CN112920363B - Thermoplastic polyurethane elastomer compatibilizer and preparation method and application thereof - Google Patents

Thermoplastic polyurethane elastomer compatibilizer and preparation method and application thereof Download PDF

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CN112920363B
CN112920363B CN202110037068.7A CN202110037068A CN112920363B CN 112920363 B CN112920363 B CN 112920363B CN 202110037068 A CN202110037068 A CN 202110037068A CN 112920363 B CN112920363 B CN 112920363B
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dihydric alcohol
diol
glyceryl
thermoplastic polyurethane
polyurethane elastomer
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CN112920363A (en
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刘芳
何经纬
张羽
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South China University of Technology SCUT
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Abstract

The invention discloses a thermoplastic polyurethane elastomer compatibilizer and a preparation method and application thereof. The compatibilizer is prepared by polymerizing aromatic polycarbonate dihydric alcohol, 1-long-chain alkanoic acid glyceride dihydric alcohol, polymer dihydric alcohol, diisocyanate and a dihydric alcohol chain extender. The thermoplastic polyurethane elastomer compatibilizer prepared by the invention is used in PC/PP alloy, can effectively improve the compatibility between PC and PP, and increases the interface bonding between two phases, thereby achieving the effect of simultaneously improving the mechanical properties of the PC/PP alloy, such as tensile strength, bending strength, impact strength and the like.

Description

Thermoplastic polyurethane elastomer compatibilizer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer alloy material compatibilizers, and particularly relates to a thermoplastic polyurethane elastomer compatibilizer, a preparation method and an application thereof, in particular to a thermoplastic polyurethane elastomer compatibilizer with a branched chain containing a long alkyl structure and a main chain containing an aromatic polycarbonate structure, a preparation method thereof and an application thereof in a PC/PP alloy material.
Background
Polycarbonate is a common thermoplastic engineering plastic, and the polycarbonate is commonly referred to as bisphenol A aromatic polycarbonate (PC for short) in the plastics industry. The PC has the advantages of excellent mechanical property, excellent thermal stability, creep resistance, dimensional stability, transparency, nontoxicity and the like, and is widely applied to a plurality of fields of automobiles, spaceflight, building materials, packaging, electronic and electric appliances, medical appliances and the like. However, PC has a high density (1.18-1.22 g/cm)3) The melt viscosity is high, the processability is poor, the notch sensitivity of the product is high, the environmental stress cracking resistance is poor, the solvent resistance is poor and the like, so that the application of the product is limited to a certain extent.
Polypropylene (PP for short) is the most extensive in the world at presentOne of the thermoplastic general-purpose plastics used. Compared with other thermoplastic general-purpose plastics, the thermoplastic general-purpose plastic has low relative density (0.90-0.91 g/cm) due to rich raw material sources and low price3) Low cost, excellent comprehensive performance, corrosion resistance, good processability and the like.
Blending modification is one of the important ways to develop cheap and excellent polymer materials. PC and PP are blended to try to obtain a polymer alloy material integrating the excellent performances of the PC and the PP. However, the structure and polarity of PC and PP are obviously different, and the compatibility between the PC and PP is poor, so that the PC/PP blending system is easily subjected to macroscopic phase separation, and the interface bonding property, the mechanical property and the like are poor, so that the significance for preparing the PC/PP alloy material is lost. Therefore, it is necessary to add a compatibilizer to reduce the interfacial tension between two phases, so as to improve the compatibility of the PC/PP alloy material, and to improve the morphological structure and performance of the PC/PP alloy material.
At present, most of compatibilizers for PC/PP blending systems are polymer grafts containing polar groups, such as maleic anhydride polypropylene grafts and acrylic ester polypropylene grafts, and the compatibilizers mainly aim at PC/PP blending systems with PP as a continuous phase. When PC exists as a continuous phase in a PC/PP blending system, the compatibilizer has limited compatibilization effect because the grafted polar group content is low and the branched chain at the reactive grafting end is short. Therefore, a novel compatibilizer with a main chain structure compatible with polar PC and a branched chain structure compatible with non-polar PP is developed through molecular structure design, so that the compatibilizer is suitable for PC/PP alloy materials with PC as a continuous phase, improves the compatibility between PC and PP, and has very important research significance.
Disclosure of Invention
In order to solve the defects of the conventional compatibilizer for PC/PP alloy materials, the invention aims to provide a compatibilizer for thermoplastic polyurethane elastomers, wherein a branched chain of the compatibilizer contains a long alkyl structure, and a main chain of the compatibilizer contains an aromatic polycarbonate structure.
