CN109293916A - Polyamide/silicone copolymers and preparation method thereof - Google Patents
Polyamide/silicone copolymers and preparation method thereof Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 27
- 229920002647 polyamide Polymers 0.000 title claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 siloxanes Chemical class 0.000 claims abstract description 34
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 11
- 150000004985 diamines Chemical group 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical group 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 150000004984 aromatic diamines Chemical group 0.000 abstract 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 210000001772 blood platelet Anatomy 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920002379 silicone rubber Polymers 0.000 description 7
- 210000004369 blood Anatomy 0.000 description 6
- 239000008280 blood Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 208000024248 Vascular System injury Diseases 0.000 description 2
- 208000012339 Vascular injury Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSEADYMLKBVVTB-UHFFFAOYSA-N 3-[methyl(trimethylsilyloxy)silyl]propan-1-amine Chemical compound C[SiH](CCCN)O[Si](C)(C)C ZSEADYMLKBVVTB-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000001501 megacaryocyte Anatomy 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 210000001243 pseudopodia Anatomy 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102200058968 rs34689457 Human genes 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 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
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of polyamide/silicone copolymers and preparation method thereof.Aliphatic or aromatic binary carboxylic acid, carbon atom number of the polyamide/silicone copolymers using carbon atom number for 2-20 are that 2-20 aliphatic or aromatic diamine, Amino End Group siloxanes are made as raw material by the method for melt polycondensation.Resulting polymers can directly carry out melt-processed, have good cryogenic mechanical performance and excellent biocompatibility, can be widely applied to the manufacturing of sports equipment and medical equipment.
Description
Technical field
The invention belongs to compound and its preparation technical fields, and in particular to polyamide/silicone copolymers and its preparation
Method.
Background technique
Nylon has excellent mechanical property, wear-resistant, easy processing, corrosion-resistant, close as a kind of important engineering plastics
The advantages that small is spent, the fields such as automobile, machinery, electric, packaging, military project are widely used in.Polarity in nylon repeating units
Amido link structure is its source for protruding mechanical performance, but also results in such material with stronger water absorbing capacity and poor life
Object compatibility, to limit it in the application of accurate device manufacture and bio-medical field.It is well known that silicon oxygen bond (Si-O) is
A kind of typical water repellent structure, as basic repetitive unit organosilicon have excellent hydrophobicity, thermostabilization, resistance to oxidation,
Low-dielectric, higher permeability, and because it, with excellent biocompatibility, is also obtained extensively in field of medicaments
It uses.Si-O structure is introduced into polymer, the low temperature of the hydrophobicity of polymer, hot property and material can be significantly improved
Intensity.
The report of the copolymer synthesized at present about organosilicon and polyamide is most of using solution polymerization process, will
The longer dimethyl silicone polymer of strand synthesizes block analog copolymer with polyamide, and random for preparing organosilicon polyamide
The report of copolymer almost without.Secondly, when synthesizing polydimethylsiloxaneblock block copolymers using solwution method, due to the two
Compatibility is very poor, is easy to produce and mutually separates, to stress concentration effect occur, influences material mechanical performance, and polymerisation in solution
Process is complicated, and the later period, there are the work such as the processing of product desolvation and solvent recovery.
Summary of the invention
The purpose of the present invention is to provide a kind of polyamide/silicone copolymers, while providing preparation method is this hair
Bright another goal of the invention.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of polyamide/siloxane random copolymers, by
Dicarboxylic acids, diamine and Amino End Group copolymeric siloxane obtain, the structural formula of repetitive unit are as follows:
In formula, R1、R2、R3、R4It independently is methylene, cycloalkylidene or arlydene and its derivative, R5For H, Cl~C30
Alkyl, naphthenic base or aryl and its derivative, and m, n independently are 2~20 integer, p, q independently be 1~10 it is whole
Number, s is 1~20 integer, and x, y are independently 1~200 integer.Copolymer number-average molecular weight of the invention is in 2w or more.
The preparation method of the polyamide/siloxane random copolymers, comprising the following steps:
1) dicarboxylic acids, diamine and Amino End Group siloxanes are added in reaction kettle；
2) in an inert atmosphere, system is first warming up to 100~160 DEG C of 1~4h of heat preservation, and it is further heated up to 200~300 DEG C
It deflates after 2~6h of reaction, the 1~2h that vacuumizes that the reaction was continued later.
In step 1), dicarboxylic acids: the molar ratio of (diamine+Amino End Group siloxanes) is (0.90~0.99): 1, binary
The molar ratio of amine and Amino End Group siloxanes is 99:1~1:99, obtains the copolymer with different silicones content.
