CN114075375B - Polyglycolic acid composition, preparation method and application thereof - Google Patents
Polyglycolic acid composition, preparation method and application thereof Download PDFInfo
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- CN114075375B CN114075375B CN202010836786.6A CN202010836786A CN114075375B CN 114075375 B CN114075375 B CN 114075375B CN 202010836786 A CN202010836786 A CN 202010836786A CN 114075375 B CN114075375 B CN 114075375B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention relates to the field of high polymer materials, and discloses a polyglycolic acid composition, a preparation method and application thereof. The composition comprises polyglycolic acid, a polyisocyanate compound and an hydrolysis-resistant stabilizer; the amount of the polyisocyanate compound is 0.5 to 5 parts by weight relative to 100 parts by weight of the polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-3 parts by weight; the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand. The polyglycolic acid composition has excellent hydrolysis resistance stability, and can prolong the storage time and prolong the service life of the product. Meanwhile, the melt viscosity and the flow property of the composition are improved, and the light transmittance of a film prepared from the composition is also improved.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyglycolic acid composition, a preparation method and application thereof.
Background
Polyglycolic acid (PGA) has excellent biocompatibility, degradability, gas barrier property and excellent mechanical properties, and has considerable market prospects in the fields of medical degradable materials and packaging materials. However, PGA, like most biodegradable polyesters, has poor moisture and heat resistance and poor hydrolysis resistance, and is easily subjected to hydrolysis and chain scission reaction at ester groups in molecular chains in the presence of water molecules, so that the product undergoes hydrolysis and degradation during molding preparation or storage and use, and the performance is reduced, thereby affecting practical application.
CN101321829a discloses a polyglycolic acid resin composition having improved water resistance, which is obtained by blending a carboxyl end-capping agent and a polymerization catalyst-inactivating agent into a polyglycolic acid resin.
CN102634001a discloses a method for improving the hydrolysis resistance of biodegradable polyesters by capping. The benzyl chloride is used as a blocking agent to carry out a blocking reaction on the biodegradable polyester polyglycolide, and the modified polyglycolide has obviously improved hydrolysis resistance and thermal stability.
However, the prior art described above only improves hydrolysis resistance by capping agents or catalyst inerting agents and does not relate to chemical adhesion enhancement of polyglycolic acid melt viscosity and flow properties.
Disclosure of Invention
The invention aims to solve the problems that the polyglycolic acid composition in the prior art is poor in hydrolysis resistance stability and easy to hydrolyze due to moisture absorption in water environment or air, and provides a polyglycolic acid composition, a preparation method and application thereof. Meanwhile, the melt viscosity and the flow property of the composition are improved, and the light transmittance of a film prepared from the composition is also improved.
In order to achieve the above object, the present invention provides, in a first aspect, a polyglycolic acid composition, wherein the composition comprises polyglycolic acid, a polyisocyanate compound, and an hydrolysis-resistant stabilizer;
the polyisocyanate compound is used in an amount of 0.5 to 5 parts by weight relative to 100 parts by weight of the polyglycolic acid composition; the dosage of the hydrolysis resistant stabilizer is 0.5-3 parts by weight;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand.
In a second aspect, the present invention provides a process for preparing a polyglycolic acid composition, wherein the process comprises the steps of:
respectively drying polyglycolic acid, an anti-hydrolysis stabilizer and a polyisocyanate ester compound, uniformly mixing, and carrying out melt blending extrusion by a double-screw extruder to obtain the polyglycolic acid composition;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand.
In a third aspect, the present invention provides a polyglycolic acid composition produced by the above-described production process.
In a fourth aspect, the present invention provides the use of a polyglycolic acid composition as described above in a degradable material or barrier packaging material.
In a fifth aspect, the present invention provides the use of the polyglycolic acid composition described above for the preparation of at least one of films, fibers and sheets.
