CN109293809B - Xylose-based polymer and preparation method and application thereof - Google Patents
Xylose-based polymer and preparation method and application thereof Download PDFInfo
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- CN109293809B CN109293809B CN201811129184.6A CN201811129184A CN109293809B CN 109293809 B CN109293809 B CN 109293809B CN 201811129184 A CN201811129184 A CN 201811129184A CN 109293809 B CN109293809 B CN 109293809B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
The invention belongs to the technical field of application of xylonic acid, and relates to a xylonic acid-based polymer, and a preparation method and application thereof. The preparation method of the xylose-based polymer comprises the following steps: firstly, mixing xylonic acid and (methyl) acrylate under the action of a catalyst to prepare a xylonic acid (methyl) acrylate prepolymer; and then heating the prepolymer to prepare the xylose-based polymer. The xylose-based polymer prepared by the invention has good solvent resistance, mechanical property and elastic property, and can be used as an elastomer material to be applied to the fields of biology, medicine, environment and the like; and the structure of the xylonic acid polymer is rich in hydroxyl groups, which is beneficial to further modification and transformation and functional application of the xylonic acid polymer, and a feasible method is provided for realizing high-value utilization of xylonic acid.
Description
Technical Field
The invention belongs to the technical field of application of xylonic acid, and particularly relates to a xylonic acid-based polymer and a preparation method and application thereof.
Background
In a lignocellulose biorefinery system, the full utilization of the hemicellulose taking xylose as a main component is a key factor limiting the industrial production of the hemicellulose and a technical bottleneck problem to be solved urgently. Xylonic acid, as a xylose oxidation product, is determined by the U.S. department of energy as one of the most promising 30 target products or chemical basic building blocks for refining biomass as a lignocellulose resource. In recent years, the technology for preparing the xylonic acid by catalyzing the xylose by the whole cell is rapidly developed, the concentration and the conversion rate of the xylonic acid product respectively reach more than 600g/L and 98 percent, and great development opportunity is provided for the efficient conversion and utilization of the xylose.
At present, the xylonic acid product is mainly applied to the fields of cement water reducing agents, concrete reinforcing agents, oil well slurry suspending agents, industrial scale removers and the like in a small molecular form, and the application form and the application range are limited. Xylonic acid is a carboxylic acid bio-based platform compound rich in polyhydroxy, and has functional groups and molecular structures for synthesizing bio-based polyester materials, so that the creation of a synthetic technology of the xylonic acid-based bio-polyester materials has important theoretical and practical significance for expanding high-valued conversion and application technologies of xylose and hemicellulose.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a xylose-based polymer, which is simple to operate, easy to implement and strong in operability, and the prepared xylose-based polymer has good mechanical property, elastic property and solvent resistance, so that the preparation of the xylose-based polymer material is realized, and a foundation is laid for the functional application of xylonic acid.
It is another object of the present invention to provide a xylitol based polymer having good mechanical properties, elastic properties and solvent resistance.
It is a further object of the present invention to provide a use of said xylitol-based polymeric material in the field of elastomeric materials to overcome the above problems or at least partially solve the above technical problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the present invention, there is provided a method of preparing a xylose-based polymer, comprising the steps of:
(a) mixing xylonic acid, polyfunctional acrylate or polyfunctional methacrylate with a solvent to prepare a prepolymer under the action of a catalyst;
(b) and heating the prepolymer to obtain the xylose-based polymer.
As a further preferable technical solution, the multifunctional acrylate comprises an epoxy group and a hydroxyl functional group in its structure;
and/or the structure of the multifunctional methacrylate contains epoxy groups and hydroxyl functional groups;
preferably, the multifunctional acrylate comprises any one of glycidyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxyhexyl acrylate or a combination of at least two of the same;
preferably, the multifunctional methacrylate comprises any one of glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate and hydroxyhexyl methacrylate or a combination of at least two thereof.
