CN115948033A - Epoxy chain extender master batch for PBAT film blowing, and preparation method and application thereof - Google Patents
Epoxy chain extender master batch for PBAT film blowing, and preparation method and application thereof Download PDFInfo
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 75
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 25
- 239000003054 catalyst Substances 0.000 claims abstract description 37
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- 238000002156 mixing Methods 0.000 claims abstract description 23
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- 235000021355 Stearic acid Nutrition 0.000 claims description 11
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- 150000003839 salts Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- KOMQGNYXBSXJTG-UHFFFAOYSA-N n,n-dimethyltetradecan-2-amine Chemical compound CCCCCCCCCCCCC(C)N(C)C KOMQGNYXBSXJTG-UHFFFAOYSA-N 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 8
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- 238000004804 winding Methods 0.000 description 3
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy chain extender master batch for PBAT film blowing, a preparation method and application thereof. The epoxy chain extender master batch consists of an A master batch and a B master batch; the preparation raw materials of the A master batch comprise the following raw materials: PBAT 90-94.5 wt%, chain extender 5-10 wt%, lubricant A0.5-1 wt%; the B master batch comprises the following raw materials: 90-94.5 wt% of PBAT, 5-10 wt% of catalyst and 0.5-1 wt% of lubricant B. The master batch A and the master batch B are respectively obtained by mixing the preparation raw materials, then performing melt extrusion granulation, and then performing air cooling and grain cutting. The invention provides application of the epoxy chain extender master batch in PBAT film blowing. According to the invention, the chain extender master batch is added in the PBAT film blowing link, so that the PBAT micro-crosslinking can be realized, the mechanical strength and the puncture resistance of the film are improved, and the film blowing process performance is not influenced.
Description
Technical Field
The invention belongs to the field of biodegradable plastics, and particularly relates to an epoxy chain extender master batch for PBAT blown film, and a preparation method and application thereof.
Background
White pollution caused by disposable plastic products is becoming more serious, and the problem of white pollution can be fundamentally solved by using biodegradable plastics. The polyethylene terephthalate-adipate-butanediol ester (PBAT) is 100 percent biodegradable, has similar mechanical property and molding processability to Polyethylene (PE), and is widely applied to the fields of biodegradable shopping bags, mulching films and the like. But the PBAT film has poor puncture resistance, so that the wide application of the PBAT film is limited, and the PBAT film is a problem which is urgently needed to be solved in the field of biodegradable packaging.
The phenomena of tire puncture resistance and rubber puncture resistance are inspired, and the problem can be solved by realizing PBAT micro-crosslinking by using the chain extender with multiple functional groups. However, the processing temperature of PBAT modified granulation manufacturers is generally about 140-160 ℃, epoxy chain extenders hardly have chain extension effect when being added at the temperature, and micro-crosslinking effect begins to appear when modification is carried out at 170-200 ℃, but the PBAT film blowing process performance is poor due to high energy consumption and micro-crosslinking, and many modified granulation manufacturers are reluctant to use the epoxy chain extenders.
Therefore, downstream film blowing manufacturers urgently need an epoxy catalyst with high chain extension reaction activity, which can be used in the film blowing link, the epoxy catalyst is diluted and added into PBAT film blowing granules, and a single-screw extruder is directly used for film blowing, so that the PBAT film with obvious micro-crosslinking effect and good puncture resistance can be prepared by crosslinking and blowing.