The invention also aims to provide a preparation method of the thermoplastic polyurethane elastomer compatibilizer.
The invention also aims to provide application of the thermoplastic polyurethane elastomer compatibilizer in PC/PP alloy materials.
The invention also aims to provide a PC/PP alloy material and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a thermoplastic polyurethane elastomer compatibilizer is prepared by polymerizing aromatic polycarbonate diol (PCDL), 1-long-chain glycerol alkanoate diol, polymer diol, diisocyanate and a diol chain extender;
the amount of the aromatic polycarbonate diol (PCDL) and the amount of the 1-long-chain alkanoic acid glyceride diol are respectively 2-12% and 0.5-4.0% of the mass of the thermoplastic polyurethane elastomer compatibilizer (namely the total mass of the aromatic polycarbonate diol, the 1-long-chain alkanoic acid glyceride diol, the polymer diol, the diisocyanate and the diol chain extender), the isocyanate index R is 0.95-1.05, namely the molar ratio of the diisocyanate to all diols (including the diol chain extender) is 0.95-1.05: 1; the ratio of the molar amount of diisocyanate to the total molar amount of the aromatic polycarbonate diol, the 1-long-chain alkanoic acid glyceride diol and the polymer diol is 2 to 3: 1.
the molecular structural formula of the thermoplastic polyurethane elastomer compatibilizer is shown as the formula (I):
Figure BDA0002893598470000031
wherein n is the average polymerization degree of aromatic polycarbonate diol (PCDL), and n is more than or equal to 1 and less than or equal to 8; x is the number of methylene in the long alkyl branch chain, and x is more than or equal to 10 and less than or equal to 24; r1R being the remainder of the diisocyanate molecular structure minus the-NCO group2R is the remaining part of the molecular structure of the polymer diol excluding the hydroxyl groups3The remaining portion of the glycol chain extender molecular structure from which the hydroxyl groups have been removed.
Preferably, the aromatic polycarbonate diol (PCDL) has the following structural formula:
Figure BDA0002893598470000032
the aromatic polycarbonate diol (PCDL) has an average degree of polymerization (n) of 1 to 8.
Preferably, the 1-long-chain glyceryl alkanoate diol is 1-glyceryl dodecanoate diol, 1-glyceryl tridecanoate diol, 1-glyceryl tetradecanoate diol, 1-glyceryl pentadecanoate diol, 1-glyceryl hexadecanoate diol, 1-glyceryl heptadecanoate diol, 1-glyceryl octadecanoate diol, at least one of 1-nonadecanoic acid glyceride dihydric alcohol, 1-eicosanoic acid glyceride dihydric alcohol, 1-heneicosanoic acid glyceride dihydric alcohol, 1-docosanoic acid glyceride dihydric alcohol, 1-tricosanoic acid glyceride dihydric alcohol, 1-tetracosanoic acid glyceride dihydric alcohol, 1-pentacosanoic acid glyceride dihydric alcohol and 1-hexacosanoic acid glyceride dihydric alcohol.
Preferably, the polymer diol is at least one of polyester diol, polyether diol, polybutadiene diol, polybutylene adipate diol, polycarbonate diol, polycaprolactone diol and polytetrahydrofuran ether diol.
More preferably, the molecular weight of the polymer diol is 1000 to 3000 (number average molecular weight).
Preferably, the diisocyanate is at least one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and naphthalene-1, 5-diisocyanate (NDI).
Preferably, the glycol chain extender is at least one of 1, 4-Butanediol (BDO), propylene glycol (PDO) and hydroquinone dihydroxyethyl ether (HQEE).
In the molecular structure of the thermoplastic polyurethane elastomer compatibilizer, the aromatic polycarbonate diol PCDL in the polar main chain is similar to the PC in structure, the compatibility of the aromatic polycarbonate diol PCDL and the PC is better, and the long alkyl branched chain structure is compatible with the nonpolar PP. The thermoplastic polyurethane can be used as a compatibilizer for PC/PP alloy materials, TPU can be preferentially distributed in a two-phase interface of PC and PP, so that a polymer generates a high-viscosity interface to obviously change the compatibility effect, and the mechanical properties such as tensile strength, bending strength, impact strength and the like of the PC/PP alloy are further improved.
