CN112266589B - Creep-resistant PBAT material and preparation method and application thereof - Google Patents
Creep-resistant PBAT material and preparation method and application thereof Download PDFInfo
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- CN112266589B CN112266589B CN202011229925.5A CN202011229925A CN112266589B CN 112266589 B CN112266589 B CN 112266589B CN 202011229925 A CN202011229925 A CN 202011229925A CN 112266589 B CN112266589 B CN 112266589B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention discloses a creep-resistant PBAT material, a preparation method and application thereof, wherein the creep-resistant PBAT material comprises the following components: 100 parts of PBAT resin; 10 to 25 parts of hyperbranched polyester; 3-5 parts of a chain extender; 0.5 to 4 portions of cross-linking agent; 0.25 to 2 parts of auxiliary crosslinking agent; 20-40 parts of a filler; 0.1 to 8 portions of other auxiliary agents. According to the invention, the hyperbranched polyester terminated by hydroxyl is added to perform crosslinking reaction with PBAT resin, so that the crosslinking density is increased, the material has good creep resistance, and meanwhile, the zero-cut viscosity of the material can be effectively reduced, and the processing energy consumption is reduced; the degradable plastic bag made of the PBAT material has high creep resistance, is not easy to deform and break, and further widens the application of the PBAT plastic bag.
Description
Technical Field
The invention relates to the technical field of degradable materials, in particular to a creep-resistant PBAT material and a preparation method and application thereof.
Background
In recent years, with the development of degradable polymers such as polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polycaprolactone (PCL) and the like, environment-friendly plastic products have become a new industrial star in the plastic industry. Although the comprehensive performance of PLA is the most excellent, the development and popularization of PLA products are severely restricted by the problems that the productivity is limited all over the world at present, the batch stability of raw materials is poor, the price is high and the like. Commercial conversion of PBAT is superior compared to that of PBAT.
PBAT is a copolymer of butylene adipate and butylene terephthalate, has excellent biodegradability, and currently, the common degradable plastic bags on the market mainly take PBAT as a base resin. Although PBAT has the characteristics of PBA and PBT, has better ductility and elongation at break, and also has better heat resistance and impact resistance, the creep resistance of a pure PBAT film is extremely poor, and deformation and fracture are easy to generate when a heavy object is loaded; in addition, the PBAT has larger zero-cut viscosity, high processing energy consumption and poorer openness during film blowing, and is not beneficial to large-scale production; the PBAT price is higher than that of the traditional petroleum-based non-biodegradable material, the material cost can be reduced by adding inorganic filler generally, but the problems of poor dispersibility, difficult processing and the like can be caused by adding excessive inorganic filler; the popularization and the application of the PBAT degradable plastic bag are limited under the above conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a PBAT material which has good creep resistance, small zero-cut viscosity and easy processing.
It is another object of the invention to provide a method for the preparation of the above creep-resistant PBAT material.
The invention is realized by the following technical scheme:
a creep-resistant PBAT material comprises the following components in parts by weight:
100 parts of PBAT resin;
10 to 25 parts of hyperbranched polyester;
3-5 parts of a chain extender;
0.5 to 4 portions of cross-linking agent;
0.25 to 2 parts of auxiliary crosslinking agent;
20-40 parts of a filler;
0.1 to 8 portions of other auxiliary agents.
The PBAT resin adopted by the invention is a general film grade PBAT resin, and concretely can be selected from Lanshan Tun river TH-801T, pasteur PBAT Ecoflex BX7011, jinlun science and technology Flex-64D or Jinhuilong Ecoworld and the like.
The hyperbranched polyester is third-generation hydroxyl-terminated hyperbranched polyester, and the number of the hydroxyl-terminated polyester is required to be more than 3. According to the invention, the research shows that the creep resistance of the PBAT material can be obviously enhanced by adding the hyperbranched polyester terminated with hydroxyl. The hyperbranched polyester has terminal hydroxyl groups, can realize ester exchange reaction with PBAT resin, is crosslinked with the PBAT resin, and increases crosslinking density, thereby enhancing the creep resistance of the material; meanwhile, the hyperbranched polyester plays a role in lubrication during processing, can effectively reduce the zero-shear viscosity of PBAT and reduce the processing energy consumption. The molecular weight of the hyperbranched polyester is not less than 2500g/mol; specifically, hyPer H104, hyPer H204, hyPer H302, hyPer H303, hyPer H304, hyPer H402, hyPer H403, etc. of Wuhan HyPer-branched resin technology, inc. can be selected.
