CN110790889A - Polarity-controllable TPU film and preparation method thereof - Google Patents
Polarity-controllable TPU film and preparation method thereof Download PDFInfo
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- CN110790889A CN110790889A CN201911140380.8A CN201911140380A CN110790889A CN 110790889 A CN110790889 A CN 110790889A CN 201911140380 A CN201911140380 A CN 201911140380A CN 110790889 A CN110790889 A CN 110790889A
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Abstract
The invention provides a polarity-controllable TPU film, which is characterized in that the preparation raw materials of the polarity-controllable TPU film comprise the following components in parts by weight: 60-70 parts of polyester diol, 20-30 parts of diisocyanate, 1-10 parts of chain extender, 5-18 parts of lignin, 0.1-0.5 part of lubricant and 0.01-0.05 part of catalyst. The lignin and other raw materials are matched with each other for synergistic interaction, so that the polarity-controllable TPU film disclosed by the invention can simultaneously meet a wider polarity controllable range, and has excellent waterproof performance, moisture permeability and air permeability, mechanical strength and ageing resistance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a polarity-controllable TPU film and a preparation method thereof.
Background
The TPU film is a high molecular material generated by the joint reaction of diisocyanate, macromolecular polyol and a chain extender, and is alternately composed of a rigid chain segment and a flexible chain segment in terms of molecular structure, and the special molecular structure enables the TPU to have excellent performances such as high wear resistance, impact resistance, oil resistance, chemical resistance and the like which are incomparable with other thermoplastic elastic materials. The TPU film is mostly smooth in surface when in use, is inconvenient to use under certain conditions, is inconvenient to use due to lack of good high temperature resistance and oxidation resistance, is poor in air permeability, can cause stuffiness in the TPU film when in use, and is lack of good air permeability and moisture permeability; and because the polarity of the TPU film is generally determined by the types and the amount of the functional groups of the selected raw materials of diisocyanate and polyol, after the proper raw materials are selected and determined, the polarity of the TPU material can be generally changed only by a chain extender, and the polarity range of the TPU which can be changed is narrow, so that the TPU film has the limitations on the selection of the raw materials, and the synthesized TPU film has the defects of weaker waterproof performance, poorer moisture permeability and air permeability, low mechanical strength and narrow application range.
CN109401282A provides a high-softness TPU film for clothes and a preparation method thereof. The TPU film comprises the following raw material components in parts by weight: 25-35 parts of diisocyanate, 60-70 parts of oligomer polyol, 10-20 parts of organic silicon, 3-5 parts of chain extender containing acid groups, 3-5 parts of aliphatic diamine, 2-5 parts of hydroxyl phosphate and 1-3 parts of catalyst.
Therefore, how to obtain a TPU film with controllable polarity, high mechanical strength and good waterproof and moisture-permeable properties is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the TPU film which simultaneously has wide polarity controllable range, good waterproof performance, good moisture permeability and air permeability, high mechanical strength and strong aging resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polarity-controllable TPU film, which is prepared from the following raw materials in parts by weight:
in the present invention, the polyester diol may be present in an amount of 60 to 70 parts by weight, for example, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, or 70 parts by weight.
In the present invention, the diisocyanate is used in an amount of 20 to 30 parts by weight, and may be, for example, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight or 30 parts by weight.
In the present invention, the weight part of the chain extender is 1 to 10 parts by weight, and may be, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
In the present invention, the weight part of lignin is 5 to 18 parts by weight, and may be, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, or 18 parts by weight.
In the present invention, the lubricant is used in an amount of 0.1 to 0.5 parts by weight, and may be, for example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, or 0.5 part by weight.
In the present invention, the weight part of the catalyst is 0.01 to 0.05 part by weight, and may be, for example, 0.01 part by weight, 0.02 part by weight, 0.03 part by weight, 0.04 part by weight, or 0.05 part by weight.
Lignin, as a second largest natural polymer, can physically or chemically bond and strengthen in TPU materials, increasing the mechanical strength and resistance to microbial attack of TPU films. The lignin-based TPU film has the advantage of controllable polarity due to the existence of the lignin three-dimensional network structure, and has the advantage of controllable reaction due to the weak reaction activity of the lignin-based TPU film compared with an isocyanate monomer.
