CN108117667B - Plasticizer, preparation method thereof and application thereof in polylactic acid - Google Patents

Plasticizer, preparation method thereof and application thereof in polylactic acid Download PDF

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CN108117667B
CN108117667B CN201711453895.4A CN201711453895A CN108117667B CN 108117667 B CN108117667 B CN 108117667B CN 201711453895 A CN201711453895 A CN 201711453895A CN 108117667 B CN108117667 B CN 108117667B
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pla
plasticizer
diisocyanate
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lactate
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CN108117667A (en
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冯立栋
孙彬
刘焱龙
张宝
项盛
边新超
李杲
陈学思
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Changchun Institute of Applied Chemistry of CAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention provides a plasticizer with a structure shown in a formula (I), a preparation method thereof and application thereof in polylactic acid (PLA): r1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group; r2Is selected from H or C1～C6An alkyl group; r3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes; n is 0 or 1. The plasticizer has good compatibility with PLA, and can obviously reduce the melting point and the glass transition temperature of PLA, thereby effectively reducing the processing temperature of PLA. It also improves the flexibility of PLA and maintains the high tensile modulus and tensile strength of PLA.

Description

Plasticizer, preparation method thereof and application thereof in polylactic acid
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a plasticizer, a preparation method thereof and application thereof in polylactic acid.
Background
Polylactic acid (PLA) is considered to be an environmentally friendly polymer material from renewable resources with the greatest development prospect in this century. PLA has excellent biocompatibility, environmental friendliness, and complete biodegradability, and is considered as an ideal substitute material for petroleum-based polymers. PLA is similar in many properties to general purpose plastics such as polyethylene, polypropylene, polystyrene, etc., and thus can be processed using conventional processing equipment. However, the wide application of PLA in the field of general plastics is limited by the defects of strong brittleness, poor impact resistance, low elongation at break, narrow processing temperature window and the like of the PLA. The flexibility and the processability of the PLA material can be effectively improved by utilizing the plasticizer.
The plasticizer is an auxiliary agent widely used in high polymer materials, and can improve the use and processing performance of the high polymer materials. The flexibility, the flexibility and the cold resistance of the high polymer material can be improved, and the strength, the modulus and the hardness of the material can be reduced, so that the high polymer material is applied to different fields; the glass transition temperature, melting temperature, softening temperature or flowing temperature of the material can be reduced, so that the viscosity of the plastic is reduced, the fluidity is increased, and the processability is improved.
The plasticizer products used for PLA modification at present mainly comprise phthalate, citrate plasticizers, polyethylene glycol and the like. These plasticizers can significantly improve the flexibility of the PLA material, resulting in a substantial increase in the elongation at break of the material, but at the expense of greatly sacrificing the strength and modulus of PLA, and the material can lose the toughening effect during storage and use due to migration of the plasticizer (such as phthalate plasticizers, citrate plasticizers, and low molecular weight polyethylene glycols) or crystallization (such as high molecular weight polyethylene glycols), thereby re-embrittling the plasticized PLA material. Furthermore, the use of phthalate plasticizers is toxic to humans and the natural environment, so that the use and development of such plasticizers are limited.
Thus, there is a need to develop new environmentally friendly migration resistant PLA plasticizers in order to improve the processability of PLA, i.e., to lower the melting point and glass transition temperature of polylactic acid.
Disclosure of Invention
In view of the above, the present invention aims to provide a plasticizer, a preparation method thereof and an application thereof in polylactic acid, wherein the plasticizer has good compatibility with polylactic acid and can reduce the melting point and the glass transition temperature of polylactic acid.
The invention provides a plasticizer with a structure shown in a formula (I):
Figure BDA0001528898380000021
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes;
and n is 0 or 1.
Preferably, said R is1Is selected from C4～C10Substituted cycloaliphatic radical, C3～C10Aliphatic radical of (2), phenyl or C1～C5An alkyl-substituted aromatic group;
the R is2Is selected from H or C1～C3Alkyl groups of (a);
the R is3Is selected from C1～C10Saturated straight-chain alkyl of (2), C2～C8Alkenyl, phenyl or C1～C5Alkyl substituted benzenes.
