CN105175715B - Copolymer and to form the preparation method of the monomer of the copolymer - Google Patents
Copolymer and to form the preparation method of the monomer of the copolymer Download PDFInfo
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- CN105175715B CN105175715B CN201510270074.1A CN201510270074A CN105175715B CN 105175715 B CN105175715 B CN 105175715B CN 201510270074 A CN201510270074 A CN 201510270074A CN 105175715 B CN105175715 B CN 105175715B
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- 0 *C(c1cc(C(O)=O)ccc1)=O Chemical compound *C(c1cc(C(O)=O)ccc1)=O 0.000 description 1
- VAEZFSGRFODIPA-UHFFFAOYSA-N CC(CCCCC(NCCCCCCNC(c(cc1)ccc1C(NCCCCCCN)=O)O)=O)=O Chemical compound CC(CCCCC(NCCCCCCNC(c(cc1)ccc1C(NCCCCCCN)=O)O)=O)=O VAEZFSGRFODIPA-UHFFFAOYSA-N 0.000 description 1
- MDKQJOKKKZNQDG-UHFFFAOYSA-N CNCCCCCCNC Chemical compound CNCCCCCCNC MDKQJOKKKZNQDG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a kind of copolymer and to form the preparation method of the monomer of the copolymer.The copolymer is the reaction product of one first monomer and a second comonomer, wherein first monomer has structure shown in formula (I), and the second comonomer has formula (II), formula (III) or structure shown in formula (IV)X A X-types (II)HO2C‑A‑CO2Wherein, Y is NH to H formulas (IV)2Or CO2H, m are to select the positive integer from 2 10；X is to stand alone as NH2Or OH；A is
Description
Technical field
The present invention is on a kind of copolymer and to form the preparation method of the monomer of the copolymer.
Background technology
Nylon 6 (nylon 6) fiber is widely used in daily life at present, such as clothing, family's decorations articles for use or other necks
Domain etc..However, compared with nylon66 fiber (nylon 66), fusing point, softening point, heat resistance and the mechanical strength of nylon 6 all compare nylon
66 is low.These unfavorable physical property limit the Exploitation Scope of the downstream application product of nylon 6 for a long time.Therefore, industry is attempted with chemistry
The technology of synthesizing mean production differentiation nylon 6, its phase improve the surcharge of nylon 6.However, in the modification of current nylon 6
Technically, the product of nylon 6 with the distribution of high uniformity sequence and two kinds of physical property of high-melting-point can not still be obtained.
The content of the invention
It is an object of the invention to substantially overcome the polyamide-based copolymer of prior art in physical property it is a variety of not
Foot, and a kind of copolymer is provided, it is reacted by a specific co-monomer (the first monomer shown in formula (I)) and second comonomer
And obtain.
It is above-mentioned forming the preparation method of the monomer of the copolymer another object of the present invention is to provide.
It is the reaction product of one first monomer and a second comonomer the invention discloses a kind of copolymer, wherein this is first single
Body has structure shown in formula (I)
Formula (I)
Wherein, Y is-NH2Or-CO2H, m are to select the positive integer from 2-10；Wherein when Y is-CO2During H, second comonomer tool
There is structure shown in formula (II) or formula (III)；And when Y is NH2When, the second comonomer has structure shown in formula (IV)
X-A-X formulas (II)
Formula (III)
HO2C-A-CO2H formulas (IV)
Wherein, X is to stand alone as-NH2Or-OH；A isOrN is to select the positive integer from 2-10；And l is to select the positive integer from 1-5.
According to another embodiment of the present invention, the present invention provides a kind of preparation method of monomer, comprising：There is formula by one
(VIII) compound of structure shown in carries out a melting processing procedure with a compound with structure shown in formula (IX), and carries out an acid
Change reaction, obtain the monomer for having shown in formula (I) structure,
Formula (I)
Formula (VIII)
Formula (IX)
Wherein, M is Na or K；M is to select the positive integer from 2-10；I is to select the positive integer from 1-3；Y is-CO2H；And Z
It is H or-OH.
Compared with prior art, the advantage of the invention is that：With prior art with hexamethylene diamine, terephthalic acid (TPA) and oneself in
Acid amides carries out the obtained copolymer of copolyreaction directly as reaction monomers and compared, and copolymer of the invention is by by originally can be
Cause what main random was distributed in backbone moleculeAnd caprolactam (and/or diamines) is first reacted,
Obtain the co-monomer containing TPA and caprolactam (or diamines) two kinds of monomers, then again by the co-monomer again with another diamines (or
Dihydroxy) monomer carries out staggered copolymerization and obtains.Copolymer obtained by the method according to the invention is in symmetry, height
It is improved in terms of the physical property such as sequence distributivity and high-melting-point.
For above and other objects of the present invention, feature and advantage can be become apparent, it is cited below particularly go out preferable implementation
Example, is described in detail below：
Embodiment
According to embodiments of the present invention, the present invention provides a kind of copolymer, comprising anti-by one first monomer and a second comonomer
The product of gained is answered, wherein first monomer has structure shown in formula (I)
Formula (I)
Wherein, Y can be-NH2Or-CO2H, m can select the positive integer from 2-10.
According to embodiments of the present invention, when Y is-CO2During H, the second comonomer, which can have shown in formula (II) or formula (III), to be tied
Structure；And when Y is NH2When, the second comonomer can have structure shown in formula (IV)
X-A-X formulas (II)
Formula (III)
HO2C-A-CO2H formulas (IV)
Wherein, X can stand alone as-NH2Or-OH；A can beOrN can select the positive integer from 2-10；And l can select the positive integer from 1-5.
