CN116120726A - Anti-aging heat-resistant polyglycolide injection molding material and preparation method thereof - Google Patents
Anti-aging heat-resistant polyglycolide injection molding material and preparation method thereof Download PDFInfo
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- 238000001746 injection moulding Methods 0.000 title claims abstract description 32
- 239000012778 molding material Substances 0.000 title claims abstract description 28
- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 24
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 88
- 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 abstract description 58
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 239000000945 filler Substances 0.000 claims abstract description 45
- 239000002667 nucleating agent Substances 0.000 claims abstract description 40
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- 235000012222 talc Nutrition 0.000 claims abstract description 21
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
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- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 8
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- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 4
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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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
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of degradable high molecular compounds, in particular to an anti-aging heat-resistant polyglycolide injection molding material and a preparation method thereof, wherein the polyglycolide injection molding material comprises the following components in percentage by mass: a main polymer, 45-85%; 5-15% of a reinforced polymer; 0.1-1% of an anti-hydrolysis agent; 0.1-0.5% of lubricant; 5-25% of filler; 3-15% of heterogeneous nucleating agent; wherein the main polymer is PGA, the reinforcing polymer is PBS and/or PBAT, and the filler and heterogeneous nucleating agent are selected from talcum powder. The toughness of the injection molding material is improved due to the addition of PBS or PBAT, and in addition, after two talcum powders with different particle diameters are respectively used as a filler and a heterogeneous nucleating agent for compounding, the mechanical property of the material can be improved, and the aging process of the material can be delayed.
Description
Technical Field
The invention relates to the technical field of degradable high molecular compounds, in particular to an anti-aging heat-resistant polyglycolide injection molding material and a preparation method thereof.
Technical Field
In recent years, with the improvement of environmental awareness of people and the implementation of plastic banning in various countries, products prepared from biodegradable materials have been gradually popularized, the biodegradable materials are degraded by composting, soil and other modes, and the final products are water and carbon dioxide. At present, besides natural biodegradable materials such as wood, bamboo, starch and the like, the biodegradable resins obtained by a synthetic mode mainly comprise polylactic acid (PLA), terephthalic acid-adipic acid butanediol copolymer (PBAT) and the like, the molecular structures of the materials are polyester, the materials can be degraded and aged slowly during the storage period due to the hydrolysis of ester bonds of products prepared by the biodegradable resins, embrittlement phenomena are generated, and particularly, the biodegradable resins relate to a plurality of products which are used repeatedly, sometimes have high-temperature and high-humidity environments during the use process, and the aging speed of the materials is higher.
The biodegradable resin produced in large scale in the global scope at present mainly comprises PLA, PBAT, PBS and the like, the PLA resin has wide application range due to the excellent comprehensive performance, and is widely applied to curtain coating, sheets, injection molding, films and 3D printing, but the PLA is basically not temperature-resistant due to the slow crystallization speed, and the thermal deformation temperature is only about 55 ℃ when the product is obtained by a conventional molding mode. In particular, in the field of injection molding materials, the lower heat distortion temperature affects the use, and on the other hand, the phenomenon of deformation easily caused by insufficient heat resistance in the transportation process is also caused, so that the current PLA injection molding product needs to reach a certain temperature resistance and needs to be subjected to in-mold or out-mold crystallization treatment, the production efficiency of the product is affected by in-mold crystallization, the product is deformed to a certain extent due to out-mold crystallization, and meanwhile, the hardware input and the energy consumption of the product are nearly doubled. PLA materials can degrade quickly under composting conditions, but degrade very slowly in the soil environment and more difficult in the marine environment.
For this reason, people put their eyes on other degradable materials, such as Polyglycolide (PGA), which can degrade not only under composting conditions but also rapidly in natural soil and seawater environments as a fully biodegradable resin, and PGA is resistant to temperatures above 120 ℃, and the rigidity and toughness of the material are very good, and the comprehensive performance is considered to be a heat-resistant biodegradable material very suitable for injection molding, but PGA is the fastest degradation rate in aliphatic polyesters due to its shortest weight unit, and its low molecular weight product is an ideal fully microbial degradation inducer. The aging embrittlement phenomenon of the product is easy to occur during the storage period due to the excessively high degradation speed, and the service performance of the product is lost.
