CN108383998B - A kind of high intensity humidity response polyhydroxyamide and preparation method thereof - Google Patents
A kind of high intensity humidity response polyhydroxyamide and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000004044 response Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 dimethyl ester compound Chemical class 0.000 claims abstract description 12
- 229940095054 ammoniac Drugs 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims description 11
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical class C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 10
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 4
- 229940014772 dimethyl sebacate Drugs 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- LRBPFPZTIZSOGG-UHFFFAOYSA-N dimethyl 2-methylpropanedioate Chemical compound COC(=O)C(C)C(=O)OC LRBPFPZTIZSOGG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VXJPCEOTZNHHOA-UHFFFAOYSA-N [K].OC Chemical compound [K].OC VXJPCEOTZNHHOA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- AYBLPISRXMEMBV-UHFFFAOYSA-N dimethyl 2,2-diethylpropanedioate Chemical compound COC(=O)C(CC)(CC)C(=O)OC AYBLPISRXMEMBV-UHFFFAOYSA-N 0.000 claims description 2
- PVRATXCXJDHJJN-UHFFFAOYSA-N dimethyl 2,3-dihydroxybutanedioate Chemical compound COC(=O)C(O)C(O)C(=O)OC PVRATXCXJDHJJN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical group 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- 125000000732 arylene group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000004952 Polyamide Substances 0.000 abstract description 9
- 229920002647 polyamide Polymers 0.000 abstract description 9
- 230000004043 responsiveness Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 125000003368 amide group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 125000000777 acyl halide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XIHOELTZBMSMCU-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(O)C(O)C(=O)O)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(O)C(O)C(=O)O)(=O)O XIHOELTZBMSMCU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MHKKFFHWMKEBDW-UHFFFAOYSA-N dimethyl 2,5-dioxocyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CC(=O)C(C(=O)OC)CC1=O MHKKFFHWMKEBDW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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 high-intensitive humidity response polyhydroxyamides and preparation method thereof.The preparation method of polyhydroxyamide is comprising steps of dissolve by heating and stir evenly dimethyl ester compound and alcohol ammoniac compounds to form reaction solution；It is added basic catalyst into reaction solution, 68~72 DEG C of heated sealed reactions 2~for 24 hours；Then reaction system is heated to 95~105 DEG C, water pump vacuumizes reaction 1~3 hour；Again by reaction system to 145~155 DEG C, oil pump vacuumizes reaction 0.5~1.5 hour；Reaction system is finally heated to 210~230 DEG C, oil pump vacuumizes reaction 0.5~1.5 hour, obtains polyhydroxyamide.The polyhydroxyamide that the present invention prepares has humidity responsiveness while the high-intensity performance for possessing polyamide, and toughness increases substantially after absorbing water, so that polyhydroxyamide has wider application prospect in terms of functional material.
Description
Technical field
The invention belongs to functionality polyamide Material Fields, are specifically related to a kind of high-intensitive humidity response polyhydroxyamide
And preparation method thereof.
Background technique
Polyamide is the macromolecule with recurring amide radical group on strand, is commonly called as nylon.Since it is with excellent heat
Performance and mechanical performance, the every field being widely used in life.With the development of science and technology functionality polyamide becomes most
One of important and most popular research field.Scientists have been prepared for various functionality polyamides at present, such as: fragrant adoption
Amide, Flameproof polyamide, ultrabranching polyamide, soluble polyamide, polyamide-imide, the high molecular materials such as polyhydroxyamide.
Wherein polyhydroxyamide receives extensive research due to unique performance.