Through the technical scheme, the polyglycolic acid composition provided by the invention and the preparation method and application thereof have the following beneficial effects:
in the invention, the polyglycolic acid composition comprises the hydrolysis-resistant stabilizer, and the hydrolysis-resistant stabilizer in the composition can react with carboxyl end groups of polyglycolic acid, reduce the concentration of the carboxyl end groups and improve the hydrolysis resistance of the polyglycolic acid.
Furthermore, in the invention, the polyglycolic acid composition comprises a polyisocyanate ester compound which can react with terminal carboxyl groups and/or terminal hydroxyl groups of the polyglycolic acid, so that the hydrolysis stability can be further improved, meanwhile, as the polyisocyanate compound can achieve the effect of chemical adhesion, the melt viscosity of the polyglycolic acid is improved, the flow property is improved, and the light transmittance of a film obtained from the polyglycolic acid composition is also improved.
Detailed Description
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.
The first aspect of the present invention provides a polyglycolic acid composition, wherein the polyglycolic acid composition comprises polyglycolic acid, a polyisocyanate compound and an hydrolysis-resistant stabilizer,
the amount of the polyisocyanate compound is 0.5 to 5 parts by weight relative to 100 parts by weight of the polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-3 parts by weight;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand.
In the invention, after the polyisocyanate compound is matched with the hydrolysis resistant stabilizer, the polyglycolic acid composition obtained by adding the polyisocyanate compound into the polyglycolic acid obtains better hydrolysis resistant stability, and simultaneously, the melt viscosity and the flow property of the composition are improved, and the light transmittance of a film prepared from the composition is also improved.
In particular, when the amounts of the polyisocyanate compound and the hydrolysis-resistant stabilizer in the polyglycolic acid composition satisfy the above-mentioned limitations, the polyglycolic acid composition has good hydrolysis-resistant stability, high melt viscosity, good fluidity, and the produced film has high light transmittance.
Further, the polyisocyanate compound is used in an amount of 1 to 3 parts by weight relative to 100 parts by weight of the polyglycolic acid; when the amount of the hydrolysis-resistant stabilizer is 0.5 to 1 part by weight, the polyglycolic acid composition has more excellent technical effects.
In the invention, polyglycolic acid with weight average molecular weight of 5-18 ten thousand is adopted as a base material, so that the obtained polyglycolic acid composition has the advantages of good hydrolysis resistance stability, high melt viscosity and good flow property, and the prepared film has high light transmittance. Further, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand.
According to the invention, the hydrolysis resistant stabilizer is selected from the group consisting of polycarbodiimides and/or carbodiimides, preferably at least one of N, N ' -dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide and N, N ' -diphenylcarbodiimide.
According to the invention, the polyisocyanate-based compound is selected from the group consisting of a diisocyanate-based compound and/or a diisocyanate prepolymer.
In the present invention, the polyisocyanate-based compound means a compound having two or more isocyanate groups.
According to the present invention, the polyisocyanate-based compound is selected from at least one of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.
According to the invention, the polyisocyanate-based compound is selected from diphenylmethane diisocyanate and/or polyisocyanate.
In the present invention, the polyisocyanate has a viscosity (25 ℃) of 150 to 250 mPas and a functionality of 2.6 to 2.7. The polyisocyanates are commercially available, for example, from the chemical production of PM200 (viscosity (25 ℃) of 150 to 250 mPa.s and functionality of 2.6 to 2.7).
According to the present invention, the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR 2. Ltoreq.40%. Times.MFR 1, preferably MFR2 is (10-30%) times.MFR 1.
In the present invention, the melt flow rate is measured according to the method GB/T3682-2000.
According to the present invention, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are W1 and W2, respectively, wherein W1-W2 is not less than 10%, preferably W1-W2 is 11-20%.
In the invention, the hydrolysis weight loss ratio W is calculated by the following formula:
in which W is 0 Initial mass for the sample; w (W) d The quality after degradation.
In a second aspect, the present invention provides a process for preparing a polyglycolic acid composition, wherein the process comprises the steps of:
respectively drying polyglycolic acid, an anti-hydrolysis stabilizer and a polyisocyanate ester compound, uniformly mixing, and carrying out melt blending extrusion by a double-screw extruder to obtain the polyglycolic acid composition;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand.