According to embodiments of the present invention, first monomer can beWherein m is to select the positive integer from 2-10.
In addition, when first monomer isWhen, should
Second comonomer is H2N-A-NH2, wherein A isOrWith
And n is to select the positive integer from 2-10.For example, second comonomer can be
Or
According to other embodiments of the present invention, when first monomer isWhen, the second comonomer may be, for example,
Or
According to certain embodiments of the invention, first monomer can beWherein m is to select the positive integer from 2-10.When first monomer
ForWhen, the second comonomer may be, for example,Or
According to certain embodiments of the invention, copolymer of the present invention can have the repetition list of the structure as shown in formula (V)
Member
Formula (V)
Wherein, A isOrM is to select from 2-10 just
Integer；And n is to select the positive integer from 2-10.
According to certain embodiments of the invention, copolymer of the present invention can have the repetition list of the structure as shown in formula (VI)
Member
Formula (VI)
Wherein m is to select the positive integer from 2-10；And l is to select the positive integer from 1-5.
According to certain embodiments of the invention, copolymer of the present invention can have the repetition of the structure as shown in formula (VII)
Unit
Formula (VII)
Wherein, A isOrM is to select from 2-10 just
Integer；And n is to select the positive integer from 2-10.
According to embodiments of the present invention, copolymer of the present invention has a melting temperature can be between about 200 DEG C to 270 DEG C
Between, such as between 240 DEG C to 265 DEG C.
The present invention also provides a kind of preparation method for being used for forming the monomer of above-mentioned copolymer, and wherein this method includes：Will
One with the compound of structure shown in formula (VIII) and a compound with structure shown in formula (IX) carry out one melt processing procedure or
One solution process.Then, the product of gained is subjected to an acidification reaction, obtains the monomer for having shown in formula (I) structure
Formula (I)
Formula (VIII)
Formula (IX)
Wherein, M is Na or K；M is to select the positive integer from 2-10；I is to select the positive integer from 0 or 1-3；Y is-CO2H；With
And Z is H or-OH.Wherein, the temperature of the melting processing procedure be between 190 DEG C to 210 DEG C, the temperature of solution process be between
Between 85 DEG C to 95 DEG C.
According to certain embodiments of the invention, wherein the product obtained by melting processing procedure or solution process is carried out into an acidification reaction
It can comprise the steps of：It will be mixed via the product obtained by the melting processing procedure with water, obtain a mixture, and with an inorganic sour water
Solution titrates the mixture, makes the pH value of the mixture up between 5 to 7, such as between 5.6 to 6.4.It is in addition, anti-in the acidifying
After answering, the moisture content of the mixture is removed and filtered.After the solid product obtained by cleaning and drying, it can obtain with formula
(I) monomer shown in structure.
According to embodiments of the present invention, the compound of structure shown in formula (VIII) should isAnd there should be the compound of structure shown in formula (IX) to beOr
Illustrate the preparation method of monomer and polymers of the present invention by the following example below, further to explain
Bright technical characteristic of the invention.
It is prepared by the monomer with formula (I) structure
Preparation example 1：N is prepared with dimethyl terephthalate (DMT) and 6-aminocaprolc acid sodium salt, N '-bis- (carboxy pentyl) is to benzene two
Formamide (BCTM)
BCTM
One reaction bulb is provided, adds 1 equivalent 6-aminocaprolc acid (6-Aminohexanoic acid, ACA) and 1 Equivalent Hydrogen
Sodium oxide molybdena (NaOH), and appropriate water is added as solvent.After reaction two hours, the reaction bulb is heated so that water to be removed, is obtained
One solid mixture.Then, the solid mixture of gained is placed in baking oven, and dried 12 hours at 90 DEG C, obtain 6- ammonia
Base caproic acid sodium salt (6-Aminohexanoic acid sodium salt, ACA-Na) solid.Then, by 0.97 gram
Dimethyl terephthalate (DMT) (dimethyl terephthalate, DMT), 2.32 grams (0.015mole) of (0.005mole) are dry
Dry 6-aminocaprolc acid sodium salt (ACA-Na) and 20ml ethylene glycol (ethylene glycol, EG), are placed in a reaction bulb
In.Then, under a nitrogen, the reaction bulb is slowly warming up to 85~90 DEG C.After reaction 14 hours, room temperature is cooled to, is added
20ml distilled water, aqueous sulfuric acid (0.1M) is slowly instilled after solid dissolving and is neutralized, its pH value is reached 6.0.Connect
, 20 hours are stood at room temperature, it was observed that there is solid to separate out and precipitate.Then, solid is collected, and this solid is placed in glass
In bottle, cleaned with the distilled water of 3 times of weight and filtering, after the step of being repeated 5 times this cleaning and filtering, solid after this cleaning in
Dried in 80 DEG C of baking ovens, obtain N, and N '-bis- (carboxy pentyl) terephthalamide (N, N '-bis (carboxypentyl)
terephthalamide、BCTM).The reaction equation of above-mentioned reaction is as follows：
N, N '-bis- (carboxyls penta are measured with differential scanning calorimetry (differential scanning calorimeter)
Base) terephthalamide, it is 204 DEG C (peak-peaks) to learn its melting temperature (Tm)；And utilize NMR spectrum and red
External spectrum analysis N, N '-bis- (carboxy pentyl) terephthalamide, the spectral information of gained are as follows：
1H NMR(D2SO4,ppm):8.53(4H,phenyl-1,4-),4.26(4H,aromatic-CON-CH2-,ACA),
3.52(4H,aliphatic-CH2-CO2-,ACA),1.88-2.37(12H,aliphatic,ACA)。
IR(cm-1):3308(NH)；3300-2930(broad,OH)；2858；1725(carbonyl of CO2H)；1640
(amide)；1570-1350；1300-800.
