CN114085355A - High-strength hydrolysis-resistant thermoplastic polyurethane elastomer material, preparation method and application - Google Patents
High-strength hydrolysis-resistant thermoplastic polyurethane elastomer material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a high-strength hydrolysis-resistant thermoplastic polyurethane elastomer material and a preparation method thereof. According to the invention, the thermoplastic polyurethane elastomer material with excellent hydrolysis resistance, higher strength and excellent processing performance is synthesized by adding the dihydroxyl/amino cage type silsesquioxane with castor oil-based diol, the tensile strength of the material is more than or equal to 45MPa, the material is soaked in deionized water at 80 ℃ for 1 week, 4 weeks and 8 weeks, the retention rates of the tensile strength respectively reach 90%, 65% and 30%, and the thermoplastic polyurethane elastomer material can be used for preparing injection molding products and extrusion products with higher requirements on hydrolysis resistance and physical strength.
Description
Technical Field
The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a high-strength hydrolysis-resistant thermoplastic polyurethane elastomer material and a preparation method and application thereof.
Background
The thermoplastic polyurethane elastomer has excellent physical property, wear resistance and biocompatibility, wide hardness adjustable range and multiple applicable processing modes, and is widely applied to various industries. The polyester type thermoplastic polyurethane elastomer is favored in partial industry fields because of higher mechanical strength compared with polyether type, but the defect of poor hydrolysis resistance of the polyester type thermoplastic polyurethane seriously limits the widening of the application field.
The widely adopted methods for improving the hydrolysis resistance of polyester thermoplastic polyurethane elastomers at present mainly comprise the following steps:
1. a large amount of hydrolysis-resistant auxiliaries such as carbodiimide or polycarbodiimide are added, the method can improve the hydrolysis resistance of the material to a certain extent, and for example, the hydrolysis resistance of the material is improved by adding the hydrolysis-resistant auxiliaries such as polycarbodiimide in Chinese patent CN201110045459. However, the improvement of the method is limited by the addition amount of the auxiliary agent, the problem of difficult dispersion of the auxiliary agent is easily caused by excessive addition amount, and the excessive auxiliary agent has certain influence on the processing performance of the material.
2. The hydrolysis resistance of the material is improved by using a multifunctional crosslinking agent and improving the crosslinking degree of the material, and the method is mainly used for casting polyurethane, paint and adhesives, for example, Chinese patent CN201010521503.5 improves the hydrolysis resistance of the material by adding castor oil alkyd resin with three or more functionalities. However, the method can obviously reduce the processability of the thermoplastic polyurethane elastomer, and even cause the problems that the material is not melted, and the hot processing cannot be carried out, and the like.
The preparation and performance study of hydroxylated silsesquioxane modified vegetable oil based polyurethane, from Master who smells the month at Jiangnan university, simply uses castor oil with an average functionality of 2.7 and heptaphenyltrihydroxysilsesquioxane with a functionality of 3 to improve the material properties. However, the product prepared by the method is a casting type polyurethane product, is not melted and dissolved, does not have secondary processing capacity, has poor microphase separation degree of the material, less than 15MPa of tensile strength and poor comprehensive performance and does not have practical value because of too short castor oil molecular chains and too much addition, and is prepared by a prepolymerization method, so that the preparation process is complicated.
Therefore, the preparation of a hydrolysis-resistant thermoplastic polyurethane material with good hot workability and high strength is a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to solve the problem that the material hydrolysis resistance is poor on the premise of ensuring the processing performance of the polyester type thermoplastic polyurethane elastomer in the prior art, and provides a high-strength high-hydrolysis-resistance thermoplastic polyurethane elastomer material.
The invention also aims to provide a preparation method of the thermoplastic polyurethane elastomer material.
It is a further object of the present invention to provide such thermoplastic polyurethane elastomer products and their use in the field of making injection molded and extruded articles that require high resistance to hydrolysis and physical strength.
