CN117004194A - Semitransparent polyglycolic acid composition and preparation method thereof - Google Patents
Semitransparent polyglycolic acid composition and preparation method thereof Download PDFInfo
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- CN117004194A CN117004194A CN202210457490.2A CN202210457490A CN117004194A CN 117004194 A CN117004194 A CN 117004194A CN 202210457490 A CN202210457490 A CN 202210457490A CN 117004194 A CN117004194 A CN 117004194A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 101
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 62
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 54
- 239000002667 nucleating agent Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 16
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 25
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a semitransparent polyglycolic acid composition and a preparation method thereof, wherein the composition comprises polyglycolic acid, a nucleating agent and an antioxidant, and the dosage of the nucleating agent is 0.1-6 parts by weight relative to 100 parts by weight of polyglycolic acid; the dosage of the antioxidant is 0.1-1.5 parts by weight; wherein the nucleating agent is an inorganic nucleating agent with the particle size of 1 to 300nm. The material prepared by the invention has good light transmittance, and the optimal light transmittance can reach 67%.
Description
Technical Field
The invention relates to the technical field of polyglycolic acid materials, in particular to a semitransparent polyglycolic acid composition and a preparation method thereof.
Background
Polyglycolic acid (PGA) is a biodegradable polymer, has excellent biodegradability, good mechanical strength and excellent gas barrier property, and is very suitable for preparing a disposable degradable film, but due to the structural characteristics of PGA, the light transmittance is only 40%, and wider application is greatly limited, so that the improvement of the light transmittance of PGA is of great significance.
Because the polyglycolic acid material has high crystallization temperature and high crystallization speed, the common nucleating agent has poor capability of regulating PGA crystallization behavior, and no practical case for effectively carrying out anti-reflection modification in the polyglycolic acid material exists in the prior research results. CN202010836786.6 discloses a polyglycolic acid composition, a preparation method and application thereof, the composition comprises polyglycolic acid, polyisocyanate compounds and an anti-hydrolysis stabilizer, but the aim is to improve the stability against hydrolysis and the light transmittance is not greatly improved.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a translucent polyglycolic acid composition and a preparation method thereof, wherein the material prepared by the present invention has good light transmittance, and the light transmittance can reach 67% optimally.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a translucent polyglycolic acid composition comprising polyglycolic acid, a nucleating agent, and an antioxidant, the nucleating agent being present in an amount of 0.1 to 6 parts by weight relative to 100 parts by weight of polyglycolic acid; the dosage of the antioxidant is 0.1-1.5 parts by weight;
wherein the nucleating agent is an inorganic nucleating agent with the particle size of 1 to 300nm.
According to the composition of the invention, the polyglycolic acid has a weight average molecular weight of 5 to 30 ten thousand, a melt index of 2.16kg at 240 ℃ of 5 to 36g/10min and a tensile modulus of 6000 to 8000Mpa. Preferably, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand, 2.16kg, and a melt index at 240 ℃ of 15 to 30g/10min.
The composition according to the invention further comprises 0-5 parts by weight of a chain extender selected from at least one of isocyanate-based chain extenders and epoxy-based chain extenders, preferably epoxy-based chain extenders. The isocyanate chain extender is preferably at least one of diphenylmethane diisocyanate and hexamethylene diisocyanate. The chain extender of the type can carry out organic modification on the inorganic nucleating agent, improve the dispersion of the inorganic nucleating agent in the material, promote the material to form a crystallization system with fine crystallization and regular distribution, and improve the transparency of the material.
The composition according to the present invention, wherein the nucleating agent is preferably used in an amount of 0.5 to 5 parts by weight relative to 100 parts by weight of polyglycolic acid; the amount of the chain extender is preferably 0 to 3 parts by weight; the antioxidant is preferably used in an amount of 0.3 to 0.8 parts by weight. It is further preferred that the nucleating agent is used in an amount of 0.5 to 2 parts by weight and the chain extender is used in an amount of 1 to 2 parts by weight with respect to 100 parts by weight of polyglycolic acid.
According to the composition of the present invention, the inorganic nucleating agent is selected from at least one of nano silica, talc, calcium carbonate and montmorillonite, preferably having a particle size of 5 to 300nm, such as, but not limited to, nano silica having a particle size of 7 to 40nm, talc having a particle size of 100 to 300nm, calcium carbonate having a particle size of 20 to 60nm, and the like. By selecting the type and particle size of the inorganic nucleating agent, the material prepared by the composition can be crystallized finely, the reflection and refraction of light can be reduced, and the light transmittance of the material can be improved.
