CN103059292B - Water-soluble copolyamides and preparation method thereof - Google Patents
Water-soluble copolyamides and preparation method thereof Download PDFInfo
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- CN103059292B CN103059292B CN201310045818.0A CN201310045818A CN103059292B CN 103059292 B CN103059292 B CN 103059292B CN 201310045818 A CN201310045818 A CN 201310045818A CN 103059292 B CN103059292 B CN 103059292B
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Abstract
The invention discloses a kind of water-soluble copolyamides and preparation method thereof, it is characterized in that described water-soluble copolyamides is with di-carboxylic acid, 2,5-furandicarboxylic acid and polyether diamine are that reaction raw materials feeds intake, and obtain water-soluble copolyamides by melt polycondensation reaction; Wherein said reaction raw materials is that 1:1 participates in reaction by carboxyl and amido by equivalence ratio, and wherein water-soluble copolyamides contains furandicarboxylic acid structural unit, and its content is the 1mol% ~ 50mol% based on acid equivalent total amount.The water-soluble copolyamides prepared, by being introduced in copolyamide polymer by biomass-based FDCA, improves the biomass rate of raw material, has better dispersing property in aqueous.
Description
Technical field
The invention belongs to synthesis of polymer material field, particularly relate to a kind of water-soluble copolyamides based on biomass material.
Background technology
The polyamide resin of homopolymerization, owing to presenting the feature of infusibility indissoluble containing a large amount of hydrogen bonds and higher degree of crystallinity.Usually the regularity can introducing some specific functional groups and saboteur's chain by the method for copolymerization improves this character.The copolyamide announced as US Patent No. 4895660 and the clear 56-93704 of Japanese Patent is obtain water-soluble by the method for sulfonation; US Patent No. 4323639 and US5688632 then adopt the method synthesizing water-solubility copolyamide introducing polyether segment.Chinese patent CN200910032093.5 then discloses a kind of anionic copolymer acid amides, by molecular chain, introduce a large amount of carboxyl and with alkaline matter in and salify and obtain water-soluble.
But the main raw material of water-soluble copolyamides prepared by prior art is all from petrochemical material, and along with the exhaustion day by day of petroleum resources and improving constantly of people's environmental consciousness, the raw material found based on renewable biomass resource carrys out the important development trend that all or part of replacement petrochemical material has become polymeric material field.In the conventional monomer of synthesizing polyamides, according to current internationally recognized definition, 11 lactan, sebacic acid and decamethylene diamine are biomass based raw material, the biomass-basedization research of hexamethylene diamine adipate and hexanolactam etc. starts in addition, and other is petrochemical industry based raw material.
Summary of the invention
The invention provides and carry out synthesizing water-solubility copolyamide and preparation method thereof with biomass-based raw material, it has higher biomass starting material rate, simple synthetic method and excellent water-soluble.Concrete technical scheme is as follows:
A kind of water-soluble copolyamides, is characterized in that described water-soluble copolyamides feeds intake for reaction raw materials with di-carboxylic acid, FDCA and polyether diamine, obtains water-soluble copolyamides by melt polycondensation reaction; Wherein said reaction raw materials is that 1:1 participates in reaction by carboxyl and amido by equivalence ratio, and wherein water-soluble copolyamides contains furandicarboxylic acid structural unit, and its content is the 1mol% ~ 50mol% based on acid equivalent total amount.
Preferably, described di-carboxylic acid is selected from aliphatic dibasic acid or cycloaliphatic diacid, and wherein said aliphatic dibasic acid is selected from 1,6-hexanodioic acid, 1,9-nonane diacid, 1,10 sebacic acid, 1, one or more arbitrary combination in 11-undecane diacid or 1,12-dodecanedioic acid; Described cycloaliphatic diacid is selected from one or more the arbitrary combination in 1,2-cyclohexane cyclohexanedimethanodibasic, 1,3-cyclohexane cyclohexanedimethanodibasic or 1,4 cyclohexanedicarboxylic acid.