The preparation method of the thermoplastic polyurethane elastomer compatibilizer comprises the following steps:
(1) adding hydroxyethylated bisphenol A and diphenyl carbonate into a reactor, heating to 120-130 ℃ under the protection of nitrogen or inert gas to melt the materials, adding a catalyst to react for 0.5-1 h, heating to 150-200 ℃ and reacting for 2-6 h under a reduced pressure condition, extracting a reaction system from a byproduct phenol in the reduced pressure reaction process, cooling and purifying to obtain aromatic polycarbonate diol (PCDL);
(2) adding polymer diol, aromatic polycarbonate diol (PCDL), a catalyst and diisocyanate into a reactor, heating to 70-100 ℃, reacting for 0.5-3 h, adding 1-long-chain glyceryl alkanoate diol, continuing to react for 1-5 h under heat preservation, cooling to 40-60 ℃, adding a diol chain extender, uniformly mixing, pouring into a preheating mould, and curing at 100-120 ℃ for 4-20 h to obtain the thermoplastic polyurethane elastomer compatibilizer.
Preferably, the molar ratio of the hydroxyethylated bisphenol A to the diphenyl carbonate in the step (1) is 1.1-2.0: 1.
preferably, the amount of the catalyst used in the step (1) is 0.1-1.0% of the total mass of the reactants.
Preferably, the catalyst in the step (1) is at least one of tetrabutyl titanate, sodium hydroxide and 4-dimethylaminopyridine.
Preferably, the pressure reducing condition in step (1) means that the pressure is reduced to below 6 KPa.
Preferably, the cooling in step (1) is cooling to room temperature.
Preferably, the purification method in step (1) is: adding a solvent into the crude product obtained by the reaction for dissolving, then carrying out liquid separation extraction, and drying to obtain purified aromatic polycarbonate diol (PCDL), wherein the mass ratio of the solvent to the crude product is (3-5): 1.
more preferably, the solvent is at least one of methanol, ethanol, dichloromethane, acetone, tetrahydrofuran, toluene, dimethyl sulfoxide, ethyl acetate, petroleum ether and cyclohexane. The drying temperature is 50-100 ℃.
Preferably, the polymer diol and the aromatic polycarbonate diol (PCDL) in the step (2) are further dried under vacuum at 100 ℃ to remove moisture before the reaction.
Preferably, the catalyst in the step (2) is at least one of dibutyltin dilaurate, stannous octoate, triethylene diamine and triethylamine.
Preferably, the amount of the catalyst used in the step (2) is 0.1-1.0% of the total mass of the reactants (the polymer diol, the aromatic polycarbonate diol, the diisocyanate and the diol chain extender).
Preferably, the mold in the step (2) is a polytetrafluoroethylene mold, and the preheating temperature is 100-120 ℃.
The reaction formula of the step (1) is as follows:
Figure BDA0002893598470000051
the thermoplastic polyurethane elastomer compatibilizer is applied to PC/PP alloy.
The PC/PP alloy material comprises, by mass, 60-80 parts of PC, 20-40 parts of PP and 2-10 parts of the thermoplastic polyurethane elastomer compatibilizer.
The preparation method of the PC/PP alloy material comprises the following steps:
uniformly mixing the components according to a preset proportion, and then carrying out bracing and dicing by using a double-screw extruder to obtain the PC/PP alloy material.
The PC/PP alloy material is applied.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a compatibilizer suitable for a PC/PP alloy material, which can effectively improve the compatibility between PC and PP and increase the interface acting force, thereby simultaneously improving the mechanical properties of the PC/PP alloy, such as tensile strength, bending strength, impact strength and the like.
Drawings
Fig. 1 is a scanning electron micrograph of application example 2 (left) and application comparative example 4 (right). It can be seen that the particle size of the PP dispersed phase in the sample section without the compatibilizer on the right is larger and nonuniform, while the sample section with the compatibilizer prepared by the invention on the left is rough, and the particle size of the PP dispersed phase is obviously reduced and more uniform, which indicates that the addition of the compatibilizer reduces the interfacial tension between PC and PP, and improves the compatibility of the PC/PP alloy material.
FIG. 2 is a DMA curve of PC/PP alloy material without compatibilizer (application comparative 4) and with compatibilizer prepared according to the present invention (application example 2). As can be seen from the figure, the PC/PP alloy material without the compatibilizer shows two loss peaks at 158 ℃ and-26 ℃, which correspond to the glass transition temperatures of PC and PP, respectively; the loss peak positions are shifted after the compatibilizer is added and are respectively at 140 ℃ and-20 ℃, which shows that the addition of the compatibilizer leads the glass transition temperatures of PC and PP to have the tendency of closing each other, and improves the compatibility between two phases.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The extruder processes in the application examples and application comparative examples of the application are as follows: the screw rotation speed is 80rpm, the feeding section temperature (zone 1) is 80 ℃, the mixing section temperature is 245 ℃, and the extrusion section temperature is 240 ℃.