In the prior art, there is also a material technology using PGA as one of the raw materials, for example, chinese patent application publication No. CN 114045015A, which discloses a fully biodegradable foam net and a preparation method thereof, wherein the foam net comprises the following components in parts by mass: 40-85 parts of PBAT (Poly vinyl acetate), 10-30 parts of PBS (poly vinyl acetate), 5-30 parts of PGA (poly vinyl acetate), 0.4-1 part of compatibilizer, 0.4-1 part of hydrolysis resistance agent, 0.8-2 parts of organic nucleating agent, 2-4 parts of inorganic nucleating agent, 0.3-0.5 part of lubricant, 0.2-0.3 part of shrinkage resistance agent, 0.4-1 part of antioxidant and 2 parts of masterbatch, the provided foaming net material has the characteristic of full natural domain degradation, particularly has the degradation capability in the water body of the marine environment, can realize the regulation and control of degradation time, and prolongs the shelf life of foaming net products.
Disclosure of Invention
In order to solve the technical problems, the inventor of the application develops a new way to improve the formula of the polyglycolide injection molding material so as to delay the aging of the material and obtain a product with excellent mechanical properties on the premise.
The invention aims at providing an anti-aging heat-resistant polyglycolide injection molding material and a preparation method of the polyglycolide injection molding material.
The specific technical scheme is as follows:
an anti-aging heat-resistant polyglycolide injection molding material comprises the following components in parts by weight:
45-85 parts of a main polymer;
5-15 parts of a reinforcing polymer;
0.04-1 part of an anti-hydrolysis agent;
0.01-0.5 parts of lubricant;
5-25 parts of filler;
3-15 parts of heterogeneous nucleating agent;
the main polymer is PGA, the reinforcing polymer is PBS and/or PBAT, the English abbreviation name PGA is polyglycolide, the PBS is polybutylene succinate, and the PBAT is polybutylene adipate/terephthalate;
the filler and the heterogeneous nucleating agent are both selected from talc.
In the technical scheme, the toughness of the PGA can be improved by adding the PBS or the PBAT, in addition, the aging performance of the material can be obviously influenced by the content of the terminal carboxyl in the PBS or the PBAT resin, and the aging speed of the material is higher, preferably, the terminal carboxyl content of the reinforced polymer is less than 30mol/t, more preferably, the terminal carboxyl content is less than 15mol/t, most preferably, the terminal carboxyl content of the PBS is less than 10mol/t.
In the formula of the polyglycolide injection molding material, the talcum powder is innovatively used as a filler and a heterogeneous nucleating agent, and the talcum powder used as the filler has relatively large particle size based on the basic function of the filler in function; and talc as a heterogeneous nucleating agent has a relatively small particle size based on the need for heterogeneous nucleation.
The inventor considers that after two types of talcum powder with different particle diameters are compounded, the talcum powder has at least the following beneficial effects:
(1) the mechanical property of the polyglycolide injection molding material can be improved, the reinforcing effect of talcum powder serving as a filler on the material after filling is reflected, the accelerating effect of talcum powder serving as a heterogeneous nucleating agent on PGA crystallization is also reflected, the crystallinity is improved, and part of the mechanical property of the material can be improved;
(2) talcum powder is slightly alkaline, which is beneficial to delaying the aging process of PGA, PBS and PBAT;
(3) experiments show that talcum powder serving as a filler not only brings a filling reinforcing effect to a material, but also improves the crystallization effect of the PGA material, because the addition of large-particle-size filler talcum powder plays a role in interval effect, so that the agglomeration effect of heterogeneous nucleating agent talcum powder with small particle size is weakened, the dispersion degree of heterogeneous nucleating agent talcum powder in the material is further increased, and crystallization is promoted;
that is, talc as a filler plays a role not only in reinforcing at the filling angle but also in enhancing the mechanical properties of the PGA material from the viewpoint of improving the crystallization effect of the PGA material.
The talcum powder is used as a filler, a certain particle size range is used as a reinforcing effect base, and preferably, the filler is talcum powder with 800-3000 meshes; more preferably, the filler is talcum powder with a mesh number of 1000-2000 meshes, and the addition amount is 10-25 parts.
