CN115322546A - Method for improving strength and toughness of polymer melt - Google Patents
Method for improving strength and toughness of polymer melt Download PDFInfo
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- CN115322546A CN115322546A CN202211128937.8A CN202211128937A CN115322546A CN 115322546 A CN115322546 A CN 115322546A CN 202211128937 A CN202211128937 A CN 202211128937A CN 115322546 A CN115322546 A CN 115322546A
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- 238000000034 method Methods 0.000 title claims abstract description 39
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- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
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- 238000005187 foaming Methods 0.000 claims abstract description 5
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention discloses a method for improving the strength and toughness of a polymer melt, belonging to the technical field of polymer processing and modification. The invention uses 90-99 weight portions of polymer A, 1-30 weight portions of reactive polymer B and 0.1-3 weight portions of functional auxiliary agent as main raw materials to be melted and blended at a certain temperature to obtain the high-melt-strength high-toughness composition. The composition provided by the invention not only has higher melt strength, but also has excellent toughness, and can be directly used for compression molding, foaming, blow molding and secondary molding to prepare thermoplastic plastic products.
Description
Technical Field
The invention relates to a method for improving the strength and toughness of a polymer melt, belonging to the technical field of polymer processing and modification.
Background
With the rapid development of polymer material industry, the application of polymer materials has penetrated into various fields of industry, agriculture and people's daily life, however, most of polymer materials are derived from petroleum base, are not easy to realize natural degradation and are difficult to recover at present. Polyglycolic acid, glycolic acid-based copolymer, polylactic acid, lactic acid-based copolymer, polyethylene terephthalate are all biodegradable high molecular materials, which have excellent degradability, no toxicity and good biocompatibility, but have the disadvantage of low melt strength in processing, so that they are modified.
The existing method for improving the melt strength, such as CN103626982A, provides a method for improving the melt strength of polyester resin, and the prepared intermediate with active functional groups breaks down the degradability of polyester system although the intermediate gets rid of the limitation of small molecules; in the process of melt processing of the ester polymer, the coupling copolymer intermediate changes the molecular chain structure of the polymer so as to improve the melt strength, and the method is easy to generate a cross-linking structure, so that the system fluidity is poor, and even the melt processability is lost.
In addition, the current methods for improving the melt strength of polyglycolic acid, glycolic acid-based copolymer, polylactic acid, lactic acid-based copolymer and polyethylene terephthalate do not effectively improve the defect of high brittleness of polyester, so that a new method for preparing a polymer composition with high melt strength and excellent toughness is greatly needed.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for simultaneously improving the melt strength and toughness of a polymer.
The invention aims to provide a method for improving the melt strength and toughness of a polymer, which is to mix, melt blend or melt extrude a reactive polymer B and a polymer A;
wherein the reactive polymer B simultaneously comprises a flexible polyester main chain and a side chain with an active group; the active group comprises at least one of anhydride, epoxy group and isocyanate;
the polymer A is at least one of polyglycolic acid, glycolic acid-based copolymer, polylactic acid, lactic acid-based copolymer and polyethylene terephthalate.
In one embodiment of the present invention, the polymer A is 85 to 99 parts by weight and the reactive polymer B is 1 to 30 parts by weight. Further preferably 90 to 99 parts of the polymer A and 10 to 30 parts of a reactive polymer.
In one embodiment of the invention, the mass ratio of polymer a to reactive polymer B is (90-99): (1-30). May preferably be (90-99): (3-30); or preferably (90-99): (5-30); or preferably (90-99): (10-30); or preferably (90-99): (20-30); or preferably (95-99): (10-30).
In one embodiment of the present invention, the method further comprises adding 0.1 to 3 parts by weight of a functional aid.
In one embodiment of the invention, the method takes 90 to 99 parts by weight of the polymer A, 1 to 15 parts by weight of the reactive polymer B and 0.1 to 3 parts by weight of the functional assistant as main raw materials to prepare the high-melt-strength high-toughness composition.