In order to achieve the purpose, the invention provides the following technical scheme:
a thermoplastic polyurethane elastomer material comprising, based on the total weight of the thermoplastic polyurethane elastomer:
in a preferred embodiment, the thermoplastic polyurethane elastomer material comprises the following components, based on the total weight of the thermoplastic polyurethane elastomer:
in a specific embodiment, the diisocyanateSelected from aromatic and/or aliphatic diisocyanates; preferably, the aromatic diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), Xylylene Diisocyanate (XDI), and the aliphatic diisocyanate is selected from Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (H)12MDI), 1, 4-cyclohexyl dimethylene diisocyanate (CHDI).
In a specific embodiment, the macrodiol is selected from polyester diol and/or polycaprolactone diol obtained by condensation of dibasic acid and diol, polycarbonate diol; preferably, the polyester diol is selected from one or more of polyethylene adipate diol, polybutylene adipate diol, and polyhexamethylene adipate diol; more preferably, the number average molecular weight of the macrodiol is 500 to 4000g/mol, and further preferably 1000 to 2000 g/mol.
In a particular embodiment, the castor oil based diol is selected from the group consisting of castor oil alcohol, modified castor oil alcohol or castor oil based diol obtained by polycondensation of alkyds; preferably, the castor oil based diol obtained by alkyd polycondensation is a diol obtained by polycondensation of ricinol or modified ricinol and a dibasic acid, or ricinoleic acid or modified ricinoleic acid and a diol, or ricinol or modified ricinoleic alcohol and ricinoleic acid or modified ricinoleic acid through alkyd polycondensation.
In a specific embodiment, the hydroxyl or amino cage silsesquioxane has a three-dimensional structure of T8, T10 and T12, preferably a cubic configuration of T8; preferably, the hydroxyl or amino cage type silsesquioxane has the hydroxyl or amino number of 2; more preferably, the structural schematic diagram of the hydroxyl or amino cage-type silsesquioxane is as follows:
wherein R is alkylene, alkyl or phenyl, R1Is a straight-chain alkyl, branched-chain alkyl or cyclic alkyl containing double hydroxyl or double amino and consisting of 3 to 10 carbon atoms, wherein in the structures of the straight-chain alkyl and the branched-chain alkyl, two hydroxyl/amino are ortho-position structures and one of the hydroxyl/amino is an end group, in the structure of the cyclic alkyl, two hydroxyl/amino are ortho-position structures, R is2Is a straight or branched chain alkyl group containing a terminal hydroxyl group or a terminal amino group consisting of 2 to 10 carbon atoms.
In a particular embodiment, the chain extender is selected from small molecule diols or diamines; preferably, the dihydric alcohol is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, hydroquinone dihydroxyethyl ether; the diamine is selected from one or more of 3,3 '-dichloro-4, 4' -diphenylmethane diamine, diethyl toluene diamine, and 3, 5-diamino isobutyl p-chlorobenzoate.
In a particular embodiment, the isocyanate index (-NCO to-OH molar ratio) is from 0.8 to 1.2, preferably from 0.95 to 1.05.
In a preferred embodiment, the raw materials for preparing the thermoplastic polyurethane elastomer material also comprise a catalyst and a mixing aid, wherein the mixing aid comprises a light stabilizer, an antioxidant and a hydrolysis stabilizer, the catalyst and the mixing aid are added in an amount of 1-18ppm and 2-5 wt% based on the total mass of all the components in claim 1.
In another aspect of the present invention, the method for preparing a thermoplastic polyurethane elastomer from the thermoplastic polyurethane elastomer material is characterized by comprising the following steps:
(1) adding the composition material of claim 1 into a heated extruder according to a certain proportion, wherein the composition material is added with a small amount of catalyst and mixing auxiliary agent besides diisocyanate, macrodiol, castor oil based diol, dihydroxy/amino cage type silsesquioxane and chain extender;
(2) reacting the components recited in (1) in the heated extruder in a one-step polymerization process to form a thermoplastic polyurethane elastomer; preferably, the extruder temperature is set between 80-240 ℃;
(3) and cooling the thermoplastic polyurethane elastomer, crushing and granulating.