It can be learnt by NMR spectrum information score, gained compound BCTM groupWithMolar ratio be 1:2.
Preparation example 2：N, N '-bis- (carboxyls are prepared with double (2- hydroxyethyls) terephthalates and 6-aminocaprolc acid sodium salt
Amyl group) terephthalamide (BCTM)-(solwution method)
By double (2- hydroxyethyls) terephthalate (bis-hydroxylethyl of 3.84 grams (0.005mole)
Terephthalate, BHET), 2.32 grams (0.015mole) dry 6-aminocaprolc acid sodium salt (ACA-Na) and 20ml second
Glycol (ethylene glycol, EG), is placed in a reaction bulb.Then, under a nitrogen, the reaction bulb is slowly warming up to 85
~90 DEG C, after carrying out reaction 14 hours, room temperature is cooled to, adds 20ml distilled water, slowly dripped after all solution is dissolved into
Enter aqueous sulfuric acid (0.1M) to be neutralized, its pH value is reached 6.0.Then, 20 hours are stood at room temperature, there is solid precipitation
And precipitate.This solid is placed in vial, is cleaned and filtered with the distilled water of 3 times of weight, is repeated 4 times what this cleaned and filtered
After step, the solid after this cleaning obtains N in being dried in 80 DEG C of baking ovens, N '-bis- (carboxy pentyl) terephthalamide (N, N '-
bis(carboxypentyl)terephthalamide,BCTM).The reaction equation of above-mentioned reaction is as follows：
With the gained of differential scanning calorimetry (differential scanning calorimeter) measurement preparation example 2
N, N '-bis- (carboxy pentyl) terephthalamides, it is 204 DEG C (peak-peaks) to learn its melting temperature (Tm)；And utilize core
Nuclear magnetic resonance spectroscopy and infrared spectrum analysis preparation example 2 gained N, N '-bis- (carboxy pentyls) terephthalamide, are obtained and preparation example
1 identical spectrum.
Preparation example 3：N, N '-bis- (carboxyls are prepared with double (2- hydroxyethyls) terephthalates and 6-aminocaprolc acid sodium salt
Amyl group) terephthalamide (BCTM)-(fusion method)
By double (2- hydroxyethyls) terephthalate (bis-hydroxylethyl of 3.84 grams (0.005mole)
Terephthalate, BHET), 2.32 grams (0.015mole) dry 6-aminocaprolc acid sodium salt (ACA-Na) be placed in a reaction bulb
In.Then, under a nitrogen, the reaction bulb is slowly warming up to 195-200 DEG C, after carrying out reaction 14 hours, is cooled to room temperature, adds
Enter 20ml distilled water, slowly instilling aqueous sulfuric acid (0.1M) after all solution is dissolved into is neutralized, and reaches its pH value
To 6.0.Then, 20 hours are stood at room temperature, there is solid to separate out and precipitate.This solid is placed in vial, with 3 times of weight
Distilled water cleaning and filtering, be repeated 4 times this cleaning and filtering the step of after, this cleaning after solid in 80 DEG C of baking ovens do
It is dry, using NMR spectrum and infrared spectrum analysis, show except obtaining N, N '-bis- (carboxy pentyl) terephthalamide
(with the identical spectrum of preparation example 1) outside, also contains about 30% accessory substance.
One is used for synthesizing N, and the method for N '-bis- (carboxy pentyl) terephthalamide is with 6-aminocaprolc acid (6-
Aminohexanoic acid, ACA) with chlorine (chloride) paraphthaloyl chloride (terephthaloyl
Chloride, TCL) with solwution method in hexamethylene diamine (hexamethylenediamine, HMDA), pyridine (pyridine) and N-
Reacted, obtained after purification and the phase of preparation example 1 in the presence of N-methyl 2-pyrrolidone N (N-Methyl-2-Pyrrolidone, NMP)
Same spectrum.(reaction equation is as follows：)。
However, the paraphthaloyl chloride (terephthaloyl chloride, TCL) as the start material is acyclic
The chloride compounds of guarantor, therefore N, the preparation method of N '-bis- (carboxy pentyl) terephthalamide are formed with paraphthaloyl chloride
For processing procedure not environmentally.
