CN102942772A - Toughening polylactic acid resin composition - Google Patents
Toughening polylactic acid resin composition Download PDFInfo
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- CN102942772A CN102942772A CN2012105168137A CN201210516813A CN102942772A CN 102942772 A CN102942772 A CN 102942772A CN 2012105168137 A CN2012105168137 A CN 2012105168137A CN 201210516813 A CN201210516813 A CN 201210516813A CN 102942772 A CN102942772 A CN 102942772A
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Abstract
The invention provides a toughening polylactic acid resin composition comprising 100 parts by weight of polylactic acid, 5-25 parts by weight of toughening agent and 0.1-1 part by weight of first antioxidant, wherein the toughening agent is a copolymer of a core-shell structure which takes butadiene-styrene copolymer as a core and takes epoxypropyl methacrylate compolymer as a shell. According to the toughening polylactic acid resin composition provided by the invention, the copolymer of the core-shell structure which takes butadiene-styrene copolymer as the core and takes epoxypropyl methacrylate compolymer as the shell is taken as the toughening agent to toughen polylactic acid, and the toughening agent can be used for effectively improving the breaking elongation, impact strength and tensile strength of the polylactic acid, so that the polylactic acid with good comprehensive performance is obtained. Mechanics performance testing results show that the impact strength of the toughening polylactic acid resin composition provided by the invention reaches up to 66.8KJ/m<2>, the breaking elongation is about 200% and the tensile strength reaches up to 56.4MPa.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of toughened polylactic resin composition.
Background technology
Poly(lactic acid) (PLA) is also referred to as polylactide, by plant amylum fermentation and lactic acid polymerizes form, its raw material sources are fully and can regenerate, production process is pollution-free, and product can biological degradation, be implemented in the circulation of occurring in nature, so poly(lactic acid) is desirable Green Polymer Material.The good thermal stability of poly(lactic acid) has good good solubility-resistence, and available various ways is processed, such as extruding, spinning, biaxial stretch-formed, injection moulding, blowing.The product of being made by poly(lactic acid) not only can biological degradation, and biocompatibility, glossiness, the transparency, feel and thermotolerance are good, therefore its purposes is very extensive, can be used as wrapping material, fiber and non-woven fabric etc., be mainly used at present the fields such as clothes, building, agricultural, forestry, papermaking and health care.Increasingly under the intense situation, it is particularly important that the development research polylactic resin seems at petroleum-based energy.
But the fragility of poly(lactic acid) is serious, and its resistance to impact shock is less than 5KJ/m
2, seriously limited its application.In the prior art, mainly adopt the toughness of the method raising poly(lactic acid) of polycomponent blending and modifying, to improve the serious shortcoming of its fragility.
Poly(lactic acid) and second component blending and modifying are a kind of method of modifying commonly used, such as the impact modified technology of poly-(ethylene-acrylate) multipolymer (EAC) of biological degradation to poly(lactic acid), the elongation at break of the PLA/EAC blend of preparation has improved 8 times, the breach resistance to impact shock is brought up to 348.4J/m (Macromolecular and Materials Engineering by 16.9J/m, 2010,295:802-811.).
Su Siling etc. have studied the toughening modifying of E-MA-GMA triblock copolymer to poly(lactic acid), end carboxyl and the terminal hydroxy group of the epoxy-functional of E-MA-GMA and PLA react, so that multipolymer and PLA have certain consistency, the impact property of PLA be improved (polymer material science and engineering, 2008,24 (4): 53-57.).
The microtexture that Liu Hongzhi etc. has studied the PLA/EBA-GMA/EMAA-Zn terpolymer interacts and interfacial adhesion, reaction has occured in PLA and EBA-GMA in the melt blending process, so that multipolymer and PLA have certain consistency, the impact property of PLA has obtained raising (Macromolecules to a certain degree, 2011,44:1513-1522.).
The poly(lactic acid) of the discovery 70:30 mass ratioes such as Yasuo Takagi with improved 16 times of (Journal of Applied PolymerScience with poly-(3-hydroxy alkane acid ester) blend of epoxy group(ing) side chain than the shock strength of PLA, 2004,93:2363-2369.).
