CN114380969B - Hydrophilic modified additive and preparation method thereof - Google Patents
Hydrophilic modified additive and preparation method thereof Download PDFInfo
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- CN114380969B CN114380969B CN202111668406.3A CN202111668406A CN114380969B CN 114380969 B CN114380969 B CN 114380969B CN 202111668406 A CN202111668406 A CN 202111668406A CN 114380969 B CN114380969 B CN 114380969B
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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Abstract
The invention belongs to the technical field of high polymer materials, and in particular relates to a hydrophilic modification additive which is blended with a polyurethane or polyurea resin system and can effectively improve the hydrophilicity of the resin system; the hydrophilic modification additive comprises the following components in parts by mass: 100 parts of glycerophosphorylcholine, 80-300 parts of diisocyanate and 10-150 parts of low molecular weight branched alcohol/amine. The invention provides a hydrophilic modification additive which has good compatibility with resin systems such as polyurethane, polyurea and the like, can be directly added into the resin such as polyurethane/polyurea and the like as a modification additive, and effectively improves the hydrophilicity and anti-adhesion property of the material; and the modified additive is not easy to soak and separate out in the water environment due to the high-density hydrogen bond between the additive and the base material, so that the problem of resin failure caused by the separation of the additive is solved, and the stability of a resin system is effectively improved. The invention also provides a preparation method of the hydrophilic modification additive, which is simple and safe.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a hydrophilic modified additive and a preparation method thereof.
Background
The hydrophilicity of the whole resin system is improved by blending and adding a hydrophilicity modifier into the resin, so that the method is a common modification method; phosphorylcholine is widely used as a hydrophilic moiety of a bio-phospholipid molecule and is modified with a resin as a hydrophilic functional group. In the prior art, MPC series hydrophilic modifier has been developed, which is blended with polyester, polyolefin and other base materials to modify, so as to effectively improve the hydrophilicity and anti-adhesion property of the material. However, researches show that the addition of the hydrophilic modifier damages the mechanical strength of the material in the process of contacting with water, and the mechanical strength of a blending system is greatly reduced along with the increase of the content of the modifier; in addition, in the water environment, the hydrophilic modifier is easy to soak out, and resin failure is easy to cause.
A composition of hydrophilic copolyesters containing polyoxyethylene diester and alkylene diester segments and optionally other components, formed from one or more polyols containing three or more hydroxyl groups or one or more polyoxyethylene glycols, or a mixture of one or more such polyols and one or more such glycols, having been modified after formation, is disclosed under the patent name CN 1036781a, with the result that the copolyesters have about 1-40% by weight of supplemental reactant segments. The hydrophilic functional groups used by the hydrophilic substances are different, the compatibility of the hydrophilic polyester with polyurethane and the like is poor, the physical interaction is low, and the hydrophilic polyester is also soaked and separated out in water environment when being used as a hydrophilic modifier.
Disclosure of Invention
Aiming at the problems of reduced mechanical strength and soaking precipitation of materials caused by blending modification of general hydrophilic modifiers, glycerophosphorylcholine is adopted as a hydrophilic functional group, and the glycerophosphorylcholine is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; and reacting the isocyanate with low molecular weight branched alcohol to generate high-density urethane groups, thus obtaining the hydrophilic modified additive. The additive contains high-content phosphorylcholine groups, has good compatibility with a polyurethane resin system, can be directly added into polyurethane resin as a modified additive, and effectively improves the hydrophilicity and anti-adhesion property of the material; and the modified additive is not easy to soak and separate out in the water environment due to the high-density hydrogen bond between the additive and the base material, so that the problem of resin failure caused by the separation of the additive is solved, and the stability of a resin system is effectively improved. In addition, the hydrophilic modification additive is formed by polymerizing glycerophosphorylcholine, diisocyanate and low-molecular-weight branched alcohol, and traditional polyurethane synthesis components such as oligomer polyol and the like are not used, so that the mechanical properties of the resin material are effectively maintained unchanged, the hydrophilicity of the added resin system is improved, the water contact angle is obviously reduced, and compared with the linear alcohol in the prior art, the additive synthesized by branched alcohol has better compatibility and processing characteristics, and the material can be effectively kept stable in water environment and is not easy to soak and separate out. The invention also provides a preparation method of the hydrophilic modified additive, which adopts the modes of mixing reaction, drying, washing and re-drying to prepare, so that the preparation process is simple, complex production equipment is not required, and the preparation process is safe and controllable.