In one embodiment of the present invention, the functional auxiliary includes at least one of an antistatic agent, an antioxidant, an anti-aging agent, an anti-hydrolysis agent, and a filler.
In one embodiment of the present invention, the flexible polyester main chain of the reactive polymer B is polymerized from at least one monomer selected from caprolactone, lactide, glycolide, adipic acid, terephthalic acid, succinic acid and butanediol.
In one embodiment of the invention, the reactive polymer B has a mass fraction of reactive groups of from 0.1 to 30%. Preferably 5% to 25%. Further preferably 15% to 25%.
In one embodiment of the invention, the reactive polymer B is prepared by melt grafting a flexible polyester with a monomer C under the action of a radical initiator; monomer C contains both a-C = C-double bond and an active group.
In one embodiment of the present invention, the monomer C may be specifically selected from at least one of glycidyl methacrylate, glycidyl acrylate, methyl methacrylate, styrene-based monomers, maleic anhydride, epoxidized unsaturated vegetable oils and fats, epoxidized cardanol, epoxidized eugenol, and unsaturated double bond-containing isocyanates.
In one embodiment of the invention, the mass ratio of flexible polyester to monomer C is 50: (1-50); preferably, 50: (5-50); further preferably 50: (15-30).
In one embodiment of the present invention, the free radical initiator is at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di (t-butylperoxy) butane, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyacetate, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, and diisopropyl peroxydicarbonate.
In one embodiment of the invention, the functional auxiliaries are in particular chosen from: irganox 1330, polycarbodiimide, JL-5P, JL-WT, antioxidant 4010 and antioxidant RD.
In one embodiment of the invention, the temperature of the melt is 110 to 180 ℃; for example, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, etc.
The invention also provides a composition with high melt strength and toughness, which comprises the following components in parts by weight: 90 to 99 parts of polymer A, 1 to 15 parts of reactive polymer B and 0.1 to 3 parts of functional additive; wherein the reactive polymer B simultaneously comprises a flexible polyester main chain and a side chain with an active group; the active group comprises at least one of anhydride, epoxy group and isocyanate;
the polymer A is at least one of polyglycolic acid, glycolic acid based copolymer, polylactic acid, lactic acid based copolymer and polyethylene terephthalate.
In an embodiment of the present invention, the preparation method of the composition specifically includes:
the method 1 comprises the steps of premixing the polymer A, the reactive polymer B and the functional auxiliary agent uniformly at room temperature according to the weight ratio, adding the premixed materials into an internal mixer for melt blending, and obtaining a high-melt-strength high-toughness composition;
or the method 2, premixing the polymer A, the reactive polymer B and the functional assistant uniformly at room temperature according to the weight ratio, adding the premixed materials into a conveying section of a double-screw extruder, and carrying out continuous melt extrusion to obtain the high-melt-strength high-toughness composition.
In one embodiment of the invention, in method 1, the melt blending time is from 1 to 15 minutes.
In one embodiment of the invention, in method 1, the melt blending temperature is 1-50 ℃ above the melting point of polymer a; the rotating speed of the rotor is 30-200 r/min. The blending temperature can be properly adjusted according to the melting temperature of the polymer A, and the rotating speed can be adjusted according to the melt viscosity of the composition. The melt blending temperature can be 5 deg.C, 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, and 50 deg.C above the melting point.
In one embodiment of the present invention, in the method 2, the temperature of screw extrusion is 1 to 50 ℃ or higher than the melting point of the polymer A, and the screw rotation speed is 50 to 300 rpm. The extrusion temperature of the screw can be properly adjusted according to the melting temperature of the polymer A, and the rotation speed of the screw can be adjusted according to the melt viscosity of the composition. The extrusion temperature can be 5 deg.C, 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, and 50 deg.C above the melting point.