As a further preferable mode, the catalyst includes any one or a combination of at least two of triethylamine, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1, 8-diazabicycloundecen-7-ene, pyridine, sodium hydroxide, potassium hydroxide and sodium carbonate.
As a further preferable technical scheme, the solvent comprises at least one of alcohols, amides, sulfones and sulfoxides;
preferably, the solvent includes at least one of methanol, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, N-ethylformamide, N-diethylformamide, and dimethylsulfoxide;
preferably, the solvent comprises at least one of methanol, N-dimethylformamide and dimethylsulfoxide.
As a further preferable technical scheme, a polymerization inhibitor is added in the step (a);
preferably, the polymerization inhibitor comprises at least one of hydroquinone, p-benzoquinone, phenothiazine, beta-phenyl naphthylamine, p-tert-butyl catechol, 1-diphenyl-2-picrylhydrazine and 2, 2, 6, 6-tetramethyl piperidine nitroxide radical;
preferably, the mass ratio of the polymerization inhibitor to the xylonic acid is 0.001-0.1: 1.
as a further preferable embodiment, a polymerization initiator is added in the step (b);
preferably, the initiator comprises at least one of azo, organic peroxy, inorganic peroxy and redox initiating systems;
preferably, the initiator comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide/N, N-dimethylaniline;
preferably, the mass ratio of the initiator to the xylonic acid is 0.001-0.1: 1.
as a further preferable technical solution, in the step (a), the molar ratio of the xylonic acid to the multifunctional acrylate or the multifunctional methacrylate is 1: 0.2 to 5;
and/or the molar ratio of the xylonic acid to the catalyst is 1: 0.01 to 5;
and/or the reaction temperature is 40-100 ℃;
and/or the reaction time is 1-24 h.
As a further preferable embodiment, in the step (b), the heating is normal pressure heating and/or reduced pressure heating;
preferably, the heating temperature is 40-100 ℃;
preferably, the heating time is 1-24 h.
According to another aspect of the invention, the invention provides a xylose-based polymer, which is prepared by the preparation method of the xylose-based polymer;
preferably, the mass ratio of the xylonic acid in the xylonic acid-based polymer is 10-80%.
According to another aspect of the invention, the invention provides the use of a polymer based on xylitol as described above in the field of elastomeric materials.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the xylonic acid-based polymer provided by the invention has the advantages that xylonic acid is taken as a raw material to creatively react with multifunctional acrylate or multifunctional methacrylate to prepare xylonic acid (methyl) acrylate prepolymer under the action of a catalyst, and then the xylonic acid-based polymer is prepared in a one-step heating polymerization mode, so that the conversion of xylonic acid from small molecules to polymers is realized, and the way is widened for high-value application of the xylonic acid.
2. The preparation method disclosed by the invention is simple to operate, scientific and reasonable, easy to implement, strong in operability and easy to realize large-scale production.
3. The xylose-based polymer prepared by the method has good mechanical property, elastic property and solvent resistance, and excellent comprehensive performance, so that the xylose-based polymer has wider application prospect and can be widely applied to the fields of biology, medicine and environment as an elastomer material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an optical photograph of a xylitol-based polymer provided in accordance with an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a xylitol-based polymer provided in accordance with an embodiment of the present invention;
FIG. 3 is a stress-strain curve of a xylitol-based polymer provided in accordance with an embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer.
In a first aspect, there is provided in at least one embodiment a method of preparing a xylitol-based polymer, comprising the steps of:
(a) mixing xylonic acid, polyfunctional acrylate or polyfunctional methacrylate with a solvent to prepare a prepolymer under the action of a catalyst;
(b) and heating the prepolymer to obtain the xylose-based polymer.