According to the invention, after the hydrolysis-resistant stabilizer, the polyisocyanate compound and the polyglycolic acid with weight average molecular weight of 5-18 ten thousand are respectively dried and uniformly mixed, the mixture is melt blended and extruded by a double-screw extruder, and the hydrolysis-resistant stabilizer reacts with the carboxyl end group of the polyglycolic acid in the melt blending extrusion process, and the polyisocyanate ester compound reacts with the carboxyl end group and/or hydroxyl end group of the polyglycolic acid to realize synergistic effect, so that the hydrolysis resistance of the polyglycolic acid can be obviously improved. In addition, the addition of the polyisocyanate compound can improve the molecular weight, the melt viscosity and the flow property of the polyglycolic acid, and the light transmittance of a film obtained by using the polyglycolic acid composition is also improved.
According to the present invention, the polyisocyanate-based compound is used in an amount of 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, relative to 100 parts by weight of polyglycolic acid; the amount of the hydrolysis-resistant stabilizer is 0.5 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight.
According to the present invention, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand.
According to the invention, the polyisocyanate-based compound is selected from the group consisting of a diisocyanate-based compound and/or a diisocyanate prepolymer.
According to the present invention, the polyisocyanate-based compound is selected from at least one of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.
According to the invention, the polyisocyanate-based compound is selected from diphenylmethane diisocyanate and/or polyisocyanate.
According to the invention, the hydrolysis resistant stabilizer is selected from the group consisting of polycarbodiimides and/or carbodiimides, preferably at least one of N, N ' -dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide and N, N ' -diphenylcarbodiimide.
In the present invention, in order to avoid hydrolysis of a mixture comprising polyglycolic acid and a hydrolysis-resistant stabilizer at the time of extrusion due to moisture in the raw materials, the polyglycolic acid, the hydrolysis-resistant stabilizer and the polyisocyanate compound are dried before melt blending and extrusion of the respective components, preferably, the drying conditions include: the temperature is 40-80 ℃; the time is 5-10h. Further, the drying temperature is preferably 42-70 ℃, and the drying time is preferably 6-8h.
In the invention, the inventor researches on the conditions of melt blending extrusion, and discovers that the degradation of polyglycolic acid and the performance degradation of the prepared polyglycolic acid composition are avoided when the polyglycolic acid, the hydrolysis resistant stabilizer and the polyisocyanate compound are subjected to melt blending extrusion under the conditions that the temperature is 230-250 ℃ and the screw rotating speed is 60-130r/min.
Still further, the conditions of melt blending extrusion include: the temperature is 235-240 ℃, and the rotating speed of the screw is 70-100r/min.
In a third aspect, the present invention provides a polyglycolic acid composition produced by the above-described process.
In the present invention, the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR 2. Ltoreq.40%. Times.MFR 1, preferably MFR2 is (10-30%) times.MFR 1.
In the present invention, the melt flow rate is measured according to the method GB/T3682-2000.
According to the present invention, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are W1 and W2, respectively, wherein W1-W2 is not less than 10%, preferably W1-W2 is 11-20%.
In the invention, the hydrolysis weight loss ratio W is calculated by the following formula:
in which W is 0 Initial mass for the sample; w (W) d The quality after degradation.
In a fourth aspect the present invention provides the use of the polyglycolic acid composition described above in a degradable material or barrier packaging material.
In a fifth aspect, the present invention provides the use of the polyglycolic acid composition described above in the preparation of at least one of a film, a fiber and a board.
The present invention will be described in detail by examples. In the following examples, the melt flow rate of the polyglycolic acid composition was measured using the GB/T3682-2000 method;
the hydrolysis weight loss ratio of polyglycolic acid and polyglycolic acid compositions is calculated by the following formula;
in which W is 0 Initial mass for the sample; w (W) d The quality after degradation.
