CN109206613A - The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer - Google Patents
The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer Download PDFInfo
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- CN109206613A CN109206613A CN201810804310.7A CN201810804310A CN109206613A CN 109206613 A CN109206613 A CN 109206613A CN 201810804310 A CN201810804310 A CN 201810804310A CN 109206613 A CN109206613 A CN 109206613A
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- elastomer
- polyamide elastomer
- polyamide
- caprolactam
- acid
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000000806 elastomer Substances 0.000 title claims abstract description 48
- 239000004952 Polyamide Substances 0.000 title claims abstract description 39
- 229920002647 polyamide Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 125000003368 amide group Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000003809 water extraction Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229960002684 aminocaproic acid Drugs 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims 1
- 229920002292 Nylon 6 Polymers 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000010792 warming Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000003951 lactams Chemical class 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- LRQKBLKVPFOOQJ-UHFFFAOYSA-N 2-aminohexanoic acid Chemical class CCCCC(N)C(O)=O LRQKBLKVPFOOQJ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium hypophosphites Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to the preparation methods of polyamide elastomer, the purposes of elastomer prepared therefrom and the elastomer.The method utilizes polyamide 6 and ending amino polyether synthesizing polyamides elastomer, and gained polyamide elastomer has high-wearing feature and high rigidity, is particularly suitable for use as footwear material.
Description
Technical field
The invention belongs to polymeric material field, it is related to the preparation method of polyamide elastomer a kind of, bullet prepared therefrom
The purposes of property body and the elastomer in footwear material, in particular to a kind of polyamide 6 method for producing elastomers, bullet prepared therefrom
Property purposes in footwear material of body and the elastomer, the method utilizes polyamide 6 and ending amino polyether synthesizing polyamides elastomer,
Gained polyamide elastomer has high-wearing feature and high rigidity, is particularly suitable for use as footwear material.
Background technique
Sport footwear, playshoes require it is light, it is comfortable and easy to wear, property retention is good, wear resistance is good, use temperature range compared with
Greatly.
Currently on the market shoes with foamed material mainly with PVC, EVA, SBS, based on PU etc., PVC sole it is cheap but
It is to wear no resistance, can not resist cold, especially winter easily snaps off sole and plasticizer is easily precipitated.EVA blending foaming material have intolerant to
The disadvantages of puncture, low temperature are hardened, skid resistance is poor, and resistance to wet skidding performance is poor after contacting with water.The wearability of SBS material, poor heat resistance；Shoes
Bottom is big to the adhesive force on ground, wears when road conditions are bad, and calorific value is big, and sole abrasion is serious.PU foamed shoe sole has matter
The advantages of ground is soft, good, comfortable and easy to wear, the excellent wearability of elasticity, flexible resistance energy, but also have easy xanthochromia, easily simultaneously
The disadvantages of fracture, elongation percentage are poor, not resistant to water, and sole is perishable, poor air permeability.
106009213 A of CN discloses a kind of preparation method of shoes anti-wear agent, including 45 parts of polyolefin elastomer, silicon
40~50 parts of oil, 0.2~0.3 part of BIPB, 0.7~1.0 part of zinc stearate, 0~7 part of white carbon black, gathers by 0.2~0.3 part of TAIC
0~0.5 part of ethylene glycol.The anti-wear agent is fabulous for the dispersibility of gel state in the material, and can be between other materials molecule
Effectively crosslinking can be formed, anti-wear agent is prevented to be precipitated.The product can have the advantages that good dispersion, wearability is good, and resistance to marring is good.CN
104430192A discloses a kind of soft abrasion-resistant rubber plastic foam material, and adds vinyltrimethoxysilane and its resin copolymerization
Object is as anti-wear agent, and usage amount 10%-15%, obtained flexibility is good, there is the high resiliency foamed material of rubber sense of touch.These skills
Art is all that the wearability of material is improved by addition antiwear assistant, the disadvantage is that auxiliary agent bad dispersibility, easy precipitation, performance guarantor
Hold that the time is short and auxiliary agent has specificity, therefore bad with other sole material caking property.
Therefore, there are still the demands of the new material of high abrasion, high rigidity for footwear material in the prior art.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of polyamide elastomer.This method process is simple, is easy to
It is control, high production efficiency, at low cost, the thermoplastic polyamide elastomer of preparation have high resiliency, high abrasion resistance, high rigidity,
The wide feature of use temperature range.It is a further object to provide the polyamide elastomers prepared by the method.