Preferably, said R is1Is selected from
Figure BDA0001528898380000022
Figure BDA0001528898380000031
Preferably, said R is1Is selected from
Figure BDA0001528898380000032
The R is2Is selected from-CH3；
The R is3Is selected from-C2H5or-C4H9。
The invention provides a preparation method of the plasticizer in the technical scheme, which comprises the following steps:
reacting diisocyanate with monohydroxy compound to obtain plasticizer with formula (I):
Figure BDA0001528898380000033
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes;
and n is 0 or 1.
Preferably, the monohydroxy compound is selected from one or more of α -hydroxy acid ester, monohydric alcohol compound and phenol compound.
Preferably, the monoalcohol compound is selected from C1～C20Aliphatic alcohols and/or aromatic alcohols.
Preferably, the α -hydroxy acid ester is selected from one or more of ethyl lactate, propyl lactate, butyl lactate, pentyl lactate, hexyl lactate, octyl lactate, dodecyl lactate, benzyl lactate, ethyl glycolate, butyl glycolate, n-propyl glycolate, isopropyl glycolate, n-octyl glycolate, ethyl 2-hydroxy-n-butyrate and ethyl 2-hydroxypentanoate.
Preferably, the diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1, 4-cyclohexyl diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, and dimethylbiphenyl diisocyanate.
The invention provides an application of the plasticizer in the technical scheme or the plasticizer prepared by the preparation method in the technical scheme in polylactic acid.
The invention provides a plasticizer with a structure shown in a formula (I): the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group; the R is2Is selected from H or C1～C6An alkyl group; the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes; and n is 0 or 1. The plasticizer has good compatibility with polylactic acid, and can obviously reduce the melting point (T) of PLAm) And glass transition temperature (T)g) Thus, the processing temperature of PLA can be effectively reduced. It also improves the flexibility of PLA and maintains the high tensile modulus and tensile strength of PLA. Fruit of Chinese wolfberryThe test result shows that: 5-30 wt% of plasticizer capable of making T of PLAgThe temperature is reduced from 61 ℃ to 57-30 ℃, and TmReducing the temperature from 176 ℃ to 175-165 ℃; 20 wt% of plasticizer can improve the elongation at break of PLA from 5% to 250% -300%; the tensile strength of the blend is 46-60 MPa; the tensile modulus of the blend is 720-1806 MPa.
Drawings
FIG. 1 is a graph showing the thermogravimetric curves of the plasticizers prepared in examples 1 to 5 of the present invention and commercially available tributyl citrate.
Detailed Description
The invention provides a plasticizer with a structure shown in a formula (I):
Figure BDA0001528898380000041
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes;
and n is 0 or 1.
In the present invention, said R1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group; preferably selected from C4～C10Substituted cycloaliphatic radical, C3～C10Aliphatic radical of (2), phenyl or C1～C5An alkyl-substituted aromatic group;
the R is1More preferably from
Figure BDA0001528898380000051
The R is1Most preferably from
Figure BDA0001528898380000052
In the present invention, said R2Is selected from H or C1～C6An alkyl group; preferably selected from H or C1～C3Alkyl groups of (a); more preferably selected from-CH3；
In the present invention, said R3Is selected from C1～C20Saturated alkyl, cycloalkyl, unsaturated hydrocarbon, phenyl or alkylbenzene; preferably selected from C1～C10Saturated alkyl of (C)2～C8Alkenyl, phenyl or C1～C5Alkyl-substituted benzenes, more preferably selected from-C2H5or-C4H9。
In the present invention, when n is 0, the plasticizer is specifically represented by formula (101):
Figure BDA0001528898380000061
when n is 1, the plasticizer is specifically represented by formula (102):
Figure BDA0001528898380000062
in a specific embodiment of the present invention, the plasticizer is specifically represented by formula (201), formula (202), formula (203), formula (204), or formula (205):
Figure BDA0001528898380000063
the invention provides a preparation method of the plasticizer in the technical scheme, which comprises the following steps:
reacting diisocyanate with monohydroxy compound to obtain plasticizer with formula (I):
Figure BDA0001528898380000071
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes;
and n is 0 or 1.