The light transmittance is measured by using a GB/T2410-2008 method;
polyglycolic acid a, weight average molecular weight 13 ten thousand, commercially available;
polyglycolic acid B, weight average molecular weight 9 ten thousand, commercially available;
polyglycolic acid C, weight average molecular weight 4 ten thousand, commercially available;
hydrolysis resistant stabilizer A, hyMax210, available from Shanghai Lang Yi functional materials Co., ltd;
hydrolysis resistant stabilizer B, S9000, available from Shanghai Pu Zhu Shangxi Co., ltd;
diphenylmethane diisocyanate (MDI) was purchased from enokak;
polyisocyanates (PMDI) were purchased from Wanhua chemistry, PM200 (25 ℃ C., mPas: 150-250, functionality 2.6-2.7).
The other raw materials used in the examples and comparative examples are all commercially available.
Test case
The polyglycolic acid composition was formed into a film and the film was tested for light transmittance.
And (3) placing the polyglycolic acid composition granules into a die, prepressing for 2min at 230 ℃ and 0MPa, die pressing for 3min at 230 ℃ and 20MPa, and cooling to 40 ℃ at 10 ℃/min under 20MPa pressure maintaining to obtain the film with the thickness of about 100 mu m.
Example 1
Drying 100 parts by weight of polyglycolic acid A and 1 part by weight of hydrolysis resistant stabilizer A for later use at a drying temperature of 70 ℃ for 8 hours; 3 parts by weight of polyisocyanate compound (MDI) are dried for standby, the drying temperature is 45 ℃, and the drying time is 7 hours; uniformly mixing the dried polyglycolic acid, the hydrolysis resistant stabilizer A and the polyisocyanate compound, and then carrying out melt blending extrusion granulation by a double-screw extruder at 235 ℃ and a screw rotating speed of 100r/min to obtain the polyglycolic acid composition A1. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 12g/10min (reduced to 35% of the melt flow rate MFR1 of comparative example 1) a melt viscosity η2 (225 ℃, strain 2%,0.1 rad/s) of 2266 Pa.s (increased to 6.0 times the melt viscosity η1 of comparative example 1), a water boiling at 50℃for 2 weeks and a hydrolysis weight loss W2 of 12.7% by weight (12.4% lower than the hydrolysis weight loss W1 of comparative example 1). After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 50.3% (8% higher than that of comparative example 1).
Example 2
Drying 100 parts by weight of polyglycolic acid A and 0.5 part by weight of hydrolysis-resistant stabilizer A for later use at a drying temperature of 70 ℃ for 8 hours; 2 parts by weight of polyisocyanate compound are dried for standby, the drying temperature is 45 ℃, and the drying time is 7 hours; uniformly mixing the dried polyglycolic acid, the hydrolysis-resistant stabilizer and the polyisocyanate compound, and then carrying out melt blending extrusion granulation by a double-screw extruder at 235 ℃ and a rotating speed of 100r/min to obtain the polyglycolic acid composition A2. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 13.2g/10min (down to 38% of the melt flow rate MFR1 of comparative example 1), a melt viscosity eta 2 (225 ℃, strain 2%,0.1 rad/s) of 2140 Pa.s (up to 5.7 times the melt viscosity eta 1 of comparative example 1), a hydrolysis weight loss W2 of 14.4wt% (10.7% lower than the hydrolysis weight loss W1 of comparative example 1) by 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 49% (6.7% higher than that of comparative example 1).
Example 3
Drying 100 parts by weight of polyglycolic acid A and 1 part by weight of hydrolysis resistant stabilizer A for later use at a drying temperature of 70 ℃ for 8 hours; 5 parts by weight of polyisocyanate compound are dried for standby, the drying temperature is 45 ℃, and the drying time is 7 hours; uniformly mixing the dried polyglycolic acid, the hydrolysis-resistant stabilizer and the polyisocyanate compound, and then carrying out melt blending extrusion granulation by a double-screw extruder at 235 ℃ and a rotating speed of 100r/min to obtain the polyglycolic acid composition A3. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The melt flow rate MFR2 of the polyglycolic acid composition was 9.9g/10min (down to 29% of the melt flow rate MFR1 of comparative example 1), the melt viscosity η2 (225 ℃ C., strain 2%,0.1 rad/s) was 2460 Pa.s (up to 6.6 times the melt viscosity η1 of comparative example 1), the hydrolysis weight loss W2 was 11.5% by weight (13.6% lower than the hydrolysis weight loss W1 of comparative example 1) after 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 51% (8.7% higher than that of comparative example 1).