Sun Shulins etc. have prepared the toughness reinforcing PLA of nucleocapsid structure ABS grafting GMA, improve the consistency of nucleocapsid toughner and PLA, thereby improved resistance to impact shock (the Journal of Applied PolymerScience of PLA, 2011,122:2992-2999.), this method of modifying has improved the resistance to impact shock of material.
Although above-mentioned blending modification method has improved the resistance to impact shock of poly(lactic acid), reduced its tensile strength.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of toughened polylactic resin composition, has higher tensile strength and resistance to impact shock.
The invention provides a kind of toughened polylactic resin composition, comprising:
The poly(lactic acid) of 100 mass parts;
The toughner of 5 ~ 25 mass parts;
0.1 the first oxidation inhibitor of ~ 1 mass parts;
Described toughner comprises that butadiene-styrene copolymer is nuclear, and methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell.
Preferably, in the described toughner, the massfraction of described butadiene-styrene copolymer is 60% ~ 80%, and the massfraction of described methyl methacrylate and glytidyl methacrylate multipolymer is 20% ~ 40%.
Preferably, in the described butadiene-styrene copolymer, divinyl and cinnamic mass ratio are (60 ~ 70): (30 ~ 40).
Preferably, in described methyl methacrylate-glytidyl methacrylate multipolymer, the mass ratio of methyl methacrylate and glytidyl methacrylate is (95 ~ 99): (1 ~ 5).
Preferably, the toughner that comprises 10 ~ 20 mass parts.
Preferably, the number-average molecular weight of described poly(lactic acid) is 5 ~ 200,000 dalton.
Preferably, described the first oxidation inhibitor is that mass ratio is the antioxidant 1010 of 1:2 and the mixture of irgasfos 168.
Preferably, described toughner prepares in accordance with the following methods:
A) polybutadiene latex, water, trisodium phosphate, glucose, ferrous sulfate, rosin soap lye and potassium hydroxide are mixed, obtain the polyhutadiene emulsion;
B) with methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene and described steps A) the polyhutadiene emulsion that obtains mixes, and carries out polyreaction, then adds the second oxidation inhibitor, obtains toughner.
Preferably, the temperature of described polyreaction is 40 ℃ ~ 120 ℃.
Compared with prior art, the invention provides a kind of toughened polylactic resin composition, comprising: the poly(lactic acid) of 100 mass parts; The toughner of 5 ~ 25 mass parts; 0.1 the first oxidation inhibitor of ~ 1 mass parts; Described toughner comprises that butadiene-styrene copolymer is nuclear, and methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell.The present invention is to comprise that butadiene-styrene copolymer is as nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are that the nucleocapsid structure multipolymer of shell is toughner, carry out toughness reinforcing to poly(lactic acid), but elongation at break, resistance to impact shock and the tensile strength of this toughner Effective Raise poly(lactic acid) obtain the good poly(lactic acid) of over-all properties.The toughened polylactic resin composition Application Areas that the present invention obtains is extensive, alternative PE, PVC etc. make various environmental protection plastic products, such as film, sheet material, sheet material, foaming product and injection-molded plastic spare etc., especially in the food product packing film field, market outlook are wide.And the blending modification method equipment for preparing this plasticizing polylactic acid resin is simple, technique is advanced, is fit to multiple process requirements.
Experimental result shows that the resistance to impact shock of plasticizing polylactic acid resin provided by the invention is up to 66.8KJ/m
2, elongation at break is about 200%, tensile strength reaches 56.4MPa.
Embodiment
The invention provides a kind of toughened polylactic resin composition, comprising:
The poly(lactic acid) of 100 mass parts;
The toughner of 5 ~ 25 mass parts;
0.1 the first oxidation inhibitor of ~ 1 mass parts;
Described toughner comprises that butadiene-styrene copolymer is nuclear, and methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell.
The present invention is to comprise that butadiene-styrene copolymer is as nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are that the nucleocapsid structure multipolymer of shell is toughner, carry out toughness reinforcing to poly(lactic acid), but elongation at break, resistance to impact shock and the tensile strength of this toughner Effective Raise poly(lactic acid) obtain the good poly(lactic acid) of over-all properties.
The present invention is preferably 5 ~ 200,000 dalton to the number-average molecular weight of described poly(lactic acid), more preferably 8 ~ 180,000 dalton.The content of described poly(lactic acid) is preferably 80 ~ 120 weight parts, more preferably 95 ~ 105 weight parts.