A further object of the present invention is to provide purposes of the polyamide elastomer in footwear material.
According to an aspect of the present invention, a kind of preparation method of polyamide elastomer is provided, this method is as follows:
A1) it is added ending amino polyether in a kettle, caprolactam, catalyst, dicarboxylic acids, under nitrogen protection,
Under 200~240 DEG C of reaction temperature, react 2~5 hours under mechanical stirring,
A2 it) is evacuated down to 500~1000Pa at 250~280 DEG C, reacts 2~5 hours, then discharges, blank and boiling water
Extraction obtains polyamide elastomer to remove residual monomer and oligomer, or
B1 caprolactam, catalyst, dicarboxylic acids, under nitrogen protection, at 150~240 DEG C) are added in a kettle
It under reaction temperature, reacts 2~5 hours under mechanical stirring, obtains prepolymer；
B2 step b1) is added in ending amino polyether) prepared by prepolymer in, and be evacuated down at 250~280 DEG C
500~1000Pa is reacted 2~5 hours, is then discharged, and simultaneously boiling water extraction is gathered blank with removing residual monomer and oligomer
Amide elastomer,
Wherein, the catalyst be selected from one or more of phosphoric acid, sulfuric acid, aminocaproic acid and sodium hypophosphite,
Wherein, the dicarboxylic acids is the succinic acid selected from malonic acid, one or more of glutaric acid and adipic acid,
Wherein, the ending amino polyether is selected from end amido polytetrahydrofuran, end amido polyethylene glycol, end amido poly- third
One or more of glycol.
Preferably, in the preparation method of above-mentioned polyamide elastomer, the number-average molecular weight of the ending amino polyether is 500
~10000, preferably 500~8000.
Preferably, in the preparation method of above-mentioned polyamide elastomer, the number-average molecular weight of polyamide hard section is 500~
10000, preferably 500~5000.
Preferably, in the preparation method of above-mentioned polyamide elastomer, the total amount based on caprolactam and ending amino polyether,
The dosage of ending amino polyether is 10wt%~30wt%.
Preferably, in the preparation method of above-mentioned polyamide elastomer, the total amount based on caprolactam and ending amino polyether,
The dosage of caprolactam is 70wt%~90wt%.
Preferably, in the above preparation method, it is based on caprolactam and amine terminated polyether total amount, the dosage of catalyst is
1wt%-10wt%, preferably 1wt%~3wt%.
Preferably, in the above preparation method, it is based on caprolactam and amine terminated polyether total amount, the dosage of binary acid is
1wt%-20wt%, preferably 1wt%~6wt%.
According to another aspect of the present invention, the polyamide elastomer according to above method preparation is provided.
The polyamide elastomer can have 20 to the 80MPa tensile strength measured according to GB/T 1040-2006.
The polyamide elastomer can have to be stretched according to 300% to 900% fracture of GB/T 1040-2006 measurement
Long rate.
The polyamide elastomer can have the shore hardness of the 40D to 70D according to GB/T 2144-2008 measurement.
The polyamide elastomer can have 0.20 to 0.50mm according to GB/T 3960-1988 measurement3/N.m-1's
Skimming wear rate.
The polyamide elastomer can have 2.10 to 2.50 relative viscosity measured according to GB/T 1632-93.
The polyamide elastomer is NB (not broken) according to the notch impact strength that GB/T 1843-2008 is measured.
According to another aspect of the present invention, purposes of the polyamide elastomer in footwear material is provided.
Preferably, the footwear material includes sole material, vamp material, material and other material for shoes in shoes.
Beneficial effect
The preparation method of polyamide elastomer of the invention has that process is simple, easily controllable, high production efficiency, at low cost
The advantages of；The polyamide elastomer of acquisition has the characteristics that high resiliency, high abrasion resistance, high rigidity, use temperature range are wide, full
Light, comfortable, the wear-resisting requirement of sufficient footwear material.Its wearability is product itself property, does not need addition anti-wear agent, reduces existing
The problem of poor compatibility that footwear material in technology using additional anti-wear agent has, auxiliary agent is easily precipitated.
Polyamide elastomer processing performance prepared in accordance with the present invention is excellent, can for example be squeezed out with known forming method, note
Product is processed into modeling, molding, the methods of blow molding.
Specific embodiment
Hereafter explain the present invention by specific embodiment, but the scope of the present invention is not limited to these embodiments, but by
Claims of the present invention come limit and may include it will be understood by those skilled in the art that in the range of various reasonable changes
Change form.