In step 2), the speed to heat up twice is 5~20 DEG C/min, and deflation time is 0.5~2h.
Compared with prior art, the positive effect of the present invention is:
(1) a kind of polyamide/silicone copolymers of structure novel are provided, the introducing of organosilicon composition can improve polyamides
The thermo-oxidative stability and surface physiological property of amine structure.The copolymer can directly carry out melt-processed, have good low temperature machine
Tool performance and excellent biocompatibility, can be widely applied to the manufacturing of sports equipment and medical equipment；
(2) present invention can prepare polyamide/silicone copolymers using the method for melt polymerization, and preparation method is easy easily
Row；Avoid solwution method synthesis polydimethylsiloxaneblock block copolymers when " compatibility is very poor ", be easy to produce mutually separation etc. ask
The appearance of topic.
Detailed description of the invention
Fig. 1 is the chemical reaction route map of polyamide/siloxane random copolymers of the present invention；
Fig. 2 is the IR Characterization spectrogram of the PA1212/Si12-20 of the method for the present invention preparation；
Fig. 3 is the chemical shift of the nuclear magnetic resonance spectroscopy and corresponding proton of the PA1212/Si12-20 of the method for the present invention preparation
Schematic diagram；
Fig. 4 is the platelet adhesion Test Drawing of the PA1212/Si12 copolymer synthesized in provided embodiment 1, and: a is
PA1212 sample；B is PA1212/Si12 sample；C is silicon rubber sample.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings.It should be pointed out that these examples mention
It is rather than to limit the contents of the present invention to facilitate understanding of the invention out.
Reagent used in the present invention is commercially available.
Embodiment 1
A kind of polyamide/silicone copolymers, by dodecanedicarboxylic acid, 12 carbon diamines, 1,3- bis- (aminopropyl) four
Tetramethyldisiloxane is copolymerized to obtain.
Preparation method, comprising the following steps:
1) in the reaction kettle with agitating device, dodecanedicarboxylic acid (9.5mol), 12 carbon diamines are sequentially added
(8mol), 1,3- bis- (aminopropyl) tetramethyl disiloxane (2mol) ,-is vacuumized-with High Purity Nitrogen gas inflated and is inflated, and repeats to grasp
Make 3 times, the air in replacement reaction kettle, with the oxygen in removal system, it is ensured that reaction is to carry out under inert gas atmosphere；It should
Dicarboxylic acids in step: the molar ratio of (diamine+Amino End Group siloxanes) is 0.95:1, and diamine and Amino End Group siloxanes rub
You are than being 4:1；
2) system starts to warm up, and is warming up at 100 DEG C with 10 DEG C/min and carries out heat preservation 2.5h, then is warming up to 10 DEG C/min
200 DEG C of reaction 4h, then deflate 1h, the reaction was continued under evacuated state 1h, obtains copolymerization product PA1212/Si12, yield
It is 85%.
The T of gained copolymer p A1212/Si12mIt is 171 DEG C, T5%(indicating 5% weightless temperature, similarly hereinafter) is 430 DEG C, is stretched
Intensity is 40MPa, elongation at break 500%, 90 ° of surface contact angle (water).
Embodiment 2
A kind of polyamide/silicone copolymers, by ten carbon dicarboxylic acids, ten carbon diamines, 1,3- bis- (aminopropyl) prestox
Tetrasiloxane is copolymerized to obtain.
Preparation method, comprising the following steps:
1) in the reaction kettle with agitating device, ten carbon dicarboxylic acids (9.7mol), ten carbon diamines are sequentially added
(7mol), 1,3- bis- (aminopropyl) octamethylcyclotetrasiloxane (3mol), by being inflated with High Purity Nitrogen gas inflated-vacuumizing-, weight
Again operate 3 times, the air in replacement reaction kettle, with the oxygen in removal system, it is ensured that reaction be under inert gas atmosphere into
Row；Dicarboxylic acids in the step: the molar ratio of (diamine+Amino End Group siloxanes) is 9.7:10, ten carbon diamines and Amino End Group
The molar ratio of siloxanes is 7:3
2) system starts to warm up, and is warming up at 120 DEG C with 15 DEG C/min speed and carries out heat preservation 2h, with 15 DEG C/min speed after
Continuous to be warming up to 230 DEG C of reaction 4h, then deflate 1h, the reaction was continued under evacuated state 1h, obtains copolymerization product PA1010/
Si10, yield 87%.
The T of gained copolymer p A1010/Si10mIt is 175 DEG C, T5%It is 431 DEG C, tensile strength 42MPa, elongation at break
It is 300%, 92 ° of surface contact angle (water).