Meanwhile, the lignin is added into a TPU system as an active filler, plays the roles of a cross-linking agent and a filling agent, has good compatibility with the TPU, and is easy to prepare homogeneous materials. Lignin is introduced in the synthesis of TPU so as to reduce the consumption of raw materials, and because phenol of the lignin can terminate free radicals through a radical structural unit, the material failure caused by ultraviolet light aging is reduced. Meanwhile, the rigid chain segment of the lignin can enhance the mechanical strength of the TPU, expand the polarity controllable range of the TPU film and improve the use temperature range of the TPU film.
Preferably, the polyester diol is any one of or a mixture of at least two of polyethylene adipate diol, polycaprolactone diol or polycarbonate diol.
Preferably, the molecular weight of the polyester diol is 500-.
Preferably, the diisocyanate is any one or a mixture of at least two of 4,4' -diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, phenylene-1, 4-diisocyanate, isophorone diisocyanate, toluene diisocyanate or 1, 5-naphthalene diisocyanate, and is preferably 4,4' -diphenylmethane diisocyanate and/or isophorone diisocyanate.
Preferably, the chain extender is a small molecule diol.
Preferably, the small molecule dihydric alcohol is any one or a mixture of at least two of 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol or 1, 3-butanediol.
Preferably, the lignin is any one of acid-precipitated lignin, hydroxymethylated lignin or acetylated hydroxymethylated lignin or a mixture of at least two of them.
In the invention, after selecting and determining a proper raw material, the invention not only controls the polarity change range of the TPU by adding lignin with different functional groups, thereby eliminating the limitation of the TPU film on the selection of the raw material, but also greatly improving the waterproof performance, the moisture permeability and air permeability, the mechanical strength and the aging resistance of the TPU film synthesized under a certain raw material by adding the lignin.
Preferably, the lubricant is any one of or a mixture of at least two of glyceryl monostearate, stearic acid amide, ethylene bis stearic acid amide, E wax or oleic acid amide.
Preferably, the catalyst is any one or a mixture of at least two of organic tin, organic bismuth or organic zinc, and is preferably dibutyl tin dilaurate.
In a second aspect, the present invention provides a preparation method of a polarity-controllable TPU film, comprising the steps of:
(1) weighing lignin and polyester dihydric alcohol according to the formula ratio, and uniformly mixing;
(2) adding the diisocyanate, the chain extender, the catalyst and the lubricant in the formula amount into the mixture obtained in the step (1), uniformly mixing, drying and extruding to obtain the TPU film.
Preferably, the mixing temperature in step (1) is 20-40 deg.C, such as 20 deg.C, 22 deg.C, 24 deg.C, 26 deg.C, 28 deg.C, 30 deg.C, 32 deg.C, 34 deg.C, 36 deg.C, 38 deg.C or 40 deg.C.
Preferably, the mixing time in step (1) is 0.5-2h, for example, 0.5h, 0.7h, 0.9h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h or 2 h.
Preferably, the mixing temperature in step (2) is 15-30 deg.C, such as 15 deg.C, 17 deg.C, 19 deg.C, 21 deg.C, 23 deg.C, 25 deg.C, 27 deg.C, 29 deg.C or 30 deg.C.
Preferably, the mixing time in step (2) is 1-3h, for example, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.3h, 2.5h, 2.7h, 2.9h or 3 h.
Preferably, the drying temperature in step (2) is 80-100 deg.C, such as 80 deg.C, 81 deg.C, 83 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 94 deg.C, 96 deg.C, 98 deg.C or 100 deg.C.
Preferably, the drying time in step (2) is 2-3h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h or 3 h.
Preferably, the method comprises the steps of:
(1) weighing lignin and polyester dihydric alcohol according to the formula ratio, and stirring for 0.5-2h at 20-40 ℃ to mix uniformly;
(2) adding the diisocyanate, the chain extender, the catalyst and the lubricant in the formula amount into the mixture obtained in the step (1), stirring for 1-3h at 15-30 ℃, uniformly mixing, drying for 2-3h at 80-100 ℃, and extruding to obtain the TPU film.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lignin and other raw materials are matched with each other for synergism, so that the polarity-controllable TPU film has a wider polarity change range, and the polarity of the TPU film can be controlled by adjusting the functional group of the lignin.