Preferably, described reaction raw materials also has lactan, and described lactan is selected oneself the one in lactan, 11 lactan or laurolactam, and its content is the 0mol% ~ 20mol% based on raw material integral molar quantity.
Preferably, the structural formula of described polyether diamine is NH
2-(CH
2cH
2o) x-CH
2-NH
2, the wherein natural number of the value of x between 2 ~ 10.
Preferably, other diamines are also had in described reaction raw materials, other diamines described are selected from aliphatic diamine or cycloalphatic diamine, wherein aliphatic diamine is selected from 1,6-hexanediamine, 1,9-nonamethylene diamine, 1,10 decamethylene diamines, 1, one or more arbitrary combination in 11-undecane diamines or 1,12-dodecamethylene diamine; Described cycloalphatic diamine is selected from one or more the arbitrary combination in 1,2-diamines butylcyclohexane, 1,3-diamines hexanaphthene or Isosorbide-5-Nitrae-diamines hexanaphthene.
Another object of the present invention is to the preparation method that a kind of described water-soluble copolyamides is provided, it is characterized in that described method comprises di-carboxylic acid, diamine, 2,5-furandicarboxylic acid and polyether diamine mixing, add water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, keep being warmed up between 230 ~ 250 DEG C after 1 ~ 2 hour, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides.
The water-soluble copolyamides that the present invention obtains can be mixed with stable aqueous dispersions, in raw material except polyether diamine all or major part derive from biomass, there is higher biomass rate, can be applicable to the field such as coating and tackiness agent
Preferably, described aliphatic dibasic acid accounts for 50 ~ 99mol% of sour total amount; Described cycloaliphatic diacid accounts for 0 ~ 20mol% of sour total amount.
Preferably, described copolyamide contains furandicarboxylic acid structural unit, and its content is 1 ~ 50mol% based on acid equivalent total amount.
In preferred raw material, described diamine is aliphatic diamine, and described aliphatic diamine is selected from 1,6-hexanediamine, 1,9-nonamethylene diamine, 1, one or more in 10 decamethylene diamines, 1,11-undecane diamines or 1,12-dodecamethylene diamine.
In preparation method of the present invention, the biomass rate of reaction raw materials reaches more than 20%, even can reach more than 40% according to selected diprotic acid kind.The water-soluble copolyamides obtained can form stable and clear aqueous dispersions.
The synthesis of concrete described water-soluble copolyamides is specifically carried out in accordance with the following steps:
By di-carboxylic acid, diamine, polyether diamine and 2,5-furandicarboxylic acid mixes, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, keep being warmed up between 230 ~ 250 DEG C after 1 ~ 2 hour, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides.
The present invention is shown by research, plant cellulose can obtain 2 by high productivity by a series of conversion, 5-furandicarboxylic acid, this is a kind of compound comparatively similar to phthalic acid on structures and characteristics, the FDCA deriving from biomass is used for the synthesis of copolyamide by the present invention, not only can improve the biomass rate of raw material, and by introducing furan nucleus, high molecular irregularity is improved further, thus obtain better water dispersible.
The water-soluble copolyamides that the present invention prepares, at 30 DEG C, sulfuric acid is solvent, and record its intrinsic viscosity between 0.3 ~ 0.6, this polyamide resin can be mixed with the aqueous solution of 1%, and clear appearance is transparent.
Water-soluble copolyamides of the present invention, wherein " water-soluble " is equal to other descriptions.As " water dispersible ", " faling apart property of water drive " and " water-based " etc.Usually, when acting on this copolyamide using water as Single Medium, its both comprised dissolving with dispersion.
