CN111303371A - Antibacterial, mildewproof, antistatic and yellowing-resistant TPU - Google Patents
Antibacterial, mildewproof, antistatic and yellowing-resistant TPU Download PDFInfo
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- CN111303371A CN111303371A CN202010291950.XA CN202010291950A CN111303371A CN 111303371 A CN111303371 A CN 111303371A CN 202010291950 A CN202010291950 A CN 202010291950A CN 111303371 A CN111303371 A CN 111303371A
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/40—High-molecular-weight compounds
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention relates to an antibacterial, antistatic and yellowing-resistant TP which comprises, by weight, 45-70 parts of high-molecular polyol, 5-12 parts of 1, 4-butanediol, 0.4-1 part of ethylenediamine, 35-40 parts of isocyanate (MDI), 0.1-1.5 parts of hexadecyl trimethyl ammonium chloride, 0.1-1.0 part of nano zinc oxide, 0.5-1 part of antioxidant and 0.5-1 part of anti-UV agent; according to the invention, the nano zinc oxide and the hexadecyl trimethyl ammonium chloride are soaked in the high molecular polyol in advance, so that no agglomeration is generated during chain extension reaction, the transparency and yellowing resistance of the TPU are affected, and the TPU can be fully dispersed in the colloid to more effectively exert the bacteriostatic property.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to an antibacterial, mildewproof, antistatic and yellowing-resistant TPU.
Background
In recent years, various public health safety incidents appear endlessly in the global scope, so the requirements on the materials of medical instruments are higher and higher, and for the TPU material used for the medical instruments, the TPU material not only needs to have certain antibacterial and bacteriostatic properties, but also needs to have certain yellowing resistance so as to ensure that the TPU material cannot easily change color and influence the use after being used for a long time, so the antistatic yellowing-resistant TPU is needed at present
Currently, bacteriostatic agents mainly include three main categories, i.e., inorganic bacteriostatic agents, organic bacteriostatic agents and natural bacteriostatic agents, wherein the inorganic bacteriostatic agent has the best effect and the longest duration, and is an ideal bacteriostatic agent, and if the inorganic bacteriostatic agent is directly added into the TPU, the inorganic bacteriostatic agent can influence the yellowing resistance of the TPU, so that the service life of the TPU is reduced, and therefore, the TPU which can resist bacteria and has the yellowing resistance is urgently needed at present.
Disclosure of Invention
The invention provides an antibacterial, mildewproof, antistatic and yellowing-resistant TPU (thermoplastic polyurethane), which is characterized by comprising, by weight, 45-70 parts of high-molecular polyol, 5-12 parts of 1, 4-butanediol, 0.4-1 part of ethylenediamine, 35-40 parts of isocyanate (MDI), 0.1-1.5 parts of hexadecyltrimethylammonium chloride, 0.1-1.0 part of nano zinc oxide, 0.5-1 part of antioxidant and 0.5-1 part of anti-UV (ultraviolet) agent.
Preferably, the high molecular polyol is polyether type dihydric alcohol, or the mixture of polyether type dihydric alcohol and polyester type dihydric alcohol;
the molecular weight of the polyether type dihydric alcohol is 1000-2000, the hydroxyl value is 56mg KOH/g, and the polyether type dihydric alcohol is prepared from PTMEG or PPG;
the polyester type dihydric alcohol is AA-14BG type, the molecular weight is 1000-3000, and the hydroxyl value is 56mg KOH/g.
A manufacturing method of antibacterial antistatic TPU comprises the following steps:
step A: mixing and standing high molecular polyol, hexadecyl trimethyl ammonium chloride and nano zinc oxide with the formula weight to fully infiltrate the hexadecyl trimethyl ammonium chloride and the nano zinc oxide;
and B: adding the isocyanate, 1, 4-butanediol and ethylenediamine in the formula ratio into the product obtained in the step A, and intensively mixing;
and C: injecting the product obtained after mixing in the step A into a double-screw machine, and setting the temperature of screws to be more than or equal to 150 ℃;
step D: and D, putting the product extruded by the double-screw extruder in the step B into water of 20 ℃ to complete granulation.
Preferably, the TPU has a hardness of from 70A to 98A.
Preferably, the hexadecyl trimethyl ammonium chloride and the ethylenediamine are subjected to negative pressure dewatering before the reaction in the step A, so that the water content is reduced by 200 PPM.
Preferably, 0.5 to 2% of the 1, 4-butanediol is involved in the chain extension reaction.
The invention has the beneficial effects that: the description is combined with the specification for specific description.
Drawings
FIG. 1 shows the results of several experiments according to the present invention.