Currently, the preparation of polyhydroxyamide mainly passes through diacid or diacid halide compound and the condensation of the diamines containing hydroxyl
Polymerization obtains.But it since esterification also easily occurs for hydroxyl and carboxyl or acyl halide group, is caused to the preparation of polyhydroxyamide
Great difficulty.Phenolic hydroxyl group is not easy to be applied to prepare fragrant adoption hydroxyl with carboxyl or acyl halide group generation esterification
Amide.Polyhydroxyamide is prepared by the aromatic diamine polymerization containing hydroxyl on diacid or diacid halide compound and phenyl ring
Method breaches the influence of carboxyl and carboxylic acid halides to hydroxyl to a certain extent.However, up to the present, the preparation of polyhydroxyamide
It is also only limitted to aromatic series, and type is seldom, significantly limits the extensive use of polyhydroxyamide.Secondly because aromatic group
In the presence of easily cyclisation forms oxazole in case of heating for phenolic hydroxyl group and amide group, largely limits polyhydroxyamide
Preparation.
Functional material becomes the research hotspot of Material Field, and wherein humidity responsive materials are received due to unique performance
Favor extensively.Humidity responsive materials lead to light after absorbing moisture due to the presence of hydrophilic radical a large amount of in macromolecular structure
Performance, thermodynamic property, electric conductivity, mechanical performance change.Due to the particularity of humidity responsive materials, answered extensively
Used in capacitance resistance field and sensory field.Current humidity responsive materials number of species are various, but most in absorption moisture
Mechanical performance generally reduces afterwards.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of high-intensitive humidity response polyhydroxyamide and its preparation sides
Method.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
A kind of high intensity humidity response polyhydroxyamide, the structural formula of the polyhydroxyamide are as follows:
Wherein, R is alkylidene, cycloalkylidene, alkenylene, sub- fragrance
Base, secondary hydroxyl, in ketone carbonyl a kind of group or a variety of groups combination；R1For methylene；N is integer, 10≤n≤1000.
Further, the structural formula of the polyhydroxyamide are as follows:
Further, the polyhydroxyamide breaking strength is 50~200MPa, and elongation at break is 1~80%；It is described poly-
After hydroxy amide water suction saturation, breaking strength is 20~60MPa, and elongation at break is 80~400%.
A kind of preparation method of the high-intensitive humidity response polyhydroxyamide, comprising the following steps:
Step 1, by 35~156 parts by weight dimethyl ester compounds and the alcohol ammoniac compounds of 28~87 parts by weight heating it is molten
It solves and stirs evenly to form reaction solution；
Be added 0.1~0.3 parts by weight basic catalyst in step 2, Xiang Suoshu reaction solution, heated sealed to 68~72 DEG C it is anti-
Answer 2~for 24 hours；
Reaction solution described in step 2 is heated to 95~105 DEG C by step 3, and water pump vacuumizes reaction 1~3 hour；
Reaction solution described in step 3 is heated to 145~155 DEG C by step 4, and oil pump vacuumizes reaction 0.5~1.5 hour；
Reaction solution described in step 4 is heated to 210~230 DEG C by step 5, and oil pump vacuumizes reaction 0.5~1.5 hour,
Obtain polyhydroxyamide.
Further, the dimethyl ester compound is the compound that two ends of chain are methyl esters group, the dimethyl ester
The structural formula of class compound isThe alcohol ammoniac compounds are that two ends of chain are amino and contain hydroxyl
The structural formula of the compound of base, the alcohol ammoniac compounds is
Further, the catalyst be any one of sodium methoxide solution, methanol potassium solution, alcohol sodium solution, it is described to urge
Agent concentration is 4.5~5.5mol/L.
Further, the dimethyl ester compound be dimethyl sebacate, it is dimethyl adipate, dimethyl malenate, right
Rutgers, repefral, cyclopropyl -1,1- dicarboxylic acid dimethyl ester, 1,4- cyclohexyl dicarboxylic acid dimethyl ester,
1,4- cyclohexanedione -2,5- dicarboxylic acid dimethyl ester, methylmalonic acid dimethyl ester, diethyl malonic acid dimethyl ester, tartaric acid diformazan
Any one of ester, apple dimethyl phthalate, furandicarboxylic acid dimethyl ester；The alcohol ammoniac compounds are 1,3- diamino -2- third
Alcohol.