In the present invention, the monohydroxy compound is one or more selected from the group consisting of α -hydroxy acid ester, monohydric alcohol compound and phenol compound.
The α -hydroxy acid ester is preferably composed of C2～C6α -hydroxy acid and monohydric alcohol compound.
In the present invention, the monohydric alcohol compound selected from the monohydroxy compounds is preferably selected from C1～C20More preferably selected from n-butanol.
In the present invention, the α -hydroxy acid ester is preferably selected from one or more of ethyl lactate, propyl lactate, butyl lactate, pentyl lactate, hexyl lactate, octyl lactate, dodecyl lactate, benzyl lactate, ethyl glycolate, butyl glycolate, n-propyl glycolate, isopropyl glycolate, n-octyl glycolate, ethyl 2-hydroxy-n-butyrate, and ethyl 2-hydroxypentanoate, and is more preferably selected from butyl lactate and/or ethyl lactate.
In the present invention, the diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1, 4-cyclohexyl diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, and dimethylbiphenyl diisocyanate.
The invention can be prepared by reacting diisocyanate with equal chemical equivalent or excessive monohydroxy compound.
And (2) adding lactate and diisocyanate according to a stoichiometric ratio, and obtaining the plasticizer shown as the formula (I) after the reaction is finished.
Some embodiments of the present invention employ reacting a diisocyanate with an excess of a monohydroxy compound, and then distilling off the unreacted monohydroxy compound under reduced pressure to obtain a plasticizer.
The reaction of the diisocyanate with the monohydroxy compound is preferably carried out in a clean, dry, ground-top three-necked flask equipped with a magnetic stirrer, a thermometer, as is well known to those skilled in the art.
In one embodiment of the invention, isophorone diisocyanate and butyl lactate are reacted for 24 hours under the condition of stirring and with the molar ratio of 1:1, and the reaction temperature is controlled not to exceed 70 ℃; cooling to 50 ℃, adding excessive n-butyl alcohol, controlling the reaction temperature to be 50-55 ℃, and reacting for 12 hours; distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 115 ℃, distilling under reduced pressure for 2h, and removing unreacted butyl lactate and n-butyl alcohol to obtain a plasticizer;
in one embodiment of the invention, hexamethylene diisocyanate and butyl lactate react for 20 hours under the stirring condition, the reaction temperature is controlled not to exceed 65-75 ℃; distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 120 ℃, distilling under reduced pressure for 1h, and removing unreacted butyl lactate to obtain a plasticizer;
in one embodiment of the invention, hexamethylene diisocyanate and ethyl lactate react for 20 hours under the stirring condition, the reaction temperature is controlled to be not more than 70-80 ℃; distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 120 ℃, distilling under reduced pressure for 1h, and removing unreacted ethyl lactate to obtain a plasticizer;
in one embodiment of the invention, under the stirring condition, isophorone diisocyanate and butyl lactate slowly raise the temperature to 80 ℃, react for 20h, raise the temperature to 120 ℃, continue to react for 20h, distill under reduced pressure with the vacuum degree of-0.095-0.1 MPa, slowly raise the temperature of the reaction solution to 120-130 ℃, distill under reduced pressure for 2h, remove unreacted butyl lactate, and obtain the plasticizer.
In one embodiment of the invention, 4, 4' -diphenylmethane diisocyanate and butyl lactate are reacted for 20 hours under the stirring condition, the reaction temperature is controlled to be not more than 75-80 ℃; distilling under reduced pressure with the vacuum degree of-0.095 to-0.1 MPa, slowly heating the reaction liquid to 120 ℃, distilling under reduced pressure for 1h, and removing unreacted butyl lactate to obtain the plasticizer.
