WO2022048584A1 - Material, preparation method therefor, and application thereof - Google Patents
Material, preparation method therefor, and application thereof Download PDFInfo
- Publication number
- WO2022048584A1 WO2022048584A1 PCT/CN2021/116155 CN2021116155W WO2022048584A1 WO 2022048584 A1 WO2022048584 A1 WO 2022048584A1 CN 2021116155 W CN2021116155 W CN 2021116155W WO 2022048584 A1 WO2022048584 A1 WO 2022048584A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- crystallinity
- structural layers
- glycolic acid
- structural
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
Definitions
- the present invention relates to polymer materials, in particular to a degradable polymer material based on the regulation of crystalline region distribution.
- Degradable polymer material refers to a polymer material that can be degraded in the sense of thermodynamics and kinetics under certain time and conditions. It is an environmentally friendly polymer material and can be used in all aspects of production and life, such as, It can be produced by blow molding to produce film products, such as shopping bags, packaging bags, garbage bags, gloves and agricultural films, etc.; can be produced by injection molding to produce container products, such as bottles, etc.; can also be produced by extrusion molding to produce sheets and Pipes, etc., such as plates, bowls, basins, lunch boxes, folders, ropes, straws, hard pipes, etc.; also can be prepared by injection molding to prepare a variety of injection molding products, such as chopsticks, cutlery, pens, stationery, toothbrushes, combs, Clothes hangers and structural parts and casings of electronic products, etc.; can also be formed by spinning (for example, melt spinning or solution spinning, etc.) to prepare fiber products, such as long fibers, short fibers, non-woven fabrics
- the existing degradable polymer materials are usually polymerized from functional group-containing monomers to form several thousand, tens of thousands, millions or even tens of millions of hydrolyzable functional groups (for example, ester groups) , amide group, acid anhydride or urethane group, etc.), so its many properties (for example, mechanical properties, processing properties, degradation properties, thermal stability, gas barrier properties, aging resistance, etc.) mainly depend on its Internal structural properties (eg, molecular chain structure, molecular chain morphology, molecular chain configuration, conformation and flexibility, molecular weight size, molecular weight distribution, crystallinity, types of hydrolyzable bonds, etc.).
- hydrolyzable functional groups for example, ester groups
- amide group for example, amide group, acid anhydride or urethane group, etc.
- its many properties for example, mechanical properties, processing properties, degradation properties, thermal stability, gas barrier properties, aging resistance, etc.
- Internal structural properties eg, molecular chain structure,
- the performance regulation of degradable polymer materials is mostly realized by using related processing aids.
- the regulation of its degradation performance is usually to add some additives (such as water absorbent, Hydrolysis promoters, anti-hydrolysis agents, etc.).
- some additives such as water absorbent, Hydrolysis promoters, anti-hydrolysis agents, etc.
- This will not only increase the processing cost of the material, but also the use of the above-mentioned additives will also control the degradation performance of the final material due to factors such as uneven dispersion in the matrix, poor compatibility with the matrix, and partial analysis. Unfavorable effects, and even undesired unstable degradation such as slow and fast, uneven degradation, etc. may occur.
- the present invention aims to provide a degradable polymer material based on the regulation of crystal region distribution, and a preparation method and application thereof.
- a material in a first aspect of the present invention, contains at least two structural layers, and adjacent structural layers have different degrees of crystallinity; the structural layers are formed of a degradable resin.
- the crystallinity of adjacent structural layers differs by 0.1-72%.
- each structural layer is formed from the same or different degradable resins.
- the degradable resin has a hydrolyzable functional group, and the hydrolyzable functional group is selected from one or more of the following: ester group, amide group, hydroxyl group, carboxyl group, acid anhydride and urethane group; for example, the degradable resin is selected from one or more of the following copolymers, mixtures, derivatives or combinations: aliphatic polyesters, polyhydroxyester ethers, polyhydroxyalkanoates, Polyanhydrides, polyamino acids, polyethylene oxides, polyphosphazenes, polyetheresters, polyesteramides, polyamides, sulfonated polyesters, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and thermoplastic polyurethane elastomers.
- the hydrolyzable functional group is selected from one or more of the following copolymers, mixtures, derivatives or combinations: aliphatic polyesters, polyhydroxyester ethers, polyhydroxyalkanoates, Polyanhydrides, polyamino
- the aliphatic polyester is selected from one or more of the following: glycolic acid homopolymer, glycolic acid copolymer, polylactic acid and its copolymer, poly- ⁇ -caprolactone (referred to as PCL), polyethylene succinate (referred to as PES), polybutylene succinate (referred to as PBS), polyadipate-terephthalate-butylene glycol (referred to as PBAT), Polysuccinic acid-terephthalic acid-butylene glycol (referred to as PBST), polysuccinic acid-adipate-butylene glycol (referred to as PBSA), polymethyl ethylene carbonate (referred to as PPC), poly Hydroxy fatty acid ester (PHA for short), and polyethylene adipate (PEA for short).
- PCL poly- ⁇ -caprolactone
- PES polyethylene succinate
- PBS polybutylene succinate
- PBAT polyadipate-terephthalate-butylene glycol
- PBST Polysuccinic
- the aliphatic polyester is selected from glycolic acid homopolymers or glycolic acid copolymers.
- the material further contains a bonding layer between two adjacent structural layers.
- a melt of degradable resin is injected between adjacent structural layers after stacking, and then compression molding is performed to form the material provided by the present invention as described above.
- the present invention provides a new idea that can accurately control the properties (eg, mechanical properties, degradation properties, heat resistance properties, etc.) of degradable polymer materials.
- Figure 1 shows the cross section of the composite structure of sheet and roll made of the material provided by the present invention.
- Figure 2 shows a schematic diagram of the material obtained in Example 1 or 2.
- Figure 3 shows a schematic diagram of the material obtained in Example 4.
- Figure 4 shows a schematic representation of the materials obtained in Examples 5 and 6.
- the degradable resin with crystallinity is made into a multi-layer structure, and the crystallinity between two adjacent layers is different.
- the distribution of the crystalline region can be achieved.
- the elongation at break and impact strength of the degradable polymer materials thus obtained can be significantly improved.
- the degradation performance of the material is related to the crystallinity to a certain extent, it can be adjusted based on the distribution of the crystalline region. To influence the degradation time of the final material, the degradation time of the final material can be controlled more accurately. On this basis, the present invention has been completed.
- the present invention provides a material having a plurality of structural layers, the structural layers are formed of degradable resin, and the crystallinity of adjacent structural layers is different.
- Each structural layer in the material provided by the present invention may be formed of the same degradable resin, or may be formed of different degradable resins.
- the crystallinity of adjacent structural layers in the material differs by 0.1-72%, such as, but not limited to, 0.1-1%, 0.2-2.5%, 0.3-1.8%, 2-10%, 3-70%, 4-15%, 5-17%, 8-40%, 9-19%, 10-22%, 13-60%, 0.5-20%, 0.1-70%, etc.
- the height of the longitudinal section of the material is generally 10 micrometers to 50 centimeters, and the number of structural layers contained therein is not limited.
- degradable resin refers to a polymer material having a hydrolyzable functional group, and the hydrolyzable functional group is selected from one or more of the following: ester group, amide group, hydroxyl group, Carboxyl, anhydride and carbamate groups.
- the degradable resin is selected from the group consisting of aliphatic polyester, polyhydroxyester ether, polyhydroxyalkanoate, polyanhydride, polyamino acid, polyethylene oxide, polyphosphazene, polyetherester, Any one or any copolymer, mixture, derivative or combination of polyamide ester, polyamide, sulfonated polyester, thermoplastic polyester elastomer or thermoplastic polyurethane elastomer.
- the aliphatic polyester includes at least one of hydroxycarboxylic acid-based aliphatic polyester, lactone-based aliphatic polyester, and glycol dicarboxylic acid-based aliphatic polyester.
- the aliphatic polyester is selected from glycolic acid homopolymers, glycolic acid copolymers, polylactic acid and its copolymers, poly- ⁇ -caprolactone (PCL for short), polybutylene glycol Ethylene glycol ester (PES for short), polybutylene succinate (PBS for short), polybutylene adipate-terephthalate (PBAT), polysuccinic acid-terephthalate Formate-butylene glycol ester (referred to as PBST), polysuccinic acid-adipate-butylene glycol ester (referred to as PBSA), polymethyl ethylene carbonate (referred to as PPC), polyhydroxy fatty acid ester (referred to as PHA) , and at least one of polyethylene adipate (PEA for short).
- PCL poly- ⁇ -caprolactone
- PES polybutylene glycol Ethylene glycol ester
- PBS polybutylene succinate
- PBAT polybutylene adipate-ter
- the aliphatic polyester is selected from glycolic acid homopolymers or glycolic acid copolymers.
- the proportion of glycolic acid repeating units can be selected to be more than 10wt%, preferably more than 50wt%, more preferably more than 70wt%, still more preferably more than 85wt%, most preferably 90 wt% or more.
- the glycolic acid copolymer contains, in addition to glycolic acid repeating units, hydroxycarboxylic acid units (for example, lactic acid units, 3-hydroxypropionic acid units, 3-hydroxybutyric acid units, 4-hydroxybutyric acid units, 6 -Hydroxycaproic acid unit, etc.), lactone-based units (for example, ⁇ -propiolactone unit, ⁇ -butyrolactone unit, ⁇ -butyrolactone unit, ⁇ -caprolactone unit, etc.), carbonate-based units ( For example, at least one of trimethylene carbonate units, etc.), and amide-based units (eg, ⁇ -caprolactam units, etc.).
- hydroxycarboxylic acid units for example, lactic acid units, 3-hydroxypropionic acid units, 3-hydroxybutyric acid units, 4-hydroxybutyric acid units, 6 -Hydroxycaproic acid unit, etc.
- lactone-based units for example, ⁇ -propiolactone unit, ⁇ -buty
- the glycolic acid copolymer is selected from glycolic acid-lactic acid copolymers.
- each structural layer in the material of the present invention can be made of degradable resins with different relative molecular weights (eg, glycolic acid homopolymer or glycolic acid-lactic acid copolymer).
- each structural layer in the material of the present invention can also be made of a degradable resin (for example, glycolic acid homopolymer or glycolic acid-lactic acid copolymer) of the same relative molecular mass.
- a degradable resin for example, glycolic acid homopolymer or glycolic acid-lactic acid copolymer
- the relative molecular mass of the glycolic acid homopolymer used in the present invention can be selected to be 10-1 million, preferably 20,000-600,000, more preferably 30,000-400,000, most preferably 40,000-300,000;
- the relative molecular mass of the glycolic acid-lactic acid copolymer can be selected to be 10,000-300,000, preferably 10,000-200,000, and more preferably 20,000-150,000.
- the crystallinity of the structural layer formed by the degradable resin can be controlled using the conventional technical means of the present invention, for example, but not limited to, by adjusting the corresponding process conditions (for example, cooling temperature, cooling rate) that can affect the crystallization when forming each structural layer. , tensile stress, etc.) to achieve.
- the corresponding process conditions for example, cooling temperature, cooling rate
- the cooling temperature is controlled to be 0-230 ° C, and the cooling rate is 0.1 -80°C/min, the structural layers A, B, C and D with different crystallinity are processed respectively, so that the crystallinity of the A layer is about 70%, the crystallinity of the B layer is about 62%, and the crystallinity of the C layer is about 56%, the crystallinity of the D layer is about 41% and so on.
- degradable resin for example, glycolic acid homopolymer
- the cooling rate is 0.1 -80°C/min
- the structural layers A, B, C and D with different crystallinity are processed respectively, so that the crystallinity of the A layer is about 70%, the crystallinity of the B layer is about 62%, and the crystallinity of the C layer is about 56%, the crystallinity of the D layer is about 41% and so on.
- crystallinity refers to the proportion of crystalline regions in a polymer, which can be determined by density method or thermal analysis method.
- the DSC method can be used to measure the crystallinity of each layer, that is, the crystallinity of the sample can be calculated by the ratio of the heat absorbed by the melting of the sample crystal region to the heat of fusion of a fully crystallized sample or a standard sample with known crystallinity. This is a conventional testing method in the field, and will not be repeated here.
- the bonding layer in the material provided by the present invention is also formed using degradable resin, which can be the same or different degradable resin as that of the structural layer, preferably the same degradable resin as one of the adjacent structural layers.
