CN115322303A - Composition for preparing polyglycolic acid material, and preparation method and application thereof - Google Patents
Composition for preparing polyglycolic acid material, and preparation method and application thereof Download PDFInfo
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- CN115322303A CN115322303A CN202110512185.4A CN202110512185A CN115322303A CN 115322303 A CN115322303 A CN 115322303A CN 202110512185 A CN202110512185 A CN 202110512185A CN 115322303 A CN115322303 A CN 115322303A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 169
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 169
- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 57
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 45
- 239000000155 melt Substances 0.000 claims abstract description 37
- 239000004971 Cross linker Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 17
- 230000004580 weight loss Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 238000007348 radical reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high molecular materials, in particular to a composition for preparing a polyglycolic acid material, the polyglycolic acid material, a preparation method and application thereof. The composition comprises: polyglycolic acid, initiator, and crosslinker; the initiator is used in an amount of 0.1 to 1 part by weight and the crosslinking agent is used in an amount of 0.9 to 3 parts by weight, relative to 100 parts by weight of polyglycolic acid; wherein the complex viscosity of the polyglycolic acid is 50-300 pas at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 20 to 50g/10min at 240 ℃ under a load of 2.16 kg. According to the invention, the modification of polyglycolic acid can be realized by regulating and controlling the proportion of each component and combining polyglycolic acid with specific parameters, so that the complex viscosity, the melt mass flow rate and the thermal stability of the polyglycolic acid material are remarkably improved.
Description
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a composition for preparing a polyglycolic acid material, the polyglycolic acid material, a preparation method and application thereof.
Background
Due to the increasing global understanding of the sustainability of materials, interest in biobased and biodegradable polymers is greatly increasing in order to avoid the use of petroleum resources. Polyglycolic acid (PGA) has a simple and regular linear molecular structure, is a simple linear aliphatic polyester, gradually degrades after a certain time of use, and finally becomes water and carbon dioxide which are harmless to the human body, animals, plants, and natural environment, and thus it is attracting attention as a biodegradable polymer material with a small environmental burden.
PGA has excellent gas barrier properties, excellent biodegradability, and good mechanical properties of high molecular weight PGA, and can be widely used as a general-purpose plastic in the plastic industry. However, PGA, as a linear aliphatic polyester, has the disadvantages of low melt viscosity and poor melt strength, and is not suitable for melt processing and molding, particularly for some processes requiring high melt strength, such as foaming, film blowing, extrusion, etc.
Therefore, there is an urgent need in the art to develop a high-viscosity polyglycolic acid material to widen the application fields of biodegradable polyglycolic acid.
Disclosure of Invention
The invention aims to overcome the problems of poor viscosity and poor melt strength of a polyglycolic acid melt in the prior art, and provides a composition for preparing a polyglycolic acid material, the polyglycolic acid material, a preparation method and application thereof, wherein the polyglycolic acid material has the advantage of high complex viscosity by adjusting the proportion of each component in the composition, so that the controllable adjustment of the melt strength of the material is realized, and the thermal stability of the material is obviously improved; meanwhile, the preparation of the polyglycolic acid material is realized by adopting a double-screw extruder, and the preparation method has strong operability and is convenient for industrial application.
In order to achieve the above object, a first aspect of the present invention provides a composition for preparing a polyglycolic acid material, the composition including: polyglycolic acid, initiator, and crosslinker; the initiator is used in an amount of 0.1 to 1 part by weight and the crosslinking agent is used in an amount of 0.9 to 3 parts by weight, relative to 100 parts by weight of polyglycolic acid;
wherein the complex viscosity of the polyglycolic acid is 50-300 pas at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 20 to 50g/10min at 240 ℃ under a load of 2.16 kg.
The invention provides a polyglycolic acid material obtained by melt-crosslinking the composition provided by the first aspect; wherein the complex viscosity of the polyglycolic acid material is 5000-25000 Pa.s at 230 ℃ and a frequency of 0.1 rad/s; the melt mass flow rate of the polyglycolic acid material is 3 to 10g/10min at 240 ℃ under a load of 2.16 kg; the polyglycolic acid material has a 5 wt.% weight loss temperature > 320 ℃.