Example 4
Drying 100 parts by weight of polyglycolic acid A and 3 parts by weight of hydrolysis resistant stabilizer B for later use at a drying temperature of 70 ℃ for 8 hours; 0.5 part by weight of polyisocyanate compound is dried for standby, the drying temperature is 45 ℃, and the drying time is 7 hours; uniformly mixing the dried polyglycolic acid, the hydrolysis-resistant stabilizer and the polyisocyanate compound, and then carrying out melt blending extrusion granulation by a double-screw extruder at 235 ℃ and a rotating speed of 100r/min to obtain the polyglycolic acid composition A4. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The melt flow rate MFR2 of the polyglycolic acid composition was 10.6g/10min (down to 31% of the melt flow rate MFR1 of comparative example 1), the melt viscosity η2 (225 ℃ C., strain 2%,0.1 rad/s) was 2395 Pa.s (up to 6.4 times the melt viscosity η1 of comparative example 1), the hydrolysis weight loss W2 was 12.7% by weight (12.4% lower than the hydrolysis weight loss W1 of comparative example 1) after 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 50% (7.7% higher than that of comparative example 1).
Example 5
A polyglycolic acid composition was prepared as described in example 1, except that: polyglycolic acid B was used instead of polyglycolic acid a.
The melt flow rate MFR2 of the polyglycolic acid composition was tested to be 20g/10min (down to the melt flow rate MFR1 of comparative example 2 * Is 1560 Pa.s (increased to 7.1 times the melt viscosity η1 of comparative example 2), and is water-boiled at 50℃for 2 weeks, the hydrolysis weight loss ratio W2 is 15.9wt% (compared with the hydrolysis weight loss ratio W1 of comparative example 2) * Reduced by 12.5%). After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 48% (7.8% higher than that of comparative example 1).
Example 6
A polyglycolic acid composition was prepared as described in example 1, except that: the temperature of melt blending extrusion was 255 ℃.
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 13.7g/10min (down to 39.9% of the melt flow rate MFR1 of comparative example 1) a melt viscosity eta 2 (225 ℃, strain 2%,0.1 rad/s) of 2080 Pa.s (up to 5.5 times the melt viscosity eta 1 of comparative example 1), a hydrolysis weight loss of 14.7wt% (10.4 wt% lower than the hydrolysis weight loss W1 of comparative example 1) by 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 50% (7.7% higher than that of comparative example 1).
Example 7
A polyglycolic acid composition was prepared as described in example 1, except that: polyisocyanates are used instead of polyisocyanates (MDI).
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 10g/10min (reduced to 29.2% of the melt flow rate MFR1 of comparative example 1) a melt viscosity η2 (225 ℃, strain 2%,0.1 rad/s) of 2450 Pa.s (increased to 6.5 times the melt viscosity η1 of comparative example 1), a hydrolysis weight loss of 11% by weight (reduced by 14.1% by weight compared to the hydrolysis weight loss W1 of comparative example 1) after 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 50.8% (8.5% higher than that of comparative example 1).
Comparative example 1
100 parts by weight of polyglycolic acid A is dried for standby, the drying temperature is 70 ℃, and the drying time is 8 hours; and (3) carrying out melt extrusion granulation on the dried polyglycolic acid by a double-screw extruder at 235 ℃ and a rotating speed of 100r/min. The preparation process conditions are shown in table 1.