In another aspect of the invention, the thermoplastic polyurethane elastomer prepared by the method has a tensile strength of not less than 45MPa for a 2mm injection test piece, and the 2mm injection test piece is soaked in deionized water at 80 ℃ for 1 week, the retention rate of the tensile strength is not less than 90%, the retention rate of the tensile strength is not less than 65%, the retention rate of the tensile strength is not less than 8 weeks, and the retention rate of the tensile strength is not less than 30% according to the test of ASTM D412 standard.
In still another aspect of the present invention, the thermoplastic polyurethane elastomer prepared by the above method can be used for preparing injection molded products and extruded products with high requirements on hydrolysis resistance and physical strength, preferably conveyor belts, seals, underwater cables and water pipes.
Compared with the prior art, the invention has the following beneficial effects:
1) the Thermoplastic Polyurethane (TPU) elastomer material has simple preparation process, can be extruded by a one-step polymerization method to obtain the thermoplastic polyurethane elastomer, can be continuously produced, and has simple and easy process.
2) The TPU material prepared by adding the cage-type silsesquioxane while using the castor oil based diol has higher strength and hydrolysis resistance, can meet the performance requirements of wading materials, and has the tensile strength retention rate of more than 90%, 65% and 30% after being soaked in deionized water at the temperature of 80 ℃ for 1 week, 4 weeks and 8 weeks, thereby having higher commercial application value.
3) The TPU material prepared by the invention has excellent processing performance, heat-resistant flame-retardant performance and dielectric performance to a certain extent.
4) The thermoplastic polyurethane elastomer prepared by the invention greatly improves the hydrolysis resistance of the material on the premise of ensuring the processing performance, and can be used for preparing injection molding products and extrusion products with higher requirements on hydrolysis resistance and physical strength, such as conveyor belts, sealing elements, underwater cables, water pipes and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A thermoplastic polyurethane elastomer material comprising, based on the total weight of the thermoplastic polyurethane elastomer:
20-50 wt% of diisocyanate; preferably 23 to 45 wt%;
10-70 wt% of macroglycol; preferably 10 to 50 wt%;
5-50 wt% of castor oil based diol; preferably 15 to 50 wt%; more preferably 15 to 40 wt%;
2-10 wt% of hydroxyl or amino cage type silsesquioxane; preferably 3-6 wt%; more preferably 3 to 5 wt%;
2-20 wt% of a chain extender; preferably 3 to 10 wt%.
The diisocyanate is selected from aromatic and/or aliphatic diisocyanate; preferably, the aromatic diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), Xylylene Diisocyanate (XDI), and the aliphatic diisocyanate is selected from Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (H)12MDI), 1, 4-cyclohexyl dimethylene diisocyanate (CHDI). More preferably, the diisocyanate is diphenylmethane diisocyanate (MDI). It is worth noting that the addition of polyisocyanates significantly increases the degree of crosslinking within the material, and diisocyanates are the choice in the present invention.
The macromolecular dihydric alcohol is at least one of polyester dihydric alcohol, polycaprolactone diol and polycarbonate diol obtained by condensing dibasic acid and dihydric alcohol; preferably polyester diol, specifically, the polyester diol is selected from one or more of polyethylene glycol adipate diol, polybutylene adipate diol and polyhexamethylene adipate diol; more preferably, the number average molecular weight of the macrodiol is 500-4000 g/mol, and even more preferably 1000-2000 g/mol. For example, a polybutylene adipate diol having a number average molecular weight of 2000. In the material, the macromolecular diol is added, so that the microphase separation degree in the material is effectively improved, and the effect of enhancing the comprehensive performance of the material is achieved.