The talcum powder is used as a heterogeneous nucleating agent, and has a nucleating effect only when reaching a certain fineness, and preferably, the heterogeneous nucleating agent is talcum powder with the mesh number of 3000-10000 meshes; further preferably, the heterogeneous nucleating agent is talcum powder with the mesh number of 5000-10000 meshes, and the adding amount is 5-12 parts.
The hydrolysis resisting agent has a carbodiimide structure, can react with carboxyl end groups of PGA, PBS and PBAT and hydrolytic carboxylic acid, prevents the self-catalyzed hydrolysis from degrading, improves the ageing resistance and the service life of the material, and is preferably selected from HyMax 1010 and HyMax210, preferably HyMax210, and the addition amount of the hydrolysis resisting agent is 0.5-1 part.
The addition of the lubricant is favorable for the stable processing and injection molding and demolding of the material, and preferably, the lubricant is selected from one or more of EBS, PE wax and erucamide, and the addition amount is preferably 0.3-0.5 part.
The preparation method of the polyglycolide injection molding material according to any one of the technical schemes comprises the following steps:
and (3) drying: drying the main polymer and the reinforcement polymer, and making the moisture content of the dried main polymer and reinforcement polymer within 200 ppm; drying the filler and the heterogeneous nucleating agent, wherein the moisture content of the dried filler and heterogeneous nucleating agent is controlled within 0.15 percent;
mixing: placing the dried main polymer, the reinforced polymer, the hydrolysis inhibitor and the lubricant into a stirrer to be uniformly stirred to form a mixed material;
extrusion: and (3) feeding the mixed material into a screw extruder to be melted, mixed and extruded at the temperature of 210-225 ℃, feeding the dried filler and heterogeneous nucleating agent into the screw extruder to be uniformly mixed with the melted material, simultaneously ensuring the vacuum degree of a vacuum system of the screw extruder to be more than-0.08 MPa, further removing residual monomers of PGA, and granulating and packaging extruded strips after air cooling bracing.
Preferably, in the drying step, the main polymer and the reinforced polymer are dried in a dehumidifying dryer at 55-70 ℃ for 4-6 hours, so that the dew point temperature of the dehumidifying dryer is below-50 ℃; and stirring the filler and the heterogeneous nucleating agent in a stirrer with a heating function for 1-2 hours, and drying at the stirring temperature of 80-100 ℃.
In summary, the technical scheme of the invention has the following main beneficial effects:
according to the PGA injection molding material provided by the embodiment of the invention, due to the addition of PBS or PBAT, the toughness of the material is improved.
In addition, after two talcum powders with different particle diameters are respectively used as a filler and a heterogeneous nucleating agent for compounding, the mechanical property of the material can be improved, and the aging process of the material can be delayed.
Further or more detailed benefits will be described in connection with specific embodiments.
Detailed Description
The invention is further illustrated by the following examples:
it should be noted that, the embodiments do not limit the scope of the claims of the present invention, and according to the technical concepts provided/proven by the embodiments, those skilled in the art can reasonably expect technical solutions to be covered in the scope of the claims of the present invention.
The evaluation methods or criteria for the sample performance involved in this example/comparative example are as follows:
heat distortion temperature：
The obtained bars were measured for heat resistance-heat distortion temperature of the material by MIT-300AT-3 heat distortion temperature tester of Bang Yi precision measuring instrument (Shanghai) Co., ltd AT a pressure of 0.45 MPa.
Tensile Strength：
According to the standard: test conditions for part 3, films and sheets in the determination of the tensile properties of GB/T1040.3-2006 plastics: dumbbell bars were 150mm long, 10mm narrow parallel width, 50mm/min stretch speed, and tested at 25℃at room temperature.
Crystallinity degree：
Measuring the crystallinity of the sample by x-ray diffraction;
specifically, the crystallinity of the sample was quantitatively analyzed by a full spectrum fitting analysis of Rietvelt refinement using an x-ray diffractometer of Miniflex600 from japan corporation;
specifically, cu radiation is used to scan in a range of 5 ° to 50 °, the scanning step length is 0.05 °, and the crystallinity (%) is represented by a ratio of a crystal area under an x-ray diffraction peak to a total area:
X c %=[S c /（S a +S c ）]×100%
wherein X is c Is crystallinity;
S c is the area of the crystal phase;
S a is the area of amorphous phase;
（S a +S c ) I.e. the total area under the x-ray diffraction peak.