The invention provides an application of the plasticizer in the technical scheme or the plasticizer prepared by the preparation method in the technical scheme in polylactic acid.
The plasticizer provided by the invention is mixed with polylactic acid, has good compatibility with the polylactic acid, and can reduce the melting point and the glass transition temperature of the polylactic acid.
The mass ratio of the plasticizer to the polylactic acid is preferably 20-80: 80-20.
The compatibility of PLA with NR series plasticizers was evaluated using formula (1) in the present invention.
Figure BDA0001528898380000091
When the two blend components are fully compatible, a single glass transition temperature (T) is exhibitedg0) And satisfyEquation (1), when the two blend components are partially compatible, theoretically shows two close to each other Tg1And Tg2However, sometimes the glass transition of the low content component is not significant, where the glass transition temperature (T) of the component-rich PLA phase is usedg,exp) Theoretical glass transition temperature (T) at full compatibility with PLA/NRg0) And comparing to determine compatibility of the two.
The obtained NR series plasticizers were tested for volatility or thermal stability using thermogravimetric analysis (TGA). And compared to the volatility or thermal stability of the traditional plasticizer tributyl citrate (TBC).
Melting points (T) of the obtained NR series of plasticizers, PLA/NR blends were tested using Differential Scanning Calorimetry (DSC)m) And glass transition temperature (T)g)。
The invention provides a plasticizer with a structure shown in a formula (I): the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group; the R is2Is selected from H or C1～C6An alkyl group; the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes; and n is 0 or 1. The plasticizer has good compatibility with polylactic acid, and can obviously reduce the melting point (T) of PLAm) And glass transition temperature (T)g) Thus, the processing temperature of PLA can be effectively reduced. It also improves the flexibility of PLA and maintains the high tensile modulus and tensile strength of PLA. The experimental results show that: 5-30 wt% of plasticizer capable of making T of PLAgThe temperature is reduced from 61 ℃ to 57-30 ℃, and TmReducing the temperature from 176 ℃ to 175-165 ℃; 20 wt% of plasticizer can improve the elongation at break of PLA from 5% to 250% -300%; the tensile strength of the blend is 46-60 MPa; in totalThe tensile modulus of the mixture is 720-1806 MPa.
In order to further illustrate the present invention, the following examples are provided to describe a plasticizer, a method for preparing the same, and the use thereof in polylactic acid in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 100g of isophorone diisocyanate (IPDI) into a sealed clean and dry ground three-neck flask which is provided with a magnetic stirrer and a thermometer, adding butyl lactate according to the molar ratio of isocyanate groups (-NCO) to butyl lactate in the IPDI being 1:1, slowly heating to 70 ℃ under the stirring condition, continuing to react for 24h, cooling to 50 ℃, adding n-butyl alcohol according to the molar ratio of IPDI to n-butyl alcohol being 1:1.3, controlling the reaction temperature to be 50-55 ℃, reacting for 12h, distilling under reduced pressure, controlling the vacuum degree to be-0.095-0.1 MPa, slowly heating the reaction liquid to 115 ℃, distilling under reduced pressure for 2h, removing unreacted n-butyl alcohol and butyl lactate, and obtaining a plasticizer NR-1# product. The preparation process is carried out in a closed system, and the tightness of the system is taken into consideration to prevent moisture in the air from entering the reaction system.
The structural formula of NR-1# is shown as a formula (201):
Figure BDA0001528898380000101
glass transition temperature (T) of NR-1# measured by DSCg) Comprises the following steps: the thermogravimetric curve of NR-1# at-3.72 ℃ measured by TGA is shown in FIG. 1, and FIG. 1 is a thermogravimetric curve of the plasticizer prepared in examples 1 to 5 of the present invention and commercially available tributyl citrate (TBC). As can be seen from fig. 1, the plasticizers provided by the present application are less volatile and more thermally stable than conventional plasticizer TBCs.