The melt flow rate MFR1 of the polyglycolic acid was tested to be 34.3g/10min, the melt viscosity η1 (225 ℃ C., strain 2%,0.1 rad/s) to be 375 Pa.s, the hydrolysis weight loss W1 to be 25.1% by weight after 2 weeks of water boiling at 50 ℃. After forming a film having a thickness of 100 μm, the light transmittance was measured to be 42.3%.
Comparative example 2
Polyglycolic acid was prepared as in comparative example 1, except that: polyglycolic acid B was used instead of polyglycolic acid a.
Melt flow Rate MFR1 of polyglycolic acid tested * 62.8g/10min, melt viscosity eta 1 * (225 ℃ C., strain 2%,0.1 rad/s) 220 Pa.s, water boiling at 50 ℃ C. For 2 weeks, hydrolysis weight loss ratio W1 * 28.4wt%. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 40.2%.
Comparative example 3
Polyglycolic acid was prepared as in comparative example 1, except that: polyglycolic acid C was used instead of polyglycolic acid a.
Melt flow Rate MFR1 of polyglycolic acid tested # 254g/10min, melt viscosity eta 1 # (225 ℃ C., strain 2%,0.1 rad/s) 60 Pa.s, water boiling at 50 ℃ C. For 2 weeks, hydrolysis weight loss ratio W1 # 34.5wt%. After forming a film having a thickness of 100 μm, the light transmittance was found to be 41.0%.
Comparative example 4
Drying 100 parts by weight of polyglycolic acid and 1 part by weight of an hydrolysis-resistant stabilizer A for later use at a drying temperature of 70 ℃ for 8 hours; uniformly mixing the dried polyglycolic acid and the hydrolysis-resistant stabilizer, and then carrying out melt blending extrusion granulation by a double-screw extruder at 235 ℃ and a rotating speed of 100r/min to obtain the polyglycolic acid composition. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 18.6g/10min (down to 54% of the melt flow rate MFR1 of comparative example 1), a melt viscosity eta 2 (225 ℃, strain 2%,0.1 rad/s) of 1200 Pa.s (up to 3.2 times the melt viscosity eta 1 of comparative example 1), a hydrolysis weight loss W2 of 17.5wt% (7.6% lower than the hydrolysis weight loss W1 of comparative example 1) after 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 47.1% (4.8% higher than that of comparative example 1).
Comparative example 5
A polyglycolic acid composition was prepared as described in example 1, except that: does not contain an anti-hydrolysis stabilizer.
The melt flow rate MFR2 of the polyglycolic acid composition was 13.4g/10min (down to 39% of the melt flow rate MFR1 of comparative example 1), the melt viscosity η2 (225 ℃ C., strain 2%,0.1 rad/s) was 2100 Pa.s (up to 5.6 times the melt viscosity η1 of comparative example 1), the hydrolysis weight loss W2 was 23.6% (1.5% lower than the hydrolysis weight loss W1 of comparative example 1) after 2 weeks of water boiling at 50 ℃. After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 46.3% (4% higher than that of comparative example 1).
Comparative example 6
A polyglycolic acid composition was prepared as described in example 1, except that: the amounts of hydrolysis-resistant stabilizer and isocyanate compound used were different from those of example 1. The amounts of the respective raw materials in the polyglycolic acid composition and the production process conditions are shown in table 1.
The polyglycolic acid composition was tested to have a melt flow rate MFR2 of 22.3g/10min (reduced to 65% of the melt flow rate MFR1 of comparative example 1) a melt viscosity η2 (225 ℃, strain 2%,0.1 rad/s) of 632 Pa.s (increased to 1.7 times the melt viscosity η1 of comparative example 1), a water boiling at 50℃for 2 weeks and a hydrolysis weight loss W2 of 20.7% (reduced by 4.4% from the hydrolysis weight loss W1 of comparative example 1). After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 45.9% (3.6% higher than that of comparative example 1).
Comparative example 7
A polyglycolic acid composition was prepared as described in example 1, except that: the weight average molecular weight of polyglycolic acid C instead of polyglycolic acid a is not within the range of claim 1.