Melt flow Rate：
The PGA raw material and the melt flow rate of the sample bars before and after aging were respectively tested by using a WKT-400 melt flow velocimeter from Jiangsu Weak instruments and meters, under the following conditions: at 235 deg.C, a load of 2160g and a pressure of 0.2982MPa.
Aging conditions：
Aging for 100 hours in a constant temperature and humidity aging box with the temperature of 65 ℃ and the humidity of 50 percent.
Examples and comparative examples are detailed below:
example 1：
PGA with a melt flow rate of 10g/10min and PBS with a carboxyl end group content of 14mol/t were dried in a desiccant dryer at 60℃for 5 hours, talc powder of 5000 mesh and talc powder of 1000 mesh according to a 1:2 are mixed in a low-speed stirrer at 90 ℃ for 1.5 hours. After drying, the PGA moisture content was 180ppm, the PBS moisture content was 150ppm, and the talc moisture content was 0.13%. Mixing PGA, PBS, and hydrolysis resisting agent HyMax 1010 and lubricant EBS in a high-speed mixer at high speed;
the mixed materials enter a double-screw extruder for melting, mixing, extruding and granulating, the extruding temperature is 215 ℃, the dried talcum powder is added into the double-screw extruder through side feeding and is uniformly mixed with the melted materials, the vacuum degree of a vacuum pump of the double-screw extruder is about-0.085 MPa, and extruded material strips are cooled and cut through an air-cooled drag chain and are packaged in time.
The mass portions of the materials are as follows:
PGA,59.2 parts;
10 parts of PBS;
1010,0.05 parts of HyMax;
EBS,0.03 part;
5000 mesh talcum powder, 6.93 parts;
13.86 parts of 1000-mesh talcum powder.
Example 2：
PGA with a melt flow rate of 15g/10min and PBS with a carboxyl end group content of 10mol/t were dried in a desiccant dryer at 65℃for 4.5 hours, talc of 7000 mesh and talc of 1250 mesh according to 8:20 are mixed in a low-speed stirrer at 95℃for 2 hours with dry stirring. After drying, the PGA moisture content was 160ppm, the PBS moisture content was 140ppm, and the talc moisture content was 0.12%. Mixing PGA, PBS, an anti-hydrolysis agent HyMax 1010 and a lubricant PE wax in a high-speed mixer at high speed;
the mixed materials enter a double-screw extruder for melt mixing, extrusion and granulation, the extrusion temperature is 210 ℃, the dried talcum powder is added into the double-screw extruder through side feeding and is uniformly mixed with the melted materials, the vacuum degree of a vacuum pump of the double-screw extruder is about-0.09 MPa, and extruded material strips are cooled and cut through an air cooling drag chain and are packaged in time.
The mass portions of the materials are as follows:
PGA,56.94 parts;
PBS,15 parts;
1010,0.04 parts of HyMax;
PE wax, 0.02 part;
7000 mesh talcum powder, 5.76 parts;
1250 mesh talcum powder, 14.4 parts.
Example 3：
PGA with a melt flow rate of 18g/10min and PBAT with a carboxyl end group content of 13mol/t were dried in a desiccant dryer at 60℃for 5 hours, talc powder 10000 mesh and talc powder 800 mesh according to 6:22 was dry stirred in a low speed mixer at 100 c for 1.5 hours. After drying, the PGA moisture content was 140ppm, the PBAT moisture content was 120ppm, and the talc moisture content was 0.10%. Uniformly mixing PGA, PBAT, an anti-hydrolysis agent HyMax210 and a lubricant erucamide in a high-speed mixer at a high speed;
the mixed materials enter a double-screw extruder for melting, mixing, extruding and granulating, the extruding temperature is 212 ℃, the dried talcum powder is added into the double-screw extruder through side feeding and is uniformly mixed with the melted materials, the vacuum degree of a vacuum pump of the double-screw extruder is about-0.09 MPa, and extruded material strips are cooled and cut through an air cooling drag chain and are packaged in time.
