CN107501116A - A kind of function monomer of polyamide, function polyamide and preparation method - Google Patents
A kind of function monomer of polyamide, function polyamide and preparation method Download PDFInfo
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- CN107501116A CN107501116A CN201710825333.1A CN201710825333A CN107501116A CN 107501116 A CN107501116 A CN 107501116A CN 201710825333 A CN201710825333 A CN 201710825333A CN 107501116 A CN107501116 A CN 107501116A
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- polyamide
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 125
- 229920002647 polyamide Polymers 0.000 title claims abstract description 125
- 239000000178 monomer Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003808 methanol extraction Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical compound C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- -1 unsaturated fatty acid methyl ester Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 11
- 235000019198 oils Nutrition 0.000 abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 239000005445 natural material Substances 0.000 abstract description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 2
- 239000008158 vegetable oil Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical class CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000009897 systematic effect Effects 0.000 description 4
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 229920001007 Nylon 4 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000034303 cell budding Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RFHAOTPXVQNOHP-UHFFFAOYSA-N fluconazole Chemical compound C1=NC=NN1CC(C=1C(=CC(F)=CC=1)F)(O)CN1C=NC=N1 RFHAOTPXVQNOHP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of function monomer of polyamide, polyamide and preparation method.Function monomer of polyamide structural formula is：Side base R1Structural formula is OCOR1' or OH.Function polyamide structure formula is：5≤n≤5000, the R on main chain2For disulfide.The preparation method of function polyamide：Function monomer of polyamide, two mercaptan and catalyst are dissolved in solvent；Protective gas argon gas is then passed to, is put into oil bath pan and reacts；Function polyamide product is obtained finally by methanol extraction.The present invention is function polyamide by synthesizing vegetable oil derivatives i.e. function monomer of polyamide come Efficient Conversion, function polyamide ultimate yield 50%~100%, function polyamide purity 90%~100%.Function polyamide of the present invention is synthesized by natural material, no free formaldehyde, without benzene, heavy metal free, meets national environmental protection material standard.Function polyamide of the present invention possesses excellent mechanical performance, mechanical property.
Description
Technical field
The invention belongs to biomass-based polymeric material field, is specifically related to a kind of function monomer of polyamide, function is gathered
Acid amides and preparation method.
Background technology
Nowadays the every aspect that we live all is flooded with the figure of thermoplastic elastomer (TPE), such as adhesive, coating, manages,
Tire and fiber.However, most of elastomers are prepared by non-renewable resources now, recyclable organism matrix thermoplastic elastomehc
Property body is still in the budding stage.Scientists also develop many by biomass-based thermoplastic elastomer (TPE), for example, biological poly
Urethane class elastomer (Donglin Tang, Christopher W.Macosko, Polym.Chem., 2014,5,3231-
3237), protein-based thermoplastic elastomer (TPE) (Karthik Nagapudi, William T.Brinkman,
Macromolecules, 2005,38 (2), pp 345-354), poly ester urethane analog thermoplastic elastomer (Janneand
Jukka V.Macromolecules, 1997,30 (10), pp 2876-2882), come from the biomass of aliphatic acid
Based elastomeric (Shu Wang, Sameer Vajjala Kesava, Enrique D.and Megan
L.Robertson, Macromolecules, 2013,46 (18), pp 7202-7212).But from mechanical property, these
Elastomer is also difficult to practical application.Then, in order to carry out the reinforcing above mechanical property, researchers have been carried out largely
Attempt, for example introduce nano SiO 2 particle enhancing elastomer performance (By Tao Wei, Lijuan Lei, Hailan
Kang, Bo Qiao, Zhao Wang, Liqun Zhang, Phil Coates, Kuo-Chih Hua and Joseph Kulig,
ADVANCED ENGINEERING MATERIALS 2012,14,No.1-2)；Add nano clay enhancing elastomer performance (Lin
(2006) 8106-8115 of Zhu, Richard P.Wool, Polymer 47) etc..
Due to social demand constantly expands, conventional petroleum resource peter out and it is the environmental consciousness of people, sustainable
The consciousness of development constantly strengthens, and explores new reproducible biomass-based thermoplastic elastomer (TPE) and is spread out to replacement is traditional with oil
The non-renewable resources such as biology are imperative for the thermoplastic elastomer (TPE) of raw material.