The invention also provides application of the high-melt-strength high-toughness composition to compression molding, foaming, blow molding and secondary molding to prepare thermoplastic plastic products.
The invention has the beneficial effects that:
(1) The method for improving the strength and toughness of the polymer melt is to melt and blend 90 to 99 parts by weight of the polymer A, 1 to 10 parts by weight of the reactive polymer B and 0.1 to 3 parts by weight of the functional additive which are used as main raw materials at a certain temperature to obtain the high-melt-strength high-toughness composition.
(2) In the invention, the reactive polymer B and the polymer A react in situ to form a long-chain branched structure during melt processing, so that the entanglement among molecular chains is obviously enhanced, and the melt strength of the polymer is improved; meanwhile, the main chain of the reactive polymer B is selected from degradable flexible polyester, so that on one hand, the system can achieve complete degradability, and on the other hand, the flexible polyester and the polymer A can be combined through chemical bonds to greatly improve the toughness of the polymer A.
(3) The ratio of the polymer A to the reactive polymer B in the present invention is in the preferable range (90 to 99): (20-30), the melt strength of the polymer can be greatly improved, because molecular chain entanglement in the system generates entanglement among long-chain branches besides linear chain intermolecular entanglement and entanglement between long-chain branches, so that the whole system is in a huge entanglement network, and the melt strength is greatly improved.
(4) In addition, the functional additives used do not substantially affect the properties of the high melt strength, high toughness compositions. The invention is easy to realize on the traditional high polymer material processing equipment, and can be directly used for compression molding, foaming, blow molding and secondary molding to prepare thermoplastic plastic products.
Drawings
FIG. 1 is a torque chart of examples 1-2 and comparative examples 1-2;
FIG. 2 is a stress-strain graph of examples 1-2 and comparative examples 1-2.
Detailed Description
The embodiments disclosed herein are examples of the present invention, which may be embodied in various forms. Therefore, specific details disclosed, including specific structural and functional details, are not intended to be limiting, but merely serve as a basis for the claims. It should be understood that the detailed description of the invention is not intended to be limiting but is intended to cover all possible modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims. The word "may" is used throughout this application in an permissive sense rather than the mandatory sense. Similarly, unless otherwise specified, the words "include", "comprises", and "consisting of" mean "including but not limited to". The words "a" or "an" mean "at least one" and the words "a plurality" mean more than one. When abbreviations or technical terms are used, these terms are meant to have a generally accepted meaning known in the art.
The purification related to the invention means that: the solid sample obtained after grafting was completely dissolved with chloroform and precipitated in methanol (chloroform to methanol volume ratio 1.
The mass fraction A of the active group epoxy group in the reactive polymer B is the peak area ratio of the nuclear magnetic hydrogen spectrum characteristic group of a purified sample according to the formula A = M 1 I 1 /M 2 I 2 Is calculated to obtain wherein I 1 Is the area of the peak characteristic of any hydrogen on the active group (epoxy group), M 1 As the relative molecular mass of the active groups, I 2 Is the characteristic peak area of the hydrogen on the alpha-carbon (ortho to the ester group) in the flexible polyester, M 2 Is the relative molecular mass of the flexible polyester monomer unit; the mass fraction A of active group acid anhydride and isocyanate in the reactive polymer B is the peak area ratio of nuclear magnetic carbon spectrum characteristic group of a purified sample according to the formula A = M' 1 I’ 1 /M’ 2 I’ 2 Calculated to obtain wherein' 1 Is the nuclear magnetism characteristic peak area of the carbonyl characteristic carbon in the active group (isocyanate/anhydride), M' 1 Is active radical relative molecular mass, l' 2 Is the area of the peak of the nuclear magnetic characteristic of the carbon on the alpha-carbon (ortho to the ester groups) in the flexible polyester, M' 2 Is the relative molecular mass of the flexible polyester monomer unit.