The mass portions of the materials are as follows:
PGA,65.94 parts;
18 parts of PBAT;
210,0.05 parts of HyMax;
erucamide, 0.01 part;
10000 mesh talcum powder, 4.68 parts;
800 meshes of talcum powder and 17.16 parts.
Comparative example 1：
Comparative example 1 only PGA was used as the extrusion material:
drying PGA with the melt flow rate of 10g/10min in a dehumidifying dryer at 70 ℃ for 4 hours, wherein the moisture content of the dried PGA is 150ppm, feeding the dried PGA into a double-screw extruder for melt mixing extrusion granulation, wherein the processing temperature is 215 ℃, the vacuum degree of a vacuum pump of the double-screw extruder is about-0.09 MPa, and cooling and cutting the extruded material strips by an air cooling drag chain and packaging in time.
Comparative example 2：
Comparative example 2 only PLA (polylactic acid) was used as an extrusion material:
and (3) drying PLA with the melt flow rate of 12g/10min in a dehumidifying dryer for 4 hours at 70 ℃, wherein the moisture content of the PLA after drying is 160ppm, feeding the dried PLA into a double-screw extruder for melt mixing, extrusion and granulation, wherein the processing temperature is 180 ℃, the vacuum degree of a vacuum pump of the double-screw extruder is about-0.09 MPa, and cooling and cutting the extruded material strips through an air cooling drag chain and packaging in time.
The product test data of examples 1-3 and comparative examples 1-2 are shown in Table 1:
table 1 product test data for examples 1-3, comparative examples 1-2
In the above test parameters, the higher the heat distortion temperature, the better the heat resistance of the material; the higher the melt flow rate of the material after the aging process, the faster the aging speed of the material.
As can be seen from Table 1, compared with the single-component PGA injection molding material (comparative example 1), the injection molding materials prepared in examples 1 to 3 have a large improvement in aging resistance and a small improvement in toughness and heat resistance; compared with the single-component PLA injection molding material (comparative example 2), the injection molding materials prepared in examples 1-3 have greatly improved heat resistance and toughness.
The following comparative examples 3 to 5 were designed by the inventor to verify the effect of talc powder of larger particle size as filler on material properties, for the technical concept of talc powder used for both filler and heterogeneous nucleating agent in the formulation:
comparative example 3：
The difference compared to example 1 is that no 1000 mesh talc was added as a filler.
Comparative example 4：
The difference compared to example 2 is only that 1250 mesh talc as filler is not added.
Comparative example 5：
The difference compared to example 3 is that 800 mesh talc as filler is not added.
The test data of the products of examples 1-3 and comparative examples 3-5 are shown in Table 2:
table 2 data of test products of examples 1 to 3 and comparative examples 3 to 5
The crystallization process of the polymer is divided into two stages of nucleation and nucleation growth, the nucleation can be realized by homogeneous nucleation or heterogeneous nucleation, the molecular chain rigidity of the PGA material molecule is high, the crystallization speed of the PGA is slow through the ordered arrangement of the self molecular chain in the cooling process, and the crystallization speed of the PGA is slow through the homogeneous nucleation, and the crystallization nucleus is formed through the ordered arrangement of the polymer chains in the absorption melt of dispersed small-size particles added into the polymer melt, the small-size particles are used as heterogeneous nucleating agents of the polymer, so that the crystallization speed of the PGA can be greatly improved, and the reason for adding heterogeneous nucleating agents in the invention is that.
The heterogeneous nucleator particles and polymer segments are substantially within a size range, specifically sized between about 1 micron and about 4 microns, corresponding to a mesh size of about 3500-14000 mesh. The addition amount of heterogeneous nucleating agent is too small, the nucleating effect is not obvious, and the excessive addition amount causes the waste of cost.
After the heterogeneous nucleating agent is added, the thermal crystallization temperature of the PGA can be increased from about 110 ℃ to about 140 ℃, and the material has a wider crystallization temperature range in the cooling process. Since the glass transition temperature of PGA is only about 38 ℃, if the crystallinity of the material is not high, the material is easily softened and deformed at a high room temperature, and after the crystallinity is improved, both the tensile strength and the heat distortion temperature of the material are improved. Meanwhile, after the crystallinity is improved, moisture in the material is more difficult to invade a polymer crystallization area in the room temperature aging process, so that the hydrolysis process of the polymer can be delayed. Thereby slowing down the aging rate of the polymer.