The beneficial effects of the present invention are:
(1) present invention prepares polyhydroxyamide by melt condensation polymerization, and amido bond and hydroxyl, which exist simultaneously, makes poly- hydroxyl
Amide has humidity responsiveness while the high-intensity performance for possessing polyamide, and toughness increases substantially after absorbing water, greatly
Application and application surface are improved greatly, so that before polyhydroxyamide has widely application in terms of the functional material
Scape.
(2) significant changes can occur polyhydroxyamide material of the present invention for mechanical performance after moisture absorption in air, more into
One step shows the increase of tensile toughness.Polyhydroxyamide moisture absorption post-tensioning intensity of the present invention is slow as humidity exposure time increases
It is slow to reduce, and elongation at break then sharply increases relatively, toughness dramatically increases.
(3) polyhydroxyamide material mechanical parameters of the present invention are as follows: the polyhydroxyamide breaking strength is
50~200MPa, elongation at break are 1~80%；After the polyhydroxyamide water suction saturation, breaking strength is 20~60MPa,
Elongation at break is 80~400%.
(4) polyhydroxyamide of the present invention is not needing addition solvent by dimethyl ester compound and alcohol ammoniac compounds
In the case where synthesize and obtain, synthetic method is simple, no pollution to the environment, and product does not need clarification, and recycling is easy.
The chemical equation of dimethyl ester compound and alcohol ammoniac compounds of the present invention is as follows:
The effect that water pump of the present invention vacuumizes is the impurity removed in reaction system；The effect that oil pump vacuumizes is to prevent instead
System is answered to be oxidized；High-temperature heating gradually increases molecular weight of product, and performance is more preferable.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of batten.
Fig. 2 shows the infrared spectrum of polyhydroxyamide 1.
Fig. 3 shows the when m- hydroscopicity curve of polyhydroxyamide 1.
Influence of 1 moisture absorption of Fig. 4 polyhydroxyamide to thermodynamic property.
Influence of 1 moisture absorption of Fig. 5 polyhydroxyamide to mechanical performance.
Fig. 6 shows the infrared spectrum of polyhydroxyamide 2.
Fig. 7 shows the load-deformation curve of polyhydroxyamide 2.
Specific embodiment
More specific detail is made to technical solution of the present invention below with reference to embodiment:
The preparation of 1 polyhydroxyamide 1 of embodiment
It prepares polyhydroxyamide 1 as follows: taking dimethyl sebacate 9.5g, 1,3-diamino-2-propanol 3.7g is mixed at 70 DEG C
It closes uniformly, 250 μ L sodium methoxide solutions (concentration 5mol/L) is added, seal 70 DEG C of heating 12h.Water pump is vacuumized and is heated to
100 DEG C of reaction 2h to reaction system no liquid exist (since reaction raw materials are liquid, byproduct of reaction methanol is also liquid,
But target product is at this moment solid under the conditions of temperature), water pump is changed to oil pump and vacuumizes and be heated to 150 DEG C of reaction 1h,
Last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 1h.After reaction, product taking-up is sealed.
As shown in Figure 2: raw material dimethyl sebacate of the present invention according to embodiment 1 after reacting, and ester group peak disappears substantially, newly
The peak of amide group is generated, representative is reacted successfully, and ester is substantially transitioned to amide group.Simultaneously there are still hydroxyl, indicate that hydroxyl exists
It is not reacted in reaction process namely polyhydroxyamide is successfully prepared in the present invention.
The preparation of 2 polyhydroxyamide 2 of embodiment
It prepares polyhydroxyamide 2 as follows: taking dimethyl adipate 3.5g, 1,3-diamino-2-propanol 1.9g is mixed at 70 DEG C
It closes uniformly, 130 μ L sodium methoxide solutions (concentration 5mol/L) is added, seal 70 DEG C of heating 10h.Water pump is vacuumized and is heated to
100 DEG C of reaction 1.5h exist to reaction system no liquid, are changed to oil pump and vacuumize and be heated to 150 DEG C water pump and react
0.9h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 0.8h.After reaction, product taking-up is sealed.