(2) According to the invention, the lignin and other raw materials are mutually matched and synergized, so that the obtained TPU film has higher strength and waterproof moisture permeability, and the water vapor transmission rate of the sample is in the range of 9000-9900g/m224h, the tensile strength range is 160N/mm from 125-.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a polarity-controllable TPU film, which comprises the following raw material components in parts by weight: 66 parts of polyethylene glycol adipate glycol (molecular weight of 2000), 20 parts of 4,4' -diphenylmethane diisocyanate, 2 parts of 1, 3-propylene glycol, 11.75 parts of acid-precipitated lignin, 0.2 part of glycerol monostearate and 0.05 part of dibutyl tin dilaurate.
The preparation method of the polarity-controllable TPU film comprises the following steps:
(1) weighing acid-precipitated lignin and polyethylene glycol adipate glycol according to the formula ratio, and stirring for 2 hours at the temperature of 20 ℃ to uniformly mix;
(2) adding the 4,4' -diphenylmethane diisocyanate, 1, 3-propylene glycol, dibutyltin dilaurate and glyceryl monostearate in the formula ratio into the mixture obtained in the step (1), stirring for 3 hours at 20 ℃, uniformly mixing, drying for 3 hours at 100 ℃, and extruding to obtain the TPU film.
Example 2
The same as example 1, except that the lignin is hydroxymethylated lignin, and the contents of other components and the preparation method are unchanged.
Example 3
The same as example 1, except that the lignin is acetylated hydroxymethylated lignin, and the contents of other components and the preparation method are unchanged.
Example 4
The embodiment provides a polarity-controllable TPU film, which comprises the following raw material components in parts by weight: 60 parts of polycaprolactone diol (with the molecular weight of 1500), 20 parts of isophorone diisocyanate, 1.85 parts of 1, 4-butanediol, 18 parts of acid-precipitated lignin, 0.1 part of glycerol monostearate and 0.05 part of dibutyl tin dilaurate.
The preparation method of the polarity-controllable TPU film comprises the following steps:
(1) weighing the acid-precipitated lignin and the polycaprolactone diol according to the formula ratio, and stirring for 0.5h at 40 ℃ to mix uniformly;
(2) adding isophorone diisocyanate, 1, 4-butanediol, dibutyl tin dilaurate and glyceryl monostearate into the mixture obtained in the step (1), stirring for 1h at 30 ℃, uniformly mixing, drying for 2h at 80 ℃, and extruding to obtain the TPU film.
Example 5
The embodiment provides a polarity-controllable TPU film, which comprises the following raw material components in parts by weight: 70 parts of poly hexamethylene carbonate diol (molecular weight is 2000), 20 parts of isophorone diisocyanate, 4.49 parts of 2-methyl-1, 3-propylene glycol, 5 parts of acid-precipitated lignin, 0.5 part of stearic acid amide and 0.01 part of dibutyl tin dilaurate.
The preparation method of the polarity-controllable TPU film comprises the following steps:
(1) weighing acid-precipitated lignin and poly (hexanediol carbonate) glycol according to the formula ratio, and stirring for 0.5h at 40 ℃ to mix uniformly;
(2) adding isophorone diisocyanate, 2-methyl-1, 3-propylene glycol, dibutyl tin dilaurate and stearic acid amide into the mixture obtained in the step (1), stirring for 1h at 30 ℃, uniformly mixing, drying for 2h at 80 ℃, and extruding to obtain the TPU film.
Example 6
As in example 5, the only difference is that the lignin is an aliphatic thiol lignin.
Example 7
The embodiment provides a polarity-controllable TPU film, which comprises the following raw material components in parts by weight: 60 parts of polytetramethylene ether glycol (molecular weight is 3000), 30 parts of 4,4' -dicyclohexylmethane diisocyanate, 2 parts of 1, 3-propylene glycol, 7.49 parts of aliphatic mercaptan lignin, 0.5 part of stearic acid amide and 0.01 part of bismuth carboxylate.