Disclosure of Invention
The invention provides a low-temperature high-efficiency epoxy chain extender master batch for PBAT (poly (butylene adipate-co-terephthalate)) blown film, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an epoxy chain extender master batch for a PBAT blown film, wherein the epoxy chain extender master batch consists of an A master batch and a B master batch, and the mass ratio of the A master batch to the B master batch is 1-3;
the preparation raw materials of the A master batch comprise the following raw material components:
carrier resin PBAT: 90-94.5 wt%
Chain extender: 5 to 10wt%
And (3) lubricant A:0.5 to 1 weight percent;
the B master batch comprises the following raw material components:
carrier resin PBAT:90 to 94.5 weight percent
Catalyst: 5 to 10 weight percent
And lubricant B:0.5 to 1 weight percent;
the chain extender is one or more of an inorganic chain extender containing polyepoxy functional groups, an ADR series chain extender ADR-4468, glycidyl ester type epoxy resin, glycidyl ether type epoxy resin and glycidyl amine type epoxy resin;
the catalyst is selected from one or more of tertiary amine, onium salt and crown ether;
the lubricant A and the lubricant B are respectively and independently selected from one or more of stearic acid, pentaerythritol ester, oxidized wax, white oil, zinc stearate and calcium stearate.
Preferably, the preparation raw material of the A master batch consists of the following raw material components:
carrier resin PBAT: 90-94.5 wt%
Chain extender: 5 to 10 weight percent
And lubricant A:0.5 to 1 weight percent.
Preferably, the preparation raw material of the B master batch comprises the following raw material components:
carrier resin PBAT: 90-94.5 wt%
Catalyst: 5 to 10wt%
And lubricant B:0.5 to 1 weight percent.
Preferably, the master batch A and the master batch B are respectively obtained by mixing the preparation raw materials, then performing melt extrusion granulation, and then performing air cooling granulation.
The PBAT can be new PBAT granules, return materials obtained by waste PBAT films and sheets, or PBAT extruder head materials, the melt flow rate is controlled to be 2-10 g/10min (190 ℃,2.16 kg), and the content of terminal carboxyl groups is controlled to be 1-30 mol/t.
Preferably, the inorganic chain extender containing the polyepoxy functional group is one or more of nano or micro-nano white carbon black, calcium carbonate, calcium silicate, mica, talcum powder and montmorillonite containing the polyepoxy functional group.
As a further preference, the inorganic chain extender containing polyepoxy functional group is prepared according to the following method: epoxy groups are modified on the surface of inorganic non-metal nano particles (such as hydrophilic white carbon black), and the modification refers to grafting a coupling agent on the surface of the inorganic non-metal nano particles in the presence of a solvent, namely in a wet process. The method specifically comprises the following steps:
(1) Preparing 5-15wt% (preferably 10 wt%) of white carbon black suspension by using ethanol and deionized water as a mixed solvent; in the mixed solvent, the mass ratio of ethanol to water is 60-80%:40-20% (preferably 70%: 30%) in a three-neck flask capable of heating and condensing for reflux;
(2) Adjusting the pH value of the white carbon black suspension to be between 3.5 and 5.5, slowly dripping a coupling agent KH560 while stirring, wherein the mass ratio of the coupling agent to the white carbon black is (15-25): 100, preferably 20:100, respectively;
(3) Heating the suspension to 65-75 ℃ (preferably 70 ℃), and stirring for reaction for 1-3h (preferably 2 h) to obtain a material A;
(4) Taking out the material A, performing centrifugal separation, and pouring out supernatant to obtain a precipitate;
(5) And then the precipitate is placed in an oven to be dried to obtain white powder, and the white powder is crushed by a high-speed crusher and sieved to obtain the inorganic chain extender containing the polyepoxy functional group.
The catalyst is one or more of tertiary amine, onium salt and crown ether. The preferred tertiary amine catalyst is one or more of 2-methylimidazole, 2-ethylimidazole, N-dimethylaniline and dodecyl dimethyl ethylamine. The preferred onium salt catalyst is one or more of ethyl triphenyl phosphonium bromide, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride and benzyl trimethyl ammonium chloride, and further preferred is ethyl triphenyl phosphonium bromide. A preferred crown ether catalyst is 18-crown ether.
The lubricants A and B are respectively and independently one or more of stearic acid, pentaerythritol ester, oxidized wax, white oil, zinc stearate and calcium stearate, and preferably stearic acid. The lubricant selected by the invention has good compatibility with PBAT, and can promote the chain extender or the catalyst to be uniformly distributed in the carrier resin. Preferably, the lubricant A is used in an amount of 5-10 wt% of the mass of the chain extender, and the lubricant B is used in an amount of 5-10 wt% of the mass of the catalyst.