The castor oil-based diol is at least one of castor oil alcohol, modified castor oil alcohol or castor oil diol obtained by alkyd polycondensation. The modified ricinoleic alcohol includes, but is not limited to, hydrogenated modified ricinoleic alcohol, and also includes chlorinated castor oil diol, brominated castor oil diol, and the like. The castor oil diol obtained by the condensation polymerization of the alkyd is a diol obtained by condensation polymerization of ricinoleic alcohol or modified ricinoleic alcohol and dibasic acid, or ricinoleic acid or modified ricinoleic alcohol and ricinoleic acid or modified ricinoleic acid, and alkyd, that is, the castor oil diol obtained by condensation polymerization of the alkyd may be obtained by condensation polymerization of ricinoleic alcohol and dibasic acid, or obtained by condensation polymerization of modified ricinoleic alcohol and dibasic acid, or obtained by condensation polymerization of ricinoleic acid and dibasic alcohol, or obtained by condensation polymerization of modified ricinoleic acid and dibasic alcohol, or obtained by condensation polymerization of the modified ricinoleic acid and the dibasic alcohol, such as ricinoleic acid ricinoleate diol, ricinoleate polyadipate ricinoleate diol, hydrogenated ricinoleate adipate diol, and the like, but not limited thereto.
The three-dimensional structures of the hydroxyl or amino cage-type silsesquioxane are T8, T10 and T12, and the cubic configuration of T8 is preferred; wherein, the hydroxyl or amino cage type silsesquioxane has the hydroxyl or amino number of 2, but not limited to, for example, the hydroxyl or amino number can also be 4, and preferably, the hydroxyl or amino cage type silsesquioxane has the hydroxyl or amino number of 2; more preferably, the structural schematic diagram of the hydroxyl or amino cage-type silsesquioxane is as follows:
wherein R is alkylene, alkyl or phenyl, for example, R is vinyl, isobutyl, phenyl, etc., but not limited thereto. R1Is a straight-chain alkyl, branched-chain alkyl or cyclic alkyl containing a double hydroxyl group or a double amino group and consisting of 3 to 10 carbon atoms, wherein in the straight-chain alkyl and branched-chain alkyl structures, two hydroxyl/amino groups are ortho-position structures and one of the hydroxyl/amino groups is a terminal group, and in the cyclic alkyl structure, two hydroxyl/amino groups are ortho-position structures, such as R1Is composed of
And the like, but are not limited thereto. R2Is a linear or branched alkyl group containing a terminal hydroxyl or terminal amino group consisting of 2 to 10 carbon atoms, e.g. R2Is composed of
The chain extender is selected from micromolecular dihydric alcohol or diamine; wherein the dihydric alcohol is selected from one or more of 1, 2-ethanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol and hydroquinone dihydroxyethyl ether, and preferably 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol and diethylene glycol; the diamine is selected from one or more of 3,3 '-dichloro-4, 4' -diphenylmethanediamine, diethyltoluenediamine, and 3, 5-diamino isobutyl p-chlorobenzoate, preferably 3,3 '-dichloro-4, 4' -diphenylmethanediamine, and diethyltoluenediamine.
On the basis of the selection of the content of each component in the set mass percentage range, the-NCO group and the-OH group preferably satisfy a certain relation, namely, the isocyanate index (-NCO to-OH molar ratio) is 0.8-1.2, preferably 0.95-1.05, and under the condition, the thermoplastic polyurethane elastomer product prepared by the invention has more excellent processing performance and secondary processing performance.
The castor oil based diol selected by the invention has longer fatty chain and branched chain, and can improve the hydrophobicity of the surface of the material; meanwhile, the selected cage-type silsesquioxane has unique molecular structure and volume, and can enhance the mechanical property, dielectric property, heat resistance and flame retardant property of the material to a certain extent.
In the experimental process, a certain amount of hydroxyl or amino cage type silsesquioxane is added while the castor oil based diol is used, so that the hydrolysis resistance of the thermoplastic polyurethane elastomer material can be better improved, and the effect is obviously improved compared with the effect of singly using the castor oil based diol.
It is well known to those skilled in the art that, based on the composite material of the present invention, some common additives, such as, but not limited to, antioxidants, flame retardants, leveling agents, etc., may be added as needed, and any minor modifications based on the present invention can not depart from the scope of the present invention.
