CN115850653A - Full TDI prepolymer with low free monomer content for pu runway and preparation method thereof - Google Patents
Full TDI prepolymer with low free monomer content for pu runway and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of TDI type prepolymer, and particularly discloses a full TDI type prepolymer with low free monomer content for a pu runway and a preparation method thereof, wherein the full TDI type prepolymer comprises the following materials: toluene isocyanate, polyether polyol, an ester solvent, a catalyst, a polymerization inhibitor and an antioxidant; the TDI prepolymer based on the toluene isocyanate and the polyether polyol is reasonably matched, so that the fluidity of the TDI prepolymer is comprehensively improved, and the viscosity and the activity are reduced; meanwhile, under the conditions of not increasing production equipment and not greatly changing the production process, the content of free TDI in the prepolymer is less than 0.2% by adding the catalyst, the polymerization inhibitor, the antioxidant and the ester solvent, and the physical indexes of tensile strength, elongation at break, impact absorption, vertical deformation and the like all meet the requirements of GB36246-2018 'sports field for surface layers of synthetic materials in middle and primary schools', so that the storage time is longer and the economic value is higher.
Description
Technical Field
The invention relates to the technical field of preparation of polyurethane prepolymers, in particular to a TDI polyurethane prepolymer with low free monomer content for a pu runway and a preparation method thereof.
Background
The polyurethane material has excellent wear resistance and elasticity and good chemical stability, and is an ideal material for paving sports grounds such as a runway. The polyurethane plastic track is also called as an all-weather track and field sports track, is suitable for any season and temperature difference, is widely used in various schools of middle and primary schools, professional stadiums, track and field tracks, semicircular areas, auxiliary areas, parks, residential quarters and other activity fields, and is a high-quality high-level stable sports ground material.
At present, the conventional prepolymer method for preparing polyurethane in a polyurethane (pu) runway mainly uses polyol and isocyanate, and the isocyanate is mostly Toluene Diisocyanate (TDI), but because the reaction of monomers in the reaction process is insufficient, more free TDI monomers exist, and the free monomers are volatile and toxic, the free TDI which exceeds the standard can cause harm to human bodies, such as symptoms of eye pain, lacrimation, conjunctival congestion, cough, chest distress, asthma, red pimple, maculopapule, contact hypersensitivity and the like, and the residual TDI can slowly react during storage, so that the viscosity of the prepolymer is gradually increased, the storage period is shortened, and the use time is limited. The low free monomer content full TDI prepolymer has longer storage period and is not easy to deteriorate.
The evaporation method adopted by developed countries to separate the free TDI in the polyurethane prepolymer has good effect, and can be reduced to below 0.3%; however, the method has large equipment investment and is difficult to popularize and apply;
the method adopts a chemical method, and after polyether glycol reacts with TDI, the residual TDI is polymerized by adding a trimerization catalyst under the conditions of not increasing production equipment and not greatly changing the production process, so that the content of free TDI is reduced.
Disclosure of Invention
The invention aims to provide a TDI prepolymer with low free monomer for a pu runway and a preparation method thereof under the conditions of not increasing production equipment and not greatly changing a production process; after the preparation is finished, the physical indexes such as tensile strength, elongation at break, impact absorption, vertical deformation and the like meet the requirements of GB36246-2018 'sports ground for surface layers of synthetic materials in primary and secondary schools', and the free TDI is less than or equal to 0.2%.
In order to solve the problems, the scheme of the invention is as follows: a TDI prepolymer with low free monomer comprises the following raw material components in parts by weight:
the optimal mixture ratio of the components is as follows: 55 parts of toluene isocyanate, 125 parts of polyether polyol, 20-30 parts of ester solvent, 0.1 part of catalyst, 0.1 part of polymerization inhibitor and 0.3 part of antioxidant.