So far, the main raw material(s) of biomass-based elastomer includes：Oleic acid, castor oil acid, PLA, protein,
Lactone, aliphatic acid and its derivative etc..These raw material all have the characteristics of renewable, source is wide, and contain functional group in itself
Reaction easy to process.But most of mechanics of elastic bodies poor-performings prepared by these raw material, even if adding nanometer afterwards
The nano particles such as silica, its mechanical property are still unable to reach preferable situation.It is biomass-based for excellent performance processed
Thermoplastic elastomer (TPE), the variation of elastomer application is realized, we need to carry out rational Molecular Design and state of aggregation knot
The finely regulating of structure.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of function monomer of polyamide, function polyamide and system
Preparation Method.
In order to realize the purpose of the present invention, present invention employs following technical scheme：
A kind of function monomer of polyamide, the structural formula of the function monomer of polyamide are as follows：
Wherein side base R1Structural formula be-OCOR1' or-
OH。
Further, the side base R1For any of following structure：
A kind of preparation method of function monomer of polyamide, comprises the following steps：
S1, take 1~1000 parts by weight unsaturated fatty acid methyl ester, 1~10 parts by weight 1,3- diaminourea -2- propyl alcohol；
S2, the unsaturated fatty acid methyl ester and 1,3- diaminourea -2- propyl alcohol be dissolved in 10~1000 parts by weight solvent
In, catalyst is added after being passed through protective gas argon gas, is reacted 2~36 hours at 40~120 DEG C；
S3, through being recrystallized to give side base R1For-OH function monomer of polyamide.
It is preferred that solvent selects tetrahydrofuran, catalyst choice sodium methoxide, the usage amount of the catalyst in the step S2
For 10-4~10 parts by weight.
A kind of preparation method of function monomer of polyamide, comprises the following steps：
S1, take 1~100 parts by weight side base R1For-OH function monomer of polyamide, 1~50 parts by weight of carboxylic acid or acid anhydrides, 5
×10-3~2 × 10-1Part by weight of catalyst；
S2, by the side base R10.1~6 part is dissolved in for-OH function monomer of polyamide, carboxylic acid or acid anhydrides and catalyst
In solvent, reacted 2~36 hours at 40~120 DEG C；
S3 and then through washing, extracting, being dried to obtain side base R1For-OCOR1' function monomer of polyamide.
It is preferred that catalyst choice dimethylamino naphthyridine in the step S1, solvent selection tetrahydrofuran in the step S2.
A kind of function polyamide being prepared by the function monomer of polyamide, the structural formula of the function polyamide is such as
Under：
5≤n≤5000；R wherein on main chain2
For disulfide.
Further, the R2For any of following structure：
A kind of preparation method of the function polyamide, comprises the following steps：
S1, by 1~100 parts by weight function monomer of polyamide, the mercaptan of 1~50 parts by weight two and 10-1~10 parts by weight are urged
Agent is dissolved in 1~100 parts by weight solvent；
S2, protective gas argon gas is then passed to, be put into 2~36h of reaction in 40~120 DEG C of oil bath pans；
S3, finally by methanol extraction obtain the function polyamide product.
It is preferred that catalyst choice azodiisobutyronitrile in the step S1, solvent selection tetrahydrofuran.
The beneficial effects of the present invention are：
The vegetable oil derivatives of synthesis are that to carry out Efficient Conversion be function polyamide to the function monomer of polyamide by the present invention,
Function polyamide ultimate yield reaches 50%~100%, and function polyamide purity is 90%~100%.The present invention is prepared
Function polyamide possess uniqueness chemical constitution, aggregated structure and excellent mechanical performance.Function polyamide of the present invention
Synthesized by natural material, no free formaldehyde, without benzene, heavy metal free meets national environmental protection material standard.The present invention is to make and can hold
Continuous, green society provides favourable approach.
Functionality polyamide of the present invention is film-made through dissolving and carries out corresponding Mechanics Performance Testing, its mechanical property ginseng
Number is：22.4~215.1Mpa of modulus of elasticity, 7~19.6Mpa of fracture strength, elongation at break are 40%~1000%.It can be seen that
Functionality polyamide of the present invention possesses excellent mechanical performance, mechanical property.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the function monomer of polyamide of embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of the function monomer of polyamide of embodiment 2.
Fig. 3 is the nucleus magnetic hydrogen spectrum of function polyamide in embodiment 6.
Fig. 4 is the stress-strain curve of the function polyamide of embodiment 6,7,8,9.
Fig. 5 is the transmission electron microscope photo of function polyamide in embodiment 7.
Embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment, following examples are only the present invention
Section Example, rather than whole embodiments.
The reagent used in following examples is bought from market, and the solvent must be done through anhydrous magnesium sulfate before the use
It is evaporated under reduced pressure after dry, azodiisobutyronitrile need to pass through recrystallization purifying.