In addition, the invention also provides a method for preparing the thermoplastic polyurethane elastomer by adopting the thermoplastic polyurethane elastomer material, which comprises the steps of adding the components into a heated extruder according to the following proportion, reacting in the heated extruder by a one-step polymerization method, and extruding to form the thermoplastic polyurethane elastomer.
Wherein the temperature of the extruder is set to be 80-240 ℃, preferably 140-230 ℃.
The proportions of the components are as follows:
20-50 wt% of diisocyanate, preferably 25-45 wt%;
10-70 wt% of macromolecular dihydric alcohol, preferably 10-50 wt%;
5-50 wt% of castor oil based diol, preferably 6-40 wt%;
2-10 wt%, preferably 3-6 wt% of hydroxyl or amino cage type silsesquioxane;
2-20 wt% of chain extender, preferably 3-10 wt%.
In addition to the above-mentioned components, small amounts of catalyst and mixing aid are also preferably added, the addition amount of the catalyst is 1-18ppm and the addition amount of the mixing aid is 2-5 wt% based on the total mass of all the above-mentioned components, and when the mixing aid is a mixture of a plurality of aids, the mixing aid can be added in the average amount of the plurality of aids.
Wherein the catalyst is a common catalyst of an isocyanate system, and is selected from one or more of organic tin, organic bismuth, organic lead, organic zinc and organic amine, such as dibutyltin dilaurate, stannous octoate, triethylenediamine, bismuth carboxylate, and the like, but is not limited thereto; the mixing auxiliary agent is common light stabilizer, antioxidant and hydrolysis stabilizer, but is not limited to the common light stabilizer, antioxidant and hydrolysis stabilizer, and a small amount of other auxiliary agents such as flame retardant and the like can also be added; wherein the light stabilizer is, for example, but not limited to, UV-327, UV328, light stabilizer 765, etc.; the antioxidant is, for example, antioxidant 1010, antioxidant 1135, etc., but is not limited thereto; the hydrolysis stabilizer is, for example, carbodiimide, polycarbodiimide or the like, but is not limited thereto.
The extruded thermoplastic polyurethane elastomer also comprises the conventional steps of cooling, crushing and granulating, and a thermoplastic polyurethane elastomer particle product with the required particle size or particle size distribution can be obtained according to the requirements of customers.
The thermoplastic polyurethane elastomer prepared by the method has the tensile strength of more than or equal to 45MPa for the 2mm injection test piece according to the test of ASTM D412 standard, the retention rate of the tensile strength of more than or equal to 90 percent for the 2mm injection test piece after being soaked in deionized water at the temperature of 80 ℃ for 1 week, the retention rate of the tensile strength of more than or equal to 65 percent for the 2mm injection test piece after being soaked for 8 weeks, and the retention rate of the tensile strength of more than or equal to 30 percent. The tensile strength of the common thermoplastic elastomer is about 30MPa, while the tensile strength of the high-strength hydrolysis-resistant thermoplastic polyurethane elastomer prepared by the invention is more than 46.5 MPa. The hydrolysis resistance of the thermoplastic elastomer is characterized by the retention rate of the tensile strength after soaking for a certain time, and generally, the higher the retention rate of the tensile strength is, the better the hydrolysis resistance is.
The thermoplastic polyurethane elastomer prepared by the invention can be used for preparing injection molding products and extrusion products with higher requirements on hydrolysis resistance and physical strength, such as conveyor belts, sealing parts, underwater cables, water pipes and the like, but is not limited to the above because of the excellent high strength and hydrolysis resistance.
The present invention is further illustrated by the following more specific examples, which are not intended to limit the scope of the invention in any way.
The following examples or comparative examples used the following sources of starting materials:
table 1 examples reagent table
The catalysts and mixing assistants in the following examples and comparative examples were added based on the total mass of the raw materials described in claim 1.