Toughened polylactic resin composition provided by the invention comprises the first oxidation inhibitor, described the first oxidation inhibitor is preferably four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010) and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) mixture of ester (irgasfos 168), described antioxidant 1010 and irgasfos 168 mass ratio are preferably 1:2; The content of described the first oxidation inhibitor is preferably 0.1 ~ 1 weight part, more preferably 0.3 ~ 0.8 weight part.
In the present invention, described toughened polylactic resin composition comprises toughner, described toughner comprises that butadiene-styrene copolymer is nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell, this butadiene-styrene copolymer is nuclear, but methyl methacrylate and glytidyl methacrylate multipolymer are elongation at break, resistance to impact shock and the tensile strength of the nucleocapsid structure toughner Effective Raise poly(lactic acid) of shell, obtain the good poly(lactic acid) of over-all properties.
In described toughner, the massfraction of described butadiene-styrene copolymer is preferably 60% ~ 80%, and more preferably 60% ~ 70%; The massfraction of described methyl methacrylate and glytidyl methacrylate multipolymer is preferably 20% ~ 40%, and more preferably 30% ~ 40%.In the described butadiene-styrene copolymer, divinyl and cinnamic mass ratio are preferably (60 ~ 70): (30 ~ 40), more preferably (60 ~ 65): (35 ~ 40).In described methyl methacrylate and the glytidyl methacrylate multipolymer, the mass ratio of methyl methacrylate and glytidyl methacrylate is preferably (95 ~ 99): (1 ~ 5), more preferably (97 ~ 99): (1 ~ 3).The content of described toughner in polylactic resin is preferably 5 ~ 25 mass parts, more preferably 10 ~ 20 mass parts.
Among the present invention, described toughner is in accordance with the following methods preparation preferably:
A) polybutadiene latex, water, trisodium phosphate, glucose, ferrous sulfate, rosin soap lye and potassium hydroxide are mixed, obtain the polyhutadiene emulsion;
B) with methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene and described steps A) the polyhutadiene emulsion that obtains mixes, carry out polyreaction, then add the second oxidation inhibitor, obtain butadiene-styrene copolymer and be nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are the toughner that the nucleocapsid structure multipolymer of shell forms.
At first polybutadiene latex, water, trisodium phosphate, glucose, ferrous sulfate, rosin soap lye and potassium hydroxide are mixed, wherein, the quality of described polybutadiene latex and the volume ratio of water are preferably 340g ~ 500g:1300mL ~ 1700mL, more preferably 360g ~ 420g:1300mL ~ 1700mL; The quality of described trisodium phosphate and the volume ratio of water are preferably 2g ~ 3g:1300mL ~ 1700mL; The quality of described glucose and the volume ratio of water are preferably 3g ~ 4g:1300mL ~ 1700mL; The quality of described ferrous sulfate and the volume ratio of water are preferably 0.05g ~ 0.1g:1300mL ~ 1700mL; The volume of described rosin soap lye and the volume ratio of water are preferably 15mL ~ 20mL:1300mL ~ 1700mL; The quality of described potassium hydroxide and the volume ratio of water are preferably 0.5g ~ 1g:1300mL ~ 1700mL.Described water is solvent, trisodium phosphate is sequestrant, glucose is for helping reductive agent, ferrous sulfate is reductive agent, the rosin soap lye is emulsifying agent, the present invention there is no particular restriction to the source of described butadiene latex, trisodium phosphate, glucose, ferrous sulfate, rosin soap lye, potassium hydroxide, can be for generally commercially available, and its purity is preferably technical grade.The median size of described butadiene latex is preferably 200nm ~ 400nm, more preferably 250nm ~ 350nm; Its solid content is preferably 40% ~ 60%, and more preferably 45% ~ 55%.The present invention there is no particular restriction to the mode of described reaction, can be reactive mode well known to those skilled in the art, and the present invention is preferably stirring reaction.The temperature of described reaction is preferably 50 ℃ ~ 80 ℃, more preferably 60 ℃ ~ 70 ℃.