As can be seen from the comparison of the data of examples 1-3, 2-4 and 3-5 in table 2, the direct effect of not adding talc filler is a decrease in crystallinity, which is due to the fact that the heterogeneous nucleating agent talc powder having a relatively large particle size, i.e. the filler talc powder rancour, has a small particle size and is easily agglomerated, has a certain interval effect, so that the agglomeration effect of the heterogeneous nucleating agent talc powder is weakened, and further, the dispersion degree of the heterogeneous nucleating agent in the material is increased during the preparation process, and the heterogeneous crystallization is promoted.
In comparative examples 3 to 5, the tensile strength and the heat distortion temperature of the material were reduced to different degrees due to the reduction of the crystallinity, and the samples prepared in comparative examples 3 to 5 were also reduced in aging resistance to different degrees as seen from the melt flow rates before and after the aging of the bars.
Therefore, the talcum powder with the enlarged particle size serving as the filler not only plays a role in reinforcing mechanical properties from the aspect of physical filling, but also can increase the overall crystallinity of the material, thereby improving the heat resistance, the tensile strength and the ageing resistance of the material.
The inventors continued intensive studies in order to further improve the heat resistance and aging resistance of the material product, and designed the following comparative examples 6 to 8 to verify the effects thereof by adopting a manner of performing surface modification treatment only on talc powder having a larger particle diameter as a filler.
Comparative example 6:
the difference compared to example 1 is that the 1000 mesh talc as filler was surface-modified, while the talc as heterogeneous nucleating agent was not surface-modified.
Comparative example 7:
the difference compared to example 2 is that 1250 mesh talc as filler is surface-modified, while talc as heterogeneous nucleating agent is not surface-modified.
Comparative example 8:
the difference compared to example 3 is that 800 mesh talc as filler was surface-modified, while talc as heterogeneous nucleating agent was not surface-modified.
For talcum powder, the surface modification by the coupling agent and the maleic anhydride graft is a modification method well known to those skilled in the art, however, in the consideration of simple operation and cost saving, the talcum powder of the invention tends to consider a simple blending modification method, and has low requirements on production environment and equipment, so the surface modification method adopted in comparative examples 6-8 adopts a silane coupling agent for modification, and specifically comprises the following steps:
preparing a solution from a silane coupling agent KH-570, uniformly stirring, dripping the solution into dried filler talcum powder, stirring for 60min, and heating and drying to obtain modified filler talcum powder, wherein the mass ratio of the filler talcum powder to KH-570 is 1:0.03.
as a conventional technical means in the art, through the common surface modification methods such as the coupling agent, the maleic anhydride graft and the like, a person skilled in the art can easily learn that the corresponding technical effects can be obtained by modifying the filler talcum powder by adopting the maleic anhydride graft and other types of coupling agents, and therefore, the selection of the modification method should not limit the protection scope of the invention.
The product test data of examples 1 to 3 and comparative examples 6 to 8 are shown in Table 3:
TABLE 3 data for product tests of examples 1-3, comparative examples 6-8
As can be seen from table 3, in the samples prepared in comparative examples 6 to 8, the modified filler talc powder can further improve the dispersity of the heterogeneous nucleating agent talc powder in the preparation process of the samples, so that the crystallinity is further improved, and accordingly, the heat resistance, tensile strength and ageing resistance of the sample materials are synchronously improved.
In addition, the inventors have conducted an in-depth analysis of the effect of the parameter of the melt flow rate of PGA in the raw material on the properties of the finished material, and have devised examples 4 to 7 below to verify the effects thereof.
Example 4：
The difference compared to example 1 is only that the PGA melt flow rate in the feed was 12g/10min.
Example 5：
The difference compared to example 1 is only that the PGA melt flow rate in the feed is 15g/10min.
Example 6：
The difference compared to example 1 is only that the PGA melt flow rate in the feed is 18g/10min.
Example 7：
The difference compared to example 1 is only that the PGA melt flow rate in the feed was 21g/10min.