The technical effects to be achieved by the invention are realized by the following technical scheme:
according to the hydrophilic modification additive, glycerophosphorylcholine is adopted as a hydrophilic functional group, and the glycerophosphorylcholine is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; the isocyanate reacts with low molecular weight branched alcohol to generate high-density urethane groups, so that the hydrophilic modified additive can be obtained; the hydrophilic property of the resin system can be effectively improved by blending with the polyurethane resin system; the hydrophilic modification additive comprises the following components in parts by mass: 100 parts of glycerophosphorylcholine, 80-300 parts of diisocyanate and 10-150 parts of low molecular weight branched alcohol.
As one of the preferable schemes, glycerophosphorylcholine is adopted as a hydrophilic functional group, and the glycerophosphorylcholine is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; the isocyanate reacts with low molecular weight branched alcohol to generate high-density urethane groups, so that the hydrophilic modified additive can be obtained; the hydrophilic property of the resin system can be effectively improved by blending with the polyurethane resin system; the hydrophilic modification additive comprises the following components in parts by mass: 100 parts of glycerophosphorylcholine, 120-182 parts of diisocyanate and 18-137 parts of low molecular weight branched alcohol.
As a preferred scheme, the mass ratio of the hydrophilic modification additive to the polyurethane resin system is (0.01-10): (90-99.99).
As a preferred embodiment, the low molecular weight branched alcohol is 1, 3-butanediol or 1, 2-hexanediol.
As a preferable mode, the diisocyanate is one or a mixture of more than two of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), 1, 5-Naphthalene Diisocyanate (NDI), xylylene Diisocyanate (XDI) and Lysine Diisocyanate (LDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100 parts by weight of dry glycerophosphorylcholine and a pre-measured amount of diisocyanate in a solvent, and reacting for a period of time at a preset temperature;
s02, adding a pre-measured amount of low molecular weight branched alcohol, and reacting for a period of time at a preset temperature to obtain a product solution;
s03, performing rotary evaporation or freeze drying on the product solution, washing for a plurality of times by using a washing solution, and performing vacuum drying at room temperature to obtain the target product.
In a preferred embodiment, in step S01, the solvent is one or more solvents selected from tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
As a preferable scheme, in the step S01, 100 parts by weight of dry glycerophosphorylcholine and a pre-measured amount of diisocyanate are mixed in a solvent and reacted for 0.5 to 12 hours at a temperature of 30 to 80 ℃.
As a preferred embodiment, in step S02, a predetermined amount of low molecular weight branched alcohol is added and reacted at a temperature of 30℃to 80℃for 0.5h to 12h.
In a preferred embodiment, in step S03, the target product is obtained by spin-evaporating or freeze-drying the product solution, washing with ethanol for several times, and vacuum-drying at room temperature.
In summary, the present invention has at least the following advantages:
1. the hydrophilic modification additive adopts glycerophosphorylcholine as a hydrophilic functional group, and the glycerophosphorylcholine is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; and reacting the isocyanate with low molecular weight branched alcohol to generate high-density urethane groups, thus obtaining the hydrophilic modified additive. The additive contains high-content phosphorylcholine groups, has good compatibility with a polyurethane resin system, can be directly added into polyurethane resin as a modified additive, and effectively improves the hydrophilicity and anti-adhesion property of the material; and the modified additive is not easy to soak and separate out in the water environment due to the high-density hydrogen bond between the additive and the base material, so that the problem of resin failure caused by the separation of the additive is solved, and the stability of a resin system is effectively improved.