In view of the fact that the existing xylonic acid products are applied to various fields in a small molecule form, the application range and the application value are limited. Further, it has been found through a search that studies on xylonic acid have been concentrated on a method for producing xylonic acid, a method for removing impurities in xylonic acid products, and the like, and no studies or reports on xylonic acid-based polymers have been found before the filing date of the present application. The invention breaks the conventional thinking of the technicians in the field, develops a new method, creatively provides the steps of mixing the xylonic acid with polyfunctional group (methyl) acrylate, preparing the xylonic acid (methyl) acrylate prepolymer under the action of a catalyst, and then preparing the xylonic acid-based polymer by heating polymerization. The method effectively overcomes the defect that xylonic acid is applied in a small molecule form in the application process in the prior art, realizes the preparation of the xylonic acid-based polymer material, widens the way for the functionalization, high-valued conversion and application of xylonic acid, and has important significance for the further development of xylonic acid-based products.
The preparation method of the xylose-based polymer is simple, mild in reaction condition, easy to implement, strong in operability and easy to realize large-scale production; the obtained xylose-based polymer has the advantages of good mechanical property, elastic property, solvent resistance and the like.
In the present invention, (meth) acrylate refers to acrylate or methacrylate.
In a preferred embodiment, in step (a), the multifunctional acrylate comprises epoxy and hydroxyl functional groups in its structure;
and/or the structure of the multifunctional methacrylate contains epoxy groups and hydroxyl functional groups.
It is understood that the multifunctional group in the present invention is bifunctional and more than bifunctional, and may be, for example, bifunctional (meth) acrylate, trifunctional (meth) acrylate, or the like. Preferably, the multifunctional group is a bifunctional group, i.e., an epoxy group and a hydroxyl group. However, the (meth) acrylate may further include other functional groups, and the present invention is not limited thereto.
According to the invention, under the action of a catalyst, xylonic acid and epoxy groups and hydroxyl functional groups in the multifunctional group (methyl) acrylate carry out esterification reaction, and unsaturated double bonds in the multifunctional group (methyl) acrylate are further crosslinked to prepare xylonic acid (methyl) acrylate prepolymer; further, a free radical is generated by heating in the presence of a free radical initiator, and then the polymerization is carried out to prepare the xylose-based polymer.
Preferably, the multifunctional acrylate includes, but is not limited to, any one of glycidyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxyhexyl acrylate or a combination of at least two thereof. It is to be understood that the present invention is not limited to a specific type of the multifunctional acrylate, and any one or a combination of at least two of the above may be used, and other types of acrylates having similar properties to those described above, such as hydroxyheptyl acrylate, hydroxyoctyl acrylate, etc., which are well known to those skilled in the art, may also be used.
Preferably, the multifunctional methacrylate includes, but is not limited to, any one of glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate and hydroxyhexyl methacrylate or a combination of at least two thereof. It is to be understood that the present invention is not limited to a specific type of the multifunctional methacrylate, and any one or a combination of at least two of the above may be used, and other types of methacrylates having similar properties to those described above, such as hydroxyheptyl methacrylate, hydroxyoctyl methacrylate, etc., which are well known to those skilled in the art, may also be used.
In a preferred embodiment, in step (a), the catalyst includes, but is not limited to, any one or a combination of at least two of triethylamine, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1, 8-diazabicycloundecen-7-ene, pyridine, sodium hydroxide, potassium hydroxide and sodium carbonate.
According to the invention, under the action of the catalyst, the xylonic acid and the (methyl) acrylate can smoothly react to prepare the xylonic acid (methyl) acrylate prepolymer. Moreover, the catalyst has good stability, wide sources and high catalytic activity, can improve the production efficiency, and ensures that the reaction condition is mild, the reaction process is stable and easy to control.
The sources of the above catalysts are not particularly limited in the present invention, and various raw materials known to those skilled in the art may be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
In a preferred embodiment, in step (a), the solvent comprises at least one of alcohols, amides, sulfones, and sulfoxides;
preferably, the solvent includes, but is not limited to, at least one of methanol, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, N-ethylformamide, N-diethylformamide, and dimethylsulfoxide;
preferably, the solvent comprises at least one of methanol, N-dimethylformamide and dimethylsulfoxide.