The preparation method of the polarity-controllable TPU film comprises the following steps:
(1) weighing aliphatic mercaptan lignin and polytetramethylene ether glycol according to the formula ratio, and stirring for 0.5h at 40 ℃ to mix uniformly;
(2) adding the formula amount of 4,4' -dicyclohexylmethane diisocyanate, 1, 3-propylene glycol, bismuth carboxylate and stearic acid amide into the mixture obtained in the step (1), stirring for 1h at 30 ℃, uniformly mixing, drying for 2h at 80 ℃, and extruding to obtain the TPU film.
Comparative example 1
The difference from example 1 is only that the chain extender is 13.75 parts by weight, no lignin is contained, and the contents of other components and the preparation method are unchanged.
Comparative example 2
The difference is only that the lignin content is 13.75 parts by weight, the chain extender is not contained, and the contents of other components and the preparation method are not changed as in example 1.
Comparative example 3
The difference from example 1 is only that 31.75 parts by weight of 4,4' -diphenylmethane diisocyanate contained no lignin, and the contents of other components and preparation method were unchanged.
Comparative example 4
The only difference from example 1 is that the polyethylene glycol adipate diol is 77.75 parts by weight, no lignin is contained, and the contents of other components and the preparation method are unchanged.
Comparative example 5
The only difference from example 1 is that 72 parts by weight of polyethylene glycol adipate diol, 25.75 parts by weight of 4,4' -diphenylmethane diisocyanate, no lignin, and the contents of other components and preparation method were the same.
Comparative example 6
The only difference from example 1 is that the polyester diol is poly (hexanediol carbonate) diol, 77.75 parts by weight, no lignin is contained, and the contents of other components and the preparation method are unchanged.
Comparative example 7
The difference from example 1 is only that 50 parts by weight of polyethylene glycol adipate glycol, 10 parts by weight of 4,4' -diphenylmethane diisocyanate, 9.75 parts by weight of 1, 3-propanediol and 30 parts by weight of acid-precipitated lignin are contained, and the contents of other components and the preparation method are not changed.
The TPU thin film materials prepared in the above examples 1-7 and comparative examples 1-6 are subjected to a water absorption test contact angle test (contact angle measuring instrument HARGE-SPCAX 2), a hydrostatic pressure resistance (measuring method GB/74744-1997), a water vapor transmission rate (measuring method GB/T1037-2000), a flexibility (namely tensile strength, measuring method GB/T528-2009) test, a tearing strength (measuring method GB/T16578.1-2008), a breaking elongation (measuring method GB/T528-2009), an aging yellowing index delta Yi (measuring method GB2409-88) under ultraviolet irradiation (no color change delta Yi is less than or equal to 1.5, a very slight color change 1.6< delta Yi is less than or equal to 3.0, a slight color change 3.1< delta Yi is less than or equal to 6.0, an obvious color change 6.1< delta Yi is less than or equal to 9.0, a large color change 9.1< delta Yi is less than or equal to 12.0, and a severe color change 12.0< delta Yi), the specific test results are shown in table 1 below:
TABLE 1
As can be seen from the data in Table 1, the water contact angles of the samples of examples 1-7 are 10-32 deg., indicating that the controllable range of polarity of the present invention is large; the hydrostatic pressure resistance ranges of the samples in examples 1-7 are between 9500-11000mm water columns, which shows that the polarity-controllable TPU film has extremely strong water-resistant stability; the water vapor transmission rate of the samples of examples 1 to 7 ranged from 9000-224h, the polarity-controllable TPU film has extremely strong moisture permeability and air permeability; the tensile strength range of the samples of examples 1-7 is 125-160N/mm, the tear strength range is 69-78MPa, and the elongation at break range is 680-765%, which shows that the polarity-controllable TPU film of the invention has high mechanical strength; the aging yellowing index delta Yi under the irradiation of ultraviolet light is in the range of 0.7-1.6, and basically does not change color, which shows that the polarity-controllable TPU film has strong aging resistance.