The unit and measurement method of some parameters and feature that are related to below in an example are as described below:
| Physical property | Unit | Test method |
| Tensile strength | MPa | GB/T 1040-2006 |
| Elongation at break | % | GB/T 1040-2006 |
| Izod notch impact strength | KJ·m-2 | GB/T 1843-2006 |
| Fusing point | ℃ | GB/T 19466-2004 |
| Heat distortion temperature | ℃ | GB/T 1634-2004 |
| Shore hardness | D | GB/T 2411-2008 |
| Glass transition temperature | ℃ | GB/T 19466-2004 |
| Relative viscosity | GB/T 12006-2009 | |
| Skimming wear rate | mm3/N.m-1 | GB/T 3960-1988 |
Sample is extracted 8 hours in boiling water, boiling water extraction yield is then calculated as follows:
In formula: m0To extract preceding sample quality, m is sample quality after extraction.
Embodiment 1- embodiment 4 is one-step technology, embodiment 5 is block copolymerization polymerization, and comparative example is the poly- second of one-step method
Glycol technique.
Embodiment 1:
1800 are added in the polymeric kettle of 5L to restrain oneself lactams, the end amido polyethylene glycol of 200 grams average molecular weights 1000,
40 g of adipic acid, 50 grams of sulfuric acid are warming up to 240 DEG C under high pure nitrogen protection and react 2 hours, then are warming up to 260 DEG C and are evacuated down to
500Pa reacts 2 hours, discharging, cooling, pelletizing, extraction, drying, finished product.
Embodiment 2:
1700 are added in the polymeric kettle of 5L to restrain oneself lactams, the poly- tetrahydro furan of the end amido of 300 grams average molecular weights 1000
It mutters, 60 g of adipic acid, 60 grams of sodium hypophosphites are warming up to 240 DEG C under high pure nitrogen protection and react 4 hours, then are warming up to 270
It DEG C is evacuated down to 800Pa to react 3 hours, discharging, cooling, pelletizing, extraction, drying, finished product.
Embodiment 3:
1500 are added in the polymeric kettle of 5L to restrain oneself lactams, the end amido polyethylene glycol of 500 grams average molecular weights 1000,
100 g of adipic acid, 60 grams of phosphoric acid are warming up to 210 DEG C under high pure nitrogen protection and react 3 hours, then are warming up to 250 DEG C and vacuumize
It is reacted 5 hours to 1000Pa, discharging, cooling, pelletizing, extraction, drying, finished product.
Embodiment 4:
1400 are added in the polymeric kettle of 5L to restrain oneself lactams, the end amido polypropylene glycol of 600 grams average molecular weights 1000,
120 g of adipic acid, 30 grams of aminocaproic acids are warming up to 220 DEG C under high pure nitrogen protection and react 4 hours, then are warming up to 280 DEG C of pumpings
Vacuum is reacted 4 hours to 600Pa, discharging, cooling, pelletizing, extraction, drying, finished product.
Embodiment 5
1800 are added in the polymeric kettle of 5L to restrain oneself lactams, 40 g of adipic acid, 50 grams of sulfuric acid, 36 grams of deionized waters,
160 DEG C are warming up under high pure nitrogen protection to react 5 hours, obtain carboxyl end group prepolymer；Then by 200 grams average molecular weights 1000
End amido polyethylene glycol be added in above-mentioned carboxyl end group prepolymer, be warming up to 260 DEG C under high pure nitrogen protection and be evacuated down to
500Pa reacts 2 hours, discharging, cooling, pelletizing, extraction, drying, finished product.
Comparative example
1800 are added in the polymeric kettle of 5L to restrain oneself lactams, the polyethylene glycol of 200 grams average molecular weights 1000,40 restrain oneself
Diacid, 50 grams of sulfuric acid are warming up to 240 DEG C under high pure nitrogen protection and react 2 hours, then are warming up to 260 DEG C and are evacuated down to 500Pa
Reaction 2 hours, discharging, cooling, pelletizing, extraction, drying, finished product.
The composition of the various embodiments described above preparation is molded into the standard batten of test by standard size, by China national mark
Standard tests its physical property, the results are shown in Table 1.