It should be understood that the present invention is not limited to the specific type of solvent, and alcohol solvents, amide solvents, sulfoxide solvents, etc. known to those skilled in the art can be used, and methanol, N-dimethylformamide or dimethyl sulfoxide is preferably used, and these solvents are more suitable for the reaction between xylonic acid and (meth) acrylate, and have the advantages of wide sources, low cost, economy, easy availability, safety, environmental protection, and good application effect.
In the present invention, the source of the above solvents is not particularly limited, and various raw materials known to those skilled in the art may be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
In a preferred embodiment, a polymerization inhibitor is added in step (a);
preferably, the polymerization inhibitor includes, but is not limited to, at least one of hydroquinone, p-benzoquinone, phenothiazine, β -phenyl naphthylamine, p-tert-butyl catechol, 1-diphenyl-2-picrylhydrazine, and 2, 2, 6, 6-tetramethyl piperidine nitroxide radical;
preferably, the mass ratio of the polymerization inhibitor to the xylonic acid is 0.001-0.1: 1, preferably 0.009-0.08: 1, more preferably 0.01 to 0.06: 1; typically, but not by way of limitation, the ratio may be 0.001: 1. 0.002: 1. 0.005: 1. 0.006: 1. 0.008: 1. 0.009: 1. 0.01: 1. 0.02: 1. 0.05: 1. 0.06: 1. 0.08: 1 or 0.1: 1;
according to the present invention, the addition of the polymerization inhibitor in the step (a) can prevent the polymerization of the (meth) acrylate monomer and reduce the reaction efficiency. In addition, the addition amount of the polymerization inhibitor in the invention is small, which is beneficial to reducing the production cost.
In a preferred embodiment, a polymerization initiator is added in step (b);
preferably, the initiator includes, but is not limited to, at least one of azo, organic peroxy, inorganic peroxy, and redox initiation systems;
preferably, the initiator includes, but is not limited to, at least one of azobisisobutyronitrile, dibenzoyl peroxide, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide/N, N-dimethylaniline;
preferably, the mass ratio of the initiator to the xylonic acid is 0.001-0.1: 1, preferably 0.009-0.08: 1, more preferably 0.01 to 0.06: 1; typically, but not by way of limitation, the ratio may be 0.001: 1. 0.002: 1. 0.005: 1. 0.006: 1. 0.008: 1. 0.009: 1. 0.01: 1. 0.02: 1. 0.05: 1. 0.06: 1. 0.08: 1 or 0.1: 1.
according to the invention, the polymerization initiator is added in the step (b) to promote the polymerization reaction between the xylonic acid prepolymers, so that the reaction rate and the conversion rate are improved. In addition, the addition amount of the polymerization initiator in the present invention is small, which contributes to reduction of production cost.
In a preferred embodiment, in step (a), the molar ratio of xylonic acid to multifunctional acrylate or multifunctional methacrylate is 1: 0.2-5, preferably 1: 0.5 to 4, and more preferably 1: 1-3; typically, but not by way of limitation, the ratio may be 1: 0.2, 1: 0.5, 1: 0.8, 1: 1. 1: 1.2, 1: 1.5, 1: 1.8, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5.
and/or the molar ratio of the xylonic acid to the catalyst is 1: 0.01 to 5, preferably 1: 0.1 to 4, and more preferably 1: 0.5 to 3.5; typically, but not by way of limitation, the ratio may be 1: 0.01, 1: 0.02, 1: 0.05, 1: 0.1, 1: 0.2, 1: 0.5, 1: 0.8, 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5.
and/or the reaction temperature is 40-100 ℃, preferably 45-90 ℃, and further preferably 50-80 ℃; typically, but not by way of limitation, the reaction temperature may be 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C.
And/or the reaction time is 1-24 h, preferably 2-22 h, and further preferably 5-20 h; typically, but not by way of limitation, the reaction time may be 1h, 2h, 5h, 6h, 8h, 10h, 12h, 14h, 15h, 16h, 18h, 20h, 22h, or 24 h.