In a second aspect, the invention provides a preparation method of an epoxy chain extender master batch for PBAT blown film, which comprises the following steps:
step 1: weighing the chain extender and the lubricant A according to the proportion, and stirring and mixing uniformly to obtain a pre-dispersed chain extender;
and 2, step: weighing carrier resin PBAT according to the proportion, and stirring and mixing the carrier resin PBAT and the chain extender pre-dispersed in the step 1 in a high-speed mixer to obtain a mixture A;
and 3, step 3: melting, extruding and granulating the mixture A through a double-screw extruder, and then air-cooling and granulating to obtain master batch A;
and 4, step 4: weighing the catalyst and the lubricant B according to the proportion, and stirring and mixing uniformly to obtain a pre-dispersed catalyst;
and 5: weighing carrier resin PBAT according to the proportion, and stirring and mixing the carrier resin PBAT and the catalyst pre-dispersed in the step 4 uniformly in a high-speed mixer to obtain a mixture B;
and 6: melting, extruding and granulating the mixture B obtained in the step 5 through a double-screw extruder, and then air-cooling and granulating to obtain B master batches;
and 7: and (3) preparing the master batch A and the master batch B according to the mass ratio of 1.
Preferably, in step 1, the stirring conditions are: stirring and mixing at room temperature, wherein the stirring speed is 200-500 rpm, and the stirring time is 3-5 min.
Preferably, in step 2, the stirring and mixing conditions are as follows: stirring at room temperature, wherein the rotating speed is 200-500 rpm, and the stirring time is 10-20 min.
Preferably, in step 3, the extrusion granulation conditions are: the rotating speed of the screw is 200-300 rpm, the feeding rate is 10-30 Hz, the processing temperature is 90-130 ℃, and the head temperature is 130 ℃.
Preferably, in step 3, the pellet cutting speed is 30 to 60rpm.
Preferably, in step 4, the stirring conditions are as follows: stirring at room temperature with a stirring speed of 200-500 rpm for 3-5 min.
Preferably, in step 5, the stirring and mixing conditions are as follows: stirring at room temperature, wherein the rotating speed is 200-500 rpm, and the stirring time is 10-20 min.
Preferably, in step 6, the extrusion granulation conditions are: the rotating speed is 200-300 rpm, the feeding rate is 10-30 Hz, the processing temperature is 90-130 ℃, and the head temperature is 130 ℃.
Preferably, in step 6, the pellet cutting speed is 30 to 60rpm.
In a third aspect, the invention provides an application of the epoxy chain extender master batch in PBAT blown film.
The application specifically comprises the following steps: after the epoxy chain extender master batch and the PBAT are weighed according to the proportion, the mixture is stirred and mixed uniformly in a high-speed mixer to obtain a mixture, and then the mixture is blown by a film blowing machine to obtain the PBAT film.
Preferably, the stirring and mixing conditions are as follows: stirring at room temperature with a stirring speed of 200-1000 rpm for 3-10 min. Further preferred stirring and mixing conditions are: the rotating speed is 400-500 rpm, and the stirring time is 3-5 min.
Preferably, the film blowing conditions are as follows: the screw rotating speed is 20-50 rpm, the film blowing temperature is 120-160 ℃, the die temperature is 140-145 ℃, the blowing ratio is 1-1, the drawing speed is 10-20 rpm, and the winding speed is 10-20 rpm.
Preferably, the mass ratio of the PBAT to the epoxy chain extender master batch is 90-98%:10-2 percent.
The invention provides a low-temperature high-efficiency epoxy chain extender master batch for PBAT (poly (epoxy ester)) blown film and a preparation method thereof. Compared with the prior art, the method has the following beneficial effects:
1: the addition is carried out in the film blowing process, and the use is simple;
2: the reaction temperature is low, the existing film blowing process is not required to be changed, and the energy conservation and consumption reduction are facilitated.
