density, hardness, fusing point, tensile strength, the resistance to various organic chemicals of body；Part as soft segment, which mainly has, gathers oneself
Lactone (PCL), polyethylene glycol (PEG), polyoxypropylene (PPG), PolyTHF (PTMG) etc., which mainly determines
Low-temperature characteristics, hygroscopicity, antistatic property, dyeability and the stability to certain chemicals of nylon thermoplastic's elastomer are determined
Etc. characteristics.Meanwhile it can be big by adjusting the type and composition ratio of hard section and soft segment, molecular weight in nylon thermoplastic's elastomer
The conditions such as small and distribution can get the TPAE productions of the different performances grades such as hardness, density, heat resistance, hygroscopicity and mechanical property
Product, to meet all kinds of demands in market.
Currently, some researchs have been done to the synthesis of nylon thermoplastic's elastomer in the prior art, 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 Polyether polyamide elastomer of the α of carbon number 4~20, ω-straight-chain aliphatic dicarboxylic acids；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 of 10 to 100 moles of % and/or bis- (aminocyclohexyl) propane
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
Branched C2-C5 polyoxyalkylenes, line style or branched substituted or unsubstituted C2-C36 alkylidenes, C6-C36 cycloalkylidenes, C6-
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 are amide-(CONH) or ester-(COO) key independently of each other；It is Chinese special
Sharp CN103772643A discloses a kind of preparation method of PA6 systems thermoplastic polyamide elastomer material.The polyamide elastomer
It is the low molecular weight PA6 performed polymers by heat resistant type modified polyurethane and end carboxyl according to mass fraction, heat resistant type is modified poly- ammonia
Ester accounts for the 10%~60% of total polymer mass, and the content of end carboxyl low molecular weight PA6 hard sections 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 is by terephthalic acid (TPA), 11- aminoundecanoic acids, aliphatic dihydroxy alcohol and 2,2'-
(1,3- phenylenes)-bisoxazoline polycondensation reaction obtains.
Invention content
Based on this, the purpose of the present invention is to provide one kind having excellent impact property and processing performance and chemical resistance
Polyether-type nylon66 fiber thermoplastic elastomer (TPE), can be applied to auto parts and components, mechanical equipment, electric equipment products, sports goods,
Or compatilizer and modified nylon agent etc. as polyester and nylon.
In order to achieve the above-mentioned object of the invention, this invention takes following technical solutions：
A kind of polyether-type nylon66 fiber thermoplastic elastomer (TPE), with following structure shown in formula I：
In formula I, a=2~4, m=5~100, n=2~20, x=3~50, y=10~100, z=1~20；
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) is by polyether Glycols, adipic acid, hexamethylene diamine, the 2,2'- (Asias 1,3- benzene
Base)-bisoxazoline is copolymerized；The polyether Glycols, adipic acid, hexamethylene diamine, 2,2'- (1,3- phenylenes)-bisoxazoline
Molar ratio be 0.01~0.2:1.01~1.2:1:0.1~0.4；
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) be its terminal hydroxy group and end carboxyl by glycidol based epoxy resin into
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) of row sealing end.
In wherein some embodiments, the polyether Glycols, adipic acid, hexamethylene diamine, 2,2'- (1,3- phenylene)-two
The molar ratio of oxazoline is 0.05~0.1:1.05~1.1:1:0.1~0.2.
In wherein some embodiments, the intrinsic viscosity of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) is 0.8~
2.0dL/g, glass transition temperature Tg>=53 DEG C, melting temperature TmIt is 243~263 DEG C.
In wherein some embodiments, the polyether Glycols are selected from polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether two
The mixture of one or more of alcohol；The number-average molecular weight of the polyether Glycols is 700~4000.
In wherein some embodiments, the polyether Glycols are selected from polyethylene glycol.
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 polyether-type nylon66 fiber thermoplastic elastomer (TPE).
Specific technical solution is as follows：
A kind of synthetic method of above-mentioned polyether-type nylon66 fiber thermoplastic elastomer (TPE), includes the following steps：
(1) adipic acid and the hexamethylene diamine after vacuum drying are added in stirring-type polymer reactor, vacuumize 3~
10min, 3~10min of logical inert gas, so recycles 5~10 times, reactant is made to be in the environment under inert gas shielding afterwards
In, it is 0.1~0.5MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 70~110 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) polyether Glycols after vacuum drying are added to step (2) with 2,2'- (1,3- phenylenes)-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, reactant is made to be 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 268~293 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 in 1MPa after reacting 0.5~4 hour, after at 268~293 times, the reaction was continued 0.5~4 hour, constant temperature
It persistently vacuumizes 0.1~2 hour, reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is one kind in 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 polymerisation forward direction is conducive to.