The composition according to the invention, the antioxidant is selected from at least one of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants, preferably hindered phenolic antioxidants and/or phosphite antioxidants; more preferably, the antioxidant is selected from at least one of antioxidant 1330, antioxidant 245, antioxidant 168, and antioxidant 626.
The invention also provides a preparation method of the polyglycolic acid composition, which comprises the following steps:
uniformly mixing polyglycolic acid, a nucleating agent, an antioxidant and optionally a chain extender, and carrying out melt blending and extrusion granulation by a double-screw extruder to obtain the polyglycolic acid composition. As used herein, "optionally" means either with or without addition.
According to the preparation method of the invention, the polyglycolic acid is dried before mixing, and the drying conditions comprise: the drying temperature is 40-80 ℃; the drying time is 4-10h, preferably 80 ℃,4h.
According to the preparation method of the invention, the conditions of melt blending include: the temperature is 225-250deg.C, preferably 230-240 deg.C; the extruder speed is 60-130r/min, preferably 90-120r/min.
In another aspect, the present invention provides a translucent polyglycolic acid material prepared by the above-described method of preparation.
Further, the above translucent polyglycolic acid material may be processed into a corresponding article using equipment known to those skilled in the art such as a tablet press, a casting machine, a film blowing machine, and the like.
Compared with the prior art, the invention has the following advantages:
according to the invention, the inorganic nucleating agent with the above type and particle size is added into the polyglycolic acid system, so that the light transmittance of the prepared material can be improved; according to the invention, the chain extender is added into the polyglycolic acid resin system, so that the molecular structure of the polyglycolic acid can be changed, and the light transmittance of the pure polyglycolic acid is improved to a certain extent; in addition, the inorganic nucleating agent and the chain extender selected by the invention have a synergistic effect in polyglycolic acid, and the chain extender can carry out organic modification on the inorganic nucleating agent and promote the dispersion of the inorganic nucleating agent, so that the light transmittance effect of the material is better.
The material prepared from the polyglycolic acid composition has good light transmittance, and the optimal light transmittance can reach 67 percent.
Detailed Description
The invention is further illustrated below in connection with the examples, but the invention is not limited to the examples listed but also includes equivalent improvements and variants of the solution defined in the claims appended hereto.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the following examples and comparative examples:
(1) Main raw materials
Polyglycolic acid, having a weight average molecular weight of 13 ten thousand, a melt index of 26g/10min (240 ℃,2.16 kg), commercially available;
inorganic nucleating agent nano silicon dioxide with the particle size of 7-40nm is purchased from Aba Ding Shiji (Shanghai) limited company;
the inorganic nucleating agent nano talcum powder has the particle size of 100-300nm and is purchased from Beijing chemical reagent Co., ltd;
the inorganic nucleating agent nano calcium carbonate has the particle size of 20-60nm and is purchased from Beijing De island gold technology Co., ltd;
the epoxy chain extender is ADR-4468; purchased from Shanghai Kaine chemical Co., ltd;
the isocyanate chain extender is diphenylmethane diisocyanate; purchased from alaa Ding Shiji (Shanghai) limited;
antioxidant A is antioxidant 168, available from Qingdao Jiejia New Material technology Co., ltd;
antioxidant B is antioxidant 1330, available from Qingdao Jiejia New Material technology Co., ltd;
the other raw materials used in the examples and comparative examples are all commercially available.
(2) Characterization and testing
The light transmittance testing method comprises the following steps:
an appropriate amount of translucent polyglycolic acid material was weighed, molded into a 50mm×50mm×0.3mm sheet, and the light transmittance of the sheet was measured by using a light transmittance meter using a GB T2410-2008 method.
The crystallinity test method comprises the following steps:
the crystallinity of the samples was characterized by DSC. Test conditions: nitrogen atmosphere, 50-240 deg.c and 10K/min. Determination of the melting enthalpy ΔH of the sample during the second heating cycle m And the crystallinity of the sample was calculated using the following relation.
Wherein DeltaH m Represents the enthalpy of fusion of PGA,represents 100% crystalline PGA with a melting enthalpy of 183.2J/g.
The following examples are presented to illustrate polyglycolic acid compositions and methods of making the same.