3: the degree of micro-crosslinking of PBAT can be flexibly controlled by the addition of the chain extender master batches A and B.
4: the master batch has good compatibility with PBAT and is easy to disperse.
Drawings
Fig. 1 is a schematic representation of an inorganic epoxy chain extender micro-crosslinked PBAT of the present invention.
Detailed Description
The invention provides a low-temperature high-efficiency epoxy chain extender master batch for PBAT film blowing and a preparation method thereof, and the invention is further described in detail by the following examples in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It is to be understood that the described embodiments are merely illustrative of some, but not all, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Testing the tensile strength and the elongation at break of the film according to the national standard test GB/T1040.3-2006; the puncture resistance of the film is tested according to the national standard GB/T37841-2019.
PBAT is TH-801T, ntun river science and technology GmbH in Xinjiang blue;
hydrophilic white carbon black: precipitated silica, hesheng silicon industries Ltd;
silane coupling agent: KH560, alatin;
chain extender ADR-4468, manufactured by BASF corporation;
small molecule glycidyl ester type epoxy resin: MF-2282, hubei Chengfeng chemical Co., ltd;
catalyst: the ethyl triphenyl phosphonium bromide, the 2-methylimidazole and the 18-crown ether are all commercial products;
lubricant: stearic acid, commercially available.
The preparation of the inorganic chain extender containing the polyepoxy functional group specifically comprises the following steps:
(1) Ethanol, deionized water and hydrophilic white carbon black according to a mass ratio of 70:30: preparing white carbon black suspension according to the proportion of 10, and placing the white carbon black suspension in a three-neck flask which can be heated and condensed to reflux;
(2) Adjusting the pH value of the white carbon black suspension to 3.5-5.5, slowly dripping the coupling agent KH560 while stirring. The mass ratio of the coupling agent to the white carbon black is 20:100, respectively;
(3) Heating the suspension to 70 ℃, and stirring for reacting for 2 hours to obtain a material A;
(4) Taking out the material A, performing centrifugal separation, and pouring out supernatant to obtain a precipitate;
(5) And then placing the precipitate in a drying oven to be dried for 12 hours at the temperature of 80 ℃ to obtain white powder, crushing the white powder by a high-speed crusher, and sieving the white powder by a 200-mesh sieve to obtain the epoxy functionalized inorganic chain extender.
The polyepoxy-functional inorganic chain extenders used in all the following experiments were prepared using the above-described method.
Example 1:
a low-temperature high-efficiency epoxy chain extender master batch for PBAT film blowing consists of two parts, namely an A master batch and a B master batch.
The master batch A comprises the following raw materials in parts by weight: PBAT: inorganic chain extender with polyepoxy functional group: stearic acid =94.5:5:0.5.
the master batch B comprises the following raw materials in parts by weight: PBAT: ethyl triphenyl phosphonium bromide: stearic acid =94.5:5:0.5.
a preparation method of low-temperature high-efficiency epoxy chain extender master batch for PBAT blown film comprises the following steps:
step 1: weighing inorganic chain extender containing polyepoxy functional group and stearic acid according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: 400rpm, stirring time: and 5min to obtain the pre-dispersed chain extender.
And 2, step: weighing the carrier resin PBAT and the pre-dispersed chain extender in the step 1 according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: stirring at 500rpm for 5min to obtain a mixture.
And step 3: and (3) melting, extruding and granulating the mixture by a double-screw extruder, wherein the rotating speed of a screw is 250rpm, the feeding rate is 10Hz, the processing temperature is 90-130 ℃, the head temperature is 130 ℃, and the granulating speed is 30rpm, so as to obtain the master batch A.
And 4, step 4: weighing ethyl triphenyl phosphonium bromide and stearic acid according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: 400rpm, stirring time: and 5min to obtain the pre-dispersed catalyst.