Also provided is a process for preparing a low free monomer TDI prepolymer for pu racetracks comprising the steps of:
(1) Respectively weighing the raw materials according to the weight parts of the formula;
(2) Putting toluene isocyanate, polyether polyol, an ester solvent and an antioxidant into a reaction kettle; heating the reaction kettle, setting the temperature to be 55-65 ℃, and stirring at the speed of 200-300r/min to ensure that substances in the reaction kettle fully react for 1-4h;
(3) Then, the temperature is increased to 75-85 ℃, and the mixture is continuously stirred, so that the substances in the reaction kettle are fully reacted for 2-6 hours to obtain uniform solution;
(4) Cooling to 55-65 deg.c, adding proper amount of trimer catalyst to make residual TDI produce polymerization reaction; measuring NCO% half an hour later;
(5) Measuring NCO% to about 10%, and adding polymerization inhibitor; stirring uniformly, keeping the temperature at 60 ℃ for 1h, and discharging.
Preferably, the polyether polyol is at least one of dihydroxy polyether polyol, trihydroxy polyether polyol and tetrahydroxy polyether polyol, and can improve the elongation, adhesion and strength of the TDI prepolymer.
Preferably, the toluene isocyanate is 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate or a mixture of two isomers or TDI-80/20, which can improve the flowability of TDI prepolymer.
Preferably, the trimerization catalyst is any one or a mixture of two of N, N-dimethylbenzylamine and N, N-diethylbenzylamine, and can accelerate the reaction and promote the trimerization of free TDI monomers in the TDI prepolymer.
Preferably, the polymerization inhibitor is one or more of phosphoric acid, benzoyl chloride, hydroquinone, p-benzoquinone, phenothiazine and p-tert-butyl catechol, and can effectively prevent the polymerization reaction from proceeding, so that the TDI prepolymer has enough storage life.
Preferably, the ester solvent is a mixture of ethyl acetate, n-butyl acetate, ethyl acetate and n-butyl acetate in any proportion, the solubility can be increased, the volatilization speed is moderate, and the storage period of the TDI prepolymer is prolonged.
Preferably, the antioxidant is at least one of 2, 6-di-tert-butyl-p-cresol, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] which can act to retard thermal oxidation of the TDI prepolymer.
Compared with the prior art, the beneficial effects are:
the embodiment of the invention mainly controls the ratio of polyether polyol and toluene diisocyanate, reasonably collocates to comprehensively improve the fluidity of TDI prepolymer and reduce the viscosity and activity; meanwhile, under the conditions of not increasing production equipment and not greatly improving the production process, the low-free TDI prepolymer is prepared by adding a catalyst, a polymerization inhibitor, an antioxidant and an ester solvent through a chemical method, so that the content of free TDI in the prepolymer is less than 0.2%, the storage time is longer, the prepolymer is not easy to deteriorate, the economic value is higher, the physical indexes such as tensile strength, elongation at break, impact absorption, vertical deformation and the like all meet the requirements of GB36246-2018 'synthetic material surface sports field in middle and primary schools', and meanwhile, the high-free TDI prepolymer has good thermal stability, good processing conditions, longer storage time and higher economic value.
Detailed Description
The embodiments of the present invention are described in further detail to make the technical solutions of the present invention easier to understand and master.
Example 1
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 55 parts of 2, 4-toluene diisocyanate, 125 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-dimethylbenzylamine, 0.1 part of benzoyl chloride and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) Adding 55 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a 500mL four-neck flask which is provided with a stirring device, a thermometer and nitrogen protection in sequence, starting stirring and heating simultaneously, and adding 125 parts of PTMEG650s when the temperature is raised to 55 ℃;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and dispersing uniformly at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; 10 parts of adjuvant (drier/ATBC = 2/8) are added and stirring is continued at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of the components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing the mixture when the gel point is reached, demolding, and continuously vulcanizing the mixture in an oven at 100 ℃ for 20 hours;
(8) And (4) after standing for 7 days at room temperature, testing the mechanical properties, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports ground for surface layers of synthetic materials in middle and primary schools'.
Example 2
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 60 parts of 2, 4-toluene diisocyanate, 120 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-dimethylbenzylamine, 0.1 part of benzoyl chloride and 0.2 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) Sequentially adding 60 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate and 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a 500mL four-neck flask provided with a stirring device, a thermometer and nitrogen protection, starting stirring and heating at the same time, and heating to 55 ℃ to add 120 parts of PTMEG650s;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, keeping the temperature for 30 minutes, and starting to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and uniformly dispersing at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing when gel points are reached, demolding, and continuously vulcanizing in an oven at 100 ℃ for 20 hours;
(8) And (4) after standing for 7 days at room temperature, testing the mechanical properties, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports ground for surface layers of synthetic materials in middle and primary schools'.