As shown in Figure 6: raw material dimethyl adipate of the present invention according to embodiment 2 after reacting, and ester group peak disappears substantially, newly
The peak of amide group is generated, representative is reacted successfully, and ester is substantially transitioned to amide group.Simultaneously there are still hydroxyl, indicate that hydroxyl exists
It is not reacted in reaction process namely polyhydroxyamide is successfully prepared in the present invention.
The preparation of 3 polyhydroxyamide 3 of embodiment
It prepares polyhydroxyamide 3 as follows: taking dimethyl malenate 13.5g, 1,3-diamino-2-propanol 9.3g is mixed at 70 DEG C
It closes uniformly, 650 μ L sodium methoxide solutions (concentration 5mol/L) is added, seal 70 DEG C of heating 10h.Water pump is vacuumized and is heated to
100 DEG C of reaction 1h exist to reaction system no liquid, and water pump is changed to oil pump and vacuumizes and be heated to 150 DEG C of reaction 0.8h,
Last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 1h.After reaction, product taking-up is sealed.
The preparation of 4 polyhydroxyamide 4 of embodiment
It prepares polyhydroxyamide 4 as follows: taking dimethyl terephthalate (DMT) 5.9g, 1,3-diamino-2-propanol 2.8g is 70
DEG C be uniformly mixed, be added 190 μ L sodium methoxide solutions (concentration 5mol/L), seal 70 DEG C of heating 10h.Water pump is vacuumized and is heated
Exist to 100 DEG C of reaction 1.5h to reaction system no liquid, water pump is changed to oil pump and vacuumizes and be heated to 150 DEG C and is reacted
0.5h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 0.8h.After reaction, reactant taking-up is sealed.
The preparation of 5 polyhydroxyamide 5 of embodiment
It prepares polyhydroxyamide 5 as follows: taking Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid dimethyl ester 6.0g, 1,3-diamino-2-propanol 5.6g
It is uniformly mixed at 70 DEG C, 360 μ L sodium methoxide solutions (concentration 5mol/L) is added, seal 70 DEG C of heating 12h.Water pump vacuumizes simultaneously
It is heated to 100 DEG C of reaction 2h to exist to reaction system no liquid, water pump is changed to oil pump and vacuumizes and be heated to 150 DEG C and is reacted
0.7h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 1h.After reaction, product taking-up is sealed.
The preparation of 6 polyhydroxyamide 6 of embodiment
It prepares polyhydroxyamide 6 as follows: taking methylmalonic acid dimethyl ester 14.6g, 1,3-diamino-2-propanol 9.3g is 70
DEG C be uniformly mixed, be added 600 μ L sodium methoxide solutions (concentration 5mol/L), seal 70 DEG C of heating 11.5h.Water pump vacuumizes and adds
Heat exists to 100 DEG C of reaction 2h to reaction system no liquid, is changed to oil pump and vacuumizes and be heated to 150 DEG C water pump and react
1h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 1h.After reaction, product taking-up is sealed.
The preparation of 7 polyhydroxyamide 7 of embodiment
It prepares polyhydroxyamide 7 as follows: taking dimethyl tartrate 17.2g, 1,3-diamino-2-propanol 9.3g is mixed at 68 DEG C
It closes uniformly, 600 μ L sodium methoxide solutions (concentration 5mol/L) is added, seal 68 DEG C of heating 2h.Water pump vacuumizes and is heated to 95
DEG C reaction 1h exists to reaction system no liquid, and water pump is changed to oil pump and vacuumizes and is heated to 145 DEG C of reaction 0.5h, finally
Oil pump, which vacuumizes, is heated to 210 DEG C of reaction 0.5h.After reaction, product taking-up is sealed.