2. The hydrophilic modified additive is prepared by polymerizing glycerophosphorylcholine, diisocyanate and low molecular weight branched alcohol, and traditional polyurethane synthesis components such as oligomer polyol are not used, so that the mechanical property of a resin material is effectively maintained unchanged, the hydrophilicity of an added resin system is improved, the water contact angle is obviously reduced, and compared with the linear alcohol in the prior art, the additive synthesized by branched alcohol has better compatibility and processing characteristics, and can effectively keep the material stable in water environment and difficult to soak and separate out.
3. The preparation method of the hydrophilic modified additive adopts the modes of mixing reaction, drying, washing and re-drying to prepare, so that the preparation process is simple, complex production equipment is not required, and the preparation process is safe and controllable.
Detailed Description
In a first aspect, the present invention provides a hydrophilic modification additive blended with a polyurethane resin system that is effective in improving the hydrophilicity of the resin system; the hydrophilic modification additive comprises the following components in parts by mass: 100 parts of glycerophosphorylcholine, 80-300 parts of diisocyanate and 10-150 parts of low molecular weight branched alcohol. In the invention, glycerophosphorylcholine is adopted as a hydrophilic functional group, and is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; and reacting the isocyanate with low molecular weight branched alcohol to generate high-density urethane groups, thus obtaining the hydrophilic modified additive. The additive contains high-content phosphorylcholine groups, has good compatibility with a polyurethane resin system, can be directly added into polyurethane resin as a modified additive, and effectively improves the hydrophilicity and anti-adhesion property of the material; and the modified additive is not easy to soak and separate out in the water environment due to the high-density hydrogen bond between the additive and the base material, so that the problem of resin failure caused by the separation of the additive is solved, and the stability of a resin system is effectively improved.
The hydrophilic modified additive is formed by polymerizing glycerophosphorylcholine, diisocyanate and low molecular weight branched alcohol, and traditional polyurethane synthesis components such as oligomer polyol are not used, so that the mechanical properties of the resin material are effectively maintained unchanged, the hydrophilicity of the added resin system is improved, the water contact angle is obviously reduced, and compared with the linear alcohol and branched alcohol synthesized additive in the prior art, the hydrophilic modified additive has better compatibility and processing characteristics, can effectively keep the material stable in water environment and is not easy to soak and separate out.
The hydrophilic modification additive of the invention can preferably comprise the following components in parts by mass: 100 parts of glycerophosphorylcholine, 120-182 parts of diisocyanate and 18-137 parts of low molecular weight branched alcohol. Further preferably, the mass ratio of the hydrophilic modification additive to the polyurethane resin system is (0.01-10): (90-99.99); the low molecular weight branched alcohol is 1, 3-butanediol or 1, 2-hexanediol; the diisocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), 1, 5-Naphthalene Diisocyanate (NDI), xylylene Diisocyanate (XDI) and Lysine Diisocyanate (LDI).
Wherein, the branched micromolecule 1, 2-hexanediol reacts with glycerophosphorylcholine to generate a substance with the following structural formula (I):
the structural formula (II) of the branched micromolecule 1, 3-butanediol and glycerophosphorylcholine, which is a substance generated by HDI reaction, is as follows:
in a second aspect, the present invention also provides a method for preparing the above hydrophilic modification additive, comprising the steps of:
s01, mixing 100 parts by weight of dry glycerophosphorylcholine and a pre-measured amount of diisocyanate in a solvent, and reacting for a period of time at a preset temperature;
s02, adding a pre-measured amount of low molecular weight branched alcohol, and reacting for a period of time at a preset temperature to obtain a product solution;
s03, performing rotary evaporation or freeze drying on the product solution, washing for a plurality of times by using a washing solution, and performing vacuum drying at room temperature to obtain the target product.