- the crystallinity of the bonding layer in the material provided by the present invention and the crystallinity of one of the adjacent structural layers may differ by 0-72%, such as, but not limited to, 0.1-1%, 0.2-2.5%, 0.3 -1.8%, 2-10%, 3-70%, 4-15%, 5-17%, 8-40%, 9-19%, 10-22%, 13-60%, 0.5-20%, 0.1 -70% etc.
- the difference between the crystallinity of the bonding layer and the crystallinity of one of the adjacent structural layers is generally not more than 10%.
- a melt of degradable resin is injected between two adjacent structural layers, and a bonding layer is formed after cooling.
- melt refers to a state in which a polymer is between the flow temperature or melting point and the decomposition temperature, and can move against intermolecular forces.
- the bonding layer in the material provided by the present invention can be completely attached to the surfaces of the two adjacent structural layers, or can be dispersed on the surfaces of the adjacent structural layers, as long as the structural layers can be connected.
- the cross-sectional area of the bonding layer is 30% or more of the surface area of the adjacent structural layer, more preferably 70% or more, and most preferably 90% or more.
- the bonding layer in the material provided by the present invention can be selected to be in complete contact with the surfaces of the two adjacent structural layers. In this case, there is no sufficient influence between the bonding layer and the structural layer. Distinguishing properties of the physical and/or chemical properties of an entire material.
- each structural layer and the bonding layer between two adjacent structural layers can be made of the same degradable resin.
- the bonding layer The structural layer may have substantially the same properties, with no essential difference between the two.
- the degradable polymer material shown in Figure 2 has a multi-layer structure, and the structural layers A, B, C, D and the bonding layers E, F, and G can be made of, for example, glycolic acid homopolymers.
- the prepared structural layers The crystallinity of A may be, for example, about 70%, the crystallinity of structure layer B may be, for example, about 62%, the crystallinity of structure layer C may be, for example, about 56%, and the crystallinity of structure layer C may be, for example, about 41%.
- the bonding layers E, F, G may respectively have the same or different crystallinity than one of the two adjacent structural layers.
- the case of the crystallinity of the bonding layer E will be described as an example:
- the crystallinity of the bonding layer E can be the same as that of the structural layer A, then the bonding layer E is equivalent to belonging to the structural layer A, that is, the bonding layer E can be regarded as a part of the structural layer A;
- the crystallinity of the bonding layer E can be the same as that of the structural layer B, then the bonding layer E is equivalent to belonging to the structural layer B, that is, the bonding layer E can be regarded as a part of the structural layer B;
- the crystallinity of the bonding layer E is different from that of the structural layers A and B.
- the bonding layer E is equivalent to becoming a structural layer by itself, that is, the bonding layer E can be regarded as a
- B has an equivalent structural layer E on the structure of the entire degradable polymer material.
- each layer eg, between structural layers, between bonding layers, or between structural layers and bonding layers
- the thickness of each layer may be the same or different.
- the thickness of each layer is the same.
- Each layer (including the structural layer and the bonding layer) in the material provided by the present invention may have a regular shape or an irregular shape (for example, a shape with a thick middle and a thin perimeter or a shape with a thin middle and a thick perimeter, or a shape with shape like a wavy cross-section, etc.).
- the shapes of each layer eg, between the structural layer and the structural layer, between the bonding layer and the bonding layer, or between the structural layer and the bonding layer) can be the same or different; preferably the shapes of the layers are the same.
- the molecular weight of each layer (including the structural layer and the bonding layer) in the material provided by the present invention may be the same or different.
- the material provided by the present invention can be prepared by the following steps:
- the first step is to make the degradable resin form a structural layer with a certain degree of crystallinity
- the melt of degradable resin is injected between adjacent structural layers after stacking, and then the material provided by the present invention is obtained by compression molding.
- structural layers with different degrees of crystallinity can be separately processed by molding methods such as extrusion molding, calendering molding, or blow molding well-known in the art.
- a calendering molding method can be used, and the cooling temperature is controlled to be 0-230° C., and the cooling rate is 0.1-80° C./min, forming a crystallinity of about 25-230° C. 72% structural layers.
- the structural layers may be stacked in any manner.
- the structural layers are sequentially stacked from bottom to top by means of lead-in parts.
- the lead mold part includes a lead mold part body, and the lead mold part body is provided with grooves and/or holes for guiding and positioning each layer of material. There are no special requirements on the selection of the shape, size, position and number of the grooves and/or holes, as long as the uniform stacking of each layer of material is sufficient.
- the injection time of the melt of the degradable resin is controlled to be 2-40 seconds, and then compression molding is performed.
- the process conditions of the compression molding can be: preheating time is 2-10 minutes, molding time is 2-15 minutes, molding temperature: 0-260°C, preferably 100-250°C, most preferably 210-240°C ;
- the molding pressure is 0.5-2MPa;
- the cooling time is 2-4 minutes, and the cooling temperature is 0-230°C, preferably 10-150°C, and most preferably 30-120°C.
- the mass injection rate of the melt can be controlled to be about 1-10 grams per second.
- the second step above can be done in the following two ways:
- the first way when there are more than 3 stacked structural layers, after injecting the melt of degradable resin between all two adjacent structural layers, press molding is performed under one process condition, and each bonding layer is obtained.
- the crystallinity is the same or similar.
- the second way when it is desired to obtain more than 3 structural layers of the material, first inject a melt of degradable resin between two adjacent structural layers, and use a certain process for molding to obtain the corresponding crystallinity. Bonding layers, and then stacking another structural layer on one of the structural layers, injecting a melt of degradable resin between the newly formed adjacent structural layers, and using a modified or unchanged process for compression molding to obtain the corresponding crystallinity the bonding layer. So on and so forth. In this way, each bonding layer with a relatively large difference in crystallinity can be obtained.
- the materials provided by the present invention can be processed by machining such as cutting, drilling, cutting, etc. to form profiles with desired shapes, including but not limited to plates, sheets, bars, strip profiles, strip profiles, disc profiles, Wire, etc., can also be made into a coil with a cross-section similar to the shape of tree rings, and can also be made into a composite structure of the above two profiles, for example, in a coil (for example, it has a shape similar to that of tree years.
- a hollow cavity can be reserved or preset at the center of the concentric circles of the cross-section of the wheel profile, and multilayer sheets can be embedded in the hollow cavity to obtain a composite structure of sheets and rolls, see Figure 1 . It can also be made into films such as barrier films, packaging films, and mulching films.
- the elongation at break and impact strength of the material provided by the present invention can be significantly improved.
- the material provided by the present invention can easily and effectively control the degradation rate of the material, and can control the degradation time more accurately.
- the present invention can control the heat deformation temperature of the final material by adjusting the crystallinity of each layer, without adding additives such as heat stabilizers, antioxidants, heat-resistant inorganic fillers, etc., to achieve heat resistance to the final material. Sexual flexibility.
- Ranges should be considered as specifically disclosed herein.
- "a range from 1 to 10" should be understood to mean every and every possible number consecutively between about 1 and about 10.
- a specific data point within a range, or even no data point within the range is specifically identified or refers only to a small number of specific points, it should be understood that any and all data points within the range are considered to be specifically stated.
- “about” is used to modify a numerical value, it means a tolerance for error of measurement within ⁇ 5% of the numerical value.
- the degradability test method involved in the following examples adopts the following test method to test the degradability of the sample material (machining can be used, and the material to be tested can be processed into a sample with a length of 20 mm ⁇ height 20 mm ⁇ width 20 mm for degradation test). test.
- Step 1) take 3 samples, weigh them, record the initial mass as M 0 , then place them in a constant temperature drying oven, and dry them at 60° C. for 24 hours;
- Step 2) Place the 3 dried samples in 3 beakers containing 75°C clean water, and immerse each sample completely in the clean water, and then place the 3 beakers in 3 same specifications. in the constant temperature and humidity test chamber (the temperature is set to 75 °C);
- Step 3) at intervals, take out the samples in 3 constant temperature and humidity test chambers, wash them with distilled water, put them in a constant temperature drying chamber, dry them at 105°C for 2 hours and weigh them, and record the remaining samples. The mass is M', and then the samples are placed in the corresponding beakers to continue the degradation experiment;
- Step 4) Calculate the degradation rate R d , the calculation formula is as follows:
- R d (M 0 -M')/M 0 ⁇ 100%.
- the sampling interval in the initial stage of the degradation experiment, can be longer (for example, the interval is 4 hours, or 6 hours, etc.), and it can be appropriately shortened in the middle and late stages of the degradation experiment Interval time (eg, 2 hour interval, 1 hour interval, or 30 minute interval, etc.).
- step 3 for the situation that the original shape of the sample in the beaker has basically disappeared, the following methods can be used to measure the quality:
- the heat deformation temperature test involved in the following examples is based on GB/T 1633-2000, and the heat deformation temperature-Vicat softening point tester is used to test the heat deformation temperature of the material.
- the sample used in the test is a long strip with a rectangular cross-section.
- the surface of the sample is flat and smooth, without bubbles, sawing marks or cracks and other defects.
- the size of the material sample to be tested is: length 120mm ⁇ height 15mm ⁇ width 10mm.
- the heat transfer medium used in the test is methyl silicone oil, the heating rate is controlled at 120 °C/hour, the center distance between the two sample supports is 100 mm, and a vertical load is applied to the sample at the midpoint of the support.
- the contact part of the sample is a semicircle with a radius of (3 ⁇ 0.2) mm.
- the maximum bending normal stress of the sample after being loaded is 4.6kg/cm 2 .
- glycolic acid homopolymer with a relative molecular mass of 243,000 using the calendering method, controlling the cooling temperature to 130 ° C and the cooling rate to 1 ° C/min, a structural layer A with a crystallinity of about 70% can be obtained.
- the relative molecular mass of 24.3 Wan's glycolic acid homopolymer adopts the extrusion molding method, and the cooling temperature is controlled to be 100 ° C and the cooling rate is 3 ° C/min, and the structural layer B with a crystallinity of about 62% can be obtained.
- the homopolymer adopts the calendering molding method, the cooling temperature is controlled to be 90 °C, and the cooling rate is 10 °C/min, and a structural layer C with a crystallinity of about 56% can be obtained.
- the molding method is used, and the cooling temperature is controlled to be 80 °C and the cooling rate is 25 °C/min, and a structural layer D with a crystallinity of about 41% can be obtained;
- the structural layer A and the structural layer B are stacked by the lead mold; the melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers A and B, and then the process condition I is used for compression molding, and the crystallinity is obtained. about 65% of the E layer;
- the structural layer C is stacked on the structural layer B by the lead mold, and then a melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers B and C, and then the process condition II is used for compression molding to obtain crystals. degree of about 60% of the F layer;
- the structural layer D is stacked on the structural layer C through the lead-molding part, and then the melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers C and D, and then the process condition III is used for compression molding to obtain crystals.
- the degree of G layer is about 42%, and the material shown in Figure 2 is obtained;
- the calendering method is used, the cooling temperature is controlled to 150 ° C, and the cooling rate is 0.5 ° C/min, and a structural layer A with a crystallinity of about 70% can be obtained.
- the relative molecular mass of 18.5 Wan's glycolic acid homopolymer adopts the extrusion molding method, the cooling temperature is controlled to 120°C, and the cooling rate is 2°C/min, and the structural layer B with a crystallinity of about 62% can be obtained.
- the homopolymer adopts the calendering method, the cooling temperature is controlled to be 100 °C, and the cooling rate is 10 °C/min, and a structural layer C with a crystallinity of about 56% can be obtained.
- a molding method is developed, the cooling temperature is controlled to be 75°C, and the cooling rate is 15°C/min, and a structural layer D with a crystallinity of about 41% can be obtained;
- the structural layer A and the structural layer B are stacked by the lead-molding member; the melt of glycolic acid homopolymer with a relative molecular mass of 156,000 is injected between the structural layers A and B, and then the process conditions I in Example 1 are used for molding. , obtaining an E layer with a crystallinity of about 65%;
- the structural layer C is stacked on the structural layer B through the lead-in part, and then a melt of glycolic acid homopolymer with a relative molecular mass of 201,000 is injected between the structural layers B and C, and then the process conditions II in Example 1 are used to carry out the process. Compression molding to obtain an F layer with a crystallinity of about 60%;
- the structural layer D is stacked on the structural layer C through the lead-in, and then a melt of glycolic acid homopolymer with a relative molecular mass of 275,000 is injected between the structural layers C and D, and then the process condition III in Example 1 is used to carry out the process. Compression molding yielded a G layer with a crystallinity of about 42% and a material as shown in Figure 2 was obtained.