And 5: weighing the carrier resin PBAT and the pre-dispersed catalyst in the step 4 according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: stirring at 500rpm for 5min to obtain a mixture.
Step 6: and melting, extruding and granulating the mixture by a double-screw extruder, wherein the rotating speed of a screw is 250rpm, the feeding rate is 10Hz, the processing temperature is 90-130 ℃, and the head temperature is 130 ℃. The granulating speed is 30rpm, and B master batch is obtained.
And 7: preparing the A master batch and the B master batch according to the mass part ratio of = 7; after weighing the chain extender master batch and the PBAT according to the mass part ratio of 95;
and 8: and (2) blowing the mixture into a film by a film blowing machine, wherein the film blowing process comprises the following steps of setting the rotating speed of a screw rod at 20rpm, setting the film blowing temperature at 120-160 ℃, setting the temperature of a neck mold at 145 ℃, setting the blowing ratio at 2.5, setting the traction speed at 10rpm and the winding speed at 12rpm, and obtaining the biodegradable PBAT film with high tensile strength and strong puncture resistance. In the PBAT film, the PBAT content is 99.725wt%, the content of the inorganic chain extender with polyepoxy functional groups is 0.175wt%, and the content of the catalyst ethyl triphenyl phosphonium bromide is 0.075wt% and 0.025wt%.
The mechanical properties of the film are shown in table 1:
TABLE 1
Namely, the puncture resistance, puncture resistance and tensile strength of the PBAT film are obviously improved compared with the pure PBAT (see the following comparative example 1), and the PBAT (comparative example 2) only added with the chain extender in the granulation stage is uniformly improved. The micro-crosslinking effect of the added chain extender master batch on improving the puncture resistance strength and other mechanical properties of the PBAT film is proved to be obvious under the low-temperature film blowing process.
Example 2
The other steps are the same as example 1, the variable is the type of the chain extender, the chain extender is an ADR oligomer type chain extender ADR-4468, and the mechanical properties of the prepared PBAT film are shown in the following table 2:
TABLE 2
Compared with comparative example 1. The ethyl triphenyl phosphonium bromide has an obvious catalytic effect on the chain extension reaction of ADR-4468, and the puncture resistance, puncture resistance and tensile strength of the prepared PBAT film are obviously improved under the condition of a low-temperature process.
Example 3
The other steps are the same as the example 1, the variable is the type of the chain extender, and the chain extender is glycidyl ester type epoxy resin MF-2282. The mechanical properties of the prepared PBAT film are shown in table 3 below:
TABLE 3
Compared with the comparative example 1, the ethyl triphenyl phosphonium bromide has an obvious catalytic effect on the chain extension reaction of the glycidyl ester type epoxy resin, and the puncture resistance, puncture resistance and tensile strength of the prepared PBAT film are obviously improved under the condition of a low-temperature process.
Example 4
The other steps are the same as example 1, the variable is the type of catalyst, and the chain extender reaction catalyst is 2-methylimidazole. The mechanical properties of the prepared PBAT film are as follows 4:
TABLE 4
Compared with the example 1, the 2-methylimidazole also has a more obvious catalytic effect on the inorganic chain extender with multi-epoxy functional groups, but the catalytic effect is not as obvious as that of ethyl triphenyl phosphine bromide. Compared with the comparative example 1, the prepared PBAT film has obviously improved puncture resistance, puncture resistance and tensile strength.
Example 5
The other steps are the same as example 1, the variable is the type of catalyst, and the chain extension reaction catalyst is 18-crown ether. The mechanical properties of the prepared PBAT film are shown in table 5 below:
TABLE 5
Compared with the example 1, the 18-crown ether has a certain catalytic effect on the inorganic chain extender with multi-epoxy functional groups, but the catalytic effect is not as obvious as that of ethyl triphenyl phosphine bromide and di-methylimidazole. Compared with the comparative example 1, the prepared PBAT film has improved puncture resistance, puncture resistance and tensile strength to a certain extent.