Example 1
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, which was purified to give a reactive polymer B (10% by mass of epoxide groups) which was designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with 10g of sgpcl and 2g of a functional aid (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 2
(1) Preparation of reactive Polymer B
A reactive polymer B (10% by mass of epoxy group) was prepared in the same manner as in example 1 by replacing glycidyl methacrylate with cardanol glycidyl ether, and was designated as seslc.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with 10g of seclc and 2g of functional aid (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 3
(1) Preparation of reactive Polymer B
The same procedure was used to prepare a reactive polymer B (10% by weight of anhydride groups) designated as SMCL by replacing the glycidyl methacrylate in example 1 with maleic anhydride.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with 10g of scpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 4
(1) Preparation of reactive Polymer B
The same procedure was used to prepare reactive polymer B (isocyanate group mass fraction: 10%) designated as STPCL by replacing glycidyl methacrylate in example 1 with 3-isopropyl-dimethylbenzyl isocyanate.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with 10g of scpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 5
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 15g of glycidyl methacrylate, 5g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, which was purified to give a reactive polymer B (15% by mass of epoxide groups) which was designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with 10g of sgpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 6
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide are melt-grafted at 130 ℃ to obtain a solid sample, and the solid sample is purified to obtain a reactive polymer B (the mass fraction of epoxy groups is 10%) which is marked as SGPCL.
(2) Preparation of high melt strength high toughness compositions
90g of polylactic acid (Mn = 130000) was melt blended with 15g of SGPCL and 3g of functional aid (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 7
(1) Preparation of reactive Polymer B
50g of a copolymer of butylene adipate and butylene terephthalate (BSF C1200), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of dicumyl peroxide are melt-grafted at 170 ℃ to obtain a solid sample, and the solid sample is purified to obtain a reactive polymer B (the mass fraction of epoxy groups is 10%) which is marked as SGPBAT.
(2) Preparation of high melt strength high toughness compositions
90g of polylactic acid (Mn = 130000), 10g of SGPBAT and 1g of functional auxiliary agent (antioxidant Irganox 1330) are premixed uniformly at room temperature, added into a conveying section of a double-screw extruder and subjected to continuous melt extrusion at 220 ℃ (50 ℃ above a melting point) to obtain the high-melt-strength high-toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 8
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, which was purified to give a reactive polymer B (10% by mass of epoxide groups) which was designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 9
(1) Preparation of reactive Polymer B
The glycidyl methacrylate in example 1 was replaced by cardanol glycidyl ether, and a reactive polymer B (10 mass percent of epoxy groups) was prepared in the same manner and recorded as seslc.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 10
(1) Preparation of reactive Polymer B
The same procedure was used to prepare a reactive polymer B (10% by mass of anhydride groups) designated as SMCL by replacing glycidyl methacrylate with maleic anhydride in example 1.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of a functional aid (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 11
(1) Preparation of reactive Polymer B
The same procedure was used to prepare reactive polymer B (isocyanate group mass fraction: 10%) designated as STPCL by replacing glycidyl methacrylate in example 1 with 3-isopropyl-dimethylbenzyl isocyanate.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of a functional aid (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 12
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 15g of glycidyl methacrylate, 5g of styrene and 0.2g of benzoyl peroxide are melt-grafted at 130 ℃ to obtain a solid sample, and the solid sample is purified to obtain a reactive polymer B (the mass fraction of epoxy groups is 15%) which is marked as SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 13
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, which was purified to give a reactive polymer B (10% by mass of epoxide groups) which was designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
99g of polyglycolic acid (Mn = 150000) was melt blended with 5g of SGPCL and 1g of functional adjuvant (antioxidant Irganox 1330) at 240 ℃ (10 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 14
(1) Preparation of reactive Polymer B
50g of a copolymer of butylene adipate and butylene terephthalate (BSF C1200), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of dicumyl peroxide were melt-grafted at 170 ℃ to give a solid sample, and the solid sample was purified to give a reactive polymer B (10% by mass of epoxy groups) designated SGPBAT.