The preparation of 8 polyhydroxyamide 8 of embodiment
It prepares polyhydroxyamide 8 as follows: taking Isosorbide-5-Nitrae-cyclohexanedione -2,5- dicarboxylic acid dimethyl ester 1.8g, 1,3- diamino -2-
Propyl alcohol 7.4g is uniformly mixed at 72 DEG C, and 100 μ L sodium methoxide solutions (concentration 5.5mol/L) are added, and seals 72 DEG C of heating for 24 hours.Water receiving
Pumping vacuum is simultaneously heated to 105 DEG C of reaction 3h and exists to reaction system no liquid, and water pump is changed to oil pump and vacuumizes and heats
To 155 DEG C of reaction 5h, last oil pump, which vacuumizes, is heated to 230 DEG C of reaction 5h.After reaction, product taking-up is sealed.
The preparation of 9 polyhydroxyamide 9 of embodiment
It prepares polyhydroxyamide 9 as follows: taking furandicarboxylic acid dimethyl ester 11.0g, 1,3-diamino-2-propanol 5.4g is 70
DEG C be uniformly mixed, be added 300 μ L sodium methoxide solutions (concentration 4.5mol/L), seal 70 DEG C of heating 12h.Water pump vacuumizes and adds
Heat exists to 100 DEG C of reaction 2h to reaction system no liquid, is changed to oil pump and vacuumizes and be heated to 150 DEG C water pump and react
3h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 3h.After reaction, product taking-up is sealed.
The preparation of 10 polyhydroxyamide 10 of embodiment
It prepares polyhydroxyamide 10 as follows: taking 1,3- dimethyl acetone-1,3-dicarboxylate 17.4g, 1,3-diamino-2-propanol
9.1g is uniformly mixed at 70 DEG C, and 700 μ L sodium methoxide solutions (concentration 5.5mol/L) are added, and seals 70 DEG C of heating for 24 hours.Water receiving pumping
Vacuum is simultaneously heated to 100 DEG C of reaction 2h and exists to reaction system no liquid, and water pump is changed to oil pump and vacuumizes and is heated to 150
DEG C reaction 3h, last oil pump, which vacuumizes, is heated to 220 DEG C of reaction 1.5h.After reaction, product taking-up is sealed.
The preparation of 10 polyhydroxyamide 10 of embodiment
It prepares polyhydroxyamide 10 as follows: allyl malonic acid dimethyl ester 3.5g, 1,3-diamino-2-propanol 1.8g being taken to exist
75 DEG C are uniformly mixed, and 150 μ L sodium methoxide solutions (concentration 5.5mol/L) are added, seal 75 DEG C of heating 22h.Water pump vacuumizes simultaneously
Be heated to 100 DEG C of reaction 1.5h and exist to reaction system no liquid, by water pump be changed to oil pump vacuumize and be heated to 155 DEG C it is anti-
2h is answered, last oil pump, which vacuumizes, is heated to 225 DEG C of reaction 1h.After reaction, product taking-up is sealed.
The following are the tests that extension test is carried out after the polyhydroxyamide water absorption test and water suction:
The batten (structure of the batten is as shown in Figure 1) with a thickness of 0.2mm is taken to place 70 DEG C of bakings in a vacuum drying oven
It weighs after dry, is denoted as G0.Batten is placed in climatic chamber after weighing, maintaining the temperature inside the box is 20 DEG C, humidity 65%, often
Batten weighing is taken out after a period of time, is denoted as Gi, i=(1,2,3,4 ...), batten is still put back in constant-humidity constant-temperature case after weighing.
Water absorption rate (the W of batten is calculated as followsi):
Wi=(Gi-G0)/G0 × 100%.
As shown in figure 3, the polyhydroxyamide of the preparation of present example 1 moisture absorption process in 65% environment, when with moisture absorption
Between increase water absorption rate increase, finally tend to balance.
As shown in figure 4, polyhydroxyamide prepared by present example 1 is in 65% environment after moisture absorption, with humidity exposure time
The glass transition temperature for increasing polyhydroxyamide reduces, and thermodynamic property changes, and indicates that material is opposite and softens, mechanical performance will
It changes.