Compare preparation example 1：
By the dimethyl terephthalate (DMT) (dimethyl terephthalate, DMT) of 0.97 gram (0.005mole),
The 6-aminocaprolc acid (6-Aminohexanoic acid, ACA) of 1.69 grams (0.015mole) and 20ml ethylene glycol
(ethylene glycol, EG), is placed in a reaction bulb.Then, under a nitrogen, the reaction bulb is slowly warming up to 85~90
DEG C, after carrying out reaction 14 hours, room temperature is cooled to, adds 20ml distilled water, slowly instilled aqueous sulfuric acid (0.1M) and carry out
Neutralize, its pH value is reached 6.0.Then, 20 hours are stood at room temperature, there is solid to separate out and precipitate.This solid is placed in glass
In glass bottle, cleaned and filtered with the distilled water of 3 times of weight, after being repeated 4 times the step of this cleans and filtered, the solid after this cleaning
In dry in 80 DEG C of baking ovens.Because 6-aminocaprolc acid can carry out self polymerization, resulting polymers meeting and dimethyl terephthalate (DMT)
Reaction, therefore the product of confusion is had in above-mentioned reaction, can not obtain N, N '-bis- (carboxy pentyl) terephthalamide
(BCTM)。
Preparation example 4：N, N '-bis- (6- aminohexanes) terephthalamides (N, N '-bis (6-aminohexyl)
Terephthalamide, BATM) preparation
BATM
A reaction bulb is taken, adds the dimethyl terephthalate (DMT) (dimethyl of 0.97 gram (0.005mole)
Terephthalate, DMT), the hexamethylene diamine (hexamethylenediamine, HMDA) of 3.06 grams (0.02mole) and
20ml ethylene glycol (ethylene glycol, EG).Under a nitrogen, 85~90 DEG C are to slowly warm up to and is reacted 14 hours.In room
Temperature is lower to stand 20 hours, has solid to separate out and precipitate.This solid is placed in vial, with the distilled water cleaning of 3 times of weight and
Filtering, after being repeated 4 times the step of this cleans and filtered, the solid after this cleaning is in dry in 80 DEG C of baking ovens.N is obtained after drying,
N '-bis- (6- aminohexanes) terephthalamide (N, N '-bis (6-aminohexyl) terephthalamide, BATM) it is solid
Body.N, N '-bis- (6- aminohexanes) are measured with differential scanning calorimetry (differential scanning calorimeter)
Terephthalamide, it is 211 DEG C (peak-peaks) to learn its melting temperature (Tm)；And utilize NMR spectrum and infrared light
Spectrum analysis N, N '-bis- (6- aminohexanes) terephthalamide, the spectral information of gained are as follows：
1H NMR(D2SO4,ppm):8.52(4H,phenyl-1,4-),4.26(4H,aromatic-CON-CH2-,
HMDA),3.91(4H,aliphatic-CH2-NH2,HMDA),1.88-2.37(16H,aliphatic,HMDA)。
IR(cm-1):3308-3294(NH)；2927；2858；1643(amide)；1570-1350；1300-800.
Its group of compound BATM can be learnt by NMR spectrum information scoreWithWhen mole ratio be 1:2.
The preparation of copolymer
Embodiment 1:It is prepared by BCTM-co-HMDA copolymers
Take a reaction bulb, add 14.2g (0.036mole) N, N '-bis- (carboxy pentyls) terephthalamide (BCTM),
4.2g (0.036mole) hexamethylene diamine (hexamethylenediamine, HMDA) and 60g water.Then, by reaction bulb temperature liter
To 85 DEG C, after solid all dissolving, display BCTM reaches with HMDA sufficiently uniformly to be mixed, and is now removed in a manner of being evaporated under reduced pressure
Moisture content is removed, the solid product resided in reaction bulb.Then, be slowly heated reaction bulb to 150 DEG C maintain 1 hour.Then, will be anti-
Answer bottle to be warming up to 180 DEG C and maintain 2 hours.Then, reaction bulb is warming up to 200 DEG C again and maintained 2 hours.Then, will react
Bottle is warming up to 220 DEG C and maintained 2 hours.Finally, reaction bulb is warming up to 250 DEG C and maintained 4 hours.After cooling, BCTM- is obtained
Co-HMDA copolymers (shallow brown white solid) (have
Repeat unit).
It is total to differential scanning calorimetry (differential scanning calorimeter) measurement BCTM-co-HMDA
Polymers, learn its melting temperature (Tm) be 261 DEG C (peak-peaks), glass transition temperature (Tg) be 75 DEG C and relative viscosity
(R.V.) it is 1.45.The analysis condition of the relative viscosity (R.V.) of co-polymer is that the nylon copolymer for taking 0.25g is positioned over
Analyze in vial, add the concentrated sulfuric acid (97wt% concentration) and be configured as 50ml solution, then under the conditions of 25 DEG C, carry out phase
Analysis to viscosity (R.V.).Utilize NMR spectrum and infrared spectrum analysis BCTM-co-HMDA copolymers, the light of gained
Spectrum information is as follows：
1H NMR(D2SO4, ppm)：8.53 (4H, phenyl, BCTM), 4.26 (4H, aromatic-CON-CH2-, ACA),
4.00 (4H, aliphatic-CON-CH2-, HMDA), 3.18 (4H, aliphatic-CH2- CON-, ACA), 1.87-2.34
(20H, aliphatic, ACA and HMDA).
13C NMR(D2SO4,ppm):178 and 172 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3304(NH)；2930；2858；1630(broad,amide)；1570-1350；1300-800.
It can be learnt by NMR spectrum information score, the group of BCTM-co-HMDA copolymersWithMol ratio
Example is 1:1:2.
The step described in embodiment 1 is repeated, carries out the 1st confirmatory experiment and the 2nd confirmatory experiment, and with differential scanning
Calorimeter (differential scanning calorimeter) measures the 1st confirmatory experiment and the 2nd confirmatory experiment institute
BCTM-co-HMDA copolymers melting temperature (Tm), respectively 262 DEG C and 261 DEG C (peak-peaks)；And measurement the
The glass transition temperature (Tg) of BCTM-co-HMDA copolymers obtained by 1 confirmatory experiment and the 2nd confirmatory experiment, it is respectively
74 and 75 DEG C.In addition, the BCTM-co- obtained by with the 1st confirmatory experiment of nuclear magnetic resonance spectroscopy and the 2nd confirmatory experiment
HMDA copolymers, as a result there is identical spectral information with the BCTM-co-HMDA of embodiment 1.Show the BCTM-co- of the present invention
The chemical composition of HMDA copolymers and its repeatability of physical property are good.
Embodiment 2:It is prepared by BCTM-co-TMDA copolymers
Carried out according to the mode that BCTM-co-HMDA co-polymers are synthesized described in embodiment 1, except by 4.2g hexamethylene diamines
(hexamethylenediamine, HMDA) is substituted with 3.18g butanediamine (tetramethylene diamine, TMDA), is obtained
To withThe combined polymerization of repeat unit
Thing BCTM-co-TMDA.