Example 3
A low free monomer all TDI based prepolymer for pu track comprising the following parts by weight of materials: 58 parts of 2, 6-toluene diisocyanate, 121 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-diethylbenzylamine, 0.1 part of benzoyl chloride and 0.3 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, including following in order in a 500mL four-necked flask equipped with stirring apparatus, thermometer and nitrogen protection add 58 parts 2, 4-toluene diisocyanate, 10 parts n-butyl acetate, 15 parts ethyl acetate, 0.3 parts tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, start stirring and heating at the same time, heat up to 55 degrees centigrade and add 121 parts PTMEG650s;
(2) After the temperature is kept at 70-72 ℃ for 2 hours, the temperature is raised to 80 ℃ and kept for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-diethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and dispersing uniformly at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing when gel points are reached, demolding, and continuously vulcanizing in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 4
A low free monomer all TDI based prepolymer for pu track comprising the following parts by weight of materials: 62 parts of 2, 4-toluene diisocyanate, 112 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-dimethylbenzylamine, 0.1 part of benzoyl chloride and 0.3 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, include following in order in one is equipped with agitating unit, thermometer and nitrogen gas introduction 500mL four-necked flask protected to add 62 parts 2, 4-toluene diisocyanate, 10 parts n-butyl acetate, 15 parts ethyl acetate, 0.3 parts tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, start stirring and heating at the same time, heat up to 55 duC and add 112 parts PTMEG650s;
(2) After the temperature is kept at 70-72 ℃ for 2 hours, the temperature is raised to 80 ℃ and kept for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, keeping the temperature for 30 minutes, and starting to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and dispersing uniformly at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; 10 parts of adjuvant (drier/ATBC = 2/8) are added and stirring is continued at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing when gel points are reached, demolding, and continuously vulcanizing in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 5
A low free monomer all TDI based prepolymer for pu track comprising the following parts by weight of materials: 66 parts of 2, 4-toluene diisocyanate, 113 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-diethylbenzylamine, 0.1 part of benzoyl chloride and 0.2 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, includes adding 66 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate, 0.2 parts of tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a 500mL four-neck flask equipped with a stirring device, a thermometer and nitrogen protection in sequence, starting stirring and heating at the same time, heating to 55 ℃, adding 113 parts of PTMEG650s;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-diethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and dispersing uniformly at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing when gel points are reached, demolding, and continuously vulcanizing in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 6
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 70 parts of 2, 4-toluene diisocyanate, 118 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-dimethylbenzylamine, 0.1 part of benzoyl chloride and 0.3 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, which comprises adding 70 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate, 0.3 part of tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a 500mL four-neck flask equipped with a stirring device, a thermometer and nitrogen protection, starting stirring and heating at the same time, heating to 55 ℃ and adding 118 parts of PTMEG650s;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and uniformly dispersing at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing when gel points are reached, demolding, and continuously vulcanizing in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 7
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 63 parts of 2, 4-toluene diisocyanate, 122 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-methylbenzylamine, 0.1 part of benzoyl chloride and 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, include following sequentially in a 500mL four-necked flask equipped with stirring apparatus, thermometer and letting in nitrogen protection add 63 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate, 0.2 parts of tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, start stirring and heating at the same time, heat up to 55 degrees centigrade and add 122 parts of PTMEG650s;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and uniformly dispersing at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of the components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing the mixture when the gel point is reached, demolding, and continuously vulcanizing the mixture in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 8
