CN114957963A - Preparation method of modified thermoplastic polyurethane resin - Google Patents
Preparation method of modified thermoplastic polyurethane resin Download PDFInfo
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Abstract
The invention relates to the field of macromolecules, in particular to a preparation method of modified thermoplastic polyurethane resin; the method provides that concentrated sulfuric acid, KMnO4 and H2O2 are used for oxidizing natural graphite powder to prepare graphene oxide; preparing graphene sheet grafted layered double hydroxide by using graphene oxide and amino modified layered double hydroxide; finally, grafting the layered double hydroxide by using thermoplastic polyurethane and graphene sheets to prepare modified thermoplastic polyurethane resin; the mechanical property analysis shows that: with the increase of the addition amount of the graphene sheet grafted layered double hydroxide, the tensile strength of the modified thermoplastic polyurethane resin is increased, and the graphene sheet grafted layered double hydroxide has an obvious reinforcing effect on the matrix thermoplastic polyurethane.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to a preparation method of modified thermoplastic polyurethane resin.
Background
The thermoplastic polyurethane has the advantages of wide raw material source, adjustable structure, biodegradability and the like, and has wide application prospect in the fields of packaging materials, coatings, aerospace, medicine and the like.
CN 202111595001.1: the invention relates to a modified polyurethane resin water-based paint with good flexibility, which comprises the following components in parts by weight: 60.0-150.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin, 0.4-1.0 part of flatting agent, 0.2-1.2 parts of dispersing agent, 0.4-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 3.0-7.0 parts of ethylene glycol, 1.5-5.0 parts of propylene glycol butyl ether, 1.5-5.0 parts of propylene glycol methyl ether acetate, 0.0-35.0 parts of pigment and filler, 0.5-1.0 part of sodium carboxymethylcellulose, 1.0-3.0 parts of polyvinyl alcohol, 0.4-1.0 part of sodium bicarbonate and 10.0-40.0 parts of deionized water; the modified polyurethane resin water-based paint with good flexibility is environment-friendly, has good sagging resistance, good impact resistance, high crosslinking density, good flexibility and other properties, and can be used for substrates of wood furniture, steel structures and the like.
CN 202111565055.3: the invention discloses a low-VOCs (volatile organic compounds) alcohol water-soluble PVP (polyvinyl pyrrolidone) modified polyurethane resin which comprises the following raw materials in parts by weight: 15-25 parts of polyether polyol, 5-10 parts of hydroxyl polyvinylpyrrolidone prepolymer, 2-5 parts of hydrophilic polyol, 1-5 parts of organic polyamine, 5-10 parts of diisocyanate, 49-52 parts of ethanol and 7-10 parts of deionized water. The polyurethane has better hydrophilicity, can adjust the ratio of alcohol to water in a large range and still has the dilutability, and is convenient for a terminal user to reasonably adjust the ratio of alcohol to water according to the equipment condition of the terminal user to improve the drying performance and ensure the production efficiency; meanwhile, the introduction of PVP greatly improves the wetting and dispersing capacity of the polyurethane on pigments, the excellent adhesive property of the PVP and the adhesion fastness of the polyurethane on various printing base materials such as OPP, PET, NY and the like.
CN 202111553461.8: the invention relates to the technical field of new materials, and discloses kaolin grafted polyphenyl ether modified polyurethane resin, wherein because styrene-butadiene rubber containing polybutadiene molecular chain segments is introduced on polyphenyl ether, and because of similar compatibility, stronger intermolecular force is generated between two phases, so that the dispersibility of the polyphenyl ether in a polyurethane matrix is effectively improved, the compatibilization effect on the polyphenyl ether is realized, kaolin with excellent mechanical property and fire resistance is grafted on a polyphenyl ether molecular chain, and after the polyphenyl ether is grafted by silane modification, the kaolin also has excellent dispersibility in the polyurethane matrix, so that the kaolin can play a role of heterogeneous nucleation during the curing of polyurethane, the crystallinity of the polyurethane is improved, the mechanical property of the polyurethane is enhanced, and the dispersed kaolin can also improve the heat resistance of the polyurethane, so that the polyurethane resin with excellent comprehensive performance is obtained, the application range of the polyurethane resin is widened.