It is total to differential scanning calorimetry (differential scanning calorimeter) measurement BCTM-co-TMDA
Polymers, learn its melting temperature (Tm) be 263 DEG C (peak-peaks), glass transition temperature (Tg) be 76 DEG C and relative viscosity
(R.V.) it is 1.52.Utilize NMR spectrum and infrared spectrum analysis BCTM-co-TMDA copolymers, the spectral information of gained
It is as follows：
1H NMR(D2SO4,ppm):8.53(4H,phenyl,BCTM),4.26(4H,aromatic-CON-CH2-,ACA),
4.00(4H,aliphatic-CON-CH2-,TMDA),3.18(4H,aliphatic-CH2-CON-,ACA),1.87-2.34
(16H, aliphatic, ACA and TMDA).
13C NMR(D2SO4,ppm):178 and 173 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3304(NH)；2930；2858；1630(broad,amide)；1570-1350；1300-800.
It can be learnt by NMR spectrum information score, its group of BCTM-co-TMDA copolymersWithMolar ratio be
1:1:2。
Embodiment 3:It is prepared by BCTM-co-EDA copolymers
Carried out according to the mode that BCTM-co-HMDA co-polymers are synthesized described in embodiment 1, except by 4.2g hexamethylene diamines
(hexamethylenediamine, HMDA) is substituted with 2.17g ethylenediamines (ethylene daimine, EDA), is hadThe co-polymer of repeat unit
BCTM-co-EDA。
It is as follows using NMR spectrum and infrared spectrum analysis BCTM-co-EDA copolymers, the spectral information of gained：
1H NMR(D2SO4,ppm):8.53(4H,phenyl,BCTM),4.26(4H,aromatic-CON-CH2-,ACA),
4.10(4H,aliphatic-CON-CH2-,EDA),3.18(4H,aliphatic-CH2-CON-,ACA),1.87-2.34(12H,
aliphatic,ACA)。
13C NMR(D2SO4,ppm):178 and 173 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3309(NH)；2930；2855；1630(broad,amide)；1570-1350；1300-800.
It can be learnt by NMR spectrum information score, its group of BCTM-co-EDA copolymersWithMolar ratio be 1:1:2.
Embodiment 4:It is prepared by BCTM-co-PDA copolymers
Carried out according to the mode that BCTM-co-HMDA is synthesized described in embodiment 1, except by 4.2g hexamethylene diamines
(hexamethylenediamine, HMDA) is substituted with 3.91g p-phenylenediamine (para-phenylenediamine, PDA), is obtained
To with repeat unitCombined polymerization
Thing BCTM-co-PDA.
It is total to differential scanning calorimetry (differential scanning calorimeter) measurement BCTM-co-PDA
Polymers, learn that its melting temperature (Tm) is 321 DEG C (broad, peak-peaks) and glass transition temperature (Tg) is 110 DEG C.Profit
It is as follows with NMR spectrum and infrared spectrum analysis BCTM-co-PDA copolymers, the spectral information of gained：
1H NMR(D2SO4,ppm):8.53(4H,phenyl,BCTM),7.11(4H,phenyl,PDA),4.26(4H,
aromatic-CON-CH2-,ACA),3.18(4H,aliphatic-CH2- CON-, ACA), 1.87-2.34 (=12H,
aliphatic,ACA)。
IR(cm-1)：3309-3270(NH)；2920；2861；1645(broad,amide)；1590-1350；1300-800.
It can be learnt by NMR spectrum information score, its group of BCTM-co-PDA copolymersWithMole ratio be
1:1:1.8-1.9。
Embodiment 5:It is prepared by BCTM-co-BHET copolymers
Carried out according to the mode that BCTM-co-HMDA co-polymers are synthesized described in embodiment 1, except by 4.2g hexamethylene diamines
(hexamethylenediamine, HMDA) is with double (2- hydroxyethyls) terephthalate tetramer (bis- of 31.38g
(chemical constitution is hydroxylethyl terephthalate tetramer), BHET tetramer) substitution, had
The co-polymer BCTM-co-BHET of repeat unit.
It is total to differential scanning calorimetry (differential scanning calorimeter) measurement BCTM-co-BHET
Polymers, it is 247 DEG C (peak-peaks) to learn its melting temperature (Tm).
Embodiment 6:It is prepared by BATM-co-AA copolymers
A reaction bulb is taken, under nitrogen environment, addition 12.98g (0.036mole) terephthalamide (N, N '-bis (6-
Aminohexyl) terephthalamide, BATM), 5.29g (0.036mole) adipic acid (adipic acid, AA) and
60g water.Then, reaction bulb temperature is risen to 85 DEG C, after solid all dissolving, display BATM and AA reaches sufficiently uniformly mixed
Close, moisture content is now removed in a manner of being evaporated under reduced pressure, the solid product resided in reaction bulb, it is small to be slowly heated to 150 DEG C of maintenances 1
When.Then, reaction bulb is warming up to 180 DEG C and maintained 2 hours.Then, reaction bulb is warming up to 200 DEG C again and maintained 2 hours.
Then, reaction bulb is warming up to 220 DEG C and maintained 2 hours.Finally, reaction bulb is warming up to 250 DEG C and maintained 4 hours.Cooling
Afterwards, hadRepeat unit
Copolymer BATM-co-AA.