- glycolic acid homopolymer with a relative molecular mass of 243,000 referring to the process of obtaining structural layer A in Example 1, a single-layer material with a crystallinity of about 70% was obtained, and its thickness was the same as that obtained in Example 1 or 2, as shown in Figure 2 Materials are the same.
- Example 3 Using a glycolic acid homopolymer with a relative molecular mass of 168,000, a method similar to Example 1 was used to obtain the material shown in Figure 3, which has structural layer A, structural layer B and structural layer C, and bonding layers E and F .
- Comparative Example 1 in Table 4 is a C-layer single-layer material (without multi-layer structure), and Comparative Example 2 is a C-layer single-layer material with a hydrolysis accelerator (dimethyl oxalate) added (addition of a hydrolysis accelerator) amount is about 0.8 wt%).
- Comparative Examples 1 and 2 were the same as those of Examples 1-1 to 6.
- Comparative Example 2 added a hydrolysis accelerator (for example, dimethyl oxalate) that can promote the degradation of the material.
- a hydrolysis accelerator for example, dimethyl oxalate
- Table 3 It can be seen from the data in Table 3 that although the use of the hydrolysis accelerator can effectively accelerate the degradation of the material, its The degradation rate is not stable.
- the time required for the three samples to reach a degradation rate of more than 95% in water at 75°C differs greatly. The maximum difference is about 20.2 hours, and the minimum difference is about 9.4 hours. This is not conducive to the realization of the material. Accurate control of degradation time.
- Example 1-1 Different from Comparative Example 2, the degradation rate of the material in Example 1-1 is relatively stable, and the time required for the three samples to reach a degradation rate of more than 95% in water at 75°C differs by no more than 4 hours. The same is true for the materials of Examples 1-2 and 1-3.
- Examples 2-6 illustrate that the present invention can control the degradability of the final material by controlling the difference in the crystallinity of each layer, and the difference between the degradation times corresponding to the three samples in each example is not more than 4 hours, This can also indicate that the present invention can achieve relatively accurate regulation of the degradability of the material.
- the material shown in FIG. 4 is obtained by a method similar to that of Example 1, which has the structural layer A and the structural layer B, and the bonding layer E.
- Example 5 Each material obtained by the method of Example 5 was tested using the degradability test method. The results are shown in Table 5, wherein the structural layer A and the bonding layer E in Examples 7-1 and 7-2 are glycolic acid-lactic acid copolymers (molecular weight is about 168,000), and structural layer B is glycolic acid homopolymer (molecular weight is about 168,000). is about 85,000); the structural layers A and B and the bonding layer E in Example 8 are both glycolic acid-lactic acid copolymers (molecular weight is about 85,000).
- Examples 7-1, 7-2 and 8 illustrate that the present invention can control the degradability of the final material by controlling the difference in crystallinity of each layer, and the difference in degradation time corresponding to the three samples in each example It is not more than 4 hours, indicating that the present invention can achieve relatively accurate regulation of the degradability of the material.
- the material shown in FIG. 4 is obtained by a method similar to that of Example 1, which has the structural layer A and the structural layer B, and the bonding layer E.
- Example 6 Each material obtained by the method of Example 6 was tested using the heat deflection temperature test method. The results are shown in Table 6.
- the structural layers A, B and the bonding layer E are all glycolic acid homopolymers (molecular weight is about 214,000).
- the thermal deformation temperature of the final material can be regulated by adjusting the crystallinity of each layer, and then the heat resistance of the final material can be effectively regulated.
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Disclosed in the present invention is a material containing at least two structural layers, and the degrees of crystallinity of adjacent structural layers are different; the structural layers are formed of a degradable resin.
Description
本发明涉及高分子材料,尤其涉及一种基于结晶区分布调控的可降解高分子材料。The present invention relates to polymer materials, in particular to a degradable polymer material based on the regulation of crystalline region distribution.
可降解高分子材料是指在一定的时间和条件下,在热力学和动力学意义上均可降解的高分子材料,其是一种环保高分子材料,可被用于生产生活的方方面面,例如,可通过吹塑成型以制备薄膜制品,如购物袋、包装袋、垃圾袋、手套和农用膜等;可以通过注射成型以制备容器制品,如瓶子等;也可以通过挤出成型以制备片材和管材等,如盘、碗、盆、饭盒、文件夹、绳子、吸管、硬质管材等;也可以通过注塑成型以制备多种注塑制品,如筷子、刀叉、笔、文具、牙刷、梳子、衣架以及电子产品的结构件和壳体等;还可通过纺丝成型(例如,熔融纺丝或溶液纺丝等)以制备纤维制品,如长纤维、短纤维、无纺布等。Degradable polymer material refers to a polymer material that can be degraded in the sense of thermodynamics and kinetics under certain time and conditions. It is an environmentally friendly polymer material and can be used in all aspects of production and life, such as, It can be produced by blow molding to produce film products, such as shopping bags, packaging bags, garbage bags, gloves and agricultural films, etc.; can be produced by injection molding to produce container products, such as bottles, etc.; can also be produced by extrusion molding to produce sheets and Pipes, etc., such as plates, bowls, basins, lunch boxes, folders, ropes, straws, hard pipes, etc.; also can be prepared by injection molding to prepare a variety of injection molding products, such as chopsticks, cutlery, pens, stationery, toothbrushes, combs, Clothes hangers and structural parts and casings of electronic products, etc.; can also be formed by spinning (for example, melt spinning or solution spinning, etc.) to prepare fiber products, such as long fibers, short fibers, non-woven fabrics, etc.
由于现有的可降解高分子材料通常是由含官能团的单体经聚合以形成相对分子质量为几千、上万、上百万甚至上千万的具有可水解官能基团(例如,酯基、酰胺基、酸酐或氨基甲酸酯基等)的聚合物,因此其诸多性能(例如,机械性能、加工性能、降解性能、热稳定性、气体阻隔性、耐老化性等)主要取决于其内部结构特性(例如,分子链结构、分子链形态、分子链构型、构象及柔顺性、分子量大小、分子量分布、结晶度、可水解键的种类等)。Because the existing degradable polymer materials are usually polymerized from functional group-containing monomers to form several thousand, tens of thousands, millions or even tens of millions of hydrolyzable functional groups (for example, ester groups) , amide group, acid anhydride or urethane group, etc.), so its many properties (for example, mechanical properties, processing properties, degradation properties, thermal stability, gas barrier properties, aging resistance, etc.) mainly depend on its Internal structural properties (eg, molecular chain structure, molecular chain morphology, molecular chain configuration, conformation and flexibility, molecular weight size, molecular weight distribution, crystallinity, types of hydrolyzable bonds, etc.).
目前,有关可降解高分子材料的性能调控,比较常规的方法多是采用相关的加工助剂来实现。例如,关于降解性能,一般情况下,一旦选定了某种可降解高分子材料,对于其降解性能的调控通常是在材料的成型加工过程中向基体树脂中添加一些助剂(例如吸水剂、促水解剂、抗水解剂等)。这不仅会增加材料的加工成本,而且上述助剂的使用也会因,例如在基体中分散不均、与基体的相容性不佳以致部分析出等因素,对最终材料的降解性能的调控产生不利影响,甚至可能会出现时慢时快、降解不均匀等不期望的非稳定性降解。At present, the performance regulation of degradable polymer materials is mostly realized by using related processing aids. For example, with regard to degradation performance, in general, once a degradable polymer material is selected, the regulation of its degradation performance is usually to add some additives (such as water absorbent, Hydrolysis promoters, anti-hydrolysis agents, etc.). This will not only increase the processing cost of the material, but also the use of the above-mentioned additives will also control the degradation performance of the final material due to factors such as uneven dispersion in the matrix, poor compatibility with the matrix, and partial analysis. Unfavorable effects, and even undesired unstable degradation such as slow and fast, uneven degradation, etc. may occur.
因此,本领域迫切需要一种能对可降解高分子材料的性能(例如,力学 性能、降解性能、耐热性能等)实现准确调控的新思路。Therefore, there is an urgent need in the art for a new idea that can accurately control the properties (for example, mechanical properties, degradation properties, heat resistance, etc.) of degradable polymer materials.
发明内容SUMMARY OF THE INVENTION
本发明旨在提供一种基于结晶区分布调控的可降解高分子材料及其制备方法和应用。The present invention aims to provide a degradable polymer material based on the regulation of crystal region distribution, and a preparation method and application thereof.
在本发明的第一方面,提供一种材料,所述材料含有至少两个结构层,且相邻结构层的结晶度不同;所述结构层由可降解树脂形成。In a first aspect of the present invention, a material is provided, the material contains at least two structural layers, and adjacent structural layers have different degrees of crystallinity; the structural layers are formed of a degradable resin.
在另一实施方式中,相邻结构层的结晶度相差0.1-72%。In another embodiment, the crystallinity of adjacent structural layers differs by 0.1-72%.
在另一实施方式中,各结构层由相同或不同的可降解树脂形成。In another embodiment, each structural layer is formed from the same or different degradable resins.
在另一实施方式中,所述可降解树脂具有水解性官能基团,所述水解性官能基团选自下述的一种或两种以上:酯基、酰胺基、羟基、羧基、酸酐和氨基甲酸酯基;例如,所述可降解树脂选自下述的一种或两种以上共聚物、混合物、衍生物或组合:脂肪族聚酯、聚羟基酯醚、聚羟基烷酸酯、聚酐、聚氨基酸、聚氧化乙烯、聚磷腈、聚醚酯、聚酰胺酯、聚酰胺、磺化聚酯、热塑性聚酯弹性体、热塑性聚酰胺弹性体、和热塑性聚氨酯弹性体。In another embodiment, the degradable resin has a hydrolyzable functional group, and the hydrolyzable functional group is selected from one or more of the following: ester group, amide group, hydroxyl group, carboxyl group, acid anhydride and urethane group; for example, the degradable resin is selected from one or more of the following copolymers, mixtures, derivatives or combinations: aliphatic polyesters, polyhydroxyester ethers, polyhydroxyalkanoates, Polyanhydrides, polyamino acids, polyethylene oxides, polyphosphazenes, polyetheresters, polyesteramides, polyamides, sulfonated polyesters, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and thermoplastic polyurethane elastomers.
在另一实施方式中,所述脂肪族聚酯选自下述的一种或两种以上:羟基乙酸均聚物、羟基乙酸共聚物、聚乳酸及其共聚物、聚-ε-己内酯(简称PCL)、聚丁二酸乙二醇酯(简称PES)、聚丁二酸丁二醇酯(简称PBS)、聚己二酸-对苯二甲酸-丁二醇酯(简称PBAT)、聚丁二酸-对苯二甲酸-丁二醇酯(简称PBST)、聚丁二酸-己二酸-丁二醇酯(简称PBSA)、聚甲基乙撑碳酸酯(简称PPC)、聚羟基脂肪酸酯(简称PHA)、和聚己二酸乙二醇酯(简称PEA)。In another embodiment, the aliphatic polyester is selected from one or more of the following: glycolic acid homopolymer, glycolic acid copolymer, polylactic acid and its copolymer, poly-ε-caprolactone (referred to as PCL), polyethylene succinate (referred to as PES), polybutylene succinate (referred to as PBS), polyadipate-terephthalate-butylene glycol (referred to as PBAT), Polysuccinic acid-terephthalic acid-butylene glycol (referred to as PBST), polysuccinic acid-adipate-butylene glycol (referred to as PBSA), polymethyl ethylene carbonate (referred to as PPC), poly Hydroxy fatty acid ester (PHA for short), and polyethylene adipate (PEA for short).
在另一实施方式中,所述脂肪族聚酯选自羟基乙酸均聚物或羟基乙酸共聚物。In another embodiment, the aliphatic polyester is selected from glycolic acid homopolymers or glycolic acid copolymers.
在另一实施方式中,所述材料还含有相邻两个结构层之间的接合层。In another embodiment, the material further contains a bonding layer between two adjacent structural layers.