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 51 parts of 2, 4-toluene diisocyanate, 136 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-diethylbenzylamine, 0.1 part of benzoyl chloride and 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, which comprises adding 51 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate, 0.2 part of tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a 500mL four-neck flask equipped with a stirring device, a thermometer and nitrogen protection, starting stirring and heating at the same time, heating to 55 ℃ and adding 136 parts of PTMEG650s;
(2) After heat preservation is carried out for 2 hours at the temperature of 70-72 ℃, the temperature is raised to 80 ℃, and heat preservation is carried out for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-diethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and uniformly dispersing at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of the components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing the mixture when the gel point is reached, demolding, and continuously vulcanizing the mixture in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
Example 9
A low free monomer all TDI prepolymer for pu track comprises the following materials in parts by weight: 53 parts of 2, 4-toluene diisocyanate, 115 parts of PTMEG650s, 10 parts of N-butyl acetate, 15 parts of ethyl acetate, 0.1 part of N, N-dimethylbenzylamine, 0.1 part of benzoyl chloride and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A low free monomer all TDI prepolymer for pu runway and its preparation method, comprising the following steps:
(1) A low free monomer full TDI prepolymer for pu runway and its preparation method, which comprises adding 53 parts of 2, 4-toluene diisocyanate, 10 parts of n-butyl acetate, 15 parts of ethyl acetate, 0.3 part of tetra [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a 500mL four-neck flask equipped with a stirring device, a thermometer and nitrogen protection, starting stirring and heating at the same time, heating to 55 ℃ and adding 115 parts of PTMEG650s;
(2) After the temperature is kept at 70-72 ℃ for 2 hours, the temperature is raised to 80 ℃ and kept for 100 minutes;
(3) Cooling to 55 ℃, adding 0.1 part of N, N-dimethylbenzylamine, controlling the temperature to be 55 ℃, preserving the temperature for 30 minutes, and beginning to measure NCO;
(4) When the NCO value reaches 10 +/-0.1 percent (a di-n-butylamine-hydrochloric acid method), adding 0.1 part of benzoyl chloride, heating to 70 ℃, and preserving heat for 60 minutes;
(5) Then cooling to below 55 ℃, filtering and discharging to obtain low free full TDI prepolymer;
(6) Mixing 80 parts of polyether polyol 330N, 10 parts of MOCA, 100 parts of No. 52 chlorinated paraffin and 200 parts of 600-mesh heavy calcium carbonate, and dispersing uniformly at a high speed of 1200rpm to obtain a mixture; putting the uniformly dispersed mixture into a reaction kettle, drying and dehydrating for 2 hours under the vacuum condition of 120 ℃ and-0.08 MPa, then stopping vacuumizing, and cooling to 65 ℃; adding 10 parts of auxiliary agent (drier/ATBC = 2/8), and continuing stirring at 65 ℃ for 0.5h;
(7) Uniformly mixing 100 parts of low free full TDI prepolymer preheated to 90 ℃ with 400 parts of the components obtained in the step (6) melted at 110 ℃, pouring the mixture into a preheated mold, pressurizing and vulcanizing the mixture when the gel point is reached, demolding, and continuously vulcanizing the mixture in an oven at 100 ℃ for 20 hours;
(8) And (3) after standing at room temperature for 7 days, performing mechanical property test, and measuring the content of free TDI and the product performance of the test piece by adopting the standard of GB36246-2018 'sports field of surface layer of synthetic material in middle and primary schools'.
To examine the properties of the low free TDI prepolymer used in pu track according to the present invention, the products prepared from the full TDI prepolymer prepared in examples 1 to 3 were applied to a plastic track surface layer, and sampled according to the GB/T14833-2020, and the prepared samples were compared with the prepolymer (ordinary prepolymer) conventionally applied to an athletic track surface layer. The results were as follows:
TABLE 1 Performance test data for examples 1-3
Table 2 performance test data for examples 1-3
In order to examine the properties of the low-free TDI prepolymer used in pu tracks, the full-TDI prepolymer prepared in examples 1 to 3 was used as a product for a plastic track surface layer, and sampled according to GB/T14833-2020, and the prepared sample was compared with a prepolymer (ordinary prepolymer) conventionally used for a ball sports ground surface layer. The results are as follows:
table 3 performance test data for examples 4-6
Table 4 performance test data for examples 4-6
In order to examine the properties of the low-free TDI prepolymer used for the pu track, the products prepared from the full-TDI prepolymer prepared in examples 1 to 3 were applied to a plastic track surface layer, samples were taken according to the regulations of GB/T14833-2020, and the prepared samples were compared with the prepolymer (common prepolymer) conventionally applied to a multifunctional sports ground surface layer. The results are as follows:
TABLE 5 Performance test data for examples 7-9
TABLE 6 Performance test data for examples 7-9
The data show that the technical effects of the invention are mainly reflected in the following aspects: the prepared TDI prepolymer with low free monomer has various performances meeting physical and mechanical indexes of various sports fields and the limit requirement of harmful substances.