The third aspect of the invention provides a preparation method of a polyglycolic acid material, wherein the method comprises the following steps:
(1) Uniformly mixing the composition provided by the first aspect to obtain a mixture;
(2) And carrying out melt extrusion on the mixture through a double-screw extruder, and granulating to obtain the polyglycolic acid material.
In a fourth aspect, the invention provides a polyglycolic acid material prepared by the method provided in the third aspect.
In a fifth aspect, the invention provides a polyglycolic acid material provided in the second aspect and/or the fourth aspect for use in degradable materials, textile fibers.
Through the technical scheme, the composition for preparing the polyglycolic acid material provided by the invention can realize modification of the polyglycolic acid by regulating and controlling the proportion of each component and combining the polyglycolic acid with specific parameters, so that the complex viscosity, the melt mass flow rate and the thermal stability of the polyglycolic acid material are obviously improved, and especially the controllable regulation of the melt strength of the polyglycolic acid material is realized.
Meanwhile, the introduction of the initiator and the crosslinking agent can reduce the thermal degradation of the polyglycolic acid during melt extrusion through a double-screw extruder, namely, the introduction of the initiator and the crosslinking agent leads the polyglycolic acid to be introduced into a relatively stable crosslinked network structure during melt extrusion, thereby improving the thermal stability of the polyglycolic acid material.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect the present invention provides a composition for the preparation of a polyglycolic acid material, the composition comprising: polyglycolic acid, initiator, and crosslinker; the initiator is used in an amount of 0.1 to 1 part by weight and the crosslinking agent is used in an amount of 0.9 to 3 parts by weight, relative to 100 parts by weight of polyglycolic acid;
wherein the complex viscosity of the polyglycolic acid is 50-300 pas at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 20 to 50g/10min at 240 ℃ under a load of 2.16 kg.
The inventor of the invention researches and finds that: an initiator and a cross-linking agent are introduced into polyglycolic acid, and the initiator and the cross-linking agent are matched with each other to modify the polyglycolic acid by adjusting the dosage of the initiator and the cross-linking agent, so that the complex viscosity, the melt mass flow rate and the thermal stability of the polyglycolic acid material can be obviously improved; meanwhile, the double-screw extruder is adopted for melt extrusion, specifically, under the condition of melt extrusion, the organic peroxide initiator is used as a free radical initiator, so that the cross-linking agent and the polyglycolic acid can generate free radical reaction to form a stable cross-linked network structure, the complex viscosity and the thermal stability of the material are improved, and the controllable adjustment of the melt strength of the material is realized.
In the present invention, when the amounts of polyglycolic acid, initiator, and crosslinking agent in the polyglycolic acid material satisfy the above-mentioned limits, a material having excellent melt strength and thermal stability can be obtained. Furthermore, in order to further improve the comprehensive performance of the polyglycolic acid material. Preferably, the initiator is used in an amount of 0.3 to 0.5 parts by weight and the crosslinking agent is used in an amount of 1 to 1.5 parts by weight, relative to 100 parts by weight of polyglycolic acid.
In the present invention, the inventors have studied and found that when the weight ratio of the initiator to the crosslinking agent is 1:0.9 to 30, a cross-linked network structure is formed by the reaction of the initiator and the cross-linking agent with the terminal group of the polyglycolic acid, so that the polyglycolic acid material obtained therefrom has excellent complex viscosity and thermal stability, and controllable melt strength.
Further preferably, the weight ratio of the initiator to the crosslinking agent is 1:2-6, the polyglycolic acid material has more excellent properties.
In the present invention, by defining the complex viscosity and melt mass flow rate of polyglycolic acid, compositions containing (specific complex viscosity and melt mass flow rate) polyglycolic acid can be processed smoothly in a melt extruder.
According to the invention, preferably, the complex viscosity of the polyglycolic acid is 100 to 250 pas at 230 ℃ and a frequency of 0.1 rad/s. By limiting the complex viscosity of polyglycolic acid, compositions containing specific polyglycolic acid materials can be processed smoothly in a melt extruder.
In the invention, the complex viscosity of the polyglycolic acid is measured by rotational rheological frequency scanning, and the test conditions are as follows: the temperature is 230 ℃, the strain is 2 percent, and the scanning frequency is 0.1-100rad/s.