The melt flow rate MFR2 of the polyglycolic acid composition was 144.8g/10min (reduced to the melt flow rate MFR1 of comparative example 3) # Is 326 Pa.s (increased) with a melt viscosity η2 (225 ℃, strain 2%,0.1 rad/s)To comparative example 3 melt viscosity η1 # 5.4 times of (a) of the above) was boiled in water at 50℃for 2 weeks, and the weight loss on hydrolysis W2 was 22.5% (higher than the weight loss on hydrolysis W1 of comparative example 3) # Reduced by 12%). After a film having a thickness of 100 μm was formed, the light transmittance was measured to be 49% (6.7% higher than that of comparative example 3).
TABLE 1
As can be seen from the results of examples and comparative examples, examples 1 to 6, in which the polyglycolic acid composition comprises a polyisocyanate compound and a hydrolysis-resistant stabilizer, have better hydrolysis-resistant stability, higher melt viscosity, better flow properties, and films prepared therefrom have more excellent light transmittance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (33)
1. A polyglycolic acid composition, wherein the composition comprises polyglycolic acid, a polyisocyanate-based compound, and an hydrolysis-resistant stabilizer;
the amount of the polyisocyanate compound is 0.5 to 5 parts by weight relative to 100 parts by weight of the polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-3 parts by weight;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand;
the hydrolysis resistant stabilizer is selected from polycarbodiimide and/or carbodiimide.
2. The composition according to claim 1, wherein the polyisocyanate-based compound is used in an amount of 1 to 3 parts by weight relative to 100 parts by weight of polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-1 weight part;
and/or, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand.
3. The composition of claim 1 or 2, wherein the hydrolysis resistant stabilizer is at least one of N, N ' -dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide, and N, N ' -diphenylcarbodiimide.
4. Composition according to claim 1 or 2, wherein the polyisocyanate-based compound is selected from a diisocyanate-based compound and/or a diisocyanate prepolymer.
5. The composition according to claim 4, wherein the polyisocyanate-based compound is at least one selected from the group consisting of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate and polyisocyanate.
6. The composition of claim 5, wherein the polyisocyanate-based compound is selected from diphenylmethane diisocyanate and/or polyisocyanate.
7. A composition according to claim 3, wherein the polyisocyanate-based compound is selected from a diisocyanate-based compound and/or a diisocyanate prepolymer.
8. The composition according to claim 7, wherein the polyisocyanate-based compound is selected from at least one of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.
9. The composition of claim 8, wherein the polyisocyanate-based compound is selected from diphenylmethane diisocyanate and/or polyisocyanate.
10. The composition of any one of claims 1, 2 or 5-9, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is less than or equal to 40% by MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are respectively W1 and W2, wherein W1-W2 is more than or equal to 10%.
11. The composition of claim 10, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is (10-30%). Times.MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are W1 and W2, respectively, wherein W1-W2 is 11-20%.
12. The composition of claim 3, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is less than or equal to 40% by MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are respectively W1 and W2, wherein W1-W2 is more than or equal to 10%.
13. The composition of claim 12, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is (10-30%). Times.MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are W1 and W2, respectively, wherein W1-W2 is 11-20%.
14. The composition of claim 4, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is less than or equal to 40% by MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are respectively W1 and W2, wherein W1-W2 is more than or equal to 10%.
15. The composition of claim 14, wherein the melt flow rates of the polyglycolic acid and the polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR2 is (10-30%). Times.MFR1;
and/or, after two weeks of water boiling at 50 ℃, the hydrolysis weight loss rates of the polyglycolic acid and the polyglycolic acid composition are W1 and W2, respectively, wherein W1-W2 is 11-20%.