Table 1
From table 1 it follows that method of the invention is by using amine terminated polyether as polymer raw, the polyamide bullet of acquisition
Property body there is lower boiling water extraction yield, higher tensile strength, elongation at break, broader temperature resistant range and lower sliding
Wear rate；Connection additionally, due to soft segment, hard section is amide group, the ester bond connection tool formed when than using non-amine terminated polyether
There is better hydrolytic Resistance.Moreover, the heat distortion temperature of elastomer of the invention is high, glass transition temperature is low, therefore makes
It is very wide with temperature range.
Claims (10)
1. a kind of preparation method of polyamide elastomer, this method are as follows:
A1) it is added ending amino polyether in a kettle, caprolactam, catalyst, dicarboxylic acids, under nitrogen protection, 200~
Under 240 DEG C of reaction temperature, react 2~5 hours under mechanical stirring,
A2 it) is evacuated down to 500~1000Pa at 250~280 DEG C, reacts 2~5 hours, then discharges, blank and boiling water extraction
To remove residual monomer and oligomer, polyamide elastomer is obtained, or
B1 caprolactam, catalyst, dicarboxylic acids, under nitrogen protection, in 150~240 DEG C of reaction) are added in a kettle
At a temperature of, it reacts 2~5 hours under mechanical stirring, obtains prepolymer；
B2 step b1) is added in ending amino polyether) prepared by prepolymer in, and be evacuated down at 250~280 DEG C 500~
1000Pa is reacted 2~5 hours, is then discharged, and simultaneously boiling water extraction obtains polyamide to remove residual monomer and oligomer to blank
Elastomer,
Wherein, the catalyst be selected from one or more of phosphoric acid, sulfuric acid, aminocaproic acid and sodium hypophosphite,
Wherein, the dicarboxylic acids is the succinic acid selected from malonic acid, one or more of glutaric acid and adipic acid,
Wherein, the ending amino polyether is selected from end amido polytetrahydrofuran, end amido polyethylene glycol, end amido polypropylene glycol
One or more of.
2. according to the method described in claim 1, wherein,
The number-average molecular weight of the ending amino polyether is 500~10000, preferably 500~8000.
3. according to the method described in claim 1, wherein,
The number-average molecular weight of polyamide hard section is 500~10000, preferably 500~5000.
4. according to the method described in claim 1, wherein,
Total amount based on caprolactam and ending amino polyether, the dosage of ending amino polyether are 10wt%~30wt%, caprolactam
Dosage be 70wt%~90wt%.
5. according to the method described in claim 1, wherein,
Based on caprolactam and amine terminated polyether total amount, the dosage of catalyst is 1wt%-10wt%, preferably 1wt%~
3wt%.
6. according to the method described in claim 1, wherein,
Based on caprolactam and amine terminated polyether total amount, the dosage of binary acid is 1wt%-20wt%, preferably 1wt%~
6wt%.
7. a kind of polyamide elastomer, method preparation according to claim 1 to 6.
8. polyamide elastomer according to claim 7, wherein
The polyamide elastomer has 20 to the 80MPa tensile strength measured according to GB/T 1040-2006,
According to GB/T 1040-2006 measure 300% to 900% elongation at break,
According to GB/T 2144-2008 measurement 40D to 70D shore hardness,
According to the 0.20 to 0.50mm of GB/T 3960-1988 measurement3/N.m-1Skimming wear rate,
According to 2.10 to 2.50 relative viscosity that GB/T 1632-93 is measured, and
The polyamide elastomer is NB according to the notch impact strength that GB/T 1843-2008 is measured, i.e., not broken.
9. purposes of the polyamide elastomer according to claim 7 or 8 in footwear material.
10. purposes according to claim 9, wherein
The footwear material includes sole material, vamp material, material and other material for shoes in shoes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804310.7A CN109206613A (en) | 2018-07-20 | 2018-07-20 | The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804310.7A CN109206613A (en) | 2018-07-20 | 2018-07-20 | The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer |
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| Publication Number | Publication Date |
|---|---|
| CN109206613A true CN109206613A (en) | 2019-01-15 |
Family
ID=64990160
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| CN201810804310.7A Pending CN109206613A (en) | 2018-07-20 | 2018-07-20 | The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer |
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| CN112745498A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of polyamide elastomer |
| CN112961305A (en) * | 2021-03-12 | 2021-06-15 | 郑州大学 | Preparation method of polyureauramide elastomer |
| CN114622299A (en) * | 2022-01-21 | 2022-06-14 | 浙江恒逸石化研究院有限公司 | Preparation method of phosphorus-containing self-flame-retardant polyether amide elastomer fiber |
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