(the R of embodiment 1-1 functions monomer of polyamide 11For-OH) preparation
Methyl undecylenate 100g, 1,3- diaminourea-propyl alcohol 1g is taken to add in 4ml tetrahydrofurans.It is passed through argon gas half an hour
Afterwards, it is positioned in 40 DEG C of oil bath pans, after adding 10ml sodium methoxides, solution becomes clarification, and under 40 DEG C of reaction conditions, reaction 20 is small
When, specific reaction equation is as follows：
White powdery solids finally are obtained by purifying, the white powdery solids are the work(that side base R1 is-OH
Can monomer of polyamide, also referred to as hydroxy amide base monomer.
The 1H NMR spectras for the function monomer of polyamide 1 that the present embodiment prepares are as shown in figure 1, display gained function is gathered
The purity of amide monomer 1 is very high.F peaks can be seen that 1,3- diaminourea-propyl alcohol success at e peaks and 3.8 at 3.38ppm from Fig. 1
Monomer is accessed, then the peak of a, b, c tri- can be seen that and contain a large amount of double bonds in monomer at 4.85ppm, at 5.0ppm and at 5.8ppm,
Condition is provided for subsequent reactions.
(the R of embodiment 1-2 functions monomer of polyamide 11For-OH) preparation
The parts by weight of methyl undecylenate 1 are taken, the parts by weight of 1,3- diaminourea-propyl alcohol 1 are added in 10 parts by weight tetrahydrofurans.It is logical
After entering argon gas half an hour, it is positioned in 40 DEG C of oil bath pans, adds 10-4After pbw of sodium methoxide, solution becomes clarification, in 40 DEG C of reactions
Under the conditions of, react 2 hours, finally by being recrystallized to give white powdery solids.
The 1H NMR spectras for the function monomer of polyamide 1 that the present embodiment prepares display that purity is very high.
(the R of embodiment 1-3 functions monomer of polyamide 11For-OH) preparation
The parts by weight of methyl undecylenate 1000 are taken, the parts by weight of 1,3- diaminourea-propyl alcohol 10 add 1000 parts by weight tetrahydrochysene furans
In muttering.After being passed through argon gas half an hour, it is positioned in 40 DEG C of oil bath pans, after adding 10 pbw of sodium methoxide, solution becomes clarification,
Under 120 DEG C of reaction conditions, react 36 hours, finally by being recrystallized to give white powdery solids.
The 1H NMR spectras for the function monomer of polyamide 1 that the present embodiment prepares display that purity is very high.
(the R of embodiment 1-4 functions monomer of polyamide 11For-OH) preparation
The parts by weight of methyl undecylenate 500 are taken, the parts by weight of 1,3- diaminourea-propyl alcohol 5 add 500 parts by weight tetrahydrofurans
In.After being passed through argon gas half an hour, it is positioned in 40 DEG C of oil bath pans, after adding 5 pbw of sodium methoxide, solution becomes clarification, at 80 DEG C
Under reaction condition, react 25 hours, finally by being recrystallized to give white powdery solids.
The 1H NMR spectras for the function monomer of polyamide 1 that the present embodiment prepares display that purity is very high.
(the R of embodiment 2-1 functions monomer of polyamide 21For-OCOR1') preparation
Function monomer of polyamide 1 prepared in 54g embodiments 1-1,12g butyric anhydrides, 40mg dimethylamino naphthyridines is taken to put
In the flask of bottom, the mixing of 3ml tetrahydrofurans is added.Reacted 10 hours at 50 DEG C, obtain settled solution, the purified function that obtains is gathered
Amide monomer 2, specific reaction equation are as follows：
R-O-R represents butyric anhydride, the 1H for the function monomer of polyamide 2 that the present embodiment prepares in aforesaid equation (2)
NMR spectra is as shown in Fig. 2 display gained monomer purity is very high.It will be evident that former f peaks at 3.8ppm in the contrast with Fig. 1
Disappear, the appearance for occurring e peaks at new peak and 2.18ppm at 4.8ppm shows that acid anhydrides success gathers with function described in embodiment 1
The hydroxyl of amide monomer 1 reacts, and successfully obtains function monomer of polyamide 2.
(the R of embodiment 2-2 functions monomer of polyamide 21For-OCOR1') preparation
Take function monomer of polyamide 1 prepared in 1 parts by weight of example 1-1,1 parts by weight butyric anhydride, 5 × 10-5Weight
Part dimethylamino naphthyridine is placed in the flask of bottom, adds the mixing of 0.1 parts by weight tetrahydrofuran.React 2 hours, clarified at 40 DEG C
Solution, through washing, extracting, being dried to obtain function monomer of polyamide 2.