According to the invention, the polyglycolic acid preferably has a melt mass flow rate of 25 to 40g/10min at 240 ℃ and a load of 2.16 kg. By limiting the melt mass flow rate of polyglycolic acid, compositions containing specific polyglycolic acid materials can be processed smoothly in a melt extruder.
In the present invention, the melt mass flow rate of the polyglycolic acid is measured in accordance with GB/T3682-2000.
In the present invention, there is a wide range of choices for the kind of the initiator as long as the initiator can initiate a radical reaction. Preferably, the initiator is an organic peroxide crosslinking agent, preferably selected from at least one of dicumyl peroxide, di-tert-butylperoxycumene and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, more preferably di-tert-butylperoxycumene.
In the present invention, there is a wide range of choices for the kind of the crosslinking agent. Preferably, the crosslinking agent is selected from at least one of tricarboxymethylpropyl trimethacrylate, triallyl isocyanurate and ethyleneglycol dimethacrylate, more preferably triallyl isocyanurate.
According to a particularly preferred embodiment of the present invention, a composition for the preparation of polyglycolic acid material consists of polyglycolic acid, an initiator, and a crosslinker; the initiator is used in an amount of 0.3 to 0.5 parts by weight and the crosslinking agent is used in an amount of 1 to 1.5 parts by weight, relative to 100 parts by weight of polyglycolic acid;
wherein the complex viscosity of the polyglycolic acid is 50-300 pas at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 20 to 50g/10min at 240 ℃ under a load of 2.16 kg.
The second aspect of the invention provides a polyglycolic acid material obtained by melt-crosslinking the composition provided by the first aspect;
wherein the complex viscosity of the polyglycolic acid material is 5000-25000 Pa.s at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid material has a melt mass flow rate of 3 to 10g/10min at 240 ℃ under a load of 2.16 kg; the polyglycolic acid material has a 5 wt.% weight loss temperature > 320 ℃.
In the invention, the complex viscosity of the polyglycolic acid material is measured by rotational rheological frequency scanning, and the test conditions are as follows: the temperature is 230 ℃, the strain is 2 percent, and the scanning frequency is 0.1-100rad/s.
In the present invention, the melt mass flow rate of the polyglycolic acid material is measured in accordance with GB/T3682-2000.
In the present invention, the 5 wt% weight loss temperature of the polyglycolic acid material is measured by TG thermogravimetric method.
According to the invention, preferably, the complex viscosity of the polyglycolic acid material is 6000 to 20000Pa · s at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid material has a melt mass flow rate of 4 to 8g/10min at 240 ℃ under a load of 2.16 kg; the 5 wt% weight loss temperature of the polyglycolic acid material is > 322 ℃.
In the present invention, the term "the composition is obtained by melt-crosslinking" means that the initiator in the composition is a radical initiator capable of initiating a radical reaction between the crosslinking agent and polyglycolic acid under melt extrusion conditions, that is, the radical of the crosslinking agent reacts with the terminal position of polyglycolic acid to form a network crosslinked structure.
The third aspect of the invention provides a preparation method of a polyglycolic acid material, wherein the method comprises the following steps:
(1) Uniformly mixing the composition provided by the first aspect to obtain a mixture;
(2) And carrying out melt extrusion on the mixture through a double-screw extruder, and granulating to obtain the polyglycolic acid material.
In the invention, a mixture containing polyglycolic acid, an initiator and a crosslinking agent is subjected to melt extrusion by using a twin-screw extruder, and the initiator and the crosslinking agent can perform free radical reaction with the polyglycolic acid under the action of the twin-screw extruder, so that the polyglycolic acid is modified, and the polyglycolic acid material has excellent complex viscosity, melt mass flow rate and thermal stability.
In the present invention, the mixing method can be widely selected as long as polyglycolic acid, an initiator and a crosslinking agent are uniformly mixed in the composition.
In the present invention, the types and/or property parameters of the polyglycolic acid, the initiator and the crosslinking agent are defined as above, and the present invention is not described herein again.
In the present invention, the conditions for the melt extrusion have a wide range of choices. Preferably, the melt extrusion conditions include: the temperature is 235-250 ℃, preferably 235-245 ℃; the rotating speed is 60-130r/min, preferably 80-100r/min. By adopting the preferable conditions, the degradation of the polyglycolic acid in the extrusion process can be reduced, and the deterioration of the performance of the prepared polyglycolic acid material is avoided.