The blend is prepared by a solution blending method. The mixture ratio of the blend is carried out according to the mass ratio of PLA/NR-1# of 95/5, 90/10, 80/20 and 70/30, 1.0g of the PLA/NR-1# blend is dissolved in 30mL of dichloromethane, after the dissolution, the dichloromethane used as a solvent is carefully evaporated, and the residual solvent is removed by keeping the temperature of the dichloromethane at 90 ℃ for 40min to obtain the final productPLA/NR-1# blend samples were obtained and tested by DSC for the glass transition temperature of the PLA/NR-1# blend. T of the PLA usedgA melting point (T) of 61.2 DEG Cm) The temperature was 176.1 ℃. The melting point (T) of the PLA phase in the blends obtained was actually testedm) Glass transition temperature (T)g,exp) And the theoretical glass transition temperature (T) at which the two components of the blend are fully compatibleg0) As shown in table 1. T of PLA phase in blendmDecreases as the content of NR-1# increases. When the content of NR-1# is less than or equal to 20wt percent, Tg,expAnd Tg0There was no significant difference, indicating that the two are completely compatible, T at a NR-1# content of 30 wt%g,expIs significantly greater than Tg0The values indicate that the NR-1# content is partially compatible at not less than 30 wt%.
TABLE 1T of PLA/NR-1# blendsmAnd TgData sheet
Figure BDA0001528898380000102
Tg0Theory T when the two components of the blend are completely compatiblegA value; t isg,exp-actual measured T of the blendgValue or T of PLA phase in blendgA value; delta Tg＝Tg0-Tg,exp。
Example 2
79.9g of Hexamethylene Diisocyanate (HDI) and 152.3g of excessive butyl lactate are added into a sealed clean and dry ground three-necked bottle provided with a magnetic stirrer and a thermometer, and the reaction is carried out for 20 hours under the stirring condition at the reaction temperature of 65-75 ℃ or below. Distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 120 ℃, distilling under reduced pressure for 1h, and removing unreacted butyl lactate to obtain a plasticizer NR-2# product. The preparation process is carried out in a closed system, and the tightness of the system is taken into consideration to prevent moisture in the air from entering the reaction system.
The structural formula of NR-2# is shown as formula (202):
Figure BDA0001528898380000111
glass transition temperature (T) of NR-2# measured by DSCg) Comprises the following steps: the thermogravimetric curve of NR-2# measured by TGA at-39.73 ℃ is shown in FIG. 1.
The blends were prepared using the solution blending method and tested as in example 1. DSC testing of PLA/NR-2# blends for Tg. T of the PLA usedgAt 61.2 ℃ and TmThe temperature was 176.1 ℃. Practical testing of the T of the PLA phase in the blends obtainedmGlass transition temperature (T) of the blendg,exp) And the theoretical glass transition temperature (T) at which the two components of the blend are fully compatibleg0) As shown in table 2. T of PLA phase in blendmDecreases as the content of NR-2# increases. T when the PLA/NR-2# blend ratio is 95/5 and 90/10g,expAnd Tg0There was no significant difference, and when the PLA/NR-2# blend ratio was 80/20 and 70/30, T wasg,expIs significantly greater than Tg0Values, which indicate partial compatibility with PLA at NR-2 #.
TABLE 2T of PLA/NR-2# blendsmAnd TgData sheet
Figure BDA0001528898380000112
Tg0Theory T when the two components of the blend are completely compatiblegA value; t isg,exp-actual measured T of the blendgValue or T of PLA phase in blendgA value; delta Tg＝Tg0-Tg,exp。
Example 3
89.8g of HDI and 140.1g of excessive ethyl lactate are added into a sealed clean and dry ground three-neck flask which is provided with a magnetic stirrer and a thermometer, the reaction temperature is controlled to be not more than 70-80 ℃ under the stirring condition, and the reaction is carried out for 20 hours. Distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 120 ℃, distilling under reduced pressure for 1h, and removing unreacted ethyl lactate to obtain a plasticizer NR-3# product. The preparation process is carried out in a closed system, and the tightness of the system is taken into consideration to prevent moisture in the air from entering the reaction system.