Further, in the step S01, the solvent is one or a mixed solvent of more than two of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; in the step S01, 100 parts by weight of dry glycerophosphorylcholine and a pre-measured amount of diisocyanate are mixed in a solvent and reacted for 0.5 to 12 hours at a temperature of 30 to 80 ℃. In step S02, a pre-metered amount of a low molecular weight branched alcohol is added and reacted for 0.5 to 12 hours at a temperature of 30 to 80 ℃. In the step S03, the product solution is subjected to rotary evaporation or freeze drying, and then is washed by ethanol for a plurality of times, and vacuum drying is carried out at room temperature, so that the target product is obtained.
The present invention will be described in detail with reference to the following specific examples, which are only preferred embodiments of the present invention and are not limiting thereof.
Example 1:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 80g of diisocyanate, and 10g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Hexamethylene Diisocyanate (HDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 80g of Hexamethylene Diisocyanate (HDI) into 200g of dimethyl sulfoxide, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 10g of 1, 3-butanediol, and reacting for 2 hours at 70 ℃ to obtain a product solution;
s03, freeze-drying the product solution, washing with ethanol for three times, and vacuum-drying at room temperature to obtain the target product.
Example 2:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 300g of diisocyanate, and 150g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Hexamethylene Diisocyanate (HDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 300g of Hexamethylene Diisocyanate (HDI) into 300g of dimethyl sulfoxide, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 150g of 1, 3-butanediol, and reacting for 8 hours at 80 ℃ to obtain a product solution;
s03, freeze-drying the product solution, washing with ethanol for three times, and vacuum-drying at room temperature to obtain the target product.
Example 3:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 98g of diisocyanate, and 23g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 2-hexanediol and the diisocyanate is Hexamethylene Diisocyanate (HDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 98g of Hexamethylene Diisocyanate (HDI) into 200g of dimethyl sulfoxide, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 23g of 1, 2-hexanediol, and reacting for 5 hours at 70 ℃ to obtain a product solution;
s03, freeze-drying the product solution, washing with ethanol for three times, and vacuum-drying at room temperature to obtain the target product.
Example 4:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 131g of diisocyanate, and 46g of low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Hexamethylene Diisocyanate (HDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 131g of Hexamethylene Diisocyanate (HDI) into 250g of dimethyl sulfoxide, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 46g of 1, 3-butanediol, and reacting for 3 hours at 60 ℃ to obtain a product solution;
s03, freeze-drying the product solution, washing with ethanol for three times, and vacuum-drying at room temperature to obtain the target product.
Example 5:
a hydrophilic modification additive comprising 100g of glycerophosphorylcholine, 261g of diisocyanate, and 137g of low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 2-hexanediol and the diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 261g of Toluene Diisocyanate (TDI) into 300g of tetrahydrofuran, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 137g of 1, 2-hexanediol, and reacting for 10 hours at 70 ℃ to obtain a product solution;
s03, carrying out rotary evaporation drying on the product solution, washing with ethanol for three times, and carrying out vacuum drying at room temperature to obtain the target product.
Example 6:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 98g of diisocyanate, and 18g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 98g of Toluene Diisocyanate (TDI) into 200g of tetrahydrofuran, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 18g of 1, 2-hexanediol, and reacting for 8 hours at 50 ℃ to obtain a product solution;
s03, carrying out rotary evaporation drying on the product solution, washing with ethanol for three times, and carrying out vacuum drying at room temperature to obtain the target product.
Example 7:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 196g of diisocyanate, and 70g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 196g of Toluene Diisocyanate (TDI) into 220g of tetrahydrofuran, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 70g of 1, 2-hexanediol, and reacting for 8 hours at 50 ℃ to obtain a product solution;
s03, carrying out rotary evaporation drying on the product solution, washing with ethanol for three times, and carrying out vacuum drying at room temperature to obtain the target product.