The embodiment of the invention mainly controls the ratio of polyether polyol to toluene diisocyanate, reasonably collocates to comprehensively improve the fluidity of the TDI prepolymer and reduce the viscosity and the activity; meanwhile, under the conditions of not increasing production equipment and not greatly changing the production process, the free TDI content in the prepolymer is less than 0.2% by adding a catalyst, a polymerization inhibitor, an antioxidant and an ester solvent, so that the prepolymer is longer in storage time, not prone to deterioration and higher in economic value, and the physical indexes of tensile strength, elongation at break, impact absorption, vertical deformation and the like all meet the requirements of GB36246-2018 'sports ground for the surface layer of the synthetic material in middle and primary schools'. Solves the problems that the polyurethane in the traditional polyurethane (pu) runway has more TDI monomers and residual TDI generated by insufficient reaction of the monomers in the reaction process and can slowly react in the storage period, so that the viscosity of the prepolymer is gradually increased, the storage period is shortened, the use time is limited and the like. When the mixture ratio is 55 parts of toluene isocyanate; 125 parts of polyether polyol; 20-30 parts of an ester solvent; 0.1 part of catalyst; 0.1 part of polymerization inhibitor; 0.3 part of antioxidant, and the TDI prepolymer developed by the invention meets the requirements of optimal physical and mechanical properties and low free TDI.
The product is suitable for polyurethane plastic runways of various schools of middle and primary schools, professional stadiums, track and field tracks, semicircular areas, auxiliary areas, parks, residential quarters and other activity fields, has good mechanical properties and low emission of harmful substances, and ensures the health of constructors and users.
Of course, the foregoing is only exemplary of the present invention, and many other embodiments of the present invention are possible. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. An all-TDI-based prepolymer for a pu track, characterized by: the weight portions of the raw material components are as follows:
2. the full TDI-based prepolymer according to claim 1, which is prepared from the following components in an optimal ratio: 55 parts of toluene isocyanate, 125 parts of polyether polyol, 20-30 parts of ester solvent, 0.1 part of catalyst, 0.1 part of polymerization inhibitor and 0.3 part of antioxidant.
3. An all TDI type prepolymer for pu's track according to claim 1, wherein: the method comprises the following steps:
(1) Weighing the raw materials according to the weight parts of the formula;
(2) Putting toluene isocyanate, polyether polyol, an ester solvent and an antioxidant into a reaction kettle; heating the reaction kettle, setting the temperature to be 55-65 ℃, and stirring at the speed of 200-300r/min to ensure that substances in the reaction kettle fully react for 1-4h;
(3) Then, the temperature is increased to 75-85 ℃, and the mixture is continuously stirred, so that the substances in the reaction kettle are fully reacted for 2-6 hours to obtain uniform solution;
(4) Cooling to 55-65 deg.c, adding proper amount of trimer catalyst to make residual TDI produce polymerization reaction; measuring NCO% after half an hour;
(5) Measuring NCO% to about 10%, adding polymerization inhibitor, stirring, keeping at 60 deg.C for 1h, and discharging.
4. The full TDI-based prepolymer of claim 1, characterized in that: the polyether polyol is at least one of dihydroxy polyether polyol, trihydroxy polyether polyol and tetrahydroxy polyether polyol.
5. The full TDI-based prepolymer of claim 1, wherein: the toluene isocyanate is any one or a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
6. The full TDI-based prepolymer of claim 1, wherein: the trimerization catalyst is any one or a mixture of two of N, N-dimethylbenzylamine and N, N-diethylbenzylamine.
7. The full TDI-based prepolymer of claim 1, wherein: the polymerization inhibitor is any one or a mixture of phosphoric acid and benzoyl chloride.
8. The full TDI-based prepolymer of claim 1, wherein: the ester solvent is a mixture of ethyl acetate, n-butyl acetate, ethyl acetate and n-butyl acetate in any proportion.
9. The full TDI-based prepolymer of claim 1, wherein: the antioxidant is at least one of 2, 6-di-tert-butyl-p-cresol, tris (2, 4-di-tert-butylphenyl) phosphite and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
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