Comparative example 1
Pure PBAT film blowing and the film blowing process are the same as example 1, and the mechanical properties of the prepared PBAT film are shown in the following table 6:
TABLE 6
Comparative example 2
Otherwise, the same as example 1, but without adding chain extender masterbatch B, PBAT was controlled: and the mass part ratio of the chain extender master batch is 95. The mechanical properties of the prepared PBAT film are shown in table 7 below:
TABLE 7
Compared with the example 1, under the condition of no catalyst, the polyepoxy functional group inorganic chain extender does not play a chain extension effect in the film blowing stage, and has no influence on the film performance.
Comparative example 3
According to the raw material feeding ratio, the catalyst is not added, the dosage of the catalyst is replaced by PBAT with the same mass, and the polyepoxy functional group inorganic chain extender is blended, melted and granulated with the PBAT in a granulation link, and the method comprises the following specific steps:
step 1: weighing carrier resin PBAT according to the mixture ratio (mass ratio, wt%): polyepoxy functional group inorganic chain extender: lubricant: (99.8: stirring at 500rpm for 5min to obtain a mixture.
Step 2: and (3) melting, extruding and granulating the mixture by a double-screw extruder, wherein the rotating speed of a screw is 250rpm, the feeding rate is 10Hz, the processing temperature is 90-130 ℃, the head temperature is 130 ℃, and the granulating speed is 30rpm to obtain the modified material.
And step 3: and (3) blowing the modified material into a film by a film blowing machine, wherein the film blowing temperature (DEG C) is 120-160 ℃, the die temperature is 145 ℃, the screw rotation speed is 20rpm, the blowing ratio is 2.5.
The mechanical properties are shown in table 8 below:
TABLE 8
Compared with the example 1, under the condition of no catalyst, the polyepoxy functional group inorganic chain extender does not play a chain extension effect in the granulation stage, and the film performance is not greatly improved in the film blowing stage.
Comparative example 4
The other steps are the same as the comparison example 3, the variable is the type of the chain extender, the chain extender is an oligomer type chain extender ADR-4468, and the chain extender and the PBAT are blended, melted and granulated in a low-temperature granulation link to obtain the film blowing material. The mechanical properties are shown in table 9 below:
TABLE 9
Compared with the comparative example 1, the oligomer type chain extender ADR-4468 does not have the chain extension effect in the low-temperature granulation stage, and the film performance is not greatly improved.
Comparative example 5
The rest is the same as the comparative example 4, but the granulation processing temperature is increased to 110-180 ℃, and the head temperature is 130 ℃; the processing temperature of the blown film is 145-190 ℃, and the temperature of the mouth mold is 155 ℃. The mechanical properties of the prepared PBAT films are shown in table 10 below.
Watch 10
Compared with the comparative example 1 and the comparative sample 4, the oligomer type chain extender ADR-4468 does not have a chain extension effect in the low-temperature granulation stage, the performances of the film are greatly improved after the granulation temperature is increased, particularly the tensile strength and the puncture resistance, the film blowing temperature is greatly increased when other processes are not changed but the film is blown, and otherwise the film is difficult to blow.
Comparative example 6
The other steps are the same as the embodiment 1, the difference is that the chain extender master batch does not comprise two components A and B, and the PBAT: epoxy functional group inorganic chain extender: ethyl triphenyl phosphonium bromide: stearic acid is fed according to the mass ratio (94.5.
Step 1: weighing the inorganic chain extender with the multi-epoxy functional group, the ethyl triphenyl phosphonium bromide and the stearic acid according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: 400rpm, stirring time: and 5min to obtain the pre-dispersing material.
Step 2: weighing carrier resin PBAT and the pre-dispersing material in the step 1 according to the proportion, stirring and mixing at normal temperature, wherein the stirring speed is as follows: stirring at 500rpm for 5min to obtain a mixture.