According to the present invention, preferably, the method further comprises: drying the polyglycolic acid in the composition prior to the mixing in step (1). In the present invention, after drying the polyglycolic acid, the mixture containing the polyglycolic acid, the initiator and the crosslinking agent is hydrolyzed at the time of extrusion due to the reduction of moisture in the polyglycolic acid.
According to the present invention, preferably, the drying conditions include: the temperature is 60-100 ℃, preferably 70-90 ℃; the time is 1-15h, preferably 6-12h.
In a fourth aspect, the invention provides a polyglycolic acid material prepared by the method provided in the third aspect.
According to the invention, preferably, the polyglycolic acid material has a complex viscosity of 5000-25000Pa · s, preferably 6000-20000Pa · s, at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid material has a melt mass flow rate of 3 to 10g/10min, preferably 4 to 8g/10min at 240 ℃ under a load of 2.16 kg; the polyglycolic acid material has a 5 wt.% weight loss temperature of > 320 deg.C, preferably > 322 deg.C.
In the invention, the complex viscosity of the polyglycolic acid material is measured by rotational rheological frequency scanning, and the test conditions are as follows: the temperature is 230 ℃, the strain is 2 percent, and the scanning frequency is 0.1-100rad/s.
In the present invention, the melt mass flow rate of the polyglycolic acid material is measured according to GB/T3682-2000.
In the present invention, the 5 wt% weight loss temperature of the polyglycolic acid material is measured by TG thermogravimetric method.
The fifth aspect of the invention provides a use of the polyglycolic acid material provided in the second aspect and/or the fourth aspect in degradable materials and textile fibers.
The present invention will be described in detail below by way of examples.
The 5 weight percent weight loss temperature of the polyglycolic acid material is measured by adopting a TG thermal weight loss method;
the melt mass flow rates of polyglycolic acid and polyglycolic acid materials were measured using GB/T3682-2000;
the complex viscosity of polyglycolic acid and polyglycolic acid materials is measured by rotational rheological frequency scanning, and the test conditions are as follows: the temperature is 230 ℃, the strain is 2 percent, and the scanning frequency is 0.1-100rad/s.
Examples 1 to 8 and comparative examples 1 to 4 the amounts of the components in the compositions for preparing polyglycolic acid materials, the weight ratios of the initiator and the crosslinking agent are shown in table 1, and the physical property parameters of the polyglycolic acid materials prepared in examples 1 to 8 and comparative examples 1 to 4 are also shown in table 1.
Example 1
(1) Drying 100 parts by weight of polyglycolic acid A1 at 80 ℃ for 10h, and uniformly mixing with 0.5 part by weight of initiator (di-tert-butylperoxyisopropyl benzene) and 1 part by weight of cross-linking agent (triallyl isocyanurate) to obtain a mixture;
wherein the melt mass flow rate (240 ℃,2.16 kg) of polyglycolic acid A1 is 30g/10min, and the complex viscosity (230 ℃,0.1 rad/s) is 200Pa s;
the weight ratio of the initiator to the cross-linking agent is 1:2;
(2) And (3) carrying out melt extrusion on the mixture by a double-screw extruder at the temperature of 240 ℃ and at the speed of 100r/min, and granulating to obtain the polyglycolic acid material S1.
Example 2
(1) Drying 100 parts by weight of polyglycolic acid A1 at 70 ℃ for 12 hours, and uniformly mixing with 0.5 part by weight of an initiator (dicumyl peroxide) and 1.5 parts by weight of a crosslinking agent (tricarboxymethylpropyl trimethacrylate) to obtain a mixture;
wherein the melt mass flow rate (240 ℃,2.16 kg) of the polyglycolic acid A1 is 30g/10min, and the complex viscosity (230 ℃,0.1 rad/s) is 200 Pa.s;
the weight ratio of initiator to crosslinker is 1:3;
(2) And (3) carrying out melt extrusion on the mixture by a double-screw extruder at 235 ℃ and 90r/min, and granulating to obtain the polyglycolic acid material S2.