The method has the advantages of low reaction temperature, short reaction time, mild reaction condition, no need of complex and expensive equipment, easy operation, good controllability, low energy consumption, high efficiency and easy realization of industrial production, and the reaction can be completed at the temperature of below 100 ℃, and the reaction can be completed within 24 hours.
In a preferred embodiment, in step (b), the heating is atmospheric heating and/or reduced pressure heating;
preferably, the heating temperature is 40-100 ℃, preferably 45-90 ℃, and further preferably 50-80 ℃; typically, but not by way of limitation, the heating temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
Preferably, the heating time is 1-24 h, preferably 2-22 h, and further preferably 3-12 h; typically, but not by way of limitation, the heating time may be 1h, 1.5h, 2h, 3h, 3.5h, 4h, 5h, 6h, 7h, 8h, 10h, 12h, 15h, 16h, 18h, 20h, 22h, or 24 h.
It is to be understood that the matters not described in detail in the description of the above raw materials and preparation methods are common parameters that can be easily conceived by those skilled in the art, and thus, detailed description thereof may be omitted.
As a preferred embodiment of the present invention, the preparation method comprises:
(a) mixing xylonic acid, polyfunctional acrylate or polyfunctional methacrylate containing epoxy groups and hydroxyl functional groups and a solvent uniformly, adding a polymerization inhibitor, and preparing a prepolymer under the action of a catalyst;
wherein, the molar ratio of the xylonic acid to the multifunctional acrylate or the multifunctional methacrylate containing epoxy groups and hydroxyl functional groups is 1: 0.2 to 5;
the molar ratio of the xylonic acid to the catalyst is 1: 0.01 to 5;
the mass ratio of the xylonic acid to the polymerization inhibitor is 1: 0.001 to 0.1;
the reaction temperature is 40-100 ℃; the reaction time is 1-24 h.
(b) Adding a polymerization initiator into the prepolymer, and carrying out normal pressure heating and/or reduced pressure heating treatment to obtain a xylose-based polymer;
wherein the heating temperature is 40-100 ℃; the heating time is 1-24 h.
In a second aspect, there is provided in at least one embodiment a xylose-based polymer, prepared using the above-described method of preparing a xylose-based polymer.
The xylonic acid-based polymer prepared by the method has the advantages of good mechanical property, elastic property, solvent resistance, excellent performance, strong adaptability and high application value, and widens the application field of xylonic acid.
Preferably, the mass ratio of the xylonic acid in the xylonic acid-based polymer is 10-80%; typically, but not limited to, the mass content of xylonic acid in the xylonic acid based polymer may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 75% or 80%.
FIG. 1 shows an optical photograph of a xylose-based polymer provided by one embodiment of the present invention; FIG. 2 shows an IR spectrum of 3400cm of a xylitol-based polymer provided by one embodiment of the present invention－1Peak of hydroxyl group at 1770cm－1Peak of ester bond at 1640cm－1The peak of hydrogen bond indicates that the structure of xyloid acid exists in the polymer system. FIG. 3 shows a stress-strain plot of a xylitol-based polymer provided by an embodiment of the present invention; as can be seen, the tensile curve of the xylitol-based polymer conforms to the tensile behavior of a typical elastomer, has a distinct elastic deformation zone and strain hardening zone, and has an elongation at break of about 278%, a tensile strength at break of about 3.09MPa, and an elastic modulus of about 80 MPa.
As can be seen from the above fig. 1 to 3, the xylose-based polymer was successfully prepared using the method of the present invention, and the xylose-based polymer had good mechanical properties.
In a third aspect, there is provided in at least one embodiment a use of a xylitol based polymer as described above in the field of elastomeric materials.
The xylonic acid-based polymer provided by the invention has good mechanical properties, elastic properties and solvent resistance, widens the way for high-value utilization of xylonic acid, and can be widely applied to the fields of elastomer materials, biological materials, medical stent materials, environment adsorption materials and the like.