在本发明的第二方面,提供一种如上所述的本发明提供的材料的制备方法,所述方法包括步骤:In a second aspect of the present invention, there is provided a method for preparing the material provided by the present invention as described above, the method comprising the steps of:
(1)使可降解树脂形成结构层;和(1) Forming a degradable resin into a structural layer; and
(2)在堆叠后相邻的结构层之间注入可降解树脂的熔体,然后模压成 型形成如上所述的本发明提供的材料。(2) A melt of degradable resin is injected between adjacent structural layers after stacking, and then compression molding is performed to form the material provided by the present invention as described above.
在本发明的第三方面,提供了一种如上所述的本发明提供的材料的应用。In the third aspect of the present invention, an application of the material provided by the present invention as described above is provided.
据此,本发明提供了一种能对可降解高分子材料的性能(例如,力学性能、降解性能、耐热性能等)实现准确调控的新思路。Accordingly, the present invention provides a new idea that can accurately control the properties (eg, mechanical properties, degradation properties, heat resistance properties, etc.) of degradable polymer materials.
图1显示本发明提供的材料所制成的片材与卷材相复合结构的横截面。Figure 1 shows the cross section of the composite structure of sheet and roll made of the material provided by the present invention.
图2显示实施例1或2得到的材料示意图。Figure 2 shows a schematic diagram of the material obtained in Example 1 or 2.
图3显示实施例4得到的材料示意图。Figure 3 shows a schematic diagram of the material obtained in Example 4.
图4显示实施例5和6得到的材料示意图。Figure 4 shows a schematic representation of the materials obtained in Examples 5 and 6.
发明人经过广泛而深入的研究,发现将具有结晶性的可降解树脂制成多层结构,相邻两层之间的结晶度不同,通过控制每层的结晶度大小,可实现结晶区的分布调控,由此制得的可降解高分子材料的断裂伸长率和冲击强度可得到显著提高,同时,由于材料的降解性能在一定程度上与结晶度有关,因此,可基于结晶区的分布调控来影响最终材料的降解时间,从而可对最终材料的降解时间实现较为准确的控制。在此基础上,完成了本发明。After extensive and in-depth research, the inventor found that the degradable resin with crystallinity is made into a multi-layer structure, and the crystallinity between two adjacent layers is different. By controlling the crystallinity of each layer, the distribution of the crystalline region can be achieved. The elongation at break and impact strength of the degradable polymer materials thus obtained can be significantly improved. At the same time, since the degradation performance of the material is related to the crystallinity to a certain extent, it can be adjusted based on the distribution of the crystalline region. To influence the degradation time of the final material, the degradation time of the final material can be controlled more accurately. On this basis, the present invention has been completed.
具体地,本发明提供一种材料,该材料具多个结构层,这些结构层由可降解树脂形成,相邻结构层之间的结晶度不同。Specifically, the present invention provides a material having a plurality of structural layers, the structural layers are formed of degradable resin, and the crystallinity of adjacent structural layers is different.
本发明提供的材料中的各结构层可由相同的可降解树脂形成,也可由不同的可降解树脂形成。Each structural layer in the material provided by the present invention may be formed of the same degradable resin, or may be formed of different degradable resins.
在本发明的一种实施方式中,材料中相邻结构层的结晶度相差0.1-72%,例如但不限于,0.1-1%、0.2-2.5%、0.3-1.8%、2-10%、3-70%、4-15%、5-17%、8-40%、9-19%、10-22%、13-60%、0.5-20%、0.1-70%等。In one embodiment of the present invention, the crystallinity of adjacent structural layers in the material differs by 0.1-72%, such as, but not limited to, 0.1-1%, 0.2-2.5%, 0.3-1.8%, 2-10%, 3-70%, 4-15%, 5-17%, 8-40%, 9-19%, 10-22%, 13-60%, 0.5-20%, 0.1-70%, etc.
在本发明的一种实施方式中,材料纵切面的高度一般在10微米-50厘米,其中所含的结构层的层数不限。In an embodiment of the present invention, the height of the longitudinal section of the material is generally 10 micrometers to 50 centimeters, and the number of structural layers contained therein is not limited.
如本发明所用,“可降解树脂”是指具有水解性官能基团的高分子材料, 所述水解性官能基团选自下述的一种或两种以上:酯基、酰胺基、羟基、羧基、酸酐和氨基甲酸酯基。As used in the present invention, "degradable resin" refers to a polymer material having a hydrolyzable functional group, and the hydrolyzable functional group is selected from one or more of the following: ester group, amide group, hydroxyl group, Carboxyl, anhydride and carbamate groups.
在本发明的一些实施方式中,所述可降解树脂选自脂肪族聚酯、聚羟基酯醚、聚羟基烷酸酯、聚酐、聚氨基酸、聚氧化乙烯、聚磷腈、聚醚酯、聚酰胺酯、聚酰胺、磺化聚酯、热塑性聚酯弹性体或热塑性聚氨酯弹性体中的任一种或任意共聚物、混合物、衍生物或组合。In some embodiments of the present invention, the degradable resin is selected from the group consisting of aliphatic polyester, polyhydroxyester ether, polyhydroxyalkanoate, polyanhydride, polyamino acid, polyethylene oxide, polyphosphazene, polyetherester, Any one or any copolymer, mixture, derivative or combination of polyamide ester, polyamide, sulfonated polyester, thermoplastic polyester elastomer or thermoplastic polyurethane elastomer.
所述脂肪族聚酯包括羟基羧酸类脂肪族聚酯、内酯类脂肪族聚酯、和二醇二羧酸类脂肪族聚酯中的至少一种。The aliphatic polyester includes at least one of hydroxycarboxylic acid-based aliphatic polyester, lactone-based aliphatic polyester, and glycol dicarboxylic acid-based aliphatic polyester.
在本发明的一些实施方式中,所述脂肪族聚酯选自羟基乙酸均聚物、羟基乙酸共聚物、聚乳酸及其共聚物、聚-ε-己内酯(简称PCL)、聚丁二酸乙二醇酯(简称PES)、聚丁二酸丁二醇酯(简称PBS)、聚己二酸-对苯二甲酸-丁二醇酯(简称PBAT)、聚丁二酸-对苯二甲酸-丁二醇酯(简称PBST)、聚丁二酸-己二酸-丁二醇酯(简称PBSA)、聚甲基乙撑碳酸酯(简称PPC)、聚羟基脂肪酸酯(简称PHA)、和聚己二酸乙二醇酯(简称PEA)中的至少一种。In some embodiments of the present invention, the aliphatic polyester is selected from glycolic acid homopolymers, glycolic acid copolymers, polylactic acid and its copolymers, poly-ε-caprolactone (PCL for short), polybutylene glycol Ethylene glycol ester (PES for short), polybutylene succinate (PBS for short), polybutylene adipate-terephthalate (PBAT), polysuccinic acid-terephthalate Formate-butylene glycol ester (referred to as PBST), polysuccinic acid-adipate-butylene glycol ester (referred to as PBSA), polymethyl ethylene carbonate (referred to as PPC), polyhydroxy fatty acid ester (referred to as PHA) , and at least one of polyethylene adipate (PEA for short).
在本发明的较佳实施方式中,所述脂肪族聚酯选自羟基乙酸均聚物或羟基乙酸共聚物。In a preferred embodiment of the present invention, the aliphatic polyester is selected from glycolic acid homopolymers or glycolic acid copolymers.
作为优选的技术方案,所述羟基乙酸共聚物中,羟基乙酸重复单元的比例可选择为10wt%以上,优选为50wt%以上,进一步优选为70wt%以上,更进一步优选为85wt%以上,最优选为90wt%以上。As a preferred technical solution, in the glycolic acid copolymer, the proportion of glycolic acid repeating units can be selected to be more than 10wt%, preferably more than 50wt%, more preferably more than 70wt%, still more preferably more than 85wt%, most preferably 90 wt% or more.
所述羟基乙酸共聚物中,除了羟基乙酸重复单元以外,还包含羟基羧酸类单元(例如,乳酸单元、3-羟基丙酸单元、3-羟基丁酸单元、4-羟基丁酸单元、6-羟基己酸单元等)、内酯类单元(例如,β-丙内酯单元、β-丁内酯单元、γ-丁内酯单元、ε-己内酯单元等)、碳酸酯类单元(例如,三亚甲基碳酸酯单元等)、和酰胺类单元(例如,ε-己内酰胺单元等)中的至少一种。The glycolic acid copolymer contains, in addition to glycolic acid repeating units, hydroxycarboxylic acid units (for example, lactic acid units, 3-hydroxypropionic acid units, 3-hydroxybutyric acid units, 4-hydroxybutyric acid units, 6 -Hydroxycaproic acid unit, etc.), lactone-based units (for example, β-propiolactone unit, β-butyrolactone unit, γ-butyrolactone unit, ε-caprolactone unit, etc.), carbonate-based units ( For example, at least one of trimethylene carbonate units, etc.), and amide-based units (eg, ε-caprolactam units, etc.).
作为优选的技术方案,所述羟基乙酸共聚物选自羟基乙酸-乳酸共聚物。As a preferred technical solution, the glycolic acid copolymer is selected from glycolic acid-lactic acid copolymers.
由于聚合物的结晶速率也会受分子量大小的影响,在相同条件下,结晶速率的不同往往会使得聚合物最终的结晶度也不尽相同。基于此,本发明材料中的各结构层可采用具有不同相对分子质量的可降解树脂(例如,羟基乙酸均聚物或羟基乙酸-乳酸共聚物)制成。Since the crystallization rate of the polymer is also affected by the size of the molecular weight, under the same conditions, different crystallization rates often lead to different final crystallinity of the polymers. Based on this, each structural layer in the material of the present invention can be made of degradable resins with different relative molecular weights (eg, glycolic acid homopolymer or glycolic acid-lactic acid copolymer).
另外,本发明材料中的各结构层也可以采用相同相对分子质量的可降解 树脂(例如,羟基乙酸均聚物或羟基乙酸-乳酸共聚物)制成。In addition, each structural layer in the material of the present invention can also be made of a degradable resin (for example, glycolic acid homopolymer or glycolic acid-lactic acid copolymer) of the same relative molecular mass.
本发明中使用的羟基乙酸均聚物的相对分子质量可选择为1000-100万,优选为2万-60万,更优选为3万-40万,最优选为4万-30万;使用的羟基乙酸-乳酸共聚物的相对分子质量可选择为1000-30万,优选为1万-20万,更优选为2万-15万。The relative molecular mass of the glycolic acid homopolymer used in the present invention can be selected to be 10-1 million, preferably 20,000-600,000, more preferably 30,000-400,000, most preferably 40,000-300,000; The relative molecular mass of the glycolic acid-lactic acid copolymer can be selected to be 10,000-300,000, preferably 10,000-200,000, and more preferably 20,000-150,000.
可以使用本发明的常规技术手段控制可降解树脂形成的结构层的结晶度,例如但不限于,通过调控在形成各结构层时所对应的能够影响结晶的工艺条件(例如,冷却温度、降温速率、拉伸应力等)来实现。例如但不限于,采用可降解树脂(例如,羟基乙酸均聚物),以现有的挤出成型、压延成型或吹塑成型等成型方法,控制冷却温度为0-230℃,降温速率为0.1-80℃/min,分别加工出结晶度不同的结构层A、B、C、D,使A层的结晶度为约70%,B层的结晶度为约62%,C层的结晶度为约56%,D层的结晶度为约41%等。The crystallinity of the structural layer formed by the degradable resin can be controlled using the conventional technical means of the present invention, for example, but not limited to, by adjusting the corresponding process conditions (for example, cooling temperature, cooling rate) that can affect the crystallization when forming each structural layer. , tensile stress, etc.) to achieve. For example, but not limited to, using degradable resin (for example, glycolic acid homopolymer), with existing extrusion molding, calendering molding or blow molding and other molding methods, the cooling temperature is controlled to be 0-230 ° C, and the cooling rate is 0.1 -80°C/min, the structural layers A, B, C and D with different crystallinity are processed respectively, so that the crystallinity of the A layer is about 70%, the crystallinity of the B layer is about 62%, and the crystallinity of the C layer is about 56%, the crystallinity of the D layer is about 41% and so on.