And 3, step 3: and (3) melting, extruding and granulating the mixture by a double-screw extruder, wherein the rotating speed of a screw is 250rpm, the feeding rate is 10Hz, the processing temperature is 90-130 ℃, the head temperature is 130 ℃, and the granulating speed is 30rpm, so as to obtain the chain extender master batch.
And 4, step 4: after weighing the chain extender master batch and the PBAT according to the mass part ratio of 95 to 5, uniformly stirring and mixing in a high mixer at normal temperature and at the rotating speed of 400rpm for 10min to obtain a mixture;
and 5: and (2) blowing the mixture into a film by a film blowing machine, wherein the film blowing process comprises the following steps of setting the rotating speed of a screw rod at 20rpm, setting the film blowing temperature at 120-160 ℃, setting the temperature of a neck mold at 145 ℃, setting the blowing ratio at 2.5, setting the traction speed at 10rpm and the winding speed at 12pm, and obtaining the biodegradable PBAT film.
TABLE 11
Compared with the comparative example 1 and the example 1, the chain extender and the catalyst are uniformly mixed, the current of an extruder is overlarge during extrusion granulation, the partial reaction of the chain extender under the action of the catalyst is caused, and the effective components are reduced in the film blowing stage, so that all the mechanical properties are lower than those of the example 1.
Comparative example 7
The other steps are the same as the example 1, in order to verify the dispersing effect of the lubricant on the chain extender and the catalyst, all the lubricant in the example 1 is removed, the same quality of PBAT is used for replacing the lubricant, and the other steps are unchanged, so that the stearic acid-free PBAT film is obtained, wherein the mechanical properties of the film are shown in the following table 12:
TABLE 12
The film prepared in comparative example 7 had gel points, because the chain extender and the catalyst were not uniformly dispersed in the PBAT in the granulation stage, and partially reacted in the blowing stage to form gel points, and further, because the dispersion was not uniform, the mechanical properties of comparative example 7 were not stable, and thus it was found that the lubricant was able to uniformly disperse the chain extender and the catalyst in the PBAT and to slightly crosslink with the PBAT in the blowing stage, and a high-performance film having stable puncture strength, puncture resistance, and tensile strength was obtained.
Claims (10)
1. The utility model provides a PBAT inflation film-blowing is with epoxy chain extender master batch which characterized in that: the epoxy chain extender master batch consists of a master batch A and a master batch B, wherein the mass ratio of the master batch A to the master batch B is 1;
the preparation raw materials of the A master batch comprise the following raw material components:
carrier resin PBAT: 90-94.5 wt%
Chain extender: 5 to 10wt%
And lubricant A:0.5 to 1 weight percent;
the B master batch comprises the following raw material components:
carrier resin PBAT:90 to 94.5 weight percent
Catalyst: 5 to 10wt%
And lubricant B:0.5 to 1 weight percent;
the chain extender is one or more of an inorganic chain extender containing polyepoxy functional groups, an ADR series chain extender ADR-4468, glycidyl ester type epoxy resin, glycidyl ether type epoxy resin and glycidyl amine type epoxy resin;
the catalyst is selected from one or more of tertiary amine, onium salt and crown ether;
the lubricant A and the lubricant B are respectively and independently selected from one or more of stearic acid, pentaerythritol ester, oxidized wax, white oil, zinc stearate and calcium stearate.
2. The epoxy chain extender masterbatch for PBAT blown film of claim 1, characterized in that: the master batch A and the master batch B are respectively obtained by mixing the preparation raw materials, then performing melt extrusion granulation, and then performing air cooling and grain cutting.
3. The epoxy chain extender masterbatch for PBAT blown film of claim 1 or 2, characterized in that: the melt flow rate of the PBAT is 2-10 g/10min (190 ℃,2.16 kg), and the content of terminal carboxyl is 1-30 mol/t.