Example 3
(1) Drying 100 parts by weight of polyglycolic acid A1 at 90 ℃ for 8 hours, and uniformly mixing with 0.3 part by weight of an initiator (2,5-dimethyl-2,5-di (tert-butylperoxy) hexane) and 1.5 parts by weight of a crosslinking agent (ethylene dimethacrylate) to obtain a mixture;
wherein the melt mass flow rate (240 ℃,2.16 kg) of polyglycolic acid A1 is 30g/10min, and the complex viscosity (230 ℃,0.1 rad/s) is 200Pa s;
the weight ratio of initiator to crosslinker is 1:5;
(2) And (3) carrying out melt extrusion on the mixture by a double-screw extruder at the temperature of 245 ℃ and at the speed of 100r/min, and granulating to obtain the polyglycolic acid material S3.
Example 4
The process of example 1 was followed except that in step (1), the amount of the initiator was replaced with 0.4 parts by weight and the amount of the crosslinking agent was replaced with 1.5 parts by weight, wherein the weight ratio of the initiator to the crosslinking agent was 4;
the rest steps are the same, and the polyglycolic acid material S4 is obtained.
Example 5
The process of example 1 was followed except that the amount of the initiator used in step (1) was replaced with 0.1 parts by weight and the amount of the crosslinking agent was replaced with 3 parts by weight, wherein the weight ratio of the initiator to the crosslinking agent was 1;
the rest steps are the same, and the polyglycolic acid material S5 is obtained.
Example 6
The process of example 1 was followed except that in step (1), the amount of the initiator was replaced with 1 part by weight and the amount of the crosslinking agent was replaced with 0.9 part by weight, wherein the weight ratio of the initiator to the crosslinking agent was 1.9;
the rest steps are the same, and the polyglycolic acid material S6 is obtained.
Example 7
The process of example 1 was followed except that in step (1) the amount of initiator was replaced with 1 part by weight and the amount of crosslinking agent was replaced with 3 parts by weight, wherein the weight ratio of initiator to crosslinking agent was 1:3;
the rest steps are the same, and the polyglycolic acid material S7 is obtained.
Example 8
The procedure of example 1 was followed except that polyglycolic acid A1 in step (1) was replaced with polyglycolic acid A2, wherein the melt mass flow rate (240 ℃,2.16 kg) of polyglycolic acid A2 was 42g/10min and the complex viscosity (230 ℃,0.1 rad/s) was 60Pa · s;
the rest steps are the same, and the polyglycolic acid material S8 is obtained.
Comparative example 1
Following the procedure of example 1, except that no initiator and crosslinker were added, the remaining steps were the same, polyglycolic acid material D1 was obtained.
Comparative example 2
The process of example 1 was followed except that in step (1) the amount of initiator was replaced with 0.1 parts by weight and the amount of crosslinker was replaced with 0.3 parts by weight, wherein the weight ratio of initiator to crosslinker was 1:3;
the rest steps are the same, and the polyglycolic acid material D2 is obtained.
Comparative example 3
The process of example 1 was followed except that the amount of initiator used in step (1) was replaced with 1.5 parts by weight, wherein the weight ratio of initiator to crosslinking agent was 3:2;
the rest steps are the same, and the polyglycolic acid material D3 is obtained.
Comparative example 4
The procedure of example 1 was followed except that polyglycolic acid A1 in step (1) was replaced with polyglycolic acid A3, wherein the melt mass flow rate (240 ℃,2.16 kg) of polyglycolic acid A3 was 60g/10min and the complex viscosity (230 ℃,0.1 rad/s) was 48Pa · s;
the rest steps are the same, and the polyglycolic acid material D4 is obtained.
TABLE 1
Note: 1-means the dosage ratio of polyglycolic acid, initiator and cross-linking agent; 2-weight ratio of initiator and crosslinker.
The data in table 1 show that the complex viscosity and the melt mass flow rate of the polyglycolic acid material can be significantly improved by using the embodiment of modifying polyglycolic acid by combining the initiator and the crosslinking agent of the present invention, specifically, the complex viscosity of the polyglycolic acid material is as high as > 5000Pa · s, the melt mass flow rate of the polyglycolic acid material is reduced to < 10g/10min, and the thermal stability is also improved to a certain extent, so that the overall performance of the polyglycolic acid material obtained by the method is significantly improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for preparing a polyglycolic acid material, the composition comprising: polyglycolic acid, initiator, and crosslinker; the initiator is used in an amount of 0.1 to 1 part by weight and the crosslinking agent is used in an amount of 0.9 to 3 parts by weight, relative to 100 parts by weight of polyglycolic acid;
wherein the complex viscosity of the polyglycolic acid is 50-300 pas at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 20 to 50g/10min at 240 ℃ under a load of 2.16 kg.