The chain extender is a prepolymer of Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol.
The thermal decomposition temperature of the cross-linking agent adopted by the invention is 130 to 150 ℃; the cross-linking agent is selected from any one of bis (4-methylbenzoyl) peroxide PMB, dibenzoyl peroxide BPO or 1, 1-bis (tert-butylperoxy) cyclohexane PHC.
The auxiliary crosslinking agent is selected from any one of ethylene glycol dimethacrylate EDGM, diallyl phthalate DVB, 1-trimethylolpropane trimethacrylate TMPTMA, divinylbenzene DVB, triallylcyanurate TAC, triallylisocyanurate TAIC or trimethallyl allyl isocyanate TMAIC.
The invention can add a large amount of filler to increase the strength of the material and reduce the cost of the material. The filler is selected from one or more of talcum powder, calcium carbonate, magnesium carbonate, barium carbonate, silicon dioxide, diatomite, mica sheet or organic montmorillonite.
The other auxiliary agents comprise any one or more of a lubricant, an antioxidant, an ultraviolet absorbent or a light stabilizer; the additive can be selected according to the requirements of material properties. The lubricant is selected from any one or more of polyethylene wax, oxidized polyethylene wax or paraffin wax; the antioxidant is selected from one or more of an antioxidant 1010, an antioxidant 1076 and an antioxidant T501; the ultraviolet absorbent is any one or more of UV531, UV234, UV326, UV327, UV328, UV329 or UV 1130; the light stabilizer is any one or more of a light stabilizer 770, a light stabilizer 944, a light stabilizer 622, a light stabilizer 2002, a light stabilizer 783 and a light stabilizer 2020.
The invention also provides a preparation method of the creep-resistant PBAT material, which comprises the following steps:
(1) Drying and dehydrating: drying PBAT resin, hyperbranched polyester and filler at 55-65 ℃ for 1.5-3.5 h;
(2) Mixing materials: according to the proportion, the PBAT resin after the hot drying and dehydration, the hyperbranched polyester, the filler and other auxiliary agents are put into a high-speed mixer to be mixed uniformly, the mixture is mixed for 40 to 80s at the rotating speed of 500 to 1000r/min, and then the rotating speed is increased to 1000 to 2000r/min to be mixed for 10 to 30s;
(3) And (3) extruding and granulating: and (3) putting the mixed material obtained in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48, eight sections are arranged for heating, and the temperature of 1-8 sections is 130,140,150, 160,165 and 165 ℃. The second charging hole is arranged in the third section of heating zone, and the third charging hole is arranged in the fifth heating zone. The chain extender is added from a second feeding port of the extruder, and the cross-linking agent and the auxiliary cross-linking agent are added from a third feeding area; extruding and granulating to obtain the creep-resistant PBAT material.
The invention also provides the application of the creep-resistant PBAT material in degradable plastic bags. The PBAT plastic film can be prepared by a film blowing process and is used for preparing PBAT degradable plastic bags.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the hyperbranched polyester with the end-capped hydroxyl group is added to perform crosslinking reaction with the PBAT resin, so that the crosslinking density is increased, and the material has good creep resistance; meanwhile, the zero-shear viscosity of the material can be effectively reduced, and the processing energy consumption is reduced; the degradable plastic bag made of the PBAT material has high creep resistance, is not easy to deform and break, and further widens the application of the PBAT plastic bag.