Example 1
10Kg of polyglycolic acid (PGA drying condition: 80 ℃ C., 4 h), 0.05Kg of nucleating agent (nano silicon dioxide), 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt blending and extrusion granulating are carried out by a double-screw extruder, so as to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 120 revolutions per minute, and the temperature of the screw extrusion blending is 230 ℃.
Example 2
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.1Kg of nucleating agent (nano silica) and 0.02Kg of antioxidant A (antioxidant 168) are stirred for 3 minutes by a high-speed stirrer, uniformly mixed, and then melt-blended and extruded to pelletize by a double-screw extruder to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 120 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Example 3
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.2Kg of nano silicon dioxide, 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt-mixed by a twin-screw extruder, extruded and granulated to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 110 revolutions per minute, and the temperature of the screw extrusion blending is 235 ℃.
Example 4
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.05Kg of nano silica, 0.1Kg of chain extender (ADR-4468), 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt-mixed by a twin-screw extruder, extruded and granulated to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 100 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Example 5
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.1Kg of ADR-4468 and 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt-blended by a twin-screw extruder, extruded and granulated to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 100 revolutions per minute, and the temperature of the screw extrusion blending is 235 ℃.
Example 6
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.1Kg of nano talcum powder, 0.2Kg of diphenylmethane diisocyanate, 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred for 3 minutes by a high-speed stirrer, and then melt-blended, extruded and granulated by a double-screw extruder to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 90 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Example 7
10Kg of polyglycolic acid (PGA, dried in the same way as in example 1), 0.2Kg of nano calcium carbonate, 0.2Kg of hexamethylene diisocyanate, 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt-blended by a twin-screw extruder, extruded and granulated to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 90 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Sheets made from the polyglycolic acid materials of examples 1-7 were tested for light transmittance and the data relating thereto are shown in Table 1.
TABLE 1
| Crystallinity/% | Transmittance/% | |
| Example 1 | 45 | 62 |
| Example 2 | 45 | 65 |
| Example 3 | 44 | 59 |
| Example 4 | 42 | 67 |
| Example 5 | 41 | 57 |
| Example 6 | 41 | 63 |
| Example 7 | 42 | 60 |
Comparative example 1
10Kg of PGA, 0.02Kg of antioxidant A and 0.02Kg of antioxidant B are stirred for 3 minutes by a high-speed stirrer, and then are subjected to melt blending and extrusion granulation by a double-screw extruder. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 120 revolutions per minute, and the temperature of the screw extrusion blending is 230 ℃.
Comparative example 2
10Kg of polyglycolic acid (PGA), 0.1Kg of nucleating agent (TMC 300, commercially available product) and 0.02Kg of antioxidant A (antioxidant 168) were stirred with 0.02Kg of antioxidant B (antioxidant 1330) by a high-speed stirrer for 3 minutes, and then melt-blended and extrusion-granulated by a twin-screw extruder. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 100 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Comparative example 3
10Kg of polyglycolic acid (PGA), 1Kg of nano silicon dioxide, 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) are stirred by a high-speed stirrer for 3 minutes and uniformly mixed, and then melt blending and extrusion granulating are carried out by a double-screw extruder, so as to obtain the polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 90 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Comparative example 4
10Kg of polyglycolic acid (PGA, dried in the same manner as in example 1), 0.2Kg of calcium carbonate (particle size 1-3 μm), 0.2Kg of hexamethylene diisocyanate, 0.02Kg of antioxidant A (antioxidant 168) and 0.02Kg of antioxidant B (antioxidant 1330) were stirred by a high-speed stirrer for 3 minutes and mixed uniformly, and then melt-blended by a twin-screw extruder, extruded and granulated to obtain a polyglycolic acid material. Wherein the length-diameter ratio of the screw of the double-screw extruder is 26/1, the rotating speed of the screw is 90 revolutions per minute, and the temperature of the screw extrusion blending is 240 ℃.
Sheets made from the polyglycolic acid materials of comparative examples 1-4 were tested for light transmittance and the data relating thereto are shown in Table 2.
TABLE 2
| Crystallinity/% | Transmittance/% | |
| Comparative example 1 | 41 | 40 |
| Comparative example 2 | 47 | 43 |
| Comparative example 3 | 49 | 45 |
| Comparative example 4 | 43 | 38 |
As can be seen from the results of examples, comparative examples and tables 1 to 2, the transmittance of the materials prepared by the system comprising polyglycolic acid, inorganic nucleating agent and antioxidant according to examples 1 to 3 of the present invention was greatly improved, and at least about 20% was improved as compared with the transmittance of 40% of pure PGA. And, referring to example 4, the optimal antireflective effect is achieved when the inorganic nucleating agent and the chain extender are added simultaneously in the polyglycolic acid system and the dosage ratio of the inorganic nucleating agent and the chain extender is controlled and the preferable particle size of the inorganic nucleating agent is matched; in addition, the transmittance of the material prepared from the system consisting of polyglycolic acid, a chain extender and an antioxidant in example 5 is improved to a certain extent compared with the pure PGA.