(2) Preparation of high melt strength high toughness compositions
95g of polyglycolic acid (Mn = 150000) was melt blended with 10g of sgpcl and 2g of functional adjuvant (antioxidant Irganox 1330) at 270 ℃ (40 ℃ above melting point) for 5 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the extruded composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 15
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide are melt-grafted at 130 ℃ to obtain a solid sample, and the solid sample is purified to obtain a reactive polymer B (the mass fraction of epoxy groups is 10%) which is marked as SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above the melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 16
(1) Preparation of reactive Polymer B
A reactive polymer B (10% by mass of epoxy group) was prepared in the same manner as in example 1 by replacing glycidyl methacrylate with cardanol glycidyl ether, and was designated as seslc.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above the melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 17
(1) Preparation of reactive Polymer B
The same procedure was used to prepare a reactive polymer B (10% by mass of anhydride groups) designated as SMCL by replacing glycidyl methacrylate with maleic anhydride in example 1.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above the melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 18
(1) Preparation of reactive Polymer B
The same procedure was used to prepare reactive polymer B (isocyanate group mass fraction: 10%) designated as STPCL by replacing glycidyl methacrylate in example 1 with 3-isopropyl-dimethylbenzyl isocyanate.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above the melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 19
(1) Preparation of reactive Polymer B
50g of polycaprolactone, 15g of glycidyl methacrylate, 5g of styrene and 0.2g of benzoyl peroxide are melt-grafted at 130 ℃ to obtain a solid sample, and the solid sample is purified to obtain a reactive polymer B (the mass fraction of epoxy groups is 15%) which is marked as SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 20
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 150000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, and the solid sample was purified to give a reactive polymer B (10% by mass of epoxide groups) which was designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 3g of SGPCL and 2g of a functional aid (antioxidant Irganox 1330) at 255 ℃ (5 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Example 21
(1) Preparation of reactive Polymer B
50g of a copolymer of butylene adipate and butylene terephthalate (BSF C1200), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of dicumyl peroxide were melt-grafted at 170 ℃ to give a solid sample, and the solid sample was purified to give a reactive polymer B (10% by mass of epoxy groups) designated SGPBAT.
(2) Preparation of high melt strength high toughness compositions
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of sgpbat and 2g of the functional aid (antioxidant Irganox 1330) at 270 ℃ (30 ℃ above melting point) for 15 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test.
Comparative example 1
100g of polylactic acid (Mn = 130000) and 1g of a functional aid (antioxidant Irganox 1330) were melt-blended at 190 ℃ for 10 minutes to obtain a composition.
Comparative example 2
95g of polylactic acid (Mn = 130000) was melt-blended with 7.13g of polycaprolactone, 1.43g of glycidyl methacrylate, 1.43g of styrene, 0.03g of benzoyl peroxide and 2g of a functional aid (antioxidant Irganox 1330) in one step at 190 ℃ for 10 minutes to obtain a composition.
Comparative example 3
(1) Preparation of Polymer B
50g of polycaprolactone (Mn = 70000), 0.05g of glycidyl methacrylate, 10g of styrene and 0.1g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, and the solid sample was purified to give a polymer B (epoxy group mass fraction 0.05%) which was designated SGPCL.
(2) Preparation of the composition
95g of polylactic acid (Mn = 130000) was melt-blended with 10g of sgpcl and 2g of a functional aid (antioxidant Irganox 1330) at 190 ℃ for 10 minutes to obtain a composition.
Comparative example 4
100g of polyglycolic acid (Mn = 150000) and 1g of a functional aid (antioxidant Irganox 1330) were melt-blended at 240 ℃ for 10 minutes to obtain a composition.
Comparative example 5
95g of polyglycolic acid (Mn = 150000) was melt-blended with 7.13g of polycaprolactone, 1.43g of glycidyl methacrylate, 1.43g of styrene, 0.03g of benzoyl peroxide and 1g of a functional aid (antioxidant Irganox 1330) in one step at 240 ℃ for 10 minutes to obtain a composition.