Example 1
Preparation of thermoplastic polyurethane elastomer compatibilizer containing 4.0 wt% of 1-dodecanoic acid glyceride dihydric alcohol and 2.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
The method comprises the following steps: preparation of aromatic polycarbonate diol (PCDL)
Adding 20.86g (66mmol) of hydroxyethylated bisphenol A and 12.84g (60mmol) of diphenyl carbonate into a reactor, heating to 130 ℃ under the protection of nitrogen to completely melt the raw materials, adding 0.034g (accounting for 0.1wt percent of reactants) of tetrabutyl titanate under stirring to react for 30min, heating to 150 ℃ and reacting under reduced pressure (the pressure is reduced to below 6 KPa), pumping a reaction system of a byproduct phenol in the reduced pressure reaction process to prepare a crude product of the aromatic polycarbonate diol, cooling the obtained crude product to room temperature, adding 110g of a mixed solvent of ethyl acetate and methanol (the volume ratio is 3:1) to dissolve, purifying the crude product by adopting a liquid separation extraction method, and finally drying under vacuum at 80 ℃ to constant weight to obtain the purified aromatic polycarbonate diol (PCDL);
the obtained aromatic polycarbonate diol had an average degree of polymerization n of 8, a molecular weight of 3052 and a hydroxyl value of 37. + -. 3 mgKOH/g.
FTIR:3402cm-1(-OH)、1749cm-1(-C＝O)、1050cm-1(Primary alcohol-C-O-), 830cm-1(bending out of benzene ring plane) 750cm-1(out-of-plane curvature of the benzene ring).
1H-NMR(600MHz，DMSO-d6)：δ1.57(27H)、δ3.71(2H)、δ3.94(2H)、δ4.19(16H)、δ4.32(16H)、δ4.85(1H)、δ6.84(18H)、δ7.09(18H)。
Step two: preparation of thermoplastic polyurethane elastomer compatibilizer containing 4.0 wt% of 1-dodecanoic acid glyceride dihydric alcohol and 2.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
Drying polycaprolactone diol (PCL, molecular weight 1000, hydroxyl value 112mgKOH/g) and the aromatic polycarbonate diol (PCDL) obtained in the step one at 100 ℃ in vacuum for later use; adding dried polycaprolactone diol (PCL) and the aromatic polycarbonate diol (PCDL), dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) obtained in the step one into a reactor in sequence according to the isocyanate index R of 1.05, heating to 100 ℃ under stirring, reacting for 0.5h, adding 1-dodecanoic acid glyceride diol, and continuing to perform heat preservation reaction for 1 h; stopping heating, adding a chain extender 1, 4-Butanediol (BDO) after the temperature of the system is reduced to 60 ℃, fully stirring and uniformly mixing, pouring into a preheated polytetrafluoroethylene mold, putting into a 100 ℃ drying oven, and curing for 20 hours to obtain a thermoplastic polyurethane elastomer solubilizer containing 4.0 wt% of 1-dodecanoic acid glyceride dihydric alcohol and 2.0 wt% of PCDL; the dosage of each component is as follows: 15.31mmol of PCL; 0.20mmol of PCDL; DBTDL accounts for 0.1 wt% of the total mass of all reactants; 50mmol of IPDI; 4.49mmol of 1-dodecanoic acid glyceride dibasic alcohol; BDO 27.62 mmol.
The thermoplastic polyurethane elastomer compatibilizer obtained in this example was characterized as follows:
FTIR:3342cm-1(-N-H-)、2956cm-1(-CH3)、2927cm-1(-CH2)、1733cm-1(-C＝O)、1609cm-1(vibration of benzene ring skeleton), 1522cm-1(-C-N-)、1236cm-1(-C-O-C-)。
Example 2
Preparation of thermoplastic polyurethane elastomer compatibilizer containing 2.0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
The method comprises the following steps: preparation of aromatic polycarbonate diol (PCDL)
Adding 25.28g (80mmol) of hydroxyethylated bisphenol A and 12.84g (60mmol) of diphenyl carbonate into a reactor, heating to 120 ℃ under the protection of nitrogen to completely melt the raw materials, adding 0.19g (accounting for 0.5wt percent of reactants) of 4-dimethylaminopyridine under stirring to react for 1h, then heating to 180 ℃ to start reduced pressure (the pressure is reduced to below 6 KPa) distillation reaction for 3h, pumping out a reaction system of phenol serving as a byproduct in the reduced pressure reaction process to prepare a crude product of the aromatic polycarbonate diol, cooling the obtained crude product to room temperature, adding 160g of dichloromethane to dissolve the crude product, purifying the crude product by adopting a liquid separation extraction method, and finally drying in vacuum at 60 ℃ to constant weight to obtain the purified aromatic polycarbonate diol (PCDL).