(the R of embodiment 2-3 functions monomer of polyamide 21For-OCOR1') preparation
Take function monomer of polyamide 1 prepared in 100 parts by weight of example 1-1,50 parts by weight butyric anhydrides, 2 × 10-1Weight
Amount part dimethylamino naphthyridine is placed in the flask of bottom, adds the mixing of 6 parts by weight tetrahydrofurans.React 36 hours, obtain clear at 120 DEG C
Clear solution, through washing, extracting, being dried to obtain function monomer of polyamide 2.
(the R of embodiment 2-4 functions monomer of polyamide 21For-OCOR1') preparation
Take function monomer of polyamide 1 prepared in 50 parts by weight of example 1-1,25 parts by weight butyric anhydrides, 1 × 10-1Weight
Amount part dimethylamino naphthyridine is placed in the flask of bottom, adds the mixing of 4 parts by weight tetrahydrofurans.React 2~36 hours, obtain at 80 DEG C
Settled solution, through washing, extracting, being dried to obtain function monomer of polyamide 2.
(the R of 3 function monomer of polyamide of embodiment 31For-OCOR1') preparation
For its preparation method with embodiment 2-1, the acid anhydrides R-O-R for not being both selection is acetic anhydride.
(the R of 4 function monomer of polyamide of embodiment 41For-OCOR1') preparation
For its preparation method with embodiment 2-1, the acid anhydrides R-O-R for not being both selection is isobutyric anhydride.
(the R of 5 function monomer of polyamide of embodiment 51For-OCOR1') preparation
For its preparation method with embodiment 2-1, the acid anhydrides R-O-R for not being both selection is benzoyl oxide.
The preparation of embodiment 6-1 functions polyamide 1
By the function monomer of polyamide 2 in 1500mg embodiments 2-1, the mercaptan of 200mg oxa-s two, and 10mg catalyst and
15ml tetrahydrofurans are added in reaction vessel.It is passed through argon gas 15 minutes, mixture is positioned in 100 DEG C of oil bath pans reacted afterwards
36 hours, specific reaction equation was as follows：
Raw material HS-R in the equation (3)2 ’- SH is the mercaptan of oxa- two, in the equation (3) on product main chain
S-R2'-S is the disulfide R2。
Function polyamide 1 is obtained by methanol extraction afterwards.The nuclear-magnetism hydrogen for the function polyamide 1 that the present embodiment prepares
Spectrogram as shown in figure 3, can be seen that at 4.85ppm, 5.0ppm and 5.8ppm that peak disappears by comparison diagram 2, then from 3.62ppm,
New peak occurs can be seen that the success of the mercaptan of oxa- two and double bond react systematic function polyamide at 2.58ppm and 1.58ppm
1。
The preparation of embodiment 6-2 functions polyamide 1
By the function monomer of polyamide 2 in 1 parts by weight of example 2-1, the mercaptan of 1 parts by weight oxa- two, and 10-1Parts by weight
Catalyst and 1 parts by weight tetrahydrofuran are added in reaction vessel.It is passed through argon gas 10 minutes, mixture is positioned over 40 DEG C of oil afterwards
2h is reacted in bath, function polyamide 1 is obtained by methanol extraction afterwards.The function polyamide 1 prepared by the present embodiment
Nucleus magnetic hydrogen spectrum figure find out that the success of the mercaptan of oxa- two reacts systematic function polyamide 1 with double bond.
The preparation of embodiment 6-3 functions polyamide 1
By the function monomer of polyamide 2 in 100 parts by weight of example 2-1, the mercaptan of 50 parts by weight oxa- two, and 10 weight
Part catalyst and 100 parts by weight tetrahydrofurans are added in reaction vessel.It is passed through argon gas 30 minutes, is afterwards positioned over mixture
36h is reacted in 120 DEG C of oil bath pans, function polyamide 1 is obtained by methanol extraction afterwards.The function of being prepared by the present embodiment
The nucleus magnetic hydrogen spectrum figure of polyamide 1 finds out that the success of the mercaptan of oxa- two reacts systematic function polyamide 1 with double bond.
The preparation of embodiment 6-4 functions polyamide 1
By the function monomer of polyamide 2 in 50 parts by weight of example 2-1, the mercaptan of 25 parts by weight oxa- two, and 5 parts by weight
Catalyst and 50 parts by weight tetrahydrofurans are added in reaction vessel.It is passed through argon gas 20 minutes, mixture is positioned over 80 DEG C afterwards
24h is reacted in oil bath pan, function polyamide 1 is obtained by methanol extraction afterwards.The function polyamides prepared by the present embodiment
The nucleus magnetic hydrogen spectrum figure of amine 1 finds out that the success of the mercaptan of oxa- two reacts systematic function polyamide 1 with double bond.