2. The composition according to claim 1, wherein the initiator is used in an amount of 0.3 to 0.5 parts by weight and the crosslinking agent is used in an amount of 1 to 1.5 parts by weight, relative to 100 parts by weight of polyglycolic acid;
preferably, the weight ratio of the initiator to the cross-linking agent is 1:0.9 to 30, preferably 1:2-6.
3. The composition of claim 1 or 2, wherein the complex viscosity of polyglycolic acid is 100-250 Pa-s at 230 ℃ and frequency 0.1 rad/s; the polyglycolic acid has a melt mass flow rate of 25 to 40g/10min at 240 ℃ under a load of 2.16 kg.
4. A composition according to any one of claims 1 to 3, wherein the initiator is an organic peroxide initiator, preferably at least one selected from dicumyl peroxide, di-tert-butylperoxycumene and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, more preferably di-tert-butylperoxycumene;
preferably, the crosslinking agent is selected from at least one of tricarboxymethylpropyl trimethacrylate, triallyl isocyanurate and ethyleneglycol dimethacrylate, more preferably triallyl isocyanurate.
5. A polyglycolic acid material obtained by melt-crosslinking the composition according to any one of claims 1 to 4;
wherein the complex viscosity of the polyglycolic acid material is 5000-25000 Pa.s at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid material has a melt mass flow rate of 3 to 10g/10min at 240 ℃ under a load of 2.16 kg; the polyglycolic acid material has a 5 wt.% weight loss temperature of > 320 ℃.
6. Polyglycolic acid material according to claim 5, wherein the complex viscosity of the polyglycolic acid material is 6000-20000 Pa-s at 230 ℃ and a frequency of 0.1 rad/s; the polyglycolic acid material has a melt mass flow rate of 4 to 8g/10min at 240 ℃ under a load of 2.16 kg; the 5 wt% weight loss temperature of the polyglycolic acid material is > 322 ℃.
7. A preparation method of a polyglycolic acid material, wherein the method comprises the following steps:
(1) Uniformly mixing the composition of any one of claims 1-4 to obtain a mixture;
(2) And carrying out melt extrusion on the mixture through a double-screw extruder, and granulating to obtain the polyglycolic acid material.
8. The method of claim 7, wherein the melt extruding conditions comprise: the temperature is 235-250 ℃, preferably 235-245 ℃; the rotating speed is 60-130r/min, preferably 80-100r/min;
preferably, the method further comprises: drying the polyglycolic acid in the composition prior to said mixing in step (1);
preferably, the drying conditions include: the temperature is 60-100 ℃, and the optimal temperature is 70-90 ℃; the time is 1-15h, preferably 6-12h.
9. A polyglycolic acid material prepared by the process of claim 7 or 8.
10. Use of a polyglycolic acid material according to any one of claims 5 to 6 and 9 in degradable materials, textile fibers.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805176A1 (en) * | 1996-04-30 | 1997-11-05 | Kureha Kagaku Kogyo Kabushiki Kaisha | Polyglycolic acid sheet and production process thereof |
| CN110468468A (en) * | 2019-08-28 | 2019-11-19 | 江苏金聚合金材料有限公司 | Polyglycolic acid complete biodegradable composite fibre and preparation method thereof |
| CN112724622A (en) * | 2020-12-24 | 2021-04-30 | 海南赛高新材料有限公司 | Modified PGA material compatibilized by adopting intercalation structure and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805176A1 (en) * | 1996-04-30 | 1997-11-05 | Kureha Kagaku Kogyo Kabushiki Kaisha | Polyglycolic acid sheet and production process thereof |
| CN110468468A (en) * | 2019-08-28 | 2019-11-19 | 江苏金聚合金材料有限公司 | Polyglycolic acid complete biodegradable composite fibre and preparation method thereof |
| CN112724622A (en) * | 2020-12-24 | 2021-04-30 | 海南赛高新材料有限公司 | Modified PGA material compatibilized by adopting intercalation structure and preparation method thereof |
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