With differential scanning calorimetry (differential scanning calorimeter) measurement BATM-co-AA copolymerization
Thing, learn its melting temperature (Tm) be 301 DEG C (peak-peaks), glass transition temperature (Tg) be 78 DEG C and relative viscosity
(R.V.) it is 1.52.Using NMR spectrum and infrared spectrum analysis BATM-co-AA copolymers, the spectral information of gained is such as
Under：
1H NMR(D2SO4,ppm):8.53(4H,phenyl,BATM),4.26(4H,aromatic-CON-CH2-,
HMDA),4.00(4H,aliphatic-CON-CH2-,HMDA),3.18(4H,aliphatic-CH2-CON-,AA),1.86-
2.36 (20H, aliphatic, HMDA and AA).
13C NMR(D2SO4,ppm):177 and 172 (amide), 131 (aromatic), 44-43,32,28-24.
IR(cm-1):3302(NH)；2930；2855；1630(broad,amide)；1570-1350；1300-800.
It can be learnt by NMR spectrum information score, its group of BCTM-co-HMDA copolymersWithMolar ratio be
1:1:2。
Embodiment 7:It is prepared by BATM-co-IPA copolymers
Take a reaction bulb, add 12.98g (0.036mole) terephthalamide (N, N '-bis (6-aminohexyl)
Terephthalamide, BATM), 6.02g (0.036mole) M-phthalic acid (isophthalic acid, IPA) and 60g
Water.Then, reaction bulb temperature is risen to 85 DEG C, after solid dissolving, moisture content is removed in a manner of being evaporated under reduced pressure, resides in reaction bulb
Interior solid product, it is slowly heated to 150 DEG C and maintains 1 hour.Then, reaction bulb is warming up to 180 DEG C and maintained 2 hours.Connect
, reaction bulb is warming up to 200 DEG C again and maintained 2 hours.Then, reaction bulb is warming up to 220 DEG C and maintained 2 hours.Finally,
Reaction bulb is warming up to 250 DEG C and maintained 4 hours.After cooling, hadThe copolymer of repeat unit
BATM-co-IPA。
It is total to differential scanning calorimetry (differential scanning calorimeter) measurement BATM-co-IPA
Polymers, without obvious melting temperature (Tm), glass transition temperature (Tg) be 115 DEG C and relative viscosity (R.V.) is 1.41.
It is as follows using NMR spectrum and infrared spectrum analysis BATM-co-IPA copolymers, the spectral information of gained：
1H NMR(D2SO4,ppm):9.02(1H,phenyl,IPA),8.53(4H,phenyl,BATM),8.45(2H,
phenyl,IPA),7.96(1H,phenyl,IPA),4.26(4H,aromatic-CON-CH2-,HMDA),4.00(4H,
aliphatic-CON-CH2-,HMDA),1.86-2.36(8H,aliphatic,HMDA)。
13C NMR(D2SO4,ppm):177 and 175 (amide), 140,132,129 (aromatic), 44-43,28-24.
IR(cm-1):3305-3300(NH)；2930；2878；1676(broad,amide)；1570-800.
It can be learnt by NMR spectrum information score, its group of BATM-co-IPA copolymersWithMolar ratio be 1:
1:2。
Comparing embodiment 1:
According to general described in document (Rwei, S.P.et al., Thermochimica Acta, 555,37-45,2013)
The synthetic method of nylon copolymer, by hexamethylene diamine (hexamethylenediamine, HMDA), terephthalic acid (TPA)
(mole ratio is 1 for (terephthalic acid, TPA) and caprolactam (caprolactam, CPL):1:2) melted
Melt copolymerization, obtain copolymer (1).
With differential scanning calorimetry (differential scanning calorimeter) measurement copolymer (1), learn
Its melting temperature (Tm) has two obvious peak values, respectively 183 DEG C and 213 DEG C (broad), and its relative viscosity is 2.0.
It is as follows using NMR spectrum and infrared spectrum analysis analysis copolymer (1), the spectral information of gained：
1H NMR:δ8.53(4H,phenyl),4.26(4H,aromatic-CON-CH2),4.00(4H,aliphatic-
CON-CH2),3.18(4H,aliphatic-CH2- CON), 1.87-2.34 (aliphatic, CPL and HMDA).
13C NMR(D2SO4,ppm):178 and 172 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3304(NH)；2930；2861；1630(broad,amide)；1570-800.
By the analysis of NMR spectrum information score, because CPL and HMDA spectral absorption peak is closely similar,
More of aliphatic absworption peaks part is overlapping, therefore only calculates aromatic radical (aromatic) and the ratio of aliphatic (aliphatic)
Example, copolymer (1) aromatic group is shown by calculatingTo aliphatic group
WithMole ratio be 1.00:2.97.
Comparing embodiment 2:
The step described in comparing embodiment 1 is repeated, confirmatory experiment is carried out, obtains polymer (2).With differential scanning calorimetry
The melting temperature (Tm) of (differential scanning calorimeter) measurement polymer (2) is 190-220 DEG C (wide
Peak).It is as follows using NMR spectrum and infrared spectrum analysis copolymer (2), the spectral information of gained：
1H NMR:δ8.53(4H,phenyl),4.26(4H,aromatic-CON-CH2),4.00(4H,aliphatic-
CON-CH2),3.18(4H,aliphatic-CH2- CON), 1.87-2.34 (aliphatic, CPL and HMDA).
13C NMR(D2SO4,ppm):δ 178 and 172 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3304(NH)；2930；2861；1630(broad,amide)；1570-800.
Aromatic radical (aromatic) and the ratio of aliphatic (aliphatic) are calculated, copolymer (2) fragrance is shown by calculating
GroupTo aliphatic groupWithRub
Your ratio is 1.00:2.98.