Meanwhile, compared with example 1, the inorganic nucleating agent is not added in comparative example 1, other kinds of nucleating agents are selected in comparative example 2, and the inorganic nucleating agent is excessively added in comparative example 3, so that the effect of improving the light transmittance is not great; comparative example 4 has no effect of improving light transmittance even though the particle diameter of the inorganic nucleating agent added is not suitable as compared with example 7.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious variations or modifications which come within the spirit of the invention are desired to be protected.
Claims (10)
1. A translucent polyglycolic acid composition characterized by: comprises polyglycolic acid, a nucleating agent and an antioxidant, wherein the dosage of the nucleating agent is 0.1-6 parts by weight relative to 100 parts by weight of polyglycolic acid; the dosage of the antioxidant is 0.1-1.5 parts by weight;
wherein the nucleating agent is an inorganic nucleating agent with the particle size of 1 to 300nm.
2. The polyglycolic acid composition of claim 1, wherein: the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand, 2.16kg, the melt index at 240 ℃ is 5-36 g/10min, and the tensile modulus is 6000-8000 Mpa; preferably, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand, 2.16kg, and a melt index at 240 ℃ of 15 to 30g/10min.
3. The polyglycolic acid composition according to claim 1 or 2, characterized in that: the chain extender is selected from at least one of isocyanate chain extender and epoxy chain extender, preferably epoxy chain extender, in an amount of 0-5 parts by weight.
4. A polyglycolic acid composition according to claim 3, wherein: wherein the nucleating agent is used in an amount of 0.5 to 5 parts by weight relative to 100 parts by weight of polyglycolic acid; the dosage of the chain extender is 0-3 parts by weight; the dosage of the antioxidant is 0.3-0.8 weight part; it is further preferred that the nucleating agent is used in an amount of 0.5 to 2 parts by weight and the chain extender is used in an amount of 1 to 2 parts by weight with respect to 100 parts by weight of polyglycolic acid.
5. The polyglycolic acid composition of any one of claims 1-4, wherein the polyglycolic acid composition comprises: the inorganic nucleating agent is at least one selected from nano silicon dioxide, talcum powder, calcium carbonate and montmorillonite.
6. The polyglycolic acid composition of any one of claims 1-5, wherein: the antioxidant is at least one selected from hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants, and is preferably hindered phenol antioxidants and/or phosphite antioxidants; more preferably, the antioxidant is selected from at least one of antioxidant 1330, antioxidant 245, antioxidant 168, and antioxidant 626.
7. The polyglycolic acid composition of any one of claims 1-6, wherein the polyglycolic acid composition comprises: wherein the amount of the nucleating agent is 0.5 to 2 parts by weight, the amount of the chain extender is 1 to 2 parts by weight, and the amount of the antioxidant is 0.3 to 0.8 part by weight, relative to 100 parts by weight of the polyglycolic acid;
wherein the weight average molecular weight of the polyglycolic acid is 10-15 ten thousand, 2.16kg, and the melt index at 240 ℃ is 15-30 g/10min; the grain diameter of the nucleating agent is 5-300nm, and the chain extender is epoxy chain extender.
8. A process for preparing a polyglycolic acid composition as defined in any one of claims 1-7, wherein: the method comprises the following steps:
uniformly mixing polyglycolic acid, a nucleating agent, an antioxidant and optionally a chain extender, and carrying out melt blending and extrusion granulation by a double-screw extruder to obtain the polyglycolic acid composition.
9. The process for producing a polyglycolic acid composition according to claim 8, wherein: the polyglycolic acid is dried prior to mixing, and the drying conditions include: the drying temperature is 40-80 ℃; the drying time is 4-10h; and/or the number of the groups of groups,
the conditions of the melt blending include: the temperature is 225-250deg.C, preferably 230-240 deg.C; the extruder speed is 60-130r/min, preferably 90-120r/min.
10. A translucent polyglycolic acid material produced by the method of any one of claims 8-9.
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