Comparative example 6
(1) Preparation of Polymer B
50g of polycaprolactone (Mn = 70000), 0.05g of glycidyl methacrylate, 10g of styrene and 0.1g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, and the solid sample was purified to give a polymer B (epoxy group mass fraction 0.05%) which was designated SGPCL.
(2) Preparation of the composition
95g of polyglycolic acid (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional adjuvant (antioxidant Irganox 1330) at 240 ℃ for 10 minutes to obtain a composition.
Comparative example 7
100g of polyethylene terephthalate (Mn = 150000) and 1g of a functional aid (antioxidant Irganox 1330) were melt-blended at 255 ℃ for 10 minutes to obtain a composition.
Comparative example 8
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 7.13g of polycaprolactone, 1.43g of glycidyl methacrylate, 1.43g of styrene, 0.03g of benzoyl peroxide and 1g of a functional assistant (antioxidant Irganox 1330) in one step at 255 ℃ for 10 minutes to obtain a composition.
Comparative example 9
(1) Preparation of Polymer B
50g of polycaprolactone (Mn = 70000), 0.05g of glycidyl methacrylate, 10g of styrene and 0.1g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, and the solid sample was purified to give a polymer B (epoxy group mass fraction 0.05%) which was designated SGPCL.
(2) Preparation of the composition
95g of polyethylene terephthalate (Mn = 150000) was melt-blended with 10g of SGPCL and 2g of a functional assistant (antioxidant Irganox 1330) at 255 ℃ for 10 minutes to obtain a composition.
It is to be noted that the polyesters used in the above various examples and comparative examples were vacuum-dried at 60 ℃ for 12 hours before use. The reactive polymer B prepared in the example has the mass fraction of 0.1-30% of acid anhydride, epoxy group and isocyanate.
The polylactic acid compositions of examples 1 to 7 and comparative examples 1 to 3 were subjected to a melt flow rate test using a melt flow rate tester, and the compositions were incubated at 190 ℃ for 5 minutes and then measured at 190 ℃ under 2.16 kg.
The polyglycolic acid compositions of examples 8 to 14 and comparative examples 4 to 6 were subjected to melt flow rate measurement using a melt flow rate meter, heat-maintained at 230 ℃ for 5 minutes, and then measured at 230 ℃ under 2.16 kg.
The polyethylene terephthalate compositions of examples 15 to 21 and comparative examples 7 to 9 were subjected to a melt flow rate test using a melt flow rate tester, and the melt flow rate was measured at 260 ℃ for 5 minutes and then at 260 ℃ under 2.16 kg.
The Melt Strength (MS) of the compositions obtained in examples 1 to 21 and comparative examples 1 to 9 was calculated by the formula (1):
in the formula: Δ L — the length of the melt extrusion diameter when reduced to half;
r 0 -the radius of initial extrusion from the extruder die;
MFR-melt flow rate, g/10min.
The compositions obtained in examples 1 to 21 and comparative examples 1 to 9 were tested for tensile strength and elongation at break using a universal testing machine in accordance with GB/T1040.1 to 2018 at a tensile rate of 10mm/min.
The melt flow rate, melt strength, tensile strength and elongation at break of each of the examples and comparative examples tested are shown in table 1.
TABLE 1 melt flow rate, melt strength, tensile strength and elongation at break for each of the examples and comparative examples
From examples 1-7 and comparative examples 1-3, it can be seen that the method of modifying polycaprolactone or butylene adipate and butylene terephthalate with glycidyl methacrylate, cardanol glycidyl ether, maleic anhydride, and 3-isopropyl-dimethylbenzyl isocyanate as active monomers and then melt blending with polylactic acid can increase the viscosity of the system, reduce the melt index from 21 to about 7, and still maintain good melt fluidity (i.e. melt processability); meanwhile, the melt strength of the polylactic acid is improved, so that the melt strength is improved from 233Pa & s to more than 4000Pa & s by about 20 times; has no great influence on the tensile strength, but obviously improves the elongation at break by more than 30 times. The final effect is similar under different processing temperatures.