Comparing embodiment 3:
The step described in comparing embodiment 1 is repeated, confirmatory experiment is carried out, obtains polymer (3).With differential scanning calorimetry
The melting temperature (Tm) of (differential scanning calorimeter) measurement polymer (3) is 185 DEG C, 192 DEG C,
And 218 DEG C.It is as follows using NMR spectrum and infrared spectrum analysis copolymer (3), the spectral information of gained：
1H NMR:δ8.53(4H,phenyl),4.26(4H,aromatic-CON-CH2),4.00(4H,aliphatic-
CON-CH2),3.18(4H,aliphatic-CH2- CON), 1.87-2.34 (aliphatic, CPL and HMDA).
13C NMR(D2SO4,ppm):178 and 172 (amide), 131 (aromatic), 44-43,33,27-24.
IR(cm-1):3304(NH)；2930；2861；1630(broad,amide)；1570-800.
Aromatic radical (aromatic) and the ratio of aliphatic (aliphatic) are calculated, copolymer (3) fragrance is shown by calculating
GroupTo aliphatic groupWith
Mole ratio be 1.00:2.98.
Comparing embodiment 4:
According to general described in document (Rwei, S.P.et al., Thermochimica Acta, 555,37-45,2013)
The synthetic method of nylon 6, by 0.8 kilogram of caprolactam (caprolactam, CPL), 0.16 kilogram of water, 0.06 kilogram
Acetic acid, temperature is risen to 180 DEG C and maintained 2 hours.Then by temperature to 220 DEG C and maintain 2 hours.Then, in general in 2 hours
Temperature is gradually heating to 260 DEG C by 220 DEG C and continued to 6 hours.Blanking and pelletizing after cooling, obtain nylon 6/poly compound.
Then, embodiment 1 and its confirmatory experiment 1 and 2, comparing embodiment 1-4 are carried out hot water can extraction quantity test, as a result
As shown in table 1.Hot water can include the step of extraction quantity experiment：Determinand is placed in a reaction bulb (determinand weight is W0),
And add the water of 15 times of the determinand weight.Then, after being heated to reflux 10 hours, the aqueous solution is removed, the solid remained is dried
It is dry to weigh (now gained weight be W1), and calculate hot water can extraction quantity ((W0-W1)/W0x100wt%).
Table 1
Remarks:CPL is representedGroup, TPA are representedGroup,
HMDA is representedGroup, AA are representedGroup.
As shown in Table 1, comparing embodiment 1-3 can be with hexamethylene diamine (hexamethylenediamine, HMDA), right
Phthalic acid (terephthalic acid, TPA) and caprolactam (caprolactam, CPL) are directly as reaction monomers
When carrying out copolyreaction, even if comparing embodiment 1-3 is all carried out with identical step, copolymer (1)-(3) its structure of gained
(recurring group ratio) and physical property (such as melting temperature and glass transition temperature) are all variant.Because compare implementation
Example 1-3 uses traditional polymerization, and the polymerisation between tri- kinds of monomers of HMDA, TPA, CPL has many different permutation and combination,
Therefore the chaotic type that copolymer product is made up of various groups with the structure of different molecular weight and different permutation and combination is copolymerized
Compound (random copolymer).In addition, between the terephthalic acid (TPA) of aromatic series and the hexamethylene diamine of fatty series and caprolactam
Compatibility is low, and the difference of the reactivity between two class terminal functional groups is big, causes the terephthalic acid (TPA) sequence in main chain point
Cloth (sequential distribution) non-homogeneous dispersion.Therefore, the rule of gained copolymer is structural poor, chemistry knot
Structure transitivity does not have repeatability, therefore is more difficult to get stable co-polymer chemical structure transitivity.Opposite, implemented by the present invention
Knowable to example 1 and its confirmatory experiment, each monomer addition before reaction and each monomer derived thing content ratio in reaction rear copolymer,
Almost there is no difference, because the monomer with formula (I) structure can be in the sequence of the backbone molecule structural homogeneity of co-polymer
Column distribution, main random can be caused to be distributed in backbone molecule scriptAnd caprolactam (or/
And diamines) first reacted, obtain containing two kinds of monomers of TPA and caprolactam (or diamines) such as formula (I) co-monomer, this is such as
The co-monomer of formula (I) carries out staggered copolymerization (Alternative with the monomer of formula (II) again
Polymerization), staggered co-polymer is obtained.In addition, the method can also make the monomer and tool with formula (I)
There is the mutual compatibility between formula (II) monomer to improve, and reduce the reactivity difference between both terminal functional groups.Therefore, relatively
In chaotic type co-polymer (random copolymer) known technology, method of the invention can improve the symmetrical of copolymer
The physical property such as property, high order column distribution and high-melting-point.It can thus improveIn copolymer chain
The distribution of uniformity sequence, obtained product is close to alternate copolymer (alternative copolymer).If it is applied to plastics
Or spinning procedure for processing, the variability of product can be reduced, and improve stability and reduce wire broken rate.
In addition, embodiment 1 and its its melting temperature of copolymer obtained by confirmatory experiment and glass transition temperature and current business
Copolymer in industry described in obtainable nylon 6 or comparing embodiment 1-4 is compared, and all has significant raising.And embodiment 1 and
The more commercially available nylon 6 of glass transition temperature and nylon66 fiber of copolymer obtained by its confirmatory experiment improve about 20-30
DEG C, and melting temperature is even close to nylon66 fiber.In addition, embodiment 1 and its copolymer its hot water obtained by confirmatory experiment can extract
Taken amount (wt%) is also come low compared with the copolymer described in nylon 6 or comparing embodiment 1-3.