The preparation of the function polyamide 2 of embodiment 7
Preparation method is not both that the function monomer of polyamide of selection is the work(that embodiment 3 prepares with embodiment 6-1
The mixture of energy monomer of polyamide 3 and the embodiment 1-1 function monomer of polyamide 1 prepared.
The images of transmissive electron microscope for the function polyamide that the present embodiment prepares is shown by Fig. 5, it is shown that function polyamides
The surface topography of amine 2, this figure clearly show the micro-structural of function polyamide 2, it was demonstrated that this material is half hitch polycrystalline macromolecule.
The preparation of the function kymene of embodiment 8
Preparation method is not both that the function monomer of polyamide of selection is the work(that embodiment 4 prepares with embodiment 6-1
Can monomer of polyamide 4.
The preparation of the function polyamide 4 of embodiment 9
Preparation method is not both that the function monomer of polyamide of selection is the work(that embodiment 5 prepares with embodiment 6-1
Can monomer of polyamide 5.
By above-described embodiment 6-1, the function polyamide prepared in 7,8,9 carries out sample film respectively, and uses cut-off knife
Shearing growth 15mm, wide 2mm, thickness 0.5mm dumbbell shape batten are used for mechanical test, and rate of extension 10mm/min, it should
Force-strain curve is as shown in figure 4, these function polyamide possess excellent mechanical performance as shown in Figure 4.In addition, R1Place is different
Function polyamide side base function polyamide can be caused to show different mechanical performances.This is that function polyamide should in different field
With providing unlimited possibility.
Claims (10)
1. a kind of function monomer of polyamide, it is characterised in that the structural formula of the function monomer of polyamide is as follows：
Wherein side base R1Structural formula be-OCOR1' or-OH.
2. function monomer of polyamide as claimed in claim 1, it is characterised in that the side base R1For any in following structure
Kind：
3. a kind of preparation method of function monomer of polyamide as claimed in claim 1, it is characterised in that comprise the following steps：
S1, take 1~1000 parts by weight unsaturated fatty acid methyl ester, 1~10 parts by weight 1,3- diaminourea -2- propyl alcohol；
S2, the unsaturated fatty acid methyl ester and DAP be dissolved in 10~1000 parts by weight solvent, led to
Catalyst is added after entering protective gas argon gas, is reacted 2~36 hours at 40~120 DEG C；
S3, through being recrystallized to give side base R1For-OH function monomer of polyamide.
4. the preparation method of function monomer of polyamide as claimed in claim 3, it is characterised in that：Solvent selects in the step S2
Tetrahydrofuran is selected, catalyst choice sodium methoxide, the usage amount of the catalyst is 10-4~10 parts by weight.
5. a kind of preparation method of function monomer of polyamide as claimed in claim 1, it is characterised in that comprise the following steps：
S1, take 1~100 parts by weight side base R1For-OH function monomer of polyamide, 1~50 parts by weight of carboxylic acid or acid anhydrides, 5 × 10-3
~2 × 10-1Part by weight of catalyst；
S2, by the side base R10.1~6 part of solvent is dissolved in for-OH function monomer of polyamide, carboxylic acid or acid anhydrides and catalyst
In, reacted 2~36 hours at 40~120 DEG C；
S3 and then through washing, extracting, being dried to obtain side base R1For-OCOR1' function monomer of polyamide.
6. the preparation method of function monomer of polyamide as claimed in claim 5, it is characterised in that：Catalyst in the step S1
Dimethylamino naphthyridine is selected, solvent selection tetrahydrofuran in the step S2.
A kind of 7. function polyamide that function monomer of polyamide as described in claim 1 is prepared, it is characterised in that the polyamides
The structural formula of amine is as follows：
5≤n≤5000；R wherein on main chain2For two
Thioether.
8. function polyamide as claimed in claim 7, it is characterised in that：The R2For any of following structure：
9. a kind of preparation method of function polyamide as claimed in claim 7, it is characterised in that comprise the following steps：
S1, by 1~100 parts by weight function monomer of polyamide, the mercaptan of 1~50 parts by weight two and 10-1~10 part by weight of catalyst
It is dissolved in 1~100 parts by weight solvent；
S2, protective gas argon gas is then passed to, be put into 2~36h of reaction in 40~120 DEG C of oil bath pans；
S3, finally by methanol extraction obtain the function polyamide product.
10. the preparation method of function polyamide as described in right 9, it is characterised in that：Catalyst choice azo in the step S1
Bis-isobutyronitrile, solvent selection tetrahydrofuran.
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