The structural formula of NR-3# is shown in formula (203):
Figure BDA0001528898380000121
glass transition temperature (T) of NR-3# measured by DSCg) Comprises the following steps: the thermogravimetric curve of NR-3# at-26.55 ℃ by TGA test is shown in FIG. 1.
Solution blend preparation and testing was the same as example 1. DSC testing of PLA/NR-3# blends for Tg. T of the PLA usedgAt 61.2 ℃ and TmThe temperature was 176.1 ℃. Practical testing of the T of the PLA phase in the blends obtainedmGlass transition temperature (T) of the blendg,exp) And the theoretical glass transition temperature (T) at which the two components of the blend are fully compatibleg0) As shown in table 3. T of PLA phase in blendmDecreases as the content of NR-3# increases. T isg,expAnd Tg0There was no significant difference, indicating that at an NR-3# content of 30 wt% or less, the two were completely compatible.
TABLE 3T of PLA/NR-3# blendsmAnd TgData sheet
Figure BDA0001528898380000122
Tg0Theory T when the two components of the blend are completely compatiblegA value; t isg,exp-actual measured T of the blendgValue or T of PLA phase in blendgA value; delta Tg＝Tg0-Tg,exp。
Example 4
Adding 89.4g of isophorone diisocyanate (IPDI) into a sealed clean and dry ground three-neck flask which is provided with a magnetic stirrer and a thermometer, adding 150.0g of excessive butyl lactate, slowly heating to 80 ℃ under the stirring condition, reacting for 20h, heating to 120 ℃, continuing to react for 20h, distilling under reduced pressure with the vacuum degree of-0.095 to-0.1 MPa, slowly heating the reaction solution to 120-130 ℃, distilling under reduced pressure for 2h, and removing unreacted butyl lactate to obtain a plasticizer NR-4 product. The preparation process is carried out in a closed system, and the tightness of the system is taken into consideration to prevent moisture in the air from entering the reaction system.
The structural formula of NR-4# is shown in formula (204):
Figure BDA0001528898380000131
glass transition temperature (T) of NR-4# measured by DSCg) Comprises the following steps: the thermogravimetry curve of NR-4# at 1.93 deg.C and by TGA test is shown in FIG. 1.
The blends were prepared using the solution blending method and tested as in example 1. DSC testing of PLA/NR-4# blends for Tg. T of the PLA usedgAt 61.2 ℃ and TmThe temperature was 176.1 ℃. Practical testing of the T of the PLA phase in the blends obtainedmGlass transition temperature (T) of the blendg,exp) And the theoretical glass transition temperature (T) at which the two components of the blend are fully compatibleg0) As shown in table 4. T of PLA phase in blendmDecreases as the content of NR-4# increases. T isg,expAnd Tg0There was no significant difference, indicating that at an NR-4# content of 30 wt% or less, the two were completely compatible.
TABLE 4T of PLA/NR-4# blendsmAnd TgData sheet
Figure BDA0001528898380000132
Tg0Theory T when the two components of the blend are completely compatiblegA value; t isg,exp-actual measured T of the blendgValue or T of PLA phase in blendgA value; delta Tg＝Tg0-Tg,exp。
Example 5
Adding 50.3g of 4, 4' -diphenylmethane diisocyanate (MDI) into a sealed clean and dry ground three-neck flask which is provided with a magnetic stirrer and a thermometer, adding 120.1g of a large amount of excessive butyl lactate, and reacting for 20 hours under the stirring condition at the reaction temperature of not more than 75-80 ℃. Distilling under reduced pressure, wherein the vacuum degree is-0.095-0.1 MPa, slowly heating the reaction solution to 120 ℃, and distilling under reduced pressure for 1h to remove unreacted butyl lactate to obtain a plasticizer NR-5# product. The preparation process is carried out in a closed system, and the tightness of the system is taken into consideration to prevent moisture in the air from entering the reaction system.
The structural formula of NR-5# is shown as formula (205):
Figure BDA0001528898380000133
Figure BDA0001528898380000141
glass transition temperature (T) of NR-5# measured by DSCg) At 16.3 deg.C, the thermogravimetry curve of NR-5# using TGA is shown in FIG. 1.