The present invention will be further described with reference to the following examples.
Example 1
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of xylonic acid and 3.2mL of hydroxyethyl methacrylate in a 50mL round-bottom flask, adding 20mL of methanol, dripping 40 mu L of triethylamine into the flask, then placing the flask in a 50 ℃ water bath, and stirring for reacting for 2 hours;
(2) preparation of a xylitol-based Polymer: and carrying out decompression rotary evaporation on the reaction solution of the xylonic acid methacrylate prepolymer at the temperature of 40 ℃ to prepare the xylonic acid based polymer. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 20 percent through a weight method test.
Example 2
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 1.6mL of glycidyl methacrylate into a 100mL round-bottom flask, adding 40mL of methanol, then adding 0.076g of 4-dimethylaminopyridine and 0.02g of hydroquinone into the flask, then placing the flask into a water bath kettle at 80 ℃, and stirring for reacting for 8 hours;
(2) preparation of a xylitol-based Polymer: 0.034g of azobisisobutyronitrile is added into the reaction solution of the xylonic acid methacrylate prepolymer, and the mixture is heated at 80 ℃ to prepare the xylonic acid based polymer. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 41 percent through a weight method test.
Example 3
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 0.8mL of glycidyl methacrylate into a 100mL round-bottom flask, adding 40mL of N, N-dimethylformamide, then adding 0.035g of 4-dimethylaminopyridine and 0.01g of hydroquinone into the flask, then placing the flask into a 60 ℃ water bath, and stirring for reacting for 12 hours;
(2) preparation of a xylitol-based Polymer: 0.068g of azobisisobutyronitrile is added into the reaction solution of the xylonic acid methacrylate prepolymer, and the xylonic acid based polymer is prepared by decompression and rotary evaporation at the temperature of 90 ℃. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 70 percent through a weight method test.
Example 4
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid acrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 2mL of hydroxypropyl acrylate into a 100mL round-bottom flask, adding 20mL of LN, N-dimethylformamide, then adding 0.07g of 4-dimethylaminopyridine and 0.03g of hydroquinone into the flask, then placing the flask into a 50 ℃ water bath, and stirring for reacting for 16 hours;
(2) preparation of a xylitol-based Polymer: 0.05g of dibenzoyl oxide is added into the reaction liquid of the xylonic acid acrylate prepolymer, and the xylonic acid based polymer is prepared by decompression rotary evaporation at the temperature of 85 ℃. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 52 percent through a weight method test.
Example 5
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid acrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 4mL of hydroxybutyl acrylate into a 100mL round-bottom flask, adding 15mL of dimethyl sulfoxide, adding 0.5g of dicyclohexylcarbodiimide and 0.03g of p-benzoquinone into the flask, placing the flask into a 70 ℃ water bath, and stirring to react for 20 hours;
(2) preparation of a xylitol-based Polymer: and adding 0.1g of potassium persulfate into the reaction liquid of the xylonic acid acrylate prepolymer, and carrying out reduced pressure rotary evaporation at 90 ℃ to prepare the xylonic acid based polymer. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 23 percent through a weight method test.
Example 6
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 4mL of glycidyl methacrylate into a 100mL round-bottom flask, adding 60mL of methanol, adding 0.5g of pyridine and 0.08g of p-phenothiazine into the flask, then placing the flask into a water bath kettle at 80 ℃, and stirring for reacting for 6 hours;
(2) preparation of a xylitol-based Polymer: and adding 0.2g of potassium persulfate into the reaction liquid of the xylonic acid methacrylate prepolymer, and carrying out reduced pressure rotary evaporation at the temperature of 60 ℃ to prepare the xylonic acid based polymer.