Detailed Description
Experimental materials:
1, 4-butanediol short chain
Ethylene diamine-bacteriostat, short chain
Isocyanate (MDI) -chain extender
Cetyl trimethyl ammonium chloride bacteriostatic agent
Nano zinc oxide-bacteriostatic agent
Antioxidant powder
anti-UV agent
Polyether glycol (PTMEG type or PPG type, molecular weight 1000-2000) -long chain with hydroxyl value of 56mg KOH/g
Polyester type diol having hydroxyl value of 56mg KOH/g (AA-14BG type, i.e., diol polymerized from AA and 14BG, molecular weight of 1000-3000) — Long-chain diol
Experimental equipment: double-screw machine
Material pretreatment:
the hexadecyl trimethyl ammonium chloride and the ethylenediamine are respectively subjected to negative pressure dewatering to ensure that the water content is lower than 200PPM, and the specific method is to continue for 4-8 hours at the temperature of 120 ℃ under the condition of negative pressure.
The first embodiment is as follows:
step 1: according to the weight components, 72 parts of PTMEG type polyether glycol, 1 part of hexadecyl trimethyl ammonium chloride and 0.6 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the PTMEG type polyether glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully soaked.
Step 2: 4 parts of 1, 4-butanediol and 0.4 part of ethylenediamine are added to the product obtained in step 1, and then 20 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
Example two
Step 1: according to the weight components, 50 parts of PTMEG type polyether glycol, 1.2 parts of hexadecyl trimethyl ammonium chloride and 0.8 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the PTMEG type polyether glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully soaked.
Step 2: 9 parts of 1, 4-butanediol and 1 part of ethylenediamine are added to the product obtained in step 1, and 37 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
Example three:
step 1: according to the weight components, 50 parts of PPG type polyether glycol, 1.2 parts of hexadecyl trimethyl ammonium chloride and 0.8 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the PPG type polyether glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully soaked.
Step 2: 9 parts of 1, 4-butanediol and 1 part of ethylenediamine are added to the product obtained in step 1, and then 20 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
Example four:
step 1: according to the weight components, 50 parts of PTMEG type polyether glycol, 20 parts of AA-BG type polyester glycol, 1 part of hexadecyl trimethyl ammonium chloride and 0.6 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the mixture of the PTMEG type polyether glycol and the AA-BG type polyester glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully soaked.
Step 2: 4 parts of 1, 4-butanediol and 0.4 part of ethylenediamine are added to the product obtained in step 1, and then 20 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
Example five:
step 1: according to the weight components, 30 parts of PTMEG type polyether glycol, 20 parts of AA-BG type polyester glycol, 1.2 parts of hexadecyl trimethyl ammonium chloride and 0.8 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the mixture of the PTMEG type polyether glycol and the AA-BG type polyester glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully infiltrated.
Step 2: 9 parts of 1, 4-butanediol and 1 part of ethylenediamine are added to the product obtained in step 1, and 37 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
Example six:
step 1: according to the weight components, 30 parts of PPG type polyether glycol, 20 parts of AA-BG type polyester glycol, 1.2 parts of hexadecyl trimethyl ammonium chloride and 0.8 part of nano zinc oxide are taken, then the hexadecyl trimethyl ammonium chloride and the nano zinc oxide with the formula amount are all put into the PPG type polyether glycol, stirred and mixed, and kept stand for at least 12 hours to enable the hexadecyl trimethyl ammonium chloride and the nano zinc oxide to be fully infiltrated.
Step 2: 9 parts of 1, 4-butanediol and 1 part of ethylenediamine are added to the product obtained in step 1, and then 20 parts of isocyanate are added to the mixture so that the isocyanate index is 1.
And step 3: 0.5 part of antioxidant and 0.5 part of UV resistant agent are mixed with the product obtained in step 2.
And 4, step 4: and (4) putting the product obtained in the step (3) into a double-screw machine, and setting the temperature of the screws to be 150 ℃.
And 5: and (4) putting the granules extruded in the step (4) into water of 20 ℃ to complete granulation.
The description is given by way of example using the "one-shot" method in the TPU industry and is not intended as a limitation on the scope of the practice of the invention.
The test results are shown in fig. 1 (note: the result of the yellowing resistant project is obtained by the anti-UV test, the "grade" is divided into 5 grades, the higher the grade is, the better the yellowing resistant performance is, the "grade" and the color difference are in a negative correlation relationship, and the formula of the color difference is as follows:
)。
in conclusion:
the invention has the characteristics of high transparency, yellowing resistance, bacteria resistance and static resistance.