The obtained aromatic polycarbonate diol had an average degree of polymerization n of 3, a molecular weight of 1342 and a hydroxyl value of 84. + -. 3 mgKOH/g.
FTIR:3455cm-1(-OH)、1733cm-1(-C＝O)、1049cm-1(Primary alcohol-C-O-), 833cm-1(bending out of benzene ring surface) 752cm-1(out-of-plane curvature of the benzene ring).
1H-NMR(600MHz，DMSO-d6):δ1.57(12H)、δ3.71(2H)、δ3.94(2H)、δ4.19(6H)、δ4.32(6H)、δ4.85(1H)、δ6.84(8H)、δ7.09(8H)。
Step two: preparation of thermoplastic polyurethane elastomer compatibilizer containing 2.0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
Drying polytetrahydrofuran ether diol (PTMG, molecular weight 1500, hydroxyl value 75mgKOH/g) and the aromatic polycarbonate diol (PCDL) obtained in the step one at 100 ℃ in vacuum for later use; adding dried polytetrahydrofuran ether diol (PTMG) and the aromatic polycarbonate diol (PCDL), triethylene diamine (TEDA) and Toluene Diisocyanate (TDI) obtained in the step one into a reactor in sequence according to the isocyanate index R of 1.02, heating to 80 ℃ under stirring, reacting for 2 hours, adding 1-octadecanoic acid glyceride diol, and continuing to perform heat preservation reaction for 3 hours; stopping heating, adding a chain extender 1, 4-Butanediol (BDO) after the temperature of the system is reduced to 60 ℃, fully stirring and uniformly mixing, pouring into a preheated polytetrafluoroethylene mold, placing into a drying oven at 110 ℃ for curing for 10 hours to obtain a thermoplastic polyurethane elastomer compatibilizer containing 2.0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of PCDLs; the dosage of each component is as follows: PTMG 15.55 mmol; 2.30mmol of PCDL; TEDA represents 0.5 wt.% of the total mass of all reactants; TDI 50 mmol; 2.15mmol of 1-octadecanoic acid glyceride dihydric alcohol; BDO 29.02 mmol.
The thermoplastic polyurethane elastomer compatibilizer obtained in this example was characterized as follows:
FTIR:3358cm-1(-N-H-)、2953cm-1(-CH3)、2927cm-1(-CH2)、1732cm-1(-C＝O)、1608cm-1(vibration of benzene ring skeleton), 1529cm-1(-C-N-)、1230cm-1(-C-O-C-)。
Example 3
Preparation of thermoplastic polyurethane elastomer compatibilizer containing 0.5 wt% of 1-hexacosanoic acid glyceride dihydric alcohol and 12.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
The method comprises the following steps: preparation of aromatic polycarbonate diol (PCDL)
Adding 37.92g (120mmol) of hydroxyethylated bisphenol A and 12.84g (60mmol) of diphenyl carbonate into a reactor, heating to 125 ℃ under the protection of nitrogen to completely melt the raw materials, adding 0.25g (0.5 wt% of reactants) of sodium hydroxide and 0.25g (0.5 wt% of reactants) of tetrabutyl titanate under stirring to react for 45min, then heating to 200 ℃ to start reduced pressure (the pressure is reduced to below 6 KPa) and distilling to react for 2h, pumping a reaction system of a byproduct phenol in the reduced pressure reaction process to prepare a crude product of aromatic polycarbonate diol, cooling the obtained crude product to room temperature, adding 250g of acetone to dissolve, purifying the crude product by adopting a liquid separation extraction method, and finally drying in vacuum at 70 ℃ to constant weight to obtain purified aromatic polycarbonate diol (PCDL);
the obtained aromatic polycarbonate diol had an average degree of polymerization n of 1, a molecular weight of 658 and a hydroxyl value of 171. + -. 3 mgKOH/g.
FTIR:3423cm-1(-OH)、1738cm-1(-C＝O)、1048cm-1(Primary alcohol-C-O-), 831cm-1(bending out of benzene ring surface) 749cm-1(out-of-plane curvature of the benzene ring).