16. A process for preparing a polyglycolic acid composition, wherein the process comprises the steps of:
respectively drying polyglycolic acid, an anti-hydrolysis stabilizer and a polyisocyanate ester compound, uniformly mixing, and carrying out melt blending extrusion by a double-screw extruder to obtain the polyglycolic acid composition;
the amount of the polyisocyanate compound is 0.5 to 5 parts by weight relative to 100 parts by weight of the polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-3 parts by weight;
the weight average molecular weight of the polyglycolic acid is 5-30 ten thousand;
the hydrolysis resistant stabilizer is selected from polycarbodiimide and/or carbodiimide.
17. The production process according to claim 16, wherein the polyisocyanate-based compound is used in an amount of 1 to 3 parts by weight relative to 100 parts by weight of the polyglycolic acid; the dosage of the hydrolysis resistant stabilizer is 0.5-1.5 parts by weight;
and/or, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand;
and/or the hydrolysis resistant stabilizer is selected from at least one of N, N ' -dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide and N, N ' -diphenylcarbodiimide.
18. The production method according to claim 16 or 17, wherein the polyisocyanate-based compound is selected from a diisocyanate-based compound and/or a diisocyanate prepolymer.
19. The process according to claim 18, wherein the polyisocyanate-based compound is at least one selected from the group consisting of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate and polyisocyanate.
20. The process according to claim 19, wherein the polyisocyanate-based compound is selected from diphenylmethane diisocyanate and/or polyisocyanate.
21. The production method according to any one of claims 16, 17, 19 or 20, wherein the drying conditions include: the temperature is 40-80 ℃; the time is 5-10h.
22. The method of manufacturing according to claim 21, wherein the drying conditions include: the temperature is 42-70 ℃; the time is 6-8h.
23. The method of manufacturing according to claim 18, wherein the drying conditions include: the temperature is 40-80 ℃; the time is 5-10h.
24. The method of manufacturing according to claim 23, wherein the drying conditions include: the temperature is 42-70 ℃; the time is 6-8h.
25. The method of any one of claims 16, 17, 19, 20, or 22-24, wherein the conditions of melt blending extrusion include: the temperature is 230-250 ℃; the rotating speed of the screw is 60-130r/min.
26. The method of manufacture of claim 25, wherein the melt blending extrusion conditions comprise: the temperature is 235-240 ℃; the rotating speed of the screw is 70-100r/min.
27. The method of manufacturing of claim 18, wherein the conditions of melt blending extrusion comprise: the temperature is 230-250 ℃; the rotating speed of the screw is 60-130r/min.
28. The method of claim 27, wherein the conditions of melt blending extrusion comprise: the temperature is 235-240 ℃; the rotating speed of the screw is 70-100r/min.
29. The method of manufacturing of claim 21, wherein the melt blending extrusion conditions comprise: the temperature is 230-250 ℃; the rotating speed of the screw is 60-130r/min.
30. The method of claim 29, wherein the conditions of melt blending extrusion comprise: the temperature is 235-240 ℃; the rotating speed of the screw is 70-100r/min.
31. A polyglycolic acid composition produced by the process of any one of claims 16-30.
32. Use of the polyglycolic acid composition of any one of claims 1-15 and claim 31 in a degradable material or barrier packaging material.
33. Use of the polyglycolic acid composition of any one of claims 1-15 and claim 31 in the preparation of at least one of a film, a fiber, and a sheet.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007291336A (en) * | 2006-03-29 | 2007-11-08 | Mitsui Chemicals Inc | Polyester resin composition |
| CN104177788A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院理化技术研究所 | Hydrolysis resistant aliphatic polyester resin composition and preparation method thereof |
| CN106432696A (en) * | 2016-08-09 | 2017-02-22 | 桂林市福泰建材有限责任公司 | Preparation method of tension-resistant polyglycollic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007291336A (en) * | 2006-03-29 | 2007-11-08 | Mitsui Chemicals Inc | Polyester resin composition |
| CN104177788A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院理化技术研究所 | Hydrolysis resistant aliphatic polyester resin composition and preparation method thereof |
| CN106432696A (en) * | 2016-08-09 | 2017-02-22 | 桂林市福泰建材有限责任公司 | Preparation method of tension-resistant polyglycollic acid |
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