Example 1
A thermoplastic polyurethane elastomer comprising the following components:
20.39 parts of diphenylmethane diisocyanate;
69.00 parts of polybutylene adipate glycol;
2.03 parts of 1, 4-butanediol;
6.42 parts of castor oil alcohol;
2.16 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R1Is composed of
The preparation method comprises the following steps:
(1) feeding a reaction mixture to a heated extruder, said reaction mixture comprising (a) diphenylmethane diisocyanate, (b) polytetramethylene glycol adipate, (c) ricinoleyl alcohol, (d) bishydroxy polyhedral oligomeric silsesquioxane, (e)1, 4-butanediol, (f) a catalyst, (g) a mixing aid;
(2) reacting the components in the step (1) in the heated extruder by a one-step polymerization method to form the thermoplastic polyurethane elastomer, wherein the temperature of the extruder is set to be 140-220 ℃, and preferably 140-230 ℃;
(3) and cooling the thermoplastic polyurethane elastomer, and crushing and granulating.
The above preparation method is applicable to all examples and comparative examples.
Example 2
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
45.21 parts of diphenylmethane diisocyanate;
27.00 parts of polybutylene adipate glycol;
5.30 parts of 1, 4-butanediol;
16.85 parts of hydrogenated castor oil alcohol;
5.64 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R1Is composed of
The preparation method is the same as example 1.
Example 3
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
27.94 parts of diphenylmethane diisocyanate;
50.00 parts of polybutylene adipate glycol;
2.65 parts of 1, 4-butanediol;
16.59 parts of ricinoleic acid and ricinoleic acid castor alcohol ester glycol;
2.82 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R1Is composed of
The preparation method is the same as example 1.
Example 4
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
37.98 parts of diphenylmethane diisocyanate;
25.00 parts of polybutylene adipate glycol;
8.87 parts of 1, 4-butanediol;
25.00 parts of poly castor oil adipate glycol;
3.15 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the number average molecular weight of the poly castor oil adipate diol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R1Is composed of
The preparation method is the same as example 1.
Example 5
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
37.63 parts of diphenylmethane diisocyanate;
20.00 parts of polybutylene adipate glycol;
8.70 parts of 1, 4-butanediol;
30.00 parts of poly (hydrogenated castor oil adipate) glycol;
3.67 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the hydrogenated castor oil adipate diol has a number average molecular weight of 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R1Is composed of
The preparation method is the same as example 1.
Example 6
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
37.93 parts of diphenylmethane diisocyanate;
10.00 parts of polybutylene adipate glycol;
8.71 parts of 1, 4-butanediol;
40.00 parts of poly (hydrogenated castor oil adipate) glycol;
3.36 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the hydrogenated castor oil adipate diol has a number average molecular weight of 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R2Is composed of
The preparation method is the same as example 1.
Example 7
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
30.83 parts of diphenylmethane diisocyanate;
10.00 parts of polybutylene adipate glycol;
5.18 parts of 1, 4-butanediol;
50.00 parts of poly castor oil adipate glycol;
3.99 parts of diamino cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3 parts of a mixing assistant.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the number average molecular weight of the poly castor oil adipate diol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R2Is composed of
The preparation method is the same as example 1.
Example 8
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
37.52 parts of diphenylmethane diisocyanate;
20.00 parts of polybutylene adipate glycol;
8.66 parts of 1, 4-butanediol;
30.00 parts of poly castor oil adipate glycol;
3.82 parts of dihydroxy cage type silsesquioxane;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the number average molecular weight of the poly castor oil adipate diol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
wherein the dihydroxyl cage type silsesquioxane has a structure of
Wherein R is
R2Is composed of
The preparation method is the same as example 1.
Comparative example 1
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
33.39 parts of diphenylmethane diisocyanate;
60.00 parts of polybutylene adipate glycol;
6.61 parts of 1, 4-butanediol;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
the preparation method is the same as example 1.
Comparative example 2
A thermoplastic polyurethane elastomer comprising the following components, based on the total weight of the thermoplastic polyurethane elastomer:
40.07 parts of diphenylmethane diisocyanate;
25.00 parts of polybutylene adipate glycol;
9.93 parts of 1, 4-butanediol;
25.00 parts of poly castor oil adipate glycol;
0.0001 part of dibutyltin dilaurate;
3.00 parts of a mixing auxiliary agent.