In wherein some embodiments, the synthetic method of the polyether-type nylon66 fiber thermoplastic elastomer (TPE), including following step
Suddenly：
(1) adipic acid and the hexamethylene diamine after vacuum drying are added in stirring-type polymer reactor, vacuumize 4~
6min, 4~6min of logical nitrogen, so recycles 5~7 times, reactant is made to be 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 80~100 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) polyether Glycols after vacuum drying are added to step (2) with 2,2'- (1,3- phenylenes)-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, so that reactant is in the environment under nitrogen protection, control is stirred
It is 0.2~0.3MPa to mix system pressure in formula polymer reactor；
(4) by stirring-type polymer reactor airtight heating to 273~283 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 273~283 DEG C 1~2 hour, constant temperature is held in 1MPa after reacting 1~2 hour
Continuous to vacuumize 0.3~1 hour, reaction terminates, and nitrogen is supplemented in discharging；
In above-mentioned steps, the titanium compound is butyl titanate.
In wherein some embodiments, the addition of the glycidol based epoxy resin be total monomer weight 0.1~
2%, the addition of the titanium compound is the 0.1~2% of total monomer weight；The monomer be polyether Glycols, adipic acid, oneself
Diamines and 2,2'- (1,3- phenylenes)-bisoxazoline.
In wherein some embodiments, the addition of the glycidol based epoxy resin be total monomer weight 0.5~
1.5%, the addition of the titanium compound is the 0.6~1.4% of total monomer weight；The monomer be polyether Glycols, oneself two
Acid, hexamethylene diamine and 2,2'- (1,3- phenylenes)-bisoxazoline.
The composition principle of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention is as follows：
In order to improve esterification reaction rate and polyether-type nylon66 fiber thermoplastic elastomer (TPE) intrinsic viscosity (i.e.
Molecular weight), hexamethylene diamine and adipic acid are carried out the amide compound that both-end carboxyl is obtained by the reaction by the present invention first, then the chemical combination
Object with polyether Glycols, 2,2'- (1,3- phenylenes)-bisoxazoline carries out that polyether-type nylon66 fiber of the present invention is obtained by the reaction
Thermoplastic elastomer (TPE), while by glycidol based epoxy resin by the terminal hydroxy group of polyether-type nylon66 fiber thermoplastic elastomer (TPE) and end
Carboxyl is blocked, and the hydrolytic resistance and thermal stability of polyether-type nylon66 fiber thermoplastic elastomer (TPE) are improved.
Polyether-type nylon66 fiber thermoplastic elastomer (TPE) provided by the present invention and its synthetic method have the following advantages：
(1) polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the invention has excellent impact property and processing performance and resistance toization
The property learned, can be applied to auto parts and components, mechanical equipment, electric equipment products, sports goods, or as the compatible of polyester and nylon
Agent and modified nylon agent etc..
(2) synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the invention is simple, is by direct melting copolymerization
Available, four steps can be carried out continuously, and time and manually more be saved than batchwise polymerization working system, while total overall reaction is not
It needs to carry out in a solvent, eliminates the follow-up complex process for removing solvent.
(3) in the synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the invention, when hexamethylene diamine and adipic acid 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
The performance of thermoplastic elastomer (TPE) can be influenced, therefore need not both may be used using additional extraction equipment come separate low molecular extractable matter
It can also be energy saving to save the time.
Description of the drawings
Fig. 1 is the synthesis process flow diagram of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention；
Fig. 2 is the nonisothermal crystallization melting curve of polyether-type nylon66 fiber thermoplastic elastomer (TPE) prepared by the embodiment of the present invention 5
Figure.
Specific implementation mode
In order to further appreciate that the feature, technological means and the specific purposes reached, function of the present invention, parsing is originally
The advantages of invention and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present invention is following (synthesis process flow diagram is see Fig. 1)：
Wherein, a=2~4, m=5~100, n=2~20, x=3~50, y=10~100, z=1~20.