4. The epoxy chain extender masterbatch for PBAT blown film of claim 1 or 2, characterized in that: the inorganic chain extender containing the polyepoxy functional group is one or more of nano or micro-nano white carbon black, calcium carbonate, calcium silicate, mica, talcum powder and montmorillonite containing the polyepoxy functional group.
5. The epoxy chain extender masterbatch for PBAT blown film of claim 1 or 2, characterized in that: the tertiary amine catalyst is one or more of 2-methylimidazole, 2-ethylimidazole, N-dimethylaniline and dodecyl dimethyl ethylamine; the onium salt catalyst is one or more of ethyl triphenyl phosphonium bromide, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride and benzyl trimethyl ammonium chloride; the crown ether catalyst is 18-crown ether.
6. The epoxy chain extender masterbatch for PBAT blown film of claim 1 or 2, characterized in that: the dosage of the lubricant A is 5-10 wt% of the mass dosage of the chain extender, and the dosage of the lubricant B is 5-10 wt% of the mass dosage of the catalyst.
7. The preparation method of the epoxy chain extender master batch for PBAT blown film according to claim 1, characterized in that: the method comprises the following steps:
step 1: weighing the chain extender and the lubricant A according to the proportion, and stirring and mixing uniformly to obtain a pre-dispersed chain extender;
and 2, step: weighing carrier resin PBAT according to the proportion, and stirring and mixing the carrier resin PBAT and the chain extender pre-dispersed in the step 1 in a high-speed mixer to obtain a mixture A;
and step 3: melting, extruding and granulating the mixture A through a double-screw extruder, and then air-cooling and granulating to obtain master batch A;
and 4, step 4: weighing the catalyst and the lubricant B according to the proportion, and stirring and mixing uniformly to obtain a pre-dispersed catalyst;
and 5: weighing the carrier resin PBAT according to the proportion, and stirring and mixing the PBAT and the catalyst pre-dispersed in the step 4 uniformly in a high-speed mixer to obtain a mixture B;
step 6: melting, extruding and granulating the mixture B obtained in the step 5 through a double-screw extruder, and then air-cooling and granulating to obtain B master batches;
and 7: and (3) preparing the master batch A and the master batch B according to the mass ratio of 1.
8. The use of the epoxy chain extender masterbatch of claim 1 or 2 in PBAT blown film.
9. The use of claim 8, wherein: the application specifically comprises the following steps: after the epoxy chain extender master batch and the PBAT are weighed according to the proportion, the mixture is stirred and mixed uniformly in a high-speed mixer to obtain a mixture, and then the mixture is blown by a film blowing machine to obtain the PBAT film.
10. The use of claim 9, wherein: the mass ratio of PBAT to the epoxy chain extender master batch is 90-98%:10-2 percent.
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| CN108102122A (en) * | 2017-12-25 | 2018-06-01 | 上海德亿化工有限公司 | A kind of degradable PBAT classes thin-film material and preparation method thereof |
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| CN113234304A (en) * | 2021-05-11 | 2021-08-10 | 贵州省材料产业技术研究院 | Biodegradable film material and preparation method of film |
| CN115058103A (en) * | 2022-08-02 | 2022-09-16 | 北京工商大学 | Preparation of epoxy cardanol-based chain extender modified PBAT-PLA composite membrane |
| CN115433441A (en) * | 2022-08-30 | 2022-12-06 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Full-biodegradable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102122A (en) * | 2017-12-25 | 2018-06-01 | 上海德亿化工有限公司 | A kind of degradable PBAT classes thin-film material and preparation method thereof |
| CN109575344A (en) * | 2018-12-26 | 2019-04-05 | 北京科方创业科技企业孵化器有限公司 | A kind of degradation plastic and preparation method thereof |
| CN113234304A (en) * | 2021-05-11 | 2021-08-10 | 贵州省材料产业技术研究院 | Biodegradable film material and preparation method of film |
| CN115058103A (en) * | 2022-08-02 | 2022-09-16 | 北京工商大学 | Preparation of epoxy cardanol-based chain extender modified PBAT-PLA composite membrane |
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