(2) The PBAT material component formula of the invention has high filler addition amount, can achieve the same using effect, reduces the cost by 15 to 30 percent, and greatly reduces the material cost of PBAT plastic bags.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PBAT resin 1: blue mountain tun river TH-801T;
PBAT resin 2: basf PBAT Ecoflex BX7011;
PBAT resin 3: jinfa science and technology Flex-64D;
PBAT resin 4: glowing of aurora ecodord;
hyperbranched polyester 1: hydroxyl-terminated hyperbranched polyester, hyPer H104, wuhan hyperbranched resin science and technology Limited, with a molecular weight of 5200g/mol;
hyperbranched polyester 2: hydroxyl-terminated hyperbranched polyester, hyPer H204, wuhan hyperbranched resins science and technology Limited, molecular weight 5400g/mol;
hyperbranched polyester 3: hydroxyl-terminated hyperbranched polyester, hyPer H302, wuhan hyperbranched resin technology Co., ltd., molecular weight 2500g/mol;
hyperbranched polyester 4: hydroxyl-terminated hyperbranched polyester, hyPer H303, wuhan hyperbranched resin science and technology Limited, with a molecular weight of 5500g/mol;
hyperbranched polyester 5: hydroxyl-terminated hyperbranched polyester, hyPer H301, wuhan hyperbranched resin technology Limited, molecular weight 920g/mol;
hyperbranched polyester 6: carboxyl-terminated hyperbranched polyester, hyPer C100, wuhan hyperbranched resins technologies ltd;
chain extender: a prepolymer of hexamethylene diisocyanate HDI and 1, 4-butanediol;
a crosslinking agent: bis (4-methylbenzoyl) peroxide PMB, dibenzoyl peroxide BPO, 1-bis (t-butylperoxy) cyclohexane PHC, commercially available;
auxiliary crosslinking agent: ethylene glycol dimethacrylate EDGM, triallyl isocyanurate TAIC, triallyl cyanurate TAC, commercially available;
filling: talcum powder, silicon dioxide, calcium carbonate and organic montmorillonite which are sold in the market;
lubricant: polyethylene wax, oxidized polyethylene wax, paraffin wax, commercially available;
antioxidant: antioxidant 1010, antioxidant 1076, antioxidant T501, commercially available;
ultraviolet absorber: UV531, UV324, UV326, commercially available;
light stabilizer: light stabilizer 770, light stabilizer 944, light stabilizer 2002, commercially available;
method for the preparation of PBAT materials of examples and comparative examples:
(1) Drying and dehydrating: the PBAT resin, the hyperbranched polyester and the filler are baked for 1.5 hours at the temperature of 55 ℃;
(2) Mixing materials: putting the hot-dried PBAT resin, the hyperbranched polyester, the filler and other auxiliaries into a high-speed mixer according to the mixture ratio, uniformly mixing the materials, mixing for 40 to 80s at the rotation speed of 500 to 1000r/min, and then increasing the rotation speed to 1000 to 2000r/min, and mixing for 10 to 30s;
(3) Extruding and granulating: and (3) putting the mixed material obtained in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48, and eight sections are arranged for heating, and the temperatures of 1 to 8 sections are 130,140,150, 160,165 and 165 ℃. The second charging hole is arranged in the third section of heating zone, and the third charging hole is arranged in the fifth heating zone. The chain extender is added from a second feeding port of the extruder, and the cross-linking agent and the auxiliary cross-linking agent are added from a third feeding area; extruding and granulating to obtain the PBAT material.
The PBAT materials prepared in the above embodiments and comparative examples are put into a film blowing machine, the temperature of screw rods in regions 1 to 4 is 130,140,150 and 165 ℃, the temperature of a die head is 165 ℃, the blow-up ratio is 1 to 4, and the thickness of the blown film is 8-12 mu m, so that the creep-resistant PBAT plastic film is obtained; and carrying out related performance tests.
Test criteria or methods for each property:
tensile strength: the test standard is GB/T1040-1992;
testing creep property: the test standard is GB/T11546.1-2008.
Table 1: the concrete proportions (in parts by weight) of the components in the examples and comparative examples and the results of various performance tests
As can be seen from the examples and comparative examples, PBAT materials prepared by adding hydroxyl-terminated hyperbranched polyester have good creep resistance and mechanical properties. Compared with the example 2, the hyperbranched polyesters of the comparative examples 1 and 2 have the advantages that the hyperbranched polyesters with too much addition amount or too small molecular weight are selected, the creep value of the film is obviously increased at room temperature for 24 hours, the creep resistance is poor, and the tensile strength is also reduced; compared with the prior art, the carboxyl-terminated hyperbranched polyester is selected in the comparative example 3, and the creep resistance and the mechanical property of the material are not improved; comparative example 4 the material has poor creep resistance and mechanical properties without adding hyperbranched polyester.