Relative to scheme of the prior art, advantage of the present invention is:
Preparation technology of the present invention, by being introduced in copolyamide polymer by biomass-based FDCA, improves the biomass rate of raw material.On the other hand, the introducing due to furan nucleus makes the regularity of polymer chain destroy, and the tendency that hydrogen bond is formed reduces, thus has better dispersing property in aqueous.This water-soluble copolyamides product (resin), owing to introducing furan nucleus in the molecular chain of aliphatic copolyamides, has both reduced the regularity of macromolecular chain, in turn introduces more wetting ability ehter bond, thus improves that it is water-soluble.On the other hand, because the raw material used comes from biomass greatly, decrease the dependence to petroleum chemicals, thus there is higher environmental protection characteristic.This polyamide resin is a kind of novel environment-friendly water-soluble copolyamides, can be applicable to the fields such as ink, coating and tackiness agent.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention, all equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.In following examples, embodiment 1 ~ 3 is the specific embodiments in the scope of the invention; Embodiment 4 ~ 5 is comparative example of the present invention; Embodiment 6 is for confirming that water-soluble copolyamides of the present invention has higher biomass starting material rate and water-soluble preferably;
The preparation of embodiment 1 water-soluble copolyamides
Specifically be prepared in accordance with the following steps:
Reaction raw materials feeds intake by following mol ratio: hexanodioic acid 25%, furandicarboxylic acid 25%, polyether diamine (x=2) 50%, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, be warmed up between 230 ~ 250 DEG C after keeping 1 ~ 2 hour again, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides.Product, at 30 DEG C, is solvent with sulfuric acid, and recording its intrinsic viscosity is 0.46;
The preparation of embodiment 2 water-soluble copolyamides
Specifically be prepared in accordance with the following steps:
Reaction raw materials feeds intake by following mol ratio: hexanodioic acid 25%, sebacic acid 12.5%, furandicarboxylic acid 12.5%, polyether diamine (x=2) 37.5%, decamethylene diamine 12.5%, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, be warmed up between 230 ~ 250 DEG C after keeping 1 ~ 2 hour again, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides product.Product, at 30 DEG C, is solvent with sulfuric acid, and recording its intrinsic viscosity is 0.42;
The preparation of embodiment 3 water-soluble copolyamides
Specifically be prepared in accordance with the following steps:
Reaction raw materials feeds intake by following mol ratio: hexanodioic acid 30%, sebacic acid 5%, furandicarboxylic acid 10%, polyether diamine (x=2) 40%, decamethylene diamine 5%, 11 lactan 10%, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, be warmed up between 230 ~ 250 DEG C after keeping 1 ~ 2 hour again, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides product.Product, at 30 DEG C, is solvent with sulfuric acid, and recording its intrinsic viscosity is 0.42;
The preparation of embodiment 4 standard copolymerization acid amides
Specifically be prepared in accordance with the following steps:
Reaction raw materials feeds intake by following mol ratio: hexanodioic acid 50%, polyether diamine (x=2) 50%, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, be warmed up between 230 ~ 250 DEG C after keeping 1 ~ 2 hour again, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides product.Product, at 30 DEG C, is solvent with sulfuric acid, and recording its intrinsic viscosity is 0.45;
The preparation of embodiment 5 standard copolymerization acid amides
Specifically be prepared in accordance with the following steps:
Reaction raw materials feeds intake by following mol ratio: hexanodioic acid 25%, sebacic acid 25%, polyether diamine (x=2) 37.5%, decamethylene diamine 12.5%, add a small amount of water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, be warmed up between 230 ~ 250 DEG C after keeping 1 ~ 2 hour again, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides product.Product, at 30 DEG C, is solvent with sulfuric acid, and recording its intrinsic viscosity is 0.41;
Embodiment 6
Calculate the biomass starting material rate of above-mentioned copolyamide, and products obtained therefrom is dissolved in the deionized water of 1% respectively, observe the state of water at normal temperature solution.
The method of calculation of biomass starting material rate are: by the total mass of the total mass of the biomass-based raw material mix unit in polymkeric substance divided by all structural units.According to internationally recognized definition, in the raw material that above-described embodiment adopts, biomass-based raw material comprises furandicarboxylic acid, 11 lactan, sebacic acid and decamethylene diamine etc.