Wherein the number average molecular weight of the polybutylene adipate glycol is 1000 g/mol;
wherein the number average molecular weight of the poly castor oil adipate diol is 1000 g/mol;
wherein the isocyanate index of the thermoplastic polyurethane elastomer is 1;
the preparation method is the same as example 1.
The examples and comparative examples are listed below:
the products obtained in the above examples and comparative examples were subjected to a performance test in which a 2mm injection molded test piece was tested in accordance with ASTM D412; the hydrolysis resistance test conditions are as follows: the 2mm injection molding test piece is soaked in deionized water at 80 ℃ for 1 week, 4 weeks and 8 weeks, then dried in an oven at 80 ℃ for 8 hours, placed in a standard laboratory environment for 8 hours, and then tested according to the ASTM D412 standard for tensile strength retention rate, and the test results are as follows:
from the above results, it can be seen that the R value and the hard segment content of example 7 of the present invention are the same as those of comparative example 1, and compared to comparative example 1 without adding castor oil based diol and hydroxyl or amino cage silsesquioxane, the tensile strength of the thermoplastic polyurethane elastomer of the present invention is improved by 17.7MPa, the retention rate of tensile strength at 1 week is 16.5% higher, the retention rate of tensile strength at 4 weeks is 45.2% higher, and the retention rate of tensile strength at 8 weeks can still reach 40.7%, but comparative example 1 has been cracked within 8 weeks and tensile strength cannot be tested; the R value and the hard segment content of the thermoplastic polyurethane elastomer in the embodiment 6 are the same as those of the comparative example 2, and compared with the comparative example 2 in which only the castor oil based diol is added but no hydroxyl or amino cage type silsesquioxane is added, the tensile strength of the thermoplastic polyurethane elastomer is improved by 18MPa, the retention rate of the tensile strength at 1 week is higher by 3.8%, the retention rate of the tensile strength at 4 weeks is higher by 19.2%, and the retention rate of the tensile strength at 8 weeks is higher by 13.4%. Therefore, the TPU material prepared by adding the cage-type silsesquioxane while using the castor oil-based diol can greatly improve the hydrolysis resistance while keeping higher tensile strength, and can meet the performance requirements of wading materials.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (11)
1. A thermoplastic polyurethane elastomer material comprising, based on the total weight of the thermoplastic polyurethane elastomer:
(1) 20-50 wt% of diisocyanate, preferably 23-45 wt%;
(2) 10-70 wt% of macromolecular dihydric alcohol, preferably 10-50 wt%;
(3) 5-50 wt% of castor oil based diol, preferably 15-50 wt%;
(4) 2-10 wt%, preferably 3-6 wt% of hydroxyl or amino cage type silsesquioxane;
(5) 2-20 wt% of chain extender, preferably 3-10 wt%.
2. The thermoplastic polyurethane elastomer material according to claim 1, wherein the diisocyanate is selected from aromatic and/or aliphatic diisocyanates; preferably, the aromatic diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), Xylylene Diisocyanate (XDI), and the aliphatic diisocyanate is selected from Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (H)12MDI), 1, 4-cyclohexyl dimethylene diisocyanate (CHDI).
3. The thermoplastic polyurethane elastomer material according to claim 1, wherein the macrodiol is selected from polyester diol and/or polycaprolactone diol obtained by condensation of dibasic acid and diol, polycarbonate diol; preferably, the polyester diol is selected from one or more of polyethylene adipate diol, polybutylene adipate diol, and polyhexamethylene adipate diol; more preferably, the number average molecular weight of the macrodiol is 500 to 4000g/mol, and further preferably 1000 to 2000 g/mol.