1H-NMR(600MHz，DMSO-d6)：δ1.57(6H)、δ3.71(2H)、δ3.94(2H)、δ4.19(2H)、δ4.32(2H)、δ4.85(1H)、δ6.84(4H)、δ7.09(4H)。
Step two: preparation of thermoplastic polyurethane elastomer compatibilizer containing 0.5 wt% of 1-hexacosanoic acid glyceride dihydric alcohol and 12.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
Drying polybutylene adipate glycol (PBAG, molecular weight of 2000 and hydroxyl value of 56mgKOH/g) and the aromatic polycarbonate glycol (PCDL) obtained in the step one at 100 ℃ in vacuum for later use; sequentially adding dried polybutylene adipate glycol (PBAG) and the aromatic polycarbonate glycol (PCDL), Triethylamine (TEA), stannous octoate and diphenylmethane diisocyanate (MDI) obtained in the step one into a reactor according to the isocyanate index R of 0.95, heating to 70 ℃ under stirring, reacting for 3 hours, adding 1-hexacosanoic acid glyceride glycol, and continuing to perform heat preservation reaction for 5 hours; stopping heating, adding a chain extender 1, 4-Butanediol (BDO) after the temperature of the system is reduced to 60 ℃, fully stirring and uniformly mixing, pouring into a preheated polytetrafluoroethylene mold, putting into a 120 ℃ oven, and curing for 4 hours to obtain a thermoplastic polyurethane elastomer compatibilizer containing 0.5 wt% of 1-hexacosanoic acid glyceride dihydric alcohol and 12.0 wt% of PCDL; the dosage of each component is as follows: PBAG 11.51 mmol; 8.02mmol of PCDL; TEA accounted for 0.5 wt% of the total mass of all reactants; stannous octoate accounts for 0.5 wt% of the total mass of all reactants; 50mmol of MDI; 0.47mmol of 1-hexacosanoic acid glyceride dibasic alcohol; BDO 32.63 mmol.
The thermoplastic polyurethane elastomer compatibilizer obtained in this example was characterized as follows:
FTIR:3360cm-1(-N-H-)、2949cm-1(-CH3)、2923cm-1(-CH2)、1723cm-1(-C＝O)、1610cm-1(vibration of benzene ring skeleton), 1525cm-1(-C-N-)、1231cm-1(-C-O-C-)。
Comparative example 1
Preparation of thermoplastic polyurethane elastomer compatibilizer containing 0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
The method comprises the following steps: preparation of aromatic polycarbonate diol (PCDL)
Adding 25.28g (80mmol) of hydroxyethylated bisphenol A and 12.84g (60mmol) of diphenyl carbonate into a reactor, heating to 120 ℃ under the protection of nitrogen to completely melt the raw materials, adding 0.19g (accounting for 0.5wt percent of reactants) of 4-dimethylaminopyridine under stirring to react for 1h, then heating to 180 ℃ to start reduced pressure (the pressure is reduced to below 6 KPa) distillation reaction for 3h, pumping out a reaction system of phenol serving as a byproduct in the reduced pressure reaction process to prepare a crude product of the aromatic polycarbonate diol, cooling the obtained crude product to room temperature, adding 160g of dichloromethane to dissolve the crude product, purifying the crude product by adopting a liquid separation extraction method, and finally drying in vacuum at 60 ℃ to constant weight to obtain the purified aromatic polycarbonate diol (PCDL).
The obtained aromatic polycarbonate diol had an average degree of polymerization n of 3, a molecular weight of 1342 and a hydroxyl value of 84. + -. 3 mgKOH/g.
FTIR:3454cm-1(-OH)、1732cm-1(-C＝O)、1049cm-1(Primary alcohol-C-O-), 832cm-1(bending out of benzene ring surface) 753cm-1(out-of-plane curvature of the benzene ring).
1H-NMR(600MHz，DMSO-d6):δ1.57(12H)、δ3.71(2H)、δ3.94(2H)、δ4.19(6H)、δ4.32(6H)、δ4.85(1H)、δ6.84(8H)、δ7.09(8H)。
Step two: preparation of thermoplastic polyurethane elastomer compatibilizer containing 0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of aromatic polycarbonate dihydric alcohol (PCDL)
Drying polytetrahydrofuran ether diol (PTMG, molecular weight 1500, hydroxyl value 75mgKOH/g) and the aromatic polycarbonate diol (PCDL) obtained in the step one at 100 ℃ in vacuum for later use; adding dried polytetrahydrofuran ether diol (PTMG) and the aromatic polycarbonate diol (PCDL), triethylene diamine (TEDA) and Toluene Diisocyanate (TDI) obtained in the step one into a reactor in sequence according to the isocyanate index R of 1.02, and heating to 80 ℃ under stirring to react for 5 hours; stopping heating, adding a chain extender 1, 4-Butanediol (BDO) after the temperature of the system is reduced to 60 ℃, fully stirring and uniformly mixing, pouring into a preheated polytetrafluoroethylene mold, putting into a drying oven at 110 ℃ for curing for 10 hours, and obtaining a thermoplastic polyurethane elastomer compatibilizer containing 0 wt% of 1-octadecanoic acid glyceride dihydric alcohol and 8.0 wt% of PCDL; the dosage of each component is as follows: PTMG 17.56 mmol; 2.44mmol of PCDL; TEDA represents 0.5 wt.% of the total mass of all reactants; TDI 50 mmol; BDO 29.02 mmol.