Embodiment 3
A kind of polyamide/silicone copolymers, by adipic acid, hexamethylene diamine, 1,3- bis- (aminopropyl) tetramethyl disiloxane
Copolymerization obtains.
Preparation method, comprising the following steps:
1) in the reaction kettle with agitating device, adipic acid (9.8mol), hexamethylene diamine (6mol), 1,3- bis- are sequentially added
(aminopropyl) tetramethyl disiloxane (4mol) repetitive operation 3 times, is set by being inflated with High Purity Nitrogen gas inflated-vacuumizing-
The air in reaction kettle is changed, with the oxygen in removal system, it is ensured that reaction is to carry out under inert gas atmosphere；Two in the step
First carboxylic acid: the molar ratio of (diamine+Amino End Group siloxanes) is 9.8:10, and the molar ratio of own diamine and Amino End Group siloxanes is
6:4
2) system starts to warm up, and is warming up at 100 DEG C with 5 DEG C/min speed and carries out heat preservation 4h, with 10 DEG C/min speed liter
270 DEG C of reaction 4h of temperature, then slow deflation 2h, the reaction was continued under evacuated state 1h obtain copolymerization product PA66/Si6, produce
Rate is 80%.
The T of gained copolymer p A66/Si6mIt is 230 DEG C, T5%It is 430 DEG C, tensile strength 65MPa, elongation at break is
400%, 95 ° of surface contact angle (water).
Embodiment 4
A kind of polyamide/silicone copolymers, by terephthalic acid (TPA), 14 carbon diamines, 1,3- bis- (aminopropyl) 20
Ten copolymeric siloxane of methyl obtains.
Preparation method, comprising the following steps:
1) in the reaction kettle with agitating device, terephthalic acid (TPA) (9.6mol), 14 carbon diamines are sequentially added
(6mol), 1,3- bis- (aminopropyl) two decamethyl, ten siloxanes (4mol), by being inflated with High Purity Nitrogen gas inflated-vacuumizing-,
Repetitive operation 3 times, the air in replacement reaction kettle, with the oxygen in removal system, it is ensured that reaction is under inert gas atmosphere
It carries out；Dicarboxylic acids in the step: the molar ratio of (diamine+Amino End Group siloxanes) is 9.6:10,14 carbon diamines and end
The molar ratio of amino silicone is 6:4
2) system starts to warm up, and is warming up at 140 DEG C with 5 DEG C/min speed and carries out heat preservation 4h, with the continuation of 5 DEG C/min speed
It heats up 290 DEG C and reacts 4h, then slow deflation 2h, the reaction was continued under evacuated state 1.5h obtains copolymerization product PA14T/
SiT, yield 80%, the speed to heat up twice are 5 DEG C/min.
The T of gained copolymer p A14T/SiTmIt is 270 DEG C, T5%It is 435 DEG C, tensile strength 60MPa, elongation at break is
220%, 97 ° of surface contact angle (water).
Embodiment 5
A kind of polyamide/silicone copolymers and preparation method thereof, difference from Example 1 is, in step 1), two
First carboxylic acid: the molar ratio of (diamine+Amino End Group siloxanes) is 0.90:1, and the molar ratio of diamine and Amino End Group siloxanes is 8:
2；In step 2), system is warming up to 160 DEG C of heat preservation 1h with 15 DEG C/min speed, and with 15 DEG C/min speed, it is further heated up to 300
DEG C reaction 2h, deflation 1h, the 2h that vacuumizes that the reaction was continued later.
Embodiment 6
A kind of polyamide/silicone copolymers and preparation method thereof, difference from Example 1 is, in step 1), two
First carboxylic acid: the molar ratio of (diamine+Amino End Group siloxanes) is 0.99:1, and the molar ratio of diamine and Amino End Group siloxanes is 8:
2；In step 2), system is warming up to 100 DEG C of heat preservation 4h with 20 DEG C/min speed, is continuously heating to 200 DEG C with 20 DEG C/min speed
6h, deflation 0.5h are reacted, the 1.5h that vacuumizes that the reaction was continued later.
Structural characterization:
To show that products therefrom is target product, using embodiment 1 method prepare PA1212/Si12-20, and to its into
Row IR Characterization, as a result as shown in Figure 2.Nuclear magnetic resonance spectroscopy test, method also are carried out to it simultaneously are as follows: first with deuterated trifluoro
Acetic acid carries out nuclear magnetic resonance spectroscopy test at 25 DEG C, and as a result and the schematic diagram of corresponding chemical displacement is as shown in Figure 3.