Examples 8 to 14 and comparative examples 4 to 6 show that the method of modifying polycaprolactone or butanediol adipate and butanediol terephthalate with glycidyl methacrylate, cardanol glycidyl ether, maleic anhydride and 3-isopropyl-dimethylbenzyl isocyanate as active monomers and then melt blending with polyglycolic acid can increase the viscosity of the system and reduce the melt index from 12.8 to about 5, but still maintain good melt fluidity; meanwhile, the melt strength of the polyglycolic acid is improved, and the melt strength is improved by nearly 50 times from 145Pa & s to more than 7000Pa & s; has no great influence on the tensile strength, but obviously improves the elongation at break by more than 20 times. And similar final effects are obtained at different processing temperatures.
Examples 9 and 10 and comparative example 3 show that the method of modifying polycaprolactone or butanediol adipate and butanediol terephthalate with glycidyl methacrylate, cardanol glycidyl ether, maleic anhydride and 3-isopropyl-dimethylbenzyl isocyanate as active monomers and then uniformly blending the modified polycaprolactone or butanediol adipate and butanediol terephthalate with polyethylene terephthalate can increase the viscosity of a system, reduce the melt index from 15.3 to about 6 and still maintain good melt fluidity; meanwhile, the melt strength of the ethylene terephthalate is improved, so that the melt strength is improved by about 11 times from 879Pa & s to 10000Pa & s; has no great influence on the tensile strength, but obviously improves the elongation at break by more than 5 times. And similar final effects at different processing temperatures.
Example 22
(1) Preparation of Polymer B
Respectively melt-grafting 50g of polycaprolactone (shown in table 2) with different amounts of glycidyl methacrylate, 10g of styrene and 0.1g of benzoyl peroxide at 130 ℃ to obtain a solid sample, and purifying the solid sample to obtain a polymer B, which is marked as SGPCL.
(2) Preparation of the composition
95g of polylactic acid (Mn = 130000) was melt-blended with 10g of sgpcl and 2g of a functional aid (antioxidant Irganox 1330) at 190 ℃ for 10 minutes to obtain a composition.
The melt flow rate, melt strength, tensile strength and elongation at break of the resulting compositions were tested as shown in table 2. TABLE 2 melt flow rate, melt strength, tensile strength and elongation at break of the compositions obtained with different amounts of glycidyl methacrylate
When the amount of the epoxy monomer is too high, the graft ratio in the system is reduced, gelation (i.e., crosslinking) is easily generated to lower the processability, and purification and subsequent steps are difficult to perform.
Example 23
(1) Preparation of reactive Polymer B
50g of polycaprolactone (Mn = 70000), 10g of glycidyl methacrylate, 10g of styrene and 0.2g of benzoyl peroxide were melt-grafted at 130 ℃ to give a solid sample, which was purified to give a reactive polymer B designated SGPCL.
(2) Preparation of high melt strength high toughness compositions
95g of polylactic acid (Mn = 130000) was melt blended with an amount of SGPCL (shown in table 3), and 2g of a functional aid (antioxidant Irganox 1330) at 190 ℃ (20 ℃ above melting point) for 10 minutes to obtain a high melt strength high toughness composition.
And (3) fully drying the blended composition, then carrying out melt fluidity test by using a melt flow tester, and carrying out hot press molding by using a flat vulcanizing machine for tensile test. The results are shown in Table 2.