The product test data of examples 1, 4 to 7 are shown in Table 4:
TABLE 4 product test data for examples 1, 4-7
Within a certain range, the higher the molecular weight of the polymer, the higher the relevant strength of the material, especially for rigid polymers such as PGA. The molecular weight of a polymer may be indirectly expressed in terms of the melt flow rate, the lower the melt flow rate, the higher the molecular weight of the polymer. For the degradation materials of the PGA type, the aging process of the material is actually a slow hydrolysis process, which is accompanied by a decrease in the molecular weight of the polymer, and the visual reaction is an increase in the melt flow rate. In the aging process of the polymer, the mechanical property of the material is rapidly lost along with the rapid decrease of the molecular weight of the polymer from the beginning to the later stage. For example, the molecular weight of the polymer is reduced from 15 ten thousand to 5 ten thousand, the mechanical property is only lost by 10 percent, but the molecular weight is reduced from 5 ten thousand to 2 ten thousand, and the mechanical property is lost by 60 percent. Therefore, in the early stage, if the molecular weight of the polymer is larger, the lower the melt flow rate is, the longer the aging time is left for the material, and at the same time, the molecular weight also affects the heat resistance, and from the viewpoint that the higher the molecular weight is, the better the heat resistance of the material is, the lower the melt flow rate of the PGA as the raw material is.
However, the lower the melt flow rate of PGA means that the larger the molecular weight of PGA, the larger the molecular weight, and the adverse effect is to the formation of the crystalline state of the material, and under the same crystallization conditions, the smaller the molecular weight of the material, the easier the molecular chain activity, and the easier crystallization will occur, and from this point of view, the higher the melt flow rate of PGA as a raw material is, instead, the better.
What is the effect of the melt flow rate of PGA as the host material on the material properties of the formulation of the invention?
Referring to the data in Table 4, from examples 1 to 4, to example 7, the melt flow rate of PGA in the raw material was gradually increased, meaning that the molecular weight of PGA was gradually decreased, and the directly affected data was an improvement in the crystallinity of the material.
The increase in crystallinity promotes the tensile strength, however, the gradual decrease in molecular weight adversely affects the tensile strength, and in the data of examples 1 and 4-7, we see that the tensile strength of the sample material tends to increase and then decrease, which the inventors believe should be due to: in the formula system, the influence of crystallinity on tensile strength is dominant in the PGA melt flow rate range of 10-15 g/10min, and the influence of molecular weight on tensile strength is larger in the PGA melt flow rate range of 15-21 g/10min.
From example 1 to example 4, to example 7:
the heat distortion temperature of the sample material gradually increases, but the rate of increase is gradual, at least because, within the scope of the examples, the effect of crystallinity on heat distortion temperature is dominant, while the molecular weight of PGA gradually decreases as the melt flow rate decreases, at which time the effect of molecular weight on heat distortion temperature gradually increases;
the aging resistance of the sample material gradually decreases, because the molecular weight of the PGA material has a larger influence on the aging resistance, and the crystallinity has a smaller influence on the aging resistance in the range of examples, and the melt flow rate of the sample bar after aging in example 7 has reached a higher degree as the melt flow rate decreases, and generally the melt flow rate range of the PGA material is selected from 10 to 21g/10min in the formulation system of the present invention.
Further additional embodiments are as follows:
example 8：
The only difference compared to example 1 is the formulation of the materials:
PGA,85 parts;
PBAT,15 parts;
210,1 parts of HyMax;
0.5 parts of EBS;
8000 portions of talcum powder;
3000 mesh talcum powder, 25 parts.
Example 9：
The only difference compared to example 1 is the formulation of the materials:
PGA,45 parts;
PBS,5 parts;
1010,0.04 parts of HyMax;
0.02 parts of EBS;
8000 mesh talcum powder, 5 parts;
2000 mesh talcum powder and 10 parts.
Example 10：
The only difference compared to example 1 is the formulation of the materials:
PGA,50 parts;
10 parts of PBS;
210,0.05 parts of HyMax;
erucamide, 0.01 part;
8000 mesh talcum powder, 3 parts;
1200 mesh talcum powder, 5 parts.
Example 11：
The only difference compared to example 1 is the formulation of the materials:
PGA,60 parts;
12 parts of PBS;
1010,0.04 parts of HyMax;
0.01 part of EBS;
5000 mesh talcum powder, 12 parts;
1000 meshes of talcum powder and 20 parts.