4. The thermoplastic polyurethane elastomer material according to claim 1, wherein the castor oil based diol is selected from the group consisting of castor oil alcohol, modified castor oil alcohol, and castor oil based diol obtained by polycondensation of alkyd; preferably, the castor oil based diol obtained by alkyd polycondensation is a diol obtained by polycondensation of ricinol or modified ricinol and a dibasic acid, or ricinoleic acid or modified ricinoleic acid and a diol, or ricinol or modified ricinoleic alcohol and ricinoleic acid or modified ricinoleic acid through alkyd polycondensation.
5. The thermoplastic polyurethane elastomer material according to claim 1, wherein the hydroxyl or amino cage silsesquioxane steric structure is T8, T10 or T12, preferably in T8 cubic configuration; preferably, the hydroxyl or amino cage type silsesquioxane has the hydroxyl or amino number of 2; more preferably, the structural schematic diagram of the hydroxyl or amino cage-type silsesquioxane is as follows:
wherein R is alkylene, alkyl or phenyl, R1Is a straight-chain alkyl, branched-chain alkyl or cyclic alkyl containing double hydroxyl or double amino and consisting of 3 to 10 carbon atoms, wherein in the structures of the straight-chain alkyl and the branched-chain alkyl, two hydroxyl/amino are ortho-position structures and one of the hydroxyl/amino is an end group, in the structure of the cyclic alkyl, two hydroxyl/amino are ortho-position structures, R is2Is a straight or branched chain alkyl group containing a terminal hydroxyl group or a terminal amino group consisting of 2 to 10 carbon atoms.
6. The thermoplastic polyurethane elastomer material according to claim 1, wherein the chain extender is selected from the group consisting of small molecule diols or diamines; preferably, the dihydric alcohol is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, hydroquinone dihydroxyethyl ether; the diamine is selected from one or more of 3,3 '-dichloro-4, 4' -diphenylmethane diamine, diethyl toluene diamine, and 3, 5-diamino isobutyl p-chlorobenzoate.
7. The thermoplastic polyurethane elastomer material according to claim 1, wherein the isocyanate index (-NCO to-OH molar ratio) is 0.8 to 1.2, preferably 0.95 to 1.05.
8. The thermoplastic polyurethane elastomer material according to any one of claims 1 to 7, wherein the raw materials for preparing the thermoplastic polyurethane elastomer material further comprise a catalyst and a mixing aid, the mixing aid comprises a light stabilizer, an antioxidant and a hydrolysis stabilizer, the addition amount of the catalyst and the mixing aid is based on the total mass of all the components in claim 1, the addition amount of the catalyst is 1 to 18ppm, and the addition amount of the mixing aid is 2 to 5 wt%.
9. The process for producing a thermoplastic polyurethane elastomer from the thermoplastic polyurethane elastomer material according to any one of claims 1 to 8, which comprises the steps of:
(1) adding the components of claim 1 into a heated extruder in a certain proportion, wherein a small amount of catalyst and mixing auxiliary agent are added in addition to diisocyanate, macrodiol, castor oil based diol, dihydroxy/amino cage type silsesquioxane and chain extender;
(2) reacting the components recited in (1) in the heated extruder in a one-step polymerization process to form a thermoplastic polyurethane elastomer; preferably, the extruder temperature is set between 80-240 ℃;
(3) and cooling the thermoplastic polyurethane elastomer, crushing and granulating.
10. The thermoplastic polyurethane elastomer prepared by the method of claim 9, wherein the tensile strength of the 2mm injection molded piece is greater than or equal to 45MPa according to the test of ASTM D412, and the 2mm injection molded piece is soaked in deionized water at 80 ℃ for 1 week, the retention rate of the tensile strength is greater than or equal to 90 percent, the soaking time is 4 weeks, the retention rate of the tensile strength is greater than or equal to 65 percent, the soaking time is 8 weeks, and the retention rate of the tensile strength is greater than or equal to 30 percent.
11. The thermoplastic polyurethane elastomer of claim 10, which is useful for the production of injection molded and extruded articles, preferably conveyor belts, seals, submarine cables, water pipes, which have high requirements on hydrolysis resistance and physical strength.
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