The blends were prepared using the solution blending method and tested as in example 1. DSC testing of PLA/NR-5# blends for Tg. T of the PLA usedgAt 61.2 ℃ and TmThe temperature was 176.1 ℃. Practical testing of the T of the PLA phase in the blends obtainedmGlass transition temperature (T) of the blendg,exp) And the theoretical glass transition temperature (T) at which the two components of the blend are fully compatibleg0) As shown in table 5. T of PLA phase in blendmDecreases as the content of NR-5# increases. T isg,expAnd Tg0There was no significant difference, indicating that at an NR-5# content of 30 wt% or less, the two were completely compatible.
TABLE 5T of PLA/NR-5# blendsmAnd TgData sheet
Figure BDA0001528898380000142
Tg0Theory T when the two components of the blend are completely compatiblegA value; t isg,exp-actual measured T of the blendgValue or T of PLA phase in blendgA value; delta Tg＝Tg0-Tg,exp。
Example 6
The plasticizers NR-1#, NR-2#, NR-3#, NR-4#, and NR-5# obtained in examples 1 to 5 and commercially available tributyl citrate (TBC) were melt-blended with PLA, and the mechanical properties of the blend were tested. The blend was melt blended at PLA/plasticizer/ADR in a mass ratio of 80/20/0.4 (ADR-4370-S, BASF, as a processing stabilizer).
PLA, plasticizer and ADR are melted and blended in an XSS-300 internal mixer according to a given proportion, the blending temperature is 190 ℃, the rotating speed of the internal mixer is 32r/min, and the blending time is 8 min. The blended sample is directly cooled in the air state at room temperature, cut into small pieces, pressed into a sheet with the thickness of 1mm on a flat vulcanizing machine at the temperature of 190 ℃ and under the pressure of 6MPa, and then placed between two thick iron plates to be quenched to the room temperature. Cutting the pressed sample into dumbbell-shaped sample strips with a punch and a cutter, wherein the effective part size is 20 multiplied by 4 multiplied by 1mm3. And (3) carrying out a tensile experiment on the sample strip on an electronic tensile machine, wherein the test temperature is 23 +/-2 ℃, and the tensile rate is 5.0 mm/min. Five bars were tested in parallel for each sample and the final results were averaged and the standard deviation calculated. Mechanical property test data for PLA/plasticizer/ADR blends Table 6 contains data for elongation at break, tensile strength, and tensile modulus for PLA/NR-1#/ADR (80/20/0.4), PLA/NR-2#/ADR (80/20/0.4), PLA/NR-3#/ADR (80/20/0.4), PLA/NR-4#/ADR (80/20/0.4), PLA/NR-5#/ADR (80/20/0.4), and PLA/TBC/ADR (80/20/0.4) blends, as shown in Table 6.
TABLE 6 mechanical Properties data for PLA/plasticizer/ADR (80/20/0.4) blends
Figure BDA0001528898380000151
The plasticizers NR-1#, NR-2#, NR-3#, NR-4# and NR-5# obtained in examples 1 to 5 all reduced the melting point (T) of PLAm) And glass transition temperature (T)g)。
It is clear from example 6 that NR-1#, NR-4# and NR-5# do not significantly increase the elongation at break of PLA, but have a small effect on the tensile strength and modulus of the blended material. Therefore, NR-1#, NR-4# and NR-5# can not improve the toughness of the PLA material, but can not obviously affect the strength and the modulus of the PLA material, and NR-1#, NR-4# and NR-5# can improve the processability of the PLA material.
Under preferential conditions, the obtained plasticizers NR-2# and NR-3# can not only lower the melting point (T) of PLAm) And glass transition temperature (T)g) And the toughness of the PLA material can be improved, and the elongation at break of the PLA can be improved from 5% to 250% -300% under the condition that the content of the plasticizers NR-2# and NR-3# is 20 wt%, and meanwhile, the higher tensile strength and tensile modulus of the material are kept.