The product test data for examples 8-11 are shown in Table 5:
TABLE 5 product test data for examples 8-11
As can be seen from Table 5, the samples prepared in examples 8 to 11 all have good heat resistance, mechanical properties and aging resistance.
In the description of the present specification, reference to the terms "embodiment," "base embodiment," "preferred embodiment," "other embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The anti-aging heat-resistant polyglycolide injection molding material is characterized by comprising the following components in parts by weight:
45-85 parts of a main polymer;
5-15 parts of a reinforcing polymer;
0.04-1 part of an anti-hydrolysis agent;
0.01-0.5 parts of lubricant;
5-25 parts of filler;
3-15 parts of heterogeneous nucleating agent;
wherein the main polymer is PGA, and the reinforcing polymer is PBS and/or PBAT;
the filler and the heterogeneous nucleating agent are both selected from talc.
2. The polyglycolide injection molding material of claim 1, wherein: the filler is talcum powder with 800-3000 meshes.
3. The polyglycolide injection molding material of claim 2, wherein: the filler is talcum powder with the mesh number of 1000-2000 meshes, and the adding amount is 10-25 parts.
4. The polyglycolide injection molding material of claim 1, wherein: the heterogeneous nucleating agent is talcum powder with the mesh number of 3000-10000 meshes.
5. The polyglycolide injection molding material of claim 4, wherein: the heterogeneous nucleating agent is talcum powder with the mesh number of 5000-10000, and the adding amount is 5-12 parts.
6. The polyglycolide injection molding material of claim 1, wherein: the carboxyl end group content of the reinforced polymer is less than 30mol/t.
7. The polyglycolide injection molding material of claim 1, wherein: the anti-hydrolysis agent is selected from one of HyMax 1010 and HyMax 210.
8. The polyglycolide injection molding material of claim 1, wherein: the lubricant is one or more selected from EBS, PE wax and erucamide.
9. The method for preparing the polyglycolide injection molding material according to any one of claims 1 to 8, comprising the steps of:
and (3) drying: drying the main polymer and the reinforcement polymer, and making the moisture content of the dried main polymer and reinforcement polymer within 200 ppm; drying the filler and the heterogeneous nucleating agent, wherein the moisture content of the dried filler and heterogeneous nucleating agent is controlled within 0.15 percent;
mixing: placing the dried main polymer, the reinforced polymer, the hydrolysis inhibitor and the lubricant into a stirrer to be uniformly stirred to form a mixed material;
extrusion: and (3) feeding the mixed material into a screw extruder to be melted, mixed and extruded at the temperature of 210-225 ℃, feeding the dried filler and heterogeneous nucleating agent into the screw extruder to be uniformly mixed with the melted material, simultaneously ensuring the vacuum degree of a vacuum system of the screw extruder to be more than-0.08 MPa, and granulating and packaging extruded bars after air cooling bracing.
10. The method of manufacturing according to claim 9, wherein: in the drying step, the main polymer and the reinforced polymer are dried in a dehumidifying dryer at 55-70 ℃ for 4-6 hours, so that the dew point temperature of the dehumidifying dryer is below-50 ℃; and stirring the filler and the heterogeneous nucleating agent in a stirrer with a heating function for 1-2 hours, and drying at the stirring temperature of 80-100 ℃.
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| JP2008260902A (en) * | 2007-04-13 | 2008-10-30 | Kureha Corp | Method for raising crystallization temperature of polyglycolic acid and polyglycolic acid resin composition having raised crystallization temperature |
| CN111154245A (en) * | 2020-01-23 | 2020-05-15 | 中科信晖(海南)新材料科技有限公司 | Fully-biodegradable dental floss rod handle and preparation method thereof |
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| JP2008260902A (en) * | 2007-04-13 | 2008-10-30 | Kureha Corp | Method for raising crystallization temperature of polyglycolic acid and polyglycolic acid resin composition having raised crystallization temperature |
| CN111154245A (en) * | 2020-01-23 | 2020-05-15 | 中科信晖(海南)新材料科技有限公司 | Fully-biodegradable dental floss rod handle and preparation method thereof |
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