Reaction mechanism
By above-mentioned reaction equation (1) and (2) it is found that both-end carboxylic is obtained by the reaction in the end carboxyl of adipic acid and the Amino End Group of hexamethylene diamine
The amide compound of base, the then end carboxyl of the amide compound of both-end carboxyl, the terminal hydroxy group of polyether Glycols, 2,2'- (1,3-
Phenylene)-bisoxazoline oxazoline group, these three groups can react to each other to obtain polyether-type nylon of the present invention
66 thermoplastic elastomer (TPE)s.By above-mentioned reaction equation (3) and (4) it is found that terminal hydroxy group and the end of polyether-type nylon66 fiber thermoplastic elastomer (TPE)
Carboxyl can with the epoxy reaction of glycidol based epoxy resin (EP), to reach polyether-type nylon66 fiber thermoplastic elastomer (TPE)
The purpose of sealing end.
Raw material used in the embodiment of the present invention is as follows：
Polyethylene glycol, number-average molecular weight 1000 are purchased from Jiangsu Hai'an Petrochemical Plant.
Polypropylene glycol, number-average molecular weight 700 are purchased from Nantong Run An Chemical Co., Ltd.s.
Polytetrahydrofuran ether glycol, number-average molecular weight 4000 are purchased from long nine Chemical Co., Ltd. in Changzhou.
Adipic acid is purchased from Zibo Shuan Ou Chemical Co., Ltd.s.
Hexamethylene diamine is purchased from Wuxi Yinda Nylon 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 polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present embodiment, includes the following steps：
(1) 147.6g (1.01mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.1MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 70 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 40g (0.01mol) polytetrahydrofuran ether glycol after vacuum drying, 21.6g (0.1mol) 2,2'- (1,3-
Phenylene)-bisoxazoline is added in the stirring-type polymer reactor in step (2), while being added the 0.1% of total monomer weight
Styrene, methyl methacrylate and glycidyl methacrylate copolymer (0.3g) as end-capping reagent, be added it is single
Medium of 0.1% butyl titanate (0.3g) of body total weight as catalyst, addition 100mL water as mass-and heat-transfer；So
After vacuumize 5min, lead to nitrogen 5min, so cycle 6 times, reactant made to be present in the environment under nitrogen protection, control stirring
System pressure is 0.1MPa in formula polymer reactor；
(4) by stirring-type polymer reactor airtight heating to 268 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 268 DEG C 4 hours, constant temperature persistently vacuumizes 0.1 hour, and reaction terminates,
Nitrogen is supplemented in discharging.
Reaction equation is as follows：
Wherein, m=55~56, n=2~20, x=3~50, y=10~100, z=1~20.
Embodiment 2：
A kind of synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present embodiment, includes the following steps：
(1) 175.4g (1.2mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.5MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 110 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 140g (0.2mol) polypropylene glycol, 86.5g (0.4mol) 2,2'- (1,3- phenylenes)-after vacuum drying
Bisoxazoline is added in the stirring-type polymer reactor in step (2), at the same be added total monomer weight 2% styrene,
Methyl methacrylate and the copolymer (10.4g) of glycidyl methacrylate are as end-capping reagent, addition total monomer weight
2% butyl titanate (10.4g) as catalyst, medium of the 150mL water as mass-and heat-transfer is added；Then it vacuumizes
5min leads to nitrogen 5min, so cycle 6 times, reactant is made to be present in the environment under nitrogen protection, and control stirring-type polymerization is anti-
It is 0.5MPa to answer system pressure in device；
(4) by stirring-type polymer reactor airtight heating to 293 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 293 DEG C 0.5 hour, constant temperature persistently vacuumizes 2 hours, reaction
Terminate, nitrogen is supplemented in discharging.
Reaction equation is as follows：
Wherein, m=11~13, n=2~20, x=3~50, y=10~100, z=1~20.
Embodiment 3：
A kind of synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present embodiment, includes the following steps：
(1) 153.4g (1.05mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.2MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 80 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 50g (0.05mol) polyethylene glycol, 21.6g (0.1mol) 2,2'- (1,3- phenylenes)-after vacuum drying
Bisoxazoline is added in the stirring-type polymer reactor in step (2), while 0.5% benzene second of total monomer weight is added
The copolymer (1.7g) of alkene, methyl methacrylate and glycidyl methacrylate is as end-capping reagent, addition total weight of monomer
Medium of 0.6% butyl titanate (2.0g) of amount as catalyst, addition 130mL water as mass-and heat-transfer；Then it takes out true
Empty 5min leads to nitrogen 5min, so cycle 6 times, reactant is made to be present 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 273 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 273 DEG C 2 hours, constant temperature persistently vacuumizes 0.3 hour, and reaction terminates,
Nitrogen is supplemented in discharging.