After obtaining the polyhutadiene emulsion, methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene are mixed with it, carry out polyreaction, then add the second oxidation inhibitor, can obtain butadiene-styrene copolymer and be nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are the toughner that the nucleocapsid structure multipolymer of shell forms.The quality of described methyl methacrylate and steps A) volume ratio of water is preferably 100g ~ 300g:1300mL ~ 1700mL, 110g ~ 230g:1300mL ~ 1700mL more preferably; The quality of described glytidyl methacrylate and steps A) volume ratio of water is preferably 2g ~ 30g:1300mL ~ 1700mL, 4g ~ 23g:1300mL ~ 1700mL more preferably; The volume of described hydrogen phosphide cumene and steps A) volume ratio of water is preferably 1mL ~ 6mL:1300mL ~ 1700mL, 2mL ~ 4.5mL:1300mL ~ 1700mL more preferably; The quality of described the second oxidation inhibitor and steps A) volume ratio of water is preferably 2g ~ 4g:1300mL ~ 1700mL, 1g ~ 2g:1300mL ~ 1700mL more preferably.The present invention there is no particular restriction to the source of described methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene, can be for generally commercially available, and its purity is preferably technical grade.The present invention there is no particular restriction to the kind of described the second oxidation inhibitor, can be oxidation inhibitor well known to those skilled in the art, also can be identical with the first oxidation inhibitor, and any one in the preferred antioxidant 1010 of the present invention or the irgasfos 168 or two kinds.The present invention is to described methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene and steps A) order by merging of the polyhutadiene emulsion that obtains there is no particular restriction, be preferably first methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene mixed, then drop to steps A) in the polyhutadiene emulsion that obtains.The temperature of described polyreaction is preferably 40 ℃ ~ 120 ℃, more preferably 60 ℃ ~ 80 ℃; The time of reaction is preferably 0.5h ~ 3h, more preferably 1h ~ 2h.
In the present invention, preferably in accordance with the following methods preparation of described toughened polylactic resin composition: described poly(lactic acid), toughner and the first oxidation inhibitor are mixed, obtain Preblend, then adopt twin screw extruder to be mixed with toughened polylactic resin composition.The present invention there is no particular restriction to the hybrid mode of described poly(lactic acid), toughner and the first oxidation inhibitor, can be hybrid mode well known to those skilled in the art, and the present invention is preferably mechanically mixing; The present invention there is no particular restriction to described twin screw extruder, can be twin screw extruder well known to those skilled in the art, and the present invention is preferably SHJ-20 type twin screw extruder; The present invention there is no particular requirement to the technique that is mixed with polylactic resin, can be the technique that is mixed with well known to those skilled in the art, be preferably, rotating speed is 80 rev/mins ~ 150 rev/mins, time is 3 minutes ~ 8 minutes, the temperature of each section of twin screw extruder is preferably 10 ℃ ~ 30 ℃ in larynx district, 150 ℃ ~ 200 ℃ in one district, 160 ℃ ~ 210 ℃ in two districts, 170 ℃ ~ 220 ℃ in three districts, 170 ℃ ~ 230 ℃ in four districts, 170 ℃ ~ 230 ℃ in five districts, 170 ℃ ~ 230 ℃ in six districts, 170 ℃ ~ 220 ℃ in seven districts, 160 ℃ ~ 210 ℃ of heads; More preferably the larynx district is 15 ℃ ~ 25 ℃, 170 ℃ ~ 180 ℃ in a district, 175 ℃ ~ 195 ℃ in two districts, 180 ℃ ~ 200 ℃ in three districts, 180 ℃ ~ 210 ℃ in four districts, 180 ℃ ~ 210 ℃ in five districts, 180 ℃ ~ 210 ℃ in six districts, 180 ℃ ~ 200 ℃ in seven districts, 175 ℃ ~ 195 ℃ of heads.
The polylactic resin that obtains is carried out Mechanics Performance Testing, and the result shows that the resistance to impact shock of toughened polylactic resin composition provided by the invention is up to 66.8KJ/m
2, elongation at break is about 200%, tensile strength reaches 56.4MPa.