如本发明所用,“结晶度”是指聚合物中结晶区域所占的比例,可以采用密度法或热分析法测定。例如可采用DSC法来测量各层的结晶度,即通过试样晶区熔融吸收的热量与完全结晶试样或已知结晶度的标准试样的熔融热之比来计算试样的结晶度。此为本领域常规的测试方法,在此不再赘述。As used in the present invention, "crystallinity" refers to the proportion of crystalline regions in a polymer, which can be determined by density method or thermal analysis method. For example, the DSC method can be used to measure the crystallinity of each layer, that is, the crystallinity of the sample can be calculated by the ratio of the heat absorbed by the melting of the sample crystal region to the heat of fusion of a fully crystallized sample or a standard sample with known crystallinity. This is a conventional testing method in the field, and will not be repeated here.
本发明提供的材料的各结构层之间有接合层,以使结构层连接,在进行模压成型后使各层复合在一起,从而使本发明提供的材料为一整体。There are bonding layers between the structural layers of the material provided by the present invention, so that the structural layers are connected, and the layers are compounded together after compression molding, so that the material provided by the present invention is integrated.
本发明提供的材料中的接合层也使用可降解树脂形成,可以采用与结构层相同的或不同的可降解树脂,优选采用同与之相邻的结构层之一相同的可降解树脂。The bonding layer in the material provided by the present invention is also formed using degradable resin, which can be the same or different degradable resin as that of the structural layer, preferably the same degradable resin as one of the adjacent structural layers.
本发明提供的材料中的接合层的结晶度和与之相邻的结构层之一的结晶度的差异可在0-72%,例如但不限于,0.1-1%、0.2-2.5%、0.3-1.8%、2-10%、3-70%、4-15%、5-17%、8-40%、9-19%、10-22%、13-60%、0.5-20%、0.1-70%等。作为优选的实施方式,一般使接合层的结晶度同与之相邻的结构层之一的结晶度的差异不超过10%。The crystallinity of the bonding layer in the material provided by the present invention and the crystallinity of one of the adjacent structural layers may differ by 0-72%, such as, but not limited to, 0.1-1%, 0.2-2.5%, 0.3 -1.8%, 2-10%, 3-70%, 4-15%, 5-17%, 8-40%, 9-19%, 10-22%, 13-60%, 0.5-20%, 0.1 -70% etc. As a preferred embodiment, the difference between the crystallinity of the bonding layer and the crystallinity of one of the adjacent structural layers is generally not more than 10%.
在本发明的一种实施方式中,向相邻两结构层之间注入可降解树脂的熔体,冷却后形成接合层。In one embodiment of the present invention, a melt of degradable resin is injected between two adjacent structural layers, and a bonding layer is formed after cooling.
如本发明所用,“熔体”是指聚合物处于流动温度或熔点和分解温度之间,克服了分子间的作用力而可以移动的一种状态。As used in the present invention, "melt" refers to a state in which a polymer is between the flow temperature or melting point and the decomposition temperature, and can move against intermolecular forces.
本发明提供的材料中的接合层可以和与其相邻的两结构层表面完全贴合, 也可以分散在相邻的结构层表面,只要能够使结构层连接即可。在本发明的一种优选实施方式中,接合层的横截面积为与之相邻的结构层表面积的30%以上,更优选为70%以上,最优选为90%以上。The bonding layer in the material provided by the present invention can be completely attached to the surfaces of the two adjacent structural layers, or can be dispersed on the surfaces of the adjacent structural layers, as long as the structural layers can be connected. In a preferred embodiment of the present invention, the cross-sectional area of the bonding layer is 30% or more of the surface area of the adjacent structural layer, more preferably 70% or more, and most preferably 90% or more.
作为优选的技术方案,本发明提供的材料中的接合层可选择为和与其相邻的两结构层表面完全贴合,在此情况下,所述接合层与结构层之间并不存在足以影响整个材料物理和/或化学性质的区别特性。As a preferred technical solution, the bonding layer in the material provided by the present invention can be selected to be in complete contact with the surfaces of the two adjacent structural layers. In this case, there is no sufficient influence between the bonding layer and the structural layer. Distinguishing properties of the physical and/or chemical properties of an entire material.
基于上述优选的技术方案,在本发明的一种实施方式中,各结构层以及相邻两结构层之间的接合层可采用相同的可降解树脂制成,在此情况下,所述接合层与结构层可具有基本相同的特性,两者之间并无本质区别。针对上述情况,下面参照附图2来做进一步说明:Based on the above preferred technical solution, in an embodiment of the present invention, each structural layer and the bonding layer between two adjacent structural layers can be made of the same degradable resin. In this case, the bonding layer The structural layer may have substantially the same properties, with no essential difference between the two. In view of the above situation, further description is made below with reference to accompanying drawing 2:
附图2所示的可降解高分子材料具有多层结构,结构层A、B、C、D和接合层E、F、G可采用例如羟基乙酸均聚物制成,所制得的结构层A的结晶度可为例如约70%,结构层B的结晶度可为例如约62%,结构层C的结晶度可为例如约56%,结构层C的结晶度可为例如约41%。接合层E、F、G可分别具有和与之相邻两结构层中的一者相同或不同的结晶度。在此,举例对接合层E的结晶度的情形进行说明:The degradable polymer material shown in Figure 2 has a multi-layer structure, and the structural layers A, B, C, D and the bonding layers E, F, and G can be made of, for example, glycolic acid homopolymers. The prepared structural layers The crystallinity of A may be, for example, about 70%, the crystallinity of structure layer B may be, for example, about 62%, the crystallinity of structure layer C may be, for example, about 56%, and the crystallinity of structure layer C may be, for example, about 41%. The bonding layers E, F, G may respectively have the same or different crystallinity than one of the two adjacent structural layers. Here, the case of the crystallinity of the bonding layer E will be described as an example:
例如,第一种情形:接合层E的结晶度可以与结构层A相同,这时接合层E相当于归属于结构层A,即接合层E可被看作是结构层A的一部分;For example, in the first case: the crystallinity of the bonding layer E can be the same as that of the structural layer A, then the bonding layer E is equivalent to belonging to the structural layer A, that is, the bonding layer E can be regarded as a part of the structural layer A;
例如,第二种情形:接合层E的结晶度可以与结构层B相同,这时接合层E相当于归属于结构层B,即接合层E可被看作是结构层B的一部分;For example, in the second case: the crystallinity of the bonding layer E can be the same as that of the structural layer B, then the bonding layer E is equivalent to belonging to the structural layer B, that is, the bonding layer E can be regarded as a part of the structural layer B;
例如,第三种情形:接合层E的结晶度与结构层A、B均不相同,这时接合层E相当于自身成为一个结构层,即接合层E可被看作是一个与结构层A、B在整个可降解高分子材料的结构上具有等同地位的结构层E。For example, in the third case: the crystallinity of the bonding layer E is different from that of the structural layers A and B. At this time, the bonding layer E is equivalent to becoming a structural layer by itself, that is, the bonding layer E can be regarded as a , B has an equivalent structural layer E on the structure of the entire degradable polymer material.
上述有关接合层E的结晶度情形的说明,同样适用于接合层F、G。The above description regarding the crystallinity of the bonding layer E applies to the bonding layers F and G in the same way.
本发明提供的材料中各层(如结构层与结构层之间、接合层与接合层之间、或结构层与接合层之间)的厚度可以相同,也可以不同。优选各层厚度相同。The thickness of each layer (eg, between structural layers, between bonding layers, or between structural layers and bonding layers) in the material provided by the present invention may be the same or different. Preferably the thickness of each layer is the same.
本发明提供的材料中的各层(包括结构层和接合层)可具有规则的形状,也可具有不规则的形状(例如,中间厚、周边薄的形状或者中间薄、周边厚的形状或者具有类似波浪形横截面的形状等)。各层(如结构层与结构层之间、接合层与接合层之间、或结构层与接合层之间)的形状可以相同,也可以不同;优选各层形状相同。Each layer (including the structural layer and the bonding layer) in the material provided by the present invention may have a regular shape or an irregular shape (for example, a shape with a thick middle and a thin perimeter or a shape with a thin middle and a thick perimeter, or a shape with shape like a wavy cross-section, etc.). The shapes of each layer (eg, between the structural layer and the structural layer, between the bonding layer and the bonding layer, or between the structural layer and the bonding layer) can be the same or different; preferably the shapes of the layers are the same.
本发明提供的材料中的各层(包括结构层和接合层)的分子量可以相同,也可以不同。The molecular weight of each layer (including the structural layer and the bonding layer) in the material provided by the present invention may be the same or different.
本发明提供的材料可以通过下述步骤制备得到:The material provided by the present invention can be prepared by the following steps:
第一步,使可降解树脂形成具有一定结晶度的结构层;The first step is to make the degradable resin form a structural layer with a certain degree of crystallinity;
第二步,在堆叠后相邻的结构层之间注入可降解树脂的熔体,然后模压成型得到本发明提供的材料。In the second step, the melt of degradable resin is injected between adjacent structural layers after stacking, and then the material provided by the present invention is obtained by compression molding.
在上述第一步中,可通过本领域熟知的挤出成型、压延成型或吹塑成型等成型方法,分别加工出结晶度不同的结构层。In the first step above, structural layers with different degrees of crystallinity can be separately processed by molding methods such as extrusion molding, calendering molding, or blow molding well-known in the art.
在本发明的一种实施方式中,例如,针对羟基乙酸聚合物,可以采用压延成型方法,控制冷却温度为0-230℃,降温速率为0.1-80℃/min,形成结晶度为约25-72%的结构层。In one embodiment of the present invention, for example, for glycolic acid polymer, a calendering molding method can be used, and the cooling temperature is controlled to be 0-230° C., and the cooling rate is 0.1-80° C./min, forming a crystallinity of about 25-230° C. 72% structural layers.
在上述第二步中,可以采用任意摆放的方式堆叠结构层。在本发明的一种实施方式中,通过引模件将结构层由下而上依次堆叠。所述引模件包括引模件本体,该引模件本体上开设有用于引导和定位各层材料的槽和/或孔。关于槽和/或孔的形状、尺寸、位置以及数量的选择并无特殊要求,只需满足各层材料的均匀堆叠即可。In the above second step, the structural layers may be stacked in any manner. In an embodiment of the present invention, the structural layers are sequentially stacked from bottom to top by means of lead-in parts. The lead mold part includes a lead mold part body, and the lead mold part body is provided with grooves and/or holes for guiding and positioning each layer of material. There are no special requirements on the selection of the shape, size, position and number of the grooves and/or holes, as long as the uniform stacking of each layer of material is sufficient.
在本发明的一种实施方式中,上述第二步中将可降解树脂的熔体的注入时间控制在2-40秒,随后进行模压成型。所述的模压成型的工艺条件可以为:预热时间为2-10分钟,模压时间为2-15分钟,模压温度:0-260℃,优选为100-250℃,最优选为210-240℃;模压压力为0.5-2MPa;冷却时间为2-4分钟,冷却温度:0-230℃,优选为10-150℃,最优选为30-120℃。In an embodiment of the present invention, in the second step above, the injection time of the melt of the degradable resin is controlled to be 2-40 seconds, and then compression molding is performed. The process conditions of the compression molding can be: preheating time is 2-10 minutes, molding time is 2-15 minutes, molding temperature: 0-260°C, preferably 100-250°C, most preferably 210-240°C ; The molding pressure is 0.5-2MPa; the cooling time is 2-4 minutes, and the cooling temperature is 0-230°C, preferably 10-150°C, and most preferably 30-120°C.
在本发明的一种优选实施方式中,熔体的质量注入速率可以控制为约1-10克/秒。In a preferred embodiment of the present invention, the mass injection rate of the melt can be controlled to be about 1-10 grams per second.
上述第二步可选用以下两种方式:The second step above can be done in the following two ways:
第一种方式:当堆叠的结构层在3个以上时,在所有相邻两结构层之间都注入可降解树脂的熔体后,在一种工艺条件下进行模压成型,所获各接合层的结晶度相同或相近。The first way: when there are more than 3 stacked structural layers, after injecting the melt of degradable resin between all two adjacent structural layers, press molding is performed under one process condition, and each bonding layer is obtained. The crystallinity is the same or similar.