Example 8:
a hydrophilically modifying additive comprising 100g of glycerophosphorylcholine, 261g of diisocyanate, and 105g of a low molecular weight branched alcohol; wherein the low molecular weight branched alcohol is 1, 3-butanediol and the diisocyanate is Toluene Diisocyanate (TDI).
The preparation method of the hydrophilic modification additive comprises the following steps:
s01, mixing 100g of dry glycerophosphorylcholine and 261g of Toluene Diisocyanate (TDI) into 220g of tetrahydrofuran, and stirring and reacting for 8 hours at 50 ℃;
s02, adding 105g of 1, 2-hexanediol, and reacting for 12 hours at 65 ℃ to obtain a product solution;
s03, carrying out rotary evaporation drying on the product solution, washing with ethanol for three times, and carrying out vacuum drying at room temperature to obtain the target product.
Comparative example 1:
based on example 1, the only difference is that: in this comparative example 1, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 2:
based on example 2, the only difference is that: in this comparative example 2, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 3:
based on example 3, the only difference is that: in this comparative example 3, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 4:
based on example 4, the only difference is that: in this comparative example 4, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 5:
based on example 5, the only difference is that: in this comparative example 5, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 6:
based on example 6, the only difference is that: in this comparative example 6, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 7:
based on example 7, the only difference is that: in this comparative example 7, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Comparative example 8:
based on example 8, the only difference is that: in this comparative example 8, an equimolar amount of a small molecule linear diol was used instead of the low molecular weight branched alcohol.
Test example 1:
the products in examples 1-8 were selected as modifying additives and blended with polyester polyurethane, respectively, in a mass ratio of 0.01:99.99, the mechanical strength and contact angle of the blend resin without modifying additive with the blend resins obtained in examples 1-8, respectively, were tested as shown in Table 1:
| contact angle | Tensile Strength | |
| Example 1 | 40° | 17MPa |
| Example 2 | 63° | 21MPa |
| Example 3 | 46° | 18MPa |
| Example 4 | 55° | 18MPa |
| Example 5 | 43° | 21MPa |
| Example 6 | 32° | 25MPa |
| Implementation of the embodimentsExample 7 | 40° | 19MPa |
| Example 8 | 45° | 20MPa |
| Does not contain modifying additive | 96° | 14MPa |
TABLE 1
As can be seen from table 1, the contact angle of the blended resin after the addition of the additive in the examples is significantly smaller than that of the blended resin without the addition of the modifying additive, and thus it can be seen that the additive can significantly improve the hydrophilic properties of the blended resin; and the tensile strength of the blended resin after the additive is added in the embodiment is obviously improved compared with that of the blended resin without the modified additive, so that the mechanical strength of the blended resin can be obviously improved by the additive.
Test example 2:
the products in examples 1-8 were selected as modifying additives and blended with polyester polyurethane, respectively, in a mass ratio of 10:90, the mechanical strength and contact angle of the blend resin without modifying additive with the blend resins obtained in examples 1-8, respectively, were tested as shown in Table 2:
| contact angle | Tensile Strength | |
| Example 1 | 43° | 24MPa |
| Example 2 | 70° | 28MPa |
| Example 3 | 56° | 24MPa |
| Example 4 | 61° | 26MPa |
| Example 5 | 48° | 29MPa |
| Example 6 | 51° | 25MPa |
| Example 7 | 44° | 27MPa |
| Example 8 | 45° | 27MPa |
| Does not contain modifying additive | 112° | 19MPa |
TABLE 2
Comparing tables 1 and 2, it can be seen that the tensile strength of the blended resin is improved to a certain extent when the proportion of the additive is larger, and thus the mechanical properties of the blended resin can be improved when the additive is added in a large dosage; in the case where the proportion of the additive to be added is large, the contact angle of the blended resin in the individual examples tends to be increased but is still in a smaller range, and it can be seen that the increase in the content of the additive in the examples has little effect on the hydrophilic properties of the blended resin.