Reaction equation is as follows：
Wherein, m=22~23, n=2~20, x=3~50, y=10~100, z=1~20.
Embodiment 4：
A kind of synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present embodiment, includes the following steps：
(1) 160.8g (1.1mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 100 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 100g (0.1mol) polyethylene glycol, 43.2g (0.2mol) 2,2'- (1,3- phenylenes)-after vacuum drying
Bisoxazoline is added in the stirring-type polymer reactor in step (2), while 1.5% benzene second of total monomer weight is added
The copolymer (6.3g) of alkene, methyl methacrylate and glycidyl methacrylate is as end-capping reagent, addition total weight of monomer
Medium of 1.4% butyl titanate (5.9g) of amount as catalyst, addition 140mL water as mass-and heat-transfer；Then it takes out true
Empty 5min leads to nitrogen 5min, so cycle 6 times, reactant is made to be present in the environment under nitrogen protection, control stirring-type polymerization
System pressure is 0.3MPa in reactor；
(4) by stirring-type polymer reactor airtight heating to 283 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 283 DEG C 1 hour, constant temperature persistently vacuumizes 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 polyether-type nylon66 fiber thermoplastic elastomer (TPE) of the present embodiment, includes the following steps：
(1) 157.8g (1.08mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 90 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 80g (0.08mol) polyethylene glycol, 32.4g (0.15mol) 2,2'- (Asias 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 (3.9g) of alkene, methyl methacrylate and glycidyl methacrylate is as end-capping reagent, addition total weight of monomer
Medium of 1% butyl titanate (3.9g) of amount as catalyst, addition 120mL water as mass-and heat-transfer；Then it vacuumizes
5min leads to nitrogen 5min, so cycle 6 times, reactant is made to be present in the environment under nitrogen protection, and control stirring-type polymerization is anti-
It is 0.3MPa to answer system pressure in device；
(4) by stirring-type polymer reactor airtight heating to 278 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 278 DEG C 1.5 hours, constant temperature persistently vacuumizes 0.5 hour, reaction
Terminate, nitrogen is supplemented in discharging.
Reaction equation is the same as embodiment 3.
The nonisothermal crystallization melting curve figure such as Fig. 2 for the polyether-type nylon66 fiber thermoplastic elastomer (TPE) that the present embodiment is prepared
It is shown, show that the peak temperature (i.e. melting temperature) of the melting peak of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) is 253.14 in figure
℃。
Comparative example 1：
A kind of synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) of this comparative example, includes the following steps：
(1) 157.8g (1.08mol) adipic acid, 116.2g (1mol) hexamethylene diamine after vacuum drying are added to stirring-type
In polymer reactor, 5min is vacuumized, afterwards logical nitrogen 5min, so cycle 6 times, reactant is made to be present in the ring under nitrogen protection
In border, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 90 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 80g (0.08mol) polyethylene glycol, 32.4g (0.15mol) 2,2'- (Asias 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 (3.9g) as catalyst, addition 120mL water as mass-and heat-transfer；Then 5min is vacuumized, nitrogen is led to
5min, so cycle 6 times, make reactant be present 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 278 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 278 DEG C 1.5 hours, constant temperature persistently vacuumizes 0.5 hour, reaction
Terminate, nitrogen is supplemented in discharging.
Reaction equation is the same as embodiment 3.
It is that embodiment 1-5 and the raw material of comparative example 1 form list below.
1 embodiment 1-5 of table and the raw material of comparative example 1 form list
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) that above-described embodiment is prepared carries out following performance test：
Tensile property：By GB/T 1040-2006 standard testings, rate of extension 50mm/min.
Impact property：By GB/T 1843-2008 standard testings, batten thickness is 4mm.
Melt index：By GB/T 3682-2000 standard testings, test temperature is 275 DEG C, is loaded as 2.16kg.
Chemical resistance：By GB/T 11547-2008 standard testings, by the injection molding sample of polyether-type nylon66 fiber thermoplastic elastomer (TPE)
Item is placed in dimethylbenzene, and the testing time is 1 day, the tensile strength of test injection molding batten.The calculation formula of performance change percentage
For：
Y is performance change percentage, X in formula1To impregnate preceding performance number, X accordingly2For a certain performance number after immersion.