The thermoplastic polyurethane elastomer compatibilizer obtained in this example was characterized as follows:
FTIR:3357cm-1(-N-H-)、2952cm-1(-CH3)、2928cm-1(-CH2)、1731cm-1(-C＝O)、1608cm-1(vibration of benzene ring skeleton) 1530cm-1(-C-N-)、1229cm-1(-C-O-C-)
Application example 1
A PC/PP alloy material comprises the following components:
PC: 60 parts;
PP: 40 parts of a mixture;
compatibilizer prepared in example 1: 10 parts.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Application example 2
A PC/PP alloy material comprises the following components:
PC: 70 parts of (B);
PP: 30 parts of (1);
compatibilizer prepared in example 2: and 2 parts.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Application example 3
A PC/PP alloy material comprises the following components:
PC: 80 parts of a mixture;
PP: 20 parts of (1);
compatibilizer prepared in example 3: 5 parts of the raw materials.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Application comparative example 1
A PC/PP alloy material comprises the following components:
PC: 60 parts;
PP: 40 parts of a mixture;
compatibilizer PP-g-GMA: 10 parts.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Comparative application example 2
A PC/PP alloy material comprises the following components:
PC: 60 parts;
PP: 40 parts of a mixture;
(1) uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Comparative application example 3
A PC/PP alloy material comprises the following components:
PC: 70 parts of (B);
PP: 30 parts of (1);
compatibilizer prepared in comparative example 1: and 2 parts.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Application comparative example 4
A PC/PP alloy material comprises the following components:
PC: 70 parts of (B);
PP: 30 parts of (1);
(1) uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Comparative application example 5
A PC/PP alloy material comprises the following components:
PC: 80 parts of a mixture;
PP: 20 parts of (1);
compatibilizer POE-g-MAH: 5 parts of the raw materials.
(1) Uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Comparative application example 6
A PC/PP alloy material comprises the following components:
PC: 80 parts of a mixture;
PP: 20 parts of (1);
(1) uniformly mixing all the components according to a preset proportion, then bracing by using a double-screw extruder, and granulating to obtain a PC/PP alloy material;
(2) finally, the sample is injection molded on an injection molding machine to obtain a standard sample, and the related performance of the standard sample is determined in the table 1.
Table 1 comparison of the properties of the application examples and the comparative examples
Figure BDA0002893598470000151
As can be seen from Table 1, the addition of the compatibilizer prepared by the invention can effectively improve the compatibility of PC and PP, and further improve the mechanical properties of the PC/PP alloy, such as tensile strength, bending strength, impact strength and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A thermoplastic polyurethane elastomer compatibilizer is characterized by being prepared by polymerizing aromatic polycarbonate dihydric alcohol, 1-long-chain alkanoic acid glyceride dihydric alcohol, polymer dihydric alcohol, diisocyanate and a dihydric alcohol chain extender;
wherein the using amounts of the aromatic polycarbonate diol and the 1-long-chain alkanoic acid glyceride diol are respectively 2-12% and 0.5-4.0% of the mass of the thermoplastic polyurethane elastomer compatibilizer, and the molar ratio of diisocyanate to all diols is 0.95-1.05: 1; the ratio of the molar weight of diisocyanate to the total molar weight of the aromatic polycarbonate diol, the 1-long-chain alkanoic acid glyceride diol and the polymer diol is 2-3: 1;
the structural formula of the aromatic polycarbonate dihydric alcohol is as follows:
Figure FDA0003299047610000011
the average polymerization degree n of the aromatic polycarbonate diol is 1-8;
the 1-long-chain glyceryl alkanoate dihydric alcohol is at least one of 1-glyceryl dodecanoate dihydric alcohol, 1-glyceryl tridecanoate dihydric alcohol, 1-glyceryl tetradecanoate dihydric alcohol, 1-glyceryl pentadecanoate dihydric alcohol, 1-glyceryl hexadecanoate dihydric alcohol, 1-glyceryl heptadecanoate dihydric alcohol, 1-glyceryl octadecanoate dihydric alcohol, 1-glyceryl nonadecanoate dihydric alcohol, 1-glyceryl eicosanoate dihydric alcohol, 1-glyceryl heneicosanoate dihydric alcohol, 1-glyceryl behenate dihydric alcohol, 1-glyceryl tricosanoate dihydric alcohol, 1-glyceryl tetracosanoate dihydric alcohol, 1-glyceryl pentacosanoate dihydric alcohol and 1-glyceryl hexacosanoate dihydric alcohol;
the polymer dihydric alcohol is at least one of polyester dihydric alcohol, polyether dihydric alcohol, polybutadiene dihydric alcohol and polycarbonate dihydric alcohol; the molecular weight of the polymer dihydric alcohol is 1000-3000.