Test example 3:
the products of examples 1-8 and comparative examples 1-8 were selected as modifying additives and blended with polyester polyurethane at a mass ratio of 10:90, respectively, and then each of the blended resins was immersed in an aqueous environment for one week, and the surface of the blended resin was observed as shown in tables 3 and 4:
TABLE 3 Table 3
| Surface condition after soaking for one week | |
| Comparative example 1 | The surface has cracks and degradation |
| Comparative example 2 | The surface has cracks and degradation |
| Comparative example 3 | The surface has cracks and obvious swelling degradation phenomenon |
| Comparative example 4 | The surface has cracks and degradation |
| Comparative example 5 | The surface has cracks and degradation |
| Comparative example 6 | The surface has cracks and obvious swelling degradation phenomenon |
| Comparative example 7 | The surface has cracks and degradation |
| Comparative example 8 | The surface has cracks and degradation |
TABLE 4 Table 4
As can be seen from tables 3 and 4, the addition of a large amount of conventional hydrophilic additive resulted in a significant decrease in the stability of the blended resin in an aqueous environment, whereas the blended resin to which the comparative additive was added exhibited significant cracking and swelling degradation phenomena in an aqueous environment. From this, the water environment stability of the material after the resin is blended with the comparative example additive is poor, and the water stability of the resin is not adversely affected by the addition of the example additive.
According to the technical scheme of the embodiment, the invention provides a hydrophilic modification additive, and aims at the problems of reduced mechanical strength and soaking precipitation of materials caused by blending modification of a general hydrophilic modifier, and the method comprises the steps of adopting glycerophosphorylcholine as a hydrophilic functional group, and mixing the glycerophosphorylcholine with excessive diisocyanate to obtain an isocyanate-terminated compound; and reacting the isocyanate with low molecular weight branched alcohol to generate high-density urethane groups, thus obtaining the hydrophilic modified additive. The additive contains high-content phosphorylcholine groups, has good compatibility with a polyurethane resin system, can be directly added into polyurethane resin as a modified additive, and effectively improves the hydrophilicity and anti-adhesion property of the material; and the modified additive is not easy to soak and separate out in the water environment due to the high-density hydrogen bond between the additive and the base material, so that the problem of resin failure caused by the separation of the additive is solved, and the stability of a resin system is effectively improved. In addition, the hydrophilic modification additive is formed by polymerizing glycerophosphorylcholine, diisocyanate and low-molecular-weight branched alcohol, and traditional polyurethane synthesis components such as oligomer polyol and the like are not used, so that the mechanical properties of the resin material are effectively maintained unchanged, the hydrophilicity of the added resin system is improved, the water contact angle is obviously reduced, and compared with the linear alcohol in the prior art, the additive synthesized by branched alcohol has better compatibility and processing characteristics, and the material can be effectively kept stable in water environment and is not easy to soak and separate out. The invention also provides a preparation method of the hydrophilic modified additive, which adopts the modes of mixing reaction, drying, washing and re-drying to prepare, so that the preparation process is simple, complex production equipment is not required, and the preparation process is safe and controllable.
While the invention has been described in conjunction with the specific embodiments above, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, all such alternatives, modifications, and variations are included within the spirit and scope of the following claims.
Claims (8)
1. A hydrophilic modification additive is characterized in that glycerophosphorylcholine is adopted as a hydrophilic functional group, and is mixed with excessive diisocyanate to obtain an isocyanate-terminated compound; the isocyanate reacts with low molecular weight branched alcohol to generate high-density urethane groups, so that the hydrophilic modified additive can be obtained; the hydrophilic property of the resin system can be effectively improved by blending with the polyurethane resin system; the hydrophilic modification additive comprises the following components in parts by mass:
100 parts of glycerophosphorylcholine
80-300 parts of diisocyanate
10-150 parts of low molecular weight branched alcohol;
the low molecular weight branched alcohol is 1, 3-butanediol or 1, 2-hexanediol;
and the mass ratio of the hydrophilic modification additive to the polyurethane resin system is 10:90.