第二种方式:当希望所获材料的结构层在3个以上时,先向两个相邻的结构层之间注入可降解树脂的熔体,采用一定工艺进行模压成型,获得相应结晶度的接合层,然后在其中一个结构层上堆叠另一结构层,在新形成的相 邻结构层之间注入可降解树脂的熔体,采用改变的或不改变的工艺进行模压成型,获得相应结晶度的接合层。依此类推。这种方式可以获得结晶度差异比较大的各接合层。The second way: when it is desired to obtain more than 3 structural layers of the material, first inject a melt of degradable resin between two adjacent structural layers, and use a certain process for molding to obtain the corresponding crystallinity. Bonding layers, and then stacking another structural layer on one of the structural layers, injecting a melt of degradable resin between the newly formed adjacent structural layers, and using a modified or unchanged process for compression molding to obtain the corresponding crystallinity the bonding layer. So on and so forth. In this way, each bonding layer with a relatively large difference in crystallinity can be obtained.
本发明提供的材料可通过切削、开孔、切割等机械加工,制成具有所需形状的型材,包括但不限于板材、片材、棒材、带状型材、条状型材、盘状型材、丝材等,也可被制成横截面类似于树木年轮形貌的卷材,还可被制成上述两种型材相复合的结构,例如,在卷材(例如,其具有类似于树木年轮形貌的横截面)的同心圆的圆心处可预留或预设中空腔,在该中空腔中可镶嵌多层片材,以制得片材与卷材相复合的结构,见图1。还可被制成阻隔膜、包装膜、地膜等薄膜。The materials provided by the present invention can be processed by machining such as cutting, drilling, cutting, etc. to form profiles with desired shapes, including but not limited to plates, sheets, bars, strip profiles, strip profiles, disc profiles, Wire, etc., can also be made into a coil with a cross-section similar to the shape of tree rings, and can also be made into a composite structure of the above two profiles, for example, in a coil (for example, it has a shape similar to that of tree years. A hollow cavity can be reserved or preset at the center of the concentric circles of the cross-section of the wheel profile, and multilayer sheets can be embedded in the hollow cavity to obtain a composite structure of sheets and rolls, see Figure 1 . It can also be made into films such as barrier films, packaging films, and mulching films.
本发明提到的上述特征,或实施例提到的特征可以任意组合。本案说明书所揭示的所有特征可与任何组合物形式并用,只要这些特征的组合不存在矛盾,所有可能的组合都应当认为是本说明书记载的范围。说明书中所揭示的各个特征,可以任何可提供相同、均等或相似目的的替代性特征取代。因此除有特别说明,所揭示的特征仅为均等或相似特征的一般性例子。The above features mentioned in the present invention or the features mentioned in the embodiments can be combined arbitrarily. All the features disclosed in this specification can be used in combination with any combination, and as long as there is no contradiction in the combination of these features, all possible combinations should be considered within the scope of this specification. Each feature disclosed in the specification may be replaced by any alternative feature serving the same, equivalent or similar purpose. Therefore, unless otherwise stated, the disclosed features are only general examples of equivalent or similar features.
本发明的主要优点在于:The main advantages of the present invention are:
1、本发明提供的材料断裂伸长率、冲击强度可得到显著提高。1. The elongation at break and impact strength of the material provided by the present invention can be significantly improved.
2、本发明提供的材料能够较为容易地对材料的降解速度进行有效调控,并且可实现对降解时间较为准确地控制。2. The material provided by the present invention can easily and effectively control the degradation rate of the material, and can control the degradation time more accurately.
3、本发明可通过调节各层的结晶度以实现对最终材料热变形温度的调控,无需添加例如热稳定剂、抗氧剂、耐热无机填料等助剂,即可实现对最终材料耐热性的灵活调控。3. The present invention can control the heat deformation temperature of the final material by adjusting the crystallinity of each layer, without adding additives such as heat stabilizers, antioxidants, heat-resistant inorganic fillers, etc., to achieve heat resistance to the final material. Sexual flexibility.
下面将结合具体实施方案对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施方案仅仅是本发明一部分实施方案,而不是全部的实施方案。本实施方案以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施方案。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施方案,都 属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and provides a detailed implementation manner and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。例如,“从1至10的范围”应理解为表示在约1和约10之间连续的每个和各个可能的数字。因此,即使该范围内的具体数据点或甚至该范围内没有数据点被明确确定或仅指代少量具体点,也应理解为该范围内的任何和所有数据点均被认为已进行明确说明。在本文中,采用术语“约”来修饰数值时,表示该数值±5%以内测量的误差容限。The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein. For example, "a range from 1 to 10" should be understood to mean every and every possible number consecutively between about 1 and about 10. Thus, even if a specific data point within a range, or even no data point within the range is specifically identified or refers only to a small number of specific points, it should be understood that any and all data points within the range are considered to be specifically stated. As used herein, when the term "about" is used to modify a numerical value, it means a tolerance for error of measurement within ±5% of the numerical value.
下面通过具体实施例对本发明技术方案进一步进行阐述,本发明若无特殊说明,所用原料均为市售产品。The technical solution of the present invention is further described below through specific examples. Unless otherwise specified in the present invention, the raw materials used are all commercially available products.
下述实施例中涉及的降解性测试方法采用以下测试方法对试样材料(可采用机加工,将待测材料加工成长20mm×高20mm×宽20mm的试样以进行降解实验)的降解性进行测试。The degradability test method involved in the following examples adopts the following test method to test the degradability of the sample material (machining can be used, and the material to be tested can be processed into a sample with a length of 20 mm × height 20 mm × width 20 mm for degradation test). test.
降解性测试方法:Degradability test method:
步骤1):取3个试样,称量,记录初始质量为M
0,随后置于恒温干燥箱中,于60℃下干燥24小时;
Step 1): take 3 samples, weigh them, record the initial mass as M 0 , then place them in a constant temperature drying oven, and dry them at 60° C. for 24 hours;
步骤2):将干燥后的3个试样分别置于盛装有75℃清水的3个烧杯中,并使每个试样完全浸没在清水中,然后将3个烧杯分别置于3个规格相同的恒温恒湿试验箱(温度设定为75℃)中;Step 2): Place the 3 dried samples in 3 beakers containing 75°C clean water, and immerse each sample completely in the clean water, and then place the 3 beakers in 3 same specifications. in the constant temperature and humidity test chamber (the temperature is set to 75 ℃);
步骤3):每间隔一段时间,分别取出3个恒温恒湿试验箱中的试样,用蒸馏水清洗干净,并放入恒温干燥箱中,于105℃下烘干2小时后称重,记录剩余质量为M’,随后再将试样分别置于相应的烧杯中,继续进行降解实验;Step 3): at intervals, take out the samples in 3 constant temperature and humidity test chambers, wash them with distilled water, put them in a constant temperature drying chamber, dry them at 105°C for 2 hours and weigh them, and record the remaining samples. The mass is M', and then the samples are placed in the corresponding beakers to continue the degradation experiment;
步骤4):计算降解率R
d,计算公式如下:
Step 4): Calculate the degradation rate R d , the calculation formula is as follows:
R
d=(M
0-M’)/M
0×100%。
R d =(M 0 -M')/M 0 ×100%.
待计算所得降解率R
d达到95%以上,停止实验。
When the calculated degradation rate R d reaches more than 95%, the experiment is stopped.
注:步骤3)中有关取样间隔时间段的选择,在降解实验初期阶段,取 样的间隔时间可以长一些(例如,间隔4小时,或6小时等),待到降解实验中后期,可适当缩短间隔时间(例如,间隔2小时,间隔1小时,或间隔30分钟等)。Note: Regarding the selection of sampling interval in step 3), in the initial stage of the degradation experiment, the sampling interval can be longer (for example, the interval is 4 hours, or 6 hours, etc.), and it can be appropriately shortened in the middle and late stages of the degradation experiment Interval time (eg, 2 hour interval, 1 hour interval, or 30 minute interval, etc.).
另外,在步骤3)中,针对烧杯中试样的原始形状已基本消失的情况,可采用以下方式来进行质量测量:In addition, in step 3), for the situation that the original shape of the sample in the beaker has basically disappeared, the following methods can be used to measure the quality:
取出恒温恒湿试验箱中的烧杯,静置,然后抽取上层清液以分离剩余固相,并将分离的剩余固相用蒸馏水清洗干净,随后放入恒温干燥箱中,于105℃下烘干2小时后称重,记录剩余固相质量为M’。Take out the beaker in the constant temperature and humidity test box, let it stand, and then extract the supernatant to separate the remaining solid phase, wash the separated remaining solid phase with distilled water, and then put it into a constant temperature drying box and dry it at 105 ° C Weigh after 2 hours and record the remaining solid phase mass as M'.
下述实施例中涉及的热变形温度测试依据GB/T 1633-2000,采用热变形温度-维卡软化点测定仪来测试材料的热变形温度。The heat deformation temperature test involved in the following examples is based on GB/T 1633-2000, and the heat deformation temperature-Vicat softening point tester is used to test the heat deformation temperature of the material.
测试所采用的试样为截面为矩形的长条,试样表面平整光滑,无气泡,无锯切痕迹或裂痕等缺陷。待测材料试样的尺寸为:长120mm×高15mm×宽10mm。The sample used in the test is a long strip with a rectangular cross-section. The surface of the sample is flat and smooth, without bubbles, sawing marks or cracks and other defects. The size of the material sample to be tested is: length 120mm × height 15mm × width 10mm.
测试所采用的传热介质为甲基硅油,升温速度控制为120℃/小时,两试样支架的中心距离为100mm,在支架的中点对试样施加垂直负载,负载杆的压头与试样接触部分为半圆形,其半径为(3±0.2)mm,实验过程中,试样受载后的最大弯曲正应力为4.6kg/cm
2。
The heat transfer medium used in the test is methyl silicone oil, the heating rate is controlled at 120 °C/hour, the center distance between the two sample supports is 100 mm, and a vertical load is applied to the sample at the midpoint of the support. The contact part of the sample is a semicircle with a radius of (3±0.2) mm. During the experiment, the maximum bending normal stress of the sample after being loaded is 4.6kg/cm 2 .