Fig. 2 and Fig. 3 is the result shows that products therefrom is target product, wherein in Fig. 2,3300cm-1It is the flexible of N-H key
Vibration absorption peak, 1635cm-1It is the stretching vibration absworption peak of C=O, 1025-1097cm-1It is the spy of Si-O-Si linear siloxane
Absorption peak is levied, this shows the isostructural presence of siloxanes in product, amido bond.
Application Example
By platelet attachment experiment come the blood compatibility of research material.Blood platelet is that megacaryocyte cytoplasm is de- in marrow
The cell fragment fallen, small in size, cell-free core, form is irregular, and the normal contents of blood platelet in blood are (100
~300) × 109A/L.When vascular injury or blood and foreign materials directly contact, blood platelet can at vascular injury or
There is the phenomenon that adhering to and being enriched in the surface of material, and will appear pseudopodium, and the blood platelet largely assembled will form network structure.It can
Come whether judgement material has blood compatibility according to blood platelet adhesion condition on the surface of the material and metamorphosis.
Three kinds of PA1212, PA1212/Si12 (1 gained of embodiment), silicon rubber thin polymer films are inhaled by 1h blood platelet
After attached processing, as a result as shown in Figure 4, as shown in Figure 4, PA1212 film surface has adhered to a large amount of blood platelet, and occurs
Serious aggregation and pseudo- foot phenomenon, and the platelet adhesion situation of PA1212/Si12 copolymer film and silicon rubber thin film surface
Similar, effect reaches the 80% of silicon rubber, a small amount of blood platelet only occurs and without there is the phenomenon that aggregation and model deformation.
Thus provable PA1212/Si12 copolymer have with the comparable blood compatibility of silicon rubber, silicon rubber is that typical physiology is lazy
Property material, be widely used in biologic medical field, polyamide/silicone copolymers blood compatibility of the invention and silicon rubber
Glue is suitable, this shows that polyamide/silicone copolymers of the invention have good physiological inertia as new polymers.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
1. a kind of polyamide/silicone copolymers, it is characterised in that: the copolymer is by dicarboxylic acids, diamine and Amino End Group
Copolymeric siloxane obtains, the structural formula of the repetitive unit of copolymer are as follows:
In formula, R1、R2、R3、R4It independently is methylene, cycloalkylidene or arlydene and its derivative, R5For H, Cl~C30Alkane
Base, naphthenic base or aryl and its derivative, and m, n independently are 2~20 integer, and p, q independently are 1~10 integer, s
It is 1~20 integer, x, y are independently 1~200 integer.
2. the preparation method of polyamide/silicone copolymers described in claim 1, it is characterised in that: the following steps are included:
1) dicarboxylic acids, diamine and Amino End Group siloxanes are added in reaction kettle；
2) in an inert atmosphere, system is first warming up to 100~160 DEG C of 1~4h of heat preservation for the first time, then it is warming up to 200 for the second time~
It deflates after 300 DEG C of 2~6h of reaction, the 1~2h that vacuumizes that the reaction was continued later.
3. the preparation method of polyamide/silicone copolymers as claimed in claim 2, it is characterised in that: in step 1), binary carboxylic
Acid: the molar ratio of (diamine+Amino End Group siloxanes) is (0.90~0.99): 1, the molar ratio of diamine and Amino End Group siloxanes
For 99:1~1:99.
4. the preparation method of polyamide/silicone copolymers as claimed in claim 2, it is characterised in that: in step 2), rise twice
The speed of temperature is 5~20 DEG C/min, and deflation time is 0.5~2h.
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| CN113045753A (en) * | 2021-03-11 | 2021-06-29 | 宁波七诺新材料科技有限公司 | Copolymerized polyamide material and application and composition thereof |
| CN113174042A (en) * | 2021-05-25 | 2021-07-27 | 郑州大学 | Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds |
| CN113185689A (en) * | 2021-05-28 | 2021-07-30 | 湖南工业大学 | Low-water-absorption copolymerized nylon resin and preparation method thereof |
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| CN113174042A (en) * | 2021-05-25 | 2021-07-27 | 郑州大学 | Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds |
| CN113185689A (en) * | 2021-05-28 | 2021-07-30 | 湖南工业大学 | Low-water-absorption copolymerized nylon resin and preparation method thereof |
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Inventor after: Cui Zhe Inventor after: Fu Peng Inventor after: Zhao Qingxiang Inventor after: Liu Minying Inventor after: Chen Chen Inventor after: Xiao Zhe Inventor after: Ji Feifei Inventor before: Cui Zhe Inventor before: Fu Peng Inventor before: Zhao Qingxiang Inventor before: Liu Minying Inventor before: Xiao Zhe Inventor before: Ji Feifei |
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