In the present application, although the elongation at break of PLA/NR-2# and PLA/NR-3# blends is lower than that of PLA/TBC blends, both the tensile strength and modulus of PLA/NR-2# and PLA/NR-3# blends are much higher than that of PLA/TBC blends.
As can be seen from the above examples, the present invention provides a plasticizer having the structure of formula (I): the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group; the R is2Is selected from H or C1～C6An alkyl group; the R is3Is selected from C1～C20Saturated straight-chain alkyl of (2), C3～C10Cycloalkyl of, C2～C20Unsaturated hydrocarbon radical, phenyl or C1～C10Alkyl-substituted benzenes; and n is 0 or 1. The plasticizer has good compatibility with polylactic acid, and can obviously reduce the melting point (T) of PLAm) And glass transition temperature (T)g) Thus, the processing temperature of PLA can be effectively reduced. It also improves the flexibility of PLA and maintains the high tensile modulus and tensile strength of PLA. The experimental results show that: 5-30 wt% of plasticizer capable of making T of PLAgThe temperature is reduced from 61 ℃ to 57-30 ℃, and TmReducing the temperature from 176 ℃ to 175-165 ℃; 20 wt% of plasticizer can improve the elongation at break of PLA from 5% to 250% -300%; the tensile strength of the blend is 46-60 MPa; the tensile modulus of the blend is 720-1806 MPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A plasticizer having the structure of formula (I):
Figure FDA0002202783660000011
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl groups of (a);
and n is 0 or 1.
2. The plasticizer according to claim 1, wherein R is1Is selected from C4～C10Substituted cycloaliphatic radical, C3～C10Aliphatic radical of (2), phenyl or C1～C5An alkyl-substituted aromatic group;
the R is2Is selected from H or C1～C3Alkyl groups of (a);
the R is3Is selected from C1～C10Saturated straight-chain alkyl groups of (1).
3. The plasticizer according to claim 1, wherein R is1Is selected from
Figure FDA0002202783660000012
Figure FDA0002202783660000021
4. A plasticizer according to claims 1 to 3, wherein R is1Is selected from
Figure FDA0002202783660000022
The R is2Is selected from-CH3；
The R is3Is selected from-C2H5or-C4H9。
5. A method for preparing the plasticizer according to any one of claims 1 to 4, comprising the steps of:
reacting diisocyanate with monohydroxy compound to obtain plasticizer with formula (I):
Figure FDA0002202783660000023
the R is1Is selected from C2～C15Aliphatic radical of (2), C3～C20A cycloaliphatic radical of, C6～C20Aromatic group of (2), C2～C10Substituted aliphatic radical, C1～C10Substituted cycloaliphatic radicals or C1～C10A substituted aromatic group;
the R is2Is selected from H or C1～C6An alkyl group;
the R is3Is selected from C1～C20Saturated straight-chain alkyl groups of (a);
and n is 0 or 1.
6. The production method according to claim 5, wherein the monohydroxy compound is one or more selected from the group consisting of α -hydroxy acid ester, monohydric alcohol compound and phenol compound.
7. The method according to claim 6, wherein the monohydric alcohol compound is selected from the group consisting of C1～C20Aliphatic alcohols and/or aromatic alcohols.
8. The method according to claim 5, wherein the α -hydroxy acid ester is selected from one or more of ethyl lactate, propyl lactate, butyl lactate, pentyl lactate, hexyl lactate, octyl lactate, dodecyl lactate, benzyl lactate, ethyl glycolate, butyl glycolate, n-propyl glycolate, isopropyl glycolate, n-octyl glycolate, 2-hydroxy-n-butyl acetate, and 2-hydroxy-ethyl valerate.
9. The method according to claim 5, wherein the diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1, 4-cyclohexyl diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, and dimethylbiphenyl diisocyanate.
10. Use of the plasticizer according to any one of claims 1 to 4 or the plasticizer prepared by the preparation method according to any one of claims 5 to 9 in polylactic acid.
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