实施例1Example 1
使用相对分子质量24.3万的羟基乙酸均聚物采用压延成型方法,控制冷却温度为130℃,降温速率为1℃/min,可以得到结晶度为约70%的结构层A,使用相对分子质量24.3万的羟基乙酸均聚物采用挤出成型方法,控制冷却温度为100℃,降温速率为3℃/min,可以得到结晶度为约62%的结构层B,使用相对分子质量24.3万的羟基乙酸均聚物采用压延成型方法,控制冷却温度为90℃,降温速率为10℃/min,可以得到结晶度为约56%的结构层C,使用相对分子质量24.3万的羟基乙酸均聚物采用挤出成型方法,控制冷却温度为80℃,降温速率为25℃/min,可以得到结晶度为约41%的结构层D;Using the glycolic acid homopolymer with a relative molecular mass of 243,000, using the calendering method, controlling the cooling temperature to 130 ° C and the cooling rate to 1 ° C/min, a structural layer A with a crystallinity of about 70% can be obtained. The relative molecular mass of 24.3 Wan's glycolic acid homopolymer adopts the extrusion molding method, and the cooling temperature is controlled to be 100 ° C and the cooling rate is 3 ° C/min, and the structural layer B with a crystallinity of about 62% can be obtained. The homopolymer adopts the calendering molding method, the cooling temperature is controlled to be 90 °C, and the cooling rate is 10 °C/min, and a structural layer C with a crystallinity of about 56% can be obtained. The molding method is used, and the cooling temperature is controlled to be 80 °C and the cooling rate is 25 °C/min, and a structural layer D with a crystallinity of about 41% can be obtained;
通过引模件堆叠结构层A和结构层B;向结构层A和B之间注入相对分子质量24.3万的羟基乙酸均聚物的熔体,随后采用工艺条件Ⅰ进行模压成型,获得结晶度为约65%的E层;The structural layer A and the structural layer B are stacked by the lead mold; the melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers A and B, and then the process condition I is used for compression molding, and the crystallinity is obtained. about 65% of the E layer;
通过引模件使结构层B上堆叠结构层C,然后向结构层B和C之间注入相对分子质量24.3万的羟基乙酸均聚物的熔体,随后采用工艺条件Ⅱ进行模压成型,获得结晶度为约60%的F层;The structural layer C is stacked on the structural layer B by the lead mold, and then a melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers B and C, and then the process condition II is used for compression molding to obtain crystals. degree of about 60% of the F layer;
通过引模件使结构层C上堆叠结构层D,然后向结构层C和D之间注入相对分子质量24.3万的羟基乙酸均聚物的熔体,随后采用工艺条件Ⅲ进行模压成型,获得结晶度为约42%的G层,并得到如图2所示的材料;The structural layer D is stacked on the structural layer C through the lead-molding part, and then the melt of glycolic acid homopolymer with a relative molecular mass of 243,000 is injected between the structural layers C and D, and then the process condition III is used for compression molding to obtain crystals. The degree of G layer is about 42%, and the material shown in Figure 2 is obtained;
其中,工艺条件Ⅰ、Ⅱ和Ⅲ如表1所示:Among them, the process conditions I, II and III are shown in Table 1:
表1Table 1
项目project | 预热时间Preheat time | 模压温度Molding temperature | 模压压力Molding pressure | 模压时间Molding time | 冷却温度cooling temperature |
工艺条件ⅠProcess conditions I | 5分钟5 minutes | 210℃210℃ | 1.2MPa1.2MPa | 6分钟6 minutes | 150℃150℃ |
工艺条件ⅡProcess condition II | 5分钟5 minutes | 210℃210℃ | 1.2MPa1.2MPa | 6分钟6 minutes | 136℃136℃ |
工艺条件ⅢProcess conditions Ⅲ | 5分钟5 minutes | 210℃210℃ | 1.2MPa1.2MPa | 6分钟6 minutes | 120℃120℃ |
实施例2Example 2
使用相对分子质量12.4万的羟基乙酸均聚物采用压延成型方法,控制冷却温度为150℃,降温速率为0.5℃/min,可以得到结晶度为约70%的结构层A,使用相对分子质量18.5万的羟基乙酸均聚物采用挤出成型方法,控制冷却温度为120℃,降温速率为2℃/min,可以得到结晶度为约62%的结构层B,使用相对分子质量24.3万的羟基乙酸均聚物采用压延成型方法,控制冷却温度为100℃,降温速率为10℃/min,可以得到结晶度为约56%的结构层C,使用相对分子质量29.6万的羟基乙酸均聚物采用挤出成型方法,控制冷却温度为75℃,降温速率为15℃/min,可以得到结晶度为约41%的结构层D;Using the glycolic acid homopolymer with a relative molecular mass of 124,000, the calendering method is used, the cooling temperature is controlled to 150 ° C, and the cooling rate is 0.5 ° C/min, and a structural layer A with a crystallinity of about 70% can be obtained. The relative molecular mass of 18.5 Wan's glycolic acid homopolymer adopts the extrusion molding method, the cooling temperature is controlled to 120°C, and the cooling rate is 2°C/min, and the structural layer B with a crystallinity of about 62% can be obtained. The homopolymer adopts the calendering method, the cooling temperature is controlled to be 100 °C, and the cooling rate is 10 °C/min, and a structural layer C with a crystallinity of about 56% can be obtained. A molding method is developed, the cooling temperature is controlled to be 75°C, and the cooling rate is 15°C/min, and a structural layer D with a crystallinity of about 41% can be obtained;
通过引模件堆叠结构层A和结构层B;向结构层A和B之间注入相对分子质量15.6万的羟基乙酸均聚物的熔体,随后采用实施例1中的工艺条件Ⅰ进行模压成型,获得结晶度为约65%的E层;The structural layer A and the structural layer B are stacked by the lead-molding member; the melt of glycolic acid homopolymer with a relative molecular mass of 156,000 is injected between the structural layers A and B, and then the process conditions I in Example 1 are used for molding. , obtaining an E layer with a crystallinity of about 65%;
通过引模件使结构层B上堆叠结构层C,然后向结构层B和C之间注入相对分子质量20.1万的羟基乙酸均聚物的熔体,随后采用实施例1中的工艺条件Ⅱ进行模压成型,获得结晶度为约60%的F层;The structural layer C is stacked on the structural layer B through the lead-in part, and then a melt of glycolic acid homopolymer with a relative molecular mass of 201,000 is injected between the structural layers B and C, and then the process conditions II in Example 1 are used to carry out the process. Compression molding to obtain an F layer with a crystallinity of about 60%;
通过引模件使结构层C上堆叠结构层D,然后向结构层C和D之间注入相对分子质量27.5万的羟基乙酸均聚物的熔体,随后采用实施例1中的工艺 条件Ⅲ进行模压成型,获得结晶度为约42%的G层,并得到如图2所示的材料。The structural layer D is stacked on the structural layer C through the lead-in, and then a melt of glycolic acid homopolymer with a relative molecular mass of 275,000 is injected between the structural layers C and D, and then the process condition III in Example 1 is used to carry out the process. Compression molding yielded a G layer with a crystallinity of about 42% and a material as shown in Figure 2 was obtained.
实施例3Example 3
使用相对分子质量24.3万的羟基乙酸均聚物,参照实施例1中获得结构层A的工艺得到结晶度约70%的单层材料,其厚度与实施例1或2获得的如图2所示材料相同。Using glycolic acid homopolymer with a relative molecular mass of 243,000, referring to the process of obtaining structural layer A in Example 1, a single-layer material with a crystallinity of about 70% was obtained, and its thickness was the same as that obtained in Example 1 or 2, as shown in Figure 2 Materials are the same.
依据GB/T 1042方法分别对实施例1和2获得的如图2所示材料及上述获得的单层材料进行材料断裂伸长率的测试。According to the GB/T 1042 method, the material shown in Figure 2 obtained in Examples 1 and 2 and the single-layer material obtained above were tested for the material elongation at break.
依据GB/T 1043方法分别对实施例1和2获得的如图2所示材料及上述获得的单层材料进行材料冲击强度的测试。According to the GB/T 1043 method, the material shown in Figure 2 obtained in Examples 1 and 2 and the single-layer material obtained above were tested for material impact strength.
结果如表2和3所示。The results are shown in Tables 2 and 3.
表2Table 2
表3table 3
实施例4Example 4
使用相对分子质量16.8万的羟基乙酸均聚物,采用与实施例1类似的方法得到如图3所示的材料,其中具有结构层A、结构层B和结构层C,以及接合层E和F。Using a glycolic acid homopolymer with a relative molecular mass of 168,000, a method similar to Example 1 was used to obtain the material shown in Figure 3, which has structural layer A, structural layer B and structural layer C, and bonding layers E and F .
采用降解性测试方法对以实施例4方法获得的各个材料以及对比例1和2进行测试。结果见表4。Each material obtained by the method of Example 4 and Comparative Examples 1 and 2 were tested using the degradability test method. The results are shown in Table 4.
表4Table 4
注:表4中的对比例1为C层单层材料(不含有多层结构),对比例2为添加有水解促进剂(草酸二甲酯)的C层单层材料(水解促进剂的添加量为约0.8wt%)。Note: Comparative Example 1 in Table 4 is a C-layer single-layer material (without multi-layer structure), and Comparative Example 2 is a C-layer single-layer material with a hydrolysis accelerator (dimethyl oxalate) added (addition of a hydrolysis accelerator) amount is about 0.8 wt%).
对比例1和2的材料厚度与示例1-1至6的材料厚度相同。The material thicknesses of Comparative Examples 1 and 2 were the same as those of Examples 1-1 to 6.
结果表明,相比于对比例1,示例1-1、1-2和1-3材料的降解速度均快于对比例1,这可能是由于示例1-1至1-3的材料因具有不同结晶度的多层结构,结晶度较低的一层往往会先于结晶度较高的一层发生程度更大的降解,而且结晶度较低的一层在降解过程中,可能会促进水向结晶度较高的一层中渗透,从而有利于加速结晶度较高的一层的降解。因此,在宏观表现上,具有多层结构(相邻两层结晶度不同)的示例1-1、1-2和1-3材料的降解速度要显著快于仅为单层结构的对比例1材料。The results show that, compared with Comparative Example 1, the degradation rates of the materials of Examples 1-1, 1-2 and 1-3 are all faster than those of Comparative Example 1, which may be due to the different materials of Examples 1-1 to 1-3. In the multi-layer structure of crystallinity, the layer with lower crystallinity tends to degrade to a greater extent before the layer with higher crystallinity, and the layer with lower crystallinity may promote water migration during the degradation process. The layer with higher crystallinity penetrates into the layer with higher crystallinity, which is beneficial to accelerate the degradation of the layer with higher crystallinity. Therefore, in terms of macroscopic performance, the materials of Examples 1-1, 1-2, and 1-3 with a multi-layer structure (the crystallinity of two adjacent layers are different) degrade significantly faster than that of Comparative Example 1, which has only a single-layer structure. Material.
对比例2相对于对比例1,添加了可促进材料降解的水解促进剂(例如, 草酸二甲酯),由表3的数据可知,虽然水解促进剂的使用可有效加快材料的降解,但是其降解速度并不稳定,3个试样在75℃水中降解率达到95%以上所需的时间相差较大,最大可相差约20.2小时,最小也要相差约9.4小时,这并不利于对材料实现降解时间的准确控制。不同于对比例2,示例1-1材料的降解速度较为稳定,3个试样在75℃水中降解率达到95%以上所需的时间相差不超过4小时。示例1-2和1-3材料同样如此。Compared with Comparative Example 1, Comparative Example 2 added a hydrolysis accelerator (for example, dimethyl oxalate) that can promote the degradation of the material. It can be seen from the data in Table 3 that although the use of the hydrolysis accelerator can effectively accelerate the degradation of the material, its The degradation rate is not stable. The time required for the three samples to reach a degradation rate of more than 95% in water at 75°C differs greatly. The maximum difference is about 20.2 hours, and the minimum difference is about 9.4 hours. This is not conducive to the realization of the material. Accurate control of degradation time. Different from Comparative Example 2, the degradation rate of the material in Example 1-1 is relatively stable, and the time required for the three samples to reach a degradation rate of more than 95% in water at 75°C differs by no more than 4 hours. The same is true for the materials of Examples 1-2 and 1-3.
示例2-6说明本发明可通过控制各层结晶度的不同,来实现对最终材料的降解性的调控,而且各示例的三个试样所对应的降解时间的差值均不超过4小时,这也可以说明本发明对材料的降解性可实现较为准确的调控。Examples 2-6 illustrate that the present invention can control the degradability of the final material by controlling the difference in the crystallinity of each layer, and the difference between the degradation times corresponding to the three samples in each example is not more than 4 hours, This can also indicate that the present invention can achieve relatively accurate regulation of the degradability of the material.
实施例5Example 5
采用与实施例1类似的方法得到如图4所示的材料,其中具有结构层A和结构层B,以及接合层E。The material shown in FIG. 4 is obtained by a method similar to that of Example 1, which has the structural layer A and the structural layer B, and the bonding layer E.
采用降解性测试方法对以实施例5方法获得的各个材料进行测试。结果见表5,其中示例7-1和示例7-2中的结构层A和接合层E为羟基乙酸-乳酸共聚物(分子量为约16.8万),结构层B为羟基乙酸均聚物(分子量为约8.5万);示例8中的结构层A和B、接合层E均为羟基乙酸-乳酸共聚物(分子量为约8.5万)。Each material obtained by the method of Example 5 was tested using the degradability test method. The results are shown in Table 5, wherein the structural layer A and the bonding layer E in Examples 7-1 and 7-2 are glycolic acid-lactic acid copolymers (molecular weight is about 168,000), and structural layer B is glycolic acid homopolymer (molecular weight is about 168,000). is about 85,000); the structural layers A and B and the bonding layer E in Example 8 are both glycolic acid-lactic acid copolymers (molecular weight is about 85,000).
表5table 5
示例7-1、7-2和8说明本发明可通过控制各层结晶度的不同,来实现对最终材料的降解性的调控,而且各示例的三个试样所对应的降解时间的差值均不超过4小时,说明本发明对材料的降解性可实现较为准确的调控。Examples 7-1, 7-2 and 8 illustrate that the present invention can control the degradability of the final material by controlling the difference in crystallinity of each layer, and the difference in degradation time corresponding to the three samples in each example It is not more than 4 hours, indicating that the present invention can achieve relatively accurate regulation of the degradability of the material.
实施例6Example 6
采用与实施例1类似的方法得到如图4所示的材料,其中具有结构层A和结构层B,以及接合层E。The material shown in FIG. 4 is obtained by a method similar to that of Example 1, which has the structural layer A and the structural layer B, and the bonding layer E.