The invention provides a kind of toughened polylactic resin composition, comprising: the poly(lactic acid) of 100 mass parts; The toughner of 5 ~ 25 mass parts; 0.1 the first oxidation inhibitor of ~ 1 mass parts; Described toughner comprises that butadiene-styrene copolymer is nuclear, and methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell.The present invention is to comprise that butadiene-styrene copolymer is as nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are that the nucleocapsid structure multipolymer of shell is toughner, carry out toughness reinforcing to poly(lactic acid), but elongation at break, resistance to impact shock and the tensile strength of this toughner Effective Raise poly(lactic acid) obtain the good poly(lactic acid) of over-all properties.The toughened polylactic resin composition Application Areas that the present invention obtains is extensive, alternative PE, PVC etc. make various environmental protection plastic products, such as film, sheet material, sheet material, foaming product and injection-molded plastic spare etc., especially in the food product packing film field, market outlook are wide.And the blending modification method equipment for preparing this plasticizing polylactic acid resin is simple, technique is advanced, is fit to multiple process requirements.
In order to further specify the present invention, below in conjunction with embodiment toughened polylactic resin composition provided by the invention is described in detail.
Embodiment 1
With water 1500mL, trisodium phosphate 2.5g, glucose 3.5g, ferrous sulfate 0.08g, potassium hydroxide 0.7g, rosin soap lye 17mL, polybutadiene latex 360g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 228g, glytidyl methacrylate 12g, hydrogen phosphide cumene 2.6mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, adding 1.5 gram masses ratio is 1: 1 antioxidant 1010 and the mixture of irgasfos 168 again, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-1.Wherein, the massfraction of butadiene-styrene copolymer is 60%, and divinyl and cinnamic mass ratio are 70:30; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 40%, and wherein the massfraction of glytidyl methacrylate is 2%.
Embodiment 2
Be that the mixture of the toughner MB-g-GMA-1 of 80,000 daltonian poly(lactic acid) and 5g embodiment 1 preparation and antioxidant 1010 that 0.5g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 3
Be that the mixture of the toughner MB-g-GMA-1 of 80,000 daltonian poly(lactic acid) and 10g embodiment 1 preparation and antioxidant 1010 that 0.3g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 4
Be that the mixture of the toughner MB-g-GMA-1 of 200,000 daltonian poly(lactic acid) and 15g embodiment 1 preparation and antioxidant 1010 that 0.3g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 5
Be that the mixture of the toughner MB-g-GMA-1 of 200,000 daltonian poly(lactic acid) and 20g embodiment 1 preparation and antioxidant 1010 that 0.8g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 6
Be that the mixture of the toughner MB-g-GMA-1 of 50,000 daltonian poly(lactic acid) and 25g embodiment 1 preparation and antioxidant 1010 that 1g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 7
With water 1500mL, trisodium phosphate 2.5g, glucose 3.5g, ferrous sulfate 0.08g, potassium hydroxide 0.7g, rosin soap lye 17mL, polybutadiene latex 360g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 173g, glytidyl methacrylate 4.5g, hydrogen phosphide cumene 4.1mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, add again 1.5 gram masses than the mixture for the antioxidant 1010 of 1:1 and irgasfos 168, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-2.Wherein, the massfraction of butadiene-styrene copolymer is 70%, and divinyl and cinnamic mass ratio are 60:40; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 30%, and wherein the massfraction of glytidyl methacrylate is 1%.
Be that the mixture of the toughner MB-g-GMA-2 of 50,000 daltonian poly(lactic acid) and the above-mentioned preparation of 25g and antioxidant 1010 that 0.1g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 8
With water 1500mL, trisodium phosphate 2.5g, glucose 3.5g, ferrous sulfate 0.08g, potassium hydroxide 0.7g, rosin soap lye 17mL, polybutadiene latex 360g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 171g, glytidyl methacrylate 9g, hydrogen phosphide cumene 4.1mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, add again 1.5 gram masses than the mixture for the antioxidant 1010 of 1:1 and irgasfos 168, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-3.Wherein, the massfraction of butadiene-styrene copolymer is 70%, and divinyl and cinnamic mass ratio are 60:40; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 30%, and wherein the massfraction of glytidyl methacrylate is 2%.
Be that the mixture of the toughner MB-g-GMA-3 of 80,000 daltonian poly(lactic acid) and the above-mentioned preparation of 25g and antioxidant 1010 that 0.5g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 9
With water 1500mL, trisodium phosphate 2.5g, glucose 3.5g, ferrous sulfate 0.08g, potassium hydroxide 0.7g, rosin soap lye 17mL, polybutadiene latex 360g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 166g, glytidyl methacrylate 22.5g, hydrogen phosphide cumene 4.1mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, adding 1.5 gram masses ratio is 1: 1 antioxidant 1010 and the mixture of irgasfos 168 again, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-4.Wherein, the massfraction of butadiene-styrene copolymer is 70%, and divinyl and cinnamic mass ratio are 60:40; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 30%, and wherein the massfraction of glytidyl methacrylate is 5%.