Example 7
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 0.4mL of glycidyl methacrylate into a 100mL round-bottom flask, adding 30mL of methanol, then adding 0.5g of dicyclohexylcarbodiimide and 0.1g of 4-dimethylaminopyridine and 0.06g of beta-phenylnaphthylamine into the flask, then placing the flask into a 50 ℃ water bath, and stirring for reacting for 6 hours;
(2) preparation of a xylitol-based Polymer: and adding 0.2g of potassium persulfate into the reaction liquid of the xylonic acid methacrylate prepolymer, and heating at 80 ℃ to prepare the xylonic acid based polymer. The mass proportion of the xylonic acid in the xylonic acid-based polymer is 73 percent through a weight method test.
Example 8
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid acrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 0.6mL of hydroxyethyl acrylate into a 100mL round bottom flask, adding 30mL of methanol, adding 0.2g of 1, 8-diazabicycloundecen-7-ene and 0.06g of 2, 2, 6, 6-tetramethylpiperidine nitroxide radical into the flask, then placing the flask in a 90 ℃ oil bath, and stirring for 18 h;
(2) preparation of a xylitol-based Polymer: 0.02g of dibenzoyl peroxide and 0.02g of N, N-dimethylaniline are added into the reaction solution of the xylonic acid acrylate prepolymer, and the mixture is heated at 100 ℃ to prepare the xylonic acid based polymer.
Example 9
A method of preparing a xylitol-based polymer, comprising the steps of:
(1) preparation of xylonic acid methacrylate prepolymer: weighing 1.0g of Xylonic Acid (XA) and 2.5mL of hydroxyhexyl methacrylate into a 100mL round bottom flask, adding 30mL of methanol, adding 0.2g of 4-dimethylaminopyridine and 0.05g of 2, 2, 6, 6-tetramethylpiperidine nitroxide radical into the flask, placing the flask in a 75 ℃ oil bath, and stirring for reacting for 10 hours;
(2) preparation of a xylitol-based Polymer: 0.025g of azobisisobutyronitrile is added into the reaction liquid of the xylonic acid methacrylate prepolymer, and the xylonic acid base polymer is prepared by decompression and rotary evaporation at the temperature of 60 ℃.
Solvent resistance and elasticity of the xylose-based polymers of some of the examples were tested and the results are shown in tables 1 and 2, respectively.
The method for testing the solvent resistance comprises the following steps: and adding 0.1g of the xylose-based polymer into 100mL of a solvent to be detected, soaking and dissolving, observing the dissolution condition, taking out after 24 hours, airing, and drying in an oven at 105 ℃ to constant weight. The mass difference of the xylitol-based polymer before and after dissolution was compared. The absence of a difference indicates that it is insoluble in the solvent.
The method for testing the elastic property comprises the following steps: calculating the elastic modulus of the xylose-based polymer through the elastic area of a tensile curve in a tensile test; the elasticity recovery coefficient of the xylose-based polymer was tested by the cyclic tensile test.
Table 1 solvent resistance of the xylose-based polymers of some of the examples
TABLE 2 elastic Properties of the xylose-based polymers of some of the examples
| Item | Modulus of elasticity (MPa) | Elastic recovery (%) |
| Example 1 | 162 | 99 |
| Example 2 | 80 | 95 |
| Example 3 | 43 | 90 |
| Example 4 | 70 | 95 |
| Example 5 | 135 | 99 |
| Example 6 | 105 | 96 |
| Example 7 | 34 | 89 |
As can be seen from tables 1 and 2 above, the resulting xylose-based polymers prepared by the process of the present invention have good solvent resistance and elastic properties.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (20)
1. A method for preparing a xylitol-based polymer, comprising the steps of:
(a) mixing xylonic acid, polyfunctional acrylate or polyfunctional methacrylate with a solvent to prepare a prepolymer under the action of a catalyst;
(b) heating the prepolymer to obtain a xylose-based polymer;
wherein the structure of the multifunctional acrylate comprises an epoxy group and a hydroxyl functional group;
and/or the structure of the multifunctional methacrylate contains epoxy groups and hydroxyl functional groups;
the molar ratio of the xylonic acid to the multifunctional acrylate or the multifunctional methacrylate is 1: 0.2 to 5;
and/or the molar ratio of the xylonic acid to the catalyst is 1: 0.01 to 5;
and/or the reaction temperature is 40-100 ℃;
and/or the reaction time is 1-24 h.