In the invention, the nano zinc oxide and the hexadecyl trimethyl ammonium chloride are soaked in the high molecular polyol in advance, so that no agglomeration is generated during chain extension reaction, the transparency and yellowing resistance of the TPU are influenced, and the TPU can be fully dispersed in the colloid to more effectively exert the bacteriostatic property;
one part of 1,4 butanediol participates in polymerization reaction and is used for forming- (HNCOO) -, the other part of the 1,4 butanediol is combined with a side chain through a hydrogen bond to improve the wear resistance, the elongation rate and the tensile strength of the product, and the nano zinc oxide and the hexadecyl trimethyl ammonium chloride are adsorbed through Van der Waals force, so that the product is more durable.
The above-described embodiments are merely preferred examples of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications in the structure, features and principles of the invention described in the claims should be included in the claims.
Claims (6)
1. The antibacterial, mildewproof, antistatic and yellowing-resistant TPU is characterized by comprising, by weight, 45-70 parts of high-molecular polyol, 5-12 parts of 1, 4-butanediol, 0.4-1 part of ethylenediamine, 35-40 parts of isocyanate (MDI), 0.1-1.5 parts of hexadecyltrimethylammonium chloride, 0.1-1.0 part of nano-zinc oxide, 0.5-1 part of antioxidant and 0.5-1 part of anti-UV agent.
2. The antibacterial, mildewproof, antistatic and yellowing-resistant TPU of claim 1, wherein the polymer polyol is polyether glycol or a mixture of polyether glycol and polyester glycol;
the molecular weight of the polyether type dihydric alcohol is 1000-2000, the hydroxyl value is 56mg KOH/g, and the polyether type dihydric alcohol is prepared from PTMEG or PPG;
the polyester type dihydric alcohol is AA-14BG type, the molecular weight is 1000-3000, and the hydroxyl value is 56mg KOH/g.
3. A method for producing the antibacterial, mildewproof, antistatic and yellowing-resistant TPU as set forth in claims 1-2, comprising the steps of:
step A: mixing and standing high molecular polyol, hexadecyl trimethyl ammonium chloride and nano zinc oxide with the formula weight to fully infiltrate the hexadecyl trimethyl ammonium chloride and the nano zinc oxide;
and B: adding the isocyanate, 1, 4-butanediol and ethylenediamine in the formula ratio into the product obtained in the step A, and intensively mixing;
and C: injecting the product obtained after mixing in the step A into a double-screw machine, and setting the temperature of screws to be more than or equal to 150 ℃;
step D: and D, putting the product extruded by the double-screw extruder in the step B into water of 20 ℃ to complete granulation.
4. The antibacterial, mildewproof, antistatic and yellowing-resistant TPU prepared by the manufacturing method according to claim 2, wherein the hardness of the TPU is 70A-98A.
5. The antibacterial, mildewproof, antistatic and yellowing-resistant TPU of claim 1, wherein the cetyltrimethylammonium chloride and the ethylenediamine are subjected to negative pressure dewatering before the reaction of step A, so that the water content is reduced by 200 PPM.
6. The antibacterial, mildewproof, antistatic and yellowing-resistant TPU of any one of claims 1 to 5, wherein 0.5 to 2 percent of the 1, 4-butanediol participates in the chain extension reaction.
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| CN202010291950.XA CN111303371A (en) | 2020-04-14 | 2020-04-14 | Antibacterial, mildewproof, antistatic and yellowing-resistant TPU |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637318A (en) * | 2021-08-26 | 2021-11-12 | 东莞市米儿塑胶原料有限公司 | Preparation method of antibacterial TPU |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096408A (en) * | 2006-06-26 | 2008-01-02 | 山东东大一诺威聚氨酯有限公司 | Yellowing-resistant transparent polyurethane elastomer combined material and using method thereof |
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| CN104140517A (en) * | 2014-08-13 | 2014-11-12 | 厦门誉匠复合材料有限公司 | High transparency non-yellowing TPU (thermoplastic polyurethane) material and preparation method thereof |
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| CN101096408A (en) * | 2006-06-26 | 2008-01-02 | 山东东大一诺威聚氨酯有限公司 | Yellowing-resistant transparent polyurethane elastomer combined material and using method thereof |
| CN101402719A (en) * | 2008-11-18 | 2009-04-08 | 广州市鹿山化工材料有限公司 | Transparent high-elasticity thermoplastic polyurethane and method of producing the same |
| CN104140517A (en) * | 2014-08-13 | 2014-11-12 | 厦门誉匠复合材料有限公司 | High transparency non-yellowing TPU (thermoplastic polyurethane) material and preparation method thereof |
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| CN113637318A (en) * | 2021-08-26 | 2021-11-12 | 东莞市米儿塑胶原料有限公司 | Preparation method of antibacterial TPU |
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