Be that the mixture of the toughner MB-g-GMA-4 of 80,000 daltonian poly(lactic acid) and the above-mentioned preparation of 25g and antioxidant 1010 that 0.5g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 10
With water 1700mL, trisodium phosphate 2.9g, glucose 3.9g, ferrous sulfate 0.09g, potassium hydroxide 0.8g, rosin soap lye 19mL, polybutadiene latex 412g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 114g, glytidyl methacrylate 6g, hydrogen phosphide cumene 4.6mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, add again 1.7 gram masses than the mixture for the antioxidant 1010 of 1:1 and irgasfos 168, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-5.Wherein, the massfraction of butadiene-styrene copolymer is 80%, and divinyl and cinnamic mass ratio are 60:40; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 20%, and wherein the massfraction of glytidyl methacrylate is 2%.
Be that the mixture of the toughner MB-g-GMA-5 of 80,000 daltonian poly(lactic acid) and the above-mentioned preparation of 25g and antioxidant 1010 that 0.3g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
Embodiment 11
With water 1700mL, trisodium phosphate 2.9g, glucose 3.9g, ferrous sulfate 0.09g, potassium hydroxide 0.8g, rosin soap lye 19mL, polybutadiene latex 412g is sequentially added in the there-necked flask successively, pass into nitrogen, temperature rises to 70 ℃, obtain mixed with polybutadiene liquid after stirring 10min, then with methyl methacrylate 111g, glytidyl methacrylate 15g, hydrogen phosphide cumene 4.6mL mixes and is added drop-wise to continuously in the above-mentioned mixed with polybutadiene liquid, drip and finish the rear reaction 1h that continues, adding 1.7 gram masses ratio is 1: 1 antioxidant 1010 and the mixture of irgasfos 168 again, obtain the emulsion of condensing after half an hour, with its dry 24h under 60 ℃ of conditions, make toughner, be designated as MB-g-GMA-6.Wherein, the massfraction of butadiene-styrene copolymer is 80%, and divinyl and cinnamic mass ratio are 60:40; The massfraction of methyl methacrylate and glytidyl methacrylate multipolymer is 20%, and wherein the massfraction of glytidyl methacrylate is 5%.
Be that the mixture of the toughner MB-g-GMA-6 of 80,000 daltonian poly(lactic acid) and the above-mentioned preparation of 25g and antioxidant 1010 that 0.3g quality proportioning is 1:2 and irgasfos 168 carries out mechanical blending and obtains Preblend with the 100g number-average molecular weight, then adopt SHJ-20 type twin screw extruder to be mixed with polylactic acid resin composition, speed setting is 100 rev/mins, 5 minutes time, each section Temperature Setting is as shown in table 1, and table 1 is the setting of each section of embodiment of the invention twin screw extruder temperature.
The plasticizing polylactic acid resin that obtains is carried out Mechanics Performance Testing, and the result is referring to table 2, the performance test results of the toughened polylactic resin composition that table 2 prepares for the embodiment of the invention.
The setting of each section of table 1 embodiment of the invention twin screw extruder temperature
The performance test results of the plasticizing polylactic acid resin that table 2 embodiment of the invention prepares
| Test event | Tensile strength | Elongation at break | Shock strength |
| Embodiment 2 | 56.4MPa | 8.7% | 7.8KJ/m 2 |
| Embodiment 3 | 52.8MPa | 17.3% | 11.1KJ/m 2 |
| Embodiment 4 | 48.3MPa | 180% | 17.0KJ/m 2 |
| Embodiment 5 | 45.8MPa | 159% | 49.9KJ/m 2 |
| Embodiment 6 | 44.3MPa | 151% | 66.8KJ/m 2 |
| Embodiment 7 | 42.9MPa | 174% | 58.7KJ/m 2 |
| Embodiment 8 | 43.6MPa | 188% | 60.2KJ/m 2 |
| Embodiment 9 | 43.8MPa | 195% | 63.5KJ/m 2 |
| Embodiment 10 | 40.6MPa | 200% | 56.4KJ/m 2 |
| Embodiment 11 | 41.3MPa | 212% | 57.9KJ/m 2 |
By above-described embodiment as can be known, the present invention is take butadiene-styrene copolymer as nuclear, methyl methacrylate and glytidyl methacrylate multipolymer are that the nucleocapsid structure multipolymer of shell is toughner, and the toughened polylactic resin composition for preparing has higher tensile strength and resistance to impact shock and elongation at break.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. toughened polylactic resin composition comprises:
The poly(lactic acid) of 100 mass parts;
The toughner of 5 ~ 25 mass parts;
0.1 the first oxidation inhibitor of ~ 1 mass parts;
Described toughner comprises that butadiene-styrene copolymer is nuclear, and methyl methacrylate and glytidyl methacrylate multipolymer are the nucleocapsid structure multipolymer of shell.