TABLE 3 melt flow Rate, melt Strength, tensile Strength and elongation at Break of the resulting compositions of SGPCL in varying amounts
The above examples demonstrate that the present invention can obtain a composition with high melt strength, high toughness and good processability, and the composition provided by the present invention not only has high melt strength but also has excellent toughness, and can be directly used for compression molding, foaming, blow molding and secondary molding to prepare thermoplastic plastic products.
Those skilled in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (10)
1. A method of increasing the melt strength and toughness of a polymer by mixing, melt blending or melt extruding a reactive polymer B with a polymer a; wherein the reactive polymer B simultaneously comprises a flexible polyester main chain and a side chain with an active group; the active group comprises at least one of anhydride, epoxy group and isocyanate; the polymer A is at least one of polyglycolic acid, glycolic acid based copolymer, polylactic acid, lactic acid based copolymer and polyethylene terephthalate.
2. The method of claim 1, wherein the polymer A is 85 to 99 parts by weight and the reactive polymer B is 1 to 30 parts by weight.
3. The method of claim 1, further comprising adding 0.1 to 3 parts by weight of a functional additive.
4. The method of claim 1, wherein the flexible polyester backbone of the reactive polymer B is polymerized from at least one monomer selected from the group consisting of caprolactone, lactide, glycolide, adipic acid, terephthalic acid, succinic acid, and butanediol.
5. The process according to claim 1, wherein the reactive polymer B has a reactive group mass fraction of 0.1 to 30%.
6. The process according to any one of claims 1 to 5, wherein the reactive polymer B is obtained by melt grafting a flexible polyester with a monomer C under the action of a free radical initiator; monomer C contains both a-C = C-double bond and an active group.
7. A composition having high melt strength and toughness produced by the process of any of claims 1-6.
8. A composition with high melt strength and toughness is characterized by comprising the following components in parts by weight: 85-99 parts of polymer A, 1-30 parts of reactive polymer B and 0.1-3 parts of functional auxiliary agent; wherein the reactive polymer B simultaneously comprises a flexible polyester main chain and a side chain with an active group; the active group comprises at least one of anhydride, epoxy group and isocyanate; the polymer A is at least one of polyglycolic acid, glycolic acid-based copolymer, polylactic acid, lactic acid-based copolymer and polyethylene terephthalate.
9. The composition of claim 8, wherein the composition is prepared by a process comprising:
the method 1 comprises the steps of premixing the polymer A, the reactive polymer B and the functional auxiliary agent uniformly at room temperature according to the weight ratio, adding the premixed materials into an internal mixer for melt blending, and obtaining a high-melt-strength high-toughness composition;
or the method 2, premixing the polymer A, the reactive polymer B and the functional auxiliary agent uniformly at room temperature according to the weight ratio, adding the premixed materials into a conveying section of a double-screw extruder, and carrying out continuous melt extrusion to obtain the high-melt-strength high-toughness composition.
10. Use of the composition of claim 7 or 8 for compression molding, foaming, blow molding, post-forming to produce thermoplastic articles.
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| US20070203261A1 (en) * | 2006-02-24 | 2007-08-30 | Board Of Trustees Of Michigan State University | Reactively blended polyester and filler composite compositions and process |
| US20120259028A1 (en) * | 2009-10-07 | 2012-10-11 | Peter Plimmer | Reactive polymeric mixture |
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|---|---|---|---|---|
| US20070203261A1 (en) * | 2006-02-24 | 2007-08-30 | Board Of Trustees Of Michigan State University | Reactively blended polyester and filler composite compositions and process |
| US20120259028A1 (en) * | 2009-10-07 | 2012-10-11 | Peter Plimmer | Reactive polymeric mixture |
| US20210198407A1 (en) * | 2018-07-13 | 2021-07-01 | Byk-Chemie Gmbh | A grafted polylactic acid |
| WO2022037349A1 (en) * | 2020-08-19 | 2022-02-24 | 国家能源投资集团有限责任公司 | Toughening degradable polyglycolic acid composition, and toughening degradable polyglycolic acid material and preparation method therefor and use thereof |
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