It can be seen from the sample test data of comparative examples 1-2 that, lacking any one of the components of lignin and the chain extender, the adjustable range of the polarity of the TPU film becomes very small, and the reduction of each mechanical strength is obvious, which proves that the lignin plays a main role in improving the performance of the TPU film, but the lignin and the chain extender are mutually matched and synergized to achieve the best waterproof performance, moisture permeability and air permeability, mechanical strength and aging resistance of the invention, which is absolutely indispensable; from the sample test data of comparative examples 3 to 6, it can be seen that the polarity change range of the TPU film was not adjusted by lignin, only by changing the content of the raw material and the kind of the polar functional group, the water contact angle was only changed between 20 ° to 25 °, the polarity range was not well adjusted, and the water resistance, moisture and air permeability, mechanical strength and aging resistance were poor; finally, it can be seen from the sample test data of comparative example 7 that when the lignin is excessive, i.e. the lignin content is not within the range, the water resistance, moisture permeability and air permeability, and various mechanical strengths are the worst, the anti-aging capability is extremely weak, the aging yellowing index Δ Yi under ultraviolet irradiation is 7.2, and the TPU film is significantly discolored.
In conclusion, the lignin and other raw materials are matched with each other for synergistic interaction, so that the polarity-controllable TPU film has a wider polarity change range, and the polarity of the TPU film can be controlled by the functional group of the lignin; meanwhile, the waterproof performance, the moisture permeability and the air permeability of the polarity-controllable TPU film are greatly improved, and various mechanical strengths of the polarity-controllable TPU film are greatly improved, and the aging degree under ultraviolet irradiation is greatly relieved.
The applicant states that the present invention is illustrated by the above examples of the polarity controllable TPU film of the present invention, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must rely on the above examples to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The polarity-controllable TPU film is characterized in that the polarity-controllable TPU film is prepared from the following raw materials in parts by weight:
2. the polarity controllable TPU film of claim 1 wherein the polyester diol is any one or a mixture of at least two of polyethylene adipate diol, polycaprolactone diol, or poly hexanediol carbonate diol;
preferably, the molecular weight of the polyester diol is 500-.
3. A polarity controllable TPU film as set forth in claim 1 or 2 wherein said diisocyanate is any one or a mixture of at least two of 4,4' -diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, phenylene-1, 4-diisocyanate, isophorone diisocyanate, toluene diisocyanate, or 1, 5-naphthalene diisocyanate, preferably 4,4' -diphenylmethane diisocyanate and/or isophorone diisocyanate.
4. The polarity controllable TPU film of any of claims 1-3 where the chain extender is a small molecule diol;
preferably, the small molecule dihydric alcohol is any one or a mixture of at least two of 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol or 1, 3-butanediol.
5. A polarity controlled TPU film as set forth in any one of claims 1 to 4 wherein said lignin is any one or a mixture of at least two of acid-precipitated lignin, hydroxymethylated lignin or acetylated hydroxymethylated lignin.
6. A polarity controlled TPU film as set forth in any one of claims 1 to 5 wherein said lubricant is any one or a mixture of at least two of glyceryl monostearate, stearamide, ethylene bis stearamide, E wax or oleamide.
7. A polarity controllable TPU film as set forth in any one of claims 1 to 6 wherein said catalyst is any one or a mixture of at least two of organotin, organobismuth or organozinc, preferably dibutyltin dilaurate.
8. A process for the preparation of a polarity controllable TPU film as claimed in any of claims 1 to 7, characterized in that the process for the preparation comprises the following steps:
(1) weighing lignin and polyester dihydric alcohol according to the formula ratio, and uniformly mixing;
(2) adding the diisocyanate, the chain extender, the catalyst and the lubricant in the formula amount into the mixture obtained in the step (1), uniformly mixing, drying and extruding to obtain the TPU film.
9. The method according to claim 8, wherein the mixing temperature in step (1) is 20-40 ℃;
preferably, the mixing time of the step (1) is 0.5-2 h;
preferably, the mixing temperature of the step (2) is 15-30 ℃;
preferably, the mixing time of the step (2) is 1-3 h;
preferably, the drying temperature in the step (2) is 80-100 ℃;
preferably, the drying time in step (2) is 2-3 h.
10. The method for preparing according to claim 8 or 9, characterized in that it comprises the following steps:
(1) weighing lignin and polyester dihydric alcohol according to the formula ratio, and stirring for 0.5-2h at 20-40 ℃ to mix uniformly;
(2) adding the diisocyanate, the chain extender, the catalyst and the lubricant in the formula amount into the mixture obtained in the step (1), stirring for 1-3h at 15-30 ℃, uniformly mixing, drying for 2-3h at 80-100 ℃, and extruding to obtain the TPU film.
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