2. toughened polylactic resin composition according to claim 1, it is characterized in that, in the described toughner, the massfraction of described butadiene-styrene copolymer is 60% ~ 80%, and the massfraction of described methyl methacrylate and glytidyl methacrylate multipolymer is 20% ~ 40%.
3. toughened polylactic resin composition according to claim 1 and 2 is characterized in that, in the described butadiene-styrene copolymer, divinyl and cinnamic mass ratio are (60 ~ 70): (30 ~ 40).
4. toughened polylactic resin composition according to claim 1 and 2, it is characterized in that, in described methyl methacrylate and the glytidyl methacrylate multipolymer, the mass ratio of methyl methacrylate and glytidyl methacrylate is (95 ~ 99): (1 ~ 5).
5. toughened polylactic resin composition according to claim 1 is characterized in that, comprises the toughner of 10 ~ 20 mass parts.
6. toughened polylactic resin composition according to claim 1 is characterized in that, the number-average molecular weight of described poly(lactic acid) is 5 ~ 200,000 dalton.
7. toughened polylactic resin composition according to claim 1 is characterized in that, described the first oxidation inhibitor is that mass ratio is the antioxidant 1010 of 1:2 and the mixture of irgasfos 168.
8. toughened polylactic resin composition according to claim 1 is characterized in that, described toughner prepares in accordance with the following methods:
A) polybutadiene latex, water, trisodium phosphate, glucose, ferrous sulfate, rosin soap lye and potassium hydroxide are mixed, obtain the polyhutadiene emulsion;
B) with methyl methacrylate, glytidyl methacrylate and hydrogen phosphide cumene and described steps A) the polyhutadiene emulsion that obtains mixes, and carries out polyreaction, then adds the second oxidation inhibitor, obtains toughner.
9. toughened polylactic resin composition according to claim 9 is characterized in that, the temperature of described polyreaction is 40 ℃ ~ 120 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517621A (en) * | 2018-03-30 | 2018-09-11 | 徐冬 | A kind of preparation method of non-woven fabrics |
| CN112280241A (en) * | 2019-07-12 | 2021-01-29 | 中国科学院福建物质结构研究所 | 3D printing photosensitive resin and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333332A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polylactic resin toughened and modified by acrylic ester copolymers and preparation method |
| CN101386703A (en) * | 2008-11-05 | 2009-03-18 | 江苏科技大学 | Polylactic acid/thermoplastic starch foam and producing method thereof |
-
2012
- 2012-12-05 CN CN201210516813.7A patent/CN102942772B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333332A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polylactic resin toughened and modified by acrylic ester copolymers and preparation method |
| CN101386703A (en) * | 2008-11-05 | 2009-03-18 | 江苏科技大学 | Polylactic acid/thermoplastic starch foam and producing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王星月等: ""PBT树脂对核壳粒子增韧聚碳酸酯结构与性能的影响"", 《高分子材料科学与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517621A (en) * | 2018-03-30 | 2018-09-11 | 徐冬 | A kind of preparation method of non-woven fabrics |
| CN112280241A (en) * | 2019-07-12 | 2021-01-29 | 中国科学院福建物质结构研究所 | 3D printing photosensitive resin and preparation method and application thereof |
| CN112280241B (en) * | 2019-07-12 | 2021-12-14 | 中国科学院福建物质结构研究所 | 3D printing photosensitive resin and preparation method and application thereof |
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