The thermoplastic polyurethane prepared by the above patents and the prior art has the defects of low tensile strength, insufficient thermal stability, uncontrollable deformation recovery and the like, so that the application of the thermoplastic polyurethane is limited, and therefore, the modification research on the thermoplastic polyurethane has important significance.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a modified thermoplastic polyurethane resin, comprising the steps of:
weighing 25-35 parts of thermoplastic polyurethane and 0.2-1 part of graphene sheet grafted layered double hydroxide according to the mass parts, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 40-70r/min, and the temperature is 160-200 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.1-0.5 part of graphene oxide according to the mass parts, dissolving in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5-1 h;
s2: 0.1-0.5 part of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after 0.5-1h of ultrasonic treatment;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 20-35 ℃, stirring for reaction for 2-4h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 60-75 ℃ and the drying time is 20-24 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 90-120 parts by mass of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26-32 parts by mass of natural graphite powder and 13-17 parts by mass of NaNO3, uniformly mixing, adding 3-7 parts by mass of KMnO4, controlling the temperature at 15-20 ℃, and reacting for 5-10 min;
s2: controlling the reaction temperature to rise to 30-40 ℃, and stirring for 20-35min to complete the oxidation reaction;
s3: slowly adding 80-120 parts of deionized water, controlling the reaction temperature to rise to 85-100 ℃, reacting for 10-20min, and performing high-temperature hydrolysis;
s4: and finally, adding 15-18 parts of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 90-98%.
Preferably, the mass percent of the H2O2 solution is 20-30%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 10-20%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 30-40 parts by weight of intercalated layered double hydroxide into 300 parts by weight of water 200-5 parts, placing the mixture in an ultrasonic water bath tank for treatment for 2-6 hours, and adding 2-5 parts by weight of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 0.05-1.5 parts of 4,4' -diaminodiphenyl sulfide and 0.3-3 parts of semicarbazide, stirring, and carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
Preferably, the reaction time is 50-60 ℃, and the reaction temperature is 2-4 h.
The reaction mechanism is as follows:
the layered double hydroxide is aminated by 3-aminopropyltriethoxysilane, and is loaded with 4,4' -diaminodiphenyl sulfide and semicarbazide through interlayer intercalation to obtain amino modified layered double hydroxide, and then the amino modified layered double hydroxide and carboxyl of graphene oxide are subjected to grafting reaction to obtain graphene sheet grafted layered double hydroxide.
The technical effects are as follows:
the invention relates to a preparation method of modified thermoplastic polyurethane resin, which adopts a melt blending method to prepare a graphene sheet grafted layered double hydroxide/thermoplastic polyurethane composite material; mechanical property analysis shows that: with the increase of the addition amount of the graphene sheet grafted layered double hydroxide, the tensile strength of the modified thermoplastic polyurethane resin is increased, and the graphene sheet grafted layered double hydroxide has an obvious reinforcing effect on the matrix thermoplastic polyurethane.
Detailed Description
The invention is further illustrated by the following specific examples:
tensile property test was carried out on a CMT6104 electronic universal (tensile) testing machine (Shenzhen Sansi longitudinal and transverse technologies GmbH). The test is carried out at room temperature, the stretching rate is 50mm/min, and the average value of five samples in each ratio test is taken.
Example 1
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 25g of thermoplastic polyurethane and 0.2g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 40r/min, and the temperature is 160 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.1g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5 h;
s2: 0.1g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.5 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into a graphene oxide aqueous solution, controlling the reaction temperature to be 20 ℃, stirring for reaction for 2 hours, carrying out vacuum filtration, drying, and grafting the graphene sheets with the layered double hydroxide.