2. The thermoplastic polyurethane elastomer compatibilizer of claim 1 wherein said diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and naphthalene-1, 5-diisocyanate;
the dihydric alcohol chain extender is at least one of 1, 4-butanediol, propanediol and hydroquinone dihydroxyethyl ether.
3. The thermoplastic polyurethane elastomer compatibilizer of claim 1, wherein said polyester diol is at least one of polybutylene adipate diol and polycaprolactone diol; the polyether diol is polytetrahydrofuran ether diol.
4. A method for preparing a thermoplastic polyurethane elastomer compatibilizer as claimed in any one of claims 1 to 3, comprising the steps of:
(1) adding hydroxyethylated bisphenol A and diphenyl carbonate into a reactor, heating to 120-130 ℃ under the protection of nitrogen or inert gas to melt the materials, adding a catalyst to react for 0.5-1 h, heating to 150-200 ℃ and reacting for 2-6 h under a reduced pressure condition, extracting a reaction system from a byproduct phenol in the reduced pressure reaction process, cooling and purifying to obtain aromatic polycarbonate dihydric alcohol;
(2) adding polymer dihydric alcohol, aromatic polycarbonate dihydric alcohol, a catalyst and diisocyanate into a reactor, heating to 70-100 ℃, reacting for 0.5-3 h, adding 1-long-chain alkanoic acid glyceride dihydric alcohol, continuing to react for 1-5 h under heat preservation, cooling to 40-60 ℃, adding a dihydric alcohol chain extender, uniformly mixing, pouring into a preheating mould, and curing at 100-120 ℃ for 4-20 h to obtain the thermoplastic polyurethane elastomer compatibilizer.
5. The method for preparing the thermoplastic polyurethane elastomer compatibilizer according to claim 4, wherein the molar ratio of the hydroxyethylated bisphenol A to the diphenyl carbonate in the step (1) is 1.1-2.0: 1; the dosage of the catalyst is 0.1-1.0% of the total mass of the reactants; the dosage of the catalyst in the step (2) is 0.1-1.0% of the total mass of the reactants.
6. The method for preparing the thermoplastic polyurethane elastomer compatibilizer according to claim 4, wherein the catalyst in the step (1) is at least one of tetrabutyl titanate, sodium hydroxide and 4-dimethylaminopyridine; and (3) the catalyst in the step (2) is at least one of dibutyltin dilaurate, stannous octoate, triethylene diamine and triethylamine.
7. The method for preparing the thermoplastic polyurethane elastomer compatibilizer according to claim 4, wherein the purification method in the step (1) is: adding a solvent into the crude product obtained by the reaction for dissolving, then carrying out liquid separation extraction, and drying to obtain the purified aromatic polycarbonate diol, wherein the mass ratio of the solvent to the crude product is (3-5): 1;
the solvent is at least one of methanol, ethanol, dichloromethane, acetone, tetrahydrofuran, toluene, dimethyl sulfoxide, ethyl acetate, petroleum ether and cyclohexane;
the cooling in the step (1) means cooling to room temperature;
before the reaction of the polymer dihydric alcohol and the aromatic polycarbonate dihydric alcohol in the step (2), vacuum drying at 100 ℃ is carried out to remove moisture; the mold is a polytetrafluoroethylene mold, and the preheating temperature is 100-120 ℃.
8. Use of a thermoplastic polyurethane elastomer compatibilizer as claimed in any one of claims 1 to 3 in a PC/PP alloy.
9. A PC/PP alloy material is characterized in that raw materials comprise, by mass, 60-80 parts of PC, 20-40 parts of PP and 2-10 parts of the thermoplastic polyurethane elastomer compatibilizer defined in any one of claims 1-3.
10. The method for preparing the PC/PP alloy material as recited in claim 9, characterized by comprising the following steps: uniformly mixing the components according to a preset proportion, and then carrying out bracing and dicing by using a double-screw extruder to obtain the PC/PP alloy material.
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