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (2)
1. a water-soluble copolyamides, is characterized in that described water-soluble copolyamides feeds intake for reaction raw materials with di-carboxylic acid, FDCA and polyether diamine, obtains water-soluble copolyamides by melt polycondensation reaction; Wherein said reaction raw materials is that 1:1 participates in reaction by carboxyl and amido by equivalence ratio, and wherein water-soluble copolyamides contains furandicarboxylic acid structural unit, and its content is the 1mol% ~ 50mol% based on acid equivalent total amount;
Described di-carboxylic acid is selected from aliphatic dibasic acid or cycloaliphatic diacid, and wherein said aliphatic dibasic acid is selected from 1,6-hexanodioic acid, 1,9-nonane diacid, 1, one or more arbitrary combination in 10 sebacic acid, 1,11-undecane diacid or 1,12-dodecanedioic acid; Described cycloaliphatic diacid is selected from one or more the arbitrary combination in 1,2-cyclohexane cyclohexanedimethanodibasic, 1,3-cyclohexane cyclohexanedimethanodibasic or 1,4 cyclohexanedicarboxylic acid;
Described reaction raw materials also has lactan, and described lactan is selected oneself the one in lactan, 11 lactan or laurolactam, and its content is the 0mol% ~ 20mol% based on raw material integral molar quantity;
The structural formula of described polyether diamine is NH
2-(CH
2cH
2o) x-CH
2-NH
2, the wherein natural number of the value of x between 2 ~ 10;
Other diamines are also had in described reaction raw materials, other diamines described are selected from aliphatic diamine or cycloalphatic diamine, wherein aliphatic diamine is selected from 1,6-hexanediamine, 1,9-nonamethylene diamine, 1, one or more arbitrary combination in 10 decamethylene diamines, 1,11-undecane diamines or 1,12-dodecamethylene diamine; Described cycloalphatic diamine is selected from one or more the arbitrary combination in 1,2-diamines butylcyclohexane, 1,3-diamines hexanaphthene or Isosorbide-5-Nitrae-diamines hexanaphthene.
2. the preparation method of a water-soluble copolyamides according to claim 1, it is characterized in that described method comprises di-carboxylic acid, diamine, 2,5-furandicarboxylic acid and polyether diamine mixing, add water as initiator, be warmed up between 140 ~ 160 DEG C in an inert atmosphere, keep being warming up between 180 ~ 220 DEG C after 1 ~ 2 hour, keep being warmed up between 230 ~ 250 DEG C after 1 ~ 2 hour, keep after 0.5 ~ 1 hour, starting decompression, be filled with rare gas element after 0.5 ~ 1 hour, after melt cooling, namely obtain water-soluble copolyamides.
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| CN113817159B (en) * | 2021-09-24 | 2023-10-13 | 珠海万通特种工程塑料有限公司 | Furandioic polyamide resin, preparation method thereof and polyamide molding composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323639A (en) * | 1978-12-01 | 1982-04-06 | Toray Industries, Inc. | Photosensitive polyamide resin composition |
| US5688632A (en) * | 1993-07-20 | 1997-11-18 | Toray Industries, Inc. | Photosensitive polymer composition containing a soluble polymer of islands-in-a-sea structure, a photopolymerizable polymer, and a photopolymerization initiator |
| CN102311546A (en) * | 2010-07-06 | 2012-01-11 | 东丽纤维研究所（中国）有限公司 | Biomass-based polyamide resin |
| CN102850541A (en) * | 2011-07-01 | 2013-01-02 | 东丽纤维研究所（中国）有限公司 | Biomass based polyamide resin |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323639A (en) * | 1978-12-01 | 1982-04-06 | Toray Industries, Inc. | Photosensitive polyamide resin composition |
| US5688632A (en) * | 1993-07-20 | 1997-11-18 | Toray Industries, Inc. | Photosensitive polymer composition containing a soluble polymer of islands-in-a-sea structure, a photopolymerizable polymer, and a photopolymerization initiator |
| CN102311546A (en) * | 2010-07-06 | 2012-01-11 | 东丽纤维研究所（中国）有限公司 | Biomass-based polyamide resin |
| CN102850541A (en) * | 2011-07-01 | 2013-01-02 | 东丽纤维研究所（中国）有限公司 | Biomass based polyamide resin |
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