Batten tensile property is tested by GB/T 1040.3-2006 after moisture absorption, rate of extension 1mm/min, in constant temperature and humidity
Under the conditions of test.
As shown in Figure 5: polyhydroxyamide prepared by present example 1 is in 65% environment after moisture absorption, with humidity exposure time
The mechanical property for increasing polyhydroxyamide changes, and the relatively small amplitude reduction of stress, strain increases considerably, and toughness promotes 60
Times or so.
As shown in Figure 7: polyhydroxyamide prepared by present example 2 equally has high intensity.
It is found through experiment that: the polyhydroxyamide moisture absorption post-tensioning intensity that the present invention prepares is slow as humidity exposure time increases
It is slow to reduce, and elongation at break then sharply increases relatively, polyhydroxyamide toughness dramatically increases.
Claims (6)
1. a kind of high intensity humidity responds polyhydroxyamide, it is characterised in that: the structural formula of the polyhydroxyamide is as follows:
Wherein, R be alkylidene, it is cycloalkylidene, alkenylene, arylene, secondary
The combination of a kind of group or a variety of groups in hydroxyl, ketone carbonyl；R1For methylene；N is integer, 10≤n≤1000.
2. high intensity humidity as described in claim 1 responds polyhydroxyamide, it is characterised in that: the knot of the polyhydroxyamide
Structure formula are as follows:
3. high intensity humidity as described in claim 1 responds polyhydroxyamide, it is characterised in that: the polyhydroxyamide fracture
Intensity is 50~200MPa, and elongation at break is 1~80%；After polyhydroxyamide water suction saturation, breaking strength is 20~
60MPa, elongation at break are 80~400%.
4. a kind of preparation method of high-intensitive humidity response polyhydroxyamide as claimed in any one of claims 1 to 3, feature
Be the following steps are included:
Step 1 dissolves by heating 35~156 parts by weight dimethyl ester compounds and the alcohol ammoniac compounds of 28~87 parts by weight simultaneously
It stirs evenly to form reaction solution；
0.1~0.3 parts by weight basic catalyst, heated sealed to 68~72 DEG C of reactions 2 are added in step 2, Xiang Suoshu reaction solution
~for 24 hours；
Reaction solution described in step 2 is heated to 95~105 DEG C by step 3, and water pump vacuumizes reaction 1~3 hour；
Reaction solution described in step 3 is heated to 145~155 DEG C by step 4, and oil pump vacuumizes reaction 0.5~1.5 hour；
Reaction solution described in step 4 is heated to 210~230 DEG C by step 5, and oil pump vacuumizes reaction 0.5~1.5 hour, obtains
Polyhydroxyamide.
The dimethyl ester compound is the compound that two ends of chain are methyl esters group, the knot of the dimethyl ester compound
Structure formula isThe alcohol ammoniac compounds are that two ends of chain are amino and the compound containing hydroxyl, institute
The structural formula for stating alcohol ammoniac compounds is
5. the preparation method of high intensity humidity response polyhydroxyamide as claimed in claim 4, it is characterised in that: the catalysis
Agent is any one of sodium methoxide solution, methanol potassium solution, alcohol sodium solution, and the catalyst concn is 4.5~5.5mol/L.
6. the preparation method of high intensity humidity response polyhydroxyamide as claimed in claim 4, it is characterised in that: the diformazan
Ester type compound is dimethyl sebacate, dimethyl adipate, dimethyl malenate, dimethyl terephthalate (DMT), O-phthalic
Dimethyl phthalate, cyclopropyl -1,1- dicarboxylic acid dimethyl ester, 1,4- cyclohexyl dicarboxylic acid dimethyl ester, 1,4- cyclohexanedione -2,5- dioctyl phthalate
Dimethyl ester, methylmalonic acid dimethyl ester, diethyl malonic acid dimethyl ester, dimethyl tartrate, any in apple dimethyl phthalate
Kind；The alcohol ammoniac compounds are 1,3-diamino-2-propanol.
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