采用热变形温度测试方法对以实施例6方法获得的各个材料进行测试。结果见表6,示例9-1至9-3中结构层A、B和接合层E均为乙醇酸均聚物(分子量为约21.4万)。Each material obtained by the method of Example 6 was tested using the heat deflection temperature test method. The results are shown in Table 6. In Examples 9-1 to 9-3, the structural layers A, B and the bonding layer E are all glycolic acid homopolymers (molecular weight is about 214,000).
表6Table 6
结果表明,针对本发明提供的材料,可通过调节各层的结晶度以实现对最终材料热变形温度的调控,进而可对最终材料的耐热性能进行有效的调控。The results show that, for the material provided by the present invention, the thermal deformation temperature of the final material can be regulated by adjusting the crystallinity of each layer, and then the heat resistance of the final material can be effectively regulated.
以上所述仅为本发明的较佳实施例而已,并非用以限定本发明的实质技术内容范围,本发明的实质技术内容是广义地定义于申请的权利要求范围中,任何他人完成的技术实体或方法,若是与申请的权利要求范围所定义的完全相同,也或是一种等效的变更,均将被视为涵盖于该权利要求范围之中。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of the essential technical content of the present invention. The essential technical content of the present invention is broadly defined within the scope of the claims of the application, and any technical entity completed by others Or method, if it is exactly the same as that defined in the scope of the claims of the application, or an equivalent change, it will be deemed to be covered by the scope of the claims.
Claims (10)
- 一种材料,其特征在于,所述材料含有至少两个结构层,且相邻结构层的结晶度不同;所述结构层由可降解树脂形成。A material, characterized in that the material contains at least two structural layers, and the crystallinity of adjacent structural layers is different; the structural layers are formed of degradable resin.
- 如权利要求1所述的材料,其特征在于,相邻结构层的结晶度相差0.1-72%。The material of claim 1, wherein the crystallinity of adjacent structural layers differs by 0.1-72%.
- 如权利要求1所述的材料,其特征在于,各结构层由相同或不同的可降解树脂形成。The material of claim 1, wherein each structural layer is formed of the same or different degradable resins.
- 如权利要求1所述的材料,其特征在于,所述可降解树脂具有水解性官能基团,所述水解性官能基团选自下述的一种或两种以上:酯基、酰胺基、羟基、羧基、酸酐和氨基甲酸酯基。The material according to claim 1, wherein the degradable resin has a hydrolyzable functional group, and the hydrolyzable functional group is selected from one or more of the following: ester group, amide group, Hydroxyl, carboxyl, anhydride and carbamate groups.
- 如权利要求1所述的材料,其特征在于,所述可降解树脂选自下述的一种或两种以上共聚物、混合物、衍生物或组合:脂肪族聚酯、聚羟基酯醚、聚羟基烷酸酯、聚酐、聚氨基酸、聚氧化乙烯、聚磷腈、聚醚酯、聚酰胺酯、聚酰胺、磺化聚酯、热塑性聚酯弹性体、热塑性聚酰胺弹性体、和热塑性聚氨酯弹性体。The material according to claim 1, wherein the degradable resin is selected from one or more of the following copolymers, mixtures, derivatives or combinations: aliphatic polyester, polyhydroxyester ether, poly Hydroxyalkanoates, polyanhydrides, polyamino acids, polyethylene oxides, polyphosphazenes, polyetheresters, polyesteramides, polyamides, sulfonated polyesters, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and thermoplastic polyurethanes Elastomer.
- 如权利要求5所述的材料,其特征在于,所述脂肪族聚酯选自下述的一种或两种以上:羟基乙酸均聚物、羟基乙酸共聚物、聚乳酸及其共聚物、聚-ε-己内酯、聚丁二酸乙二醇酯、聚丁二酸丁二醇酯、聚己二酸-对苯二甲酸-丁二醇酯、聚丁二酸-对苯二甲酸-丁二醇酯、聚丁二酸-己二酸-丁二醇酯、聚甲基乙撑碳酸酯、聚羟基脂肪酸酯、和聚己二酸乙二醇酯。The material according to claim 5, wherein the aliphatic polyester is selected from one or more of the following: glycolic acid homopolymer, glycolic acid copolymer, polylactic acid and its copolymers, polyglycolic acid -ε-caprolactone, polyethylene succinate, polybutylene succinate, polybutylene adipate-terephthalate, polysuccinate-terephthalate- Butylene glycol ester, polysuccinate-adipate-butylene glycol ester, polymethylethylene carbonate, polyhydroxy fatty acid ester, and polyethylene adipate.
- 如权利要求5所述的材料,其特征在于,所述脂肪族聚酯选自羟基乙酸均聚物或羟基乙酸共聚物。6. The material of claim 5, wherein the aliphatic polyester is selected from glycolic acid homopolymers or glycolic acid copolymers.
- 如权利要求1-7任一项所述的材料,其特征在于,所述材料还含有相邻 两个结构层之间的接合层。The material according to any one of claims 1-7, characterized in that, the material further comprises a bonding layer between two adjacent structural layers.
- 一种如权利要求1-8任一项所述的材料的制备方法,其特征在于,所述方法包括步骤:A method for preparing a material according to any one of claims 1-8, wherein the method comprises the steps of:(1)使可降解树脂形成结构层;(1) making the degradable resin form a structural layer;(2)在堆叠后相邻的结构层之间注入可降解树脂的熔体,然后模压成型形成如权利要求1-8任一项所述的材料。(2) The melt of degradable resin is injected between adjacent structural layers after stacking, and then the material according to any one of claims 1-8 is formed by compression molding.
- 一种如权利要求1-8任一项所述的材料的应用。1. Use of a material as claimed in any one of claims 1-8.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010921365.3 | 2020-09-04 | ||
CN202010921365.3A CN111941967B (en) | 2020-09-04 | 2020-09-04 | Material and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022048584A1 true WO2022048584A1 (en) | 2022-03-10 |
Family
ID=73357610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/116155 WO2022048584A1 (en) | 2020-09-04 | 2021-09-02 | Material, preparation method therefor, and application thereof |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN111941967B (en) |
WO (1) | WO2022048584A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115093640A (en) * | 2022-07-30 | 2022-09-23 | 山东立卓睡眠科技有限公司 | Degradable PE fiber tube, preparation method and application of degradable PE fiber tube as pillow inner filler |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111941967B (en) * | 2020-09-04 | 2023-03-24 | 上海浦景化工技术股份有限公司 | Material and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060040119A1 (en) * | 2002-07-11 | 2006-02-23 | Yosuke Egawa | Biodegradable laminate sheet and molded item from biodegradable laminate sheet |
CN1860026A (en) * | 2003-10-01 | 2006-11-08 | 三菱树脂株式会社 | Biodegradable layered sheet |
CN105477690A (en) * | 2014-09-17 | 2016-04-13 | 上海微创医疗器械(集团)有限公司 | Multilayer degradable tube and stent and preparation method thereof |
CN107718813A (en) * | 2017-09-26 | 2018-02-23 | 江南大学 | A kind of high-performance fiber base all-polymer composite board and preparation method thereof |
CN111098574A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Full-biodegradable high-water-resistance film and preparation method and application thereof |
CN111941967A (en) * | 2020-09-04 | 2020-11-17 | 上海浦景化工技术股份有限公司 | Material and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003147177A (en) * | 2001-11-16 | 2003-05-21 | Mitsubishi Plastics Ind Ltd | Biodegradable sheet, fabricated article using sheet and process for fabricated sheet |
AR058496A1 (en) * | 2005-10-26 | 2008-02-06 | Dow Global Technologies Inc | ELASTIC ARTICLES OF MULTIPLE LAYERS |
CN100556642C (en) * | 2007-06-06 | 2009-11-04 | 中国科学院化学研究所 | The regulate and control method of aliphatic poly adipic acid fourth diester material degradation performance |
WO2011139052A2 (en) * | 2010-05-06 | 2011-11-10 | (주)Lg화학 | Multilayered sheet, and method for preparing same |
PT3060601T (en) * | 2013-10-27 | 2021-03-12 | Tipa Corp Ltd | Biodegradable sheet |
JP6754756B2 (en) * | 2014-09-25 | 2020-09-16 | ダウ グローバル テクノロジーズ エルエルシー | Polyolefin-based elastic film structure, laminate, and method thereof |
US10682834B2 (en) * | 2017-03-31 | 2020-06-16 | Toray Plastics (America), Inc. | Antifog polyester lidding film for CPET trays |
JP2019059059A (en) * | 2017-09-25 | 2019-04-18 | 三井化学株式会社 | Laminated structure |
CN111001045B (en) * | 2020-01-07 | 2021-12-14 | 西安医学院第二附属医院 | Degradable ureteral stent and manufacturing method thereof |
-
2020
- 2020-09-04 CN CN202010921365.3A patent/CN111941967B/en active Active
-
2021
- 2021-09-02 WO PCT/CN2021/116155 patent/WO2022048584A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060040119A1 (en) * | 2002-07-11 | 2006-02-23 | Yosuke Egawa | Biodegradable laminate sheet and molded item from biodegradable laminate sheet |
CN1860026A (en) * | 2003-10-01 | 2006-11-08 | 三菱树脂株式会社 | Biodegradable layered sheet |
CN105477690A (en) * | 2014-09-17 | 2016-04-13 | 上海微创医疗器械(集团)有限公司 | Multilayer degradable tube and stent and preparation method thereof |
CN107718813A (en) * | 2017-09-26 | 2018-02-23 | 江南大学 | A kind of high-performance fiber base all-polymer composite board and preparation method thereof |
CN111098574A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Full-biodegradable high-water-resistance film and preparation method and application thereof |
CN111941967A (en) * | 2020-09-04 | 2020-11-17 | 上海浦景化工技术股份有限公司 | Material and preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115093640A (en) * | 2022-07-30 | 2022-09-23 | 山东立卓睡眠科技有限公司 | Degradable PE fiber tube, preparation method and application of degradable PE fiber tube as pillow inner filler |
Also Published As
Publication number | Publication date |
---|---|
CN111941967B (en) | 2023-03-24 |
CN111941967A (en) | 2020-11-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022048584A1 (en) | Material, preparation method therefor, and application thereof | |
US8362157B2 (en) | Polylactic acid composition and molding comprising the composition | |
TWI304426B (en) | ||
WO2018070490A1 (en) | Biodegradable nonwoven fabric | |
JP5494484B2 (en) | Polylactic acid resin composition and film | |
KR101194358B1 (en) | Polyester nonwoven fabrics, its preparation method and carpet primary backing substrate | |
JPH09111107A (en) | Biodegradable film or sheet and biodegradable plastic molding | |
KR102395895B1 (en) | Biodegradable composite fiber and non-woven fabric including the same | |
JP6316631B2 (en) | Laminated body and method for producing the same | |
JP5234689B2 (en) | Polyester film for simultaneous transfer of molding | |
TWI764202B (en) | Sound-absorbing air duct for vehicle containing polyester fiber with low melting point | |
KR101894773B1 (en) | Polyester Nonwoven Fabric, Method for Manufacturing The Same, and Primary Backing Substrae for Carpet Comprising The Same | |
US20100304066A1 (en) | Polylactic acid filament nonwoven fabric and production method thereof | |
CN113817148B (en) | Polylactic acid copolymer, preparation method and application thereof, and preparation method of blend film | |
JP2015178692A (en) | Method for producing nanofiber and nanofiber | |
JP4219207B2 (en) | Biodegradable complex | |
JP4390302B2 (en) | Non-woven fabric for molding having biodegradability, method for producing the same, and container-shaped product using the nonwoven fabric | |
TWI743592B (en) | Polyester resin for adhesive strength-improved binder and polyester fiber using the same | |
JP2022526952A (en) | Multi-component thermoplastic product | |
JP2019073809A (en) | Biodegradable filament nonwoven fabric having thermal moldability | |
JP3280927B2 (en) | Degradable recording sheet and recording card | |
JP5391666B2 (en) | Biaxially stretched film | |
JP5155643B2 (en) | Polylactic acid resin, polylactic acid resin composition, and molded article thereof | |
TW202248312A (en) | Biaxially oriented film, laminate, and environment-friendly packing material comprising the film | |
CN1132532A (en) | New fiberballs |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21863648 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21863648 Country of ref document: EP Kind code of ref document: A1 |