2. The method of claim 1, wherein the multifunctional acrylate comprises any one or a combination of at least two of glycidyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate and hydroxyhexyl acrylate.
3. The method of claim 1, wherein the multifunctional methacrylate comprises any one or a combination of at least two of glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate and hydroxyhexyl methacrylate.
4. The method of claim 1, wherein the catalyst comprises any one or a combination of at least two of triethylamine, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1, 8-diazabicycloundecen-7-ene, pyridine, sodium hydroxide, potassium hydroxide, and sodium carbonate.
5. The method of claim 1, wherein the solvent comprises at least one of alcohols, amides, sulfones, and sulfoxides.
6. The method of claim 5, wherein the solvent comprises at least one of methanol, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, N-ethylformamide, N-diethylformamide, and dimethylsulfoxide.
7. The method of claim 5, wherein the solvent comprises at least one of methanol, N-dimethylformamide, and dimethylsulfoxide.
8. The method according to any one of claims 1 to 7, wherein a polymerization inhibitor is added in step (a).
9. The method of claim 8, wherein the polymerization inhibitor comprises at least one of hydroquinone, p-benzoquinone, phenothiazine, β -phenylnaphthylamine, p-tert-butylcatechol, 1-diphenyl-2-picrylhydrazine, and 2, 2, 6, 6-tetramethylpiperidine nitroxide radical.
10. The method for preparing a xylose-based polymer according to claim 8, wherein the mass ratio of the polymerization inhibitor to the xylonic acid is 0.001 to 0.1: 1.
11. the method of any of claims 1 to 7, wherein a polymerization initiator is added in step (b).
12. The method of preparing a xylosic acid based polymer according to claim 11, characterized in that the initiator comprises at least one of azo type, organic peroxy type, inorganic peroxy type and redox initiation system type.
13. The method of claim 12, wherein the initiator comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide/N, N-dimethylaniline.
14. The method for preparing a xylonic acid based polymer according to claim 11, wherein the mass ratio of the initiator to the xylonic acid is 0.001-0.1: 1.
15. the method for preparing a xylitol-based polymer according to claim 1, wherein in step (b), the heating is atmospheric heating and/or reduced pressure heating.
16. The method for preparing a xylitol-based polymer according to claim 1, wherein the heating temperature is 40-100 ℃.
17. The method for preparing a xylitol-based polymer according to claim 1, wherein the heating time is 1-24 h.
18. A xylose-based polymer characterized by being produced by the method for producing a xylose-based polymer according to any one of claims 1 to 17.
19. The xylonic acid based polymer according to claim 18, wherein the mass proportion of xylonic acid in the xylonic acid based polymer is 10-80%.
20. Use of a xylitol-based polymer according to claim 18 or 19, in the field of elastomeric materials.
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|---|---|---|---|---|
| US4466834A (en) * | 1983-01-03 | 1984-08-21 | W. R. Grace & Co. | Corrosion inhibiting additive for cement compositions |
| WO2003078347A2 (en) * | 2002-03-13 | 2003-09-25 | W.R. Grace & Co.-Conn | Beneficiated water reducing compositions |
| CN107337597A (en) * | 2016-05-03 | 2017-11-10 | 济南圣泉集团股份有限公司 | A kind of synthetic method of xylonic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4466834A (en) * | 1983-01-03 | 1984-08-21 | W. R. Grace & Co. | Corrosion inhibiting additive for cement compositions |
| WO2003078347A2 (en) * | 2002-03-13 | 2003-09-25 | W.R. Grace & Co.-Conn | Beneficiated water reducing compositions |
| CN107337597A (en) * | 2016-05-03 | 2017-11-10 | 济南圣泉集团股份有限公司 | A kind of synthetic method of xylonic |
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