Claims (9)
1. A creep-resistant PBAT material is characterized by comprising the following components in parts by weight:
100 parts of PBAT resin;
10 to 25 parts of hyperbranched polyester;
3-5 parts of a chain extender;
0.5 to 4 portions of cross-linking agent;
0.25 to 2 parts of auxiliary crosslinking agent;
20-40 parts of a filler;
0.1-8 parts of other auxiliary agents;
the hyperbranched polyester is selected from third-generation hydroxyl-terminated hyperbranched polyester;
the molecular weight of the hyperbranched polyester is not less than 2500g/mol.
2. The creep-resistant PBAT material of claim 1, wherein the number of the terminal hydroxyl groups of the hyperbranched polyester is more than 3.
3. The creep-resistant PBAT material of claim 1, wherein the chain extender is a prepolymer of hexamethylene diisocyanate HDI and 1, 4-butanediol.
4. The creep-resistant PBAT material of claim 1, characterized in that the thermal decomposition temperature of the cross-linking agent is 130 to 150 ℃; the cross-linking agent is selected from any one of bis (4-methylbenzoyl) peroxide PMB, dibenzoyl peroxide BPO or 1, 1-bis (tert-butylperoxy) cyclohexane PHC.
5. The creep-resistant PBAT material according to claim 1, characterized in that the co-crosslinking agent is selected from any one of ethylene glycol dimethacrylate EDGM, diallyl phthalate DVB, 1-trimethylolpropane trimethacrylate TMPTMA, divinylbenzene DVB, triallylcyanurate TAC, triallylisocyanurate TAIC or tri-allylisocyanate TMAIC.
6. The creep-resistant PBAT material according to claim 1, characterized in that the filler is selected from any one or more of talc, calcium carbonate, magnesium carbonate, barium carbonate, silica, diatomaceous earth, mica flakes or organo montmorillonite.
7. The creep-resistant PBAT material according to claim 1, characterized in that the other auxiliaries comprise any one or more of lubricants, antioxidants, uv absorbers or light stabilizers; the lubricant is selected from any one or more of polyethylene wax, oxidized polyethylene wax or paraffin wax; the antioxidant is selected from one or more of an antioxidant 1010, an antioxidant 1076 and an antioxidant T501; the ultraviolet absorbent is any one or more of UV531, UV234, UV326, UV327, UV328, UV329 or UV 1130; the light stabilizer is any one or more of a light stabilizer 770, a light stabilizer 944, a light stabilizer 622, a light stabilizer 2002, a light stabilizer 783 or a light stabilizer 2020.
8. The method for preparing the creep-resistant PBAT material according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) Drying and dehydrating: baking PBAT resin, hyperbranched polyester and a filler at 55 to 65 ℃ for 1.5 to 3.5h;
(2) Mixing materials: according to the proportion, the PBAT resin after the hot drying and dehydration, the hyperbranched polyester, the filler and other auxiliary agents are put into a high-speed mixer to be mixed uniformly, the mixture is mixed for 40 to 80s at the rotating speed of 500 to 1000r/min, and then the rotating speed is increased to 1000 to 2000r/min to be mixed for 10 to 30s;
(3) Extruding and granulating: putting the mixed material obtained in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 48, and eight sections are arranged for heating, wherein the temperatures of 1 to 8 sections are 130,140,150, 160,165 and 165 ℃; the second feeding port is arranged in a third section heating zone, and the third feeding port is arranged in a fifth heating zone; the chain extender is added from a second feeding port of the extruder, and the cross-linking agent and the auxiliary cross-linking agent are added from a third feeding area; extruding and granulating to obtain the creep-resistant PBAT material.
9. Use of the creep-resistant PBAT material according to any of claims 1 to 7 in degradable plastic bags.
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| CN114516950B (en) * | 2022-04-21 | 2022-07-15 | 富海(东营)新材料科技有限公司 | Hyperbranched PBAT polyester and preparation method thereof |
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| CN104559152A (en) * | 2014-12-19 | 2015-04-29 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester in PA6 (polyamide 6) |
| CN105331078A (en) * | 2015-12-02 | 2016-02-17 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester to plastic processing |
| CN110615978B (en) * | 2019-10-16 | 2022-01-25 | 苏州市新广益电子有限公司 | Degradable environment-friendly garbage bag and manufacturing method thereof |
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