Intrinsic viscosity：By GB/T 1632-2008 standard testings, solvent is the concentrated sulfuric acid.
Glass transition temperature：By GB/T 19466.2-2004 standard testings.
Melting temperature：By GB/T 19466.3-2004 standard testings.
Hydrolytic resistance：The injection molding batten of polyether-type nylon66 fiber thermoplastic elastomer (TPE) is 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 is：
Y is performance change percentage, X in formula1For performance number before corresponding boiling, X2For a certain performance number after boiling.
Thermally decompose initial temperature：By GB/T 13464-2008 standard testings.
The performance test results are as shown in table 2.
The performance list of 2 embodiment 1-5 of table and the polyether-type nylon66 fiber thermoplastic elastomer (TPE) of comparative example 1
Compared with Example 5, the polyether Glycols of embodiment 1 are polytetrahydrofuran ether glycol to embodiment 1, and embodiment 5
Polyether Glycols be polyethylene glycol, so the carbochain of the structural unit of embodiment 1 to grow compared to embodiment 5, amide
Key density is low compared with embodiment 5, polyether Glycols, 2,2'- (1,3- phenylene)-bisoxazoline, the catalyst Ti being added
Sour four butyl esters to lack compared with embodiment 5, from Table 2, it can be seen that the drawing of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) of embodiment 1
Intensity, melt index, chemical resistance, glass transition temperature, melting temperature, hydrolytic resistance and thermal decomposition initial temperature is stretched to be higher than
Embodiment 5, and notch impact strength and intrinsic viscosity will be less than embodiment 5.
Compared with Example 5, the polyether Glycols of embodiment 2 are polypropylene glycol to embodiment 2, and the polyethers two of embodiment 5
First alcohol is polyethylene glycol, so the carbochain of the structural unit of embodiment 2 to grow compared to embodiment 5, amido bond density compared with
Wanting for embodiment 5 is low, while the polyether Glycols of its addition, 2,2'- (1,3- phenylene)-bisoxazoline, catalyst metatitanic acid four
Butyl ester is more compared with embodiment 5, from Table 2, it can be seen that the notch punching of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) of embodiment 2
Hit intensity and intrinsic viscosity are and tensile strength, melt index, chemical resistance, glass transition temperature, molten higher than embodiment 5
Embodiment 5 will be less than by melting temperature, hydrolytic resistance and thermal decomposition initial temperature.
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 ether type nylon66 fiber thermoplastic elastomer (TPE) is active terminal hydroxy group and end carboxyl, and it is sweet that embodiment 5 is added to end-capping reagent shrink
Type epoxy resins.From Table 2, it can be seen that comparative example 1 adds end-capping reagent glycidol based epoxy resin, system due to not having
The performance of the polyether-type nylon66 fiber thermoplastic elastomer (TPE) obtained is all less than embodiment 5.
Embodiment 3~5 is to adjust polyether Glycols, 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
Go out, with polyether Glycols, 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, polyether-type nylon66 fiber thermoplastic elastomer (TPE)
Notch impact strength and intrinsic viscosity gradually increase, and tensile strength, melt index, chemical resistance, glass transition temperature, molten
Melt temperature, hydrolytic resistance and thermal decomposition initial temperature then to continuously decrease.Wherein, the polyether-type nylon66 fiber thermoplastic elastomehc of embodiment 5
The comprehensive performance of property body is best.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, 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, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, 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 the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of polyether-type nylon66 fiber thermoplastic elastomer (TPE), which is characterized in that it is with following structure shown in formula I：
In formula I, a=2~4, m=5~100, n=2~20, x=3~50, y=10~100, z=1~20；
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) is by polyether Glycols, adipic acid, hexamethylene diamine, 2,2'- (1,3- phenylenes)-
Bisoxazoline is copolymerized；The polyether Glycols, adipic acid, hexamethylene diamine, 2,2'- (1,3- phenylenes)-bisoxazoline rub
You are than being 0.01~0.2:1.01~1.2:1:0.1~0.4；
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) is that its terminal hydroxy group and end carboxyl are sealed by glycidol based epoxy resin
The polyether-type nylon66 fiber thermoplastic elastomer (TPE) at end.
2. polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 1, which is characterized in that the polyether Glycols,
Adipic acid, hexamethylene diamine, 2,2'- (1,3- phenylenes)-bisoxazoline molar ratio be 0.05~0.1:1.05~1.1:1:0.1~
0.2。
3. polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 1, which is characterized in that the polyether-type nylon66 fiber
The intrinsic viscosity of thermoplastic elastomer (TPE) is 0.8~2.0dL/g, glass transition temperature Tg>=53 DEG C, melting temperature TmIt is 243~263
℃。
4. according to claim 1-3 any one of them polyether-type nylon66 fiber thermoplastic elastomer (TPE)s, which is characterized in that the polyethers
Dihydric alcohol is selected from the mixture of one or more of polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol；It is described poly-
The number-average molecular weight of ether dihydric alcohol is 700~4000.
5. polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 4, which is characterized in that the polyether Glycols choosing
From polyethylene glycol.
6. according to claim 1-3 any one of them polyether-type nylon66 fiber thermoplastic elastomer (TPE)s, which is characterized in that the shrink
Glycerine 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 polyether-type nylon66 fiber thermoplastic elastomer (TPE)s, which is characterized in that
Include the following steps：
(1) adipic acid after vacuum drying is added to hexamethylene diamine in stirring-type polymer reactor, vacuumizes 3~10min, after
3~10min of logical inert gas, so recycles 5~10 times, so that reactant is in the environment under inert gas shielding, control is stirred
It is 0.1~0.5MPa to mix system pressure in formula polymer reactor；
(2) by stirring-type polymer reactor airtight heating to 70~110 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) polyether Glycols after vacuum drying are added to 2,2'- (1,3- phenylenes)-bisoxazoline in step (2)
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, it is 0.1~0.5MPa to control system pressure in stirring-type polymer reactor；
(4) by stirring-type polymer reactor airtight heating to 268~293 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
It is deflated to normal pressure, after the reaction was continued at 268~293 times 0.5~4 hour, constant temperature is lasting after reacting 0.5~4 hour in 1MPa
It vacuumizes 0.1~2 hour, reaction terminates, the topping up in discharging；
In above-mentioned steps, the inert gas is one kind in 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 polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 7, which is characterized in that including with
Lower step：
(1) adipic acid after vacuum drying is added to hexamethylene diamine in stirring-type polymer reactor, vacuumizes 4~6min, after
4~6min of logical nitrogen, so recycles 5~7 times, reactant is made to be in the environment under nitrogen protection, and control stirring-type polymerization is anti-
It is 0.2~0.3MPa to answer system pressure in device；
(2) by stirring-type polymer reactor airtight heating to 80~100 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) polyether Glycols after vacuum drying are added to 2,2'- (1,3- phenylenes)-bisoxazoline in step (2)
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, reactant is made to be 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 273~283 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
It is deflated to normal pressure, after the reaction was continued at 273~283 DEG C 1~2 hour, constant temperature is persistently taken out after reacting 1~2 hour in 1MPa
Vacuum 0.3~1 hour, reaction terminates, and nitrogen is supplemented in discharging；
In above-mentioned steps, the titanium compound is butyl titanate.
9. the synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 7 or 8, which is characterized in that institute
The addition for stating glycidol based epoxy resin is the 0.1~2% of total monomer weight, and the addition of the titanium compound is monomer
The 0.1~2% of total weight；The monomer is polyether Glycols, adipic acid, hexamethylene diamine and 2,2'- (1,3- phenylenes)-dioxazole
Quinoline.
10. the synthetic method of polyether-type nylon66 fiber thermoplastic elastomer (TPE) according to claim 9, which is characterized in that described
The addition of glycidol based epoxy resin is the 0.5~1.5% of total monomer weight, and the addition of the titanium compound is monomer
The 0.6~1.4% of total weight；The monomer is that polyether Glycols, adipic acid, hexamethylene diamine and 2,2'- (1,3- phenylenes)-two are disliked
Oxazoline.
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|---|---|---|---|---|
| CN112210076A (en) * | 2019-07-11 | 2021-01-12 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN113024802A (en) * | 2021-03-03 | 2021-06-25 | 四川大学 | Thermoplastic nylon elastomer containing pyrrolidone structure amorphous nylon segment and preparation method and application thereof |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210076A (en) * | 2019-07-11 | 2021-01-12 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN112210076B (en) * | 2019-07-11 | 2023-08-15 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN113024802A (en) * | 2021-03-03 | 2021-06-25 | 四川大学 | Thermoplastic nylon elastomer containing pyrrolidone structure amorphous nylon segment and preparation method and application thereof |
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