Therefore, its property of copolymer of the present invention is significantly better than commercial nylon 6 as shown in Table 1.Compared with nylon66 fiber,
Copolymer of the present inventionGroup content can be more than 49mole%, and Tm and Tg also close to
Or better than nylon66 fiber, therefore the application market for substituting nylon66 fiber that has an opportunity.The other embodiment of the present invention 1 and its confirmatory experiment 1-2
Understand, copolymer of the present invention has high repeatability (i.e. the stability of chemical constitution transitivity is high), is especially suitable for
Commercialization (stability is the most important conditional parameter of commercialization, i.e., has identical property per series-produced copolymer).
From the above embodiment of the present invention 1-7 and comparing embodiment 1-4 experimental result, since the present invention is with formula
(I) the monomer substitution terephthalic acid (TPA) (terephthalic acid, TPA) of structure comes and diamines or amide-type monomer reaction shape
Into copolymer, may be such thatGroup is uniformly distributed in copolymer chain, obtains alternate copolymer
(alternative copolymer) (has as described in Example 1
The copolymer of repeat unit, with the main chain that sequentially forms of [- CPL-TPA-CPL-HMDA-], (CPL is represented for itGroup, TPA are representedGroup and HMDA are representedGroup), there is high fusing point, softening point, heat resistance, mechanical strength, and low heat
Water can extraction quantity.
Although embodiments of the invention and its advantage are disclosed above, it will be appreciated that any art
Middle tool usually intellectual, without departing from the spirit and scope of the present invention, when can change, substitute with retouching.In addition, this hair
Bright protection domain be not necessarily limited by processing procedure in specification in the specific embodiment, machine, manufacture, material composition, device,
Method and step, any those of ordinary skill in the art can understand existing or future from disclosure of the present invention
Processing procedure, machine, manufacture, material composition, device, method and the step developed, as long as can be here in the embodiment
Implement more or less the same function or the more or less the same result of acquisition all can be used according to the invention.Therefore, protection scope of the present invention bag
Include above-mentioned processing procedure, machine, manufacture, material composition, device, method and step.In addition, each claim composition is other
Embodiment, and protection scope of the present invention also includes the combination of each claim and embodiment.
Claims (9)
1. a kind of copolymer, it is the reaction product of the first monomer and second comonomer,
Wherein first monomer is
Wherein, m is to select the positive integer from 2-10；
Wherein, the second comonomer has structure shown in formula (III)；
Wherein, l is to select the positive integer from 1-5.
2. copolymer as claimed in claim 1, the wherein second comonomer are
3. copolymer as claimed in claim 1, the wherein copolymer have the repeat unit of the structure as shown in formula (VI), wherein m is
Select the positive integer from 2-10；And l is to select the positive integer from 1-5.
4. copolymer as claimed in claim 1, the wherein copolymer have a melting temperature between 220 DEG C to 270 DEG C.
5. a kind of preparation method of copolymer, comprising：
It will be melted with the compound of structure shown in formula (VIII) and the compound with structure shown in formula (IX) or solution
Processing procedure, and acidification reaction is carried out, the first monomer for having shown in formula (I) structure is obtained,
Wherein, M is Na or K；M is to select the positive integer from 2-10；I is to select the positive integer from 1-3；Y is-CO2H；And Z be H or-
OH；And
First monomer and second comonomer are reacted, obtain copolymer as claimed in claim 1, wherein the second comonomer has
Structure shown in formula (III)
Wherein, l is to select the positive integer from 1-5.
6. the temperature of the preparation method of copolymer as claimed in claim 5, the wherein solution process is between 85 DEG C to 95 DEG C
Between.
7. the preparation method of copolymer as claimed in claim 5, the temperature of the wherein melting processing procedure is between 190 DEG C to 210
Between DEG C.
8. the preparation method of copolymer as claimed in claim 5, the wherein acidification reaction include：
It will be mixed via the product obtained by the melting or solution process with water, obtain a mixture, and with an inorganic acid aqueous solution
The mixture is titrated, makes the pH value of the mixture up between 5 to 7.
9. the preparation method of copolymer as claimed in claim 5, wherein the compound with structure shown in formula (VIII) isAnd it is with the compound of structure shown in formula (IX)
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| CN108727585B (en) * | 2017-04-17 | 2021-04-13 | 台湾化学纤维股份有限公司 | Polyamide and preparation method thereof |
| CN108178831B (en) * | 2017-12-28 | 2020-06-02 | 湖南文理学院 | Preparation method of PA (66-co-6T) copolymer |
| CN108192094B (en) * | 2018-02-06 | 2020-06-02 | 湖南文理学院 | Preparation method of PA (6-co-6T) copolymer |
| CN109180933A (en) * | 2018-07-26 | 2019-01-11 | 东华大学 | High heat resistance alternating copolymerization amide resin and preparation method thereof |
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| US5393902A (en) * | 1994-04-26 | 1995-02-28 | Lever Brothers Company, Division Of Conopco, Inc. | Process for the preparation of bis(amidocarboxylic acids) |
| JP2005517783A (en) * | 2002-02-21 | 2005-06-16 | シュティヒティング ダッチ ポリマー インスティテュート | Copolymer containing one or more amide segments |
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| US2851443A (en) * | 1955-04-26 | 1958-09-09 | Eastman Kodak Co | Quenchable copolyesters of a glycol, terephthalic acid and an alkylene diamine dicarboxylate and their preparation |
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| US4556697A (en) * | 1983-07-25 | 1985-12-03 | The Standard Oil Company | Alternating copolyamide prepared on a polymer matrix |
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