Preferably, the drying temperature is 60 ℃ and the drying time is 20 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 90g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26g of natural graphite powder and 13g of NaNO3, uniformly mixing, adding 3g of KMnO4, controlling the temperature at 15 ℃, and reacting for 5 min;
s2: controlling the reaction temperature to rise to 30 ℃, and stirring for 20min to complete the oxidation reaction;
s3: slowly adding 80g of deionized water, controlling the reaction temperature to rise to 85 ℃, reacting for 10min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 15g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 90%.
Preferably, the mass percent of the H2O2 solution is 20%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 10%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 30g of intercalated layered double hydroxide into 200g of water, placing the mixture in an ultrasonic water bath for treatment for 2 hours, and adding 2g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 0.05g of 4,4' -diaminodiphenyl sulfide and 0.3g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
Preferably, the reaction time is 50 ℃, and the reaction temperature is 2 h.
Example 2
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 28g of thermoplastic polyurethane and 0.5g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 50r/min, and the temperature is 170 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.2g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.6 h;
s2: 0.2g of amino modified layered double hydroxide is taken to be dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.6 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 25 ℃, stirring for reaction for 2.5h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 65 ℃ and the drying time is 21 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 100g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 28g of natural graphite powder and 14g of NaNO3, uniformly mixing, adding 4g of KMnO4, controlling the temperature at 16 ℃, and reacting for 6 min;
s2: controlling the reaction temperature to rise to 34 ℃, and stirring for 25min to complete the oxidation reaction;
s3: slowly adding 90g of deionized water, controlling the reaction temperature to rise to 90 ℃, reacting for 14min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 16g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the concentrated sulfuric acid is 92% by mass.
Preferably, the mass percent of the H2O2 solution is 24%.
Preferably, the mass percentage of the dilute hydrochloric acid solution is 14%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 34g of intercalated layered double hydroxide into 230g of water, placing the mixture in an ultrasonic water bath for treatment for 3 hours, and adding 3g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 0.5g of 4,4' -diaminodiphenyl sulfide and 1g of semicarbazide are kept stirred, and after reaction, the amino modified layered double hydroxide is obtained by suction filtration, washing and vacuum drying.
Preferably, the reaction time is 54 ℃ and the reaction temperature is 2.5 h.
Example 3
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 32g of thermoplastic polyurethane and 0.8g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 60r/min, and the temperature is 180 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.4g of graphene oxide, dissolving in 50mL of deionized water, carrying out ultrasonic treatment for 0.8h, and diluting the water solution to 400 mL;
s2: 0.4g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.8 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature at 30 ℃, stirring for reaction for 3.5h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 70 ℃ and the drying time is 23 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 110g of concentrated sulfuric acid with the temperature of 4 ℃ into a reactor, stirring, slowly adding 30g of natural graphite powder and 16g of NaNO3, uniformly mixing, then adding 6g of KMnO4, controlling the temperature at 18 ℃, and reacting for 9 min;
s2: controlling the reaction temperature to rise to 38 ℃, and stirring for 30min to complete the oxidation reaction;
s3: slowly adding 110g of deionized water, controlling the reaction temperature to rise to 95 ℃, reacting for 18min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 17g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 96%.
Preferably, the mass percent of the H2O2 solution is 28%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 18%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 38g of intercalated layered double hydroxide into 280g of water, placing the mixture in an ultrasonic water bath for treatment for 5 hours, and adding 4g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 1g of 4,4' -diaminodiphenyl sulfide and 2g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction, and obtaining the amino modified layered double hydroxide.
Preferably, the reaction time is 58 ℃ and the reaction temperature is 3.5 h.
Example 4
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 35g of thermoplastic polyurethane and 1g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 70r/min, and the temperature is 200 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.5g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after 1-hour ultrasonic treatment;
s2: 0.5g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 1 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 35 ℃, stirring for reaction for 4 hours, carrying out vacuum filtration, drying, and grafting the graphene sheets with the layered double hydroxide.