2. the hydrophilic modification additive according to claim 1, wherein glycerophosphorylcholine is used as the hydrophilic functional group, and the glycerophosphorylcholine is mixed with an excess of diisocyanate to obtain the isocyanate-terminated compound; the isocyanate reacts with low molecular weight branched alcohol to generate high-density urethane groups, so that the hydrophilic modified additive can be obtained; the hydrophilic property of the resin system can be effectively improved by blending with the polyurethane resin system; the hydrophilic modification additive comprises the following components in parts by mass:
100 parts of glycerophosphorylcholine
120-182 parts of diisocyanate
18-137 parts of low molecular weight branched alcohols.
3. The hydrophilic modification additive according to claim 1 or 2, wherein the diisocyanate is one or a mixture of two or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), 1, 5-Naphthalene Diisocyanate (NDI), xylylene Diisocyanate (XDI), lysine Diisocyanate (LDI).
4. A method of preparing a hydrophilically modifying additive as claimed in any one of claims 1 to 3, comprising the steps of:
s01, mixing 100 parts by weight of dry glycerophosphorylcholine and a pre-measured amount of diisocyanate in a solvent, and reacting for a period of time at a preset temperature;
s02, adding a pre-measured amount of low molecular weight branched alcohol, and reacting for a period of time at a preset temperature to obtain a product solution;
s03, performing rotary evaporation or freeze drying on the product solution, washing for a plurality of times by using a washing solution, and performing vacuum drying at room temperature to obtain the target product.
5. The method according to claim 4, wherein in the step S01, the solvent is one or more solvents selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
6. The preparation method according to claim 4, wherein in the step S01, 100 parts by mass of dry glycerophosphorylcholine and a predetermined amount of diisocyanate are mixed in a solvent and reacted at a temperature of 30 to 80℃for 0.5 to 12 hours.
7. The process according to claim 4, wherein in step S02, a predetermined amount of low molecular weight branched alcohol is added and reacted at a temperature of 30℃to 80℃for 0.5h to 12h.
8. The method according to claim 4, wherein in step S03, the target product is obtained by spin-evaporating or freeze-drying the product solution, washing with ethanol for a plurality of times, and vacuum-drying at room temperature.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4689386A (en) * | 1984-11-07 | 1987-08-25 | Biocompatibles Ltd. | Biocompatible surfaces |
| CN1569917A (en) * | 2004-05-11 | 2005-01-26 | 四川大学 | Polyurethane material with side chain possessing fluorophosphatidylcholine and its preparation method |
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| ATE545674T1 (en) * | 2006-09-01 | 2012-03-15 | Univ Tokai Educational System | DIAMINE COMPOUND WITH PHOSPHORYLCHOLINE GROUP, POLYMER THEREOF AND PRODUCTION METHOD THEREOF |
| JP2011162522A (en) * | 2010-02-15 | 2011-08-25 | Tokai Univ | Phosphorylcholine group-containing diol compound, and the group-containing polymer |
| CN106674484B (en) * | 2016-12-28 | 2019-09-24 | 山东师范大学 | A kind of side chain group containing Phosphorylcholine polyether polyurethane material and preparation method thereof |
| CN111234170A (en) * | 2020-01-15 | 2020-06-05 | 中国科学院长春应用化学研究所 | Polyurethane material, preparation method thereof and application of polyurethane material in artificial meniscus material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4689386A (en) * | 1984-11-07 | 1987-08-25 | Biocompatibles Ltd. | Biocompatible surfaces |
| CN1569917A (en) * | 2004-05-11 | 2005-01-26 | 四川大学 | Polyurethane material with side chain possessing fluorophosphatidylcholine and its preparation method |
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