Preferably, the drying temperature is 75 ℃ and the drying time is 24 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 120g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 32g of natural graphite powder and 17g of NaNO3, uniformly mixing, adding 7g of KMnO4, controlling the temperature at 20 ℃, and reacting for 10 min;
s2: controlling the reaction temperature to rise to 40 ℃, and stirring for 35min to complete the oxidation reaction;
s3: slowly adding 120g of deionized water, controlling the reaction temperature to rise to 100 ℃, reacting for 20min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 18g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 98%.
Preferably, the mass percent of the H2O2 solution is 30%.
Preferably, the mass percentage of the dilute hydrochloric acid solution is 20%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 40g of intercalated layered double hydroxide into 300g of water, placing the mixture in an ultrasonic water bath for treatment for 6 hours, and adding 5g of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 1.5g of 4,4' -diaminodiphenyl sulfide and 3g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction, and obtaining the amino modified layered double hydroxide.
Preferably, the reaction time is 60 ℃ and the reaction temperature is 4 h.
Comparative example 1
The same procedure as in example 3 was repeated except that the graphene sheet was not added to graft the layered double hydroxide;
comparative example 2
The same procedure as in example 3 was repeated except that graphene oxide was not added;
comparative example 3
The procedure is as in example 3 except that the amino-modified layered double hydroxide is not added;
| tensile strength/MPa | |
| Example 1 | 15.3 |
| Example 2 | 16.5 |
| Example 3 | 17.1 |
| Example 4 | 16.9 |
| Comparative example 1 | 7.2 |
| Comparative example 2 | 7.9 |
| Comparative example 3 | 8.6 |
Claims (10)
1. A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 25-35 parts of thermoplastic polyurethane and 0.2-1 part of graphene sheet grafted layered double hydroxide according to the mass parts, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
2. The method for producing a modified thermoplastic polyurethane resin according to claim 1, wherein: the rotating speed of the mixing mill is 40-70r/min, and the temperature is 160-200 ℃.
3. The method for producing a modified thermoplastic polyurethane resin according to claim 1, wherein: the preparation method of the graphene sheet grafted layered double hydroxide comprises the following steps:
s1: weighing 0.1-0.5 part of graphene oxide according to the mass parts, dissolving in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5-1 h;
s2: 0.1-0.5 part of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after 0.5-1h of ultrasonic treatment;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 20-35 ℃, stirring for reaction for 2-4h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
4. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the drying temperature is 60-75 ℃, and the drying time is 20-24 h.
5. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the preparation method of the graphene oxide comprises the following steps:
s1: adding 90-120 parts by mass of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26-32 parts by mass of natural graphite powder and 13-17 parts by mass of NaNO3, uniformly mixing, adding 3-7 parts by mass of KMnO4, controlling the temperature at 15-20 ℃, and reacting for 5-10 min;
s2: controlling the reaction temperature to rise to 30-40 ℃, and stirring for 20-35min to complete the oxidation reaction;
s3: slowly adding 80-120 parts of deionized water, controlling the reaction temperature to rise to 85-100 ℃, reacting for 10-20min, and performing high-temperature hydrolysis;
s4: and finally, adding 15-18 parts of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
6. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percentage of the concentrated sulfuric acid is 90-98%.
7. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percentage of the H2O2 solution is 20-30%.
8. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percent of the dilute hydrochloric acid solution is 10-20%.
9. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the preparation method of the amino modified layered double hydroxide comprises the following steps:
adding 30-40 parts by weight of intercalated layered double hydroxide into 300 parts by weight of water 200-5 parts, placing the mixture in an ultrasonic water bath tank for treatment for 2-6 hours, and adding 2-5 parts by weight of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 0.05-1.5 parts of 4,4' -diaminodiphenyl sulfide and 0.3-3 parts of semicarbazide, stirring, and carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
10. The method for producing a modified thermoplastic polyurethane resin according to claim 9, wherein: the reaction time is 50-60 ℃, and the reaction temperature is 2-4 h.
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